JPH08183632A - Low melting point glass - Google Patents
Low melting point glassInfo
- Publication number
- JPH08183632A JPH08183632A JP32586394A JP32586394A JPH08183632A JP H08183632 A JPH08183632 A JP H08183632A JP 32586394 A JP32586394 A JP 32586394A JP 32586394 A JP32586394 A JP 32586394A JP H08183632 A JPH08183632 A JP H08183632A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- low melting
- mol
- melting point
- transition point
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、低融点ガラス、特に非
鉛系の低融点ガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low melting point glass, and more particularly to a lead-free low melting point glass.
【０００２】[0002]
【従来の技術】低融点すなわち低ガラス転移点を示すガ
ラスとして鉛系のものがよく知られている。鉛化合物を
含まないガラスについては、低温封着用途や樹脂複合用
途を目的にしてリン酸と酸化亜鉛を含む組成のガラスが
開発されている。例えば、米国特許第４９４０６７７号
明細書、同第５０２１３６６号明細書、同第４９９６１
７２号明細書、同第５１２２４８４号明細書、同第５２
５２５２３号明細書、同第５２５６６０４号明細書に
は、Ｐ2 Ｏ5 、ＺｎＯ、Ｒ2 Ｏ（Ｒ：Ｌｉ、Ｎａ、Ｋ）
を基本とする組成の低融点ガラスが開示されている。2. Description of the Related Art Lead-based glass is well known as a glass having a low melting point, that is, a low glass transition point. As for a glass containing no lead compound, a glass having a composition containing phosphoric acid and zinc oxide has been developed for the purpose of low-temperature sealing and resin composite use. For example, U.S. Pat. Nos. 4,940,677, 5,021,366, 4,9961.
No. 72, No. 5122484, No. 52
52523 and 5256604 describe P 2 O 5 , ZnO, R 2 O (R: Li, Na, K).
A low melting glass having a composition based on is disclosed.
【０００３】また、米国特許第５２４６４８４号明細
書、同第５２８１５６０号明細書には、Ｐ2 Ｏ5 、Ｓｎ
Ｏ、ＺｎＯを基本とする組成の低融点ガラスが開示され
ている。一方、特開昭５１−１４６５１０号公報、特開
昭５２−１１２１１号公報、特開昭５２−１３３３１１
号公報、特開昭５２−１３３３１３号公報には、低融点
ガラス組成物として、Ｐ2 Ｏ5 、ＺｎＯ、Ｒ2 Ｏ、Ｂ2
Ｏ3 からなるガラスが開示されている。Further, US Pat. Nos. 5,246,484 and 5,281,560 describe P 2 O 5 , Sn.
A low melting glass having a composition based on O and ZnO is disclosed. On the other hand, JP-A-51-146510, JP-A-52-11211, and JP-A-52-13311.
And JP Sho 52-133313, as a low melting glass composition, P 2 O 5, ZnO, R 2 O, B 2
A glass of O 3 is disclosed.
【０００４】[0004]
【発明が解決しようとする課題】しかし、これらのガラ
スは低融点ではあるが、温度上昇にともない粘性が急激
に低下するため成形性が低く、ファイバーや中空体など
の所望の形状のガラスを成形するのが困難であった。ま
た、耐水性も必ずしも十分ではなかった。本発明は、低
融点のガラスであって、成形性が良好で、かつ、耐水性
にも優れるガラスを提供することを目的とする。However, although these glasses have a low melting point, their viscosity is drastically lowered with increasing temperature, so that they have low formability and can be formed into desired shapes such as fibers and hollow bodies. It was difficult to do. Moreover, the water resistance was not always sufficient. An object of the present invention is to provide a glass having a low melting point, which has good moldability and is also excellent in water resistance.
【０００５】[0005]
【課題を解決するための手段】本発明は、モル％表示で
次の組成を有する低融点ガラスを提供する。 Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ ５〜２５％、 ＺｎＯ＋ＭｇＯ ３５〜５５％、 Ｐ2 Ｏ5 ２０〜３５％、 Ａｌ2 Ｏ3 １〜 ５％、 Ｂ2 Ｏ3 ８〜２０％。The present invention provides a low melting glass having the following composition in terms of mol%. Li 2 O + Na 2 O + K 2 O 5~25%, ZnO + MgO 35~55%, P 2 O 5 20~35%, Al 2 O 3 1~ 5%, B 2 O 3 8~20%.
【０００６】本発明の低融点ガラスは、具体的には、５
００℃以下のガラス転移点を示すものが好ましい。次
に、本ガラスの組成限定理由について説明する。The low melting point glass of the present invention is specifically 5
Those having a glass transition point of 00 ° C. or lower are preferable. Next, the reasons for limiting the composition of the present glass will be described.
【０００７】Ｌｉ2 Ｏ、Ｎａ2 Ｏ、Ｋ2 Ｏは、合計量が
５〜２５モル％であることが必要である。Ｌｉ2 Ｏ、Ｎ
ａ2 Ｏ、Ｋ2 Ｏは、１種類のみを用いても２種類以上混
合して用いても支障ない。合計量が５モル％未満ではガ
ラス転移点が高くなり、合計量が２５モル％超ではとガ
ラスの耐水性が低下するため不適当である。The total amount of Li 2 O, Na 2 O and K 2 O must be 5 to 25 mol%. Li 2 O, N
a 2 O, K 2 O is no problem even by using a mixture of two or more be used only one type. If the total amount is less than 5 mol%, the glass transition point will be high, and if the total amount exceeds 25 mol%, the water resistance of the glass will decrease, which is unsuitable.
【０００８】ＺｎＯ、ＭｇＯは、合計量が３５〜５５モ
ル％であることが必要である。ＺｎＯ、ＭｇＯは１種類
のみを用いても２種類混合して用いても支障ない。合計
量が３５モル％未満では、ガラスの耐水性が十分でな
く、５５モル％超ではガラス転移点が上昇したりガラス
の失透性が増大するため不適当である。The total amount of ZnO and MgO must be 35 to 55 mol%. ZnO and MgO may be used alone or as a mixture of two kinds. If the total amount is less than 35 mol%, the water resistance of the glass is not sufficient, and if it exceeds 55 mol%, the glass transition point increases and the devitrification of the glass increases, which is unsuitable.
【０００９】Ｐ2 Ｏ5 は、２０モル％未満ではガラス化
し難くなり、３５モル％超では耐水性が低下するため不
適当である。If P 2 O 5 is less than 20 mol%, vitrification tends to be difficult, and if it exceeds 35 mol%, the water resistance tends to be low.
【００１０】Ａｌ2 Ｏ3 は、１モル％未満では耐水性が
低下し、５モル％超では溶解が困難で均質なガラスが得
られないため不適当である。If Al 2 O 3 is less than 1 mol%, the water resistance is lowered, and if it exceeds 5 mol%, it is difficult to melt and a homogeneous glass cannot be obtained.
【００１１】Ｂ2 Ｏ3 は、８モル％未満では温度上昇に
対するガラスの粘性の低下が急激であり所望の形状に成
形し難く、２０モル％超ではガラス転移点が上昇し耐水
性も低下するため不適当である。When B 2 O 3 is less than 8 mol%, the viscosity of the glass is drastically lowered with respect to temperature rise and it is difficult to mold it into a desired shape. When it exceeds 20 mol%, the glass transition point is increased and the water resistance is also decreased. Therefore, it is inappropriate.
【００１２】そしてこれらの範囲のうち、 Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ ７〜２０モル％、 ＺｎＯ＋ＭｇＯ ４２〜４８モル％、 Ｐ2 Ｏ5 ２５〜３０モル％、 Ａｌ2 Ｏ3 １〜 ３モル％、 Ｂ2 Ｏ3 ９〜１５モル％ からなる組成のガラスはガラス転移点が低く、耐水性に
も優れ、粘性の温度に対する傾きも緩やかなため、特に
好ましい。Of these ranges, Li 2 O + Na 2 O + K 2 O 7 to 20 mol%, ZnO + MgO 42 to 48 mol%, P 2 O 5 25 to 30 mol%, Al 2 O 3 1 to 3 mol%, Glass having a composition of 9 to 15 mol% B 2 O 3 is particularly preferable because it has a low glass transition point, excellent water resistance, and a gentle viscosity gradient with respect to temperature.
【００１３】Ｌｉ2 Ｏ、Ｎａ2 Ｏ、Ｋ2 Ｏ成分の原料と
しては、Ｌｉ2 ＣＯ3 、Ｎａ2 ＣＯ3 、Ｋ2 ＣＯ3 など
の炭酸塩の他、水酸化物、硫酸塩、塩化物、リン酸塩化
合物などが使用できる。ＺｎＯ、ＭｇＯ成分の原料とし
ては、ＺｎＯ、ＭｇＯなどの酸化物の他、リン酸亜鉛な
どのリン酸塩や水酸化マグネシウムなどの水酸化物、硫
酸亜鉛などの硫酸塩が使用できる。Ｐ2 Ｏ5 成分の原料
としては、正リン酸（Ｈ3 ＰＯ4 ）やリン酸アンモニウ
ムなどの他、アルカリ成分や亜鉛、アルミニウム成分と
の化合物の形で使用してもよい。Ａｌ2 Ｏ3 成分の原料
としては、酸化アルミニウム、水酸化アルミニウムなど
が使用できる。Ｂ2 Ｏ3 成分の原料としては、無水ホウ
酸（Ｂ2 Ｏ3 ）やホウ酸（Ｈ3 ＢＯ3）、ホウ砂（Ｎａ2
Ｂ4 Ｏ7 ・１０Ｈ2 Ｏ）などが使用できる。The raw materials for the Li 2 O, Na 2 O and K 2 O components include carbonates such as Li 2 CO 3 , Na 2 CO 3 and K 2 CO 3 as well as hydroxides, sulfates and chlorides. , Phosphate compounds and the like can be used. As a raw material for the ZnO and MgO components, oxides such as ZnO and MgO, phosphates such as zinc phosphate, hydroxides such as magnesium hydroxide, and sulfates such as zinc sulfate can be used. As the raw material of the P 2 O 5 component, in addition to orthophosphoric acid (H 3 PO 4 ) and ammonium phosphate, it may be used in the form of a compound with an alkali component, zinc, and an aluminum component. As a raw material for the Al 2 O 3 component, aluminum oxide, aluminum hydroxide or the like can be used. As a raw material for the B 2 O 3 component, boric anhydride (B 2 O 3 ), boric acid (H 3 BO 3 ), borax (Na 2
B 4 O 7 · 10H 2 O) can be used.
【００１４】本発明の低融点ガラスの製造手段として
は、特に制限がなく、例えば、原料を調合して得られ
た、原料粉体または濃厚な水溶液やスラリーを１２０〜
４００℃で乾燥・仮焼した後、白金るつぼ中で８００〜
１５００℃で溶融する方法が好適である。このガラス融
液は、適宜公知の方法で種々の形態のガラスに成形でき
る。また、本発明の組成のガラス原料は高濃度の水溶液
やスラリーにすることができるので、この水溶液やスラ
リーを、電気炉中や火炎中に直接噴霧することによって
粉末状あるい微小中空体状のガラスを製造したりするこ
とができる。The method for producing the low melting point glass of the present invention is not particularly limited, and for example, a raw material powder or a concentrated aqueous solution or slurry obtained by blending raw materials can be used in the range of 120 to
After drying and calcination at 400 ℃, 800 ~ in a platinum crucible
A method of melting at 1500 ° C. is preferable. This glass melt can be appropriately formed into various forms of glass by a known method. Further, since the glass raw material of the composition of the present invention can be made into a high-concentration aqueous solution or slurry, by directly spraying this aqueous solution or slurry into an electric furnace or a flame, a powder or a fine hollow body is obtained. Glass can be manufactured.
【００１５】本発明のガラスにおいては、本発明の効果
を損なわない範囲において上記以外の成分が上記成分の
合計量に対し、外掛けで１０重量％未満存在していても
支障ない。例えば、ガラスの清澄性を改良したり、中空
ガラス体を作製する目的で原料中に添加した成分あるい
は原料にともなって配合されたＳＯ3 成分、ＣＯ2 成
分、Ｈ2 Ｏ成分が得られたガラス体中に残存してもよ
い。In the glass of the present invention, components other than those described above may be present in an amount of less than 10% by weight with respect to the total amount of the above components within a range that does not impair the effects of the present invention. For example, a glass obtained with a component added to the raw material for the purpose of improving the clarity of the glass or for producing a hollow glass body, or an SO 3 component, a CO 2 component, and a H 2 O component blended with the raw material. It may remain in the body.
【００１６】[0016]
【実施例】表１に示した組成のガラス２００ｇになるよ
うに原料を調合し、これを白金るつぼにいれて１３００
℃で１時間溶融した後、ステンレス板上に流し出して板
状のガラスを成形した後、徐冷した。表１に組成をモル
％表示で示し、表２には同じ組成を重量％に換算して表
示する。なお、番号４および７の組成においては、亜鉛
原料の一部として硫酸亜鉛を用いたので、ガラス中には
それぞれ表１および表２に示した成分の他に、３重量％
および０．３重量％のＳＯ3 が含まれていた。ガラス中
に含まれるＳＯ3 量は蛍光Ｘ線により分析した。番号１
〜１３は本発明の実施例であり、番号１４〜２０は比較
例である。[Examples] Raw materials were mixed so that 200 g of glass having the composition shown in Table 1 was prepared, and this was placed in a platinum crucible for 1300.
After melting at 0 ° C for 1 hour, it was cast on a stainless steel plate to form a plate-shaped glass, and then gradually cooled. The composition is shown in Table 1 in mol%, and in Table 2, the same composition is shown in terms of weight%. In the compositions of Nos. 4 and 7, since zinc sulfate was used as a part of the zinc raw material, in the glass, in addition to the components shown in Tables 1 and 2, 3 wt%
And 0.3% by weight of SO 3 . The amount of SO 3 contained in the glass was analyzed by fluorescent X-ray. Number 1
Nos. 13 to 13 are examples of the present invention, and Nos. 14 to 20 are comparative examples.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】表３に、得られたガラスの物性を示す。ガ
ラス転移点および結晶化温度は、ＤＴＡで測定した。熱
膨張計で、５０℃から３００℃までの平均線膨張係数を
測定した。耐水性として、板状のガラス試料を９０℃の
水中に２０時間浸漬した後の単位面積あたりの重量減少
量として示す。これらのガラスを１００メッシュ以下に
粉砕し、体積で０．５ｃｃに相当する量を１／２インチ
（１２．８ｍｍ）の直径でプレス成形し、アルミナ基板
上にのせ、７００〜９００℃で熱処理したときにガラス
が軟化流動して得られたフローボタンの直径を測定する
ことによって粘性の温度変化を評価した結果も示す。Table 3 shows the physical properties of the obtained glass. The glass transition point and the crystallization temperature were measured by DTA. The average linear expansion coefficient from 50 ° C. to 300 ° C. was measured with a thermal expansion meter. The water resistance is shown as the amount of weight loss per unit area after a plate-shaped glass sample was immersed in 90 ° C. water for 20 hours. These glasses were crushed to 100 mesh or less, and an amount corresponding to 0.5 cc in volume was press-formed with a diameter of 1/2 inch (12.8 mm), placed on an alumina substrate, and heat-treated at 700 to 900 ° C. Also shown are the results of evaluating the temperature change of viscosity by measuring the diameter of the flow button obtained when the glass softened and flowed.
【００２０】さらに、得られたフローボタンの外観か
ら、ガラスの失透性を調べた。実施例のガラスは、優れ
た耐水性を示し、５００℃以下のガラス転移点を示し
た。フローボタンの直径の測定により、温度上昇にとも
なう粘性の変化が小さく、７００℃でも失透しないこと
がわかった。このことは成形性が良好であることを意味
する。比較例のガラスは、これらのいずれかの特性ある
いはすべてが実施例より悪かった。Further, the devitrification of the glass was examined from the appearance of the obtained flow button. The glasses of the examples exhibited excellent water resistance and a glass transition point of 500 ° C. or lower. From the measurement of the diameter of the flow button, it was found that the change in viscosity with a rise in temperature was small and it did not devitrify even at 700 ° C. This means that the moldability is good. The comparative glass had some or all of these properties worse than the examples.
【００２１】[0021]
【表３】 [Table 3]
【００２２】[0022]
【発明の効果】本発明によれば、ガラス転移点が５００
℃以下と低く、耐水性に優れ、温度に対する粘性の傾き
が小さいため種々の形状への成形性に優れたガラスが得
られる。According to the present invention, the glass transition point is 500.
Since it is as low as ℃ or less, it has excellent water resistance, and the inclination of viscosity with respect to temperature is small, it is possible to obtain glass excellent in formability into various shapes.
Claims (2)
ス。 Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ ５〜２５％、 ＺｎＯ＋ＭｇＯ ３５〜５５％、 Ｐ2 Ｏ5 ２０〜３５％、 Ａｌ2 Ｏ3 １〜 ５％、 Ｂ2 Ｏ3 ８〜２０％。1. A low melting glass having the following composition in terms of mol%. Li 2 O + Na 2 O + K 2 O 5~25%, ZnO + MgO 35~55%, P 2 O 5 20~35%, Al 2 O 3 1~ 5%, B 2 O 3 8~20%.
１の低融点ガラス。2. The low melting glass according to claim 1, which has a glass transition point of 500 ° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32586394A JPH08183632A (en) | 1994-12-27 | 1994-12-27 | Low melting point glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32586394A JPH08183632A (en) | 1994-12-27 | 1994-12-27 | Low melting point glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08183632A true JPH08183632A (en) | 1996-07-16 |
Family
ID=18181463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32586394A Pending JPH08183632A (en) | 1994-12-27 | 1994-12-27 | Low melting point glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08183632A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1275622A1 (en) * | 2001-07-13 | 2003-01-15 | Sumita Optical Glass, Inc. | An optical glass for molding |
| EP1338574A1 (en) * | 2002-02-13 | 2003-08-27 | Asahi Glass Co., Ltd. | Glass fiber and thermoplastic resin composition |
| US6809049B2 (en) | 2000-05-25 | 2004-10-26 | Noritake Co., Ltd. | Glass compositions and glass forming materials comprising said compositions |
| EP1555247A1 (en) | 2004-01-16 | 2005-07-20 | Schott AG | Optical glass in particular for press-moulded optical elements |
| US7151064B2 (en) | 2001-10-30 | 2006-12-19 | Sumita Optical Glass, Inc. | Optical glass suitable for mold forming |
| US7425518B2 (en) | 2003-02-19 | 2008-09-16 | Yamato Electronic Co., Ltd. | Lead-free glass material for use in sealing and, sealed article and method for sealing using the same |
| US7585798B2 (en) | 2003-06-27 | 2009-09-08 | Yamato Electronic Co., Ltd. | Lead-free glass material for use in sealing and, sealed article and method for sealing using the same |
-
1994
- 1994-12-27 JP JP32586394A patent/JPH08183632A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6809049B2 (en) | 2000-05-25 | 2004-10-26 | Noritake Co., Ltd. | Glass compositions and glass forming materials comprising said compositions |
| EP1275622A1 (en) * | 2001-07-13 | 2003-01-15 | Sumita Optical Glass, Inc. | An optical glass for molding |
| US6784128B2 (en) | 2001-07-13 | 2004-08-31 | Sumita Optical Glass, Inc. | Optical glass for molding |
| US7151064B2 (en) | 2001-10-30 | 2006-12-19 | Sumita Optical Glass, Inc. | Optical glass suitable for mold forming |
| EP1338574A1 (en) * | 2002-02-13 | 2003-08-27 | Asahi Glass Co., Ltd. | Glass fiber and thermoplastic resin composition |
| US7001858B2 (en) | 2002-02-13 | 2006-02-21 | Asahi Glass Company, Limited | Glass fiber and thermoplastic resin composition |
| US7425518B2 (en) | 2003-02-19 | 2008-09-16 | Yamato Electronic Co., Ltd. | Lead-free glass material for use in sealing and, sealed article and method for sealing using the same |
| US7585798B2 (en) | 2003-06-27 | 2009-09-08 | Yamato Electronic Co., Ltd. | Lead-free glass material for use in sealing and, sealed article and method for sealing using the same |
| EP1555247A1 (en) | 2004-01-16 | 2005-07-20 | Schott AG | Optical glass in particular for press-moulded optical elements |
| US7396787B2 (en) | 2004-01-16 | 2008-07-08 | Schott Ag | Optical glass and process for making precise-pressed optical elements therefrom as well as said optical elements |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0494358B1 (en) | Alkali zinc halophosphate glasses | |
| JP2003095697A (en) | Sealing composition | |
| EP0480188A2 (en) | Sealing materials and glasses | |
| JP5416917B2 (en) | Glass | |
| US4820660A (en) | Light transmitting calcium phosphate glass-ceramics | |
| EP0514639A1 (en) | Zinc phosphate low temperature glasses | |
| US4362819A (en) | Moldable fluoroaluminophosphate glasses | |
| JPH0585490B2 (en) | ||
| JPH11292564A (en) | Tin borophosphate glass and sealing material | |
| CN102015561A (en) | Optical glass | |
| EP0078082B1 (en) | Precision pressed optical components made of glass and glass suitable therefor | |
| JPS60171244A (en) | Optical glass | |
| JP3339647B2 (en) | Lead-free low melting glass and sealing glass composition | |
| JPS58217451A (en) | Niobium oxide-containing formable fluorophosphate glass | |
| JPH06191875A (en) | Phosphate glass of alkaline metal and copper | |
| WO2003072518A1 (en) | Optical glass | |
| EP0048120A1 (en) | Glass envelopes for tungsten-halogen lamps and production thereof | |
| JP3797679B2 (en) | Optical glass | |
| JPH08183632A (en) | Low melting point glass | |
| JPH05262533A (en) | Optical glass | |
| JP3987174B2 (en) | Optical glass for precision press molding | |
| JPH09301735A (en) | Optical glass | |
| JP2004168593A (en) | Optical glass | |
| WO2000009456A1 (en) | Lead-free glasses | |
| RU2169712C1 (en) | High-strength polycrystalline glass and method of its producing |