WO2007114222A1

WO2007114222A1 - Amorphous glass tablet and tablet-integrated exhaust tube

Info

Publication number: WO2007114222A1
Application number: PCT/JP2007/056810
Authority: WO
Inventors: Noriaki Masuda
Original assignee: Nippon Electric Glass Co., Ltd.
Priority date: 2006-04-03
Filing date: 2007-03-29
Publication date: 2007-10-11
Also published as: JP2007297266A; JP5257824B2; KR20080083110A; KR101005486B1

Abstract

[PROBLEMS] To provide an amorphous glass tablet of bismuth glass that exhibits appropriate fluidity at hermetical bonding of an exhaust tube for planar display unit, etc., being resistant to softening deformation at subsequent exhaust step at 370° to 420°C, and that avoids the situations of exhaust tube shifting leading to clogging of exhaust hole and perforation leading to airtightness deterioration. [MEANS FOR SOLVING PROBLEMS] There is provided an amorphous glass tablet containing a low-melting-point glass and a refractory filler, characterized in that the low-melting-point glass has a glass composition containing, by mole in terms of oxide, 30 to 60% Bi2O3, 10 to 40% B2O3 and 10 to 50% ZnO, and that the refractory filler has a composition containing, by mole in terms of oxide, 30 to 100% SiO2, 0 to 45% Al2O3, 0 to 35% ZnO, 0 to 20% ZrO2, 0 to 20% TiO2, 0 to 10% Li2O and 0 to 25% MgO.

Description

Specification

Non-crystalline glass tablet and tablet integrated exhaust pipe

Technical field

TECHNICAL FIELD [0001] The present invention relates to an amorphous glass tablet used for sealing an exhaust pipe for a flat display device such as a plasma display panel (hereinafter referred to as PDP), and a tablet-integrated exhaust pipe using the same. .

Background art

Conventionally, glass has been used as a sealing material for electronic components, flat display devices, and the like. Glass is excellent in chemical durability and heat resistance as compared with a resin-based adhesive, and is suitable for ensuring airtightness of a flat display device or the like.

[0003] These glasses are required to have various properties such as mechanical strength, fluidity, and electrical insulation depending on the application, but at least the fluorescence properties of phosphors used in flat display devices are inferior. It is required to be usable at a temperature that does not allow them to be used. Therefore, as a glass satisfying the above characteristics, a lead fluoric acid-based glass containing a large amount of PbO (see, for example, Patent Document 1) has been widely used.

[0004] However, recently, environmental problems have been pointed out with respect to PbO contained in lead borate glass, and it is desired to replace the lead borate glass power with glass containing no PbO. For this reason, various low-melting-point glasses have been developed as substitutes for lead borate glasses. Among them, bismuth glass (Bi O— B O system) described in Patent Document 2 etc.

2 3 2 3 (also called glass) is expected to be an alternative candidate because it has the same characteristics as lead borate glass in terms of chemical durability and mechanical strength.

[0005] By the way, in a flat display device such as a PDP, a glass tube called an exhaust pipe is attached for the purpose of exhausting the inside or filling a rare gas after exhausting. Further, the exhaust pipe is attached so that the position of the exhaust hole provided in the panel of the flat display device and the opening at the tip of the exhaust pipe coincide with each other before being subjected to the exhaust process.

[0006] When installing the exhaust pipe, the inclination of the exhaust pipe is reduced as much as possible with respect to the panel so that it can be easily connected to the exhaust equipment, and the exhaust pipe is attached perpendicularly to the panel surface. In addition, it is required to mount the flat display device so that the airtightness is maintained while maintaining the light emission capability. In the subsequent process, it is necessary to attach the exhaust pipe to the panel with such a strength that the exhaust pipe will not break or the mounting part will not peel off.

[0007] Conventionally, for attaching an exhaust pipe, a method of applying a slurry containing a low-melting-point glass powder to the tip of the exhaust pipe, holding the exhaust pipe upright on the panel, and firing is widely used. It was. In this method, in order to prevent the organic components from decomposing and volatilizing during the firing and contaminating the inside of the flat display device, the exhaust pipe is heated in advance to remove (debinder) the organic components in the slurry coating layer. Is done. However, in this method, the flatness of the low-melting glass layer remaining after removing the organic component of the slurry coating layer is deteriorated. For this reason, the exhaust pipe on the panel tends to be inclined, and in some cases, it is sealed in that state. Further, the gap between the low melting point glass layer and the panel is not filled, and there is a problem that the airtightness cannot be maintained.

[0008] Therefore, as a method for sealing the exhaust pipe to the panel, a glass tablet obtained by molding glass powder into a ring shape with good surface flatness (also referred to as press frit, glass sintered body, glass molded body, etc.) ) Is used. The glass tablet has an insertion hole for inserting the exhaust pipe. After inserting the exhaust pipe into this insertion hole and aligning the tip of the exhaust pipe with the position of the exhaust hole on the panel, The exhaust pipe is attached to the panel by firing at the sealing temperature and softening the glass tablet.

[0009] When exhausting after attaching an exhaust pipe, a relatively high temperature is used to increase exhaust efficiency.

(For example, 370-420 ° C). At this time, the glass tablet is softly deformed and the exhaust pipe is moved to block the exhaust hole! The glass tablet has a hole! The airtightness is not impaired. Heat resistance that can be fixed so that the exhaust pipe does not move at ~ 420 ° C is required.

[0010] In order to satisfy the above characteristics, a crystalline glass tablet is used in which the glass tablet crystallizes after an exhaust pipe is attached to the panel. If the glass tablet crystallizes after attaching the exhaust pipe to the panel, then the exhaust pipe moves so that the glass tablet does not deform softly even when exhausted at a temperature of 370-420 ° C. There is no such thing as blocking or loss of airtightness due to holes in the glass tablet. Crystallinity As a material of the glass tablet, for example, the glasses described in Patent Documents 3 and 4 are used.

Patent Document 1: Japanese Patent Laid-Open No. 63-315536

Patent Document 2: JP-A-6-24797

Patent Document 3: Japanese Patent Laid-Open No. 2001-122640

Patent Document 4: Japanese Patent Laid-Open No. 2001-10843

Disclosure of the invention

Problems to be solved by the invention

[0011] The glass tablet is produced through a plurality of independent heating processes as follows. First, a binder is added to a sealing glass powder containing a low-melting glass powder and a refractory filler powder to form a slurry. Thereafter, this slurry is put into a granulator such as a spray dryer to produce granules of sealing glass powder. At that time, the granules of the sealed glass powder are heat-treated in a temperature range (about 100 to 200 ° C.) where the solvent evaporates. Further, the produced sealing glass powder granules are put into a mold designed to have a predetermined size, and are dry press-molded into a ring shape to produce a pressed body. Next, in a baking furnace such as a belt furnace, the binder remaining in the pressed body is decomposed and volatilized, and sintered at the softening point of the low melting point glass to produce a glass tablet. In addition, the firing in the firing furnace may be performed a plurality of times. If the firing is performed a plurality of times, the sintering strength of the glass tablet is improved, and the glass tablet can be prevented from being broken or broken.

[0012] Generally, a low-melting glass used for a glass tablet is required to have a thermal stability that does not cause crystals to precipitate in a glass tablet manufacturing process in which a plurality of heat processes are separately performed. If even a small amount of crystals are deposited on the glass tablet during the glass tablet manufacturing process, the glass tablet will crystallize before the exhaust pipe is sealed to the flat panel display panel during the sealing process. In addition, the airtightness in the flat display device cannot be secured.

[0013] Against this background, attempts have been made to produce crystalline glass tablets using various crystalline glasses. Patent Document 3 discloses a PbO—ZnO—BO SiO-based crystalline low-melting-point glass powder having a mass percentage display of 80% or more and less than 99.99%, 0.01 to 5 % Of zircon powder, more than 1% and less than 19.99% α-alumina powder and 0-10% low expansion ceramic filler, a composition consisting essentially of a-4PbO-BO crystal powder

2 3 and at least one of Pb O powder is added in a total amount of 0.0001 to 3%.

3 4

A wearing composition is disclosed. This sealing composition can easily adjust the crystals precipitated in the glass by adding a small amount of crystal seeds, and is considered suitable for producing a crystalline glass tablet. However, this sealing composition is a lead borate glass and does not satisfy the lead reduction requirement from the environmental viewpoint in recent years.

[0014] In Patent Document 4, WO, ZrO, and NbO components are added to the PO-SnO-based glass.

2 5 3 2 2 5 Introducing a crystalline low-melting-point glass that promotes crystallization of glass, improves chemical durability and heat resistance, exhibits good fluidity, and has strong adhesive strength. In addition, by adding a low thermal expansion refractory filler to the crystalline low melting point glass powder, it is possible to minimize the increase in the sealing temperature and achieve good fluidity. It is described that a sealing composition having a much smaller thermal expansion coefficient (α 2) and having strong adhesive strength can be obtained while maintaining the same. Specifically, P O 20 to 45%, SnO 45 to 75%, WO 0.5 to 10%, MgO

2 5 3

%, CaO 0-10%, SrO 0-10%, BaO 0-10%, SiO 0-5%, B O 0-

2 2 3

Crystal composed of 5%, AlO 0-5%, ZrO 0.1-5%, NbO 0.1-10%

2 3 2 2 5

Low melting glass is described. This crystalline low melting point glass does not contain PbO in the glass composition, and thus satisfies the recent lead reduction requirements. However, this crystalline low-melting-point glass contains SnO as a main component, and SnO is easily oxidized by thermal decomposition of a binder added in the process of producing a glass tablet to become SnO. In the glass

2

When SnO is oxidized to SnO, crystals are remarkably deposited on the glass, resulting in multiple heat treatment steps.

2

It becomes difficult to produce the glass tablet which passes through. On the other hand, if no noinder is added to the glass powder during the manufacturing process of the glass tablet, the manufacturing efficiency will be significantly reduced, so the above problem is considered serious.

[0015] On the other hand, bismuth-based glass is actually in the characteristics such as thermal stability and still does not reach the characteristics of lead borate glass. In other words, bismuth glass is thermally unstable compared to lead borate glass, so it is possible to control crystal precipitation by heat treatment. Have difficulty. If the precipitation of crystals is early, the exhaust pipe cannot be sealed with the glass tablet, and the fluidity of the glass tablet cannot be secured, and the airtightness in the flat display device cannot be ensured. On the other hand, when the precipitation of crystals is slow, the glass tablet is easily softened and deformed in the exhaust process, and the exhaust pipe moves to close the exhaust hole, or the glass tablet cannot be secured to ensure airtightness in the flat display device. Therefore, from the above situation, it is difficult for a crystalline glass tablet composed of bismuth-based glass that requires control of crystal precipitation to ensure airtightness in a flat display device. It is difficult to use for sealing exhaust pipes, and has not yet been put to practical use.

[0016] In addition, a method using an amorphous glass tablet that does not require control of crystal precipitation can be adopted. However, when an amorphous glass tablet using a conventional bismuth glass is exhausted at a temperature of 370 to 420 ° C, The glass tablet is easily softly deformed and the exhaust pipe moves to block the exhaust hole, or the glass tablet has a hole and the airtightness is lost. In this case, the above situation does not occur if the furnace is kept at a low temperature below the glass transition temperature in the exhaust process, but if the temperature during the exhaust process is lowered in the manufacture of a flat display device, the exhaust time will not be lengthened. Therefore, a decrease in production efficiency is not a very effective measure.

[0017] Therefore, the present invention flows well when sealing an exhaust pipe for a flat panel display device, etc., and the force is softly deformed in the exhaust process of 370 to 420 ° C provided thereafter 1. Moves to block the exhaust vent! It is a technical problem to obtain a non-crystalline glass tablet made of bismuth-based glass that does not cause a situation where there is a hole or a hole!

Means for solving the problem

[0018] As a result of diligent efforts, the present inventor, in an amorphous glass tablet containing a low-melting glass and a refractory filler, represents the low-melting glass in the form of mol% in terms of the following oxides.

twenty three

30-60%, B O 10

Regulated in the range of 3-40%, ZnO 10-50%, metaphysical filler

2 The composition of SiO 30 in terms of weight% in terms of the following oxide

2 to 100%, Al O 0

2 3 to 45%, ZnO 0 to 35%, ZrO 0

2-20%, TiO 0 0

2-20%, Li O

2-10%, MgO 0-25

It is found that the above technical problem can be solved by restricting to%, and is proposed as the present invention. Here, in the present invention, “non-crystalline” means that a crystallization peak is detected at a temperature of 500 ° C. or lower when the temperature is raised at 10 ° C.Z in a macro-type differential thermal analyzer. It refers to things that cannot. In addition, since sealing of flat display devices and the like is usually performed at 550 ° C. or lower, if the sealing layer of flat display devices or the like has a glass luster, “amorphous” glass was used. It can be handled as a thing. “Low melting point glass” refers to a glass having a soft spot of 500 ° C. or lower as measured by a macro-type differential thermal analyzer. Sarako, “soft spot” refers to the temperature (TB) at the inflection point as shown in Figure 3 as measured with a macro-type differential thermal analyzer.

[0019] In the amorphous glass tablet of the present invention, when the glass composition of the low-melting glass is regulated as described above, the thermal stability of the glass can be improved. Therefore, in the amorphous glass tablet of the present invention, when the crystal is deposited on the glass tablet in the manufacturing process of the glass tablet that has undergone multiple heat treatment processes, and the deposited crystal grows when the glass tablet is used, Does not occur. As a result, the fluidity of the glass tablet due to crystal precipitation does not occur, and the airtightness in the flat display device can be reliably maintained. In addition, the non-crystalline glass tablet of the present invention does not cause defects due to crystal precipitation even when the sealing temperature is set to 500 ° C. or higher in the manufacturing process of the flat display device. It can contribute to improvement.

[0020] Further, the above glass composition has the advantage that the glass has a low soft softness point and has excellent fluidity in addition to excellent thermal stability. Therefore, since the non-crystalline glass tablet of the present invention has excellent flowability of glass, the reaction at the interface between the panel and the glass tablet proceeds sufficiently, and the sealing strength between the panel and the exhaust pipe is remarkably increased. Can be raised. As a result, the exhaust pipe can be greatly contributed to maintaining the long-term reliability of the PDP, where the exhaust pipe is not damaged or peeled off. In other words, the non-crystalline glass tablet of the present invention does not cause a decrease in fluidity due to devitrification, and since the soft softness point of the glass is low, the original good fluidity of the sealing material. Can be maximized. Furthermore, in the sealing step, the low melting point glass flows well, so that an accurate sealing shape can be formed for sealing the exhaust pipe. As a result, the glass tablet, the exhaust pipe, and the glass It is possible to prevent the occurrence of cracks at the interface between the tablet and the panel. In particular, since the amorphous glass tablet of the present invention flows well even at a sealing temperature of 480 ° C. or lower, it can contribute to the improvement of the production efficiency of flat display devices and the like. [0021] Further, the low melting point glass according to the present invention is a glass mainly composed of Bi 2 O, BO and ZnO.

2 3 2 3

Yes, even if it does not contain PbO, good thermal stability and fluidity can be obtained, so it can meet recent environmental demands.

[0022] In the amorphous glass tablet of the present invention, the composition of the refractory filler is regulated as described above. Here, the refractory filler includes both crystalline materials such as ceramics and amorphous materials such as glass. When the refractory filler is a crystalline material, if the constituent component of the crystalline material is in the above range in terms of weight%, it is determined that the refractory filler is a refractory filler according to the present invention. It should be noted that the components of the refractory filler do not exclude the inclusion of unspecified components. The unspecified components are optional components like ZrO, TiO, Li 0, and MgO.

2 2 2

The When the composition of the refractory filler is regulated as described above, a part of the component of the refractory filler (surface layer portion of the refractory filler) can be dissolved in the low-melting glass in the sealing step of a flat panel display device or the like. In general, the melting point of a refractory filler is several hundred or more higher than that of glass. Therefore, if a part of the filler can be appropriately dissolved in the glass in the sealing step of the flat panel display device, it becomes possible to increase the melting point of the glass tablet after the sealing step, which is provided thereafter. The glass tablet will not be easily softly deformed in the exhaust process at 420 ° C, and the exhaust pipe will not move and will block the exhaust hole, and there will be no situation where the airtightness is lost due to the hole. That is, the non-crystalline glass tablet of the present invention, as a matter of course, can enjoy the same benefits as the non-crystalline glass tablet, in addition to the non-crystalline glass. There are no problems caused by the precipitation of crystals in the tablet.

[0023] Further, by regulating the composition of the refractory filler according to the present invention as described above, the amount of the refractory filler dissolved in the sealing step can be easily controlled within an appropriate range, and the post-sealing step can be performed. The melting point raising effect of the amorphous glass tablet can be enjoyed to the maximum. That is, the fire-resistant filler according to the present invention can dissolve only the surface layer portion of the fire-resistant filler by regulating the composition as described above. The effect of increasing the melting point of the amorphous glass tablet after the sealing step without impairing the effect, the effect of improving the mechanical strength, etc. can be enjoyed. In addition, since the fire resistant filler of the present invention has good compatibility (compatibility) with bismuth glass, Even if a part of the refractory filler is dissolved in the glass, crystals are not deposited on the glass tablet in the sealing process in which the thermal stability of the glass tablet is not impaired.

[0024] Generally, the heat treatment temperature in the glass tablet manufacturing process is lower than the sealing temperature, and the heat treatment time is as short as about 10 minutes. Therefore, in the fire resistant filler according to the present invention, the fluidity of the glass tablet is not impaired due to the heat treatment in the glass tablet manufacturing process which is difficult to melt in the glass tablet manufacturing process.

[0025] According to the present invention having the above-described configuration, the glass tablet easily flows in the exhaust process of 370 to 420 ° C, which flows well when sealing the exhaust pipe for a flat display device and the like, and the force is provided thereafter. It is possible to obtain a non-crystalline glass tablet made of bismuth-based glass that does not deform softly and does not cause a situation where the exhaust pipe moves to block the exhaust hole or the airtightness is lost due to the hole being formed. .

[0026] Secondly, the amorphous glass tablet of the present invention is a non-crystalline glass tablet containing a low-melting glass and a refractory filler. Indication: Bi O 30-60%, BO 10-40%, ZnO 10-50

2 3 2 3

%, BaO + SrO + MgO + CaO 0-15%, CuO 0-10%, FeO 0-5%, SiO

twenty three

+ A1 O 0-15%, WO 0-5%, SbO 0-5%, In O + GaO 0-5%

2 2 3 3 2 3 2 3 2 3 Characterized by containing.

[0027] Thirdly, the amorphous glass tablet of the present invention is characterized by containing 40 to 95% of a low-melting glass and 5 to 60% of a refractory filler in volume%.

[0028] Fourth, the amorphous glass tablet of the present invention is characterized in that the refractory filler is a crystalline product having cordierite (2MgO-2AlO-5SiO) as the main crystal.

2 3 2

[0029] Fifth, the amorphous glass tablet of the present invention is characterized by substantially not containing PbO. In the present invention, “substantially no PbO” means a case where the content of PbO is lOOOppm or less.

[0030] Sixth, the amorphous glass tablet of the present invention is characterized by having a soft shear point of 350 to 470 ° C. Here, “softening point” refers to a value measured with a macro-type differential thermal analyzer.

[0031] Seventh, the amorphous glass tablet of the present invention is a yield point of the amorphous glass tablet. (° C), and T (° C) is the deformation point of the amorphous glass tablet after baking at 480 ° C for 30 minutes. Attached. Where

2 2 1

“Bend point” refers to the value measured with a push-bar thermal expansion measurement (TMA) device. 3 at 480 ° C

The temperature increase / decrease rate in the 0-minute firing is 2 ° CZ, and the temperature increase starts at the room temperature. When the temperature reaches room temperature, the temperature decrease ends.

[0032] Eighth, the amorphous glass tablet of the present invention is characterized by being used for sealing an exhaust pipe for a flat display device.

[0033] Ninthly, the amorphous glass tablet of the present invention is characterized by being used for an exhaust pipe for PDP.

[0034] Tenthly, the tablet-integrated exhaust pipe of the present invention is characterized in that the non-crystalline glass tablet of V, which is one of the above, is attached to the tip of the expanded exhaust pipe. . Here, the “exhaust pipe tip” refers to the surface portion of the exhaust pipe whose diameter has been enlarged. The exhaust pipe bottom surface and the outer peripheral side surface of the exhaust pipe that are in contact with the panel over the enlarged diameter portion. Point to. Further, the non-crystalline glass tablet includes not only an embodiment in which the non-crystalline glass tablet is adhered to only the tip portion of the exhaust pipe but also an embodiment in which the amorphous glass tablet is adhered to a part of the tip portion of the exhaust pipe.

[0035] Eleventhly, in the tablet-integrated exhaust pipe of the present invention, any one of the amorphous glass tablet and the high-melting-point tablet are attached to the tip of the expanded exhaust pipe. The amorphous glass tablet is attached to the front end side of the expanded exhaust pipe, and the high melting point tablet is attached to the rear end side of the amorphous glass tablet. “High-melting-point tablets” are made using a material with a heat resistance of 520 ° C or higher (in the case of glass, the soft spot when measured with a macro-type differential thermal analyzer is 520 ° C or higher). Refers to a tablet made.

The invention's effect

[0036] The amorphous glass tablet of the present invention flows well when sealing an exhaust pipe for a flat panel display device, etc., and the softness is easily softened in the exhaust process of 370 to 420 ° C provided thereafter.匕 There is no deformation, and the exhaust pipe does not move and closes the exhaust hole, or there is no hole and the airtightness is not lost. As a result, the amorphous glass tablet of the present invention can increase the soft spot of the glass tablet after the sealing step, even though the glass is amorphous. Therefore, it is possible to enjoy the same benefits as the crystalline glass tablet. Since the glass tablet of the present invention is non-crystalline, it is extremely difficult to control the crystal precipitation, in which crystals do not precipitate on the glass tablet in the glass tablet manufacturing process and the flat panel display sealing process. There is no problem caused by the precipitation of crystals in the tablet. Therefore, the amorphous glass tablet of the present invention has the same or better characteristics as the crystalline glass tablet. In particular, the bismuth glass has poor thermal stability compared to the lead borate glass. Considering the fact that it was impossible to mass-produce crystalline glass tablets, the effect of the present invention is considered to be great.

BEST MODE FOR CARRYING OUT THE INVENTION

[0037] The reason why the glass composition of the low-melting glass in the amorphous glass tablet of the present invention is limited as described above will be described below.

[0038] BiO is a main component for lowering the softening point. Its content is 30 to 60 mole ^_0/0,

twenty three

Preferably 35 to 55 moles ^_0/0, more preferably 35 to 50 mole ^_0/0, more preferably from 35 to 45 molar%. If the content of BiO is less than 30 mol%, the softening point of the glass becomes high.

twenty three

It becomes difficult to seal at a low temperature of 500 ° C or less. On the other hand, the content of BiO is more than 60 mol%

twenty three

In such a case, the glass becomes thermally unstable, and the glass tends to be devitrified during melting or firing.

[0039] B 2 O is a component that forms a glass network of bismuth-based glass, and is an essential component.

twenty three

is there. Its content is 10 to 40 mole ^_0/0, preferably from 12 to 35 mole ^_0/0, more preferably 15-30 mol%, more preferably 15 to 25 mol%. Low BO content by 10 mol%

twenty three

Otherwise, the glass becomes thermally unstable and the glass tends to devitrify when melted or fired. On the other hand, when the content of B 2 O is more than 0 mol%, the viscosity of the glass becomes too high.

twenty three

It becomes difficult to seal at a low temperature of o ° c or less.

[0040] ZnO is a component that has an effect of suppressing devitrification when the glass is melted or fired.

Its content is 10 to 50 mole ^_0/0, preferably from 12 to 45 mole ^_0/0, more preferably 15 to 40 molar ^_0/0, more preferably 20 to 35 mole ^_0/0. When the content of ZnO is less than 10 mole ^_0/0, the effect of suppressing devitrification at the time of melting or during sintering of the glass is difficult to obtain. If the ZnO content is higher than 50 mol%, the glass composition lacks balance, and conversely the thermal stability of the glass. As a result, the glass tends to be devitrified.

[0041] BaO, SrO, MgO, and CaO have an effect of suppressing devitrification when the glass is melted or fired. These components can be contained in a total amount of up to 15 mol%. When the total content of these components is more than 15 mole ^_0/0, too high glass軟I匕点, it is difficult to seal in the following low temperature 500 ° C.

[0042] The content of BaO is more preferably 1 to 10 mol ^_0/0 preferably fixture 2-6 mol ^_0/0. When the content of BaO is less than 1 mol%! /, It becomes difficult to obtain the effect of suppressing devitrification when the glass is melted or fired. When the content of ZnO is more than 10 mole ^_0/0, lack the balance of the glass composition, the thermal stability of the glass is impaired to the contrary, the result, the glass tends to be devitrified.

[0043] SrO, MgO, the content of each of CaO is more preferably 0 to 5 mole ^_0/0 preferably fixture 0-2 mol ^_0/0. If the content of each component is more than 5 mol%, the glass tends to devitrify and phase separation.

[0044] CuO has an effect of suppressing devitrification when the glass is melted or fired, and can be added up to 10 mol%. If the CuO content is more than 10 mol%, the glass tends to be devitrified and the fluidity of the glass tends to be impaired.

[0045] Fe 2 O has an effect of suppressing devitrification when glass is melted or fired, and its content

twenty three

Is preferably 0 to 5 mol%, more preferably 0.1 to 2 mol%. Fe O content is 5 mol

twenty three

If it is more than%, the balance in the glass composition will be lost, and conversely, the thermal stability of the glass will be impaired, and as a result, the glass will be easily devitrified.

[0046] SiO and Al 2 O are components that improve the weather resistance of glass. Its content is the total amount

2 2 3

15 mol ^_0/0 force S, and more preferably from 0 to 10 mol ^_0/0. If the total amount of these components is more than 15 mol%, the soft softness point of the glass becomes too high, and it becomes difficult to seal at a low temperature of 500 ° C or lower. In particular, the content of SiO is preferably 0 to 10 mol%, more preferably 0 to 5 mol%.

2

Good. The content of Al 2 O is preferably 0 to 5 mol%, more preferably 0 to 2 mol%.

twenty three

[0047] WO is a component for suppressing devitrification of glass, and its content is 0 to 5 mol%.

Three

Preferred is 0 to 2 mol%. In bismuth glass, in order to lower the soft spot of the glass, it is necessary to increase the content of BiO.

2 3 2 3

Then, glass power crystals are precipitated during firing, and the fluidity of the glass tends to be hindered. In particular, when the content of BiO is 0 mol% or more, the tendency becomes remarkable. But screw

twenty three

In mass-based glass, by adding WO appropriately, the content of BiO is 40 monolayers.

3 2 3

Even if it is more than%, the situation where the thermal stability of glass falls can be suppressed. However, if the WO content exceeds 5 mol%, the balance in the glass composition is lost, and conversely

Three

The thermal stability of the glass is impaired, and as a result, the glass is easily devitrified.

[0048] SbO is a component for suppressing devitrification of glass, and its content is 0 to 5 mol%.

twenty three

It is preferred instrument 0-2 mole ^_0/0 is more preferable. SbO is a network structure of bismuth glass

twenty three

Sb is added to bismuth-based glass.

2 o

Three

Reduces the thermal stability of the glass even when the content of BiO is 0 mol% or more.

twenty three

Can be deterred. However, if the SbO content is more than 5 mol%,

twenty three

The balance of the glass yarn is lost, and the thermal stability of the glass is impaired. As a result, the glass is easily devitrified.

[0049] In O and Ga O are not essential components, but are components for suppressing devitrification of glass.

2 3 2 3

The total content is preferably 0 to 5 mol%, more preferably 0.1 to 3 mol%. Sb O

2 has the effect of stabilizing the network structure of bismuth-based glass.

Three

In this case, the content of Bi 2 O is 40 mol% by adding In O and Ga 2 O as appropriate.

Even if it is 2 3 2 3 2 3 or more, a situation in which the thermal stability of the glass is lowered can be suppressed. However, an In O, the content of Ga O is more than 5 mole ^_0/0, lack the balance of the glass composition

2 3 2 3

Conversely, the thermal stability of the glass is impaired, and as a result, the glass is easily devitrified. In addition,

In content of content is 0-5 mol ^_0/0 more preferably tool Ga O of O is 0 to 2 mol ^_0/0 Gayori

2 3 2 3

preferable.

[0050] Lithium, Na, K, and Cs oxides are components that lower the soft melting point of glass, and have the effect of promoting devitrification of glass during melting, so the total amount is 2 mol%. It is preferable that:

[0051] When P O is added in an amount of force, which is a component that suppresses devitrification at the time of melting, is greater than 1 mol%,

twenty five

This is preferable because the glass is likely to phase separate during melting.

[0052] MoO: La O, Y 2 O, CeO, and Gd 2 O suppress glass phase separation during melting

3 2 3 2 5 2 2 3

If the total amount of these components is more than 3 mol%, the soft spot of the glass will increase, Baking at a temperature below ° C.

[0053] In addition, any other components, leaving at be added Caro to 5 mole ^_0/0 within a range not to impair the properties of the glass.

[0054] The reason why the composition of the refractory filler is limited as described above in the amorphous glass tablet of the present invention will be described below.

[0055] SiO is a component that increases the melting point of the amorphous glass tablet after the sealing step.

2

Both a component to lower the thermal expansion coefficient of the refractory filler, the content thereof is 30 to 1 00 weight ^_0/0, preferably from 35 to 85 weight ^_0/0, more preferably 40 to 70 weight ^_0/0 is there. SiO

2 If the content is less than 30% by weight, the effect of increasing the melting point of the amorphous glass tablet after the sealing process is poor. SiO should be used alone as a refractory filler.

2

Tochidaru.

[0056] Al O is a component that increases the melting point of the amorphous glass tablet after the sealing step,

twenty three

Its content is 0 to 45% by weight, preferably 10 to 40% by weight. Al O content is 4

twenty three

If it is more than 5% by weight, crystals tend to precipitate on the glass tablet in the sealing step.

[0057] ZnO is a component for lowering the thermal expansion coefficient of the refractory filler, and its content is 0 to 35 wt%, preferably 0 to 30 wt%. When the content of ZnO is more than 35% by weight, the effect of lowering the thermal expansion coefficient of the refractory filler becomes poor, and in addition, the amount of refractory filler leached out in the sealing process decreases.

[0058] ZrO is a component that increases the melting point of the amorphous glass tablet after the sealing step,

2

Its content is 0 to 20% by weight. If the ZrO content is more than 20% by weight,

2

Crystals are likely to precipitate on the glass tablet.

[0059] TiO is a component for reducing the thermal expansion coefficient of the refractory filler, and its content

2

Is 0 to 20% by weight. If the TiO content is more than 20% by weight, glass will be used in the sealing process.

2

Crystals are likely to precipitate on the tablet.

[0060] Li 2 O is a component for accelerating the dissolution of the refractory filler in the sealing process.

2

The content is 0 to 10% by weight. If the Li O content is more than 10% by weight, sealing

2

Crystals are likely to precipitate on the glass tablet in the process.

[0061] MgO is a component for promoting dissolution of the refractory filler after the sealing step. There, the content thereof is 0 to 25 wt%, preferably 0 to 20 wt%, more preferably 10 to 20 wt ^_0/0. When the content of MgO is more than 25 weight ^_0/0, crystal glass tablet is likely to precipitate in the sealing step.

[0062] In addition, other components may be contained within a range that does not impair the properties of the refractory filler (preferably up to 10% by weight)! / ヽ.

[0063] In the amorphous glass tablet of the present invention, the refractory filler can be used as either a glass or a crystalline material as long as it is within the above composition range. The use of such a material is preferable because it can improve the mechanical strength of the amorphous glass tablet that lowers the thermal expansion coefficient of the refractory filler. In addition, when glass is used as the refractory filler, it is possible to increase the amount of the refractory filler that is melted, and as a result, the effect of increasing the melting point of the amorphous glass tablet after the sealing process is increased.

[0064] The refractory filler according to the present invention has a low thermal expansion coefficient in a crystal or quartz glass mainly composed of cordierite, β-quartz solid solution, zinc petalite, β-eucryptite, garnite and the like. At the same time, the effect of increasing the melting point after the sealing step is great, which is preferable. In particular, the crystalline material with cordierite as the main crystal has a good compatibility with bismuth-based glass, which has a large melting point increasing effect after the sealing process because the amount of refractory filler dissolved in the glass is large in the sealing process. Therefore, even if the amount of the refractory filler is large, the thermal stability of the glass is not impaired, that is, the crystal precipitation is not promoted in the sealing step, which is preferable. In addition, a refractory filler other than the refractory filler having the above composition (for example, tin oxide, zirconium oxide, alumina, etc.) can be appropriately added for the purpose of increasing the mechanical strength of the glass.

[0065] In the refractory filler according to the present invention, the particle ratio (integrated value) of 5 m or less when measured with a laser diffraction particle size distribution analyzer is preferably 15% or more, more preferably 20% or more. More preferably 35% or more. If the proportion of particles of 5 m or less in the refractory filler is less than 15%, the amount of the refractory filler that dissolves in the glass in the sealing process decreases, and as a result, the effect of increasing the melting point after the sealing process is obtained. .

[0066] The amount of the refractory filler dissolved in the glass in the sealing step increases as the specific surface area of the refractory filler increases. In the refractory filler according to the present invention, BET specific surface area measurement The specific surface area value measured with the apparatus is preferably 0.5 to 3.5 m ² Zg, more preferably 0.6 to 1.2 mg. If the specific surface area of the refractory filler is less than 0.5 m ² / g, the amount of the refractory filler dissolved in the glass becomes too large in the sealing process, which may impair the fluidity of the glass tablet. When the specific surface area value of the refractory filler is more than 3.5 m ² / g, the amount of the refractory filler that dissolves in the glass during the sealing process decreases, and as a result, the effect of increasing the melting point after the sealing process becomes difficult to obtain. .

[0067] mixing proportion of the low melting point glass (low-melting glass powder) and refractory filler (refractory filler powder), low-melting glass is 40 to 95 volume ^_0/0, 5 to 60 vol% refractory filler it is good better tool low-melting glass strength 0-90 volume ^_0/0, more preferably refractory filler 10 to 60 volume ^_0/0. The reason for specifying the ratio of the two in this way is that when the amount of the refractory filler is less than 5% by volume, it is difficult to obtain the effect of decreasing the thermal expansion coefficient or the effect of increasing the mechanical strength. If this happens, the fluidity of the glass tablet will deteriorate, and there will be a possibility that it will be impossible to seal tightly.

[0068] In addition, when sealing high strain point glass (thermal expansion coefficient 85 X 10 "V ° O, soda plate glass (thermal expansion coefficient 90 X 10 ^_7 Z ° C), etc., non-crystalline glass tablet The coefficient of thermal expansion is preferably designed to be about 10-30 X 10 ^_7 Z ° C lower than the material to be sealed, which means that the distortion applied to the amorphous glass tablet after sealing is compressed (compressed). This is to prevent the destruction of the amorphous glass tablet.

[0069] The amorphous glass tablet of the present invention preferably contains substantially no PbO.

The amorphous glass tablet of the present invention can be made into an embodiment without containing PbO in the low-melting glass and the refractory filler. If the amorphous glass tablet is substantially free of Pb 2 O, it can meet recent environmental requirements.

[0070] In the amorphous glass tablet of the present invention, the soft spot of the amorphous glass tablet is preferably 350 to 470 ° C force S, more preferably 390 to 450 ° C. If the soft glass point of the amorphous glass tablet is lower than 350 ° C, the glass tablet can be easily softened in the subsequent exhaust process unless the melting amount of the refractory filler is extremely increased in the sealing process.匕 Deformation will cause the exhaust pipe to move and block the exhaust hole, or the glass tablet will have a hole and airtightness will be lost. The soft spot of amorphous glass tablets is higher than 450 ° C. May not flow sufficiently, and airtightness in the flat display device may not be secured.

[0071] In the amorphous glass tablet of the present invention, the yield point of the amorphous glass tablet is T (° C), and the yield point of the amorphous glass tablet after baking at 480 ° C for 30 minutes. T (

1 2

It is preferable to satisfy the relationship of T—T≥5 ° C

2 1 2 1

It is even more preferable to satisfy the relationship of T—T≥10 ° C. T

When 2 1 2 T <5 ° C, it is difficult to enjoy the unique effect of the present invention, in which the soft tablet point raising effect of the glass tablet after the sealing step is insufficient. That is, T 2— T

1 If the temperature is 5 ° C, the glass tablet can be easily softly deformed by the exhaust stroke, and the exhaust pipe may move to block the exhaust hole, or the glass tablet may have a hole and airtightness may be impaired. . T -T≥5 ° C relationship

twenty one

In order to satisfy this requirement, it is effective to select the material of the refractory filler and set the particle size to an appropriate value as described above.

[0072] In the non-crystalline glass tablet of the present invention, the yield point of the non-crystalline glass tablet is T (° C), and calcined at a temperature of (soft point + 50) ° C for 30 minutes. It is preferable to satisfy the relationship of T—T≥5 ° C, where T (° C) is the yield point of the amorphous glass tablet of T

3 3 1 3

— It is more preferable to satisfy the relationship of T≥7 ° C T — To satisfy the relationship of T≥10 ° C

1 3 1

Further preferred. If T-T is 5 ° C, the soft spot of the glass tablet is raised after the sealing process.

3 1

It is difficult to enjoy the peculiar effects of the present invention that are poor in effect. In other words, if T 3 T 1 <5 ° C, the glass tablet easily deforms softly in the exhaust process, and the exhaust pipe moves to block the exhaust hole, or the glass tablet has a hole and the airtightness is impaired. There is a risk of being. T 3 -T

In order to satisfy the relationship of ≥5 ° C, it is effective to select the material of the refractory filler and set the particle size to an appropriate value as described above. Here, the temperature increase / decrease rate in "(soft soft spot + 50) ° C firing for 30 minutes" is 2 ° CZ minutes, the temperature rise starts from room temperature, and the temperature drops when it reaches room temperature. Exit. In addition, the measurement sample of T is separately amorphous.

Three

The softening point of a powder sample used for the production of porous glass tablets was measured with a macro-type differential thermal analyzer, and the same powder sample was calcined at a temperature 10 ° C higher than the soft saddle point for 30 minutes. use. The rate of temperature increase / decrease in this firing is 2 ° CZ, and the temperature increase starts from room temperature and ends when the temperature reaches room temperature.

[0073] The amorphous glass tablet of the present invention is used for sealing an exhaust pipe for a flat display device. It is preferable. Flat display devices such as PDP and field emission display (FED) need to use an exhaust pipe to evacuate the inside. Glass is usually used for sealing the exhaust pipe in order to ensure the airtightness of the flat display device. In addition, after sealing the exhaust pipe, the inside of the flat display device is put into a high vacuum state by a vacuum pump or the like through the exhaust pipe. At this time, in order to make the inside of the flat display device into a high vacuum state in a short time, it becomes more advantageous to exhaust at a high temperature. Accordingly, since the soft glass point of the amorphous glass tablet of the present invention increases after the sealing process, the heat treatment temperature of the exhaust process provided thereafter can be increased, and the manufacturing process of the flat display device can be improved. It can be shortened.

[0074] In the PDP exhaust process, it is known that the exhaust efficiency can be improved by increasing the exhaust temperature. Specifically, if the exhaust temperature is increased, the time required for the exhaust will be several tens of hours or even 10 hours. It can be shortened to a certain extent, and the inside of the PDP device can be made high vacuum. If the inside of the PDP device can be evacuated to a high vacuum, the content of adhering impurities inside the device can be reduced, so that the purity of the rare gas components to be sealed later inside the device can be increased. Characteristics can be improved. As described above, the amorphous glass tablet of the present invention has a soft saddle point that rises after the sealing step, and therefore can appropriately meet such a demand. Furthermore, since the glass tablet of the present invention is non-crystalline, in addition to the above-mentioned advantages, the crystal tablet does not precipitate in the glass tablet in the glass tablet manufacturing process and the flat panel display sealing process. There are no problems caused by the precipitation of crystals in crystalline glass tablets that are difficult to control. In particular, the PDP manufacturing process takes a long time for heat treatment compared to other flat panel display devices, and the use of crystalline glass tablets makes it extremely difficult to control crystal precipitation. The significance of using non-crystalline glass tablets is great.

[0075] The non-crystalline glass tablet of the present invention can have various shapes such as a ring shape, a cylindrical shape, a triangular prism, and a quadrangular prism that are not particularly limited in shape. In particular, assuming the sealing of the exhaust pipe, the shape of the amorphous glass tablet can be securely fixed to the exhaust pipe without closing the exhaust hole of the panel. Is preferred.

[0076] In the amorphous glass tablet of the present invention, the filling rate is 65% or more (preferably 70%). % Or more, particularly 75% or more) is preferable. In this way, the dimensional change can be reduced in the sealing step, and the fluidity of the amorphous tablet can be increased. Here, “filling ratio” refers to a value of {(actual density of non-crystalline tablet) / (theoretical density of non-crystalline tablet)} X 10 0 (%).

[0077] The amorphous glass tablet of the present invention can be produced through a plurality of independent heating processes as follows. First, a binder or a solvent is added to a sealing glass powder containing a low melting glass powder and a refractory filler powder to form a slurry. Thereafter, this slurry is put into a granulator such as a spray dryer to produce granules of sealing glass powder. At that time, the granules are heat-treated at a temperature at which the solvent evaporates (about 100 to 200 ° C.). The granule particle size is preferably about 20 to 250 m. In this way, the filling property into the mold can be improved. Further, the produced granules are put into a mold designed to have a predetermined size, and are dry press-molded into a ring shape to produce a pressed body. Next, the binder remaining in the pressed body is decomposed and volatilized in a baking furnace such as a belt furnace, and fired at about the soft spot of the low melting point glass to produce an amorphous glass tablet. In addition, the firing in the firing furnace may be performed a plurality of times. If the firing is performed a plurality of times, the strength of the amorphous glass tablet is improved, and the loss or breakage of the amorphous glass tablet can be suppressed. .

[0078] Solvents to be added to the sealing glass powder include N, N'-dimethylformamide (DMF), a terbinol, higher alcohol, _butyl latatatone (γ-BL), tetralin, butyral carbitol acetate, ethyl acetate, Isoamyl acetate, diethylene glycol monoethylenoateolene, diethyleneglycolenomonoethylenoate acetate, benzenoreal alcohol, toluene, 3-methoxy 3-methylbutanol, water, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol monomono butylene ethere, tripropylene glycoleno monomethylol ether, tripropylene glycol monomono butylene ether, propylene carbonate DOO, dimethyl sulfoxide (DMSO), it is possible for Ν- methyl-2-pyrrolidone or the like is used. In particular, DMF and toluene are preferable because they have an appropriate boiling point and good solubility of rosin and the like. [0079] As the binder to be added to the sealing glass powder, acrylic resin, ethyl cellulose, polyethylene glycol, polyethylene glycol derivatives, nitrocellulose, polymethyl styrene, polyethylene carbonate, methacrylic acid ester and the like can be used. In particular, acrylic resin and low molecular weight polyethylene glycol are preferable because of their good thermal decomposability.

[0080] The amorphous glass tablet of the present invention is preferably used as a tablet-integrated exhaust pipe by being attached to the tip of the expanded exhaust pipe. With the above configuration, it is possible to simplify the exhaust pipe installation work that eliminates the need to simultaneously align the three parts of the panel, the amorphous glass tablet, and the exhaust pipe in the exhaust hole. it can. In order to manufacture such a tablet-integrated exhaust pipe, it is necessary to baked with the amorphous glass tablet inserted into the exhaust pipe, and to adhere the amorphous glass tablet to the tip of the exhaust pipe. . In such a case, it is generally possible to employ a method in which the exhaust pipe is fixed with a jig, and an amorphous glass tablet is inserted into the exhaust pipe in this state and fired. As a jig for fixing the exhaust pipe, it is preferable to use a material to which the amorphous glass tablet is not fused. For example, a carbon jig or the like can be used. Adhesion between the exhaust pipe and the amorphous glass tablet can be done in a short time of about 5 to 10 minutes near the soft melting point of the low melting point glass. However, the amount of low-melting point glass melted by the refractory filler is extremely small, and the soft spot of the amorphous glass tablet does not rise unduly. Furthermore, the amorphous glass tablet of the present invention has good thermal stability, and crystals are not deposited on the amorphous glass tablet in the bonding process between the exhaust pipe and the amorphous glass tablet. Crystals are not unduly deposited on the amorphous glass tablet in the sealing process of the device.

As the exhaust pipe, a product grade “FE-2” manufactured by Nippon Electric Glass Co., Ltd. is suitable. This exhaust pipe has a coefficient of thermal expansion of 85 X 10 ^_7 Z ° C and a heat resistant temperature of 550 ° C. For example, an exhaust pipe with an outer diameter of 5 mm and an inner diameter of 3.5 mm can be used. As the exhaust pipe, it is preferable to form a flare or flange at the tip and expand the diameter of the tip of the exhaust pipe. Various methods can be adopted as a method of expanding the diameter of the tip of the exhaust pipe. However, several kinds of treatment can be performed by heating the tip of the exhaust pipe using a gas burner while rotating the tip. A method of processing into a predetermined shape using a tool is preferable because it is excellent in mass productivity.

FIG. 1 shows an example of a tablet-integrated exhaust pipe having such a configuration. Fig. 1 is a cross-sectional view of a tablet-integrated exhaust pipe. The tip of the exhaust pipe 1 is enlarged in diameter, and the amorphous glass tablet 2 is bonded to the tip of the exhaust pipe on the panel side. .

[0083] In the amorphous glass tablet of the present invention, an amorphous glass tablet and a high melting point tablet are attached to the tip of the expanded exhaust pipe, and the amorphous glass tablet is expanded. It is preferable that the high-melting-point tablet is used as a tablet-integrated exhaust pipe attached to the rear end side rather than the amorphous glass tablet. If the tablet-integrated exhaust pipe is configured in this way, it is attached to the tip side of the amorphous glass tablet force S exhaust pipe, so the area in contact with the panel etc. when attaching the exhaust pipe to the panel etc. The exhaust pipe is wider than the case of only the exhaust pipe, and the exhaust pipe can be made to stand on the panel etc. stably, and it becomes easy to install vertically without tilting with respect to the panel etc. In addition, if the tablet-integrated exhaust pipe is configured in this way, when the amorphous glass tablet is fixed to the exhaust pipe in the process of manufacturing the tablet-type exhaust pipe, the jig and the amorphous glass tablet By placing a high melting point tablet between them, it is possible to manufacture a tablet-integrated exhaust pipe, that is, it is not necessary to use a special jig in the manufacture of a tablet-integrated exhaust pipe, and the manufacturing process is simplified. be able to.

[0084] In the tablet-integrated exhaust pipe having the above structure, the amorphous glass tablet is preferably fixed to the outer peripheral surface of the tip of the glass tube. More preferably, it is fixed only to the outer peripheral surface of the front end portion of the glass tube, and is not fixed to the front end surface of the front end portion of the glass tube, that is, the surface bonded to the panel or the like. In this way, it becomes easy to prevent the glass from flowing into the exhaust holes formed in the panel or the like. In addition, if the high melting point tablet is not directly attached to the exhaust pipe but is fixed to the exhaust pipe via an amorphous glass tablet, the high melting point tablet part is fixed with a clip in the sealing process and the exhaust pipe is added. It is preferable because it can be sealed.

[0085] As the high melting point tablet, it is preferable to use commercial grades “ST-4” and “FN-13” manufactured by Nippon Electric Glass Co., Ltd. as materials. The high melting tablet is made of the above amorphous glass tab It can be produced by the same method as the lett. Moreover, ceramics or a metal can also be used as a material as a high melting point tablet.

FIG. 2 shows an example of a tablet-integrated exhaust pipe having such a configuration. Fig. 2 is a cross-sectional view of the tablet-integrated exhaust pipe. The tip of the exhaust pipe 1 has an enlarged diameter. The flange portion of the exhaust pipe 1 Are adhered. On the other hand, the high melting point tablet 3 is not bonded to the outer peripheral surface side of the exhaust pipe 1. The amorphous glass tablet 2 is attached to the front end side of the flange portion la, and the high melting point tablet 3 is attached to the rear end side of the flange portion la rather than the amorphous glass tablet 2. Example 1

[0087] Hereinafter, the present invention will be described in detail based on examples.

[0088] Tables 1 to 4 show the low-melting glass of the examples (samples A to N) and the low-melting glass of the comparative example (samples 0 and P). Samples A to P shown in Tables 1 to 4 were prepared as follows.

[0089] First, a glass batch prepared by preparing raw materials such as various oxides and carbonates so as to have the glass composition shown in Tables 1 to 4 was prepared and placed in a platinum crucible at 900 to 1000 ° C. At 1 to 2 hours. Next, a part of the molten glass was poured out into a stainless steel mold, and the other molten glass was formed into a thin piece with a water-cooled roller. A sample for measuring the thermal expansion coefficient and the like was subjected to a predetermined slow cooling treatment (annealing) after molding. Finally, the glass flakes were pulverized by a ball mill and passed through a sieve having an opening of 75 m to obtain samples having an average particle diameter of about 10 m.

[0090] Using the above samples, the glass transition point, yield point, softening point, thermal expansion coefficient and devitrification state in the temperature range of 30 to 300 ° C were evaluated. The results are shown in Tables 1-4.

[0091] [Table 1] Sample ABCDE

39. 2 41. 9 38. 5 47. 4 47. 4 23. 6 22. 2 23. 0 18. 7 20. 2 24. 5 23. 4 27. 5 25. 5 23. 3 Glass composition 6.1 2. 8 2. 0 2. 3 2. 5

(m o 1%) 5. 9 8. 5 5. 0 5. 0 5.5

0. 7 0. 7 0. 7 0. 6 0. 6

3.3

0. 5 0. 5 0. 5 Glass s transition point (° c) 355 345 360 340 340 Sag point () ⁰ OOOO 0OTc 390 400 404 379 383 Softening point ΓΟ 425 415 435 400 405 Thermal expansion coefficient

110 1 1 2 105 1 15 1 15

(X 10- ⁷ /.c)

Devitrification state ○ ○ ○ ○ ○

[0092] [Table 2]

[0093] [Table 3]

[0094] [Table 4]

[0095] The soft saddle point was determined by a macro-type differential thermal analyzer using a powder sample. The heating rate was 10 ° CZ. [0096] The glass transition point, the thermal expansion coefficient in the temperature range of 30 to 300 ° C, and the yield point were determined by a well-known push rod type thermal expansion measurement device.

[0097] The devitrification state was evaluated by observing crystals in the sample using an optical microscope (magnification 100 times) after firing Samples A to P at 500 ° C for 30 minutes. Those that were devitrified were marked with “◯”, and those with devitrification were marked with “X”. For each sample, a powder having a weight corresponding to the density of each sample was dry-pressed into a button shape having an outer diameter of 20 mm using a die. The heating / cooling rate was 10 ° CZ.

Tables 5 to 8 show Examples (Sample Nos. 1 to 15) and Comparative Examples (Sample Nos. 16 to 20). The material used for the amorphous glass tablet was prepared by mixing a low melting glass powder and a refractory filler powder in a mixing ratio as shown in the table.

[0099] [Table 5]

[0100] [Table 6]

[0101] [Table 7] Example

Sample o.

1 1 12 1 3 1 1 5

K L M N M

Glass

Mixing ratio 70 65 67. 5 70 65

(Volume ° /.) Fireproof coat ', Yellite coat "Yellite coat ^÷ Yellite Koza, Yellite quartz glass

Filler 30 35 32. 5 30 35 Softening point (.C) 450 405 440 437 4 1 Sag O

(Softening point + 1 X) 402 380 400 397 400

(Softening point +5 Ot) 410 390 410 406 41 2

Coefficient of thermal expansion

68. 1 69. 2 67. 7 71. 3

(X 10 1 ⁷ Z ° c) 68.4

[0102] [Table 8]

[0103] Cordierite (crystal), willemite (crystal), and quartz glass were used as the refractory filler powder. Cordierite is prepared by mixing magnesium oxide, aluminum oxide, and silicon oxide at a ratio of 2MgO'2AlO-5SiO, and after mixing, baked at 1400 ° C for 10 hours.

2 3 2

Then, the fired product was pulverized and passed through a 325 mesh stainless steel sieve to obtain an average particle diameter of 5 m. Willemite is zinc oxide, Kei arsenide, aluminum oxide - 70% ZnO and © beam weight ^_0/0, SiO 25%, formulated to be A10 5% of the composition,

2 2 3

After mixing, the mixture was baked at 1440 ° C for 15 hours, and then the baked product was pulverized and passed through a 250 mesh stainless steel sieve to obtain an average particle size of 10 m. Quartz glass with an average particle size of 10 μm was used.

[0104] The softening point was determined by a macro-type differential thermal analyzer using a powder sample.

[0105] The glass transition point, the thermal expansion coefficient in the temperature range of 30 to 300 ° C, and the yield point were determined by a well-known push rod type thermal expansion measurement device. For the measurement of the yield point, samples fired for 30 minutes at a temperature of (soft spot + 10 ° C) and those fired for 30 minutes at a temperature of (softening point + 50 ° C) were tested. Used as a fee. The sample was fired at a temperature increase / decrease rate of 2 ° CZ. Note that the temperature of (softening point + 10 ° C) corresponds to the temperature when the glass tablet is sintered in a baking furnace, and the temperature of (softening point + 50 ° C) is used in the manufacture of flat display devices. It corresponds to the sealing temperature. In addition, the yield point measured using a sample fired at a temperature of (softening point + 10 ° C) corresponds to T, and measured using a sample fired at a temperature of (softening point + 50 ° C). The yield point is equivalent to T

3 Furthermore, no crystals were deposited on the samples No. 1 to 15 in any firing.

[0106] As is clear from Tables 5 to 7, Sample Nos. 1 to 15 have a thermal expansion coefficient of 67.0 to 71.3 X 10 ^_7 Z ° C in the temperature range of 30 to ³⁰⁰ ° C. It was consistent with the thermal expansion coefficient of the high strain point glass substrate. Samples Nos. 1 to 15 have a softening point of 400 to 450 ° C and can be sealed at a low temperature of 500 ° C or less.

[0107] Samples Nos. 1 to 15 use cordierite or quartz glass as the fireproof filler, so compared to when fired at a temperature of (soft spot + 10 ° C), When firing at a temperature of (softening point + 50 ° C), the yield point increased by 6-12 ° C. Therefore, it can be seen that the non-crystalline tablets produced using Samples Nos. 1 to 15 have an increased soft spot during the sealing process and are less likely to flow during the subsequent exhaust process. As a matter of course, the non-crystalline tablets according to Sample Nos. 1 to 15 can be kept at the sealing temperature for about 60 minutes as in the PDP sealing process, for example, by increasing the sealing time. The increase in the yield point can be further increased. On the other hand, sample Nos. 16 to 20 use willemite as a refractory filler, and therefore fired at a temperature of (softening point + 10 ° C) and at a temperature of (softening point + 50 ° C). In that case, the yield point was almost the same.

Industrial applicability

As is apparent from the above description, the amorphous glass tablet of the present invention is suitable for sealing applications such as exhaust pipes such as PDP, FED, plasma addressed liquid crystal display, and fluorescent display tube. Furthermore, the amorphous glass tablet of the present invention is used for sealing a display such as a cathode ray tube (CRT), for forming an insulating dielectric layer such as a fluorescent display tube or a PDP, for magnetic head-cores or between cores and sliders. For sealing, sealing of electronic parts such as crystal units and IC packages, sealing of sheathed heaters and sealing of thermos bottles Is also suitable.

Brief Description of Drawings

FIG. 1 is a cross-sectional view showing a tablet-integrated exhaust pipe of the present invention.

FIG. 2 is a cross-sectional view showing a tablet-integrated exhaust pipe of the present invention.

FIG. 3 is a schematic diagram showing the soft spot of glass when measured with a macro-type differential thermal analyzer. Explanation of symbols

[0110] 1 Exhaust pipe

2 Amorphous glass tablet

3 High melting point tablet

Claims

The scope of the claims

[1] In an amorphous glass tablet containing a low melting glass and a refractory filler,

Low melting point glass strength As a glass composition, Bi O 30 ~

twenty three

60%, B O 10-40%, ZnO 10-50%,

twenty three

And the refractory filler is composed of SiO 30-in terms of the following oxide-based weight% as a composition:

2

100%, AlO 0-45%, ZnO 0-35%, ZrO 0-20%, TiO 0-20%, Li

2 3 2 2 2

Amorphous glass tablet containing 0-10% O and 0-25% MgO

[2] Furthermore, low melting point glass BaO + SrO + MgO + CaO 0-15%, CuO 0-10%,

Fe O 0-5%, SiO + A1 O 0-15%, WO 0-5%, Sb O 0-5%, In O

2 3 2 2 3 3 2 3 2

The amorphous glass layer according to claim 1, characterized by containing + GaO 0-5%.

3 2 3

Bullet.

[3] The amorphous glass tablet according to claim 1 or 2, which contains 40 to 95% of low-melting glass and 5 to 60% of a refractory filler in terms of volume%.

[4] The amorphous glass tablet according to any one of claims 1 to 3, wherein the refractory filler is a crystalline material having cordierite as a main crystal.

[5] The amorphous glass tablet according to any one of [1] to [4], which is substantially free of PbO.

[6] The soft saddle point of the amorphous glass tablet is 350 to 470 ° C.

The amorphous glass tablet in any one of -5.

[7] When the yield point of the amorphous glass tablet is T (° C) and the yield point of the amorphous glass tablet after baking at 480 ° C for 30 minutes is T (° C),

2

An amorphous glass tablet characterized by satisfying the relationship of T-T≥5 ° C.

twenty one

[8] The amorphous glass tablet according to any one of [1] to [7], which is used for sealing an exhaust pipe for a flat display device.

[9] The amorphous glass tablet according to [8], wherein the flat display device is a plasma display panel.

[10] The amorphous glass according to any one of [1] to [9] above, at the tip of the expanded exhaust pipe A tablet-integrated exhaust pipe with a tablet attached.

The non-crystalline glass tablet according to any one of claims 1 to 9 and the high melting point tablet are attached to the tip of the expanded exhaust pipe, and the non-crystalline glass tablet is expanded. A tablet-integrated exhaust pipe, which is attached to the front end side of the exhaust pipe, and the high melting point tablet is attached to the rear end side of the amorphous glass tablet.