EP0435923B1 - Leitfähige polymerzusammensetzung - Google Patents

Leitfähige polymerzusammensetzung Download PDF

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Publication number
EP0435923B1
EP0435923B1 EP89910755A EP89910755A EP0435923B1 EP 0435923 B1 EP0435923 B1 EP 0435923B1 EP 89910755 A EP89910755 A EP 89910755A EP 89910755 A EP89910755 A EP 89910755A EP 0435923 B1 EP0435923 B1 EP 0435923B1
Authority
EP
European Patent Office
Prior art keywords
carbon black
conductive polymer
less
heater according
ptc 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
EP89910755A
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English (en)
French (fr)
Other versions
EP0435923A1 (de
Inventor
Jeff Shafe
O. James Straley
Gordon Mccarty
Ravinder K. Oswal
Bernadette A. Trammell
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
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Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22933384&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0435923(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Raychem Corp filed Critical Raychem Corp
Priority to EP97201655A priority Critical patent/EP0803879B1/de
Publication of EP0435923A1 publication Critical patent/EP0435923A1/de
Application granted granted Critical
Publication of EP0435923B1 publication Critical patent/EP0435923B1/de
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Classifications

    • 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
    • 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

Definitions

  • This invention relates to electrical heaters containing PTC conductive polymer compositions.
  • Conductive polymer compositions which exhibit PTC (positive temperature coefficient of resistance) behavior are well-known and are particularly useful for self-regulating strip heaters and circuit protection devices.
  • Conductive polymer compositions generally contain a crystalline polymer matrix and a carbon black dispersed in the matrix. Carbon blacks vary in particle size, surface area, structure, and surface chemistry, all of which influence the properties, e.g. flexibility and conductivity, of conductive polymers containing them.
  • the surface chemistry of a carbon black can be altered by heat or chemical treatment, either during the production of the carbon black or in a post-production process, e.g. by oxidation. Oxidized carbon blacks frequently have a pH less than 5.0, and a high resistivity.
  • Carbon blacks having low resistivity are generally used to make PTC conductive polymers -- see for example U.S. Patent Nos. 4,237,441 (van Konynenburg et al.) and 4,388,607 (Toy et al.).
  • U.S. Patent No. 4,277,673 discloses self-regulating heaters in which the PTC conductive polymer comprises a highly resistive carbon black.
  • Kelly uses a process to make self-regulating heaters, in which a PTC composition which comprises an organic fluoropolymer matrix which has a crystallinity of at least 5%, and at least 4% by weight of the composition of a carbon black having a pH of less than 4 is melt extruded as a strip around a pair of wire electrodes, and the extrudate is then annealed (i.e. held at a temperature above the melting point of the polymer) for an extended time.
  • the conductive polymer as initially extruded, has a very high resistivity, and the annealing is necessary in order to reduce the resistivity to a useable level.
  • conductive polymers containing highly resistive carbon blacks anneal more rapidly than conductive polymers in which only conductive carbon blacks are present.
  • Conductive polymers are usually shaped by melt extrusion. Thin layers of conductive polymers can also be produced by solvent-based processes, and the resulting products have relatively low resistivity but suffer from poor stability.
  • laminar conductive polymer heaters having good stability can be made through the use of thick film inks containing a crystalline fluoropolymer and a carbon black having a pH of less than 4.0. Accordingly, this invention provides an electrical heater which
  • the conductive polymer composition in the heaters of the invention exhibits PTC behavior in the operating temperature range of the heater, i.e. it has an R 14 value of at least 2.5 or an R 100 value of at least 10 (and preferably both), and preferably also has 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.
  • a composition having "ZTC" character increases in resistivity by less than 6 times, preferably less than 2 times, in any 30°C temperature range within the operating range of the heater.
  • the carbon blacks used in this invention have a pH less than 4.0, preferably less than 3.0, measured prior to mixing with the polymer.
  • a carbon black generally has a relatively high volatile content, i.e. a high amount of oxygen chemisorbed on its surface. The amount of oxygen can be increased by oxidation in a post-production process. The resulting carbon black will have a higher surface activity.
  • Particularly preferred are carbon blacks having a ratio of resistivity (in ohm-cm) to particle size (in nanometers) less than or equal to 0.1, preferably less than or equal to 0.09, particularly less than or equal to 0.08. The resistivity is determined by the procedure described in Columbian Chemicals Company bulletin "The Dry Resistivity of Carbon Blacks" (AD1078).
  • nonoxidized carbon blacks may be treated, e.g. by heat or appropriate oxidizing agents, to produce carbon blacks with appropriate surface chemistry.
  • conductive fillers may be used in combination with the low pH carbon black.
  • These fillers may comprise nonoxidized carbon black (i.e. a carbon black with a pH of at least 5.0), graphite, metal, metal oxide, or any combination of these.
  • the low pH carbon black is present in amount at least 5%, preferably at least 10%, particularly at least 20%, e.g. 25 to 100%, by weight of the total conductive filler, and/or in amount at least 5%, preferably at least 6%, particularly at least 8%, by weight of the solid components of the total composition.
  • the fluoropolymers used in this invention have a crystallinity of at least 5%, preferably at least 10%, particularly at least 15%, e.g. 20 to 30%.
  • Suitable polymers include polyvinylidene fluoride, ethylene/tetrafluoroethylene copolymers, and terpolymers of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene; and blends of two or more such polymers.
  • fluoropolymer is used herein to denote a polymer which contains at least 10%, preferably at least 25%, by weight of fluorine, or a mixture of two or more such polymers.
  • the blend In order to achieve specific physical or thermal properties for some applications, it may be desirable to blend one crystalline polymer with another polymer, either crystalline or amorphous. When there are two or more polymers in the composition, the blend must have a crystallinity or at least 5%.
  • the crystallinity, as well as the melting point T m are determined from a DSC (differential scanning calorimeter) trace on the conductive polymer composition.
  • the T m is defined as the temperature at the peak of the melting curve. If the composition comprises a blend of two or more polymers, T m is defined as the lowest melting point measured for the composition (often corresponding to the melting point of the lowest melting component).
  • the composition may comprise additional components, e.g. inert fillers, antioxidants, flame retardants, prorads, stabilizers, dispersing agents. Mixing is preferably conducted by solvent-blending.
  • the composition may be crosslinked by irradiation or chemical means.
  • the resistivity of the conductive polymer composition depends on the function of the heater, the dimensions of the PTC element, and the power source to be used.
  • the resistivity may be, for example, 10 to 1000 ohm-cm for heaters powered at 6 to 60 volts, or 1000 to 10,000 ohm-cm or higher for heaters powered at voltages of at least 110 volts.
  • the laminar PTC element may be of any shape to meet the requirements of the heater, and may be screenprinted or applied in any suitable configuration.
  • the electrodes are in the form of metal sheet or conductive (e.g. metal- or carbon-filled) paint.
  • the heaters of the invention show improved stability under thermal aging and electrical stress.
  • the resistance at 20°C measured after aging i.e. R f50
  • the resistance at 20°C measured after aging is from 0.25 R i to 1.75 R i , preferably from 0.40 R i to 1.60 R i , particularly from 0.50 R i to 1.50 R i , where R i is the initial resistance at 20°C.
  • the resistance at 20°C after 300 hours, R f300 is generally from 0.50 R i to 1.50 R i , preferably from 0.60 R i to 1.40 R i , particularly from 0.70 R i to 1.30 R i . It is to be understood that if a heater meets the resistance requirement when tested at a temperature greater than T m , it will also meet the requirement when tested at T m . Similar results will be observed when the heater is actively powered by the application of voltage. The change in resistance may reflect an increase or decrease in heater resistance. In some cases, the resistance will first decrease and then increase during the test, possibly reflecting a relaxation of mechanically-induced stresses followed by oxidation of the polymer. Particularly preferred compositions may exhibit stability which is better than a 30% change in resistance.
  • the invention is illustrated by the following examples, some of which are comparative examples, as indicated by an asterisk *.
  • an ink was prepared by blending the designated percent by weight (of solids) of the appropriate carbon black with dimethyl formamide in a high shear mixer.
  • the solution was the filtered and powdered KynarTM 9301 (a terpolymer of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene with a melting point of about 88°C, available from Pennwalt) in amount equal to (100 - % carbon black) was added to the filtrate and allowed to dissolve over a period of 24 to 72 hours. (Approximately 60% solvent and 40% solids was used in making the ink).
  • ElectrodeagTM 461SS available from Acheson Colloids
  • Samples of each ink were aged in ovens at temperatures of 65, 85, 107 and 149°C. Periodically, the samples were removed from the oven and the resistance at room temperature (nominally 20°C), R t , was measured. Normalized resistance, R n , was determined by dividing R t by the initial room temperature resistance, R i . The extent of instability was determined by the difference between R n and 1.00.
  • Those inks which comprised carbon blacks with a pH of less than 4 were generally more stable than the inks comprising higher pH blacks.
  • inks were prepared using KynarTM 9301 as a binder and incorporating the carbon blacks listed in Table IV.
  • the resistance vs. Temperature characteristics were measured by exposing samples of each ink to a temperature cycle from 20°C to 82°C.
  • the height of the PTC anomaly was determined by dividing the resistance at 82°C (R 82 ) by the resistance at 20°C (R 20 ). It was apparent that at comparable resistivity values, the PTC anomaly was higher for the low pH carbon blacks than for the high pH carbon blacks.
  • DBP is a measure of the structure of the carbon black and is determined by measuring the amount in cubic centimeters of dibutyl phthalate absorbed by 100 g of carbon black.
  • Wt% represents the percent by weight of the total solids content of the ink that is carbon black.
  • Rho is the resistivity of the ink in ohm-cm.
  • PTC Height is the height of the PTC anomaly as determined by R 82 /R 20 .
  • R CB is the dry resistivity of the carbon black in powder form under a 5 kg load.
  • R CB /D is the ratio of the dry resistivity of the carbon black to the particle size.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Thermistors And Varistors (AREA)

Claims (7)

  1. Elektrische Heizvorrichtung, welche
    (I) enthält:
    (A) ein PTC-Element, das aus einer leitfähigen Polymerzusammensetzung aufgebaut ist, die (i) PTC-Verhalten zeigt, (ii) einen spezifischen Widerstand von 10 bis 10.000 Ohm-cm hat, und (iii) enthält:
    (a) eine organische Fluorpolymermatrix, die eine Kristallinität von mindestens 5% und einen Schmelzpunkt Tm hat, und
    (b) mindestens 4 Gew.-% der Zusammensetzung aus einem Rußschwarz, das einen pH von weniger als 4,0 hat; und
    (B) zwei Elektroden, die mit einer elektrischen Stromquelle verbunden werden können, um Strom durch das PTC-Element zu leiten;
    (II) so ausgelegt ist, daß sie dann, wenn sie 50 Stunden lang auf Tm gehalten wird und anschließend auf 20 °C gekühlt wird, bei 20 °C einen Widerstand von 0,25 Ri bis 1,75 Ri hat; wobei Ri den Anfangswiderstand bei 20 °C bezeichnet;
    dadurch gekennzeichnet, daß
    (III) das PTC-Element ein laminares Element ist, das durch Auftragen eines Polymerdickfilmfarbstoffes, der das organische Fluorpolymer, das Rußschwarz und ein Lösungsmittel enthält, hergestellt wird; und
    (IV) die Elektroden Metallblechelektroden oder Elektroden aus leitfähiger Farbe sind, die an dem PTC-Element angebracht sind.
  2. Heizvorrichtung nach Anspruch 1, dadurch gekennzeichnet, daß das PTC-Element durch Siebdrucken des Polymerdickfilmfarbstoffes hergestellt wird.
  3. Heizvorrichtung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Rußschwarz, das einen pH von weniger als 4,0 hat, der einzige leitfähige Füllstoff in der leitfähigen Polymerzusammensetzung ist.
  4. Heizvorrichtung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Rußschwarz einen pH von weniger als 3,0 hat.
  5. Heizvorrichtung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Zusammensetzung ferner (i) Rußschwarz, das einen pH von mindesten 5,0 hat, oder (ii) Graphit enthält.
  6. Heizvorrichtung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Rußschwarz eine solche Partikelgröße von D Nanometer und einen solchen spezifischen Trokkenwiderstand RCB hat, daß (RCB/D) kleiner oder gleich 0,1 ist.
  7. Heizvorrichtung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das leitfähige Polymer vernetzt ist.
EP89910755A 1988-09-20 1989-09-15 Leitfähige polymerzusammensetzung Expired - Lifetime EP0435923B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97201655A EP0803879B1 (de) 1988-09-20 1989-09-15 Leitfähige Polymerzusammensetzung

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US24705988A 1988-09-20 1988-09-20
US247059 1988-09-20
PCT/US1989/004010 WO1990003651A1 (en) 1988-09-20 1989-09-15 Conductive polymer composition

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP97201655A Division EP0803879B1 (de) 1988-09-20 1989-09-15 Leitfähige Polymerzusammensetzung
EP97201655.4 Division-Into 1997-06-03

Publications (2)

Publication Number Publication Date
EP0435923A1 EP0435923A1 (de) 1991-07-10
EP0435923B1 true EP0435923B1 (de) 1997-12-17

Family

ID=22933384

Family Applications (2)

Application Number Title Priority Date Filing Date
EP97201655A Expired - Lifetime EP0803879B1 (de) 1988-09-20 1989-09-15 Leitfähige Polymerzusammensetzung
EP89910755A Expired - Lifetime EP0435923B1 (de) 1988-09-20 1989-09-15 Leitfähige polymerzusammensetzung

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP97201655A Expired - Lifetime EP0803879B1 (de) 1988-09-20 1989-09-15 Leitfähige Polymerzusammensetzung

Country Status (8)

Country Link
EP (2) EP0803879B1 (de)
JP (2) JP2876549B2 (de)
KR (1) KR100224945B1 (de)
AT (2) ATE262725T1 (de)
CA (1) CA1334480C (de)
DE (2) DE68928502T2 (de)
HK (1) HK1021613A1 (de)
WO (1) WO1990003651A1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1267672B1 (it) * 1994-01-17 1997-02-07 Hydor Srl Composto resistivo termosensibile, suo metodo di realizzazione ed uso
DE10310722A1 (de) 2003-03-10 2004-09-23 Tesa Ag Elektrisch erwärmbare Haftklebemasse
DE102007007617A1 (de) 2007-02-13 2008-08-14 Tesa Ag Intrinsisch erwärmbare heißschmelzklebrige Flächengebilde
DE102008034748A1 (de) 2008-07-24 2010-01-28 Tesa Se Flexibles beheiztes Flächenelement
DE102008063849A1 (de) 2008-12-19 2010-06-24 Tesa Se Beheiztes Flächenelement und Verfahren zu seiner Befestigung
DE102009010437A1 (de) 2009-02-26 2010-09-02 Tesa Se Beheiztes Flächenelement
US20130193384A1 (en) * 2012-01-31 2013-08-01 E. I. Du Pont De Nemours And Company Polymer thick film positive temperature coefficient carbon composition
JP7309444B2 (ja) * 2018-07-05 2023-07-18 キヤノン株式会社 樹脂組成物、樹脂成形体、樹脂積層体、カートリッジ、画像形成装置、樹脂成形体の製造方法、樹脂積層体の製造方法およびカートリッジの製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237441A (en) * 1978-12-01 1980-12-02 Raychem Corporation Low resistivity PTC compositions
US4277673A (en) * 1979-03-26 1981-07-07 E-B Industries, Inc. Electrically conductive self-regulating article
US4591700A (en) * 1980-05-19 1986-05-27 Raychem Corporation PTC compositions
EP0123540A3 (de) * 1983-04-20 1985-01-02 RAYCHEM CORPORATION (a California corporation) Leitfähige Polymere und diese enthaltende Einrichtungen
US4668857A (en) * 1985-08-16 1987-05-26 Belton Corporation Temperature self-regulating resistive heating element
AU589714B2 (en) * 1985-12-06 1989-10-19 Sunbeam Corp. PTC compositions containing a non-surface treated carbon black having an intermediate resistivity for reduced annealing

Also Published As

Publication number Publication date
KR900702544A (ko) 1990-12-07
WO1990003651A1 (en) 1990-04-05
CA1334480C (en) 1995-02-21
DE68929517T2 (de) 2005-02-03
ATE161354T1 (de) 1998-01-15
EP0803879A1 (de) 1997-10-29
DE68929517D1 (de) 2004-04-29
JP2876549B2 (ja) 1999-03-31
HK1021613A1 (en) 2000-06-16
ATE262725T1 (de) 2004-04-15
EP0803879B1 (de) 2004-03-24
JPH04500745A (ja) 1992-02-06
JP2955281B2 (ja) 1999-10-04
DE68928502T2 (de) 1998-06-18
KR100224945B1 (ko) 1999-10-15
EP0435923A1 (de) 1991-07-10
DE68928502D1 (de) 1998-01-29
JPH11144907A (ja) 1999-05-28

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