EP0138082A1 - Gas-discharge arrester and fabrication method - Google Patents

Gas-discharge arrester and fabrication method Download PDF

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Publication number
EP0138082A1
EP0138082A1 EP84111068A EP84111068A EP0138082A1 EP 0138082 A1 EP0138082 A1 EP 0138082A1 EP 84111068 A EP84111068 A EP 84111068A EP 84111068 A EP84111068 A EP 84111068A EP 0138082 A1 EP0138082 A1 EP 0138082A1
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Prior art keywords
activator
gas discharge
molybdenum
nickel
electrodes
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EP84111068A
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German (de)
French (fr)
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EP0138082B1 (en
Inventor
Franz Watzke
Gerhard Ing. Grad. Lange
Jürgen Ing. grad. Boy
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Siemens AG
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Siemens AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
    • H01T1/00—Details of spark gaps
    • H01T1/20—Means for starting arc or facilitating ignition of spark gap
    • H01T1/22—Means for starting arc or facilitating ignition of spark gap by the shape or the composition of the electrodes

Definitions

  • the present invention relates to a gas discharge arrester according to the preambles of claims 1 or 2.
  • gas discharge arresters are known from DE-OS 2619866.
  • the activator mass which is introduced into the gas discharge conductor contains barium aluminum, an alkali metal halide and titanium. By adding titanium, the response voltage should be kept stable and a long service life should be achieved.
  • the object on which the present invention is based is to reduce the sample scatter and the collective scatter of the electrical values of the gas discharge arrester and to increase the thermal and electrical load capacity of the arrester without having to accept a change in its electrical characteristic values.
  • composition according to the invention is practically two-stage gettering. Gases that form at low temperatures below about 900 ° C are gettered by the barium aluminum, but if the temperature of the activating mass briefly rises above 1000 ° C, these substances are released by the barium aluminum and taken over by the tungsten or molybdenum.
  • Tungsten is particularly suitable for very high peak currents and the associated very strong heating of the activator, while molybdenum is advantageous and also more cost-effective in the case of moderate overheating.
  • tungsten in particular has the particular advantage that a particularly low sputtering occurs, that is to say that very little material evaporates from the electrodes. Evaporating material leads to metal layers on the housing, which in turn increase the capacity of the surge arrester. The increase in capacity must be avoided for many applications, in particular for high-frequency applications. The use of molybdenum is sufficient for this, unless extreme demands make it necessary to use tungsten.
  • composition of the activator according to the invention is an increased tendency to form sintered metal. This results in layers that are much more adhesive, especially when using nickel, than without the addition of molybdenum or tungsten. For this it is advantageous if the activator contains equal parts by weight of nickel and molybdenum.
  • the proportion of molybdenum, if sufficient adhesive strength is ensured, is advantageously matched to the required amount of barium aluminum, the proportion by weight of barium aluminum being equal to that of Molybdenum advantageously behaves like 1: 3.
  • the adhesive strength is usually sufficient in the presence of alkali metal, when nickel is used in cases of low mechanical stress.
  • Surge arresters according to the invention are advantageously produced by a method in which an activator mass which contains the necessary starting substances in powder form is applied to at least one electrode, in that the arrester is closed gas-tight and then subjected to a temperature treatment and an electrical formation by means of current surges and the current surges are measured in this way that the temperature in the activator is briefly raised above 1000 ° C.
  • the arrester is closed gas-tight and then subjected to a temperature treatment and an electrical formation by means of current surges and the current surges are measured in this way that the temperature in the activator is briefly raised above 1000 ° C.
  • the starting substances are advantageously mixed in the form of powder with a grain size between 0.2 ⁇ m and 50 ⁇ m, mixed with a chemically inactive liquid to form a paste and thus applied to the electrodes.
  • Alcohol for example, is suitable as a chemically inactive liquid.
  • An activator composition having the following composition is advantageously used for the process described: 25% by weight to 90% by weight alkali metal halide
  • potassium is released from these masses, which reduces the work function for the electrodes, the haloqenide being bound by the getter metals.
  • the potassium that forms in the liquid state also binds the activator; when it cools, the activator adheres sufficiently firmly.
  • the potassium-containing embodiment does not result in electrically conductive deposits on the housing wall even when sputtering
  • the sputtering in the example described with equal proportions by weight of nickel and molybdenum has already been reduced to such an extent that this composition can also be used for arresters with ignition marks on the inside of the insulator can, without the ignition lines evaporating and thus the surge voltage increases inadmissibly.
  • the barium aluminum alloy When executed using nickel powder, the barium aluminum alloy acts as an emission-determining substance.
  • the nickel content forms a heat-dissipating sintered structure and, together with the molybdenum, forms a firmly adhering layer on the electrode.
  • the molybdenum powder component in turn forms the getter described for base gas components.

Landscapes

  • Thermistors And Varistors (AREA)
  • Manufacture Of Electron Tubes, Discharge Lamp Vessels, Lead-In Wires, And The Like (AREA)
  • Gas-Filled Discharge Tubes (AREA)
  • Conductive Materials (AREA)

Abstract

Gasentladungsableiter enthalten zur Reduktion der Austrittsarbeit der Elektronen einen Aktivator, der beispielsweise ein Alkalimetall oder Nickel enthält. Zur Getterung von Gasen, die bei der Herstellung oder beim Betrieb im Überspannungsableiter entstehen können, dienen Getterstoffe, beispielsweise BaAl. Mit diesen Stoffen lassen sich die Streuungen der Ansprechspannung klein halten, solange der Aktivator nur mäßig erwärmt wird. Die Erfindung schlägt nun für hohe Belastungen einen Aktivator vor, welcher ein Alkalimetall oder Nickel und dazu Bariumaluminium enthält, wobei als zusätzlicher Stoff Wolfram und/oder Molybdän anwesend ist. Ein derartiger Aktivator gewährleistet gleichbleibende Werte der Ansprechspannung und eine enge Streuung dieser Werte auch nach hoher elektrischer und thermischer Belastung, eine häufige Schaltung der höchstzulässigen Stromstärke ist ohne störende Änderung seiner elektrischen Daten möglich. Die Erfindung eignet sich für Gasentladungsableiter für Schaltzwecke.To reduce the work function of the electrons, gas discharge conductors contain an activator which contains, for example, an alkali metal or nickel. Getter materials, for example BaAl, are used for gettering gases that can arise during manufacture or during operation in the surge arrester. With these substances, the scatter of the response voltage can be kept small as long as the activator is only moderately heated. For high loads, the invention now proposes an activator which contains an alkali metal or nickel and, in addition, barium aluminum, tungsten and / or molybdenum being present as an additional substance. Such an activator ensures constant values of the response voltage and a narrow spread of these values even after high electrical and thermal loads, frequent switching of the maximum permissible current is possible without disturbing changes in its electrical data. The invention is suitable for gas discharge arresters for switching purposes.

Description

Die vorliegende Erfindung betrifft einen .Gasentladungsableiter nach den Oberbegriffen der Patentansprüche 1 oder 2. Derartige Gasentladungsableiter sind aus der DE-OS 2619866 bekannt. Gemäß dieser DE-OS enthält die Aktivatormasse, die in den Gasentladungsbleiter eingebracht wird, Bariumaluminium, ein Alkalihalogenid und Titan. Durch den Zusatz von Titan soll die Ansprechspannung stabil gehalten und eine hohe Lebensdauer erreicht werden.The present invention relates to a gas discharge arrester according to the preambles of claims 1 or 2. Such gas discharge arresters are known from DE-OS 2619866. According to this DE-OS, the activator mass which is introduced into the gas discharge conductor contains barium aluminum, an alkali metal halide and titanium. By adding titanium, the response voltage should be kept stable and a long service life should be achieved.

Demgegenüber besteht die Aufgabe, die der vorliegenden Erfindung zugrundeliegt, in einer Verkleinerung der Exemplarstreuung und der Kollektivstreuung der elektrischen Werte des Gasentladungsableiters und in einer Erhöhung der thermischen und elektrischen Belastbarkeit des Ableiters, ohne eine Änderung seiner elektrischen Kennwerte hinnehmen zu müssen.In contrast, the object on which the present invention is based is to reduce the sample scatter and the collective scatter of the electrical values of the gas discharge arrester and to increase the thermal and electrical load capacity of the arrester without having to accept a change in its electrical characteristic values.

Diese Aufgabe wird durch die kennzeichnenden Merkmale der Ansprüche 1 oder 2 gelöst. Der Zusatz von Wolfram und/oder Molybdän anstelle von Titan ergibt eine beträchtliche Verbesserung der Strombelastbarkeit des Ableiters. Dies hat seinen Grund anscheinend darin, daß Wolfram und Molybdän erst über 1000°C in nennenswertem Maße als Getterwerkstoffe wirksam werden und daß auch bei noch beträchtlich höheren Temperaturen die einmal angelagerten Gase nicht mehr freigegeben werden. Dadurch können bei Strombelastunqen, die wesentlich höher sind als die im Stand der Technik zulässigen, noch sehr viele Schaltungen durchgeführt werden, ohne daß sich die Ansprechspannung ändert. Der Ableiter ist daher für Schaltanwendungen und als Uberspannungsableiter mit langer Lebensdauer besonders gut geeignet.This object is achieved by the characterizing features of claims 1 or 2. The addition of tungsten and / or molybdenum instead of titanium results in a considerable improvement in the current carrying capacity of the arrester. This is apparently due to the fact that tungsten and molybdenum only become effective as getter materials to a significant extent above 1000 ° C. and that the gases once deposited are no longer released even at considerably higher temperatures. As a result, a large number of circuits can still be carried out at current loads which are significantly higher than those permitted in the prior art without the response voltage changing. The arrester is therefore particularly well suited for switching applications and as a surge arrester with a long service life.

Bei der erfindungsgemäßen Zusammensetzung liegt praktisch eine Zweistufen-Getterung vor. Gase, die sich bei geringen Temperaturen unter etwa 900°C bilden, werden vom Bariumaluminium gegettert, wenn aber die Temperatur der Aktivierunqsmasse kurzzeitig über 1000°C steigt, werden diese Stoffe vom Bariumaluminium wieder abgegeben und vom Wolfram oder Molybdän übernommen.The composition according to the invention is practically two-stage gettering. Gases that form at low temperatures below about 900 ° C are gettered by the barium aluminum, but if the temperature of the activating mass briefly rises above 1000 ° C, these substances are released by the barium aluminum and taken over by the tungsten or molybdenum.

Dabei eignet sich Wolfram insbesondere für sehr hohe Spitzenströme und damit verbundene sehr starke Erhitzung des Aktivators, während Molybdän bei mäßiger Überhitzung vorteilhaft und dazu kostengünstiger ist.Tungsten is particularly suitable for very high peak currents and the associated very strong heating of the activator, while molybdenum is advantageous and also more cost-effective in the case of moderate overheating.

In einer Aktivierungsmasse unter Verwendung von Nickel hat insbesondere der Zusatz von Wolfram den besonderen Vorteil, daß eine besonders geringe Kathodenzerstäubung eintritt, daß also besonders wenig Material von den Elektroden abdampft. Abdampfendes Material führt zu Metallschichten auf dem Gehäuse, welche ihrerseits wiederum die Kapazität des Überspannunqsableiters vergrößern. Die Kapazitätsvergrö- ßerung muß für viele Einsatzfälle vermieden werden, so insbesondere für Hochfrequenzanwendungen. Hierfür reicht der Einsatz von Molybän aus, soweit nicht extreme Forderunqen den Einsatz von Wolfram nötig machen.In an activation mass using nickel, the addition of tungsten in particular has the particular advantage that a particularly low sputtering occurs, that is to say that very little material evaporates from the electrodes. Evaporating material leads to metal layers on the housing, which in turn increase the capacity of the surge arrester. The increase in capacity must be avoided for many applications, in particular for high-frequency applications. The use of molybdenum is sufficient for this, unless extreme demands make it necessary to use tungsten.

Ein weiterer besonderer Vorteil der erfindungsgemäßen Zusammensetzung des Aktivators besteht in einer erhöhten Neigung zur Bildung von Sintermetall. Dadurch entstehen insbesondere beim Einsatz von Nickel erheblich haftfestere Schichten als ohne die Zugabe von Molybdän oder Wolfram. Hierfür ist es vorteilhaft, wenn der Aktivator gleiche Gewichtsanteile von Nickel und Molybdän enthält.Another particular advantage of the composition of the activator according to the invention is an increased tendency to form sintered metal. This results in layers that are much more adhesive, especially when using nickel, than without the addition of molybdenum or tungsten. For this it is advantageous if the activator contains equal parts by weight of nickel and molybdenum.

Der Anteil von Molybdän wird, sofern eine ausreichende Haftfestigkeit gewährleistet ist, vorteilhaft auf die erforderliche Menge von Bariumaluminium abgestimmt, wobei sich der Gewichtsanteil von Bariumaluminium zu dem von Molybdän vorteilhaft wie 1:3 verhält. Die Haftfestigkeit reicht bei der Anwesenheit von Alkalimetall in der Regel, bei Verwendung von Nickel in Fällen geringerer mechanischer Beanspruchung aus.The proportion of molybdenum, if sufficient adhesive strength is ensured, is advantageously matched to the required amount of barium aluminum, the proportion by weight of barium aluminum being equal to that of Molybdenum advantageously behaves like 1: 3. The adhesive strength is usually sufficient in the presence of alkali metal, when nickel is used in cases of low mechanical stress.

Erfindungsgemäße Überspannungsableiter werden vorteilhaft durch ein Verfahren hergestellt, bei dem auf zumindest eine Elektrode eine Aktivatormasse aufgebracht wird, welche die erforderlichen Ausganqssubstanzen in Pulverform enthält, indem der Ableiter gasdicht verschlossen und danach einer Temperaturbehandlung und einer elektrischen Formierung durch Stromstöße unterzogen und die Stromstöße so bemessen werden, daß die Temperatur im Aktivator kurzzeitig über 1000°C angehoben wird. Durch dieses Verfahren werden zunächst alle flüchtigen Stoffe durch das Bariumaluminium gegettert, bei der Erhöhung der Temperatur aber wieder abqegeben und vom Wolfram bzw. vom Molvbdän fest gebunden. Sie können daher auch bei hohen Belastungen im Betrieb zu keinen Störungen mehr führen.Surge arresters according to the invention are advantageously produced by a method in which an activator mass which contains the necessary starting substances in powder form is applied to at least one electrode, in that the arrester is closed gas-tight and then subjected to a temperature treatment and an electrical formation by means of current surges and the current surges are measured in this way that the temperature in the activator is briefly raised above 1000 ° C. By this process, first all volatiles are gettered by the Bariumaluminium, but again ESpecify in increasing the temperature from q and tied from tungsten or from Molvbdän. Therefore, they can no longer lead to malfunctions even under high loads during operation.

Bei diesem Verfahren werden die Ausgangssubstanzen vorteilhaft in Form von Pulver mit einer Korngröße zwischen 0,2µm und 50 µm vermengt, mit einer chemisch inaktiven Flüssigkeit zu einer Paste angerührt und so auf die Elektroden aufgebracht. Als chemisch inaktive Flüssiqkeit eignet sich beispielsweise Alkohol.In this process, the starting substances are advantageously mixed in the form of powder with a grain size between 0.2 μm and 50 μm, mixed with a chemically inactive liquid to form a paste and thus applied to the electrodes. Alcohol, for example, is suitable as a chemically inactive liquid.

Für das beschriebene Verfahren wird vorteilhaft eine Aktivatormasse mit der folqenden Zusammensetzung verwendet: 25Gew% bis 90Gew% Alkalihalogenid

Figure imgb0001
An activator composition having the following composition is advantageously used for the process described: 25% by weight to 90% by weight alkali metal halide
Figure imgb0001

Besonders günstiqe Werte werden unter Verwendung einer Aktivatormasse mit der folgenden Zusammensetzung erhalten: 60Gew% Kaliumchlorid

  • 10Gew% Bariumaluminium
  • 30Gew% Molybdän.
Particularly favorable values are obtained using an activator composition with the following composition: 60% by weight potassium chloride
  • 10% by weight barium aluminum
  • 30% by weight molybdenum.

Aus diesen Massen wird bei dem beschriebenen Temperprozeß Kalium freigesetzt, welches die Austrittsarbeit für die Elektroden herabsetzt, wobei das Haloqenid durch die Gettermetalle gebunden wird. Das im flüssigen Zustand entstehende Kalium bindet außerdem den Aktivator, beim Erkalten entsteht eine ausreichend feste Haftung des Aktivators.In the annealing process described, potassium is released from these masses, which reduces the work function for the electrodes, the haloqenide being bound by the getter metals. The potassium that forms in the liquid state also binds the activator; when it cools, the activator adheres sufficiently firmly.

Während die Kalium enthaltende Ausführungsform auch bei Kathodenzerstäubung keine elektrisch leitenden Niederschläge auf der Gehäusewand ergibt, ist beim beschriebenen Beispiel mit gleichen Gewichtsanteilen von Nickel und Molybdän die Kathodenzerstäubung bereits so weit reduziert, daß diese Zusammensetzung auch für Ableiter mit Zündstrichen auf der Innenseite des Isolators eingesetzt werden kann, ohne daß die Zündstriche bedampfen und damit die Ansprechstoßspannung unzulässig ansteigt.While the potassium-containing embodiment does not result in electrically conductive deposits on the housing wall even when sputtering, the sputtering in the example described with equal proportions by weight of nickel and molybdenum has already been reduced to such an extent that this composition can also be used for arresters with ignition marks on the inside of the insulator can, without the ignition lines evaporating and thus the surge voltage increases inadmissibly.

Bei der Ausführung unter Verwendung von Nickelpulver wirkt die Bariumaluminiumlegierung als emissionsbestimmender Stoff. Der Nickelanteil bildet ein wärmeableitendes Sintergerüst und mit dem Molybdän zusammen eine fest haftende Schicht auf der Elektrode. Der Molybdän-Pulveranteil bildet wiederum den beschriebenen Getter für unedle Gasanteile.When executed using nickel powder, the barium aluminum alloy acts as an emission-determining substance. The nickel content forms a heat-dissipating sintered structure and, together with the molybdenum, forms a firmly adhering layer on the electrode. The molybdenum powder component in turn forms the getter described for base gas components.

Claims (8)

1. Gasentladungsableiter, in welchem sich zwei oder mehrere Elektroden gegenübertehen, wobei zumnindest eine dieser Elektroden mit einem Aktivator beschichtet ist, wobei dieser Aktivator zumindest ein Alkalimetall und eine Bariumaluminium- Legierung enthält, dadurch gekennzeichnet, daß der Aktivator zusätzlich metallisches Wolfram und/oder Molybdän enthält.1. Gas discharge arrester in which two or more electrodes face each other, at least one of these electrodes being coated with an activator, this activator containing at least one alkali metal and one barium aluminum alloy, characterized in that the activator additionally contains metallic tungsten and / or molybdenum contains. 2. Gasentladungableiter, in welchem sich zwei oder mehrere Elektroden gegenüberstehen, wobei zumindest eine dieser Elektroden mit einem Aktivator beschichtet ist, welcher eine Bariumaluminium-Legierung enthält, dadurch gekennzeichnet, daß der Aktivator zusätzlich metallisches Nickel und metallisches Wolfram und/oder Molybdän enthält.2. Gas discharge conductor in which two or more electrodes face each other, at least one of these electrodes being coated with an activator which contains a barium aluminum alloy, characterized in that the activator additionally contains metallic nickel and metallic tungsten and / or molybdenum. 3. Gasentladungsableiter nach Anspruch 2, gekennzeichnet durch gleiche Gewichtsanteile von Nickel und Molybdän.3. Gas discharge arrester according to claim 2, characterized by equal parts by weight of nickel and molybdenum. 4. Gasentladungsableiter nach einem der Ansprüche 1 bis 3, gekennzeichnet durch das Verhältnis des Gewichtsanteiles von Bariumaliminium zum Gewichtsanteil von Molybdän von 1:3.4. Gas discharge arrester according to one of claims 1 to 3, characterized by the ratio of the weight fraction of barium aluminum to the weight fraction of molybdenum of 1: 3. 5. Verfahren zur Herstellung eines Gasentladungsableiters nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß auf zumindest eine Elektrode eine Aktivatormasse aufgebracht wird, welche die erforderlichen Ausgangssubstanzen in Pulverform enthält, daß der Ableiter gasdicht verschlossen und danach einer Temperaturbehandlung und einer elektrischen Formierung durch wird Stromstöße unterzogen und daß die Stromstöße so bemessen sind, daß die Temperatur im Aktiovator kurzzeitig über 1000°C angehoben wird.5. A method for producing a gas discharge arrester according to one of claims 1 to 4, characterized in that an activator mass is applied to at least one electrode, which contains the required starting substances in powder form, that the arrester is sealed gas-tight and then subjected to a temperature treatment and an electrical formation is subjected to power surges and that the power surges are dimensioned so that the temperature in the actuator is briefly raised above 1000 ° C. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Ausgangssubstanzen des Aktivators in Form von Pulver mit einer Korngröße zwischen 0,2µm und 50µm vermengt, mit einer chemisch inaktiven Flüssigkeit zu einer Paste angerührt und so auf die Elektroden aufgebracht werden.6. The method according to claim 5, characterized in that the starting substances of the activator are mixed in the form of powder with a grain size between 0.2 µm and 50 µm, mixed with a chemically inactive liquid to form a paste and thus applied to the electrodes. 7. Verfahren nach einem der Ansprüche 4 bis 6,gekennzeichnet durch die Verwendung einer Aktivatormasse mit der folgenden Zusammensetzung: 25Gew% bis 90Gew% Alkalihalogenid
Figure imgb0002
 7. The method according to any one of claims 4 to 6, characterized by the use of an activator composition having the following composition: 25% to 90% by weight alkali halide
Figure imgb0002
 8. Verfahren nach Anspruch 7, gekennzeichnet durch die Verwendung einer Aktivierungsmasse mit der folgenden Zusammensetzung: etwa 60Gew% Kaliumchlorid
Figure imgb0003
 8. The method according to claim 7, characterized by the use of an activation mass with the following composition: about 60% by weight potassium chloride
Figure imgb0003
EP84111068A 1983-09-30 1984-09-17 Gas-discharge arrester and fabrication method Expired EP0138082B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3335602 1983-09-30
DE19833335602 DE3335602A1 (en) 1983-09-30 1983-09-30 GAS DISCHARGE ARRESTER AND MANUFACTURING METHOD

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EP0138082A1 true EP0138082A1 (en) 1985-04-24
EP0138082B1 EP0138082B1 (en) 1988-01-27

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EP (1) EP0138082B1 (en)
JP (1) JPS6095875A (en)
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EP0242590B1 (en) * 1986-04-22 1989-06-07 Siemens Aktiengesellschaft Gas-discharge surge arrester
US5671114A (en) * 1993-05-26 1997-09-23 Siemens Aktiengesellschaft Gas-filled overvoltage diverter

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US3266861A (en) * 1962-09-21 1966-08-16 Philips Corp Method of applying an alkali-earth metal getter
DE1270698B (en) * 1963-01-23 1968-06-20 Philips Nv Electric discharge tubes with a non-evaporating gas binder and method for producing this gas binder layer
DE2537964A1 (en) * 1975-08-26 1977-03-10 Siemens Ag Gas surge voltage arrester - has electrode coating of alkali halogenide, titanium hydride and barium aluminium alloy
EP0017875A1 (en) * 1979-04-11 1980-10-29 Siemens Aktiengesellschaft Method for producing an electrode activating substance for a gas-discharge tube

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242688A1 (en) * 1986-04-22 1987-10-28 Siemens Aktiengesellschaft Surge arrester
US4739439A (en) * 1986-04-22 1988-04-19 Siemens Aktiengesellschaft Overvoltage arrester
EP0242590B1 (en) * 1986-04-22 1989-06-07 Siemens Aktiengesellschaft Gas-discharge surge arrester
US5671114A (en) * 1993-05-26 1997-09-23 Siemens Aktiengesellschaft Gas-filled overvoltage diverter
EP0700589B1 (en) * 1993-05-26 1998-07-22 Siemens Aktiengesellschaft Gas-filled overvoltage diverter

Also Published As

Publication number Publication date
DE3469119D1 (en) 1988-03-03
EP0138082B1 (en) 1988-01-27
US4665337A (en) 1987-05-12
DE3335602A1 (en) 1985-04-18
JPS6095875A (en) 1985-05-29
JPH0223996B2 (en) 1990-05-28

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