CN101484395A - Plasma display panel and method for manufacturing the same - Google Patents

Plasma display panel and method for manufacturing the same Download PDF

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Publication number
CN101484395A
CN101484395A CNA2007800246921A CN200780024692A CN101484395A CN 101484395 A CN101484395 A CN 101484395A CN A2007800246921 A CNA2007800246921 A CN A2007800246921A CN 200780024692 A CN200780024692 A CN 200780024692A CN 101484395 A CN101484395 A CN 101484395A
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China
Prior art keywords
glass
dielectric layer
moo
plasma display
display device
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CNA2007800246921A
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Chinese (zh)
Inventor
长谷川真也
井上修
河濑觉
中田泰彦
横田和弘
越须贺强
丰田诚司
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Publication of CN101484395A publication Critical patent/CN101484395A/en
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Abstract

This invention provides a plasma display panel comprising a display electrode (5) and an address electrode (10) which cross each other, at least one of the display electrode (5) and the address electrode (10) being covered with a first glass-containing first dielectric layer (6). The first glass is a Bi2O3-containing glass. The electrode covered with the first dielectric layer (6) comprises at least one of silver and copper. The first glass further comprises 0 to 4% by weight of MoO3 and 0 to 4% by weight of WO3. The total content of MoO3 and WO3 in the first glass is in the range of 0.1 to 8% by weight.

Description

Plasma display device and manufacture method thereof
Technical field
The present invention relates to plasma display device and manufacture method thereof.
Background technology
In recent years, flat-panel monitors such as plasma display device (below, be sometimes referred to as " PDP "), FED, liquid-crystal display are as realizing slim light-weighted indicating meter and being attracted attention.
These flat-panel monitors possess: the front panel and the backplate that comprise glass substrate and configuration constitutive requirements thereon.Also have, front panel and backplate are configured to opposed mutually, and peripheral part is sealed.
As mentioned above, PDP has the front panel of making and backplate is opposed, with the structure of its periphery with the glass for sealing sealing-in.Front panel comprises the front glass substrate, is formed with the striated show electrode on its surface, and then, be formed with dielectric layer and protective layer thereon.In addition, backplate comprises back side glass substrate, is formed with address electrode with striated in its surface, is formed with dielectric layer thereon, and then, between adjacent address electrode, be formed with the next door, between the adjacent next door that forms, be formed with luminescent coating.
Front panel and backplate both sides' electrode quadrature and opposed mutually, under this state, its outer edge of sealing-in.The enclosed space that forms in inside is filled with discharge gas.
Also have, show electrode is a pair of with two formations, and this a pair of show electrode and address electrode clip discharge space and clover leaf zone becomes the unit that pictorial display is played contribution.
Below, specify the dielectric layer of PDP.The dielectric layer of PDP is formed on the electrode, therefore, requires to have high insulativity, requires to have low specific inductivity in order to suppress to consume electric power, for fear of peeling off or crackle etc. and require matched coefficients of thermal expansion with glass substrate.And then the dielectric layer of glass substrate formation requires to be the high amorphous glass of visible light transmissivity usually in order to utilize well as display light efficient from the light that fluor produces in front.
The glass paste that dielectric layer will contain glass powder, resin, solvent, inorganic filler according to circumstances or mineral dye usually utilizes screen printing etc. to be coated on the glass substrate, carries out drying, burns till and form.On the other hand, as the glass substrate that is used in PDP,, use the soda-lime glass that utilizes float glass process to make usually from price or easily acquired viewpoint etc.Therefore, burning till under the condition below 600 ℃ of the distortion that glass substrate does not take place of glass paste carried out.
The dielectric layer that uses in PDP need burn till under the temperature of the distortion that does not cause glass substrate, therefore, need form with the lower glass of fusing point.Therefore, the current main PbO-SiO as main raw material that uses with PbO 2Be glass.
The dielectric layer of such PDP forms by burning till the glass paste that contains resin or solvent, therefore, because carbon-containing impurities is residual, causes dielectric layer painted, and brightness reduces sometimes.To reduce this situation is purpose, has proposed to have added MoO in the glass that contains PbO 3Or Sb 2O 3Transparency electrode lining with glass (for example, opening communique 2001-No. 151532) with reference to the spy.
And then, for consideration, made progress the exploitation that does not contain plumbous dielectric layer to problem of environment, for example, proposed to have used Bi 2O 3-B 2O 3-ZnO-R 2O is the dielectric layer (for example, opening communique 2001-No. 139345 with reference to the spy) of glass (R:Li, Na, K).In addition, contain in use under the situation of glass of alkalimetal oxide, for reduce on the aluminium electrode by the pore that burns till generation, proposed to have added CuO, CoO, MoO 3Or the glass of NiO (for example, opening communique 2002-No. 362941) with reference to the spy.
As mentioned above, proposed to use the dielectric layer that does not contain plumbous glass in the past, but owing to containing in order to realize that low softening point replaces the plumbous bismuth oxide that uses, dielectric layer or the flavescence of front glass substrate sometimes.The mechanism that this flavescence takes place thinks as described below.
In front the show electrode that is provided with of glass substrate or overleaf the address electrode that is provided with of glass substrate use Ag or Cu, when forming dielectric layer, carry out burn till the time, Ag or Cu ionization, stripping and spreading in dielectric layer or glass substrate sometimes.The Ag ion of this diffusion or Cu ion are contained Sn ion (divalence) reduction, gelatinizing under the sort of situation easily in the alkalimetal ion in the dielectric layer or bismuth oxide compound, the front glass substrate.Under the situation of Ag or the such gelatinizing of Cu, in dielectric layer or front glass substrate, the flavescence that so-called variable color is yellow or brown (for example, J.E.SHELBY and J.VITKO.Jr Journal of Non-Crystalline Solids vol50 (1982) 107-117) takes place.The light of the glass absorbing wavelength 400nm of such flavescence, therefore, in PDP, blue brightness reduces, or produces the variation of colourity, therefore, especially becomes problem in front in the plate.In addition,, therefore become the reason that the dielectric voltage withstand of dielectric layer reduces, and because to separate out much larger than the big colloidal particle of ionic, therefore, the light of reflecting ﹠ transmitting dielectric layer becomes the reason of the brightness that reduces PDP because the colloid of Ag or Cu is an electroconductibility.
Summary of the invention
The objective of the invention is in view of the above problems, provide to possess the high dielectric layer of proof voltage, suppress the flavescence of dielectric layer or glass substrate, and, the high plasma display device and the manufacture method thereof of reliability of insulation breakdown also suppressed.
To achieve these goals, plasma display of the present invention, it has cross one another show electrode and address electrode, and at least one electrode that is selected from described show electrode and address electrode is contained first dielectric layer lining of first glass, wherein, described first glass is for containing Bi 2O 3Glass, and contained by the described electrode of described first dielectric layer lining and to be selected from least a of silver and copper, described first glass also contains the MoO of 0～4wt% 3, 0～4wt% WO 3, and be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
In addition, in plasma display device of the present invention, can the Bi of described first glass will be contained in 2O 3Containing ratio be made as 2～40wt%.
In addition, in plasma display device of the present invention, preferred described first glass contains following composition at least as moiety,
SiO 2：0～15wt％
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
MoO 3：0～4wt％
WO 3：0～4wt％，
Be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.In this case, except above-mentioned composition, described first glass contains as moiety and is selected from Li 2O, Na 2O and K 2O at least a also can, be contained in the Li of described first glass 2O, Na 2O and K 2The total of the containing ratio of O for example can be the scope of 0.1～10wt%.
In addition, in plasma display device of the present invention, more preferably described first glass contains following composition at least as moiety,
SiO 2：0～15wt％
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O: greater than 0.1wt% and be below the 10wt%
MoO 3：0～4wt％
WO 3：0～4wt％，
Be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.In addition, as other examples of preferred composition, can enumerate glass as described below, described first glass contains as follows at least as moiety,
SiO 2: greater than 2wt% and be below the 15wt%
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O：0.1～10wt％
MoO 3：0～4wt％
WO 3：0～4wt％
Be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
In addition, in plasma display device of the present invention, can enumerate glass as described below as preferred composition, described first glass is as moiety, contain at least as follows,
SiO 2: greater than 2wt% and be below the 15wt%
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O: greater than 0.1wt% and be below the 10wt%
MoO 3：0～4wt％
WO 3：0～4wt％
Be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
In having first glass of above-mentioned preferred compositing range, Li 2O, Na 2O and K 2The containing ratio of O can be as described below,
Li 2Below the O:0.17wt%
Na 2Below the O:0.36wt%
K 2Below the O:0.55wt%
And Li 2O+Na 2O+K 2Below the O:0.55wt%.
The present invention also provides a kind of manufacture method of plasma display device, it is included in and disposes first glass material that contains first glass on the substrate that is formed with electrode, described first glass material is burnt till, form the operation of first dielectric layer of the described electrode of lining thus, wherein, described first glass is for containing Bi 2O 3Glass, and contained by the described electrode of described first dielectric layer lining and to be selected from least a of silver and copper, described first glass also contains the MoO of 0～4wt% 3, 0～4wt% WO 3, and be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
At plasma display device of the present invention and utilize in the plasma display device that the manufacture method of plasma display device of the present invention obtains (below, be recited as the plasma display device that obtains by the present invention), described first glass contains Bi 2O 3Therefore composition as realizing low softening pointization, can form the dielectric layer that is substantially devoid of lead (PbO).Also have, in this manual, " being substantially devoid of " is the meaning of allowing not this composition of the minimum trace that characteristic is exerted an influence, and specifically, containing ratio is 0.1wt%, preferred 0.05wt%.Thereby in plasma display device of the present invention, the lead that is contained in first glass can be for below the 0.1wt%, below the preferred 0.05wt%.
The plasma display device that obtains by the present invention contains in being contained in first dielectric layer and is selected from MoO 3And WO 3At least a.Thereby, even and under the situation of dielectric layer diffusion, also with MoO as the normally used Ag of electrode materials or Cu ionization 3Or WO 3Generate stable compound, therefore, can suppress Ag or Cu cohesion and the situation of gelatinizing.Thus, suppress the flavescence of the dielectric layer that the gelatinizing of Ag or Cu causes.In addition, under the situation that forms electrode on the glass substrate too, to Ag or the Cu and the MoO of glass substrate diffusion 3Or WO 3Generate stable compound, also can suppress the flavescence of the dielectric layer that the gelatinizing of Ag or Cu causes.And then, according to plasma display device of the present invention, not only can suppress flavescence, but also other drawbacks that can suppress to follow the colloidal of Ag or Cu to generate, for example, the reduction of the reduction of the dielectric voltage withstand of dielectric layer or the brightness of PDP.
In addition, first glass of the plasma display device that obtains by the present invention contains Bi 2O 3(for example, containing ratio is 2～40wt%), therefore, as the low softening point glass that contains, can realize using the plasma display device that replaces the glass of flint glass in the dielectric layer of covering electrodes.
In addition, in the plasma display device that obtains by the present invention, first glass can contain suitable moiety as implied above, and then, can also contain and be selected from Li 2O, Na 2O and K 2O's is at least a.Thus, can suppress the dielectric layer that the gelatinizing of Ag or Cu causes or the flavescence or the insulation breakdown of glass substrate, and, can utilize to be selected from Li 2O, Na 2O and K 2O's is at least a, reduces the softening temperature of glass, or with its adjusting.In addition, bear these compositions (Li of the effect that reduces softening temperature by interpolation 2O, Na 2O and K 2O), can reduce the key element of bearing same function and improving specific inductivity is Bi 2O 3Containing ratio, therefore, can reduce the specific inductivity of dielectric layer, or with its adjusting.
Description of drawings
Fig. 1 is the sectional view of the embodiment of expression PDP of the present invention.
Fig. 2 is the sectional view of another embodiment of expression PDP of the present invention.
Fig. 3 is that the part of structure of the PDP of presentation graphs 1 cuts stereographic map.
Fig. 4 is expression MoO 3And WO 3Containing ratio and b *The figure of the relation of value.
Embodiment
Below, embodiments of the present invention are described.Also have, the following description is an example of the present invention, and the present invention is not limited to these.
＜plasma display device 〉
Fig. 3 is the local section stereographic map of primary structure of the PDP of expression present embodiment.Fig. 1 is the sectional view of PDP shown in Figure 3.
This PDP is the AC surface discharge type, and dielectric layer (first dielectric layer) is formed by aftermentioned first glass, in addition, has and the routine in the past identical structure of PDP.
This PDP is applying front panel 1 and backplate 8 and constitute.Front panel 1 possesses: the dielectric material protective layer 7 that striated show electrode 5, dielectric layer (first dielectric layer) 6 that covers show electrode 5 and the magnesium oxide that front glass substrate 2, the nesa coating 3 that is formed at its medial surface (faces of discharge space 14 sides) and bus electrode 4 constitute constitutes.This dielectric layer 6 uses aftermentioned first glass.
In addition, backplate 8 comprises: the dielectric layer 11 of back side glass substrate 9, the striated address electrode 10 that is formed at its medial surface (faces of discharge space 14 sides), overlay address electrode 10, the luminescent coating 13 that is arranged on the dielectric layer 11 and is disposed at the banded next door 12 between the adjacent address electrode 10 and forms between adjacent next door 12.Next door 12 isolates each address electrode 10 mutually, forms discharge space 14.Luminescent coating 13 clips next door 12 with red-emitting phosphors layer 13 (R), green-emitting phosphor layer 13 (G) and blue phosphor layers 13 (B) and is arranged in order and forms for can display color.
Fluor as constituting luminescent coating 13 for example, can use material as follows.
Blue emitting phophor BaMgAl 10O 17: Eu
Green-emitting phosphor Zn 2SiO 4: Mn
Red-emitting phosphors Y 2O 3: Eu
It is mutually orthogonal that front panel 1 and backplate 8 are configured to the long side direction separately of show electrode 5 and address electrode 10, and show electrode 5 and address electrode 10 are opposed mutually, use sealing-in parts (not shown) to engage.Show electrode 5 and address electrode 10 form by containing at least a material that is selected from silver (Ag) and copper (Cu).
(pressure about 400～600Torr) is enclosed the discharge gas (inclosure gas) that is made of rare gas compositions such as He, Xe, Ne with 53.3kPa～79.8kPa in discharge space 14.Show electrode 5 be on the nesa coating 3 that ITO (indium tin oxide) or stannic oxide constitute in order to ensure good electrical conductivity the stacked bus electrode 4 that constitutes by the stacked film of Ag film or Cr/Cu/Cr and forming.
Show electrode 5 is connected with the driving circuit (not shown) of outside respectively with address electrode 10, utilizes the voltage that is applied by driving circuit, discharges at discharge space 14.The fluor that is contained in luminescent coating 13 is ultraviolet ray exited by the short wavelength's (wavelength 147nm) who follows this discharge and produce, sends visible light.
Dielectric layer 6 can and burn till the glass paste that contains first glass by coating and form.
More particularly, for example, representative is utilizes web plate method, rod to be coated with method, roller coating machine, mould to be coated with machine, scraper plate etc., coating glass paste, the method for burning till.But, be not limited to this, for example, also can contain the method that the sheet of first glass burns till and form by attaching.
In order to ensure photopermeability, below the preferred 50 μ m of the thickness of dielectric layer 6.In order to ensure insulativity, more than the preferred 1 μ m.The for example preferred 3 μ m of the thickness of dielectric layer 6～50 μ m.
Details for first glass that contains in dielectric layer 6 carries out aftermentioned, but in the present embodiment, contains MoO in dielectric layer 6 3And WO 3At least one side, therefore, though the metal that in bus electrode 4, contains (Ag or Cu) ionization, in dielectric layer 6 diffusion, also suppress metallic colloidization.Therefore, suppress the flavescence of dielectric layer 6 or the reduction of proof voltage.
In addition, the problem of flavescence is being substantially devoid of plumbous glass in order to use, and replaces composition to use as it and contains Bi 2O 3Or has the tendency that especially becomes showy under the situation of the glass of alkalimetal oxide.But, in the present embodiment, utilize and contain MoO 3And WO 3At least one side's glass form dielectric layer 6, therefore, can suppress the generation of flavescence, especially containing Bi 2O 3Glass in its effect big.Thereby, according to present embodiment as can be known, can realize not containing lead and suppress the dielectric layer 6 of the generation of flavescence.
And then, use as described above and contain MoO 3And WO 3At least one side's glass form dielectric layer 6, can also suppress the flavescence of front glass substrate 2.Usually, the glass substrate that is used in PDP is made by float glass process.Sn has been sneaked on the surface of the glass substrate of making by float glass process.This Sn reduction Ag ion or Cu ion, therefore the colloid of generation Ag and Cu, needed to grind the surface of the glass substrate of making by float glass process in the past, removed Sn.With respect to this, in the present embodiment, utilize the MoO that is contained in dielectric layer 6 3And WO 3At least one side suppress the gelatinizing of Ag and Cu, therefore, even for to have the glass substrate of Sn also can use at remained on surface.Thus, do not need grinding glass substrate, obtain to reduce the effect of worker ordinal number.Also have, the containing ratio that is contained in the Sn of (residual) glass substrate for example is 0.001～5wt%.
Secondly, illustrate that the dielectric layer of lining show electrode 5 shown in Figure 2 forms the example of double-deck PDP.
PDP shown in Figure 2 is provided with first dielectric layer 15 of lining show electrode 5 and outside the structure of second dielectric layer 16 of configuration on first dielectric layer 15, is and Fig. 1 and the identical structure of PDP shown in Figure 3 except replacing dielectric layer 6, forming.Also have, for Fig. 1 and the identical parts mark same-sign of PDP shown in Figure 3, omit its explanation.
As shown in Figure 2, first dielectric layer, 15 lining nesa coatings 3 and bus electrode 4, the second dielectric layers 16 set and are first dielectric layer 15 that is covered.
For under this double-deck situation, the dielectric layer 6 of at least the first dielectric layer 15 and Fig. 1 and PDP shown in Figure 3 is identical, contains: contain MoO at dielectric layer 3And WO 3At least one side, first glass that adds up to 0.1～8wt% of its containing ratio.Thus, the colloid that suppresses Ag or Cu at least in first dielectric layer 15 is separated out flavescence and the proof voltage reduction that causes.In addition, in first dielectric layer 15, suppress the ionic diffusion of Ag or Cu, therefore,, also can suppress the variable color (flavescence) of second dielectric layer 16 or the reduction of proof voltage even in second dielectric layer 16, contain the glass of the composition of easy generation flavescence.
Thereby, can under the situation of the problem of not worrying flavescence, select the glass composition that requires specification to second dielectric layer 16 corresponding to PDP.Narrate in the back about second glass that is contained in second dielectric layer 16, but for example in second dielectric layer 16, also can use the low SiO of permittivity ratio lead glass or bismuth glass 2-B 2O 3-ZnO be glass composition (specific inductivity under room temperature, the 1MHz is roughly as follows, lead glass: 10～15, bismuth glass: 8～13, SiO 2-B 2O 3-ZnO is a glass: 5～9).By using SiO in second dielectric layer 16 2-B 2O 3-ZnO is a glass composition, can reduce the specific inductivity of dielectric layer integral body (dielectric layer that comprises first dielectric layer 15 and second dielectric layer 16), can reduce the consumption electric power of PDP.
Double-deck dielectric layer like this can be after forming first dielectric layer 15, applies and burn till the glass material that contains second dielectric layer, 16 usefulness glass compositions (second glass) thereon and form.In this case, the glass that is used in first dielectric layer 15 preferably has the softening temperature higher than the softening temperature of the glass that is contained in second dielectric layer.
In addition, in order to ensure the insulation of the electrode 3,4 and second dielectric layer 16 and prevent surface reaction, the thickness of preferred first dielectric layer 15 is more than the 1 μ m.
In addition, in order to suppress to see through the loss of light, preferably the thickness that the thickness of first dielectric layer 15 and second dielectric layer 16 is added up is below the 50 μ m, in order to ensure insulativity, more than the preferred 3 μ m.
As mentioned above, the PDP of present embodiment also can and then be included in second dielectric layer 16 that is provided with on first dielectric layer 15.Like this, by second dielectric layer 16 that formation has the desired characteristics different with first dielectric layer 15, can realize more high performance PDP.For example, use as second dielectric layer 16 under the situation of the little dielectric material of permittivity ratio first dielectric layer 15, and only compare, can reduce consumption electric power with the situation of first dielectric layer, 15 formation dielectric layers.In addition, use as second dielectric layer 16 under the situation of the transmitances dielectric material higher, and only compare, can improve transmitance with the situation of first dielectric layer, 15 formation dielectric layers than first dielectric layer 15.
In the PDP that comprises second dielectric layer 16, second dielectric layer 16 contains second glass, and the moiety of described second glass can contain and is selected from Li 2O, Na 2O and K 2O's is at least a.Thus, can reduce the softening temperature of second glass, or with its adjusting.In addition, these that bear the effect that reduces softening temperature by interpolation (are selected from Li 2O, Na 2O and K 2O's is at least a), can reduce the key element of bearing same function and specific inductivity being uprised is Bi 2O 3Containing ratio, therefore, can reduce the specific inductivity of dielectric layer, or with its adjusting.By reducing the specific inductivity of dielectric layer, can realize consuming the low PDP of electric power.
Also have, illustrated that in the present embodiment dielectric layer is double-deck situation, even but be under the situation of the multilayered structure more than three layers at dielectric layer, also, first dielectric layer 15 of lining show electrode 5 contains MoO as long as comprising 3And WO 3At least one side, first glass that adds up to 0.1～8wt% of its containing ratio just can suppress the generation of flavescence or the reduction of proof voltage.
In addition, in the present embodiment, describe the dielectric layer 6 and first dielectric layer 15 of the show electrode 5 of lining front panel 1 in detail, but the dielectric layer 11 of the address electrode 10 by the backplate 8 that will be covered is made as identical with dielectric layer 6 in above-mentioned explanation, can suppress the generation of painted (flavescence) at dielectric layer 11 or back side glass substrate 9 places or the reduction of proof voltage.That is, be contained in the glass of dielectric layer 11 for containing Bi 2O 3Glass, and address electrode 10 contains and is selected from least a of silver and copper, described glass and then with MoO 3Be made as 0～4wt%, with WO 3Be made as 0～4wt%, and MoO 3And WO 3The total of containing ratio be made as the scope of 0.1～8wt%, can access above-mentioned effects such as flavescence inhibition thus.
As mentioned above, the PDP of present embodiment is substantially devoid of plumbous dielectric layer by using above-mentioned first glass, can forming, and can suppress the reduction of the display characteristic that the variable color (flavescence) of dielectric layer causes or the reduction of proof voltage.
Also have, as suitable PDP of the present invention, that representative is the surface discharge type PDP that illustrates in the present embodiment, but is not limited to this, also goes for opposed discharge-type.
In addition, be not limited to the AC type,, also go for possessing the DC type PDP of dielectric layer even be the PDP of DC type.
＜the first glass 〉
In the present invention, form on this point at the glass of the dielectric layer of the flavescence of finding to suppress glass substrate and dielectric layer and have feature.Below, first glass in the dielectric layer (first dielectric layer) that is used in covering electrodes in PDP of the present invention is described.
In the present embodiment, the glass that contains in the dielectric layer of covering electrodes is for containing Bi 2O 3Glass, and then, contain the MoO of 0～4wt% 3, 0～4wt% WO 3, and be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.Thus, can be suppressed at dielectric layer and the flavescence of glass substrate and the generation of insulation breakdown that the gelatinizing of the Ag that uses in the electrode or Cu causes.
In electrode, contain under the situation of Ag, show that the reasons are as follows of these effects is described.Known Ag and MoO 3Under the low temperature below 580 ℃, generate so-called Ag easily 2MoO 4, Ag 2Mo 2O 7, Ag 2Mo 4O 13Compound.The firing temperature of dielectric material is 550 ℃～600 ℃, therefore, thinks the Ag that spreads to dielectric layer from electrode when burning till +With the MoO in the dielectric layer 3Reaction generates compound and stabilization.That is Ag, +Be not reduced and stabilization, therefore, suppress cohesion and become the colloidal situation.Equally, Ag and WO 3Also generate Ag easily 2WO 4, Ag 2W 2O 7, Ag 2W 4O 13Compound and stabilization.
In addition, containing MoO 3, WO 3Glass form, in glass, have MoO 4 2-, WO 4 2-, when burning till from the Ag of electrode diffusion +By these captures and stabilization.That is, think Ag +Not only not gelatinizing, the diffusion in dielectric layer also is suppressed.Equally, in electrode, contain under the situation of Cu, also suppress Cu +Diffusion, therefore, think that final minimizing becomes colloidal Cu, suppress the generation of flavescence and the reduction of proof voltage.
In order to obtain aforesaid effect, with the MoO that is contained in the glass 3And WO 3The total of containing ratio be made as more than the 0.1wt%.
In addition, if the MoO in the glass 3And WO 3Containing ratio become many, MoO then 3And WO 3The painted of the glass that causes separately becomes remarkable.Thereby, for the transmitance that makes dielectric layer does not reduce, with MoO 3, WO 3Containing ratio separately is made as below the 4wt%.In addition, contain MoO 3And WO 3Both glass with only contain MoO 3And WO 3Either party's situation compare, can suppress the loss of transmitance, can obtain reducing the effect of flavescence more reliably.Thereby, more preferably use and contain MoO 3And WO 3Both glass.Containing MoO 3And WO 3Under the situation of both glass, each composition can be contained to higher limit (4wt%) separately, therefore, MoO 3And WO 3The adding up to below the 8wt% of containing ratio.
Also have, above-mentioned is to have put down in writing MoO 3, WO 3Be matched with the situation that glass is formed, in glass powder, mixed MoO but use 3, WO 3The mixed powder of powder also can.Burn till if dispose mixed powder on electrode, then compare with situation about cooperating in glass is formed, uniformity coefficient reduces sometimes, and the transmitance of dielectric layer reduces, but has the effect of certain flavescence minimizing.
And then, based on MoO 3And WO 3The effect that reduces of flavescence also effective the dielectric layer that uses the glass that will contain as composition to form from the PbO that brought into use in the past, but use be substantially devoid of in the dielectric layer plumbous, that plumbous containing ratio forms as the glass below the 0.1wt% more effective.
This is because from the glass that began to realize the necessary PbO of low softening point in order to realize not containing in the past, needing instead, composition contains alkalimetal oxide or bismuth oxide, these compositions promote the diffusion of Ag or Cu, or reduce ion easily, therefore, increased flavescence.Especially, containing Bi 2O 3Glass in, based on MoO 3And WO 3The more remarkable effect that reduces of flavescence.
In the present embodiment, preferably be contained in glass in the dielectric layer of covering electrodes contain at least as moiety as follows,
SiO 2：0～15wt％
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
MoO 3：0～4wt％
WO 3：0～4wt％
Be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.Below, sometimes the composition shown in above-mentioned is called (dielectric layer with) glass of present embodiment.
In addition, the glass of present embodiment is as moiety, can also contain to be selected from Li 2O, Na 2O and K 2O's is at least a, is contained in the Li of described glass 2O, Na 2O and K 2The total of the containing ratio of O for example can be 0.1～10wt%.
As the dielectric layer of present embodiment a example with the composition of glass, for example can enumerate following composition, contain:
SiO 2：0～15wt％
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O: greater than 0.1wt% and be below the 10wt%
MoO 3：0～4wt％
WO 3：0～4wt％
Be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
As the dielectric layer of present embodiment another example with the composition of glass, for example can also enumerate following composition, contain:
SiO 2: greater than 2wt% and be below the 15wt%
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O：0.1～10wt％
MoO 3：0～4wt％
WO 3：0～4wt％
Be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
As the dielectric layer of present embodiment with the composition of glass so that another example, for example can also enumerate following composition, contain:
SiO 2: greater than 2wt% and be below the 15wt%
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O: greater than 0.1wt% and be below the 10wt%
MoO 3：0～4wt％
WO 3：0～4wt％
Be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
Details is in the back narration, but conduct more effectively suppresses an example of the composition of flavescence in the PDP of high-resolution, for example, can enumerate following composition, the Li of the dielectric layer of present embodiment in the glass 2O, Na 2O and K 2The containing ratio of O is as described below,
Li 2Below the O:0.17wt%
Na 2Below the O:0.36wt%
K 2Below the O:0.55wt%
Li 2O+Na 2O+K 2Below the O:0.55wt%.
The qualification reason of these compositions (composition in the glass of present embodiment) secondly, is described.
SiO 2Not necessary composition, but have effect aspect the stabilization of glass, below the preferred 15wt% of its containing ratio.If SiO 2Containing ratio surpass 15wt%, then softening temperature uprises, burning till under the temperature that is difficult to sometimes stipulate.SiO 2Containing ratio more preferably below the 10wt%.And then, residual for the bubble that reduces after burning till, preferably reduce the glass viscosity when burning till, for this reason, preferably with SiO 2Containing ratio be made as below the 1wt%.In the manufacturing of PDP, after forming, also passes through dielectric layer heat treatment step.Therefore, at this moment, under the situation of the glass crystallization that forms dielectric layer, the transmitance that dielectric layer takes place sometimes reduces or crackle.Therefore, in the operation of back, comprise under the heat treated situation under a plurality of high temperature, in order to suppress the crystallization of glass, preferably with SiO 2Containing ratio be made as greater than 2wt%, more preferably more than the 2.1wt%.In addition, by with SiO 2Be made as such scope, also obtain improving the water-proof effect of glass, therefore, when glass powder is made, especially, can prevent by going bad that the powder moisture absorption causes.In addition, can reduce, can suppress the bad influence of counter plate display performance to the absorption of burning film forming moisture.
B 2O 3Be dielectric layer among the PDP of present embodiment with the necessary composition of glass, its containing ratio is 10～50wt%.If B 2O 3Containing ratio surpass 50wt%, then the weather resistance of glass reduces, in addition, thermal expansivity diminishes, and softening temperature uprises, burning till under the temperature that is difficult to stipulate.In addition, if the not enough 10wt% of its containing ratio, then glass becomes unstable, loses transparent easily.B2O 3Preferred scope be 15～50wt%.
ZnO be dielectric layer among the PDP of present embodiment with one of main component of glass, aspect stabilized glass, have effect.The containing ratio of ZnO in the glass of present embodiment is 15～50wt%.If the containing ratio of ZnO surpasses 50wt%, then easy crystallization can not get stable glass sometimes.In addition, if the not enough 15wt% of its containing ratio, then softening temperature uprises, burning till under the temperature that is difficult to stipulate.In addition, if the containing ratio of ZnO is few, then forfeiture is transparent easily burning till back glass, therefore, and in order to obtain stable glass, more than the preferred 26wt% of its containing ratio.In addition, for the characteristic that improves the protective layer that forms on dielectric layer is a discharge delay, the containing ratio of preferred ZnO is more than the 26wt%, and then more preferably more than the 32wt%.
Al 2O 3Be not necessary composition, but have effect aspect the stabilization of glass, its containing ratio is below the 10wt%.If surpass 10wt%, then may lose transparently, in addition, softening temperature uprises, burning till under the temperature that is difficult to stipulate.Al 2O 3The preferred 8wt% of containing ratio below, in addition, more than the preferred 0.01wt%.By with Al 2O 3Containing ratio be made as more than the 0.01wt%, obtain more stable glass.
Bi 2O 3Be dielectric layer among the PDP of present embodiment with one of main component of glass, have the reduction softening temperature, improve the effect of thermal expansivity.Its containing ratio is 2～40wt%.If Bi 2O 3Containing ratio surpass 40wt%, the glass easy crystallization that becomes then.In addition, if surpass 30wt%, then thermal expansivity becomes big, and in addition, it is excessive that specific inductivity becomes, and improves to consume electric power.In addition, less than 2wt%, then softening temperature uprises, burning till under the temperature that is difficult to stipulate as if its containing ratio.Bi 2O 3The preferred scope of containing ratio be 2～30wt%.
MgO is not necessary composition, but is being used for having effect aspect the stabilization of glass, and its content is below the 5wt%.Because, then may when glass is made, lose transparent if surpass 5wt%.
The alkaline-earth metals oxide of CaO, SrO, BaO has and improves water tolerance, suppresses the phase-splitting of glass, relatively improves the effect of thermal expansivity.These containing ratio add up to 5～38wt%.If the containing ratio of CaO, SrO, BaO total over 38wt%, then lose transparently sometimes, in addition, it is excessive that thermal expansivity becomes.In addition, under the situation of these total less than 5wt%, be difficult to obtain above-mentioned effect.
And then, more preferably ZnO and Bi 2O 3The total (ZnO+Bi of containing ratio 2O 3) be 35～65wt%.Low in order to make softening temperature, under the desired temperatures below 600 ℃ not with electrode reaction, the dielectric material that transmitance is superior is preferably with (ZnO+Bi 2O 3) be made as more than the 35wt%.But, if these total over 65wt%, the glass problem of easy crystallization that becomes then takes place.
And then, as Bi 2O 3Containing ratio and B 2O 3Total (B with the containing ratio of ZnO 2O 3+ ZnO) [the Bi of ratio 2O 3/ (B 2O 3+ ZnO)] value preferred below 0.5.With B 2O 3And ZnO compares Bi 2O 3Bring the increase of specific inductivity, therefore,, can form the low dielectric layer of specific inductivity, can reduce consumption electric power by being made as above-mentioned scope.
In order to prevent the flavescence of dielectric layer, glass does not preferably contain alkalimetal oxide (Li 2O, Na 2O and K 2But in the present embodiment, contain the MoO that suppresses flavescence O), 3, WO 3, therefore, except above composition, can also contain and be selected from Li 2O, Na 2O and K 2O's is at least a.Be made as more than the 0.1wt% by the alkalimetal oxide that will be contained in glass, can reduce softening temperature, or regulate each rerum natura.For example, softening temperature can be reduced, therefore, Bi can be reduced with same function 2O 3Containing ratio.Can reduce specific inductivity thus.But if the containing ratio of alkalimetal oxide surpasses 10wt%, then thermal expansivity becomes excessive, and is therefore not preferred.
In addition, if the surface irregularity of dielectric layer then sees through scattering of light, therefore, transmitance takes place sometimes reduce, or the problem of the display performance of PDP reduction.The levelling property of the dielectric layer after therefore, hope is burnt till is good.In order to obtain good levelling property, preferred Li 2O, Na 2O and K 2Total (the Li of the containing ratio of O 2O+Na 2O+K 2O) greater than 0.1wt%, more preferably more than the 0.11wt%.
On the other hand, in high-resolution panel more, has bar number, the tendency that flavescence increases along with the electrode that increases per unit area.In order to suppress flavescence in the high-resolution panel, the containing ratio of preferred as alkali oxide compound still less contains Li 2Li under the situation of O 2Below the preferred 0.17wt% of the containing ratio of O, contain Na 2Na under the situation of O 2Below the preferred 0.36wt% of the containing ratio of O, contain K 2K under the situation of O 2Below the preferred 0.55wt% of the containing ratio of O.In addition, in order in the high-resolution panel, to suppress flavescence, Li effectively 2O, Na 2O and K 2Below the preferred 0.55wt% of the total of the containing ratio of O, more preferably below the 0.36wt%, and then below the preferred 0.17wt%.In addition, by with Li 2O, Na 2O and K 2The containing ratio of O is made as such scope, also obtains improving the water-proof effect of glass, and therefore, it is rotten to prevent especially that when glass powder is made moisture absorption by powder from causing.In addition, can reduce, can suppress the bad influence of counter plate display performance to the absorption of burning film forming moisture.
The dielectric layer of present embodiment contains mentioned component with glass, typically says only to comprise mentioned component, but so long as obtain effect of the present invention, just can contain other compositions.Below the preferred 10wt% of the total of the containing ratio of other compositions, more preferably below the 5wt%.As other compositions, for example, can enumerate the adjusting for softening temperature and thermal expansivity, the stabilization of glass and the raising of chemical durability etc. and the composition of interpolation, specifically, can enumerate Rb 2O, Cs 2O, TiO 2, ZrO 2, La 2O 3, Nb 2O 5, TeO 2, Ag 2O, SnO, CeO 2And CuO etc.
The dielectric layer of present embodiment can be used as the dielectric layer of the glass substrate that is fit to PDP with glass material uses.As the common glass substrate that is used in PDP, have by float glass process and make, the luffer boards glass that obtains easily is soda-lime glass or the high strain-point glass of using exploitation as PDP usually.These glass have the thermotolerance, 75 * 10 till 600 ℃ usually -7～85 * 10 -7/ ℃ thermal expansivity (coefficient of linear thermal expansion).
The dielectric layer of PDP is after glass substrate coating glass paste, burns till and forms.Therefore, burn till and under the condition below 600 ℃ of the softening transform that does not cause glass substrate, to carry out.In addition, for peeling off and crackle of the perk that prevents glass substrate, dielectric layer, need make the thermal expansivity of the glass composition that constitutes dielectric layer reduce 0～25 * 10 than glass substrate -7/ ℃ about.And then if the specific inductivity height of dielectric layer is then big at the electrorheological that electrode stream is crossed, it is big that the consumption electric power of PDP becomes, therefore not preferred.
Therefore, with being substantially devoid of under the situation of dielectric layer that plumbous crown glass forms PDP, preferably use composition with described scope, and softening temperature below 600 ℃, thermal expansivity is 60～85 * 10 -7/ ℃, specific inductivity is the Nonlead glass composition below 12.And then if peeling off or crackle of consider suppressing that strain etc. causes realizes the situation of the yield rate more than 90%, then preferred thermal expansivity is 65 * 10 -7～85 * 10 -7/ ℃.In addition, consume electric power in order further to reduce, more preferably specific inductivity is below 11.
Also have, as long as obtain effect of the present invention, the amount that is contained in the glass of dielectric layer does not just limit especially, but usually preferred 50wt% above (for example more than the 80wt% or more than the 90wt%).As an example, only form dielectric layer basically and also can by glass.In the present embodiment, the glass ingredient that constitutes dielectric layer typically is the glass with the composition shown in above-mentioned, does not contain lead in being contained in the glass ingredient of dielectric layer.
In the PDP of present embodiment, state in the use under the situation of dielectric layer of front panel that glass forms PDP, in order under the situation of not sacrificing optical characteristics, to improve strength of glass or to regulate thermal expansivity, can add inorganic filler or mineral dye.As inorganic filler or mineral dye, for example, can enumerate aluminum oxide, titanium oxide, zirconium white, zircon, trichroite, quartz etc.
In addition, also can use above-mentioned glass to be overlayed on the electrode that forms on the backplate of PDP.In this case, also can improve strength of glass simultaneously or regulate thermal expansivity with optical characteristics such as raising reflection characteristics be purpose, adds inorganic filler or mineral dye.As inorganic filler or mineral dye, for example, can enumerate aluminum oxide, titanium oxide, zirconium white, zircon, trichroite, quartz etc.
＜the second glass 〉
At as shown in Figure 2 dielectric layer is under the double-deck situation, about be contained in the layer that do not contact with electrode promptly the glass (second glass) of second dielectric layer be specifically described.This second glass is for the reduction softening temperature, and the purpose of reduction specific inductivity, preferably contains to be selected from Li 2O, Na 2O and K 2O's is at least a.If form second dielectric layer by the glass that can realize low specific inductivity like this, then can reduce the consumption electric power of PDP.Below, two examples of second glass are described.
In the present embodiment,, contain at least as moiety as the glass of first example of second glass that in the formation of second dielectric layer, uses:
SiO 2：0～15wt％
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
Li 2O+Na 2O+K 2O：0.1～10wt％
MgO：0～5wt％
CaO ten SrO ten BaO:5～38wt%
In the present embodiment,, contain at least as moiety as the glass of second example of second glass that in the formation of second dielectric layer, uses:
SiO 2：0～30wt％
B 2O 3：25～80wt％
ZnO：0～50wt％
Al 2O 3：0～10wt％
Li 2O+Na 2O+K 2O：5～20wt％
MgO：0～5wt％
CaO+SrO+BaO：0～15wt％
Above-mentioned first and second routine glass all can be realized low softening temperature, and can also realize low specific inductivity.Especially, to be substantially devoid of the composition that improves specific inductivity be Bi to the glass of second example 2O 3, therefore, can realize lower specific inductivity.Thereby, use first and second example of second glass, form under the situation of second dielectric layer, can reduce the specific inductivity of dielectric layer, therefore, can reduce the consumption electric power of PDP.
＜glass paste 〉
The glass that uses in the dielectric layer in the PDP of present embodiment uses with the state of powder usually.By add the tackiness agent that is used to give printing or solvent etc. to the glass powder of above-mentioned present embodiment, obtain the glass paste.By this glass paste is coated on the electrode that forms on the glass substrate, and it is burnt till, can form the dielectric layer of coated electrode.On this dielectric layer, use electron beam evaporation plating method etc., form the protective layer of the thickness of regulation.Also have, the formation of protective layer is not limited to the electron beam evaporation plating method, can be undertaken by sputtering method or ion electroplating method.
The glass paste comprises glass powder, solvent and resin (tackiness agent).Glass powder is that dielectric layer among the PDP of the invention described above is with the powder of glass composition.The composition that the glass paste contains beyond these compositions also can, for example, contain tensio-active agent, development accelerant, bonding auxiliary agent, halation and prevent the additive according to various purposes such as agent, preserving stabilizer, defoamer, oxidation retarder, UV light absorber, pigment, dyestuff.
As long as the resin (tackiness agent) that is contained in the glass paste is low with the reactivity of low-melting glass powder.For example, from viewpoints such as chemical stability, cost, securities, wish that derivatived cellulose, polyvinyl alcohol, polyvinyl butyral acetal, polyoxyethylene glycol, carbonic ethers such as soluble cotton, methylcellulose gum, ethyl cellulose, carboxy methyl cellulose are that resin, urethane are that resin, acrylic resin, melamine are resin etc.
Solvent in the glass paste is so long as get final product with the reactivity of glass powder is low.For example, from viewpoints such as chemical stability, cost, security and with the viewpoint of the intermiscibility of adhesive resin, can enumerate ethylene glycol monoalkyl ether classes such as acetic acid butyl ester, 3-ethoxy-propionic acid ethyl ester, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether; Ethylene glycol monoalkyl ether acetate classes such as ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate; Diethylene glycol dialkyl ether classes such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol dipropyl ether, Diethylene Glycol dibutyl ether; Propylene-glycol monoalky lether classes such as propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol list propyl ether, propylene glycol single-butyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; Propylene glycol alkyl ether acetic acid ester classes such as propylene glycol monomethyl ether, propylene glycol list ethyl ether acetic ester, propylene glycol list propyl ether acetic ester, propylene glycol single-butyl ether acetic ester; The lactic acid methyl ester, the lactic acid ethyl ester, the ester class of lactic acid such as lactic acid butyl ester, the formic acid methyl ester, the formic acid ethyl ester, formic acid amyl group ester, the acetic acid methyl ester, the acetic acid ethyl ester, the acetic acid propyl diester, the acetic acid isopropyl esters, the acetic acid isobutyl, acetic acid amyl group ester, acetic acid isopentyl ester, the acetic acid polyhexamethylene, acetic acid 2-(ethyl hexyl) ester, the propionic acid methyl ester, the propionic acid ethyl ester, the propionic acid butyl ester, butyric acid methyl ester (butyric acid methyl ester), butyric acid ethyl ester (butyric acid ethyl ester), butyric acid propyl diester (butyric acid propyl diester), the ester class of butyric acid isopropyl esters aliphatic carboxylic acids such as (butyric acid isopropyl esters); Carbonates such as vinyl carbonate, propylene carbonate; Alcohols such as terpinol, benzyl alcohol; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; Ketones such as butanone, 2-heptanone, 3-heptanone, 4-heptanone, pimelinketone; 2-hydroxy-propionic acid ethyl ester, 2-hydroxyl-2-methylpropanoic acid ethyl ester, oxyethyl group acetic acid ethyl ester, the hydroxacetic acid ethyl ester, 2-hydroxyl-3-methyl butyric acid methyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-methoxyl group butylacetic acid ester, 3-methyl-3-methoxyl group butylacetic acid ester, acetate of butyl carbitol, 3-methyl-3-methoxyl group butyl propionic ester, 3-methyl-3-methoxyl group butyl butyric ester, 2,2,4-trimethylammonium-1,3-pentane diol mono isobutyrate acetoacetic acid methyl ester, the acetoacetic acid ethyl ester, the pyruvic acid methyl ester, the pyruvic acid ethyl ester, the M-nitro benzoic acid ethyl ester, ester classes such as acetic acid benzyl ester; N-methyl-2-pyrrolidone, NN-dimethyl formamide, N-methylformamide, N, acid amides such as N-N,N-DIMETHYLACETAMIDE are molten drug etc.These solvents may be used alone, can also be used in combination two or more.
The containing ratio of regulating the solvent in the glass paste in the scope of handling is handled or applied to plasticity or flowability (viscosity) at paste for being fit to be shaped.
Also have, this glass paste can also be applicable to the formation of the dielectric layer that covers the electrode that forms on the PDP backplate.
The manufacture method of＜PDP 〉
Below, an example of the manufacture method of PDP is described.The making method of front panel at first, is described.
The manufacture method of the PDP of present embodiment comprises: be formed with on the substrate of electrode the glass material (first glass material) that configuration contains first glass, this glass material is burnt till, form the operation of the dielectric layer (first dielectric layer) of the described electrode of lining thus.First glass can use the glass of the composition with above-mentioned middle explanation as used herein.At this, when being covered the dielectric layer of the show electrode that plate in front forms, formation used the example of above-mentioned operation to describe.
The making method of front panel at first, is described.
Interarea at smooth front glass substrate forms a plurality of transparency electrodes with striated.Secondly, after silver coating paste on the transparency electrode, heating front glass substrate integral body is burnt till silver-colored paste thus, forms bus electrode.Form show electrode like this.
Secondly,, utilize the scraper plate coating process, will contain dielectric layer among the PDP of present embodiment is coated on the front glass substrate with the glass paste of glass composition above-mentioned interarea to cover the mode of show electrode.Then, front glass substrate integral body was kept 30 minutes down at 90 ℃, secondly the dry glass paste, carries out burning till in 10 minutes under the temperature of 560～590 ℃ scopes.Form dielectric layer like this.
Dielectric layer glass is the glass of above-mentioned middle explanation as used herein.
Secondly, utilize the electron beam evaporation plating method, magnesium oxide (MgO) film forming is burnt till on dielectric layer, form protective layer.
Make front panel like this.
As shown in Figure 2, about dielectric layer is the manufacture method of double-deck PDP, same as described above, to cover the mode of show electrode, to contain the glass paste coating of first dielectric layer with glass (first glass), and dry, burn till after, will contain the glass paste coating of second dielectric layer in the mode that covers first dielectric layer that forms with glass (second glass), and dry, burn till, form second dielectric layer.
Secondly, the making method of backplate is described.
After an interarea of smooth back side glass substrate applied many with silver-colored paste with striated, heating back side glass substrate integral body was burnt till silver-colored paste, thus the calculated address electrode.
Secondly,, utilize the scraper plate coating process, the glass paste is coated on the above-mentioned interarea of back side glass substrate in the mode of overlay address electrode.Then, front glass substrate integral body was kept 30 minutes down at 90 ℃, secondly the dry glass paste, carries out 10 minutes burn till under the temperature of 560～590 ℃ scopes.Form dielectric layer like this.
At this, as dielectric layer glass, can use present embodiment PDP in above-mentioned glass.In this case, contain the glass paste of above-mentioned glass, and carry out drying, burn till, form dielectric layer by coating.
Secondly, coating glass paste between adjacent address electrode, heating back side glass substrate integral body is burnt till the glass paste, forms the next door.
Secondly, in adjacent next door each other, coating R, G, B fluorescent ink liquid of all kinds are heated to 500 ℃ with back side glass substrate, burn till above-mentioned fluorescent ink liquid, remove the interior resinous principle (tackiness agent) of fluorescent ink liquid etc. thus, form luminescent coating.
Secondly, use seal glass, applying front panel and backplate.Then, be high vacuum for the exhaust gas inside of sealing after, enclose rare gas.
Obtain PDP like this.Also have, above-mentioned PDP and manufacture method thereof are an example, and the present invention is not limited to this.
[embodiment]
Below, use embodiment, further describe the present invention.
The making of＜glass and evaluation 〉
Make the sample of the glass that uses in the dielectric layer of PDP of the present invention.The composition of the sample of the glass that uses in the dielectric layer of PDP of the present invention has been shown in table 1～7.In addition, in table 8～11, illustrated and be used to investigate MoO of the present invention 3And WO 3The flavescence that causes of interpolation reduce effect and the composition of the sample of the glass made.The sample of the glass shown in table 12 and the table 13 is the glass that uses about in PDP of the present invention, the sample that can use during the preferred containing ratio that illustrates that each forms.Also have, in table, SiO 2Deng being labeled as SiO 2
[table 1]
Glass composition/No. 1 2 3 4 5 6 7 8 9 10
SiO2 15.00 9.70 1.00 14.90 9.30 12.00 1.60 1.50
B2O3 27.30 29.50 30.90 10.00 15.00 50.00 24.20 30.60 23.40 26.90
ZnO 27.00 26.80 26.00 33.60 35.70 26.00 15.00 31.80 39.70 50.00
Al2O3 0.30 2.70 1.70 0.70 3.20 0.70 5.10 0.80 1.10 1.30
Bi2O3 23.20 16.00 11.00 28.30 19.70 9.50 18.10 13.70 12.40 8.10
MgO 1.20
CaO 5.50 16.90 5.40 1.30 5.50 2.60
SrO 1.20 4.10 2.20
BaO 6.40 5.60 10.50 5.60 12.50 13.70 21.00 19.70 10.10 8.40
Li2O 1.20
Na2O 1.30
K2O 1.80
MoO3 0.80 3.00 2.00 0.10 0.60 0.50 2.00 0.50
WO3 0.30 0.50 1.00 3.00
Second-order transition temperature (℃) 492 493 485 491 492 469 489 477 480 473
Softening temperature (℃) 593 589 581 590 588 572 598 574 576 569
Thermal expansivity (* 10 -7/℃) 64 64 70 74 72 65 75 71 72 68
Specific inductivity 10.4 11.0 9.7 10.9 10.3 8.9 9.5 10.0 10.0 9.8
Stability, glass A A A B A A A A A A
Comprehensive evaluation B B A B A A B A A A
a * -2.2 -3.0 -2.5 -2.0 -1.9 -3.0 -2.8 -2.2 -1.7 -2.5
b * 3.1 2.2 2.4 3.5 3.2 4.5 2.6 2.9 1.8 3.9
[table 2]
Glass composition/No. 11 12 13 14 15 16 17 18 19 20
SiO2 10.00 1.20 1.60 1.10 3.80 3.50 4.00 5.60 2.00
B2O3 25.20 31.10 24.30 24.20 35.40 27.50 28.00 15.50 18.60 30.60
ZnO 24.00 26.60 37.90 39.00 36.30 26.00 27.50 30.10 38.80 33.60
Al2O3 10.00 8.00 0.10 0.60 2.20 4.40 0.80 0.80 0.70
Bi2O3 25.30 24.30 15.70 13.00 2.00 18.80 30.00 40.00 23.10 19.40
MgO 0.30 0.50
CaO 1.90 3.30 7.20 6.20 3.80 4.60 3.10 8.10 12.00 5.20
SrO 5.20 6.80 3.00 1.80
BaO 3.10 6.10 7.90 7.60 16.80 16.40 1.50 2.50
Li2O 2.00
Na2O 1.30 1.50
K2O
MoO3 0.30 0.30 1.00 0.20 0.50 0.80 2.00
WO3 0.50 0.30 0.50 0.70 1.00
Second-order transition temperature (℃) 490 475 472 479 490 488 461 470 489 472
Softening temperature (℃) 595 582 571 580 592 590 566 565 579 570
Thermal expansivity (* 10 -7/℃) 64 65 72 73 70 72 72 85 80 68
Specific inductivity 10.7 10.3 10.1 10.0 8.2 10.2 10.8 12.0 11.0 10.4
Stability, glass B A A B A A A A A A
Comprehensive evaluation B A A B A A A B A A
a * -2.5 -1.9 -2.0 -1.7 -1.8 -2.2 -2.0 -2.1 -1.8 -2.2
b * 2.9 2.0 2.2 2.4 2.0 2.5 2.3 2.5 2.0 2.4
[table 3]
Glass composition/No. 21 22 23 24 25 26 27 28 29 30
SiO2 2.70 2.50 0.80 3.40 0.80 3.20 0.30 1.40 0.60 4.50
B2O3 32.10 37.70 29.00 36.00 29.50 33.70 26.70 32.80 28.40 17.50
ZnO 31.10 27.60 27.10 28.60 26.40 32.60 30.20 32.10 27.80 35.00
Al2O3 0.30 0.30 0.60 0.70 0.80 0.50 0.50 1.50 1.00
Bi2O3 23.00 26.40 3.80 25.80 3.80 24.50 3.60 26.70 3.50 29.90
MgO 5.00
CaO 4.30 5.00 38.00 2.50 10.80 10.70
SrO 5.00 38.00 0.90 4.90
BaO 1.00 5.00 38.00 1.60 22.30
Li2O 0.10
Na2O
K2O
MoO3 0.50 0.50 0.50 0.50 0.50 1.00
WO3 0.70 0.70 0.70 0.70 1.30
Second-order transition temperature (℃) 469 470 487 467 491 465 492 461 492 480
Softening temperature (℃) 572 573 585 570 590 568 592 562 590 569
Thermal expansivity (* 10 -7/℃) 62 64 83 63 84 64 80 63 81 80
Specific inductivity 10.5 10.7 8.6 10.8 9.1 10.8 9.6 10.8 9.4 10.8
Stability, glass A A B A B A B A B A
Comprehensive evaluation B B B B B B B B B A
a * -2.3 -2.4 -2.4 -2.2 -2.6 -2.3 -2.5 -2.2 -2.4 -2.0
b * 2.8 2.7 3.0 2.8 3.3 2.8 3.1 2.7 3.0 2.9
[table 4]
Glass composition/No. 31 32 33 34 35 36
SiO2 5.60 4.50 5.60 4.50 5.60 5.60
B2O3 18.00 17.50 18.00 17.50 18.00 18.00
ZnO 31.20 35.00 31.20 35.00 31.20 31.20
Al2O3 0.90 0.90 0.90 0.90
Bi2O3 25.50 29.90 25.50 29.90 25.50 25.50
MgO
CaO 8.00 10.70 8.00 10.70 8.00 8.00
SrO
BaO
Li2O 10.00 2.00
Na2O 0.10 10.00 3.00
K2O 0.10 10.00 5.00
MoO3 0.80 1.00 0.80 1.00 0.80 0.80
WO3 1.30 1.30
Second-order transition temperature (℃) 475 480 477 481 475 475
Softening temperature (℃) 565 570 567 570 571 572
Thermal expansivity (* 10 －7/℃) 83 80 83 81 84 84
Specific inductivity 10.7 11.0 10.6 11.0 10.7 10.5
Stability, glass A A A A A A
Comprehensive evaluation A A A A A A
a * -2.2 -1.8 -2.2 -2.0 -2.0 -2.4
b * 4.1 3.0 4.6 2.9 4.2 4.3
[table 5]
Glass composition/No. 37 38 39 40 41 42 43 44 45
SiO2 15.00 9.70 1.00 14.35 9.30 2.10 10.00
B2O3 27.30 29.40 30.79 10.00 15.00 50.00 30.10 26.90 25.10
ZnO 27.00 26.79 26.00 33.60 35.70 26.00 31.65 50.00 23.90
Al2O3 0.30 2.70 1.70 0.70 3.20 0.55 0.80 1.30 10.00
Bi2O3 23.00 16.00 11.00 28.30 19.70 9.50 13.70 8.10 25.14
MgO 1.20
CaO 5.50 16.90 5.40 1.30 2.60 1.90
SrO 1.20 4.10 2.20
BaO 6.40 5.60 10.50 5.60 12.39 13.70 19.70 8.10 3.10
Li2O 0.11 0.05 0.10 0.05 0.05
Na2O 0.06 0.18 0.11 0.10 0.10 0.12
K2O 0.20 0.27 0.15 0.20 0.19
MoO3 0.80 3.00 2.00 0.10 0.50 0.50
WO3 0.30 0.50 0.50
Second-order transition temperature (℃) 490 491 484 488 491 467 478 470 490
Softening temperature (℃) 591 588 581 586 588 570 575 566 593
Thermal expansivity (* 10 -7/℃) 64 65 70 75 72 65 72 69 64
Specific inductivity 10.4 11.0 9.8 11.2 10.3 8.9 10.1 9.8 10.8
Stability, glass A A A B A A A A B
Comprehensive evaluation B A A B A A A A B
a * -2.2 -3.0 -2.5 -2.1 -1.8 -3.0 -2.3 -2.4 -2.5
b * 3.2 2.5 2.5 3.6 3.3 4.5 3.0 4.0 3.0
[table 6]
Glass composition/No. 46 47 48 49 50 51 52 53 54
SiO2 1.20 1.10 3.80 3.50 4.00 5.60 2.70 2.50
B2O3 31.10 24.30 35.40 27.40 28.00 15.50 18.60 32.10 37.70
ZnO 26.60 37.90 36.30 26.00 27.50 29.90 38.80 31.10 27.60
Al2O3 8.00 0.10 0.60 2.20 4.40 0.80 0.80 0.30 0.30
Bi2O3 24.15 15.70 2.00 18.79 30.00 40.00 22.90 22.89 26.25
MgO 0.30 5.00
CaO 3.30 7.20 3.80 4.60 2.93 8.10 12.00 4.30 5.00
SrO 5.20 3.00 1.80
BaO 6.10 7.75 16.20 16.40 1.50 1.00
Li2O 0.10 0.05
Na2O 0.05 0.05 0.20 0.05 0.20 0.10 0.05
K2O 0.10 0.10 0.30 0.11 0.07 0.10 0.11 0.10
MoO3 0.30 1.00 0.70 0.20 0.50 0.80 0.50 0.50
WO3 0.30 0.50 1.00
Second-order transition temperature (℃) 474 472 488 486 460 469 488 469 470
Softening temperature (℃) 582 570 590 588 564 564 577 570 572
Thermal expansivity (* 10 -7/℃) 65 72 71 72 72 85 80 62 64
Specific inductivity 10.3 10.1 8.3 10.3 10.8 12.0 11.0 10.5 10.7
Stability, glass A A A A A B A A A
Comprehensive evaluation A A A A A B A B B
a * -1.9 -2.0 -1.9 -2.2 -2.0 -2.1 -1.9 -2.3 -2.3
b * 2.1 2.2 2.2 2.5 2.4 2.6 2.1 2.8 2.8
[table 7]
Glass composition/No. 55 56 57 58 59 60 61 62 63 64
SiO2 0.80 3.40 0.80 3.20 0.30 1.40 0.60 6.19 6.00 6.00
B2O3 28.50 36.00 29.00 33.70 26.20 32.65 28.40 18.70 18.70 18.70
ZnO 27.10 28.60 26.40 32.60 30.20 32.10 27.60 38.93 38.93 38.93
Al2O3 0.60 0.70 0.80 0.50 0.50 1.50 1.00 0.51 0.51 0.51
Bi2O3 380 25.65 3.80 24.35 3.60 26.70 3.50 23.10 23.10 22.91
MgO
CaO 38.00 2.50 10.80 5.50 5.50 5.50
SrO 5.00 38.00 0.90 4.90 6.50 6.50 6.50
BaO 5.00 38.00 1.60 22.30
Li2O 0.10 0.10 0.10 0.17
Na2O 0.20 0.05 0.20 0.05 0.20 0.36
K2O 0.20 0.10 0.20 0.10 0.20 0.15 0.20 0.55
MoO3 0.50 0.50 0.50 0.40 0.40 0.40
WO3 0.70 0.70 0.70 0.70
Second-order transition temperature (℃) 486 467 489 465 490 461 490 483 482 481
Softening temperature (℃) 583 568 587 568 590 560 590 577 575 574
Thermal expansivity (* 10 -7/℃) 83 63 85 64 81 63 81 76 78 78
Specific inductivity 8.7 10.8 9.3 10.8 9.6 10.9 9.4 10.8 10.9 11.0
Stability, glass B A B A B A B A A A
Comprehensive evaluation B B B B B B B A A A
a * -2.4 -2.2 -2.7 -2.3 -2.5 -2.2 -2.4 -1.9 -1.9 -2.0
b * 3.2 2.8 3.5 2.9 3.3 2.8 3.2 2.7 2.7 2.8
[table 8]
Glass composition/No. 71 72 73 74 75 76 77 78
SiO2 3.10 3.10 3.10 3.09 3.07 3.01 2.98 2.95
B2O3 17.50 17.49 17.48 17.45 17.33 16.98 16.80 16.63
ZnO 35.00 34.98 34.97 34.89 34.64 33.94 33.60 33.24
Al2O3 0.50 0.50 0.50 0.50 0.49 0.49 0.48 0.48
Bi2O3 31.40 31.39 31.37 31.31 31.09 30.45 30.14 29.82
CaO 12.50 12.49 12.48 12.46 12.38 12.13 12.00 11.88
MoO3 0.05 0.10 0.30 1.00 3.00 4.00 5.00
WO3
Second-order transition temperature (℃) 472 472 472 473 474 476 479 479
Softening temperature (℃) 569 569 570 570 572 574 577 578
Thermal expansivity (* 10 -7/℃) 82 82 82 82 82 83 83 83
Specific inductivity 11.8 11.7 11.7 11.8 11.8 11.9 11.9 11.9
Stability, glass A A A A A A A B
Comprehensive evaluation B B B B B B B D
a * -2.1 -2.1 -2.1 -2.2 -2.2 -2.2 -2.2 -
b * 6.1 6.0 4.9 4.1 3.0 2.4 2.2 -
[table 9]
Glass composition/No. 79 80 81 82 83 84 85 86 87
SiO2 3.10 3.10 3.09 3.07 3.01 2.98 2.95 2.91 2.85
B2O3 17.49 17.48 1745 17.33 16.98 16.80 16.63 16.45 16.10
ZnO 34.98 34.97 34.89 34.64 33.94 33.60 33.24 32.90 32.20
Al2O3 0.50 0.50 0.50 0.49 0.49 0.48 0.48 0.47 0.46
Bi2O3 31.39 31.37 31.31 31.09 30.45 30.14 29.82 29.52 28.89
CaO 12.49 12.48 12.46 12.38 12.13 12.00 11.88 11.75 11.50
MoO3 3.00 4.00
WO3 0.05 0.10 0.30 1.00 3.00 4.00 5.00 3.00 4.00
Second-order transition temperature (℃) 472 472 472 474 477 478 480 480 482
Softening temperature (℃) 569 569 570 571 573 575 577 581 584
Thermal expansivity (* 10 -7/℃) 82 82 82 82 83 82 83 83 84
Specific inductivity 11.7 11.8 11.8 11.8 11.8 11.9 11.9 12.0 12.0
Stability, glass A A A A A A B A A
Comprehensive evaluation B B B B B B D B B
a * -2.1 -2.1 -2.1 -2.2 -2.2 -2.3 - -2.4 -2.4
b * 6.1 5.0 4.5 3.8 2.9 2.7 - 2.0 1.8
[table 10]
Glass composition/No. 88 89 90 91 92 93 94 95
SiO2 4.00 4.00 4.00 3.99 3.96 3.88 3.84 3.80
B2O3 20.66 20.65 20.64 20.60 20.46 20.04 19.84 19.63
ZnO 37.28 37.26 37.25 37.17 36.90 36.16 35.78 35.42
Al2O3 0.23 0.23 0.23 0.23 0.23 0.22 0.22 0.22
Bi2O3 27.14 27.13 27.11 27.06 26.87 26.33 26.06 25.78
CaO 10.55 10.54 10.53 10.51 10.44 10.23 10.12 10.02
K2O 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.13
MoO3 0.05 0.10 0.30 1.00 3.00 4.00 5.00
WO3
Second-order transition temperature (℃) 483 483 484 485 486 487 487 489
Softening temperature (℃) 570 571 571 572 573 575 576 578
Thermal expansivity (* 10 -7/℃) 75 75 76 76 77 78 78 79
Specific inductivity 11.1 11.1 11.2 11.3 11.4 11.6 11.6 11.8
Stability, glass A A A A A A A B
Comprehensive evaluation B B B B B B B D
a * -2.0 -2.0 -1.9 -2.0 -1.9 -2.0 -2.1 -
b * 5.8 5.7 4.7 4.1 3.3 2.9 2.8 -
[table 11]
Glass composition/No. 96 97 98 99 100 101 102 103 104
SiO2 4.00 4.00 3.99 3.96 3.88 3.84 3.80 3.76 3.68
B2O3 20.65 20.64 20.60 20.46 20.04 19.84 19.63 19.42 19.01
ZnO 37.26 37.25 37.17 36.90 36.16 35.78 35.42 35.06 34.30
Al2O3 0.23 0.23 0.23 0.23 0.22 0.22 0.22 0.21 0.21
Bi2O3 27.13 27.11 27.06 26.87 26.33 26.06 25.78 25.51 24.97
CaO 10.54 10.53 10.51 10.44 10.23 10.12 10.02 9.91 9.70
K2O 0.14 0.14 0.14 0.14 0.14 0.14 0.13 0.13 0.13
MoO3 3.00 4.00
WO3 0.05 0.10 0.30 1.00 3.00 4.00 5.00 3.00 4.00
Second-order transition temperature (℃) 483 483 484 484 486 486 487 488 490
Softening temperature (℃) 570 571 571 572 574 576 577 579 582
Thermal expansivity (* 10 -7/℃) 76 77 77 77 78 79 79 80 80
Specific inductivity 11.2 11.2 11.3 11.4 11.6 11.7 11.8 11.9 12.0
Stability, glass A A A A A A B A A
Comprehensive evaluation B B B B B B D B B
a * -1.9 -2.0 -2.0 -2.0 -2.1 -2.1 - -2.1 -2.1
b * 5.8 4.9 4.4 3.7 3.2 3.1 - 2.5 24
[table 12]
Glass composition/No. 111 112 113 114 115 116 117 118 119 120
SiO2 15.10 14.90 12.10 1.30 1.90 1.90 0.10 2.80 2.90
B2O3 22.40 9.80 50.20 24.40 28.40 32.20 36.30 21.10 27.50 29.30
ZnO 27.30 32.80 27.10 14.00 50.20 26.00 33.30 26.00 30.40 32.40
Al2O3 0.50 2.50 0.10 5.30 2.20 10.20 4.40 1.00 0.50 0.60
Bi2O3 29.30 29.20 8.30 18.30 6.60 19.70 1.70 40.90 27.50 29.70
MgO 6.00
CaO 4.20 4.30 2.10 4.20 6.50 5.00 4.80
SrO 0.40 2.60 1.60 2.90
BaO 5.10 5.90 14.00 21.20 4.10 6.00 15.00 4.10
Li2O 1.20
Na2O
K2O 1.90
MoO3 0.30 0.30 0.30 0.60 0.30 0.30 0.30 0.30 0.30 0.30
WO3 1.00
Second-order transition temperature (℃) 498 - 481 493 - 499 506 - - 468
Softening temperature (℃) 602 - 578 605 - 601 604 - - 564
Thermal expansivity (* 10 -7/℃) 60 - 59 73 - 62 65 - - 59
Specific inductivity 10.8 - 8.6 11.0 - 10.1 7.9 - - 10.8
Stability, glass B D B C D B B D D B
Comprehensive evaluation C D C D D C C D D C
[table 13]
Glass composition/No. 121 122 123 124 125 126 127 128 129 130 131
SiO2 0.80 2.80 0.30 2.90 0.30 1.10 0.30 5.60 5.60 5.60 5.60
B2O3 28.80 33.40 29.90 34.30 25.90 34.40 27.10 17.00 17.00 17.00 17.00
ZnO 26.50 29.00 26.20 28.50 32.00 27.80 30.10 31.20 31.20 31.20 31.20
Al2O3 1.30 0.80 1.10 1.10 0.90 1.60 0.70 0.90 0.90 0.90 0.90
Bi2O3 3.80 29.00 4.00 28.10 2.20 30.00 3.20 25.50 25.50 25.50 25.50
MgO
CaO 38.50 1.80 15.00 8.00 8.00 8.00 8.00
SrO 4.70 38.20 1.00 9.80
BaO 4.80 38.40 2.00 13.50
Li2O 11.00 3.00
Na2O 11.00 3.00
K2O 11.00 5.00
MoO3 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.80 0.80 0.80 0.80
WO3
Second-order transition temperature (℃) - 462 - 458 496 462 - 473 473 472 473
Softening temperature (℃) - 561 - 560 601 558 - 571 569 570 569
Thermal expansivity (* 10 -7/℃) - 58 - 58 81 59 - 86 86 87 87
Specific inductivity - 10.6 - 10.7 10.3 10.7 - 10.0 10.1 10.0 10.0
Stability, glass D B D B C B D B B B B
Comprehensive evaluation D C D C D C D C C C C
The ratio of composition shown in each table be weight percentage (wt%).To become the mode mixing raw material of the composition shown in table 1～13, in 1100～1200 ℃ electric furnace, use platinum crucible, fusion one hour.Also have, the melten glass that obtains is pushed with sheet brass, glass cullet are made in sharply cooling thus.
(evaluation of glass)
Use miniature differential thermal analysis meter to measure the softening temperature of glass, adopted the value of second endotherm(ic)peak.With glass cullet fusion again, form the bar of 4mm * 4mm * 20mm, use thermomechanical analyzer, measure second-order transition temperature and thermal expansivity.With glass cullet fusion again, form the plate of 20mm * 20mm * thickness 3mm, at its surperficial electrode evaporation, use the LCR survey meter, under frequency 1MHz, measure specific inductivity.Estimate stability, glass by differential thermal analysis meter for the observation that the mensuration that changes and the crystalline that carries out based on opticmicroscope have or not.
The result who estimates, and comprehensive evaluation be illustrated in table 1～13.Also have, be defined as follows described about the A in the evaluation of stability, glass, B, C, D.
A: vitrifying takes place, and, in addition, also confirm less than crystallization by opticmicroscope by the variation of differential thermal analysis affirmation less than accompanying crystallizationization.
B: vitrifying takes place, and confirm the variation of accompanying crystallizationization, confirm less than crystallization by opticmicroscope by differential thermal analysis.
C:,,, do not observe based on the crystalline diffraction peak, but confirm crystallization by opticmicroscope by X-ray diffraction method confirming enthalpy change than softening temperature pyritous temperature province though vitrifying takes place.
D: vitrifying does not take place when glass is made.
In addition, in table 1～13, comprehensive evaluation be with softening temperature less than 600 ℃, be more preferably less than 595 ℃, specific inductivity is below 12, more preferably below 11, thermal expansivity is 60 * 10 -7～85 * 10 -7/ ℃, more preferably 65 * 10 -7～85 * 10 -7/ ℃ the scope situation be the target benchmark, and then be considered as the stability of glass and comprehensive evaluation.
In addition, A, B, C, the D about comprehensive evaluation is defined as follows described.
A: as stabilization, and each physics value is in preferred target properties scope, and each rerum natura is also balanced.
B: as stabilization, each physics value is in the target properties scope, but at least one of each physics value is outside the scope of preferred target properties.
C: as stabilization, but at least one of each physics value is outside the scope of target properties.
D: vitrifying does not take place, invalid as glass material.
As can be known clear and definite from table 1～11, each test portion that satisfies the sample of preferred compositing range in the glass that uses among the PDP of the present invention all has 60～85 * 10 in 30～300 ℃ temperature range -7/ ℃ thermal expansivity, softening temperature is below 600 ℃, specific inductivity is below 12, and is also good as the stability of glass.
Sample shown in table 12 and the table 13 obtains a part of rerum natura result lower than the sample shown in table 1～7 etc. because existence breaks away from the composition of the preferred compositing range of the glass that uses in PDP of the present invention.
The making of＜PDP and evaluation 〉
Below, in order to investigate the MoO among the present invention 3And WO 3The flavescence that causes of interpolation reduce effect, use the sample of glass with the composition shown in table 1～11, make PDP, the result of evaluation is shown.
(making of glass powder)
To become the mode of the composition shown in the table respectively, the blending raw material also mixes, and in 1100～1200 ℃ electric furnace, uses platinum crucible, fusion 1 hour.Then, utilize two roller methods, make glass cullet, utilize ball mill, the powder glass cullet are made powder.
The median size of the embodiment that makes, the glass powder of comparative example is 1.5～3.5 μ m.
(preparation of glass paste)
To and make its weight ratio become 5:30 ground as the α-terpinol of solvent as the ethyl cellulose of resin and mix and stir, preparation contains the solution of organic composition.Then, this solution and the glass powder that is illustrated in embodiment in the table, comparative example are respectively mixed with weight ratio 65:35,, mix also dispersion, the formulate glass paste with three rollers.
(making of PDP)
On the face of the front glass substrate that the smooth soda-lime glass of the about 2.8mm of thickness constitutes,, and make its drying with the material of the pattern coating ITO (transparency electrode) of regulation.Secondly, will then, heat above-mentioned front glass substrate, burn till above-mentioned silver-colored paste thus, form show electrode as the silver-colored paste of the mixture of silver powder and organic vehicle with many of wire coatings.
Use the scraper plate coating machine, above-mentioned glass paste is coated on the front panel of having made show electrode.Then, above-mentioned front glass substrate was kept 30 minutes down at 90 ℃, the dry glass paste burnt till under 570 ℃ temperature 10 minutes, formed dielectric layer thus.
Utilize the electron beam evaporation plating method, magnesium oxide (MgO) evaporation is burnt till it on above-mentioned dielectric layer then, form protective layer thus.
On the other hand, make backplate by following method.At first, utilize screen printing, will be formed on the back side glass substrate that constitutes by soda-lime glass with striated based on the address electrode of silver.Then, form dielectric layer.Secondly, between the adjacent address electrode on the dielectric layer, form the next door.The next door forms by carrying out screen printing repeatedly and burning till.
Secondly, the phosphor paste of the surface applied of the dielectric layer that exposes between the wall of next door and the next door red (R), green (G), blue (B) is dried and burns till, and makes luminescent coating.
Use seal glass, the front panel and the backplate of fitting and making.Also have, with the inside of discharge space with high vacuum (1 * 10 -4Pa) after the degree exhaust, making its pressure ground that becomes regulation enclose Ne-Xe is discharge gas.Like this, make PDP.
(evaluation of PDP)
In the display surface side of the panel of making, use the color colour-difference meter, measure its painted situation.Separately glass is illustrated in table 1～4 and table 7, the table 8 as the measurement result among the PDP of dielectric material.Also has a in the table *And b *Based on L *a *b *Color appearance system.a *Value representation: under the big situation of forward change, red grow, under the big situation of negative sense change, green grow.b *Value representation: under the big situation of forward change, yellow grow, under the big situation of negative sense change, blue grow.Usually, a *Value is-5～+ 5 scope, and b *Under the situation of value for-5～+ 5 scope, do not observe the painted of front panel.Especially, about yellow, b *The size of value exerts an influence, therefore, as PDP, b *The scope of value preferred-5～+ 5.
Shown in table 1～7, as the material that is used in dielectric layer, about possessing the sample of good rerum natura, confirm the problem that flavescence does not take place.
In addition, from the result of table 8～11 as can be known, do not contain MoO 3And WO 3The two sample (sample 71,88), contain MoO 3And WO 3The either party but containing ratio is the b of the sample (sample 72,79,89,96) of 0.05wt% *Value surpasses 5, finds the generation of flavescence.In addition, contain MoO 3And WO 3The either party but therefore containing ratio is the glass of the sample (sample 78,85,95,102) of the 5wt% gonorrhoea that becomes, can not carry out painted mensuration.With respect to this, contain MoO 3And WO 3The either party, its containing ratio is the b of other samples of 0.1wt%～4wt% *Value is below 5, confirms the generation that has suppressed flavescence.And then, contain MoO 3And WO 3The b of the two sample (sample 86,87,103,104) *Be worth forr a short time, confirm effect that flavescence suppresses than the situation height that only contains the either party than other samples.
With MoO 3, WO 3Containing ratio and b *The relation of measurement result be illustrated among Fig. 4.As can be known from the results, MoO 3, WO 3Containing ratio be under the above situation of 0.1wt%, b *Value is along with MoO 3, WO 3Containing ratio increase and reduce, and become+value below 5, confirm the problem of having improved flavescence.
In addition, MoO 3, WO 3Containing ratio be the above b of 0.1wt% *The panel that value is low does not cause the insulation breakdown of dielectric material yet under the situation of operation PDP.
The embodiment of the PDP of above-mentioned explanation is the example that dielectric layer is made of one deck, even but with the dielectric layer of above-mentioned explanation as first dielectric layer, and then form second dielectric layer thereon, and form under the double-deck situation, also obtain identical evaluation effect.Also have, in this case, the example of composition of glass that is used in second dielectric layer is as shown in table 14.
[table 14]
Glass is formed First example Second example
SiO2 11.1 11.8
B2O3 22.8 36.4
ZnO 17.5 37.2
Al2O3 4.5 1.6
Bi2O3 25.0
BaO 16.8
Li2O 2.3
K2O 13.0
Utilizability on the industry
Plasma display device of the present invention can be fit to be applied to dielectric layer that coating show electrode or address electrode use by the plasma display device that does not contain plumbous glass and form, and can provide the reliability that has suppressed flavescence and insulation breakdown high plasma display device.

Claims (24)

1. plasma display device, it has cross one another show electrode and address electrode, and at least one electrode that is selected from described show electrode and address electrode is contained first dielectric layer lining of first glass, wherein,
Described first glass is for containing Bi 2O 3Glass, and contained by the described electrode of described first dielectric layer lining and to be selected from least a of silver and copper,
Described first glass also contains the MoO of 0～4wt% 3, 0～4wt% WO 3, and be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
2. plasma display device according to claim 1, wherein,
Be contained in the Bi of described first glass 2O 3Containing ratio be 2～40wt%.
3. plasma display device according to claim 2, wherein,
Described first glass contains following composition at least as moiety,
SiO 2：0～15wt％
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O: greater than 0.1wt% and be below the 10wt%
MoO 3：0～4wt％
WO 3：0～4wt％，
And, be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
4. plasma display device according to claim 2, wherein,
Described first glass contains following composition at least as moiety,
SiO 2: greater than 2wt% and be below the 15wt%
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O：0.1～10wt％
MoO 3：0～4wt％
WO 3：0～4wt％，
And, be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
5. plasma display device according to claim 2, wherein,
Described first glass contains following composition at least as moiety,
SiO 2: greater than 2wt% and be below the 15wt%
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O: greater than 0.1wt% and be below the 10wt%
MoO 3：0～4wt％
WO 3：0～4wt％，
And, be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
6. according to each described plasma display device in the claim 3～5, wherein,
Li in described first glass 2O, Na 2O and K 2The containing ratio of O is as follows,
Li 2Below the O:0.17wt%
Na 2Below the O:0.36wt%
K 2Below the O:0.55wt%,
And, Li 2O+Na 2O+K 2Below the O:0.55wt%.
7. plasma display device according to claim 1, wherein,
The containing ratio that is contained in the lead of described first glass is below the 0.1wt%.
8. plasma display device according to claim 1, wherein,
Also contain second dielectric layer that on described first dielectric layer, is provided with.
9. plasma display device according to claim 8, wherein,
Described second dielectric layer contains second glass, and described second glass contains as moiety and is selected from Li 2O, Na 2O and K 2O's is at least a.
10. plasma display device according to claim 9, wherein,
Described second glass contains following composition at least as moiety,
SiO 2：0～15wt％
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
Li 2O+Na 2O+K 2O：0.1～10wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％。
11. plasma display device according to claim 9, wherein,
Described second glass contains following composition at least as moiety,
SiO 2：0～30wt％
B 2O 3：25～80wt％
ZnO：0～50wt％
Al 2O 3：0～10wt％
Li 2O+Na 2O+K 2O：5～20wt％
MgO：0～5wt％
CaO+SrO+BaO：0～15wt％。
12. plasma display device according to claim 1, wherein,
Described electrode by described first dielectric layer lining is formed on the glass substrate, and described glass substrate contains Sn.
13. the manufacture method of a plasma display device, it is included in first glass material that configuration contains first glass on the substrate that is formed with electrode, and described first glass material is burnt till, and forms the operation of first dielectric layer of the described electrode of lining thus, wherein
Described first glass is for containing Bi 2O 3Glass, and contained by the described electrode of described first dielectric layer lining and to be selected from least a of silver and copper,
Described first glass also contains the MoO of 0～4wt% 3, 0～4wt% WO 3, and be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
14. the manufacture method of plasma display device according to claim 13, wherein,
Be contained in the Bi of described first glass 2O 3Containing ratio be 2～40wt%.
15. the manufacture method of plasma display device according to claim 14, wherein,
Described first glass contains following composition at least as moiety,
SiO 2：0～15wt％
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O: greater than 0.1wt% and be below the 10wt%
MoO 3：0～4wt％
WO 3：0～4wt％，
And, be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
16. the manufacture method of plasma display device according to claim 14, wherein,
Described first glass contains following composition at least as moiety,
SiO 2: greater than 2wt% and be below the 15wt%
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O：0.1～10wt％
MoO 3：0～4wt％
WO 3：0～4wt％，
And, be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
17. the manufacture method of plasma display device according to claim 14, wherein,
Described first glass contains following composition at least as moiety,
SiO 2: greater than 2wt% and be below the 15wt%
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％
Li 2O+Na 2O+K 2O: greater than 0.1wt% and be below the 10wt%
MoO 3：0～4wt％
WO 3：0～4wt％，
And, be contained in the MoO of described first glass 3And WO 3The scope that adds up to 0.1～8wt% of containing ratio.
18. according to the manufacture method of each described plasma display device in the claim 15～17, wherein,
Li in described first glass 2O, Na 2O and K 2The containing ratio of O is as follows,
Li 2Below the O:0.17wt%
Na 2Below the O:0.36wt%
K 2Below the O:0.55wt%,
And, Li 2O+Na 2O+K 2Below the O:0.55wt%.
19. the manufacture method of plasma display device according to claim 13, wherein,
The containing ratio that is contained in the lead of described first glass is below the 0.1wt%.
20. the manufacture method of plasma display device according to claim 13, wherein,
Also comprise: configuration contains second glass material of second glass on described first dielectric layer, and described second glass material is burnt till, and forms the operation of second dielectric layer thus.
21. the manufacture method of plasma display device according to claim 20, wherein,
Described second glass contains as moiety and is selected from Li 2O, Na 2O and K 2O's is at least a.
22. the manufacture method of plasma display device according to claim 21, wherein,
Described second glass contains following composition at least as moiety,
SiO 2：0～15wt％
B 2O 3：10～50wt％
ZnO：15～50wt％
Al 2O 3：0～10wt％
Bi 2O 3：2～40wt％
Li 2O+Na 2O+K 2O：0.1～10wt％
MgO：0～5wt％
CaO+SrO+BaO：5～38wt％。
23. the manufacture method of plasma display device according to claim 21, wherein,
Described second glass contains following composition at least as moiety,
SiO 2：0～30wt％
B 2O 3：25～80wt％
ZnO：0～50wt％
Al 2O 3：0～10wt％
Li 2O+Na 2O+K 2O：5～20wt％
MgO：0～5wt％
CaO+SrO+BaO：0～15wt％。
24. the manufacture method of plasma display device according to claim 13, wherein,
Described substrate is a glass substrate, and described glass substrate contains Sn.
CNA2007800246921A 2006-06-28 2007-06-15 Plasma display panel and method for manufacturing the same Pending CN101484395A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP177857/2006 2006-06-28
JP2006177857 2006-06-28
JP272247/2006 2006-10-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111484245A (en) * 2020-04-30 2020-08-04 四川旭虹光电科技有限公司 High-strength low-dielectric-constant low-dielectric-loss glass and preparation and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111484245A (en) * 2020-04-30 2020-08-04 四川旭虹光电科技有限公司 High-strength low-dielectric-constant low-dielectric-loss glass and preparation and application thereof

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