EP0038713B1 - Leitende, Füllstoffe enthaltende Polymermassen - Google Patents

Leitende, Füllstoffe enthaltende Polymermassen Download PDF

Info

Publication number
EP0038713B1
EP0038713B1 EP81301764A EP81301764A EP0038713B1 EP 0038713 B1 EP0038713 B1 EP 0038713B1 EP 81301764 A EP81301764 A EP 81301764A EP 81301764 A EP81301764 A EP 81301764A EP 0038713 B1 EP0038713 B1 EP 0038713B1
Authority
EP
European Patent Office
Prior art keywords
composition
volume
carbon black
arc
polymer component
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
Application number
EP81301764A
Other languages
English (en)
French (fr)
Other versions
EP0038713A3 (en
EP0038713A2 (de
Inventor
Joseph Hill Evans
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.)
Raychem Corp
Original Assignee
Raychem 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 Raychem Corp filed Critical Raychem Corp
Priority to AT81301764T priority Critical patent/ATE29329T1/de
Publication of EP0038713A2 publication Critical patent/EP0038713A2/de
Publication of EP0038713A3 publication Critical patent/EP0038713A3/en
Application granted granted Critical
Publication of EP0038713B1 publication Critical patent/EP0038713B1/de
Expired legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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 conductive polymer compositions and devices containing them, especially circuit protection systems.
  • Conductive and semi-conductive compositions comprising carbon black dispersed in a polymer are known. They may have room temperature resistivities ranging from less than 1 ohm - cm to 10 8 ohm - cm or more, and may exhibit positive temperature coefficient (PTC) behaviour zero temperature coefficient (ZTC or constant wattage) behaviour or negative temperature coefficient (NTC) behaviour.
  • PTC positive temperature coefficient
  • ZTC zero temperature coefficient
  • NTC negative temperature coefficient
  • US 3351882 discloses a device which comprises a PTC element composed of two electrodes and a conductive polymer composition, the composition comprising a polymer having carbon black dispersed therein.
  • the invention provides an electrical device which comprises:
  • the PTC compositions defined above are particularly useful in circuit protection devices as described in the contemporaneously filed European Application Nos. 0,038,715, 0,038,716 and 0,038,717.
  • compositions can be any of the PTC compositions which are disclosed in the prior art and the earlier applications referred to above, which have a resistivity at 23°C of less than 10 6 ohm - cm, which comprise 20 to 91% by volume of a conductive filler which consists essentially of carbon black and/or graphite, and which have been modified by the inclusion of at least one arc-controlling additive as defined in Claim 1.
  • the invention is especially valuable in relation to circuit protection devices, which usually have a resistance below 50 ohms, at 23°C as described in European Published Application No. 0,038,715, and in which the PTC composition has low resistivity at 23°C, e.g. below 20 ohm ⁇ cm, preferably below 10 ohm - cm, especially below 2 ohm - cm.
  • the preferred arc-controlling additive for use in the present invention is alumina trihydrate, Al 2 O 3 ⁇ 3H 2 0.
  • Another additive is magnesia hydrate.
  • the conductive filler and the arc-controlling additive preferably have a total surface area of at least 1,800, especially at least 3,000, particularly at least 4,000, m2/100 cm 3 of composition, with higher values, e.g., at least 8,000 m 2 /100 cm 3 , at least 10,000 m 2 /100 cm 3 and at least 12,000 m 2 /100 cm 3 being particularly preferred.
  • the composition should contain an effective amount of the arc-controlling additive, typically 5 to 65%, preferably 10 to 35%, by volume of the composition.
  • the composition can also contain further additives which are known to enhance the effectiveness of anti-tracking additives in insulating compositions.
  • additives include the phosphorus- containing compounds disclosed in British Patent No. 1,575,465 and the oxide of elements of the transition series, lanthanide series or non-transuranic actinide series disclosed in British Patents Nos. 1,337,951 and 1,337,952.
  • the conductive filler in the composition preferably consists essentially of at least one carbon black.
  • the carbon black is selected with a view to the electrical characteristics desired in the composition, as taught by the various patents and applications referred to above.
  • the carbon black preferably has a particle size, D, which is from 20 to 150 nm (millimicrons) and a surface area, S in m 2 /g such that S/D is not more than 10.
  • the quantity is less than 1.
  • the polymer component in the composition which may comprise one or more polymers, preferably has a crystallinity of at least 1%, especially at least 5%, particularly at least 10%.
  • the polymer component consists essentially of one or more crystalline polymers selected from polyolefins and copolymers of at least one olefin and at least one polar comonomer copolymerisable therewith, e.g. polyethylene or polypropylene.
  • suitable polymers are referred to in the patents and applications referred to above.
  • compositions may be substantially free of cross-linking or may be cross-linked, e.g. to a gel fraction of at least 0.4 or 0.6.
  • compositions free of cross-linking are preferred, because the presence of cross-linking tends to increase the likelihood of formation of carbonaceous conductive paths when arcing takes place.
  • the composition can be prepared by dispersing the carbon black or graphite, the arc-controlling additive and any other additives in the polymer component in any suitable way.
  • the composition can be shaped by molding or extrusion or another melt-shaping technique into an element of the desired shape, any cross-linking thereof being carried out after such shaping.
  • Conductive polymer compositions comprising a crystalline polymer component, at least 4% by volume of carbon black and at least 4% by volume of a non-conductive particulate filler, the total surface area of the carbon black and filler being at least 1800 m 2 /100 cm 3 of composition, are described and claimed in the contemporaneously filed application corresponding to European Published Application No. 0,038,718.
  • the invention is illustrated by the following Examples.
  • the words Fumex, Marlex, Sterling and Maglite are UK Registered Trade Marks.
  • Marlex 6003 is a high density polyethylene with a melt index of 0.3 which is available from Phillips Petroleum Co.
  • the antioxidant used was an oligomer of 4,4-thio bis (3-methyl-6-t-butyl phenol) with an average degree of polymerization of 3-4, as described in U.S. Patent No. 3,986,981.
  • Hydral 705 is alumina trihydrate.
  • the granulated final mix was melt extruded in the form of a strip about 1.27 cm wide and about 0.27 cm thick, using a cross-head die, around a pair of pre-heated 20 AWG (diameter 0.095 cm) 19-32 stranded nickel-plated copper wires whose centers were 0.6 cm apart.
  • the extruded product was cut into 2.5 cm lengths, and the polymeric composition removed from half of each length to produce a circuit control device as shown in Figure 4 of the contemporaneously filed application corresponding to European Published Application No. 0,038,716.
  • Example 2 the Master Batch ingredients were blended in a pre-heated Banbury mixer, and the mixture dumped, cooled and granulated. 67 g of the granulated mixture was banded on a 7.6 cm electric roll mill, and the Hydral was added in portions to give a uniform mixture; mixing was continued for several more minutes and the mixture was then removed from the mill, cooled, granulated and compression- molded into slabs.
  • Example 3 the Master Batch ingredients were blended in a pre-heated Banbury mixer, and the mixture dumped, cooled and granulated. 67 g of the granulated mixture was banded on a 3 inch electric roll mill, and the Hydral was added in portions to give a uniform mixture; mixing was continued for several more minutes and the mixture was then removed from the mill, cooled, granulated and compression- molded into slabs.
  • Example 4 the procedure described for Example 2 was followed, using the different ingredients shown in Table 2, except that 50 g of the granulated Master Batch was used and 50 g of the filler (Maglite D) added to it.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Ceramic Engineering (AREA)
  • Electromagnetism (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Thermistors And Varistors (AREA)
  • Conductive Materials (AREA)

Claims (8)

1. Elektrische Vorrichtung, welche aufweist: (1) ein PTC-Element, bestehend aus einer Zusammensetzung von leitfähigem Polymeren, die PTC-Verhalten zeigt und eine organische Polymerkomponente und in der Polymerkomponente verteilt eine leitfähige kohlenstoffhaltige Füllstoffkomponente enthält, und (2) mindestens zwei Elektroden zum Hindurchleiten von Strom durch das PTC-Element, dadurch gekennzeichnet, dass das PTC-Element aus einer Zusammensetzung besteht, welche einen spezifischen Widerstand bei 23°C von weniger als 106 Ohm cm hat und aufweist:
(a) 20 bis 91 Vol.% einer organischen Polymerkomponente;
(b) 4 bis 65 Vol.% leitfähige Füllstoffkomponente, die im wesentlichen aus Russ und/oder Graphit besteht; und
(c) einen Lichtbogensteuerungszusatz, der ein hydratisiertes anorganisches Teilchenförmiges Material ist, das in der Polymerkomponente dispergiert ist.
2. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, dass der Lichtbogensteuerungszusatz in einer Menge von 5 bis 65 Vol.%, vorzugsweise 10 bis 35 Vol.%, der Zusammensetzung enthalten ist.
3. Vorrichtung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Lichtbogensteuerungszusatz Aluminiumtrihydrat ist.
4. Vorrichtung nach Anspruch 1, oder 3, dadurch gekennzeichnet, dass der leitfähige Füllstoff und der Lichtbogensteuerungzusatz eine Gesamtoberfläche von mindestens 1800 m2 je 100 cm3 der Zusammensetzung haben.
5. Vorrichtung nach einem der vorhergehenden Ansprüche 2 bis 4, dadurch gekennzeichnet, dass die polymere Komponente eine Kristallinität von mindestens 5% hat und die Komponente des leitfähigen Füllstoffes (a) Russ von einer Teilchengrösse, D, aufweist, welche 20 bis 150 nm beträgt und eine solche Oberfläche, S, in m2/g hat, dass S/D nicht mehr als 10 beträgt, und (b) in einer solchen Menge anwesend ist, dass die Zusammensetzung einen spezifischen Widerstand von weniger als 20 Ohm - cm bei 23°C hat.
6. Vorrichtung nach Anspruch 5, dadurch gekennzeichnet, dass die Menge
Figure imgb0006
weniger als 1 ist.
7. Vorrichtung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass sie eine Schaltungsschutzvorrichtung von einem spezifischen Widerstand bei 23°C von weniger als 50 Ohm, vorzugsweise 0,1 bis 25 Ohm, ist.
8. Vorrichtung nach Anspruch 7, dadurch gekennzeichnet, dass die leitfähige Polymerzusammensetzung einen spezifischen Widerstand von weniger als 10 Ohm · cm hat und
(a) 20 bis 91 Vol.% einer Polymerkomponente von einer Kristallinität von mindestens 10%;
(b) 4 bis 65 Vol.% Russ; und
(c) 5 bis 65 Vol.% Aluminiumtrihydrat

enthält, wobei der Russ und das Aluminiumtrihydrat eine Gesamtoberfläche von mindestens 1800 m2/100 cm' Zusammensetzung hat.
EP81301764A 1980-04-21 1981-04-21 Leitende, Füllstoffe enthaltende Polymermassen Expired EP0038713B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81301764T ATE29329T1 (de) 1980-04-21 1981-04-21 Leitende, fuellstoffe enthaltende polymermassen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14198980A 1980-04-21 1980-04-21
US141989 2002-05-10

Publications (3)

Publication Number Publication Date
EP0038713A2 EP0038713A2 (de) 1981-10-28
EP0038713A3 EP0038713A3 (en) 1981-11-18
EP0038713B1 true EP0038713B1 (de) 1987-09-02

Family

ID=22498109

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81301764A Expired EP0038713B1 (de) 1980-04-21 1981-04-21 Leitende, Füllstoffe enthaltende Polymermassen

Country Status (7)

Country Link
EP (1) EP0038713B1 (de)
JP (1) JPS56161463A (de)
AT (1) ATE29329T1 (de)
CA (1) CA1176453A (de)
DE (1) DE3176415D1 (de)
GB (1) GB2074169B (de)
HK (1) HK83089A (de)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4413301A (en) 1980-04-21 1983-11-01 Raychem Corporation Circuit protection devices comprising PTC element
EP0099717A3 (de) * 1982-07-20 1986-09-17 The British Petroleum Company p.l.c. Leitfähige Harzmassen aus ungesättigten Polyestern
EP0190772B1 (de) * 1982-11-17 1991-05-08 Kabushiki Kaisha Meidensha Elektrisch leitfähiger Kunststoff
EP0250776B1 (de) 1983-06-30 1992-06-10 RAYCHEM CORPORATION (a Delaware corporation) Methode zur Erkennung und Beschaffung von Information über die Veränderungen von Variablen
JPS6028195A (ja) * 1983-07-27 1985-02-13 松下電器産業株式会社 ヒ−タ
JPS6053560A (ja) * 1983-09-05 1985-03-27 Dainichi Seika Kogyo Kk 導電性ポリフエニレンサルフアイド樹脂組成物
US4528213A (en) * 1983-11-22 1985-07-09 Rca Corporation EMI/RFI Shielding composition
US4774024A (en) * 1985-03-14 1988-09-27 Raychem Corporation Conductive polymer compositions
US4647896A (en) * 1985-03-14 1987-03-03 Raychem Corporation Materials for packaging circuit protection devices
US4884163A (en) * 1985-03-14 1989-11-28 Raychem Corporation Conductive polymer devices
JPS62119272A (ja) * 1985-11-19 1987-05-30 Mitsubishi Petrochem Co Ltd 樹脂抵抗体
JPH0777161B2 (ja) * 1986-10-24 1995-08-16 日本メクトロン株式会社 Ｐｔｃ組成物、その製造法およびｐｔｃ素子
DE3722480A1 (de) * 1987-07-08 1989-01-19 Kabelmetal Electro Gmbh Kriechstromfest isolierende formteile
US5166658A (en) * 1987-09-30 1992-11-24 Raychem Corporation Electrical device comprising conductive polymers
US4924074A (en) * 1987-09-30 1990-05-08 Raychem Corporation Electrical device comprising conductive polymers
US4907340A (en) * 1987-09-30 1990-03-13 Raychem Corporation Electrical device comprising conductive polymers
WO1990003681A1 (en) * 1988-09-20 1990-04-05 Raychem Limited Circuit protection arrangement
US5122775A (en) * 1990-02-14 1992-06-16 Raychem Corporation Connection device for resistive elements
US5174924A (en) * 1990-06-04 1992-12-29 Fujikura Ltd. Ptc conductive polymer composition containing carbon black having large particle size and high dbp absorption
US5089801A (en) * 1990-09-28 1992-02-18 Raychem Corporation Self-regulating ptc devices having shaped laminar conductive terminals
US6111234A (en) * 1991-05-07 2000-08-29 Batliwalla; Neville S. Electrical device
DE60239096D1 (de) * 2001-07-02 2011-03-17 Mitsui Du Pont Fluorchemical Elektrisch leitfähige Fluorpolymerzusammensetzung
JP6729410B2 (ja) * 2017-01-17 2020-07-22 トヨタ自動車株式会社 全固体電池

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3351882A (en) * 1964-10-09 1967-11-07 Polyelectric Corp Plastic resistance elements and methods for making same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1207401A (fr) * 1955-07-21 1960-02-16 Thomson Houston Comp Francaise Isolant pour appareils électriques
GB1185473A (en) * 1966-09-14 1970-03-25 British Insulated Callenders Improvements in Conductive or Semi-Conductive Fibrous Sheet Material.
JPS5136876A (en) * 1974-09-25 1976-03-27 Hitachi Ltd Sairisuta no reetokokasokuteihoho narabini sochi
JPS5179140A (ja) * 1974-12-28 1976-07-09 Furukawa Electric Co Ltd Handodenseijushisoseibutsu
GB1604735A (en) * 1978-04-14 1981-12-16 Raychem Corp Ptc compositions and devices comprising them
US4237441A (en) * 1978-12-01 1980-12-02 Raychem Corporation Low resistivity PTC compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3351882A (en) * 1964-10-09 1967-11-07 Polyelectric Corp Plastic resistance elements and methods for making same

Also Published As

Publication number Publication date
EP0038713A3 (en) 1981-11-18
JPH0428744B2 (de) 1992-05-15
CA1176453A (en) 1984-10-23
ATE29329T1 (de) 1987-09-15
JPS56161463A (en) 1981-12-11
DE3176415D1 (en) 1987-10-08
HK83089A (en) 1989-10-27
GB2074169B (en) 1983-12-21
EP0038713A2 (de) 1981-10-28
GB2074169A (en) 1981-10-28

Similar Documents

Publication Publication Date Title
US5049850A (en) Electrically conductive device having improved properties under electrical stress
EP0038713B1 (de) Leitende, Füllstoffe enthaltende Polymermassen
US5178797A (en) Conductive polymer compositions having improved properties under electrical stress
US4545926A (en) Conductive polymer compositions and devices
US5140297A (en) PTC conductive polymer compositions
US4845838A (en) Method of making a PTC conductive polymer electrical device
EP0038715B1 (de) Schaltungsschutzeinrichtung
US4774024A (en) Conductive polymer compositions
US4514620A (en) Conductive polymers exhibiting PTC characteristics
US5227946A (en) Electrical device comprising a PTC conductive polymer
CA1175098A (en) Circuit protection devices
US5195013A (en) PTC conductive polymer compositions
US4884163A (en) Conductive polymer devices
US4955267A (en) Method of making a PTC conductive polymer electrical device
US4818439A (en) PTC compositions containing low molecular weight polymer molecules for reduced annealing
EP0038718B1 (de) Leitfähige Polymer-Zusammensetzung mit Füllstoffen
EP0063440B1 (de) Strahlungsvernetzung der PTC-leitfähigen Polymere
US6277303B1 (en) Conductive polymer composite materials and methods of making same
GB2036754A (en) Low resistivity ptc compositions
EP0417204B1 (de) Polymer-ptc-zusammenstellung und elektrische vorrichtung daraus
US4951382A (en) Method of making a PTC conductive polymer electrical device
US5925276A (en) Conductive polymer device with fuse capable of arc suppression
US4951384A (en) Method of making a PTC conductive polymer electrical device
EP0971366B1 (de) Leitfähiges Verbundmaterial und Verfahren zu seiner Herstellung
EP0138424B1 (de) Elektrische Vorrichtungen mit leitfähigen Polymeren mit positivem Temperaturkoeffizienten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

17P Request for examination filed

Effective date: 19810429

AK Designated contracting states

Designated state(s): AT BE CH DE FR IT LI NL SE

AK Designated contracting states

Designated state(s): AT BE CH DE FR IT LI NL SE

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19870902

REF Corresponds to:

Ref document number: 29329

Country of ref document: AT

Date of ref document: 19870915

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3176415

Country of ref document: DE

Date of ref document: 19871008

ITF It: translation for a ep patent filed

Owner name: MODIANO & ASSOCIATI S.R.L.

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19920427

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19920430

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19930430

Ref country code: CH

Effective date: 19930430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19931101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EAL Se: european patent in force in sweden

Ref document number: 81301764.7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20000406

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000411

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000417

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20000622

Year of fee payment: 20

BE20 Be: patent expired

Free format text: 20010421 *RAYCHEM CORP.

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20010429

EUG Se: european patent has lapsed

Ref document number: 81301764.7