JP3628045B2 - Crystalline sealant glass and method of manufacturing information display device using the same - Google Patents

Description

【００５５】
【発明の効果】
本発明の結晶性シーラントガラスは、短時間で、高強度の封着ができる。かかる結晶性シーラントガラスはパネルガラスとフアンネルガラスとを封着するブラウン管の製造、２枚の基板ガラスを封着するプラズマディスプレイの製造に特に適する。
【図面の簡単な説明】
【図１】結晶性ガラスのＤＴＡ特性を示すグラフ[0001]
[Industrial application fields]
The present invention relates to a crystalline sealant glass and a method for manufacturing an information display device such as a cathode ray tube or a plasma display using the same.
[0002]
[Prior art]
For various types of sealing, such as sealing between panel glass and funnel glass in the manufacture of a cathode ray tube, crystalline sealant glass that precipitates a crystalline phase on the glass by firing is used.
[0003]
The process of crystallizing glass is divided into a process of generating nuclei in glass and a process of growing crystals around the nuclei. In general, when producing crystallized glass, as means for promoting the precipitation of the crystal phase, 1) a nucleation substance is put in advance in the melting process of the glass. The method of using is known. For the crystalline sealant glass, the method 2) is generally used.
[0004]
In particular, in the case of crystalline sealant glass for assembling a high vacuum vessel such as a cathode ray tube or a medium vacuum vessel such as a plasma display, a large tensile stress is always applied to the sealing region, so it can withstand it. Such a sufficient strength is required for the fired body of the sealant glass. For this reason, generally, a crystalline sealant glass in which two or more crystal phases are precipitated by firing is used, and the strength of the fired body is ensured by the interaction of the crystal phases.
[0005]
As such a crystalline sealant glass, there is a PbO—B ₂ O ₃ —SiO ₂ —ZnO—BaO-based glass, and there is a glass containing a small amount of zircon. Such crystalline sealant glass, _{fired, 2PbO · ZnO · B 2 O} 3 crystal phase precipitates to a first, 4PbO _· B 2 _{O 3} crystal phase is deposited on the second.
[0006]
FIG. 1 shows the DTA characteristics of such a crystalline sealant glass. The left vertical axis represents the calorific value (or endothermic amount) of the glass, the right vertical axis represents the firing temperature of the glass, and the horizontal axis represents time. The temperature was raised from room temperature to 440 ° C. at a rate of 10 ° C./min, and the temperature was maintained at a holding temperature of 440 ° C. for firing. In FIG. 1, the crystalline glass softens in the region a, flows in the region b, and a crystalline phase precipitates in the region c. One th peak _{C 1} is the exothermic peak of the crystal phase 2PbO _· ZnO · B 2 _{O 3} precipitated to a first, a second peak _{C 2} crystalline phase 4PbO _· B 2 _{O 3} precipitated Second Exothermic peak.
[0007]
However, in such a crystalline sealant glass, a plurality of crystalline phases are sequentially precipitated as shown in FIG. 1, so that by comparison with a crystalline sealant glass having only a single crystalline phase, the precipitation is completed. It was insufficient in that it took a long time and productivity was inferior.
[0008]
In addition, in order to ensure the strength of the sealing portion, not only the strength of the fired body of the crystalline sealant glass, but also the mutual diffusion of the elements constituting the crystalline sealant glass and the glass to be bonded is sufficiently generated and firmly fixed to each other. It is important to bond and prevent the interface between the crystalline sealant glass and the glass to be bonded sufficiently to cause concentration of wet stress.
[0009]
Therefore, after the powdery or paste-like crystalline sealant glass is softened once by firing, sufficient interdiffusion and sufficient flow are produced until the start of precipitation of the crystalline phase, and the time required to ensure ideal wetting is ensured. It takes a relatively long time when these times are combined.
[0010]
Conventionally, as a method for shortening the crystal phase precipitation time, it has been known to use a relatively low melting point oxide in the composition of the crystalline sealant glass, but in general, the precipitation of the crystal phase is promoted. In addition, the flow time from melting to the start of precipitation of the crystal phase is shortened, and there is a problem that sufficient wettability cannot be ensured.
[0011]
As another method, it is also known that a sealant glass in which a crystal phase is precipitated is pulverized and the particles are used as crystal nuclei (Japanese Patent Laid-Open No. 62-226828). However, even in this method, since the main component of the crystal nucleus is the crystal phase that precipitates first, if the amount necessary to shorten the precipitation time of the crystal phase that precipitates second and later is added, the flow time described above is also increased. It is shortened and the same problem occurs.
[0012]
[Problems to be solved by the invention]
The present invention has been made to solve the above-described problems, and does not cause a decrease in strength, shortens the time required for sealing and improves productivity, and information using the same An object is to provide a display device.
[0013]
[Means for Solving the Problems]
The present invention includes a crystalline glass powder that precipitates a plurality of crystal phases having different precipitation times and a crystal nucleus, and the composition of the crystalline glass powder is 60 to 85% by weight of PbO and 5 to 15 % by weight of B ₂ O _3. %, ZnO 8 to 18% by weight, SiO ₂ 0 to 5% by weight, BaO 0 to 5% by weight, and the crystal nuclei are precipitated first in the crystalline glass in the crystalline glass. A crystalline sealant glass containing more than the crystal phase to be produced, and a method of manufacturing a cathode ray tube and a plasma display using the crystalline sealant glass.
[0014]
In the present invention, the precipitation time of the crystalline phase of the crystalline glass refers to the time from the time when the glass reaches the holding temperature during firing to the time when the exothermic peak due to the precipitation of the crystalline phase occurs on the DTA curve of the glass.
[0015]
The crystalline glass powder in the present invention precipitates a plurality of crystal phases with different precipitation times by firing. The crystalline glass powder preferably has as little difference as possible between the precipitation time of the first crystal phase and the second and subsequent crystal phases.
[0016]
The kind of the crystal phase and the composition of the glass powder are not particularly limited as long as they satisfy the manufacturing process of the molded body to be sealed and various properties required for the molded body. Examples of such glass powder include the following.
[0017]
PbO—B ₂ O ₃ —SiO ₂ —BaO,
PbO—TiO ₂ —SiO ₂ ,
SiO ₂ —ZnO—BaO—Al ₂ O ₃ ,
TiO ₂ —SiO ₂ —ZnO—CaO—Al ₂ O ₃ ,
PbO—SiO ₂ —Al ₂ O ₃ ,
PbO—ZnO—B ₂ O ₃ ,
_{P 2 O 5 -ZnO-Li 2} O-Na 2 O-K 2 O.
[0018]
On the other hand, the crystal nuclei contain a larger amount of crystal phase that is precipitated after the second firing of the crystalline glass powder than the crystal phase that is precipitated first. In this crystal nucleus, when the content of the crystal phase precipitated after the second is less than the content of the crystal phase precipitated first, the time for precipitation of the crystal phase precipitated after the second on the glass is increased by firing. At the same time, the wettability decreases and the object of the present invention cannot be achieved.
[0019]
The content of the crystal phase precipitated after the second in the crystal nucleus is preferably 10% (wt%, the same applies hereinafter) or more. If the content is less than 10%, the properties of the sealant glass may be impaired, which is not preferable. On the other hand, the content of the crystal phase that precipitates first in the crystal nucleus is a range in which the fluidity is sufficiently secured and the precipitation time of the crystal phase that precipitates first is adjusted too long. And less is preferable.
[0020]
The content of crystal nuclei is preferably such that the second and subsequent crystal phases precipitated in the crystalline glass are 1 to 20000 ppm (weight ppm, the same applies hereinafter) by weight relative to the crystalline sealant glass. When the content of the crystal phase precipitated after the second is less than 1 ppm, it is not preferable because the precipitation time of the crystal phase precipitated after the second becomes long, and when it exceeds 20000 ppm, the fluidity at the time of sealing is lowered, which is not preferable. The content of the crystal phase precipitated after the second is particularly preferably 1 to 6000 ppm in the above range.
[0021]
In manufacturing a cathode ray tube, when sealing panel glass and funnel glass, it is preferable to use the following crystalline sealant glass because high strength sealing can be performed in a short time at a low temperature.
[0022]
That is, the composition of the crystalline glass powder is in the range of PbO 60-85%, B ₂ O ₃ 5-15%, ZnO 8-18%, SiO ₂ 0-5%, BaO 0-5%. The crystal phase that is secondly precipitated in the glass is 4PbO · B ₂ O ₃ and the content of the 4PbO · B ₂ O ₃ crystal phase contains 1 to 6000 ppm of crystal nuclei with respect to the crystalline sealant glass. The crystal nucleus contains more 4PbO.B ₂ O ₃ crystal phase than the crystal phase first precipitated in the crystalline glass.
[0023]
The reasons for limiting the composition of this crystalline glass powder are as follows.
[0024]
If the PbO content is less than 60%, the viscosity increases and the sealing temperature must be increased, which may significantly impair the properties of the components in the container. I can't wear it.
[0025]
When the content of B ₂ O ₃ is less than 5%, the softening point becomes high and the fluidity is impaired, and when it exceeds 15%, the chemical durability is deteriorated.
[0026]
If the ZnO content is less than 8%, the softening point becomes too high to be crystallized, and if it exceeds 18%, devitrification is likely to occur when producing crystalline glass.
[0027]
By containing SiO ₂ , the water resistance can be improved. If the content exceeds 5%, the viscosity increases and the sealing temperature increases.
[0028]
By containing BaO, the solubility of the crystalline glass is improved. If the content exceeds 5%, the thermal expansion coefficient becomes too large.
[0029]
The more preferable crystalline sealant glass used for sealing the panel glass and the funnel glass is as follows.
[0030]
That is, the composition of the crystallizable glass powder, there _{PbO 70~81%, B 2 O 3} 7~10%, ZnO 10~14%, SiO 2 1~3%, in the range of 1 to 3% BaO, crystalline The crystal phase that is secondly precipitated in the glass is 4PbO · B ₂ O ₃ , and the crystal nucleus content is such that the content of the 4PbO · B ₂ O ₃ crystal phase is 1 to 5000 ppm with respect to the crystalline sealant glass , Alumina 0 to 10%, zircon 0.05 to 5%, the balance is made of crystalline glass powder, and the crystal nucleus contains more 4PbO · B ₂ O ₃ crystal phase than the first crystal phase precipitated in crystalline glass To do.
[0031]
By containing alumina, the strength of the fired body of the crystalline sealant glass can be improved. If the content exceeds 10%, the fluidity is deteriorated, which is not preferable.
[0032]
Zircon is a component that shortens the precipitation time of the crystal phase (2PbO.ZnO.B ₂ O ₃ ) that is first precipitated in the crystalline glass. If the content of zircon is less than 0.05%, the effect is not obtained, and if it exceeds 10%, the precipitation time of the first crystal phase is too short, so that wetting becomes insufficient and airtightness is lowered, which is not preferable.
[0033]
A cathode ray tube using such a crystalline sealant glass can be manufactured as follows.
[0034]
According to a conventional method, a crystalline sealant glass and a vehicle are mixed to prepare a slurry. As this vehicle, various types such as those obtained by dissolving nitrocellulose in amyl acetate can be used. This slurry is applied to the adhesive surface of the funnel glass. Next, the panel glass on which a phosphor or the like is previously mounted is placed on the funnel glass so that the adhesion surface thereof is in contact with the adhesion surface of the funnel glass. This is then heated and fired at 420-460 ° C. for 5-25 minutes.
[0035]
By this firing, the crystalline glass powder is first softened and then fluidized, and is sufficiently wetted with the bonding surfaces of the panel glass and funnel glass. Then, the crystal glass, is one th crystalline phase as a precipitate is _{2PbO · ZnO · B 2 O 3} , then the second 4PbO _· B 2 _{O 3} higher sealing strength by precipitation of a crystalline phase Done.
[0036]
When manufacturing a plasma display panel, the following are preferable as the crystalline sealant glass used for sealing two substrate glasses.
[0037]
That is, the composition of the crystallizable glass powder, there _{PbO 70~81%, B 2 O 3} 7~10%, ZnO 10~14%, SiO 2 1~3%, in the range of 1 to 3% BaO, crystalline The crystal phase that is secondly precipitated in the glass is 4PbO · B ₂ O ₃ , and the crystal nucleus content is such that the content of the 4PbO · B ₂ O ₃ crystal phase is 1 to 5000 ppm with respect to the crystalline sealant glass , Low expansion filler 2-30%, zircon 0.05-5%, the balance is made of crystalline glass powder, low expansion filler is lead titanate, cordierite, β-eucryptite, β-spodumene, β-quartz solid solution And at least one selected from silica, and the crystal nucleus contains more 4PbO.B ₂ O ₃ crystal phase than the first crystal phase precipitated in the crystalline glass.
[0038]
The low expansion filler acts to reduce the thermal expansion of the fired body of the crystalline sealant glass and to match the thermal expansion of the substrate glass. If the content of the low expansion filler is less than 2%, such an effect is not sufficient, and there is residual stress in the sealing portion, and the strength is lowered. This is not preferable because the wettability is insufficient and the airtightness and strength are lowered.
[0039]
A plasma display using such a crystalline sealant glass can be manufactured as follows.
[0040]
A crystalline sealant glass and a vehicle are mixed to form a slurry. This vehicle is the same as described in the manufacture of the cathode ray tube. Next, this slurry is applied to the periphery of the substrate glass on which electrodes and the like have been previously formed. Next, another substrate glass is placed thereon, and then heated and baked at 420 to 500 ° C. for 5 to 40 minutes.
[0041]
By this firing, the crystalline glass powder first softens and then flows to sufficiently wet the bonding surface of the substrate glass. _{Then, 2PbO · ZnO · B 2 O} 3 crystal phase precipitates in The first is in the crystalline glass, the second to 4PbO _· B 2 _{O 3} sealing the crystal phase and excellent precipitated strength is completed.
[0042]
【Example】
According to a conventional method, a crystalline glass powder of 75% PbO, 9% B ₂ O ₃ , 12% ZnO, 2% SiO _{2 and} 2% BaO was prepared.
[0043]
When the crystallizable glass powder is fired for 35 minutes at 440 ° C., the crystalline phase of 2PbO _· ZnO · B 2 _{O 3} is deposited to a first, that the crystalline phase of 4PbO _· B 2 _{O 3} is deposited on the second X Confirmed with a line diffractometer.
[0044]
The fired body was photographed with an electron microscope, image-processed to determine the area ratio of the crystal phase and the like. As a result, the 2PbO · ZnO · B ₂ O ₃ crystal phase, the 4PbO · B ₂ O ₃ crystal phase, and glass The ratio was approximately 5: 3: 2.
[0045]
Then _{PbO: B 2 O 3 = 4} : 1 was vitrified by melting by heating the blended raw material such that the molar ratio. Next, this was made into flakes, reheated and crystallized to synthesize 4PbO.B ₂ O ₃ crystal nuclei.
[0046]
The crystalline glass powder, alumina, zircon, and crystal nuclei were mixed at a weight ratio shown in Table 1 (the content of the crystalline glass powder is the balance), and nine kinds of crystalline sealant glasses (Examples: Examples 1 to 5, Comparative examples: Examples 6 to 9) were obtained.
[0047]
This crystalline sealant glass was measured for DTA characteristics (temperature rising from room temperature to 440 ° C. at a rate of 10 ° C./min and holding temperature at a holding temperature of 440 ° C.), and flow time t _b (region b in FIG. To the time from the start of heat generation) to the second crystal phase precipitation time t _c .
[0048]
Separately from this, the flow button diameter was measured as an indicator of fluidity and wettability. The flow button diameter is obtained by pressure-molding 10 g of a crystalline sealant glass into a cylindrical shape having a diameter of 12.7 mm, firing the molded body on a glass substrate at 440 ° C. for 10 minutes, and determining the diameter of the fired body. When sealing the panel glass and the funnel glass, the flow button diameter is preferably 26 mm or more, particularly preferably 26.5 mm or more.
[0049]
The above crystalline glass powder, lead titanate, zircon, and crystal nucleus (4PbO.B ₂ O ₃ ) are mixed at a weight ratio shown in Table 1 (the content of the crystalline glass powder is the balance), and five types of crystalline sealants are mixed. Glass (Example: Examples 10-12, Comparative example: Examples 13-14) was obtained.
[0050]
The crystalline sealant glass was measured for DTA characteristics (temperature rising from room temperature to 470 ° C. at a rate of 10 ° C./min and holding at a holding temperature of 470 ° C.), flow time t _b , precipitation time t _{c of the} second crystal phase. Asked.
[0051]
The flow button diameter of this crystalline sealant glass was also measured. The flow button diameter was measured by holding at 470 ° C. for 10 minutes. When sealing the substrate glass of a plasma display, the flow button diameter is preferably 24.5 mm or more, particularly preferably 25 mm or more.
[0052]
The crystal nuclei in Example 9 (Comparative Example) and Example 14 (Comparative Example) are 2PbO · ZnO · B ₂ O ₃ crystal phase, 4PbO · B ₂ O ₃ crystal phase, and 5: 3: 2 weight of glass, respectively. It was contained in a proportion.
[0053]
Table 1 As is clear, crystalline sealant glass of the present invention, the flow time t _b is relatively long, the flow button diameter is large and, second deposition time t _c of the crystal phase or short.
[0054]
[Table 1]

[0055]
【The invention's effect】
The crystalline sealant glass of the present invention can be sealed with high strength in a short time. Such crystalline sealant glass is particularly suitable for the production of a cathode ray tube for sealing panel glass and funnel glass, and for the manufacture of a plasma display for sealing two substrate glasses.
[Brief description of the drawings]
FIG. 1 is a graph showing DTA characteristics of crystalline glass.

Claims (9)

It contains a crystalline glass powder that precipitates a plurality of crystal phases having different precipitation times and a crystal nucleus, and the composition of the crystalline glass powder is 60 to 85% by weight of PbO, 5 to 15% by weight of B ₂ O ₃ , and ZnO 8. -18% by weight, SiO ₂ 0-5% by weight, BaO 0-5% by weight, the number of crystal nuclei in the crystalline glass is more than the first crystal phase precipitated in the crystalline glass Contains crystalline sealant glass. Crystalline phase precipitated in second in crystal glass is 4PbO _· B 2 _{O 3,} an amount the content of 4PbO _· B 2 _{O 3} crystalline phase is 1 to 6000 ppm by weight with respect to the crystal sealant glass The crystalline sealant glass according to claim 1, comprising: Composition PbO 70 to 81 _wt% of a crystalline glass powder, _B 2 O 3 7 to 10 wt%, ZnO 10 to 14 wt%, _SiO 2 1 to 3 wt%, the range of BaO 1 to 3% by weight, The crystal phase that is secondly precipitated in the crystalline glass is 4PbO · B ₂ O ₃ , and the amount of the 4PbO · B ₂ O ₃ crystal phase is 1 to 5000 ppm by weight with respect to the crystalline sealant glass. 2. The crystalline sealant glass according to claim 1, wherein the crystal nucleus, the alumina is 0 to 10% by weight, the zircon is 0.05 to 5% by weight, and the balance is a crystalline glass powder. Composition PbO 70 to 81 _wt% of a crystalline glass powder, _B 2 O 3 7 to 10 wt%, ZnO 10 to 14 wt%, _SiO 2 1 to 3 wt%, the range of BaO 1 to 3% by weight, The crystal phase that is secondly precipitated in the crystalline glass is 4PbO · B ₂ O ₃ , and the amount of the 4PbO · B ₂ O ₃ crystal phase is 1 to 5000 ppm by weight with respect to the crystalline sealant glass. Crystal nucleus, low expansion filler 2 to 30% by weight, zircon 0.05 to 5% by weight, the balance is made of crystalline glass powder, low expansion filler is lead titanate, cordierite, β-eucryptite, β-spodumene The crystalline sealant glass according to claim 1, which is at least one selected from β-quartz solid solution and silica. 2PbO · ZnO · B ₂ O ₃ The crystal phase is precipitated first and 4PbO · B ₂ O ₃ Crystalline glass powder that precipitates the crystal phase second, and 4PbO · B ₂ O ₃ The crystal phase is 2PbO · ZnO · B ₂ O ₃ A crystalline sealant glass containing crystal nuclei containing more than the crystalline phase, wherein the composition of the crystalline glass powder is 60 to 85% by weight of PbO, B ₂ O ₃   5 to 15% by weight, ZnO 8 to 18% by weight, SiO ₂   0 to 5% by weight, BaO 0 to 5% by weight, 4PbO · B ₂ O ₃ A crystalline sealant glass containing crystal nuclei in an amount of 1 to 6000 ppm by weight with respect to the crystalline sealant glass. 2PbO · ZnO · B ₂ O ₃ The crystal phase is precipitated first and 4PbO · B ₂ O ₃ Crystalline glass powder that precipitates the crystal phase second, and 4PbO · B ₂ O ₃ The crystal phase is 2PbO · ZnO · B ₂ O ₃ A crystalline sealant glass containing crystal nuclei containing more than the crystalline phase, the composition of the crystalline glass powder being 70 to 81% by weight of PbO, B ₂ O ₃   7-10 wt%, ZnO 10-14 wt%, SiO ₂   1 to 3% by weight, BaO 1 to 3% by weight, 4PbO · B ₂ O ₃ Crystal nucleus in an amount of 1 to 5000 ppm by weight with respect to the crystalline sealant glass, 0 to 10% by weight of alumina, 0.05 to 5% by weight of zircon, and the balance being crystalline glass Crystalline sealant glass made of powder. 2PbO · ZnO · B ₂ O ₃ The crystal phase is precipitated first and 4PbO · B ₂ O ₃ Crystalline glass powder that precipitates the crystal phase second, and 4PbO · B ₂ O ₃ The crystal phase is 2PbO · ZnO · B ₂ O ₃ A crystalline sealant glass containing crystal nuclei containing more than the crystalline phase, the composition of the crystalline glass powder being 70 to 81% by weight of PbO, B ₂ O ₃   7-10 wt%, ZnO 10-14 wt%, SiO ₂   1 to 3% by weight, BaO 1 to 3% by weight, 4PbO · B ₂ O ₃ Crystal nucleus in an amount of 1 to 5000 ppm by weight with respect to the crystalline sealant glass, 2 to 30% by weight of low expansion filler, 0.05 to 5% by weight of zircon, the balance being crystalline A crystalline sealant glass made of glass powder, wherein the low expansion filler is at least one selected from lead titanate, cordierite, β-eucryptite, β-spodumene, β-quartz solid solution and silica. The crystalline sealant glass according to claim 1, 2 , 3, 5 or 6 is interposed in a sealing portion between panel glass and funnel glass and baked at 420 to 460 ° C for 5 to 25 minutes. A method for producing a sealed cathode ray tube. A plasma display for sealing the two substrate glasses by providing the crystalline sealant glass of claim 1 , 4 or 7 in a sealing region of the two substrate glasses and baking at 420 to 500 ° C for 5 to 40 minutes. Method.

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