WO2007105550A1

WO2007105550A1 - Process for melting glass and glass

Info

Publication number: WO2007105550A1
Application number: PCT/JP2007/054385
Authority: WO
Inventors: Takemi Kikutani; Yoshinori Nishikawa; Nobutoshi Itou
Original assignee: Nippon Electric Glass Co., Ltd.
Priority date: 2006-03-13
Filing date: 2007-03-07
Publication date: 2007-09-20
Also published as: JP5170817B2; KR100984753B1; CN101360688A; JP2007277076A; KR20080047624A; CN101360688B

Abstract

[PROBLEMS] To provide a process for melting glass which enables long-period and repeated melting of SnO-P2O5 glasses, which glasses are liable to corrode a melting vessel made of platinum, and which little causes the deterioration of glass with constituents of a melting vessel even if the constituents thereof penetrate into molten glass in the melting step; and glass. [MEANS FOR SOLVING PROBLEMS] A process for melting glass by melting a glass raw material batch in a melting vessel, characterized in that the melting vessel is one made of zirconium or a zirconium alloy.

Description

Specification

Glass melting method and glass

Technical field

The present invention relates to a glass melting method and glass, and in particular, various ceramic packages.

, Sealing of electronic components such as magnetic heads, sealing of various display devices, plasma display panel (PDP) partition walls, sealing of double metal containers of thermos bottles, and glass melting methods and glasses suitable for various optical glasses Is.

Background art

[0002] Sealing materials used in electronic components and display devices such as ceramic packages and magnetic heads can be sealed at low temperatures so as not to adversely affect elements such as ICs and crystal units, and thermal expansion It is required that the coefficient matches that of the object to be sealed.

Until now, as a sealing material satisfying these characteristics, PbO-B 0 glass, or

twenty three

Various composite materials obtained by adding a refractory filler to these glasses have been proposed (for example, see Patent Document 1).

[0004] However, recently, from an environmental point of view, it has been required to remove lead, which is an environmentally hazardous substance, from glass. As an alternative to PbO-BO glass, SnO-P0 glass is

2 3 2 5 has been proposed (see, for example, Patent Documents 2 and 3).

[0005] By the way, PbO _B 0 glass usually has a platinum melting capacity excellent in heat resistance and corrosion resistance.

twenty three

It is produced by melting a glass raw material in a vessel. In general, PbO -B O glass

In 2 3, the melting temperature is low, so there is no problem such as breakage of the melting container with less erosion of the platinum melting container after melting.

[0006] On the other hand, SnO-PO glass is made of platinum as soon as it erodes the platinum melting vessel during melting.

twenty five

Since cracks may occur in the melting container, there is a problem that the platinum melting container cannot be used for a long period of time. In addition, platinum is a very expensive metal, and if the platinum melting vessel is replaced in a short period of time, the melting cost will increase.

[0007] Because of these circumstances, as described in Patent Documents 4 to 6, the SnO 2 -P 2 O-based glass

2 5 An expensive silica (quartz) melting vessel is used for melting. Patent Document 1: JP-A-2-229738

Patent Document 2: Japanese Patent Laid-Open No. 11 292564

Patent Document 3: Japanese Patent Laid-Open No. 2001-48579

Patent Document 4: Japanese Patent No. 2628007

Patent Document 5: Japanese Patent Publication No. 7_25567

Patent Document 6: JP-A-9-235136

Disclosure of the invention

Problems to be solved by the invention

[0008] Since the silica melting containers described in Patent Documents 4 to 6 have a small coefficient of thermal expansion, after the molten glass is poured out, the glass remaining in the silica melting container has a coefficient of thermal expansion. It is difficult to align. If the coefficients of thermal expansion of the two are inconsistent, the silica melting vessel is likely to crack due to the difference in thermal expansion coefficient, and the melting vessel cannot be used for a long period of time.

[0009] It is also conceivable to use an inconel metal melting vessel having heat resistance as the melting vessel. However, since Inconel metal contains Cr in the metal, a large amount of Cr dissolves in the glass when it is melted to color the glass, and the dissolved Cr makes the glass unstable.

[0010] Therefore, the technical problem of the present invention is that SnO_P〇 which easily corrodes a platinum melting vessel

25 A method of melting glass that can repeatedly melt glass, etc. over a long period of time, and does not cause the glass to denature even if the components of the melting container are eluted into the molten glass during melting. And to provide glass.

Means for solving the problem

[0011] As a result of repeating various experiments to solve the above technical problem, the present inventors have found that when a melting container made of zirconium or a zirconium alloy is used as the melting container, SnO_PO is highly corrosive. The melting vessel is less likely to be eroded even when glass-based glass is melted

twenty five

In addition, it is found that the elution component does not denature the glass even if the melting container is difficult to break and the constituent components of the melting container are dissolved in the glass at the time of melting, and is proposed as the present invention. That is, the glass melting method of the present invention is a glass material prepared The glass is melted in a melting container, and the melting container is made of dinoleconium or a zirconium alloy.

[0012] Secondly, the glass melting method of the present invention is characterized by melting in an inert atmosphere or a reducing atmosphere. Here, “inert atmosphere” refers to a vacuum environment (below ΙΟΟΤοιτ), a rare gas atmosphere such as N, Ar, and He, and “reducing atmosphere” refers to oxygen at normal pressure.

2

This refers to an atmosphere that has a concentration of 10% by volume or less and injects a reducing gas such as hydrogen or hydrocarbon.

[0013] Third, the glass melting method of the present invention is characterized in that the glass contains 20 to 70 mol% of SnO as a glass composition.

[0014] Fourthly, the glass melting method of the present invention is characterized in that the glass contains, as a glass composition, mol%, SnO 20-70%, PO 10-50%, BO 0-30%. Attached.

2 5 2 3

[0015] Fifth, the glass melting method of the present invention has a purity of 97% by mass or more of dinoleconium and contains one or more selected from the group of Hf, Fe and Cr as impurities. It is characterized by this.

[0016] Sixth, the glass melting method of the present invention is such that the zirconium alloy contains zirconium, Sn,

It is characterized by being a Zircaloy alloy containing one or more selected from the group of Fe, Cr and Ni.

Seventh, the method for melting glass according to the present invention is such that the zirconium alloy is a zirconium iron alloy.

It is characterized by being either a zirconium copper alloy or a zirconium aluminum alloy.

[0018] Eighth, the glass of the present invention is characterized in that it is produced by the glass melting method described above.

Ninth, the glass of the present invention has a glass composition with a ZrO of 100 to 3000 pp in terms of mass.

2

It is characterized by containing m.

[0020] Tenth, the glass of the present invention has a glass composition, SnO 20 to 70% by mole ^_0/0, P_〇

twenty five

Contains 10-50%, B 0-30%, and contains 100-3000 ppm of ZrO in terms of mass

2 3 2

Characterized by

[0021] Eleventh, the glass of the present invention is used for sealing electronic parts or display devices. Characterized by

The invention's effect

[0022] The glass melting method of the present invention is a SnO—PO system glass that easily corrodes the melting vessel.

2 5 etc. can be melted repeatedly over a long period of time, and even if the components of the melting vessel elute into the glass during melting, it is difficult to alter the glass.

[0023] In the method for melting glass according to the present invention, since zirconium-zirconium alloy is used as a melting container, the heat resistance and corrosion resistance of the melting container can be ensured. A melting vessel made of zirconia is a glass melting temperature (eg 70

0 ~: 1000 ° C) and does not deform and melts highly corrosive SnO1 PO glass etc.

twenty five

However, it has an advantage that the melting container is not easily corroded.

[0024] In addition, a melting vessel made of dinoleconium or dinoleconium alloy has characteristics that make it difficult to devitrify the glass in addition to difficult to separate the glass even if zirconium or the like elutes into the glass during melting. is doing. In addition, the effects described below can be enjoyed by leaching dinoleconium and the like into the glass during melting.

[0025] Further, since zirconium-zinoleconium alloy has excellent malleability and strength, melting containers of various shapes can be produced. In addition, Zinoleconium-zirconium alloy is cheaper than platinum, and thus can lower the melting cost. BEST MODE FOR CARRYING OUT THE INVENTION

[0026] In the glass melting method of the present invention, it is preferable to melt in an inert atmosphere or a reducing atmosphere. If zirconium or a zirconium alloy is left in the atmosphere in the melting temperature range (for example, 700 to 1000 ° C.), the surface of zirconium or zirconium alloy is oxidized and its toughness is easily impaired. This tendency is particularly noticeable when the melting temperature is 900 ° C or higher. As a result, the melting container is subject to stress failure when subjected to thermal shock or when the melting container is cooled. If it is melted in an inert atmosphere or a reducing atmosphere, the zirconium-zinoleconium alloy is difficult to oxidize, so the above-mentioned situation in which the melting vessel is difficult to break can be effectively avoided.

[0027] The glass melting method of the present invention does not exclude the aspect of melting in the air, but if it is melted in an inert atmosphere or a reducing atmosphere, in addition to the above-mentioned advantages. In addition, since the life of the melting container can be increased, the melting cost can be reduced.

[0028] In the case of SnO-containing glass, especially SnO-P0 glass, inert atmosphere or reducing property

twenty five

Melting in an atmosphere is more preferable because it can also enjoy the advantage of preventing oxidation of SnO. In SnO_PO glass, SnO in the glass composition is acid.

twenty five

If it becomes, the fluidity of the glass is impaired during firing. Here, if the SnO content is less than 20%, the merit of using a melting vessel made of zirconium zirconium alloy becomes poor. Conversely, if the SnO content is more than 70%, the glass loses during melting. It becomes easy to see through, and the glass production efficiency is impaired. Therefore, the content of SnO is mol%, preferably 20 to 70 ^o / ο, more preferably f to 20 to 65 ^o / _o , and further (preferably to 30 to 60 ^o / ο).

In the glass melting method of the present invention, zirconium has a purity of 97% by mass or more, preferably 99% by mass or more, and is selected from the group consisting of Hf, Fe and Cr as impurities 1 Species or two or more can be included. Hf, Fe, and Cr are preferably expressed in terms of mass%, and Hf is 3% or less and Fe + Cr is 0.2% or less. If the purity of zirconium is less than 97% by mass, impurity components may be dissolved during melting and the glass may be altered, which is not preferable.

[0030] In the glass melting method of the present invention, the zirconium alloy is a zircaloy (equivalent to ASTM R6080 2 or equivalent to ASTM R60804) in which one or more selected from the group strength of Sn, Fe, Cr and Ni are added. ), Zirconium iron alloys, zirconium copper alloys, and zirconium aluminum alloys are preferred. These zirconium alloys are excellent in corrosion resistance, heat resistance, workability, etc., and can be suitably used as a melting vessel.

[0031] Zircaloy, Sn, Fe, Cr, the addition amount of Ni is, Sn 1. 0~2 · 0% by weight ^_0/0 Display, Fe

The power of being 0.05 to 0.3%, Cr of 0.05 to 0.2%, and Ni of 0.02 to 0.1%. Addition of these components can prevent excessive corrosion resistance.

[0032] In the glass melting method of the present invention, the thickness of the melting container is preferably 1 to 5 mm.

3 mm is more preferable. By doing so, it is possible to prevent cracking of the melting container without impairing the workability of the melting container.

[0033] In the glass melting method of the present invention, in a vacuum atmosphere, the melting temperature is 800 to 140.

0 ° C is preferred. In the case of an inert atmosphere, the melting temperature is preferably 800 to 1100 ° C. . Further, if the melting temperature is set to 800 to 1000 ° C, the glass can be appropriately melted. When the melting temperature is high, the valence of Sn changes to divalent power and tetravalent, that is, SnO is oxidized immediately and when the melting temperature is low, unmelted components of the glass raw material tend to remain after melting.

[0034] In the glass melting method of the present invention, by eluting zirconium from zirconium or a zirconium alloy, the ZrO content in the glass composition is 100 to 100 in terms of mass.

2

It is desirable to set it at 3000 ppm (preferably 200 to 2000 ppm, more preferably 300 to 1000 ppm). In this way, it is possible to improve the weather resistance and moisture resistance of the glass without adversely affecting the glass properties such as devitrification resistance. Especially for SnO-PO glass

twenty five

In other words, if zirconium is eluted from zirconium or a zirconium alloy, the eluted component acts as a reducing agent, and the situation where SnO in the glass composition is oxidized can be suppressed. If the ZrO content is less than lOOppm, the weather resistance and moisture resistance of the glass will be improved.

2

It becomes difficult. If the ZrO content is greater than 3000 ppm, the softening point of the glass will rise and

2

It becomes difficult to seal.

[0035] It should be noted that equipment that is in direct contact with molten glass, such as stirring blades and gas pipes, is usually made of platinum. Therefore, if these facilities are also made using zirconium or a zirconium alloy, the advantages of the melting vessel described above can be enjoyed.

[0036] Since the glass produced by the glass melting method of the present invention has a low melting point property, it is preferably SnO-P- glass. SnO1 P O-based glass has a glass composition and

2 5 2 5

And, in Monore ^_0/0, having SnO 20 to 70% P_〇 10-50%, the B_〇 0-30%

2 5 2 3

Is preferred.

[0037] The reason why the glass composition of the SnO-PO glass is limited as described above will be described below.

twenty five

[0038] SnO is a component that lowers the melting point of glass. If the SnO content is less than 30%, the viscosity of the glass becomes high, the firing temperature becomes too high, and sealing becomes impossible at a low temperature. If the SnO content exceeds 70%, vitrification becomes difficult. In particular, if there is a large amount of SnO, the glass tends to be devitrified at the time of firing. Therefore, devitrification of the glass at the time of firing is not allowed. In some cases, the SnO content is preferably 60% or less. ,. In addition, if the SnO content is 40% or more, the fluidity of the glass can be improved, and the airtight reliability of electronic parts, etc. Is more preferable.

[0039] PO is a glass-forming oxide, a component that stabilizes glass, and its content

twenty five

Is 10 to 50%, preferably 15 to 45%, more preferably 20 to 35%. P O content

If the amount is less than 10%, the stability of the glass will be insufficient. P O content from 50%

twenty five

If the amount is too high, the moisture resistance of the glass will deteriorate.

[0040] B 2 O is not an essential component but is a glass-forming component and is contained in the glass composition.

twenty three

Thus, the glass can be stabilized. The content of B 2 O is 0-30%, preferably

twenty three

Is 2 to: 15%. B O content is 30. If it is more than / o, the viscosity of the glass will increase and it will be low.

twenty three

It becomes difficult to seal with temperature.

[0041] Further, the SnO_PO glass based on the present invention has a glass composition in addition to the above components.

twenty five

, Zn ○ 0 to 20%, Mg ○ 0 to 20%, A1 ○ 0 to 10%, Si ○ 0 to 15%, La ○ 0

2 3 2 2 3

~ 10%, R〇 (R〇 is the total amount of Li〇, Na〇, K〇 and / or Cs〇) 0-20%

2 2 2 2 2 2 Can be contained. The reason why these components are limited to the above range will be described below.

[0042] Although ZnO is not an essential component, it is a network-modifying oxide and has a large effect of stabilizing the glass, so it is desirable to contain 4% or more. However, if the ZnO content exceeds 20%, devitrification tends to occur on the glass surface during firing. In addition, when the sealing process is a long time (for example, 1 hour or more), the glass surface tends to be devitrified, specifically in the PDP sealing process. . In such a case, the content of ZnO may be 5 to 15%.

[0043] MgO is a network-modifying oxide and has an effect of stabilizing the glass. If MgO exceeds 20%, devitrification tends to occur on the glass surface during firing. The MgO content is preferably 0 to 5%.

[0044] Al 2 O is an intermediate oxide. Al O is not an essential component, but it stabilizes the glass.

2 3 2 3

In addition, it is desirable to contain it because it also has the effect of reducing the thermal expansion coefficient. However, if it exceeds 10%, the softening temperature rises and the fluidity of the glass during firing is hindered. When considering the stability of glass, thermal expansion coefficient, fluidity, etc., Al O content

2 3 The amount is more preferably:! ~ 5%. [0045] SiO is a glass-forming oxide. Si〇 is not an essential component, but suppresses devitrification

twenty two

Since it is effective, it is desirable to contain it. If it exceeds 15%, the softening temperature rises and the fluidity during firing becomes extremely poor. In consideration of fluidity as a low melting point material, the content of Si 2 O is preferably 0 to 10%.

2

[0046] R0 is not an essential component, but at least one of the R0 components is 0.

twenty two

By containing 1% or more, the sealing strength with the object to be sealed can be increased. However, if the content of R0 exceeds 20%, the glass tends to devitrify during firing. In firing

2

When devitrification resistance and glass fluidity are required, the content of R〇 should be 10% or less.

2

It is desirable.

[0047] Furthermore, the SnO_PO glass according to the present invention has a glass composition in addition to the above components.

twenty five

Various components can be added. For example, for the purpose of stabilizing glass, WO

Three

, Mo〇, Nb〇, Ti〇, Cu〇, Mn〇, R'〇 (R'〇 is Mg〇, Ca〇, Sr〇 and / or

3 2 5 2

Or the total amount of BaO) or the like can be contained in a total amount of 0 to 35%, preferably 0 to 25%. If the total amount of these components exceeds 35%, the glass composition will be unbalanced, and the glass will be unstable, and the glass will be easily devitrified during molding. In addition, In 2 O or the like can be added to increase the weather resistance and moisture resistance of the glass.

twenty three

[0048] The content of the stabilizing component and the reason for limitation will be described below.

[0049] The contents of WO and MoO are each preferably 0 to 20%, particularly preferably 0 to 10%.

3 3

. When these components exceed 20%, the viscosity of the glass becomes high and it becomes impossible to seal at a low temperature immediately.

[0050] The contents of NbO and TiO are each 0 to 15%, particularly preferably 0 to 10%.

2 5 2

. If these components exceed 15%, the tendency to devitrify the glass tends to increase.

[0051] The CuO and MnO contents are preferably 0 to 10%, particularly 0 to 5%, respectively. If these components exceed 10%, the glass tends to become unstable.

[0052] The total content of R'O is preferably 0 to 15%, particularly preferably 0 to 5%. R'O is 15

If it exceeds%, the glass tends to be unstable.

[0053] In O can be used for the purpose of obtaining high weather resistance and moisture resistance. In O content

2 3 2 3 The content is preferably 0-5%. If the In O content is more than 5%, In〇 is expensive Since this is a raw material, the cost of the glass raw material will rise.

[0054] From an environmental viewpoint, it is preferable that PbO is not substantially contained in the glass composition. Here, “substantially no PbO” refers to the case where the content of PbO in the glass composition is 100 Oppm or less.

[0055] The glass of the present invention, as a glass composition, in mol ^_0/0, Sn_〇 20 to 70%, PO 10.about.5

twenty five

Contains 0%, B O 0-30%. Furthermore, in the glass of the present invention, the glass is glass

twenty three

It is preferable to contain 100 to 3000 ppm of ZrO in the composition.

2

It is more preferable to have the power to contain 300-1000ppm S especially preferred. In this way, the weather resistance and moisture resistance of the glass can be improved. ZrO content is 10

2

If it is less than Oppm, the weather resistance and moisture resistance of the glass will be improved. ZrO content

2 Power More than 000ppm, it becomes difficult to seal at low temperature. ZrO, as mentioned above,

2

It can be introduced into the glass composition by melting using a glass melting container or the like.

The glass of the present invention can be suitably produced by the above glass melting method.

SnO1 PO glass obtained by the glass melting method, or the glass composition

twenty five

SnO—PO glass having 270-380. It has a glass transition temperature of C, about 400-60

twenty five

It is a low melting glass showing good fluidity in the temperature range of 0 ° C. These Sn_〇 - PO based glass, 90 in a temperature range of ^{30~250 ° C: 150 X 10 _} 7 / ° C of about

twenty five

It has a thermal expansion coefficient.

[0057] SnO—PO glass having such characteristics matches the thermal expansion coefficient of the object to be sealed.

twenty five

Glass powder, it can be used alone as a sealing material.

[0058] On the other hand, if the article to be sealed and the thermal expansion coefficient does not match, such as alumina ^{(70 X 10- 7 / ° C} ), high strain point glass ^{(85 X 10- 7, .C)} , soda lime glass (90 X 10—So, when sealing C) etc., refractory filler powder is added to SnO_PO glass powder to form a composite material.

twenty five

Just do it. Thermal expansion coefficient of the composite material, it is important to lower rather designed about 5~30 X 10- ⁷ / ° C with respect to the article to be sealed. In this way, the stress applied to the sealing layer can be set to the compression (compression) side to prevent destruction of the sealing layer. In this case, what is necessary is just to prepare so that it may become 45-95 volume% of glass powder, and 5-55 volume% of refractory filler powder.

[0059] Fluorescent display tube (VFD), field emission display (FED), PDP, cathode When sealing a wire tube (CRT), it is preferable to adjust the thermal expansion coefficient of the sealing material to about 60: 100 X 10 ^_7 / ° C.

[0060] Various refractory filler powders such as willemite ceramic, β-eucryptite, lead titanate ceramic, cordierite, tin oxide solid solution, zircon ceramic, mullite, quartz glass, alumina, etc. as refractory filler May be added. In addition to adjusting the thermal expansion coefficient, for example, refractory filler powder can be added to improve mechanical strength. From an environmental point of view, it is preferable that the refractory filler powder does not substantially contain PbO.

Example

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

[0062] Tables 1 and 2 show examples (No .:! To 9) of the present invention, and Table 3 shows comparative examples (Nos. 10 to 12).

[0063] [Table 1]

(Note) Zircaloy 2: ASTM G ra de R60802 phase ¾

Zircaloy 4: ASTM G ra de e R60804 equivalent

[0064] [Table 2] Example

No.6 No.7 No.8 No.9

SnO 52.5 61 43 55

31 19.5 24 20

Glass B ₂ 0 ₃ 0 2 22.5 5.5

Composition ZnO 12,5 2 5.5 4

(mo) Si0 ₂ 1.5 1.5 0 0

2ί ₂ 0 ₃ 0.5 2 1.5 1

Li ₂ 0 0.5 2 2.5 3.5

Na ₂ 0 1.5 0.5 0 0

20 0 0.5 0.5 1

W0 ₃ 0 9 0 10

ln ₂ 0 ₃ 0 0 0.5 0

Melting container Zr Le 2 2 Zr Shire force Roy 4

Melting temperature (° C) 800 900 950 950

Melting atmosphere N ₂ Ar He N ₂

Glass transition point (° c) 287 320 335 323

Thermal expansion coefficient (X10_ ⁷ / ° G) 121 110 103 111

Firing atmosphere Air N ₂ N ₂

Flow diameter (mm) 23.5 22.1 20.4 21.0

Zr0 ₂ content (ppm) 1850 1150 700 1200

Cracking of melting container O O O O

(Note) Zircaloy 2: ASTM G ra de e R60802 equivalent

Zircaloy 4: ASTM G ra d e R6 O 8 O 4 equivalent

[0065] [Table 3]

[0066] Various oxides, carbonate raw materials and the like were prepared so as to have the glass compositions in the table, and glass raw materials were produced. This glass raw material was put into a melting container shown in the table, and melted at the melting temperature in the table for 2 hours in the melting atmosphere in the table.

[0067] Next, the molten glass in the melting vessel was poured out between a pair of rotating rollers, and a film-like glass sample was prepared while rapidly cooling the molten glass with one rotating roller. The formed film-like glass is pulverized with a ball mill and then passed through a sieve with a mesh size of 105 xm. About 10 / m glass powder was obtained. The molten glass in the melting container was poured out into a carbon mold, and a plate-like glass sample was produced.

[0068] The glass transition point was determined by differential thermal analysis (DTA), and the thermal expansion coefficient was determined by a push rod thermal expansion measurement (TMA) apparatus.

[0069] The flow diameter was evaluated by the following flow button test. First, the formed glassy glass was pulverized by a ball mill and then passed through a sieve having an aperture of 105 am to obtain a glass powder having an average particle size of about 10 μm. Next, a powder having a mass corresponding to the true specific gravity of the obtained glass powder was weighed and pressed into a button shape having a diameter of 20 mm using a mold to obtain a button-shaped powder formed body. Subsequently, this powder compact was placed on a window glass and then fired in the atmosphere shown in the table. As firing conditions, the temperature was increased to a firing temperature of 450 ° C. at a rate of 10 ° C./minute, held at 450 ° C. for 10 minutes, and then cooled to room temperature at 10 ° C./minute. Finally, the diameter of the button after firing was measured with a digital caliper. The diameter of this button should be at least 20 mm when used as a sealing material.

[0070] "Cracking of the melting container" was evaluated by visually determining whether or not cracks occurred in the melting container by leaving the melting container at room temperature after pouring the molten glass from the melting container. The case where there was no crack, “◯”, and the case where there was a crack, “X”.

[0071] "ZrO content in glass" was measured by fluorescent X-ray analysis. The numbers in the table

2

Is a numerical value in terms of mass.

[0072] As is clear from Tables 1 and 2, Example Nos .:! To 9 had a flow diameter of 20 mm or more in the flow button test in which cracking of the melting vessel was eliminated, and the obtained glass characteristics were also good. The Zr 2 O content was 700 to 1900 ppm.

2

On the other hand, as is apparent from Table 3, in Comparative Examples No. 10 and 12, cracks occurred in the melting container, and in Comparative Example No. 11, the molten glass was strongly colored green, and the powder glass was also devitrified. As a result, the flow diameter did not flow as 18 mm, and the glass properties were impaired.

Industrial applicability

[0074] As described above, the glass melting method and glass of the present invention include various ceramic packages, sealing of electronic components such as a magnetic head, sealing of various display devices, PDP partition walls, and double metal thermos. Suitable for container sealing and various optical glasses.

Claims

The scope of the claims

[I] The glass melting method in which the prepared glass raw material is melted in a melting container,

A method for melting glass, characterized in that the melting vessel is made of zirconium or a dinoleconium alloy.

[2] The method for melting glass according to claim 1, wherein the melting is performed in an inert atmosphere or a reducing atmosphere.

[3] glass, as a glass composition, in mol ^_0/0, the melting method of a glass according to claim 1 or 2, characterized in that it contains 20% to 70% of Sn_〇.

[4] glass, as a glass composition, in mol ^_0/0, SnO 20 to 70% P_〇 10-50%, B_〇

2 5 2

Melting of the glass according to any one of claims 1 to 3, characterized by comprising 0-30%

Three

Method.

[5] The purity of zirconium is 97% by mass or more, and contains one or more selected from the group of Hf, Fe, and Cr as impurities. The method for melting glass as described in 1.

[6] Zirconium alloy strength Zirconium, Sn, Fe, Cr, and Ni group power One of the selected Zircaloy alloys containing at least one selected from any one of claims 1-4 The method for melting glass as described in 1.

[7] The glass melting method according to any one of [1] to [4], which is any one of zirconium alloy strength S, zirconium iron alloy, zirconium copper alloy, and zirconium aluminum alloy.

[8] A glass produced by the method for melting glass according to any one of claims 1 to 7.

[9] The glass contains 100 to 3000 ppm of ZrO as a glass composition in terms of mass.

2

The glass according to claim 8.

As [10] glass composition in mole ^_0/0, SnO 20 to 70% P_〇 10-50%, B_〇 0-30

2 5 2 3

The glass is characterized by containing 100% to 3000ppm of ZrO in terms of mass.

2

Su.

[II] It is used for sealing an electronic component or a display device. Glass in any one.