JPH07126037A - Glass for bonding and sealing - Google Patents
Glass for bonding and sealingInfo
- Publication number
- JPH07126037A JPH07126037A JP27145393A JP27145393A JPH07126037A JP H07126037 A JPH07126037 A JP H07126037A JP 27145393 A JP27145393 A JP 27145393A JP 27145393 A JP27145393 A JP 27145393A JP H07126037 A JPH07126037 A JP H07126037A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- pbo
- sealing
- zno
- bao
- 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.)
- Granted
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
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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)
- Magnetic Heads (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は接着・封止用ガラスにか
かり、特に磁気ヘッドの封着に好適な接着・封止用ガラ
スに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive / sealing glass, and more particularly to an adhesive / sealing glass suitable for sealing a magnetic head.
【０００２】[0002]
【従来技術とその問題点】接着・封止用ガラスとしてPb
O 系、特に PbO−B2O3系、 PbO−B2O3−SiO2系、PbO −
B2O3−ZnO 系、 PbO−B2O3−SiO2−Al2O3 系等の低融点
ガラスが広く採用されることはよく知られるところであ
る。[Prior art and its problems] Pb as a glass for adhesion and sealing
O system, in particular PbO-B 2 O 3 -based, PbO-B 2 O 3 -SiO 2 system, PbO -
It is well known that low melting glass such as B 2 O 3 —ZnO type and PbO—B 2 O 3 —SiO 2 —Al 2 O 3 type is widely adopted.
【０００３】しかし上記低融点ガラスは、金属、セラミ
ックの接着・封止用としては勿論、磁気ヘッド封着用と
しては耐水、耐薬品性が不充分で、被接着材料とも反応
し被接着材料を変質し易い、ガラスの硬度が低い等の難
点があり、またPbO を多量に含有するため、加熱加工作
業中に有害なPbO の揮散により作業環境を悪化させ、あ
るいは水と接触するとPbイオンが溶出し公害問題を誘起
する等、問題点も多い。However, the low melting point glass has insufficient water resistance and chemical resistance not only for adhering and sealing metals and ceramics but also for magnetic head sealing, and reacts with the adhered material to alter the adhered material. However, since it contains a large amount of PbO, it deteriorates the working environment due to harmful PbO volatilization during heat processing, or Pb ions elute when it comes into contact with water. There are many problems such as inducing pollution problems.
【０００４】これに対し、特開昭61−36135 号、特開昭
61−111935号には、V2O5−P2O5系にTeO2等を含み、磁気
ヘッドの接着・封止用に供する低融点ガラスが開示され
ている。しかし耐水・耐薬品性や硬度等に難点があり、
またV2O5自体熱安定性に劣り、着色不透明になり易い等
の問題もある。On the other hand, Japanese Patent Laid-Open Nos. 61-36135 and 61-36135
No. 61-111935 discloses a low melting point glass containing TeO 2 and the like in the V 2 O 5 -P 2 O 5 system and used for adhesion and sealing of a magnetic head. However, there are drawbacks in water resistance, chemical resistance, hardness, etc.
In addition, V 2 O 5 itself has poor thermal stability and tends to become colored and opaque.
【０００５】他方、特開昭62−128946号にはTeO2−P2O5
−PbO −(ZnO＋Li2O) 系に各種任意成分を含み、光学材
料として好適で低融点ガラスでもあるテルライトガラス
が開示されている。しかし磁気ヘッド封着用ガラスとし
ての開示、示唆はしてない。またPbO が多いケースにお
いては前記同様の公害上の問題が危惧される。さらに、
開示実施例は耐水・耐薬品性に劣っていたり、硬度が不
充分であったりする等、磁気ヘッドの接着・封止用とし
ては満足できるものではない。On the other hand, in Japanese Patent Laid-Open No. 62-128946, TeO 2 -P 2 O 5
-PbO - includes various optional ingredients (ZnO + Li 2 O) system, tellurite glass which is also a suitable low-melting glass as an optical material is disclosed. However, it is not disclosed or suggested as a glass for magnetic head sealing. Also, in the case of a large amount of PbO, the same pollution problem as above is feared. further,
The disclosed examples are not satisfactory for adhesion / sealing of magnetic heads because of poor water resistance / chemical resistance, insufficient hardness, and the like.
【０００６】なお磁気ヘッドの接着・封止用ガラスにお
いては、熱膨張率が磁性体のそれとよく適合しているこ
と、作業温度が磁性体の特性を損ねない程度の温度域で
あること、耐水、耐薬品性に優れること、高い硬度を有
すること、機械的強度が高いこと、透視性を有するこ
と、磁性体との相互反応がないこと、磁気的絶縁性に優
れること等が要求される。これらファクターは二律背反
的な要素もあっていずれをも十二分に満足させるのは困
難であるが、本発明は多くのファクターにおいて適合
し、あるいは公知のガラスに比べ優れた接着・封止用ガ
ラスを提供するものである。In the glass for bonding / sealing the magnetic head, the coefficient of thermal expansion is well matched to that of the magnetic material, the working temperature is in a temperature range that does not impair the characteristics of the magnetic material, and the water resistance is high. It is required to have excellent chemical resistance, high hardness, high mechanical strength, transparency, no mutual reaction with magnetic materials, and excellent magnetic insulation. It is difficult to satisfy all of these factors because there are trade-off factors, but the present invention is suitable for many factors or is superior to known glass for bonding and sealing glass. Is provided.
【０００７】[0007]
【問題点を解決するための手段】本発明は、 mol％表示
で、P2O5 20 〜60％、TeO2 10 〜50％、PbO 0 〜10％、
ZnO 0 〜20％、BaO 0 〜20％、Li2O 0〜20％、Bi2O3 0
〜10％の範囲で、PbO 、ZnO 、BaO 、Li2OおよびBi2O3
の和が25〜40％である接着・封止用ガラス、前記接着・
封止用ガラスにおいて、更に 0≦Pb＜1 ％であること、
から構成される。[Means for Solving the Problems] The present invention, in mol% display, P 2 O 5 20 to 60%, TeO 2 10 to 50%, PbO 0 to 10%,
ZnO 0-20%, BaO 0-20%, Li 2 O 0-20%, Bi 2 O 30
In the range of up to 10%, PbO, ZnO, BaO, Li 2 O and Bi 2 O 3
Glass for adhesion / sealing, whose sum is 25-40%,
In the sealing glass, 0 ≦ Pb <1%,
Composed of.
【０００８】なお、特に磁気ヘッドの接着・封止用ガラ
スにおいては、熱膨張率が磁性体の100 〜140 ／℃程度
の熱膨張率とよく適合していること、作業温度が磁性体
の特性を損ねない 500〜 600℃程度であること、耐水、
耐薬品性に優れること、比較的高い硬度を有すること、
機械的強度が高いこと、透視性を有すること、磁性体と
の相互反応がないこと、磁気的絶縁性に優れること等が
要求されるが、本発明の接着・封止用ガラスは多くのフ
ァクターにおいて適合し、あるいは公知のガラスに比べ
優れた特性を示すものである。Particularly, in the glass for bonding and sealing magnetic heads, the coefficient of thermal expansion is well matched with the coefficient of thermal expansion of about 100 to 140 / ° C. of the magnetic material, and the working temperature is characteristic of the magnetic material. It is about 500-600 ℃, water resistance,
Excellent chemical resistance, relatively high hardness,
High mechanical strength, transparency, no interaction with magnetic materials, excellent magnetic insulation, etc. are required, but the glass for bonding and sealing of the present invention has many factors. In the above, it is suitable, or exhibits excellent characteristics as compared with known glasses.
【０００９】本成分系において、P2O5は mol％で20〜60
％の範囲においてガラス形成が良好で安定しており、他
方60％を越えるとガラスの耐水、耐薬品性を悪化させ、
また20％未満であるとガラス形成を不安定にする。TeO2
は同様に10〜50％の範囲においてガラス形成が良好で安
定しており、50％を越えるとガラス形成を不安定にし、
ガラスの硬度を低下させ、10％未満ではガラスの耐水性
を悪化させる等不具合が生ずる。In this component system, P 2 O 5 is 20 to 60 mol%.
%, The glass formation is good and stable, while when it exceeds 60%, the water resistance and chemical resistance of the glass deteriorate,
Further, if it is less than 20%, the glass formation becomes unstable. TeO 2
Similarly, glass formation is good and stable in the range of 10 to 50%, and when it exceeds 50%, glass formation becomes unstable,
If the hardness of the glass is reduced, and if it is less than 10%, problems such as deterioration of water resistance of the glass occur.
【００１０】PbO は安定した低融点ガラスを得るうえで
きわめて有用であるが、ガラスの硬度を低下させ、特に
10％を越えると被接着体との相互反応を生じ易く、また
ガラスの耐水性を劣化させ、更に水への溶出による公害
問題も大きいので10％以下とし、好ましくは 1％未満と
すべきである。PbO is extremely useful for obtaining a stable low-melting glass, but it lowers the hardness of the glass,
If it exceeds 10%, mutual reaction with the adherend tends to occur, the water resistance of the glass is deteriorated, and the pollution problem due to elution into water is large, so it should be 10% or less, preferably less than 1%. is there.
【００１１】BaO はPbO の前記欠点を補ううえで重要で
あり、特にPbO が僅少またはPbO を含有しないケースに
おいては 5％以上の導入が好ましい。なお、20％を越え
ると耐失透性が悪化する。BaO is important for compensating the above-mentioned drawbacks of PbO, and it is preferable to introduce 5% or more in the case where PbO is very small or does not contain PbO. If it exceeds 20%, the devitrification resistance deteriorates.
【００１２】Li2Oは溶融性を改善し安定したガラスを
得、ガラスの耐水性を向上するうえで有効であるが、20
％を越えると耐水性を悪化させ、接着に際して被接着体
との反応も起生し易いので20％以下とする。なお 5〜20
％の範囲で導入することが望ましい。Li 2 O is effective in improving the meltability and obtaining a stable glass and improving the water resistance of the glass.
If it exceeds 20%, the water resistance is deteriorated and a reaction with the adherend is likely to occur during adhesion, so the content is made 20% or less. 5 to 20
It is desirable to introduce in the range of%.
【００１３】ZnO もガラスの安定性、耐水性向上に有効
であるが、20％を越えると失透が生じ易く、ガラス形成
も困難となる。Bi2O3 はガラスの耐水性、硬度向上に有
効であるが、10％を越えるとガラス形成を不安定とし、
ガラスを製造する際の溶融・成形性に劣る。ZnO is also effective in improving the stability and water resistance of glass, but if it exceeds 20%, devitrification is likely to occur and glass formation becomes difficult. Bi 2 O 3 is effective in improving the water resistance and hardness of glass, but if it exceeds 10%, glass formation becomes unstable,
Poor meltability and moldability when producing glass.
【００１４】さらに、PbO 、ZnO 、BaO 、Li2OおよびBi
2O3 の和が40％を越えると、相対的にガラス形成成分で
あるP2O5およびTiO2が過少となりガラス形成が困難とな
り、他方25％未満ではガラスの耐水性、硬度、あるいは
ガラス製造時の均質性、清澄性を含めた易溶性において
劣る。Furthermore, PbO, ZnO, BaO, Li 2 O and Bi
If the sum of 2 O 3 exceeds 40%, the glass forming components P 2 O 5 and TiO 2 are relatively small, and it becomes difficult to form glass. On the other hand, if the sum is less than 25%, the water resistance, hardness, or glass It is inferior in homogeneity at the time of production and easy solubility including clarity.
【００１５】なお、硬度、耐水性等を向上するために例
えばSiO2、TiO2、Al2O3 、SrO 等を、ガラスの安定性を
向上するためにB2O3、V2O5等を、溶融性の改善のために
Na2O、K2O 、MgO 、CaO 等を、あるいは熱膨張率を調整
するために前掲した成分を 5％以下程度の範囲で適宜導
入することができる。It should be noted that, for example, SiO 2 , TiO 2 , Al 2 O 3 and SrO are used to improve hardness and water resistance, and B 2 O 3 and V 2 O 5 are used to improve glass stability. To improve the meltability
Na 2 O, K 2 O, MgO, CaO, or the like, or the above-mentioned components for adjusting the coefficient of thermal expansion can be appropriately introduced in a range of about 5% or less.
【００１６】[0016]
【実施例】以下に実施例を例示し本発明を説明する。 〔試料調整〕P2O5源としてオルトリン酸、TeO2源として
二酸化テルル、PbO 源として酸化鉛、ZnO 源として亜鉛
華、BaO 源として炭酸バリウム、Li2O源として炭酸リチ
ウム、Bi2O3 源として酸化ビスマス、Al2O3 源として水
酸化アルミニウム、B2O3源としてほう酸を使用し、ガラ
ス組成換算で表１に示す目標割合で調合し、アルミナ坩
堝に充填後、坩堝に蓋をし、予め1050℃ないし1200℃の
適宜温度に加熱保持した電気炉内にセットし20〜30分間
溶融した。得られた溶融物をいったんカーボンプレート
上に流し出し、さらにこれを電気炉内で徐冷してガラス
試料を得た。EXAMPLES The present invention will be described below with reference to examples. [Sample preparation] Orthophosphoric acid as a P 2 O 5 source, Tellurium dioxide as a TeO 2 source, Lead oxide as a PbO source, Zinc white as a ZnO source, Barium carbonate as a BaO source, Lithium carbonate as a Li 2 O source, Bi 2 O 3 Using bismuth oxide as a source, aluminum hydroxide as an Al 2 O 3 source, and boric acid as a B 2 O 3 source, and compounding at a target ratio shown in Table 1 in terms of glass composition, filling the alumina crucible, and then capping the crucible. Then, it was set in an electric furnace which was previously heated and maintained at an appropriate temperature of 1050 ° C to 1200 ° C and melted for 20 to 30 minutes. The obtained melt was once poured onto a carbon plate and then gradually cooled in an electric furnace to obtain a glass sample.
【００１７】各成分組成を表１に示す。The composition of each component is shown in Table 1.
【００１８】[0018]
【表１】 [Table 1]
【００１９】〔物性測定〕各試料を、シリカガラスを標
準物質とする示差熱膨張計により、昇温速度 5℃／min
の条件で熱膨張を測定し、30〜300 ℃の平均熱膨張率、
ガラス転移点、屈伏点を求めた。別にビッカース微小硬
度計によりビッカース硬度を測定し、また95℃の蒸留水
に20時間浸漬して重量減少率 (耐水性) を求めた。[Measurement of physical properties] Each sample was measured with a differential thermal dilatometer using silica glass as a standard substance at a heating rate of 5 ° C./min.
Measure the thermal expansion under the conditions of, the average coefficient of thermal expansion of 30 ~ 300 ℃,
The glass transition point and the yield point were determined. Separately, the Vickers hardness was measured with a Vickers microhardness meter, and the weight loss rate (water resistance) was determined by immersing the Vickers hardness in distilled water at 95 ° C for 20 hours.
【００２０】さらに、前記耐水性試験において、測定後
の液中への溶出Pbに関し、塩酸滴下による白濁、白沈
(PbCl2)の生成について観察・定性分析し、白濁、白沈
が認められないもの (○で表示) 、僅かに白沈が認めら
れるもの (△) 、白沈が明白なもの (×) に区分して評
価した。これら物性測定の結果を表１に併せて示す。Further, in the water resistance test, with respect to Pb dissolved in the liquid after measurement, white turbidity and white precipitation caused by dropping hydrochloric acid
The formation of (PbCl 2 ) was observed and qualitatively analyzed, and white turbidity and white sedimentation were not observed (marked with ○), slight white sedimentation was observed (△), and white sedimentation was obvious (×). It was divided and evaluated. The results of these physical property measurements are also shown in Table 1.
【００２１】〔結果〕表１において、本発明にかかる実
施例1 〜実施12に対し、比較例1 は〔ZnO ＋BaO ＋Li2O
＋Bi2O3 ＋PbO 〕の和が過剰なケース、比較例2 はTeO2
を含まないケース、比較例3 、4 は先述した公知例に開
示されたもので、うち比較例3 はPbOが過剰なケース、
比較例4 は〔ZnO ＋BaO ＋Li2O＋Bi2O3 ＋PbO 〕の和が
過少なケースを示す。[Results] In Table 1, in comparison with Examples 1 to 12 according to the present invention, Comparative Example 1 shows [ZnO + BaO + Li 2 O
+ Bi 2 O 3 + PbO] is excessive, the comparative example 2 is TeO 2
The case not containing, Comparative Examples 3 and 4 are disclosed in the above-mentioned publicly known examples, of which Comparative Example 3 is a case where PbO is excessive,
Comparative Example 4 shows the sum is too small case of [ZnO + BaO + Li 2 O + Bi 2 O 3 + PbO ].
【００２２】表示から明らかなとおり、実施例において
はいずれも屈伏点が300 ℃〜400 ℃台半ばと低く、従っ
て接着・封止作業も500 ℃以下ないし600 ℃程度と磁性
材料を損なうようなこともなく、ガラスの熱膨張率は10
0 ×10-7／℃ないし140 ×10 -7／℃台であって、磁性体
材料の熱膨張率に相応して適宜選択・設計でき、ガラス
の耐水性も良好で、Pb溶出も皆無ないし僅少であり、ま
たガラスの硬度も殆どが300 ないし400 台と良好な結果
を示し、他方比較例はガラスの耐水性あるいは更にPb溶
出において劣り、または屈伏点が高い等、磁気ヘッド封
着用として不適当であることを示す。As is clear from the display, in the embodiment
All have low yield points in the mid 300 to 400 ° C range,
The adhesion and sealing work is magnetic at less than 500 ° C or 600 ° C.
The thermal expansion coefficient of glass is 10 without damaging the material.
0 x 10-7/ ° C or 140 x 10 -7/ ° C range, magnetic material
Glass can be selected and designed appropriately according to the coefficient of thermal expansion of the material.
Has good water resistance and no or only minimal Pb elution.
The hardness of the glass is almost 300 to 400, which is a good result.
On the other hand, the comparative example shows the water resistance of the glass or further Pb dissolution.
Magnetic head seal, such as poor output or high yield point
Indicates that it is not suitable for wearing.
【００２３】[0023]
【発明の効果】本発明によれば金属、セラミックの接着
・封止用、殊に磁気ヘッドの接着・封止用として有用で
あり、熱膨張率を磁性体のそれと適合させることがで
き、接着・封止温度も磁性体の特性を損なうことのない
作業温度範囲であり、耐水性に優れてPb溶出も皆無ない
し僅少であり、比較的高い硬度を有する等、その工業上
の利用価値は多大である。INDUSTRIAL APPLICABILITY According to the present invention, it is useful for adhering / sealing metals and ceramics, particularly for adhering / sealing magnetic heads, and the coefficient of thermal expansion can be adapted to that of a magnetic material.・ The sealing temperature is a working temperature range that does not impair the magnetic properties, has excellent water resistance, has little or no Pb elution, and has a relatively high hardness. Is.
Claims (2)
〜50％、PbO 0 〜10％、ZnO 0 〜20％、BaO 0 〜20％、
Li2O 0〜20％、Bi2O3 0 〜10％の範囲で、PbO 、ZnO 、
BaO、Li2OおよびBi2O3 の和が25〜40％であることを特
徴とする接着・封止用ガラス。In 1. A mol% display, P 2 O 5 20 ~60% , TeO 2 10
~ 50%, PbO 0 ~ 10%, ZnO 0 ~ 20%, BaO 0 ~ 20%,
Li 2 O 0 to 20%, Bi 2 O 3 0 to 10%, PbO, ZnO,
Glass for adhesion and sealing, characterized in that the sum of BaO, Li 2 O and Bi 2 O 3 is 25 to 40%.
求項１記載の接着・封止用ガラス。2. The bonding / sealing glass according to claim 1, wherein 0 ≦ PbO <1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5271453A JP2987039B2 (en) | 1993-10-29 | 1993-10-29 | Glass for bonding and sealing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5271453A JP2987039B2 (en) | 1993-10-29 | 1993-10-29 | Glass for bonding and sealing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07126037A true JPH07126037A (en) | 1995-05-16 |
| JP2987039B2 JP2987039B2 (en) | 1999-12-06 |
Family
ID=17500245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5271453A Expired - Fee Related JP2987039B2 (en) | 1993-10-29 | 1993-10-29 | Glass for bonding and sealing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2987039B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009097264A1 (en) * | 2008-01-30 | 2009-08-06 | Basf Catalysts Llc | Glass frits |
| US7754629B2 (en) * | 2006-11-30 | 2010-07-13 | Corning Incorporated | Phosphotellurite-containing glasses, process for making same and articles comprising same |
| JP2011512426A (en) * | 2008-01-30 | 2011-04-21 | ビーエーエスエフ ソシエタス・ヨーロピア | Conductive ink having organometallic modifier |
| US8308993B2 (en) | 2008-01-30 | 2012-11-13 | Basf Se | Conductive inks |
| WO2015166226A1 (en) * | 2014-04-28 | 2015-11-05 | Johnson Matthey Public Limited Company | Conductive paste, electrode and solar cell |
| WO2018149802A1 (en) * | 2017-02-15 | 2018-08-23 | Basf Se | Glass frit, conductive paste and use of the conductive paste |
| KR102144685B1 (en) * | 2019-03-29 | 2020-08-14 | 전남대학교산학협력단 | Manufacturing method for digital metal-ceramic prosthesis and glass melt bond |
-
1993
- 1993-10-29 JP JP5271453A patent/JP2987039B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7754629B2 (en) * | 2006-11-30 | 2010-07-13 | Corning Incorporated | Phosphotellurite-containing glasses, process for making same and articles comprising same |
| WO2009097264A1 (en) * | 2008-01-30 | 2009-08-06 | Basf Catalysts Llc | Glass frits |
| US7736546B2 (en) | 2008-01-30 | 2010-06-15 | Basf Se | Glass frits |
| JP2011512426A (en) * | 2008-01-30 | 2011-04-21 | ビーエーエスエフ ソシエタス・ヨーロピア | Conductive ink having organometallic modifier |
| US7935279B2 (en) | 2008-01-30 | 2011-05-03 | Basf Se | Glass frits |
| US8308993B2 (en) | 2008-01-30 | 2012-11-13 | Basf Se | Conductive inks |
| US8383011B2 (en) | 2008-01-30 | 2013-02-26 | Basf Se | Conductive inks with metallo-organic modifiers |
| RU2494983C2 (en) * | 2008-01-30 | 2013-10-10 | Басф Се | Glass frits |
| WO2015166226A1 (en) * | 2014-04-28 | 2015-11-05 | Johnson Matthey Public Limited Company | Conductive paste, electrode and solar cell |
| CN106463197A (en) * | 2014-04-28 | 2017-02-22 | 庄信万丰股份有限公司 | Conductive paste, electrode and solaode |
| WO2018149802A1 (en) * | 2017-02-15 | 2018-08-23 | Basf Se | Glass frit, conductive paste and use of the conductive paste |
| KR102144685B1 (en) * | 2019-03-29 | 2020-08-14 | 전남대학교산학협력단 | Manufacturing method for digital metal-ceramic prosthesis and glass melt bond |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2987039B2 (en) | 1999-12-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |