JPH07126035A - Low-melting glass - Google Patents
Low-melting glassInfo
- Publication number
- JPH07126035A JPH07126035A JP27145493A JP27145493A JPH07126035A JP H07126035 A JPH07126035 A JP H07126035A JP 27145493 A JP27145493 A JP 27145493A JP 27145493 A JP27145493 A JP 27145493A JP H07126035 A JPH07126035 A JP H07126035A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- low
- melting glass
- sealing
- thermal expansion
- 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
- 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
-
- 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
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
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】本発明は低融点ガラスにかかり、
光学ガラス、音響光学ガラス、赤外透過性ガラス等とし
て、更に金属やセラミックの接着や封止用、特に磁気ヘ
ッドの接着・封止用ガラスとして好適な低融点ガラスに
関する。The present invention relates to a low melting point glass,
The present invention relates to a low-melting glass suitable as an optical glass, an acousto-optical glass, an infrared transmissive glass, etc., and also as a glass for adhering or sealing a metal or ceramic, particularly for adhering or sealing a magnetic head.
【０００２】[0002]
【従来技術とその問題点】例えば金属やセラミックの接
着や封止にPbO 系の低融点ガラスが広く利用されてお
り、一例として PbO−B2O3系をベースとして、 PbO−B2
O3−SiO2系、PbO −B2O3−ZnO 系、 PbO−B2O3−SiO2−
Al2O3 系等のガラスはよく知られるところである。しか
しPbO 成分を含むため、加熱加工作業環境を悪化し、ま
た水と接触するとPbを溶出して公害問題を誘起するこ
と、硬度が不充分であること、耐水、耐薬品性に劣るこ
と、被接着材料とも反応し易いこと等問題点が少なくな
い。BACKGROUND OF THE INVENTION Low-melting glass has been widely used in the PbO-based adhesion and sealing, for example metal or ceramic, a PbO-B 2 O 3 -based as the base as an example, PbO-B 2
O 3 -SiO 2 system, PbO -B 2 O 3 -ZnO-based, PbO-B 2 O 3 -SiO 2 -
Glasses such as Al 2 O 3 series are well known. However, since it contains PbO component, it deteriorates the working environment of heating and processing, and when it comes into contact with water, it elutes Pb and induces pollution problems, insufficient hardness, poor water resistance and chemical resistance, There are many problems such as easy reaction with adhesive materials.
【０００３】また、特開昭62−128946号にはTeO2−P2O5
−PbO −(ZnO＋Li2O) 系で、光学材料等に利用されるテ
ルライトガラスが開示されている。しかし、PbO 成分を
必須とするため、上記同様にPbによる弊害が危惧され
る。Further, in JP-A-62-128946, TeO 2 -P 2 O 5
-PbO - In (ZnO + Li 2 O) system, tellurite glass to be used for optical materials is disclosed. However, since the PbO component is essential, the harmful effect of Pb is feared as in the above.
【０００４】これに対し、例えば特開昭61−36135 号、
特開昭61−111935号には、V2O5−P2O5系を主体としTeO2
等を含んだ低融点ガラスで、磁気ヘッドの接着・封止を
目的としたガラスが開示されている。しかし、耐水、耐
薬品性に劣り、着色、不透明になり易く、硬度が低く、
被接着材とも反応し易い等やはり問題が多い。On the other hand, for example, JP-A-61-36135,
Japanese Patent Laid-Open No. 61-111935 discloses that TeO 2 is mainly composed of V 2 O 5 -P 2 O 5 system.
A glass having a low melting point including, for example, a glass for bonding and sealing a magnetic head is disclosed. However, it is inferior in water resistance and chemical resistance, tends to become colored and opaque, has low hardness,
There are still many problems such as easy reaction with the adherend.
【０００５】低融点ガラスはそれ自体低い処理温度でガ
ラス製造できるものであり、特にセラミックや金属の接
着・封止に利用される。その場合、熱膨張率が被接着材
料のそれとよく適合していること、作業温度が適合して
いること、耐水、耐薬品性に優れること、被接着材料と
の相互反応がないこと、機械的強度が高いこと等が要求
され、更に磁気ヘッド封着分野においては、熱膨張率の
磁性材料との適合性、磁性材料との非反応性、磁気絶縁
性、透視性、硬度等も重要なファクターであるが、前記
公知例はこれらを満足し得ない。本発明はそれらファク
ターを満足する新たな低融点ガラスを提供するものであ
り、勿論光学ガラス、赤外透過性ガラス等としても適用
できるものである。The low-melting glass itself can be manufactured at a low processing temperature, and is particularly used for bonding and sealing ceramics and metals. In that case, the coefficient of thermal expansion is well matched to that of the material to be adhered, the working temperature is compatible, it has excellent water resistance and chemical resistance, there is no interaction with the material to be adhered, mechanical High strength is required, and in the field of magnetic head sealing, compatibility of magnetic expansion coefficient with magnetic material, non-reactivity with magnetic material, magnetic insulation, transparency, hardness, etc. are also important factors. However, the above-mentioned known example cannot satisfy these. The present invention provides a new low melting point glass satisfying those factors, and can be applied as an optical glass, an infrared transmissive glass and the like as a matter of course.
【０００６】[0006]
【問題点を解決するための手段】本発明は、 mol％表示
で、P2O5 5〜60、TeO2 20 〜90、ZnF2 5〜60の範囲から
なる低融点ガラス、前記低融点ガラスにおいて、特にP2
O5 10 〜30％、TeO2 20 〜70％、ZnF2 20〜60％の範囲
であること、から構成される。[Means for Solving the Problems] The present invention provides a low-melting glass containing P 2 O 5 5 to 60, TeO 2 20 to 90 and ZnF 2 5 to 60 in mol%, and the low melting glass. , Especially P 2
O 5 10 to 30%, TeO 2 20 to 70%, and ZnF 2 20 to 60%.
【０００７】本発明においては、光学ガラス、赤外透過
性ガラス等としても好適であるが、接着・封止用ガラス
として優れた特性を有する。すなわち、適宜成分組成を
選択することにより熱膨張率を100 ×10-7／℃以下程度
から130 ×10-7／℃程度のものが得られるので、金属、
セラミック、特に磁気ヘッド材料の熱膨張率に応じ適宜
採用でき、屈伏点も300 〜400 ℃台であるので 500〜60
0 ℃程度で変質しないような金属、セラミック等の被接
着材料を接着・封止でき、耐水性においても優れ、硬度
も高く、また、磁気ヘッドの接着・封止においても磁性
材料との相互反応がなく、磁気的絶縁性に優れる等、各
種金属、セラミック等の接着は勿論、特に磁気ヘッド封
着用に適応した諸特性を備えるものである。In the present invention, it is suitable as an optical glass, an infrared transmissive glass, etc., but has excellent properties as an adhesive / sealing glass. That is, by appropriately selecting the component composition, a material having a thermal expansion coefficient of about 100 × 10 −7 / ° C. or less to about 130 × 10 −7 / ° C. can be obtained.
It can be appropriately adopted according to the coefficient of thermal expansion of ceramics, especially magnetic head materials.
Adhesive materials such as metals and ceramics that do not deteriorate at around 0 ° C can be adhered and sealed, have excellent water resistance, and have high hardness. Also, in the adhesion and sealing of magnetic heads, mutual reaction with magnetic materials It has various characteristics suitable for sealing magnetic heads, as well as adhesion of various metals and ceramics, such as excellent magnetic insulating properties.
【０００８】本成分系において、P2O5は mol％で 5〜60
％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5％未満であってもガラス形成を不安定にする。好
適には10〜30％の範囲とするものである。In this component system, P 2 O 5 is 5 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 5%, the glass formation becomes unstable. It is preferably in the range of 10 to 30%.
【０００９】TeO2は同様に20〜90％の範囲においてガラ
ス形成が良好で安定しており、90％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、20％未満で
は耐水性を悪化させる等不具合が生ずる。好適には20〜
70％の範囲とするものである。TeO 2 likewise has good and stable glass formation in the range of 20 to 90%, and when it exceeds 90%, it makes glass formation unstable and lowers the hardness of glass, and when it is less than 20%, it has a water resistance. A problem such as aggravation occurs. Preferably 20 ~
The range is 70%.
【００１０】ZnF2は前記P2O5−TeO2系に 5〜60％の範囲
で導入するものであり、ガラスの耐水性を向上し、硬度
を増大する等の作用を有するが、 5％未満ではそれら作
用が効果的でなく、60％を越えるとガラス形成を困難と
し、失透を生じ易くなる。好適には20〜60％の範囲とす
るものである。ZnF 2 is introduced into the P 2 O 5 —TeO 2 system in the range of 5 to 60%, and has the effects of improving the water resistance of glass and increasing the hardness, etc. If it is less than 60%, these actions are not effective, and if it exceeds 60%, glass formation becomes difficult and devitrification is likely to occur. It is preferably in the range of 20 to 60%.
【００１１】なお、更にガラスの硬度、耐水性等を向上
するために例えばSiO2、TiO2、Al2O 3 、SrO 、ZnO 、Ba
O 、Bi2O3 等を、ガラスの安定性を向上するためにB
2O3、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上記
成分を10％以下程度の範囲で適宜導入することができ
る。但しPbO 等有害な成分は実質的に含まないこととす
る。Further, the hardness and water resistance of the glass are further improved.
For example SiO2, TiO2, Al2O 3 , SrO, ZnO, Ba
O, Bi2O3B to improve the stability of the glass
2O3, V2OFiveEtc. to improve the meltability.2OK2O 2, MgO
, CaO, etc., or in order to adjust the coefficient of thermal expansion
Ingredients can be introduced appropriately within the range of 10% or less
It However, it does not contain harmful components such as PbO.
It
【００１２】[0012]
【実施例】以下実施例を例示して本発明を詳述する。The present invention will be described in detail below with reference to examples.
【００１３】〔試料調製〕P2O5源としてオルトリン酸、
TeO2源として二酸化テルル、ZnF2源としてフッ化亜鉛
(４水塩) を使用し、各原料をガラス組成のP2O5・TeO2
・ZnF2の所定モル比率で混合し、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試料を得た。
前記各試料のガラス組成 (モル百分率) を表１に示す。[Sample Preparation] Orthophosphoric acid as a P 2 O 5 source,
Tellurium dioxide as a TeO 2 source, zinc fluoride as a ZnF 2 source
(Tetrahydrate) is used, and each raw material is made of P 2 O 5 · TeO 2 having a glass composition.
-ZnF 2 was mixed at a predetermined molar ratio, filled into an alumina crucible, covered with a crucible, set in an electric furnace heated and maintained at an appropriate temperature of 1050 ° C to 1200 ° C in advance, 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 sample.
Table 1 shows the glass composition (mol percentage) of each sample.
【００１４】〔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。またビッカース微小硬
度計により硬度を測定し、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 heated with a differential thermal expansion meter 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. The hardness was measured with a Vickers micro hardness meter, and the weight loss rate (water resistance) was determined by immersing in distilled water at 95 ° C for 20 hours.
【００１５】結果を表１に併せて示す。The results are also shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
【００１７】〔結果〕表１中実施例1 〜9 は本発明組成
範囲のもの、比較例1 、2 は組成範囲を外れたものを示
す。[Results] In Table 1, Examples 1 to 9 are in the composition range of the present invention, and Comparative Examples 1 and 2 are out of the composition range.
【００１８】表示から明らかなとおり、本発明のものは
熱膨張率が100 〜130 ×10-7／℃程度と、広い範囲で被
接着金属、セラミックと適合でき、屈伏点も300 ℃ない
し400 ℃台、従って作業温度も500 〜600 ℃程度と低く
設定できるので多くの金属、セラミックの接着・封止用
に採用でき、耐水性 (重量減少率) も 2％以下、殊に0.
1 ％以下のものが得られる等非常に優れ、水へのPb溶出
も皆無と公害が生ずる恐れもなく、ビッカース硬度が30
0 〜400 と比較的高い硬度を有する等接着・封止用ガラ
スとして好適である。As is clear from the indication, the present invention has a coefficient of thermal expansion of about 100 to 130 × 10 −7 / ° C., which is compatible with a wide range of metals and ceramics to be adhered, and has a yield point of 300 to 400 ° C. The table, and therefore the working temperature can be set as low as 500 to 600 ° C, can be used for bonding and sealing many metals and ceramics, and the water resistance (weight reduction rate) is 2% or less, especially 0.
Very good, such as 1% or less, no Pb elution into water, no risk of pollution, Vickers hardness of 30
It is suitable as a glass for adhesion / sealing having a relatively high hardness of 0 to 400.
【００１９】なお、比較例はいずれもガラス形成が困難
またはガラス化し得ないことが明白である。It is obvious that the glass formation of each of the comparative examples is difficult or cannot be vitrified.
【００２０】[0020]
【発明の効果】本発明によれば、熱膨張率が 100以下〜
130 ×10-7／℃程度と、広い範囲で被接着金属、セラミ
ックと適合でき、屈伏点も300 ℃ないし400 ℃台、従っ
て作業温度も500 〜600 ℃程度と低く設定できるので多
くの金属、セラミックの接着・封止用に採用でき、耐水
性に優れ、公害問題の恐れもなく、ビッカース硬度が30
0 〜400 と比較的高い硬度を有する等接着・封止用ガラ
スとして好適であり、あるいは光学ガラス、音響光学ガ
ラス、赤外透過性ガラス等としても採用できる。According to the present invention, the coefficient of thermal expansion is 100 or less.
It is compatible with adherend metals and ceramics in a wide range of 130 × 10 -7 / ℃, and the yield point is in the range of 300 ℃ to 400 ℃, so the working temperature can be set as low as 500 to 600 ℃, so many metals, It can be used for adhesion and sealing of ceramics, has excellent water resistance, there is no fear of pollution problems, and Vickers hardness is 30.
It is suitable as an adhesive / sealing glass having a relatively high hardness of 0 to 400, or can be adopted as an optical glass, an acousto-optical glass, an infrared transmitting glass, or the like.
Claims (2)
0、ZnF2 5〜60の範囲からなる低融点ガラス。1. P 2 O 5 5 to 60, TeO 2 20 to 9 in mol% display
0, the low melting point glass comprising a range of ZnF 2 5 to 60.
〜60％の範囲からなる請求項１記載の低融点ガラス。2. P 2 O 5 10 to 30%, TeO 2 20 to 70%, ZnF 2 20
The low melting glass according to claim 1, wherein the glass has a range of -60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5271454A JP2944387B2 (en) | 1993-10-29 | 1993-10-29 | Low melting glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5271454A JP2944387B2 (en) | 1993-10-29 | 1993-10-29 | Low melting glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07126035A true JPH07126035A (en) | 1995-05-16 |
| JP2944387B2 JP2944387B2 (en) | 1999-09-06 |
Family
ID=17500260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5271454A Expired - Fee Related JP2944387B2 (en) | 1993-10-29 | 1993-10-29 | Low melting glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2944387B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008007681A1 (en) | 2006-07-14 | 2008-01-17 | Central Glass Company, Limited | Organic-inorganic hybrid glassy material and its fabrication method |
| US7451619B2 (en) | 2003-06-26 | 2008-11-18 | Central Glass Company, Limited | Organic-inorganic hybrid glassy materials and their production processes |
| US7728095B2 (en) | 2006-02-10 | 2010-06-01 | Central Glass Company, Limited | Organic-inorganic hybrid glassy material and its production process |
| US7802450B2 (en) | 2003-03-14 | 2010-09-28 | Central Glass Company, Limited | Organic-inorganic hybrid glassy materials and their production processes |
| CN102557436A (en) * | 2010-12-16 | 2012-07-11 | 中国科学院西安光学精密机械研究所 | Mid-infrared anhydrous tellurate glass and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6344425B1 (en) * | 1999-11-19 | 2002-02-05 | Corning Incorporated | Fluorotellurite, amplifier glasses |
-
1993
- 1993-10-29 JP JP5271454A patent/JP2944387B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7802450B2 (en) | 2003-03-14 | 2010-09-28 | Central Glass Company, Limited | Organic-inorganic hybrid glassy materials and their production processes |
| US7451619B2 (en) | 2003-06-26 | 2008-11-18 | Central Glass Company, Limited | Organic-inorganic hybrid glassy materials and their production processes |
| US7728095B2 (en) | 2006-02-10 | 2010-06-01 | Central Glass Company, Limited | Organic-inorganic hybrid glassy material and its production process |
| WO2008007681A1 (en) | 2006-07-14 | 2008-01-17 | Central Glass Company, Limited | Organic-inorganic hybrid glassy material and its fabrication method |
| CN102557436A (en) * | 2010-12-16 | 2012-07-11 | 中国科学院西安光学精密机械研究所 | Mid-infrared anhydrous tellurate glass and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2944387B2 (en) | 1999-09-06 |
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