JPS63129036A - Glass having low melting point - Google Patents
Glass having low melting pointInfo
- Publication number
- JPS63129036A JPS63129036A JP26981186A JP26981186A JPS63129036A JP S63129036 A JPS63129036 A JP S63129036A JP 26981186 A JP26981186 A JP 26981186A JP 26981186 A JP26981186 A JP 26981186A JP S63129036 A JPS63129036 A JP S63129036A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- melting point
- low melting
- low
- metal oxide
- 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
- 239000011521 glass Substances 0.000 title claims abstract description 54
- 238000002844 melting Methods 0.000 title claims abstract description 51
- 230000008018 melting Effects 0.000 title claims abstract description 50
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 239000000075 oxide glass Substances 0.000 claims abstract description 6
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 10
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910003438 thallium oxide Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 9
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 239000005304 optical glass Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- DASUJKKKKGHFBF-UHFFFAOYSA-L thallium(i) carbonate Chemical compound [Tl+].[Tl+].[O-]C([O-])=O DASUJKKKKGHFBF-UHFFFAOYSA-L 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 229910015421 Mo2N Inorganic materials 0.000 description 1
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- -1 cao Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000939 field's metal Inorganic materials 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- WHOPEPSOPUIRQQ-UHFFFAOYSA-N oxoaluminum Chemical compound O1[Al]O[Al]1 WHOPEPSOPUIRQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、低融点ガラスに係り、いわゆる半田ガラスと
して知られ、ガラス、セラミックス或は金属の同種及び
異種接合に用いられると共に、実際には電気・電子部品
の接合や各（１材料の表面被覆或は導電性塗料として広
く用いられる低融点ガラスに関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a low melting point glass, which is known as a so-called solder glass, and is used for bonding the same and different types of glass, ceramics, or metals, and is actually used for joining glass, ceramics, or metals. It relates to low-melting glass that is widely used for bonding electrical and electronic parts, as surface coatings for various materials, and as conductive paints.
［従来の技術とその問題点］
従来、低融点ガラスとしてＰｂＯ−８２０３系ノモノヲ
基本にしｒＰｂｏ−ＺｎＯ−８２０３系（７）モ（Ｆ）
ヤＰｂｏ−８ｉ ０２−８２０３系のもの等が使用され
ている。而して、種々の特性を向上させるために以下の
ような金属酸化物をこれらの低融点ガラス中に含有させ
ている。すなわち、耐水性と電気特性を向上させる観点
から、上述の低融点ガラスにｃａｏ、ｚｎｏ、ＢａＯ等
の二価の金属酸化物を含有させることが行われている。[Conventional technology and its problems] Conventionally, PbO-8203 type glass has been used as a base for low melting point glass, and rPbo-ZnO-8203 type (7) type (F) has been used as a base.
YaPbo-8i 02-8203 series etc. are used. In order to improve various properties, the following metal oxides are contained in these low melting point glasses. That is, from the viewpoint of improving water resistance and electrical properties, divalent metal oxides such as cao, zno, and BaO are incorporated into the above-mentioned low melting point glass.
また、熱膨服係数を大きくする観点からＬｉ２Ｏ、Ｎａ
ｚＯ１Ｋ２０等のアルカリ金属酸化物を含有させること
が行われている。しかし、この場合、低融点化にはほと
んど効果がなく、しかも、電気的性質を著しく劣化させ
る問題がある。また、表面張力を下げ、ガラスの流動性
を良くする観点からＶ２ Ｏ５を含有させることが行わ
れている。このような種々の金属酸化物の含有による特
性改善が行われているが、基本となるガラス形成酸化物
が８２０３であるため、吸水性が著しいと言う問題があ
る。また、Ａｌ２Ｏ２やＳｉＯ２が含有されている場合
には、融点の上昇を避けることができない問題がある。In addition, from the viewpoint of increasing the thermal expansion coefficient, Li2O, Na
Incorporation of alkali metal oxides such as zO1K20 has been carried out. However, in this case, there is a problem in that there is little effect on lowering the melting point, and moreover, the electrical properties are significantly deteriorated. Additionally, V2 O5 is included in the glass from the viewpoint of lowering the surface tension and improving the fluidity of the glass. Although properties have been improved by including various metal oxides, since the basic glass-forming oxide is 8203, there is a problem of significant water absorption. Further, when Al2O2 or SiO2 is contained, there is a problem that the melting point cannot be avoided.
本発明は、かかる点に鑑みてなされたものであり、融点
が極めて低く、かつ、低ガラス転移点および低軟化点で
あると共に、熱膨張率の小さい低融点ガラスを提供する
ものである。The present invention has been made in view of these points, and provides a low melting point glass that has an extremely low melting point, a low glass transition point, a low softening point, and a low coefficient of thermal expansion.
［問題点を解決するための手段１
本発明は、二酸化テルル（ＴｅＯ２）〜酸化タリフラム
（Ｔｆｆ２０）系酸化物ガラスに一価もしくは二価の金
ａｌｉｌ！化物を含有してなることを特徴とする低融点
ガラスである。[Means for Solving the Problems 1] The present invention provides tellurium dioxide (TeO2) to talifram oxide (Tff20) based oxide glass containing monovalent or divalent gold alil! It is a low melting point glass characterized by containing a chemical compound.
ここで、本発明の低融点ガラスの用途は、低融点である
ことから半田ガラス、ガラスシール材にあり、また、誘
電率が３０〜３５とｐｂｏ−８２０３系ガラスの２〜３
倍であることがら１ｌＩＩコンデンサーにあり、また、
比重が大で屈折率が大きいことから光学ガラスにあり、
また、低融点であることからレーザ光照射により容易に
ガラス状態と結晶状態との間の変換ができ３躾ガラスと
して光ディスクのレーザー書き込み材料にあり、更に温
度検知センサー等にあるものである。Here, the low melting point glass of the present invention is used in solder glass and glass sealing materials due to its low melting point, and has a dielectric constant of 30 to 35, which is 2 to 3 of PBO-8203 glass.
It is twice as large as the 1lII capacitor, and
It is found in optical glass because of its high specific gravity and high refractive index.
In addition, since it has a low melting point, it can be easily converted between a glass state and a crystalline state by laser beam irradiation, and is used as a material for laser writing of optical disks, as well as in temperature detection sensors.
また、本発明における一価の金属゛酸化物は、Ｌ １２
０ＳＮａ２０．に２０（７）少なくともイスレか一種で
あり、二価の金Ｔ！ｈ酸化物は、ＣａＯｌＭＱＯ，Ｚｎ
Ｏ，ＳｒＯ，ＣｄＯ，ＢａＯ１ＰｂＯの少なくともいず
れか一種である。Furthermore, the monovalent metal oxide in the present invention is L 12
0SNa20. 20 (7) is at least one kind of isle and bivalent gold T! h oxides are CaOlMQO, Zn
It is at least one of O, SrO, CdO, and BaO1PbO.
また、二酸化テルル（ＴｅＯ２）、 酸化タリ・ラム（
ＴＱ２０）及び−画もしくは二価の金ａｒＩｉ化物の組
成比は、金ａｍ化物をＭＯとすると、ＸＭＯ−２０ＴＱ
２０−（８０−Ｘ）Ｔｅ０２の式を満足するように設定
する。ここで、Ｘ、２０及び８０の単位はｍ０１％であ
る。例えば、ＭＯがＰｂＯの場合Ｘの値は１〜２０に設
定し、ＭＯがＺｎＯの場合は１〜１５に、ＭＯがＭａＯ
ｌＢａｄ、ＣｄＯの場合Ｘの値は１〜１０に、ＭＯがＳ
ｒＯの場合Ｘの値は１〜５に、夫々設定する。このよう
な範囲に設定するのは、所定のガラス状態を得るためで
ある。In addition, tellurium dioxide (TeO2), tali-rum oxide (
The composition ratio of TQ20) and divalent gold arIi compound is XMO-20TQ
20-(80-X)Te02 is set to satisfy the equation. Here, the units of X, 20 and 80 are m01%. For example, if the MO is PbO, set the value of X to 1 to 20, if the MO is ZnO, set it to 1 to 15, and if the MO is MaO
For lBad, CdO, the value of X is 1 to 10, and MO is S.
In the case of rO, the value of X is set to 1 to 5, respectively. The reason for setting it in such a range is to obtain a predetermined glass state.
而して、第１図の示す誘電率（Ｓｒ）と各成分のｍ０１
％の特性図から明らかなように、ＭＯの添加ｎｏｔ％の
増加に伴いＰｂＯ系では誘電率のＩＵ ハ上昇シテオリ
、２０ＰｂＯ−２０Ｔｎ２０−６０Ｔｅ０２ ｒ５ｒ−
３！５．３．２０ＰｂＯ−２５ＷＯｉ−５５ＴｅＯｚで
Ｓｒ−３８，７という各県での夫々最高値を示している
。その反面他の〜１０の添加では、誘電率の値は、直線
的に減少し、その中かでもＭｏ２Ｎ加の場合は、最高の
減少率を示し、ｌ Ｑｍｏ １％ＭＱＯの場合Ｔｌ１２
０組成でＳｒ−３３，５から２５．９（減少率２２．７
％）に、ＷＯ３組成でＳｒ−３５，３ｈｋら２９．５（
減少率１６．４％）と大きく減少している。Therefore, the dielectric constant (Sr) shown in Fig. 1 and m01 of each component
As is clear from the characteristic diagram of 20PbO-20Tn20-60Te02 r5r-
3!5.3.20PbO-25WOi-55TeOz and Sr-38 and 7, respectively, are the highest values in each prefecture. On the other hand, for the other ~10 additions, the dielectric constant value decreases linearly, among which the addition of Mo2N shows the highest rate of decrease, and in the case of lQmo 1%MQO, Tl12
0 composition, Sr-33.5 to 25.9 (reduction rate 22.7
%), Sr-35,3hk et al.29.5(
This is a significant decrease (decrease rate of 16.4%).
また、第２因は、密度と各成分のｍ０１％の関係を示し
ている。Ｐｂｏのような重い元素を添加すれば当然密度
は大きくなり、ＰｂＯを添加した本発明の低融点ガラス
の場合、６．３〜７．０と極めて高い値となっている。Moreover, the second factor shows the relationship between density and m01% of each component. Naturally, if a heavy element such as Pbo is added, the density increases, and in the case of the low melting point glass of the present invention to which PbO is added, it has an extremely high value of 6.3 to 7.0.
このように密度が高いので屈折率も大きくなり、光学ガ
ラスとしての用途に適するものである。Since the density is thus high, the refractive index is also high, making it suitable for use as optical glass.
また、本発明の低融点ガラスは、第３図に示す融点と各
ＭＯの添加ｍｏ１％の特性図から明らかなように、添加
ＭＯの融点に左右されずに低融点となっていることが分
る。すなわち、第３図は２０Ｔｊ２ｒＯ−８０ＴｅＯ２
（液相線温度＜ＴＬ＞−３３７℃）におけるＴｅ０ｚを
、所定ｍｏ１％づつ各種二価元素酸化物（ＭＯ）で置換
したときの液相ＰＪ温度の変化を示している。同図から
明らかなように５ｒＯ（融点−２４３０℃、以下単に２
４３０℃のように記す）、Ｃｄ０（＞９００℃）、Ｂａ
ｄ（１８２０℃）の添加により液相線温度は大きく増加
する。Ｍｇ０（２８００℃）、ＺｎＯ（＞１８００℃）
の添加では５ｍ０１％でわずかに極大を示しそのＩＩや
かに減少している。また、ＰｂＯ（８９０℃）の添加で
はｉ ｏｍｏ ＋％で極大であり、１５ｍｏ １％で（
へ小値をとなっている。このように各ＭＯの融点を比較
しても分るように、その大小が２０Ｔａ２Ｏ−８０Ｔｅ
Ｏ２に及ぼす一般的な傾向はみられないが、必ずし５も
添加ＭＯの融点が高くても本発明の低融点ガラスの融点
は高くなっていない。例えばＭｑｏ、ＺｎＯ，ＰｂＯ添
加の組成では、全置換範囲で液相線温度が４００℃以下
と言う低い値を示している。特にＭＱＯ，ＺｎＯは、そ
の融点が穫めて高いにも拘らず、置換凹が多くなっても
あまり液相線温度を上昇させることがなく、低い液相線
温度の値を保っている。Furthermore, as is clear from the characteristic diagram of the melting point and the added mo1% of each MO shown in Figure 3, the low melting point glass of the present invention has a low melting point independent of the melting point of the added MO. Ru. That is, Fig. 3 shows 20Tj2rO-80TeO2
It shows the change in liquid phase PJ temperature when Te0z at (liquidus temperature <TL> -337° C.) is replaced with various divalent element oxides (MO) at a predetermined mole % of 1%. As is clear from the figure, 5rO (melting point -2430℃, hereinafter simply 2
430℃), Cd0 (>900℃), Ba
The addition of d (1820°C) significantly increases the liquidus temperature. Mg0 (2800℃), ZnO (>1800℃)
In the case of addition of , it shows a slight maximum at 5m01% and then decreases rapidly. In addition, when adding PbO (890°C), it reaches a maximum at i omo +%, and at 15mo 1% (
It has become a small value. As can be seen by comparing the melting points of each MO, the magnitude is 20Ta2O-80Te.
Although there is no general tendency to affect O2, the melting point of the low melting point glass of the present invention does not necessarily increase even if the melting point of the added MO is as high as 5. For example, in a composition with additions of Mqo, ZnO, and PbO, the liquidus temperature shows a low value of 400° C. or less over the entire substitution range. In particular, MQO and ZnO, although their melting points are extremely high, do not increase the liquidus temperature much even when the number of substitution cavities increases, and maintain a low liquidus temperature value.
また、本発明の低融点ガラスは、次ぎのようにして製造
することができる。低融点ガラスを製造するための試薬
としては、ＴｅＯ２（９９％）を始め各種の所定の酸化
物試薬を使用することができる。先ず、各試薬を目的の
組成に秤量混合した後、白金ルツボを用いて電気炉中で
溶融し、短時間の保持と強い撹拌後、リング状のステン
レス金型に流し出し、ガラス試料とする。しかし、この
ままの状態では試料に内部応力歪みが残留していて破裂
の可能性があるので、予めｆｖｌｏ以下の低温に加熱し
た別の電気炉に直ちに投入し、応力除去焼鈍しを行なう
。得られたガラスは全て淡い〜濃黄色を呈している。Moreover, the low melting point glass of the present invention can be manufactured as follows. As a reagent for producing low melting point glass, various predetermined oxide reagents including TeO2 (99%) can be used. First, each reagent is weighed and mixed to the desired composition, then melted in an electric furnace using a platinum crucible, held for a short time and stirred strongly, and then poured into a ring-shaped stainless steel mold to form a glass sample. However, if left as is, internal stress strain remains in the sample and there is a possibility of it bursting, so it is immediately placed in another electric furnace preheated to a low temperature below fvlo to perform stress relief annealing. All of the obtained glasses exhibit a pale to deep yellow color.
ところで、ＴｅＯ２（ｎ点＝７２５°Ｃ）自体は、比較
的蒸発し易く、融点以上の極度の高温での溶融は、揮発
による組成変動が十分に考えられる。By the way, TeO2 (n point = 725°C) itself is relatively easy to evaporate, and melting at an extremely high temperature above the melting point is highly likely to result in compositional fluctuations due to volatilization.
しかし、本発明の低融点ガラスの場合、予め行なった質
量分析によると、融点＋５０℃〜１５０℃にて試料を溶
融させても全く組成変動は見られないことが確認されて
いる。従って、このような融点温度の範囲で試料の溶解
を行なう。However, in the case of the low melting point glass of the present invention, according to mass spectrometry conducted in advance, it has been confirmed that no compositional change is observed even when the sample is melted at a temperature of +50°C to 150°C. Therefore, the sample is melted within such a melting point temperature range.
［作用］
本発明にかかる低１点ガラスによれば、二酸化テルル（
ＴｅＯ２）〜酸化タリウム（Ｔり２０）系酸化物ガラス
に、−圃の金属酸化物としてＬ ｉ ２０％Ｎａ２０Ｓ
Ｋ２０（ｌＶｌ：ｔ＜と６いずれか一種を、また、二価
の金ｔｉ１Ｍ化物としてＣａＯｌＭｏｂ、ＺｎＯ，Ｓｒ
Ｏ，ＣｄＯ，ＢａＯ１ＰｂＯの少なくともいずれか一種
を含有させているので、融点、ガラス転移点及び軟化点
のいずれもが低く、しかも、熱膨張係数（α）を２．１
５ＸＩＯ４１，、’ｄｅｇ以下に下げることができる。[Function] According to the low point glass according to the present invention, tellurium dioxide (
TeO2) to thallium oxide (T20)-based oxide glass, Li 20% Na20S as a field metal oxide
K20 (lVl:t
Since it contains at least one of O, CdO, and BaO1PbO, the melting point, glass transition point, and softening point are all low, and the coefficient of thermal expansion (α) is 2.1.
It can be lowered to 5XIO41,,'deg or less.
更に含有させる前記金属酸化物の種類、量を調整するこ
とにより、被封止材料とのマツチングも制ＤＯできるも
のでる。また、誘電率（Ｓｒ）は、３０以上（測定周波
数１００ＫＨ２）であり、高誘電率ガラスとして使用で
きるものである。また、密度（ρ）は、６．０〜７．０
（９／ｃｍ３）を越すものであり、高屈折率を有して
光学ガラスとして利用できるものである。Furthermore, by adjusting the type and amount of the metal oxide to be contained, it is possible to control DO matching with the material to be sealed. Further, the dielectric constant (Sr) is 30 or more (measurement frequency 100KH2), and it can be used as a high dielectric constant glass. In addition, the density (ρ) is 6.0 to 7.0
(9/cm3), has a high refractive index, and can be used as an optical glass.
［実施例］
以下、本発明の実施例について図面を参照して説明する
。[Examples] Examples of the present invention will be described below with reference to the drawings.
市販の酸化テルル、酸化鉛、炭酸タリウムの各試薬を酸
化テルル５０〜９８ｍｏ１％、酸化鉛Ｏ〜４５ｍ０１％
、炭酸タリウムＯ〜４５ｍ０１％の組成範囲内で精秤、
混合した。ここで、酸化タリウムの試薬として炭酸タリ
ウム（Ｔｎ２ＣＯ２）を使用したのは、これを加熱する
ことによって炭酸ガスをとばし、酸化タリウムを得るか
らである。Commercially available tellurium oxide, lead oxide, and thallium carbonate reagents were mixed with tellurium oxide 50 to 98 mo1% and lead oxide O to 45 mo1%.
, accurately weighed within the composition range of thallium carbonate O ~ 45m01%,
Mixed. Here, thallium carbonate (Tn2CO2) was used as a reagent for thallium oxide because by heating it, carbon dioxide gas is evaporated and thallium oxide is obtained.
次ぎに、混合した試薬を白金ルツボに入れ、電気炉内で
加熱、溶融した。加熱温度は、ｒｌｉ点よりも５０〜１
００℃高い温度とした。加熱温度は、必要に応じて２０
０〜２５０℃高くしても良い。試薬が溶融した後、短時
間の保持と撹拌を行なった。Next, the mixed reagents were placed in a platinum crucible and heated and melted in an electric furnace. The heating temperature is 50~1 higher than the rli point.
The temperature was set to 00°C higher. The heating temperature can be adjusted to 20°C as necessary.
The temperature may be increased by 0 to 250°C. After the reagents were melted, a brief hold and stirring was performed.
これによって均一な融液とし、金型（白金皿でも良い）
に流しだし急冷した。このようにして６０Ｔｆｆｉ２０
−２５ＰｂＯ−１５ＴｅＯ２からなる低融点ガラスを製
造した。ここで、６０は、Ｔ（１２０の低融点ガラス中
に占るｍｏ１％であり、２５は、ＰｂＯのｎｏｔ％、１
５は、ＴｅＯ２のｍｏ１％である。この低融点ガラスの
液相Ｉ！ｊ温度（ＴＬ−２８０℃）、ガラス転移点（Ｔ
Ｏ−１４５℃）、結晶化温度（ＴＣ−１７３℃）、誘電
率（Ｓｒ−３３，１）、密度（、ｃ＋−７，００）及び
熱膨張係数（α−２，５０Ｘ１０ろ）を調べたところ以
下の通りであった。This makes the melt uniform, and molds it into a mold (a platinum plate is fine).
Pour it into the water and cool it down quickly. In this way 60Tffi20
A low melting point glass consisting of -25PbO-15TeO2 was produced. Here, 60 is mo1% in the low melting point glass of T (120), 25 is not% of PbO, 1
5 is mo1% of TeO2. Liquid phase I of this low melting point glass! jTemperature (TL-280℃), glass transition point (T
O-145℃), crystallization temperature (TC-173℃), dielectric constant (Sr-33,1), density (c+-7,00) and thermal expansion coefficient (α-2,50X10) were investigated. The situation was as follows.
先ず、第４図は、この低融点ガラスの等液相線湯度特性
を示している。図中ＸＸＸで囲まれた領域は、ガラス化
範囲を示している。この領域から図中左下に向かう程、
すなわち、１℃２０゜ＰｂＯのｍ０１％が増加する方向
に従って、また、等Ｔｅ０２ｍ１％（図中左右方向）で
はＴａ２Ｏのｍ０１％が多い程、液相ｍ温度は減少して
いることが分る。そして、ガラス化範囲境界付近の３０
ＴＭ２０−５ＰｂＯ−６５ＴｅＯｚ、２５Ｔρ２０−１
５ＰｂＯ−６０ＴｅＯ２では、それぞれ２９３℃、２８
１℃と遂に３００℃を下回り、酸化物系ガラスとしては
特別低い値が得られている。First, FIG. 4 shows the isoliquidus temperature characteristics of this low melting point glass. The area surrounded by XXX in the figure indicates the vitrification range. From this area towards the bottom left of the figure,
That is, it can be seen that the liquidus m temperature decreases as m01% of Ta2O increases in the direction in which m01% of PbO increases at 1° C. 20°, and at equal Te02m1% (left and right direction in the figure). And 30 near the vitrification range boundary
TM20-5PbO-65TeOz, 25Tρ20-1
For 5PbO-60TeO2, 293℃ and 28℃, respectively.
1°C, which is finally below 300°C, which is an especially low value for an oxide glass.
次ぎに、第５図はこの低融点ガラスの等ガラス転移点の
特性を示し、第６図は、等結晶化温度特）生を夫々示し
ている。これらの特性の傾向も前述の等液相１１温度特
性と同様であり、Ｔｌ２Ｏ。Next, FIG. 5 shows the characteristics of the iso-glass transition point of this low melting point glass, and FIG. 6 shows the characteristics of the iso-crystallization temperature. The trends of these characteristics are also similar to the temperature characteristics of the isoliquid phase 11 described above, and Tl2O.
ＰｂＯのｍ０１％が増加するにつれ、また、等ＴｅＱ２
ｍＯ１％では、Ｔｌ２Ｏのｍ０１％が多い程、ガラス転
移点及び結晶化温度は低下していることが分る。また、
ガラス転移点については、Ｔｇ＜１５０℃の範囲が、Ｔ
ａ２Ｏの高濃度側でｖＡ測されている。As m01% of PbO increases, also the same TeQ2
It can be seen that at mO1%, the glass transition point and crystallization temperature decrease as the m01% of Tl2O increases. Also,
Regarding the glass transition point, the range of Tg<150°C is T
vA is measured on the high concentration side of a2O.
次ぎに、第７図は、この低融点ガラスの等誘電率ｔ１性
（ａｔ１００Ｈ２）を示している。誘電率の変化は、Ｐ
ｂＯの含有伍が増加するに従って、つまり図中では左か
ら右へ行くに従って誘電率の値が増加していることが分
る。この低融点ガラスの誘電率の値は、３２〜３６と従
来の低融点ガラスとして用いられている８２０３系のも
のに比べて２〜３倍以上の高い値であることが分る。つ
まり、このＴｌ２Ｏ−ＰｂＯ−ＴｅＯ２系のものは、低
融点高誘電率のガラスとみなすことができ、複合機能性
を生かしたニーズに対応できるものと考えられる。Next, FIG. 7 shows the isoelectric constant t1 property (at100H2) of this low melting point glass. The change in dielectric constant is P
It can be seen that the dielectric constant value increases as the content of bO increases, that is, as one goes from left to right in the figure. It can be seen that the dielectric constant value of this low melting point glass is 32 to 36, which is 2 to 3 times higher than that of the 8203 series glass used as a conventional low melting point glass. In other words, this Tl2O--PbO--TeO2-based glass can be regarded as a glass with a low melting point and high dielectric constant, and is considered to be able to meet the needs of making use of its composite functionality.
第８図は、この低融点ガラスの密度の変化を示している
。密度は、Ｔｌ２Ｏ，ＰｂＯのｍ０１％が増加するにつ
れ増す傾向にある。そして、Ｔａ２Ｏ、ＰｂＯの高濃度
領域では、ρが７．０（９／ｃｍ３）程度の高密度を持
ったガラスか領域が存在し、これらはまた高屈折率を示
すと考えられ、光学ガラスとして有用なものである。FIG. 8 shows the change in density of this low melting point glass. The density tends to increase as m01% of Tl2O and PbO increases. In the high concentration region of Ta2O and PbO, there is a glass region with a high density of ρ of about 7.0 (9/cm3), which is also thought to exhibit a high refractive index, and is used as an optical glass. It is useful.
［発明の効果］
以上説明した如く、本発明にかかる低融点ガラスによれ
ば、融点が極めて低く、かつ、低ガラス転移点および低
軟化点であると共に、熱膨張率の小さい特性を有するも
のである。[Effects of the Invention] As explained above, the low melting point glass of the present invention has an extremely low melting point, a low glass transition point, a low softening point, and a low coefficient of thermal expansion. be.
第１図は、誘電率と添加成分のｍ０１％との関係を示す
特性図、第２図は、密度と添加成分のｍ０１％との関係
を示す特性図、第３図は、融点と添加成分のｍ０１％と
の関係を示す特性図、第４図は、実施例の低融点ガラス
の等液相温度特性を示す特性図、第５図は、同の低融点
ガラスの等ガラス転移点の特性を示す特性図、第６図は
、同の低融点ガラスの等結晶化温度特性を示す特性図、
第７図は、同の低融点ガラスの等誘電率特性を示す特性
図、第８図は、同の低融点ガラスの密度の変化を示す特
性図である。
出願人代理人 弁理士 鈴江武彦
’Ａ２ＦＯＡ ’ｉ ａ ｍｏ９ ％ （Ｘ ）第３
図
適 み
Ｄｅｎｓｉｔｙ、ア （ｇ／ｃｍ３）
−＠ へ穿
Ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ 、εｒ （
１００ｋＨｚ ）１０ｏＴｅＯ２
第４図
第５図
＋０ＯＴｅＯｚ
第６図
第７図Figure 1 is a characteristic diagram showing the relationship between dielectric constant and m01% of additive components, Figure 2 is a characteristic diagram showing the relationship between density and m01% of additive components, and Figure 3 is a characteristic diagram showing the relationship between density and m01% of additive components. Figure 4 is a characteristic diagram showing the iso-liquidus temperature characteristics of the low melting point glass of the example, and Figure 5 is the characteristic of the equal glass transition point of the same low melting point glass. FIG. 6 is a characteristic diagram showing the equal crystallization temperature characteristics of the same low melting point glass.
FIG. 7 is a characteristic diagram showing the isoelectric constant characteristics of the same low melting point glass, and FIG. 8 is a characteristic diagram showing changes in density of the same low melting point glass. Applicant's representative Patent attorney Takehiko Suzue 'A2FOA'i a mo9% (X) No. 3
Dielectric constant, εr (
100kHz) 10oTeO2 Fig. 4 Fig. 5 +0OTeOz Fig. 6 Fig. 7
Claims (2)
ｌ２＿Ｏ）系酸化物ガラスに一価もしくは二価の金属酸
化物を含有してなることを特徴とする低融点ガラス。(1) Tellurium dioxide (TeO_2) ~ thallium oxide (T
12_O)-based oxide glass containing a monovalent or divalent metal oxide.
Ｋ＿２Ｏの少なくともいずれか一種であり、二価の金属
酸化物が、ＣａＯ、ＭｇＯ、ＺｎＯ、ＳｒＯ、ＣｄＯ、
ＢａＯ、ＰｂＯの少なくともいずれか一種であることを
特徴とする特許請求の範囲第１項記載の低融点ガラス。(2) The monovalent metal oxide is Li_2O, Na_2O,
K_2O, and the divalent metal oxide is CaO, MgO, ZnO, SrO, CdO,
The low melting point glass according to claim 1, characterized in that it is at least one of BaO and PbO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26981186A JPS63129036A (en) | 1986-11-14 | 1986-11-14 | Glass having low melting point |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26981186A JPS63129036A (en) | 1986-11-14 | 1986-11-14 | Glass having low melting point |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63129036A true JPS63129036A (en) | 1988-06-01 |
Family
ID=17477499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26981186A Pending JPS63129036A (en) | 1986-11-14 | 1986-11-14 | Glass having low melting point |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63129036A (en) |
-
1986
- 1986-11-14 JP JP26981186A patent/JPS63129036A/en active Pending
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