CN101305442A - Display device, vent pipe with glass ring, phosphate glass ring, and process for producing the same - Google Patents

Abstract

This invention reduces the amount of lead used in a display device and improves moisture resistance of the display device. A display device (51) comprises a panel (1b) provided with a hole (11), a glass ring (13) formed of a lead-free phosphate glass, and an exhaust pipe (12) covering the hole. The glass ring joins the inner face of the pipe to the outer face of the panel. The glass ring is located on the inner side of the pipe and thus is not attacked by moisture contained in the outside air.

Description

Display apparatus, the breather pipe that has glass ring, phosphate glass ring and manufacture method thereof

Technical field

The present invention relates to display apparatus such as plasm display panel or field emission escope, more particularly, relate to the superior display apparatus of air-tightness of light excitation source space.In addition, the present invention relates to be fit to the breather pipe that has glass ring and the phosphate glass ring of the manufacturing of such display apparatus.

Background technology

Display apparatus such as plasm display panel (below, be called PDP) or field emission escope (below, be called FED) are attracted attention as realizing big pictureization and slim light-weighted thin display equipment.

In such display apparatus, between a counter plate, be formed with the light excitation source space.This light excitation source space for example is meant under the situation of PDP and is filled with the space of rare gas as the discharge space of the discharge gas of main body, the suitable space, space of the electron ray that for example under the situation of FED, electron source the is emitted vacuum space of taking out damply again, demanding air-tightness.

When making display apparatus, need to regulate the atmosphere in the light excitation source space.The adjusting of atmosphere is carried out via being installed to be the pipe (breather pipe) that is communicated with the hole that is formed at panel (through hole).Breather pipe is usually in order to improve the bond stability with panel, to use among pipe with the superior front end shape of stability, for example Fig. 7 A as the pipe with wide diameter portion 53 or flange part 52 shown in the pipe 12.In addition, the pipe on panel install and use the front end opening that the conduct shown in the ring 22 among Fig. 7 A embeds pipe the time the stage portion of pallet be formed at the glass ring on the surface of internal perisporium face.After aligned in position with the through hole of air vent hole, breather pipe and glass ring, make the glass ring fusion, form glass component, thus, pipe 12 is installed on the panel 1b according to the mode that covering is formed at the hole 11 of panel 1b via glass component 23 shown in Fig. 7 B.

The glass ring of the shape of the complexity shown in Fig. 7 A is not easy do not following that crackle breaks, forming under the situation of the unfavorable condition such as rotten of shortcoming, glass, and the material that can use to be limited to lead oxide be glass.

From the viewpoint of conservation of natural environment, as the material of glass ring, replacing lead in the past is glass, seeks to use the glass material that does not contain lead composition.As the recommendation thing of glass material, for example, open 2003-238199 communique and spy the spy and open and proposed to contain phosphorous oxide (P in the 2004-182584 communique ₂O ₅) glass material (phosphate glass material).

But, use the phosphate glass material, be difficult to form the shape of the complexity of front end shape, and crackle breaks or damaged few glass ring such as rotten with the superior breather pipe of corresponding stability.

Under the situation of using the phosphate glass material, because phosphorous oxide (P ₂O ₅) show high hygroscopy, therefore, be that the situation of glass material is compared with having used lead, the resistance to water of glass ring significantly reduces.Show the reason of high hygroscopy as phosphorous oxide, carry out four-coordination with oxygen atom when can enumerate phosphorus atoms and be 5 valencys and cause existence in the phosphorous oxide to have the unsettled branch point group of three total oxygen.Moisture in the absorption atmosphere of such branch point group and the tendency of stabilisation is stronger.The resistance to water that is difficult to have used the glass ring of phosphate glass material is increased to and has used lead is the level of the situation of glass.

Therefore,, can not form the glass ring that is formed with stage portion shown in Fig. 7 A, be not easy the display apparatus long lifetime that to use this glass ring to make yet there to be damaged state even use the phosphate glass material.Under the glass component that is formed by glass ring shown in Fig. 7 B exposes externally air state, be difficult to stop fully moisture in the extraneous air to the contact at the position of exposing, therefore, under the situation of having used the phosphate glass material, because moisture, the integral body of glass component is corroded, and reduces the air-tightness of light excitation source space.

The position that the corrosion of the moisture of phosphate glass parts is not limited to expose, and the essential factor that is extended to the integral body of glass component can be enumerated situation as described below, that is: the end face of breather pipe is not close to panel with the degree that enters that can intercept the moisture in the extraneous air.The inventor draws through discussion, when on panel, breather pipe being installed, even will be additional between the two load be increased to can insulation panel or the limit of the breakage of breather pipe near, also be difficult to flatten the stage portion of the ring that disposes between the end of breather pipe and the panel, the end face that makes breather pipe with above-mentioned degree near to above-mentioned panel.

Summary of the invention

Even the objective of the invention is to use under the situation of phosphate glass material, also improve the resistance to continual dampness energy of display apparatus as the material that is used at the glass ring (glass component) that breather pipe is installed on the panel.And then, the object of the present invention is to provide the breather pipe that has glass ring and the phosphate glass ring and the manufacture method thereof of the manufacturing that is fit to this display apparatus.

The invention provides a kind of display apparatus, comprise: form porose panel; The phosphate glass parts; Be installed on the described panel via described phosphate glass parts, and cover the pipe in described hole, wherein, described phosphate glass parts engage along at least a portion of the internal face of described pipe and the part of described panel, and the full week of the end face of the described hole side of described pipe contacts with described panel.

The present invention is provided for making the breather pipe that has glass ring of aforementioned display device equipment from the another side, possess: breather pipe and the phosphate glass ring that engages along at least a portion of the internal face of described breather pipe.

The present invention is provided for making the phosphate glass ring of aforementioned display device equipment from the another side, as the shape that contacts with at least a portion of the internal face of the pipe of on panel, installing, has the suitable face of outer peripheral face with the rotary body of stipulating, and, as the shape that contacts with the part of panel, end face with through hole opening, with respect to the gradient of the described outer peripheral face on the plane of the rotating shaft direct cross of described rotary body in scope greater than 0 degree and less than 90 degree, described phosphate glass ring is substantially devoid of adhesive.

The present invention provides the manufacture method of above-mentioned phosphate glass ring from the another side, comprise: will contain the phosphate glass material and under 25 ℃ atmosphere, be shaped for solid and boiling point glass frit adhesion agent composition at the adhesive below 400 ℃, obtain having the suitable face of outer peripheral face with the rotary body of regulation, and have the operation of formed body ring of the end face of through hole opening; Heat described formed body ring, remove the adhesive of described adhesive and remove operation.

In this manual, " basically " do not contained adhesive and is meant that the known organic content that uses as the adhesive of glass at not enough 1ppm, more particularly is the scope of not enough 1ppb." ppm " expression quality PPM, " ppb " expression quality parts per billion (ppb).Organic content for example uses gas chromatograph quality analysis known method evaluations such as (GC-MS) to get final product.

According to the present invention as can be known, even material as the ring (glass component) relevant with the installation of pipe on the panel, used phosphate glass, also can intercept moisture in the extraneous air, can improve the resistance to continual dampness energy of display apparatus to the contact of this glass component.

Description of drawings

Fig. 1 is the profile of an example of display apparatus of the present invention.

Fig. 2 is the exploded perspective view of an example of display apparatus of the present invention.

Fig. 3 A is the figure of an example that is used to illustrate the manufacture method of display apparatus of the present invention.

Fig. 3 B is the figure of an example that is used to illustrate the manufacture method of display apparatus of the present invention.

Fig. 4 A is the profile of an example of the breather pipe of the phosphate glass ring that uses in the manufacturing of display apparatus of the present invention and built-in this glass ring.

Fig. 4 B is used for illustrating that display apparatus pipe of the present invention is installed on the figure of an example of the state on the panel via the phosphate glass parts.

Fig. 5 A is another routine profile of the breather pipe of the phosphate glass ring that uses in the manufacturing of display apparatus of the present invention and built-in this glass ring.

Fig. 5 B is used for illustrating display apparatus of the present invention, and pipe is installed on the figure of another example of the state on the panel via the phosphate glass parts.

Fig. 6 A is another routine profile of the breather pipe of the phosphate glass ring that uses in the manufacturing of display apparatus of the present invention and built-in this glass ring.

Fig. 6 B is used for illustrating that display apparatus pipe of the present invention is installed on the figure of another example of the state on the panel via the phosphate glass parts.

Fig. 7 A is used to illustrate that comparative example reaches the profile of the structure of the glass ring of example in the past.

Fig. 7 B is used for illustrating comparative example and routine in the past display apparatus, and pipe is installed on the figure of the state on the panel via glass component.

Fig. 8 is another routine profile of the breather pipe of the built-in glass ring that uses in the manufacturing of display apparatus of the present invention.

Embodiment

Below, an example of embodiments of the present invention is described.

＜1. manage

Light excitation source space in the display apparatus is by during fabrication, is installed on after breather pipe on this panel regulates internal atmosphere the panel side of sealing breather pipe and the end of opposition side and airtight sealing via the mode that is formed at the air vent hole of panel with covering.In this manual, be not limited to the pipe of two sides' open-ended state, the pipe under such side's the pent state in end also can be used as pipe and handles.

Manage the shape that the shape that preferably has the bond stability that can improve pipe and panel promptly makes the stress of the contact portion that is applied to pipe and panel disperse easily.For example, can enumerate and have pipe portion and the flange part that is connected with this pipe portion, and flange part forms the structure and for example of the end face of the hole side in the pipe, have thin tube part and diameter greater than thin tube part and rely on the structure and for example of the wide diameter portion of panel side configuration than thin tube part, basically do not have thin tube part, and diameter is along with structure that becomes big wide diameter portion near panel etc.By forming wide diameter portion or flange part, can increase the point diameter of pipe, the bond stability under the situation that increase keeps pipe perpendicular to panel at the front end of pipe.

Shape as wide diameter portion, for example, constant shape is (for example on the prolonging direction of pipe can to enumerate (1) interior external diameter, cylindrical shape shown in the pipe 16 of Fig. 5 A), and for example (2) contain external diameter in first, with with this in first external diameter different second in the shape of external diameter, more particularly (2A) becomes big along with relying on end face, its amplification degree is constant or (for example become big shape along with relying on end face, tubaeform shown in the pipe 12 of Fig. 4 A), the amplification degree of external diameter is along with relying on the shape that end face diminishes (for example, hanging shown in the pipe 19 of Fig. 6 A bell) (2B), external diameter becomes big shape along with relying on end face interimly (2C), the shape that enlarges once more after external diameter temporarily narrows down along with relying on end face (2D) etc.

Also have, below, for convenience of explanation, will with above-mentioned (1), (2A) and (2B) pipe with wide diameter portion of suitable shape be called the pipe that has cylindrical portion, have the pipe of flare and have the pipe that hangs clock portion.

In addition, the material of pipe does not limit especially, but the viewpoint from panel, installing sleekly, preferred glass is as material.

In display apparatus, pipe is formed at the mode in the hole of panel with covering as mentioned above, with disposing with the panel state of contact in full week of the end face of this hole side.Contact with panel in the full week of above-mentioned end face is to instigate above-mentioned end face and panel near to intercepting contacting of moisture in the phosphate glass parts that are disposed in the pipe and the extraneous air, can prevent the degree of the deterioration of the glass component that the moisture in the extraneous air causes, and be not precluded within state shown in the embodiment described later, that between above-mentioned end face and panel, have the interval of less than 5 μ m.

＜2. phosphate glass parts 〉

In display apparatus, the phosphate glass parts are in the state that engages along the part of at least a portion of the internal face of pipe and panel as mentioned above.The phosphate glass parts make the full week of pipe end face contact with panel as described above, do not become the state that is exposed to extraneous air.Do not become state that the phosphate glass parts are exposed to extraneous air not the phosphate glass parts in the drain be exposed to the state of extraneous air via the gap of allowing the less than 5 μ m that between the end face of pipe and panel, exist.

From will managing the viewpoint that is installed on securely on the panel, preferably phosphoric acid is that full week of outside wall surface of glass component and then whole the internal face along pipe of outside wall surface engage.Have at pipe under the situation of wide diameter portion, from identical viewpoint, preferably phosphoric acid is at least a portion joint of glass component along the internal face of wide diameter portion.

If the shape of phosphate glass parts is formed the suitable shape of outer peripheral face that has with the rotary body of stipulating, then realize above-mentioned engagement state easily.As the outer peripheral face of rotary body of regulation, can illustration with respect to the gradient of the outer peripheral face on the plane of the rotating shaft direct cross of rotary body in face shape greater than the scope of 0 degree and less than 90 degree.The profile of rotary body pipe for the pipe that has cylindrical portion, have the pipe of flare and have under the situation of the pipe that hangs clock portion, pref. cylindrical, truncated cone and hang bell respectively.

Like this, phosphate glass parts in display apparatus have the suitable shape of outer peripheral face with the rotary body of stipulating, with respect to the gradient of the outer peripheral face on the plane of the rotating shaft direct cross of rotary body in scope greater than 0 degree and less than 90 degree, the state that engages with at least a portion of the internal face of pipe on outer peripheral face also can.The phosphate glass parts can be that the profile of rotary body is cylindrical, truncated cone or hangs bell.

From another viewpoint of mounting pipe securely on panel, preferably phosphoric acid is that the area that engages with panel of glass component is big as far as possible.

The phosphate glass parts as described later, under the state in the pipe that phosphate glass ring is disposed at breather pipe, after being disposed at this breather pipe on the panel, heated phosphoric is a glass ring, makes its fusion and forms.

Phosphate glass ring forms as described below, that is: by containing P ₂O ₅-SnO system, P ₂O ₅-SnO-ZnO system, P ₂O ₅-SnO-SiO ₂System, P ₂O ₅-SnO-Al ₂O ₃System, P ₂O ₅-SnO-B ₂O ₃The principal component (principal component of glass web formed body) that conducts such as system form the eyed structure of glass contains phosphorous oxide (P ₂O ₅) the phosphate glass material and under the atmosphere of normal temperature and pressure (25 ℃, 101325Pa), be the glass frit adhesion agent composition of the adhesive of the sublimability below 400 ℃ for solid and boiling point, after obtaining the formed body ring, more than the vitrification point with the phosphate glass material, the temporary firing temperature of not enough softening point, more particularly be 250～450 ℃ of heating, the formed body ring carried out unsticking mixture and sintering and form.

Therefore, the phosphate glass material does not contain lead, in addition, is substantially devoid of adhesive.Concrete aftermentioned, if but use the frit of the state of adhesive residue, then when being used for that breather pipe is installed on heating on the panel, existing glass rotten, or produce the crack, maybe can not pipe be installed on the situation on the panel securely.

From the internal face that improves breather pipe and the viewpoint of zygosity, preferably phosphoric acid is that the whole mask of the full Zhou Youqi outside wall surface of at least a portion of outside wall surface of glass ring and then outside wall surface has the shape that contacts with the internal face of breather pipe.As such shape, can illustration have the suitable face of outer peripheral face with the rotary body of regulation, and, have the shape of the end face of through hole opening.As the outer peripheral face of rotary body of regulation, can illustration shown in Fig. 4 A, with respect to the gradient of the outer peripheral face on the plane of the rotating shaft direct cross of rotary body in face shape greater than the scope of 0 degree and less than 90 degree.The profile of rotary body pipe for the pipe that has cylindrical portion, have the pipe of flare and have under the situation of the pipe that hangs clock portion, pref. cylindrical, truncated cone and hang bell respectively.

Above-mentioned phosphate glass material can be for containing 20 moles of phosphorous oxide (P more than the % by the oxide benchmark ₂O ₅) state, but from the viewpoint of the reduction of the resistance to water of anti-stop ring, preferred P ₂O ₅Containing ratio on be limited to 50 moles of %.

The phosphate glass material also contains tin oxide (SnO) also can.If contain 15 moles of above SnO oxides of % by the oxide benchmark, then can keep the low softening point of glass, simultaneously, can improve the resistance to water of ring.Maintain the viewpoint of high level from the stability with glass, the containing ratio of preferred SnO is 60 moles of %.

As the adhesive (organic substance) of above-mentioned sublimability, can illustration be selected from a kind of of camphor (240 ℃ of boiling points), naphthalene (218 ℃ of boiling points) and anthracene (354 ℃ of boiling points).The organic substance of sublimability does not residue in the glass ring more than the vitrification point of phosphate glass material and 250～450 ℃ of following complete obiterations specifically of the temporary firing temperature of not enough softening point.The organic substance of sublimability is hydrophobicity (in molecule not possess hydrophilic property group) and has firm cohesive force, therefore, and as can be effective by the adhesive that various low-melting glass material form glass ring.

Therefore the above-mentioned adhesive that with camphor is representative, as mentioned above, easily forms the glass ring that does not have residual adhesive because its sublimability can roughly be removed fully by burning till (adhesive is removed operation) temporarily.When using with camphor in order to form glass ring, using phosphorous oxide (P as glass material to the above-mentioned adhesive of representative ₂O ₅) and tin oxide (SnO), have in the situation of glass ring of complicated outside wall surface shape especially effective.The glass intensity that contains SnO is lower, and the bad influence that residual adhesive causes is especially serious.In addition, the shape of ring is complicated more, is difficult to make its stress equilibrium homogenizing more, and the damaged incidence that the rotten or residual adhesive of glass causes increases.

If residual in glass ring have an adhesive, then when the installation exercise of the pipe on panel, glass is rotten sometimes, or produces the crack, maybe pipe can not be installed on the panel securely.The resistance to water of glass that contains phosphorous oxide is low and apt to deteriorate, but the above-mentioned organic substance adhesive that with camphor is representative has so-called sublimability, therefore, remove at adhesive and to make also sharply volatilization in the relevant operation with ring beyond the operation, produce to air-flow away from the direction of formed body ring.Thus, hinder moisture near the formed body ring, when the formation operation of glass ring, the phosphate glass of protection poor water resistance makes its influence that is not subjected to moisture, thereby can prevent that it is rotten.Therefore, can be not have crackle to break or the state of defective such as shortcoming easily forms the phosphate glass ring with complicated outside wall surface shape.

If use adhesive, for example spy do not have sublimability to open that macromolecules such as disclosed polyethylene carbonic ester, polyvinyl alcohol derivative, polymethylstyrene are adhesive in the 2004-182584 communique, form glass ring, though then can remove heating in the operation by adhesive, this macromolecular structure is decomposed to a certain degree, but be difficult to remove fully, in glass ring, retain the adhesive more than a certain amount of.In addition, the residue after the decomposition sometimes causes that the glass ring generation is damaged.In addition, if the adhesive that uses unlike above-mentioned adhesive with sublimability rapid volatilization and have sublimability, then be difficult to hinder moisture when the formation operation of ring near glass material, phosphate glass is rotten sometimes.

With respect to the scope of the preferred 1 quality % of the organic content～20 quality % of the sublimability of phosphate glass material, the more preferably scope of 5 quality %～15 quality %.By making content is more than the 1 quality %, and phosphate glass material more reliably can bond.In addition, be below the 20 quality % by making content, the organic state of residual sublimability not in the ring after can realizing more reliably burning till temporarily.Like this, the containing ratio of the adhesive in the glass frit adhesion agent composition is more than the 1 quality % and the scope below the 20 quality % with respect to the phosphate glass material preferably.

Above-mentioned glass frit adhesion agent composition is for example by adding organic solvent 50～150 mass parts in organic phosphate glass material 100 mass parts that contain sublimability in the scope with 1 quality %～20 quality %, after fully stirring, evaporating dry below 30 ℃ and preparing.In order to reduce the organic content of the sublimability in the glass frit adhesion agent composition, preferably under the low temperature of trying one's best and evaporate dry in the short time.Therefore, as organic solvent, preferred use boiling point is the organic solvent below 100 ℃, and then preferably to use boiling point be organic solvent below 85 ℃, more particularly preferably use ethanol, isopropyl alcohol, diethanol, diethyl ether, isopropyl ether, acetone, butanone, ethyl acetate, carrene, chloroform, 1,2-dichloroethanes etc.

The phosphate glass material also can be for also containing ZnO, SiO ₂, Al ₂O ₃, B ₂O ₃Deng state.These compositions help the formation of glass, and performance improves the raising of the stability of glass, the control of thermal characteristics, the effects such as raising of resistance to water.But, if the containing ratio surplus, then the become rising that softening point takes place easily, mobile reduction, the crystallization of glass etc., therefore, above-mentioned ZnO to B ₂O ₃The containing ratio of composition be ZnO:0.5～10 mole %, SiO preferably by the oxide benchmark ₂: 1～10 mole of %, Al ₂O ₃: 1～10 mole of %, B ₂O ₃: 0.5～5 mole of %.

The phosphate glass material also can be for also containing Li ₂O, Na ₂O, K ₂O, MgO, CaO, SrO, BaO, V ₂O ₅, TeO ₂, CuO, Bi ₂O ₃, TiO ₂, MnO ₂, ZrO ₂, Nb ₂O ₅, MoO ₃, WO ₃, rare-earth oxide etc. state.If add these compositions, then further control the thermal characteristics of glass composition easily, or further improve intensity easily.

The phosphate glass material also can be the state of the lead-free filler that also contains fire resistance.As the lead-free filler of fire resistance, can illustration be selected from cordierite, willemite, forsterite, anauxite, zircon, mullite, beta-eucryptite, β-spodumene, cristobalite, barium titanate, aluminium titanates, titanium oxide, tin oxide, aluminium oxide, zirconia, phosphorous oxide zirconium, quartz glass, sialon (サ ィ ァ ロ Application), silicon nitride, carborundum, β-quartz solid solution, the formula that reaches by AD ₂(MO ₄) ₃The expression compound at least～kind.Wherein, in above-mentioned formula, A is at least a element that is selected from Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni and Mn, and D is at least a element that is selected from Zr, Ti, Sn, Nb, Al, Sc and Y, and M is at least a element that is selected from P, Si, W and Mo.

Be contained in the amount of lead-free filler of the fire resistance of frit, scope that can illustration 0～70 quality %, the scope of preferred illustration 5～50 quality %.When making display apparatus, preferably reduce coefficient of thermal expansion poor of panel and glass ring as far as possible.The fire resistance filler has the effect of coefficient of thermal expansion of control glass, and therefore, the kind or the amount of the fire resistance filler by selecting to be contained in glass ring can reduce coefficient of thermal expansion poor of glass ring and panel.

As mentioned above, use above-mentioned glass frit adhesion agent composition, obtain phosphate glass ring, and heated phosphoric is glass ring and makes its fusion, thus, obtains the phosphate glass parts.Therefore, phosphate glass ring and phosphate glass parts become the state that is substantially devoid of lead and organic substance adhesive.In addition, phosphate glass ring and phosphate glass parts will definitely be to contain 20 moles of phosphorous oxide more than the % by oxide-base.In addition, phosphate glass ring and phosphate glass parts can also contain tin oxide.

＜display apparatus 〉

As display apparatus, can illustration PDP or FED.Below, as PDP, an example of the display apparatus of the present invention that is elaborated.

The structure of＜3-1.PDP 〉

Fig. 1 is the profile of an example of the structure of expression PDP.In this PDP51, comprise the front panel of substrate 1a (front substrate) and comprise substrate 1b (back substrate) rear board opposed and dispose, between them, be formed with discharge space 2 (light excitation source space).The material of substrate 1a and 1b does not limit especially, but uses glass usually.Shown in Fig. 4 B, form porosely 11 at substrate 1b, the pipe 12 of coverage hole 11 is installed on the interarea of the substrate 1b of a side opposite with discharge space 2.

Contacting in full week of the end face of the hole side of pipe 12 with rear board.More particularly, the flange part 52 that is connected with the pipe portion of pipe 12 contacts with substrate 1b in full week.The inboard of pipe 12 (in the pipe) engages with phosphate glass parts 13.Phosphate glass parts 13 are not exposed in the extraneous air.In PDP51, by the periphery of periphery sealed wall 3 hermetic sealing substrate 1a and 1b.In addition, the end (thin tube part) of the opposition side of the hole side of pipe 12 is sealed.

Configuration comprises electrode group 4, dielectric layer 5 and the protective layer 6 of keeping electrode and scan electrode, configuration data electrode 7, dielectric layer 8 and next door 9 on substrate 1b on substrate 1a.PDP51 has so-called three-electrode structure.Also have, in Fig. 1, the number of next door among the PDP of reality or data electrode is elliptically illustrated.

Fig. 2 is the stereogram that has separated the PDP51 under the state of substrate 1a and substrate 1b.Also have, in Fig. 2, omit the diagram of periphery sealed wall 3 and glass component 13, the part of substrate 1a and 1b only is shown.

As shown in Figure 2, on substrate 1a, dispose striated scan electrode 41 in parallel to each other and keep electrode 42, by scan electrode 41 and keep electrode 42 and form show electrodes 43 as electrode group 4.Scan electrode 41 and keep electrode 42 and have structure respectively at transparency electrode (scan electrode) 41a and last stacked bus electrode (scan electrode) 41b of transparency electrode (keeping electrode) 42a and bus electrode (keeping electrode) 42b.As the material of transparency electrode 41a and 42a, can illustration ITO (IndiumTin Oxide), tin oxide etc.As the material of bus electrode 41b and 42b, can illustration aluminium, copper and silver etc.At scan electrode 41 with keep between the electrode 42 display quality of the promising raising black of configuration, improve the black film 40 that constitutes by glass and black pigment that is called as black streaking of the contrast of image.Each electrode and the black film 40 that are contained in electrode group 4 for example can be formed on the substrate 1a by screen printing.

In addition, dispose the dielectric layer 5 that covers show electrode 43 on substrate 1a, on dielectric layer 5, more particularly discharge space 2 sides at dielectric layer 5 dispose the protective layer 6 that is used to protect dielectric layer 5.Dielectric layer 5 plays the effect of the capacitor of store charge when the PDP51 display image.As the material of dielectric layer 5 and protective layer 6, respectively can illustration low-melting glass and MgO.

On substrate 1b, dispose the address electrode 7 of dielectric layer 8, next door 9 and striated.Dielectric layer 8 address electrode 7 that is configured to be covered, next door 9 is configured to be parallel to each other.Between adjacent next door 9, dispose luminescent coating 10.Discharge space 2 is split into pixel by next door 9.Luminescent coating 10 comprises rubescent, green or blue fluorophor.The material of address electrode 7 and dielectric layer 8 can use and bus electrode and dielectric layer 5 identical materials.As the material in next door 9, can illustration glass and pigment.

Substrate 1a and 1b be arranged opposite as described below, that is: make protective layer 6 and next door 9 towards discharge space 2, and makes striated electrode group 4 and address electrode 7 be quadrature under the situation of observing from the interarea of substrate 1a and 1b.In discharge space 2, be filled with the discharge gas of rare gas such as comprising neon or xenon.The pressure of the discharge gas in the discharge space 2 for example can be 53329～79993Pa (scope of 400～600Torr).

PDP51 is by applying image signal voltage selectively to show electrode 43, make the discharge gas plasma discharge, the ultraviolet ray exited fluorophor that is contained in luminescent coating 10 by producing makes the fluorophor of excitation send redness, green or blueness and color display.

In PDP51, as mentioned above, be not exposed in the extraneous air with the relevant glass component of mounting pipe on panel.Thus, prevent that the moisture in the extraneous air from contacting with above-mentioned glass component, the situation of etching glass parts, the generation of revealing slowly in the bonding part of inhibition panel and pipe, therefore, performance preferable image display performance, and, the long-term air pressure that keeps well in the discharge space is kept normal discharge.

The manufacture method of＜3-2.PDP 〉

PDP51 for example can make as described below.

(making of front panel)

On the interarea of the front substrate 1a that the soda-lime glass by the about 2.6mm of thickness constitutes, form show electrode as described below.Also have, utilizing print process to form the example of show electrode this illustrate, but in addition, can utilize also that mould is coated with method, the scraper plate coating process waits and forms.

At first, on surface substrate, apply the material (ITO) of transparency electrode, be dried with the pattern of regulation.Therewith concurrently, prepare the photonasty paste that hybrid metal (Ag) powder, organic vehicle and photoresist (photolysis resin) form.Secondly, after overlapping photonasty paste ground coating on the ITO pattern, apparatus has the mask covering of pattern of the show electrode of formation.Then, begin exposure, the photonasty paste is developed and burn till (firing temperatures about 590～600 ℃) from this mask.Thus, on transparency electrode 41a, 42a, form bus electrode 41b, 42b.As the metal material of bus electrode, replace Ag, can use Pt, Au, Cu, Al, Ni, Cr, tin oxide, indium oxide etc.

Also have, if use such photomask method, be that the stencil printing of the line width of 100 μ m is compared then with the limit in the past, can be with the live width about bus electrode graph thinning to 30 μ m, thereby it is preferred, do not utilize vacuum vapour deposition or sputtering method etc. with after the electrode material film forming but do not get rid of, utilize etch processes and the use of the known formation method that forms.

Secondly, on the show electrode that forms, use the stencil printing coating to contain the paste that non-lead is dielectric glass.By burning till after the dried during certain, form dielectric layer 5.As non-lead is the dielectric glass material, can illustration P ₂O ₅-SnO system, P ₂O ₅-SnO-ZnO system, Bi ₂O ₃System, ZnO-B ₂O ₃-SiO ₂Glass powders such as system.

Then, utilize sputtering method to form the protective layer 6 that the magnesium oxide by the about 1 μ m of thickness constitutes on the surface of dielectric layer 5.By above operation, make front panel.

(making of rear board)

Utilizing stencil printing on the surface of the back substrate 1b that the soda-lime glass by the about 2.6mm of thickness constitutes will be that the conductive material coating of principal component be the striated of certain intervals with metal (Ag), the address electrode 7 of the about 5 μ m of formation thickness.

Then, utilize stencil printing to contain the paste that non-lead is dielectric glass from the address electrode that forms with about 20～30 μ m coating of thickness.During necessarily, burn till after the dried, form dielectric layer 8 thus.

Secondly, on the dielectric layer 8 be the next door 9 that forms highly about 60～100 μ m between each adjacent address electrode.Next door 9 can be the paste of dielectric glass by use the non-lead use in the formation of dielectric layer 8 for example, burns till behind the screen printing repeatedly and forms.

At last, use pump, between the adjacency next door, spray any the fluorescent ink (15 * 10 that comprises redness (R) fluorophor, green (G) fluorophor, blueness (B) fluorophor from the nozzle of diameter 60 μ m ^-3Pas), it is contacted with the sidewall in next door and the dielectric film that exposes between adjacent next door.At this moment, make on the long side direction of panel next door 9 and move, with striated coating fluorescent ink.Then, near 500 ℃, burnt till 10 minutes, form luminescent coating 10.By above operation, can make rear board.

Also have,, for example, can use following fluorophor as each fluorophor of RGB.

Red-emitting phosphors; Y ₂O ₃: Eu ³⁺

Green-emitting phosphor; Zn ₂SiO ₄: Mn ²⁺

Blue emitting phophor; BaMgAl ₁₀O ₁₇: Eu ²⁺

Fluorescent ink is for example prepared by each fluorescent material 50 quality %, ethyl cellulose 1.0 quality % and solvent (α-terpineol) the 49 quality % that mix volume average particle size 2.0 μ m with sand mill.

(making of PDP)

In front on the interarea of at least one side's of plate or rear board panel, apply in mode and to contain the glass paste that non-lead is the dielectric glass material around one week of periphery of this interarea.As this non-lead is frit, can illustration Bi ₂O ₃System, ZnO-B ₂O ₃-SiO ₂System waits the mixed-powder of the lead-free filler powder of low-melting glass powder or these low melting point powder and fire resistance.

Behind the drying coated paste of certain hour, with the non-lead in the glass paste be near the softening point of frit, more particularly 350～450 ℃ burn till temporarily, form the periphery sealing thus with parts 14.The time of burning till temporarily for example was made as 30 minutes.In this manual, with periphery sealing as described later and then burn till and make its fusion with parts 14, and with it as 3 processing of the periphery sealed wall between sealing front panel and the rear board.

Secondly, as shown in Figure 3A, so that the mode of address electrode 7 quadratures of the electrode group 4 of front panel and rear board, with the two panels arranged opposite.And then, for be communicated with as the hole 11 that is formed at the air vent hole of rear board, be that the breather pipe of representative is configured to contacting with rear board in full week of the end face of its hole side with the pipe 12 shown in Fig. 4 A to have flare.At this moment, the internal face of breather pipe and glass ring 15 with the truncated cone shown in Fig. 4 A are that the glass ring of representative engages.

The install and use phosphate glass ring and the breather pipe that are in respectively under the separate and distinct state of the breather pipe on the panel carry out also can backward, but preferably be bonded under the state of side of this ring, use the breather pipe that has glass ring of the inside that is disposed at breather pipe to carry out at least a portion that makes above-mentioned phosphate glass ring along the internal face of the pipe portion of breather pipe.If use the breather pipe have glass ring, breather pipe and glass ring are moved integratedly, therefore, easily make the axle of the through hole of the air vent hole that is formed at panel and ring and breather pipe consistent.

Then, be under high 30～50 ℃ temperature of the softening point of frit with the non-lead of parts 14 than being contained in the sealing of glass ring 15 and periphery, more particularly burnt till 30 minutes under 380～500 ℃, thus, make the sealing of glass ring 15 and periphery with parts 14 fusions, form phosphate glass parts 13 shown in Fig. 3 B and the periphery sealed wall 3 between sealing panel.

Then, via breather pipe, with the exhaust gas inside of discharge space to high vacuum state (about 1.0 * 10 ^-4Pa), then Ne-Xe system or discharge gass such as He-Ne-Xe system, He-Ne-Xe-Ar system are filled to its inside and become the pressure of regulation (till this is about 66.5～101kPa).Then, the end of the opposition side of hole 11 sides in the heating breather pipe, the end (thin tube part) of opposite with a substrate 1b side in other words side makes this terminal wall pipe deposited, and sealed discharging space 2 thus.By above operation, finish PDP51.

The breather pipe that has a glass ring is disposed at the inside of breather pipe as mentioned above under the state that phosphate glass ring engages along at least a portion of the internal face of the pipe portion of breather pipe in the side that makes this ring.In this manual, in having the breather pipe of glass ring, glass ring engages the state of the internal face that is meant the pipe portion that is engaged in breather pipe with the internal face of breather pipe, the state that glass ring engages with flange part is meant the state that glass ring does not engage with the internal face of breather pipe.

The breather pipe that has a glass ring preferably in the pipe that phosphate glass ring is for example embedded breather pipe after, be heated to the residual degree of through hole of ring, and make its fusion, again for example, embed via known adhesives in the pipe of breather pipe, be in the state that the bond strength of the internal face of breather pipe and ring is enhanced thus, but as long as ring is difficult for from the breather pipe landing, the state that ring embeds in the pipe of breather pipe simply is also passable.

From the viewpoint of breather pipe is installed on panel more firmly, the preferred end face that is in phosphate glass ring of using is than the breather pipe that has glass ring under the more outstanding state of the end face of breather pipe.More particularly, for example, as shown in Figure 8, preferably under the degree that does not hinder with full week of the end face of breather pipe and the configuration of panel state of contact, the end face 55 that phosphate glass ring 15 preferably is in than pipe 12 relies on the outstanding state in the outside.In the installation exercise of the breather pipe on panel, usually, glass ring and breather pipe are configured to the gravity of glass ring is applied towards the thin tube part of breather pipe.Therefore, if use the end face be in ring to rely on the breather pipe that has glass ring of the outstanding state in the outside, then when above-mentioned installation exercise, can make the glass ring touch panel more reliably that is in molten condition than the end face of breather pipe.

Embodiment

Below, the example of the embodiment of display apparatus of the present invention is described.

(embodiment 1)

Embodiment 1 is the PDP that makes as described below, that is: use the phosphate glass ring 15 of the profile shown in Fig. 4 A and having to make, and pipe is installed on (with reference to Fig. 4 B) panel 1b in the mode of coverage hole 11 and built-in glass component 13 corresponding to the pipe that has flare 12 of the wide diameter portion 53 of the internal face shape of the profile of this glass ring 15 with truncated cone.

(1) preparation of glass frit adhesion agent composition

As the phosphoric acid tin monoxide is frit, has P under the situation of preparation by the mole % demonstration of oxide benchmark ₂O ₅: the glass powder 90 quality % of the composition of 30 moles of %, SnO:60 mole %, ZnO:10 mole %, add acetone 100 mass parts to this frit with as mixture 100 mass parts of the camphor 10 quality % of adhesive as solvent, then, it is used mixing 10 minutes of ball mill.Then, under the atmosphere below 30 ℃, placed 30 minutes, make the acetone evaporated of interpolation, make mixture dry, thus formulate glass material binder combination.

(2) making of phosphate glass ring

The glass frit adhesion agent composition is filled in the metal pattern former of the ring that is used to form profile with truncated cone, carry out pressure forming then, formation has the formed body ring of the profile of truncated cone, then, be heated to 360 ℃, remove adhesive, and, burn till this formed body ring, make the phosphate glass ring 15 of profile with truncated cone.

(3) have the making of the breather pipe of glass ring

After phosphate glass ring being embedded in the pipe of the pipe 12 have flare, under 420 ℃, burn till, thus, make the breather pipe that has glass ring 54 shown in Fig. 4 A.

(4) making of PDP

Use has the breather pipe 54 of glass ring, makes PDP shown in Figure 1.Concrete step when making this PDP is according to the manufacture method of above-mentioned PDP.The firing temperature that is used to form periphery sealed wall 3 and phosphate glass parts 13 is set at 450 ℃.So that pressure becomes the mode of 0.53 atmospheric pressure (400Torr), in discharge space, fill Xe-Ne gas as discharge gas.

(embodiment 2)

Embodiment 2 is the PDP that make as described below, that is: use above-mentioned glass powder 80 quality % and as the mixed-powder 90 quality % of the cordierite 20 quality % of fire resistance lead-free filler, with mixture as the camphor 10 quality % of adhesive, formulate glass material binder combination, use the phosphate glass ring with columniform profile 17 of this glass frit adhesion agent composition making shown in Fig. 5 A, use this phosphate glass ring 17, with the pipe that has columnar portion 16 that has corresponding to the wide diameter portion 53 of the internal face shape of the profile of this phosphate glass ring 17, in addition, make PDP in the same manner with embodiment 1, among this PDP with coverage hole 11, and the mode of built-in glass component 18 will be managed installation (with reference to Fig. 5 B) on panel 1b.

(embodiment 3)

Embodiment 3 is the PDP that make as described below, that is: replace camphor, adhesive uses naphthalene, replace acetone, solvent uses ethanol and formulate glass material binder combination, use this glass frit adhesion agent composition to make as shown in Figure 6A the phosphate glass ring 20 that hangs bell profile that has, use this phosphate glass ring 20, the pipe 19 that hangs clock portion that has with wide diameter portion 53 with internal face shape corresponding with the profile of this glass ring 20, in addition, make PDP in the same manner with embodiment 1, with coverage hole 11, and the mode of built-in glass component 21 is installed (with reference to Fig. 6 B) pipe on panel 1b in this PDP.

(comparative example 1)

Comparative example 1 is the PDP that makes as described below, that is: replace the glass ring of shape built-in in the pipe, the stage portion of the pallet of the pipe 12 that has flare except that becoming shown in Fig. 7 A is used the phosphate glass ring 22 on the surface that is formed at internal face, make PDP in the same manner with embodiment 1, in this PDP, under the state that the glass component 23 that forms making these glass ring 22 fusions and the outside wall surface of pipe (outside the pipe) and end face, panel 1b engage, mounting pipe on panel 1b (with reference to Fig. 7 B).

(example 1 in the past)

Example 1 was the PDP that makes as described below in the past, as frit, except replacing the phosphate glass material, had PbO:66 mole %, B under the situation of using the mole % by the oxide benchmark to represent that is: ₂O ₃: 30 moles of %, SiO ₂: the lead oxide glass frit of the composition of 4 moles of % end 60 quality % and be beyond the frit as the lead oxide that the mixture of the lead titanates 40 quality % of fire resistance filler constitutes, make PDP in the same manner with comparative example 1.

[evaluation of glass component]

Embodiment 1～3, comparative example 1 and the glass component relevant with the installation of pipe on panel in the example 1 in the past are heated to 400 ℃ from room temperature (25 ℃), measure the gas that produces with gas chromatograph quality analysis (GC-MS), obtain the residual adhesive amount in the glass component separately thus.The results are shown in the table 1.

[evaluation of PDP]

Carry out embodiment 1～3, comparative example 1 and the lighting test of the PDP of example 1 in the past, estimate the brightness of panel.Luminance meter (display color analyzer) is used in the evaluation of brightness, and the PDP of (after the long-term humidity test) carries out to the PDP after the firm manufacturing with after placing 100 days under the high humidity environment of 70 ℃ of 95%RH.It the results are shown in the table 1.Brightness of illumination is expressed as brightness that the PDP with the example in the past 1 after firm manufacturing obtains and is made as relative value under 100% the situation.

[table 1]

By gas chromatograph quality analysis (GC-MS), measure the organic amount that contains in the relevant glass component of the installation of pipe among the embodiment 1～3 with on the panel, the equal not enough 1ppb of its result confirms and does not contain adhesive substantially.

In addition, do not illustrate in the table 1, but by visual or microscopic examination, observe embodiment 1～3, comparative example 1 and the result of the glass ring that in the past used in the example 1, do not find all that crackle breaks or shortcoming etc. damaged.Will be after embodiment 1～3, comparative example 1 and the glass frit adhesion agent composition that in the past used in the example 1 be configured as 20cm φ * 10cm cylindrical, compare at the goods that under 360 ℃ it are fired into at embodiment 1～3, comparative example 1 and the glass ring that used in the example 1 in the past, estimate the rotten result of glass, all do not find rotten.

The PDP of embodiment 1～3 is as shown in table 1, confirms: after resistance to continual dampness test, also to throw light on initial value separately and the brightness that equates of the initial value of example in the past, bring into play superior resistance to continual dampness.On the other hand, do not observe the illumination after resistance to continual dampness is tested among the PDP of comparative example 1, resistance to continual dampness is poor.

Also have, in comparative example 1, the end face of the hole side of pipe and panel be spaced apart 85 μ m.On the other hand, in embodiment 1～3, the equal less than 5 μ m in the bottom surface of the hole side of pipe and the interval of panel, the end face of pipe contacts basically with panel.

In addition, the PDP of embodiment 1 and comparative example 1 is placed under the environment of (1) 90 ℃ of 95%RH, (2) 107 ℃ of 95%RH, (3) 120 ℃ of 95%RH, (4) 121 ℃ of 100%RH, fate till investigation PDP does not throw light on, its result, be (1) 32 day, (2) 67 days, (3) 28 days, (4) 3 days in comparative example 1, with respect to this, among the embodiment 1 be that (1) surpasses 200 days, (2) surpass 80 days, (3) surpass 70 days, (4) above 37 days.

In comparative example 1, the phosphate glass parts relevant with the installation of pipe on the panel are exposed in the extraneous air, and the end face of pipe is not fully near panel, therefore, the integral body that is considered to glass component is by the humidity corrosion in the extraneous air, and the air-tightness of discharge space reduces and to cause.On the other hand, think in embodiment 1～3, contact with panel that the moisture that hinders in the extraneous air contacts with phosphate glass parts relevant for the installation of the pipe on the panel by the end face that makes pipe, thus air-tightness that can the long term maintenance discharge space.

Utilizability on the industry

According to the present invention as can be known, in the display apparatus such as FED or PDP, can cut down harmful Learn the i.e. plumbous use amount of material, reduce the bad influence to natural environment, and, can improve that it is long-term Moisture resistance properties.

Claims (25)

1. a display apparatus comprises: form porose panel; The phosphate glass parts; Be installed on the described panel and cover the pipe in described hole via described phosphate glass parts, wherein,

Described phosphate glass parts engage with the part of described panel along at least a portion of the internal face of described pipe,

The full week of the end face of the described hole side of described pipe contacts with described panel.

2. display apparatus according to claim 1, wherein,

Described pipe has: pipe portion and the flange part that is connected with described pipe portion, described flange part forms the end face of the described hole side of described pipe.

3. display apparatus according to claim 1, wherein,

Described pipe has thin tube part and wide diameter portion, and the diameter of this wide diameter portion is greater than described thin tube part, and is configured in than described thin tube part and relies on described panel side, and described phosphate glass parts engage along at least a portion of the internal face of described wide diameter portion.

4. display apparatus according to claim 1, wherein,

Described pipe has wide diameter portion, and diameter becomes big to this wide diameter portion along with close described panel, and described phosphate glass parts are along at least a portion joint of the internal face of described wide diameter portion.

5. display apparatus according to claim 1, wherein,

Described phosphate glass parts have the suitable shape of outer peripheral face with the rotary body of stipulating, and described outer peripheral face with respect to the gradient on the plane of the rotating shaft direct cross of described rotary body in scope greater than 0 degree and less than 90 degree, and on described outer peripheral face, engage with at least a portion of described internal face.

6. display apparatus according to claim 5, wherein,

The profile of described rotary body is cylindrical, truncated cone or hangs bell.

7. display apparatus according to claim 1, wherein,

Described phosphate glass parts contain 20 moles of phosphorous oxide more than the % by the oxide benchmark.

8. display apparatus according to claim 7, wherein,

Described phosphate glass parts also contain tin oxide.

9. breather pipe that has glass ring, it is used to make the described display apparatus of claim 1, wherein, possesses:

Breather pipe; And

Phosphate glass ring, its at least a portion along the internal face of described breather pipe engages.

10. the breather pipe that has glass ring according to claim 9, wherein,

The end face of described phosphate glass ring is more outstanding laterally than the end face of described breather pipe.

11. the breather pipe that has glass ring according to claim 9, wherein,

Described breather pipe has: pipe portion and the flange part that is connected with described pipe portion, and described flange part forms the end face of described breather pipe.

12. the breather pipe that has glass ring according to claim 9, wherein,

Described breather pipe has: thin tube part and wide diameter portion, this wide diameter portion diameter be greater than described thin tube part, and be configured in the front that more relies on described pipe than described thin tube part, and described phosphate glass ring engages along at least a portion of the internal face of described wide diameter portion.

13. the breather pipe that has glass ring according to claim 9, wherein,

Described breather pipe has wide diameter portion, and diameter becomes big to this wide diameter portion along with the front end of close described breather pipe,

Described phosphate glass ring engages along at least a portion of the internal face of described wide diameter portion.

14. the breather pipe that has glass ring according to claim 9, wherein,

Described phosphate glass ring has the suitable shape of outer peripheral face with the rotary body of stipulating, described outer peripheral face with respect to the gradient on the plane of the rotating shaft direct cross of described rotary body in scope greater than 0 degree and less than 90 degree, and on described outer peripheral face, engage with at least a portion of described internal face.

15. the breather pipe that has glass ring according to claim 14, wherein,

The profile of described rotary body is cylindrical, truncated cone or hangs bell.

16. the breather pipe that has glass ring according to claim 9, wherein,

Described phosphate glass ring contains 20 moles of phosphorous oxide more than the % by the oxide benchmark.

17. the breather pipe that has glass ring according to claim 16, wherein,

Described phosphate glass ring also contains tin oxide.

18. a phosphate glass ring, it is used to make the described display apparatus of claim 1, wherein,

As the shape that contacts with at least a portion of the internal face of the pipe of on panel, installing, have the suitable face of outer peripheral face with the rotary body of regulation, and, as the shape that contacts with the part of panel, have the end face of through hole opening,

Described outer peripheral face with respect to the gradient on the plane of the rotating shaft direct cross of described rotary body in scope greater than 0 degree and less than 90 degree, and

Described phosphate glass ring is substantially devoid of adhesive.

19. phosphate glass ring according to claim 18, wherein,

The profile of described rotary body is truncated cone or hangs bell.

20. phosphate glass ring according to claim 18, wherein,

Contain 20 moles of phosphorous oxide more than the % by the oxide benchmark.

21. phosphate glass ring according to claim 20, wherein,

Also contain tin oxide.

22. the manufacture method of a phosphate glass ring, it is the manufacture method of the described phosphate glass ring of claim 18, wherein, comprising:

The glass frit adhesion agent composition that will contain phosphate glass material and adhesive is shaped, and described adhesive is being that solid and boiling point are below 400 ℃ under 25 ℃ the atmosphere, thereby obtain having the suitable face of outer peripheral face with the rotary body of regulation, and have the operation of formed body ring of the end face of through hole opening;

Heat described formed body ring, remove the adhesive of described adhesive and remove operation.

23. the manufacture method of phosphate glass ring according to claim 22, wherein,

Described adhesive is be selected from camphor, naphthalene and anthracene at least a.

24. the manufacture method of phosphate glass ring according to claim 22, wherein,

The containing ratio of the described adhesive in the described glass frit adhesion agent composition is more than the 1 quality % and the scope below the 20 quality % with respect to described phosphate glass material.

25. the manufacture method of phosphate glass ring according to claim 22, wherein,

The heating-up temperature that described adhesive is removed operation is more than 200 ℃ and the scope below 450 ℃.

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