WO1999031677A1 - Dispositif electrique - Google Patents

Dispositif electrique Download PDF

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Publication number
WO1999031677A1
WO1999031677A1 PCT/US1998/026328 US9826328W WO9931677A1 WO 1999031677 A1 WO1999031677 A1 WO 1999031677A1 US 9826328 W US9826328 W US 9826328W WO 9931677 A1 WO9931677 A1 WO 9931677A1
Authority
WO
WIPO (PCT)
Prior art keywords
temperature
conductive
conductive polymer
polymer composition
attached
Prior art date
Application number
PCT/US1998/026328
Other languages
English (en)
Inventor
Naofumi Miyasaka
Shou-Mean Fang
Original Assignee
Tyco Electronics Corporation
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 Corporation filed Critical Tyco Electronics Corporation
Priority to DE69837771T priority Critical patent/DE69837771T2/de
Priority to JP2000539488A priority patent/JP4459438B2/ja
Priority to EP98962060A priority patent/EP1042765B1/fr
Publication of WO1999031677A1 publication Critical patent/WO1999031677A1/fr

Links

Classifications

    • 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

  • This invention relates to electrical devices comprising conductive polymers, .and a method of making such devices.
  • circuit protection devices which comprise conductive polymer compositions which exhibit PTC (positive temperature coefficient of resistance) behavior are well-known and are used as circuit protection devices and heaters.
  • Such circuit protection devices containing low resistivity conductive polymer compositions, respond to changes in ambient temperature and/or current conditions. Under normal conditions, a circuit protection device remains in a low temperature, low resistance state when in series with a load in an electrical circuit. When exposed to an overcurrent or overtemperature condition, however, the device increases in resistance, effectively shutting down the current flow to the load in the circuit.
  • the device it is desirable that the device have as low a resistance as possible in order to minimize the contribution to the total resistance of the electrical circuit during normal operation. Furthermore, a low resistance allows the device to have a higher hold current, i.e.
  • low resistance devices can be made from a given composition by changing dimensions, e.g. making the distance between the electrodes very small or the device area very large, small devices are preferred. Such devices occupy less space on a circuit board and generally have desirable thermal properties.
  • this invention provides an electrical device which comprises
  • the device having been prepared by a method which comprises the steps of
  • the invention provides a method of making an electrical device which comprises
  • a resistive element which (i) has a thickness of at most 0.51 mm, (ii) is crosslinked to the equivalent of at least 2 Mrads, and (iii) is composed of a conductive polymer composition which comprises (1) a polymeric component having a crystallinity of at least 20% and a melting point T m , -and
  • the invention provides a battery assembly which comprises
  • Figure 1 is a cross-sectional view of a device of the invention
  • Figure 2 is a top view of a device of the invention
  • Figure 3 is a top view of a first conductive lead which forms part of a device of the invention.
  • Figure 4 is a top view of a device of the invention with a second conductive lead attached;
  • Figure 5 is a top view of a device of the invention comprising an insulating layer
  • Figure 6 is a graph showing the resistance distribution for devices made by a method of the invention and two comparative methods.
  • the electrical device of the invention comprises a resistive element composed of a conductive polymer composition, and first and second metal foil electrodes which are attached to, and sandwich, the resistive element.
  • the conductive polymer composition comprises a polymeric component, and dispersed therein, a particulate conductive filler.
  • the polymeric component comprises one or more polymers, one of which is preferably a crystalline polymer having a crystallinity of at least 20% as measured in its unfilled state by a differential scanning calorimeter.
  • Suitable crystalline polymers include polymers of one or more olefins, particularly polyethylene such as high density polyethylene; copolymers of at least one olefin and at least one monomer copolymensable therewith such as ethylene/acrylic acid, ethylene/ethyl acrylate, ethylene/vinyl acetate, and ethylene/rjutyl acrylate copolymers; melt-shapeable fluoropolymers such as polyvinylidene fluoride (PVDF) and ethylene/tetrafluoroethylene copolymers (ETFE, including terpolymers); and blends of two or more such polymers.
  • PVDF polyvinylidene fluoride
  • ETFE ethylene/tetrafluoroethylene copolymers
  • the polymeric component generally comprises 40 to 90% by volume, preferably 45 to 80% by volume, especially 50 to 75% by volume of the total volume of the composition.
  • 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. CaCO3), 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 element is preferably laminar and may be of any shape, e.g. rectangular, square, circular, or annular.
  • the resistive element often has a thickness of at most 1.02 mm (0.040 inch), and, for many applications, is much thinner, i.e. has a thickness of at most 0.51 mm (0.020 inch), preferably at most 0.38 mm (0.015 inch).
  • the composition used in the resistive element exhibits positive temperature coefficient (PTC) behavior, i.e. it shows a sha ⁇ 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 R14 value of at least 2.5 and/or an RlOO value of at least 10, and it is preferred that the composition or device should have an R30 value of at least 6, where R14 is the ratio of the resistivities at the end and the beginning of a 14°C range, RlOO is the ratio of the resistivities at the end and the beginning of a 100°C range, and R30 is the ratio of the resistivities at the end and the beginning of a 30°C range.
  • R14 is the ratio of the resistivities at the end and the beginning of a 14°C range
  • RlOO is the ratio of the resistivities at the end and the beginning of a 100°C range
  • R30 is the ratio of the resistivities at the end and the beginning
  • Suitable conductive polymer compositions are disclosed in U.S. Patent Nos.
  • 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 Co ⁇ oration, 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 Tj 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-, to T 2 to T-,.
  • 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 g glass transition temperature
  • T- 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 ] 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-, to T 2 may be any convenient rate, e.g. 2 to 30°C/minute.
  • the rate from T, to T 2 may the same as or different from the rate from T 2 to T-,.
  • 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 ⁇ O ⁇ 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.
  • 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 of 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 Co ⁇ oration, published May 14, 1998).
  • FIG. 1 shows in cross- section electrical device 1 of the invention 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.
  • 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 3 shows a top view of first conductive lead 15, which has a first part 16 which is attached to first electrode 1 1 , and a second part 17 which extends across opening 27 of PTC component 3.
  • first part 16 covers the whole surface of first electrode 1 1.
  • Second part 17 of first lead 15, which covers at least a part of opening 27, is used to make direct electrical contact, via solder, pressure, or a weld, to a button terminal of a battery.
  • the second part 17 covers at least a part of 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.
  • a positive terminal of a battery is placed inside opening 27', no short circuit occurs because no electrical contact is made between the terminal and PTC component 3.
  • the invention is illustrated by the following examples, in which Examples 1 and 2 are comparative examples. The following steps were conducted for each example:
  • a first compound was prepared by preblending 54% by weight carbon black (RavenTM 430U, available from Columbian Chemicals) with 46% by weight high density polyethylene (PetrotheneTM LB832, available from Millenium; "HDPE”) in a Henschel blender, mixing the blend in a Buss kneader, and extruding into pellets.
  • a second compound was prepared by preblending 51.4% by weight carbon black with 48.6% by weight HDPE in the same way.
  • Pellets of the first and second compounds were preblended to give a final compound having 52.7% by weight carbon black and 47.3% by weight HDPE, and this compound was extruded through a sheet die using an Egan extruder to give a sheet with a thickness of 0.25 mm (0.010 inch).
  • the extruded sheet was laminated between two layers of electrodeposited nickel foil having a thickness of about 0.033 mm (0.0013 inch) (available from Fukuda) by using a press set at 200°C.
  • the laminated sheet was solder-dipped into a solder formulation of 63% lead/37% tin heated to 230°C, and devices having the shape shown in Figure 2 were punched from the laminated sheet.
  • First .and second conductive leads as shown in Figures 3 and 4, were attached to the PTC device by means of 63/37 lead/tin solder, which was reflowed in a hot-air oven which increased in temperature from 30°C to a maximum temperature of 230°C over about 2 minutes.
  • An insulating layer of liquid crystalline polymer was then applied by means of transfer or injection molding.
  • the devices were thermally cycled six times, each cycle being from -40 to 80 to 40°C at a rate of l°C/minute with a 60 minute dwell at -40°C and 80°C.
  • Device preparation was conducted as shown in Table I, with numbers 1 to 4 indicating the sequential order of the process steps as they were conducted.
  • the resistance at 25°C was measured for one hundred devices prepared for each example.
  • the resulting devices had an average resistance at least 5% higher than that of devices of the invention (Example 3).

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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)

Abstract

L'invention concerne un dispositif électrique (1) contenant un élément (9) résistant composé d'une composition polymère conductrice présentant un coefficient de température positif, laquelle est fixée à deux électrodes (11, 13) en forme de lames métalliques. Le dispositif est préparé selon un procédé consistant (a) à découper le dispositif dans un stratifié contenant la composition polymère conductrice placée entre les deux lames de métal; (b) à exposer le dispositif après découpage à au moins une excursion thermique entre une première température correspondant au plus à (Tm - 100) °C et une seconde température correspondant au plus à (Tm - 25) °C; et (c) à réticuler la composition polymère conductrice après ladite excursion thermique. Les dispositifs de l'invention présentent une faible résistance et sont utilisés comme dispositifs de protection de circuits.
PCT/US1998/026328 1997-12-15 1998-12-10 Dispositif electrique WO1999031677A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE69837771T DE69837771T2 (de) 1997-12-15 1998-12-10 Verfahren zur herstellung einer elektrischen vorrichtung
JP2000539488A JP4459438B2 (ja) 1997-12-15 1998-12-10 電気デバイスを製造する方法及びバッテリ組立体を製造する方法
EP98962060A EP1042765B1 (fr) 1997-12-15 1998-12-10 Methode de fabrication d'un dispositif electrique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US99070797A 1997-12-15 1997-12-15
US08/990,707 1997-12-15

Publications (1)

Publication Number Publication Date
WO1999031677A1 true WO1999031677A1 (fr) 1999-06-24

Family

ID=25536456

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/026328 WO1999031677A1 (fr) 1997-12-15 1998-12-10 Dispositif electrique

Country Status (7)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2709631C1 (ru) * 2016-06-22 2019-12-19 Тюрингишес Институт Фюр Текстиль- Унд Кунстштофф-Форшунг Е.В. Электропроводящее формованное изделие с положительным температурным коэффициентом

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102176357A (zh) 2003-06-23 2011-09-07 泰科电子雷伊化学株式会社 Ptc热敏电阻和电路保护方法
WO2007066725A1 (fr) * 2005-12-09 2007-06-14 Tyco Electronics Raychem K.K. Procédé de fabrication d’un dispositif ptc
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0344734A1 (fr) * 1988-06-01 1989-12-06 Matsushita Electric Industrial Co., Ltd. Composition chauffante pour l'autorégulation de la température
EP0484138A2 (fr) * 1990-10-31 1992-05-06 Daito Communication Apparatus Co. Ltd. Composition de résistance à coefficient de température positif
EP0522863A1 (fr) * 1991-07-12 1993-01-13 Daito Communication Apparatus Co. Ltd. Dispositif à coefficient de température positif
EP0730282A2 (fr) * 1995-02-28 1996-09-04 Unitika Ltd. Elément PTC et procédé de fabrication
EP0844622A1 (fr) * 1995-08-07 1998-05-27 K.K. Raychem Dispositif c.t.p. et bloc d'alimentation l'utilisant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0344734A1 (fr) * 1988-06-01 1989-12-06 Matsushita Electric Industrial Co., Ltd. Composition chauffante pour l'autorégulation de la température
EP0484138A2 (fr) * 1990-10-31 1992-05-06 Daito Communication Apparatus Co. Ltd. Composition de résistance à coefficient de température positif
EP0522863A1 (fr) * 1991-07-12 1993-01-13 Daito Communication Apparatus Co. Ltd. Dispositif à coefficient de température positif
EP0730282A2 (fr) * 1995-02-28 1996-09-04 Unitika Ltd. Elément PTC et procédé de fabrication
EP0844622A1 (fr) * 1995-08-07 1998-05-27 K.K. Raychem Dispositif c.t.p. et bloc d'alimentation l'utilisant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2709631C1 (ru) * 2016-06-22 2019-12-19 Тюрингишес Институт Фюр Текстиль- Унд Кунстштофф-Форшунг Е.В. Электропроводящее формованное изделие с положительным температурным коэффициентом
RU2709631C9 (ru) * 2016-06-22 2020-06-04 Тюрингишес Институт Фюр Текстиль- Унд Кунстштофф-Форшунг Е.В. Электропроводящее формованное изделие с положительным температурным коэффициентом

Also Published As

Publication number Publication date
CN1155011C (zh) 2004-06-23
DE69837771T2 (de) 2008-01-17
JP4459438B2 (ja) 2010-04-28
CN1283304A (zh) 2001-02-07
EP1042765B1 (fr) 2007-05-09
DE69837771D1 (de) 2007-06-21
EP1042765A1 (fr) 2000-10-11
JP2002509348A (ja) 2002-03-26
TW408343B (en) 2000-10-11
ATE362185T1 (de) 2007-06-15

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