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EP1042765B1 - Verfahren zur herstellung einer elektrischen vorrichtung - Google Patents

Verfahren zur herstellung einer elektrischen vorrichtung Download PDF

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Publication number
EP1042765B1
EP1042765B1 EP98962060A EP98962060A EP1042765B1 EP 1042765 B1 EP1042765 B1 EP 1042765B1 EP 98962060 A EP98962060 A EP 98962060A EP 98962060 A EP98962060 A EP 98962060A EP 1042765 B1 EP1042765 B1 EP 1042765B1
Authority
EP
European Patent Office
Prior art keywords
temperature
conductive
conductive polymer
polymer composition
resistive element
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.)
Expired - Lifetime
Application number
EP98962060A
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English (en)
French (fr)
Other versions
EP1042765A1 (de
Inventor
Naofumi Miyasaka
Shou-Mean Fang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TE Connectivity Corp
Original Assignee
Tyco Electronics Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tyco Electronics Corp filed Critical Tyco Electronics Corp
Publication of EP1042765A1 publication Critical patent/EP1042765A1/de
Application granted granted Critical
Publication of EP1042765B1 publication Critical patent/EP1042765B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/30—Apparatus or processes specially adapted for manufacturing resistors adapted for baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/027—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient consisting of conducting or semi-conducting material dispersed in a non-conductive organic material

Definitions

  • EP-A- 0730282 discloses a PTC element comprising a conductive sheet of a crystalline polyolefin matrix, and a conductive filler, having provided on both sides thereof an electrode of a metallic foil.
  • this invention provides a method of making an electrical device which comprises
  • the invention also provides a method for making a battery assembly which comprises the steps of
  • the particulate conductive filler which is dispersed in the polymeric component may be any suitable material, including carbon black, graphite, metal, metal oxide, conductive coated glass or ceramic beads, particulate conductive polymer, or a combination of these.
  • the filler may be in the form of powder, beads, flakes, fibers, or any other suitable shape.
  • the quantity of conductive filler needed is based on the required resistivity of the composition and the resistivity of the conductive filler itself. For many compositions the conductive filler comprises 10 to 60% by volume, preferably 20 to 55% by volume, and for low resistivity compositions used for low resistance circuit protection devices, especially 25 to 50% by volume of the total volume of the composition.
  • the conductive polymer composition may comprise additional components, such as antioxidants, inert fillers, nonconductive fillers, radiation crosslinking agents (often referred to as prorads or crosslinking enhancers, e.g. triallyl isocyanurate), stabilizers, dispersing agents, coupling agents, acid scavengers (e.g. CaCO 3 ), or other components. These components generally comprise at most 20% by volume of the total composition. Dispersion of the conductive filler and other components into the polymeric component may be achieved by any suitable means of mixing, e.g. melt-processing or solvent-mixing.
  • the mixed composition can be melt-shaped by any suitable method, e.g.
  • the composition used in the resistive element exhibits positive temperature coefficient (PTC) behavior, i.e. it shows a sharp increase in resistivity with temperature over a relatively small temperature range.
  • PTC positive temperature coefficient
  • the term "PTC” is used to mean a composition or device which has an R 14 value of at least 2.5 and/or an R 100 value of at least 10, and it is preferred that the composition or device should have an R 30 value of at least 6, where R 14 is the ratio of the resistivities at the end and the beginning of a 14°C range, R 100 is the ratio of the resistivities at the end and the beginning of a 100°C range, and R 30 is the ratio of the resistivities at the end and the beginning of a 30°C range.
  • the compositions used in devices of the invention show increases in resistivity which are much greater than those minimum values.
  • first and second laminar electrodes which are attached to the first face and the second face, respectively, of the resistive element.
  • the conductive polymer composition be extruded or otherwise formed into a sheet onto which the electrodes may be attached to form a laminate, i.e. the conductive polymer is sandwiched between the foils.
  • Both first and second electrodes comprise a conductive material, and are preferably metal in the form of a foil, e.g. nickel, copper, brass, stainless steel, or an alloy of one or more of these metals, although one or both of the electrodes may comprise a conductive paint or graphite layer.
  • a tie layer e.g. a conductive adhesive, may be used to attach the electrode to the resistive element.
  • the first and second electrodes comprise an electrodeposited metal foil, e.g. nickel, copper, or nickel-coated copper.
  • an electrodeposited metal foil e.g. nickel, copper, or nickel-coated copper.
  • Appropriate electrodes are disclosed in U.S. Patents Nos. 4,689,475 (Matthiesen) and 4,800,253 (Kleiner et al), and in International Publication No. WO95/34081 (Raychem Corporation, published December 14, 1995).
  • the device may also comprise an insulating layer, which provides electrical and environmental protection to the device.
  • the insulating layer generally covers some or all of the metal foil electrodes and any exposed surfaces of the resistive element.
  • Suitable insulating materials include polymers such as polyamide, polybutylene terephthalate, a polyester, polyethylene, polyvinylidene fluoride, liquid crystalline polymers, or an epoxy resin.
  • the device in a cutting step, is cut from a laminate comprising the conductive polymer composition positioned between two metal foils.
  • cutting is used to include any method of isolating or separating the resistive element of the device from the laminate, e.g. dicing, punching, shearing, cutting, etching and/or breaking as described in International Publication No. WO95/34084 (published December 14, 1995).
  • the device is then subjected to a thermal treatment step.
  • the thermal treatment step comprises at least one excursion from a first temperature T 1 to a second temperature T 2 .
  • the thermal treatment step includes a return to the first temperature after exposure to the second temperature, thus creating a cycle from T 1 to T 2 to T 1 .
  • the first temperature is at most (T m - 100)°C, preferably at most (T m - 120)°C, particularly at most (T m - 150)°C, where T m is the melting point of the polymeric component, as measured by the peak of the endotherm of a differential scanning calorimeter.
  • T m is defined as the temperature of the highest temperature peak.
  • the second temperature is at most (T m - 25)°C, preferably at most (T m - 35)°C, particularly at most (T m - 50)°C.
  • T 1 is often at a temperature below room temperature, i.e. less than 20°C.
  • the device is exposed to at least two thermal cycles, preferably at least three thermal cycles. For some applications, the device may be exposed to many more thermal cycles, e.g. six thermal cycles.
  • the device is held at both the first and the second temperatures for sufficient time to ensure that the entire device reaches the designated temperature.
  • the time period during which the device is held may be the same or different at T 1 and T 2 , but is generally at least 1 minute, preferably at least 3 minutes, more preferably at least 5 minutes, particularly at least 10 minutes, more particularly at least 15 minutes, especially at least 30 minutes, e.g. 60 minutes, as measured from the time the device reaches the designated temperature.
  • Any suitable heat source may be used during the thermal treatment step, e.g. an oven (particularly a programmable oven) or other environmental chamber, or a heat lamp.
  • the rate of temperature increase from T 1 to T 2 may be any convenient rate, e.g. 2 to 30°C/minute.
  • the rate from T 1 to T 2 may the same as or different from the rate from T 2 to T 1 .
  • the conductive polymer composition is crosslinked.
  • Crosslinking can be accomplished by chemical means or by irradiation, e.g. using an electron beam or a Co 60 ⁇ irradiation source.
  • the level of crosslinking depends on the required application for the composition, but is generally less than the equivalent of 200 Mrads, and is preferably substantially less, i.e. from 1 to 20 Mrads, preferably from 1 to 15 Mrads, particularly from 2 to 10 Mrads for low voltage (i.e. less than 60 volts) applications.
  • Useful circuit protection devices for applications of less than 30 volts can be made by irradiating the device to at least 2 Mrads but at most 10 Mrads.
  • first and second conductive leads are attached to first and second electrodes, respectively.
  • the conductive leads allow easy connection of the electrodes to the source of electrical power, e.g. a battery or a power source, or into the circuit, and can be used to control the thermal output of the device.
  • the conductive leads which often are supplied as part of a lead frame for ease in manufacture, are preferably attached to the electrodes by means of an intermediate layer, e.g. solder or a conductive adhesive.
  • This lead attachment step preferably occurs after the cutting step and before the thermal treatment step.
  • Other assembly processes e.g. application of the electrically insulating layer such as an epoxy resin or other polymer, are preferably conducted during an assembly step, which includes the lead attachment step and occurs after the cutting step and before the thermal treatment step.
  • devices in which the conductive polymer has a low resistivity i.e. less than 100 ohm-cm, preferably less than 20 ohm-cm, particularly less than 10 ohm-cm, more particularly less than 5 ohm-cm, especially less than 2 ohm-cm, e.g. less than 1 ohm-cm, can be prepared.
  • the device generally has a resistance at 20°C of less than 1 ohm, preferably less than 0.5 ohms, particularly less than 0.25 ohms, e.g. 0.050 to 0.150 ohms.
  • Devices made by the method according to the invention are particularly suitable for use in a battery assembly, in which the device is preferably attached to the first or second terminal of a battery.
  • the attachment may be directly between the battery and the first or second electrode, or between the battery and the first conductive lead which is attached to the first electrode, or the second conductive lead which is attached to the second electrode.
  • the device is physically and electrically attached to a button terminal.
  • the device may be attached to either the negative or the positive terminal of the battery.
  • Batteries suitable for use include nickel-cadmium, nickel-metal hydride, alkaline, or lithium batteries. Often the battery assembly comprises two or more batteries. Such a battery assembly is shown in International Publications Nos. WO97/06538 (K.K. Raychem, published February 20, 1997) and WO98/20567 (Raychem Corporation, published May 14, 1998).
  • FIG. 1 shows in cross-section electrical device 1 comprising PTC component 3, first conductive lead 15, second conductive lead 18, and insulating material 23.
  • PTC component 3 comprises first electrode 11, second electrode 13 and resistive element 9 composed of a conductive polymer sandwiched therebetween.
  • resistive element 9 composed of a conductive polymer sandwiched therebetween.
  • both electrodes opposing each other form first surface 43 and second surface 41.
  • PTC component 3 comprises surfaces 41 and 43, outer periphery 5 and inner periphery 7 and is in the form of a disk with an opening 27 in the center.
  • the inner periphery 7 defines the opening 27.
  • Figure 4 shows a top view of second conductive lead 18, which comprises first part 19 and second part 21.
  • First part 19 is attached to second electrode 13 and covers at least part of the surface of second electrode 13.
  • Second part 21 extends away from outer periphery 5 and can be bent, if necessary, to make electrical contact to a second battery or other electrical component.
  • First and second conductive leads 15,18 can be made from any suitable material, e.g. nickel, stainless steel, copper, or an alloy such as brass or bronze. For ease of manufacture second lead 18 is often part of a lead frame.
  • Figure 5 shows a top view of device 1 which as been encapsulated by electrically insulating layer 23.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Noodles (AREA)

Claims (9)

  1. Verfahren zur Herstellung einer elektrischen Vorrichtung (1), die folgendes umfaßt:
    (A) ein Widerstandselement (9), das aus einer leitfähigen Polymerzusammensetzung zusammengesetzt ist, die PTC-Verhalten zeigt und die folgendes umfaßt:
    (1) eine Polymerkomponente mit einer Kristallinität von mindestens 20% und einem Schmelzpunkt Tm und
    (2) einen in der Polymerkomponente dispergierten partikelförmigen leitfähigen Füllstoff; und
    (B) zwei Elektroden (11, 13), die (i) an dem Widerstandselement (9) befestigt sind, (ii) Metallfolien umfassen und (iii) mit einer elektrischen Stromquelle verbunden werden können,
    wobei das Verfahren die folgenden Schritte umfaßt:
    (a) Abschneiden einer Vorrichtung (1) von einem Schichtwerkstoff, der die zwischen zwei Metallfolien positionierte leitfähige Polymerzusammensetzung umfaßt;
    (b) Aussetzen der Vorrichtung (1) nach dem Abschneideschritt mindestens einer Temperaturexkursion von einer ersten Temperatur, die höchstens (Tm - 100)°C beträgt, bis zu einer zweiten Temperatur, die höchstens (Tm - 25)°C beträgt; und
    dadurch gekennzeichnet, daß das Verfahren ferner den folgenden Schritt umfaßt:
    (c) Vernetzen der leitfähigen Polymerzusammensetzung nach der Temperaturexkursion.
  2. Verfahren nach Anspruch 1, das den folgenden Schritt umfaßt: Befestigen mindestens eines leitfähigen Leiters (15) an einer der Metallfolien-Elektroden nach Schritt (a) und vor Schritt (b).
  3. Verfahren nach Anspruch 1 oder 2, bei dem die Vorrichtung (1) in Schritt (c) zu dem Äquivalent von 1 bis 20 Mrads vernetzt worden ist.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Polymerkomponente Polyethylen, ein Ethylen-Copolymer oder ein Fluorpolymer umfaßt.
  5. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Vorrichtung (1) in Schritt (b) mindestens einem thermischen Zyklus von der ersten Temperatur zur zweiten Temperatur und zurück zur ersten Temperatur ausgesetzt wird.
  6. Verfahren nach einem der vorhergehenden Ansprüche, wobei in Schritt (b) die erste Temperatur T1 weniger als 23 °C beträgt.
  7. Verfahren nach Anspruch 1, wobei:
    (1) das Widerstandselement (9) (i) eine Dicke von höchstens 0,51 mm hat und (ii) zu dem Äquivalent von mindestens 2 Mrads vernetzt wird und
    (2) in Schritt (b) die Vorrichtung (1) nach dem Abschneideschritt mindestens einem thermischen Zyklus von einer ersten Temperatur, die höchstens (Tm - 100)°C beträgt, bis zu einer zweiten Temperatur, die höchstens (Tm - 25)°C beträgt, und zurück zur ersten Temperatur ausgesetzt wird.
  8. Verfahren nach Anspruch 7, wobei die Vorrichtung (1) in Schritt (b) mindestens drei thermischen Zyklen ausgesetzt wird.
  9. Verfahren zur Herstellung einer Batterieanordnung, die folgenden Schritte umfassend:
    (1) Bereitstellen einer Batterie, die einen ersten und einen zweiten Anschluß umfaßt; und
    (2) Herstellen einer Vorrichtung (1) nach Anspruch 1und
    (a) Befestigen einer ersten leitfähigen Leitung (15) an der ersten Elektrode (11) der Vorrichtung (1) und
    (b) Befestigen eines zweiten leitfähigen Leitung (18) an der zweiten Elektrode (13) der Vorrichtung (1);
    (3) Inkontaktbringen der Vorrichtung (1) mit dem ersten Anschluß der Batterie, so daß die erste leitfähige Leitung (15) in physischem und elektrischem Kontakt mit diesem Anschluß ist.
EP98962060A 1997-12-15 1998-12-10 Verfahren zur herstellung einer elektrischen vorrichtung Expired - Lifetime EP1042765B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US99070797A 1997-12-15 1997-12-15
US990707 1997-12-15
PCT/US1998/026328 WO1999031677A1 (en) 1997-12-15 1998-12-10 Electrical device

Publications (2)

Publication Number Publication Date
EP1042765A1 EP1042765A1 (de) 2000-10-11
EP1042765B1 true EP1042765B1 (de) 2007-05-09

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EP98962060A Expired - Lifetime EP1042765B1 (de) 1997-12-15 1998-12-10 Verfahren zur herstellung einer elektrischen vorrichtung

Country Status (7)

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EP (1) EP1042765B1 (de)
JP (1) JP4459438B2 (de)
CN (1) CN1155011C (de)
AT (1) ATE362185T1 (de)
DE (1) DE69837771T2 (de)
TW (1) TW408343B (de)
WO (1) WO1999031677A1 (de)

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JPWO2004114331A1 (ja) 2003-06-23 2006-08-03 タイコ エレクトロニクス レイケム株式会社 Ｐｔｃサーミスタ、および回路の保護方法
CN100479072C (zh) * 2005-08-05 2009-04-15 聚鼎科技股份有限公司 过电流保护元件
CN100472674C (zh) * 2005-08-19 2009-03-25 聚鼎科技股份有限公司 过电流保护元件
JP5274019B2 (ja) * 2005-12-09 2013-08-28 タイコエレクトロニクスジャパン合同会社 Ｐｔｃデバイスの製造方法
CN101026029B (zh) * 2006-02-17 2010-05-12 聚鼎科技股份有限公司 过电流保护元件
WO2017220747A1 (de) * 2016-06-22 2017-12-28 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Elektrisch leitfähige formkörper mit positivem temperaturkoeffizienten

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KR920003015B1 (ko) * 1988-06-01 1992-04-13 마쯔시다덴기산교 가부시기가이샤 자체온도 제어발열체 조성물
JPH04167501A (ja) * 1990-10-31 1992-06-15 Daito Tsushinki Kk Ｐｔｃ素子
JPH0521207A (ja) * 1991-07-12 1993-01-29 Daito Tsushinki Kk Ｐｔｃ素子
TW298653B (de) * 1995-02-28 1997-02-21 Yunichica Kk
KR19990036224A (ko) * 1995-08-07 1999-05-25 준 이시오까 Ｐｔｃ 소자 및 그것을 이용한 전지 조립체

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Also Published As

Publication number Publication date
DE69837771D1 (de) 2007-06-21
ATE362185T1 (de) 2007-06-15
WO1999031677A1 (en) 1999-06-24
DE69837771T2 (de) 2008-01-17
JP2002509348A (ja) 2002-03-26
CN1155011C (zh) 2004-06-23
TW408343B (en) 2000-10-11
CN1283304A (zh) 2001-02-07
JP4459438B2 (ja) 2010-04-28
EP1042765A1 (de) 2000-10-11

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