WO2002035557A1 - Polymère électro-conducteur, élément de protection anti-surintensité et procédés de production correspondants - Google Patents

Polymère électro-conducteur, élément de protection anti-surintensité et procédés de production correspondants Download PDF

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Publication number
WO2002035557A1
WO2002035557A1 PCT/JP2001/009403 JP0109403W WO0235557A1 WO 2002035557 A1 WO2002035557 A1 WO 2002035557A1 JP 0109403 W JP0109403 W JP 0109403W WO 0235557 A1 WO0235557 A1 WO 0235557A1
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WO
WIPO (PCT)
Prior art keywords
conductive particles
weight
conductive
conductive polymer
parts
Prior art date
Application number
PCT/JP2001/009403
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English (en)
Japanese (ja)
Inventor
Ayumi Kochi
Koichi Morimoto
Hideki Tanaka
Original Assignee
Matsushita Electric Industrial Co., Ltd.
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 Matsushita Electric Industrial Co., Ltd. filed Critical Matsushita Electric Industrial Co., Ltd.
Publication of WO2002035557A1 publication Critical patent/WO2002035557A1/fr

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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

Definitions

  • the present invention relates to a conductive polymer having a P ⁇ C (positive temperature coefficient) characteristic used as a circuit protection against overcurrent of various electronic devices.
  • the present invention relates to a current protection device (hereinafter, PTC device) and a method for manufacturing the same, a conductive polymer used for the same, and a method for manufacturing the same.
  • PTC device current protection device
  • Conductive polymers with PTC properties exhibit a property in which the resistance value increases sharply at a certain temperature.
  • the composition is such that a crystalline polymer with a crystallinity of at least 10% and carbon black with a small specific surface area such as carbon black It is a mixture in which conductive particles are dispersed.
  • the cause of the above mixture having the PTC property is that the conductive path between the filled conductive particles is cut off due to rapid thermal expansion at the melting point of the crystalline polymer. Due to this phenomenon, a conductive polymer having a PTC characteristic with a large resistance rise rate can be obtained.
  • the conventional conductive polymer has a high-density polyethylene having a crystallinity of 70 to 90%, an average particle diameter D (nm) of 20 to 150 nm, a specific surface area S (mVg) and an average particle diameter D.
  • a conductive mixture is produced by kneading a carbon black having a ratio S / D of 10 or less and a surface treating agent with two rolls heated to 150 ° C for 20 minutes.
  • the mixture obtained in the previous step is taken out into a sheet, cooled, and cut into a sheet of 150 ⁇ 150 mm.
  • Small pieces of the sheet obtained in this way Sandwiched from both sides by 35 m thick nickel electrolytic foil as an electrode, 1 90 ° C, 70 k gZcm 2 in 3 minutes heating and pressure molding, processed into electrodes with flat thickness 0. 25 mm.
  • this sample was irradiated with an electron beam of 1 OMrad from one side in an electron beam irradiation apparatus, and then irradiated with 1 OMrad from the other side. Cut out into samples.
  • the role of the surface treatment agent is to uniformly disperse the conductive particles in the crystalline polymer.
  • the mixing weight ratio of the surface treatment agent is high, after the PTC element is manufactured, heat causes excess surface treatment agent to flow to the surface due to heat, which not only deteriorates the appearance of the product, but also reduces the properties such as the resistance value of the element. Fluctuated, and it was not possible to achieve the intended purpose.
  • An object of the present invention is to solve the conventional problems as described above, and to provide a conductive polymer having stable characteristics by optimizing the addition amount of a surface treatment agent, a method for producing the same, a PTC element, and a method for producing the same. Is what you do.
  • DISCLOSURE OF THE INVENTION The present invention relates to a conductive polymer obtained by mixing a crystalline polymer, conductive particles dispersed in the crystalline polymer, and a surface treatment agent, wherein the mixing weight ratio of the surface treatment agent is 1 0.1 to 1.0 parts by weight based on 00 parts by weight.
  • FIG. 1 is a diagram showing a comparison of the resistance-temperature characteristics between the PTC element according to the first embodiment of the present invention and Comparative Example 1.
  • the conductive polymer of the present invention is a crystalline polymer, a conductive polymer obtained by mixing conductive particles and a surface treating agent dispersed in the crystalline polymer.
  • the surface treatment agent is used in an amount of 0.1 to 1.0 part by weight based on 100 parts by weight of the conductive particles.
  • the surface treatment agent used in the present invention is an aluminum-based coupling agent or a titanium-based coupling agent, and can stabilize the properties of the conductive polymer.
  • an aluminum-based coupling agent improves the dispersibility of a carbon black pigment in a resin and improves the coloring property.
  • the electrical properties are concerned, if the carbon black is sufficiently dispersed in the resin, the volume resistivity of the mixed resin will be high, which makes the mixed resin unsuitable as a conductive resin.
  • the present inventors have found that in a specific carbon black Z crystalline polymer Z coupling agent system, even if the carbon black is sufficiently dispersed in the resin, the volume resistance does not increase. I found that. Furthermore, it has been found that when this system is applied to a polymer PTC, the PTC characteristics of the conductive polymer are improved.
  • the method for producing a conductive polymer of the present invention comprises the steps of: dissolving 0.1 to 1.0 parts by weight of a surface treating agent in a solvent with respect to 100 parts by weight of conductive particles; A step of adding and mixing the particles, a step of drying the solvent and then adsorbing the surface treatment agent on the surface of the conductive particles, and a step of mixing the conductive particles having the surface treatment agent adsorbed thereon and the crystalline polymer And from.
  • the surface treatment agent can be uniformly adsorbed on the conductive particles, the crystalline polymer and the conductive particles can be surely dispersed, and the conductive polymer has stable characteristics. Is obtained.
  • the solvent By drying the solvent in a heated state at 75 to 85 ° C, the solvent is surely dried and a stable quality conductive polymer can be obtained.
  • the conductive particles are heated at a temperature of 85 ° C. in a vacuum, so that the electrical characteristics of the obtained conductive polymer can be made more stable.
  • the PTC element of the present invention uses the above-mentioned conductive polymer of the present invention.
  • the method for producing a PTC element of the present invention comprises the steps of dissolving 0.1 to 1.0 parts by weight of a surface treating agent in a solvent with respect to 100 parts by weight of conductive particles, and adding the conductive particles to the solution. And drying the solvent, adsorbing the surface treatment agent on the surface of the conductive particles, mixing the conductive particles with the surface treatment agent adsorbed with the crystalline polymer and processing them into sheets Performing the steps of: laminating the sheet with the electrode sheet; irradiating the laminated sheet with an electron beam to crosslink radiation; and cutting the radiation-crosslinked laminated sheet into small pieces to form a conductive polymer element. And a step of forming a terminal electrically connected to the element. According to the manufacturing method of the present invention, a PTC element having stable characteristics can be provided.
  • the mixture obtained in the preceding step is taken out from the two hot rolls into a sheet, cooled, and cut into a sheet of 150 ⁇ 150 mm.
  • the sheet obtained in this manner is sandwiched between both sides of the sheet with a 35-mm-thick nickel electrolytic foil as an electrode, and heated and pressed at 190 ° C, a temperature of 70 kgZcm 2 and a pressure of 3 minutes. Then, it is processed into a 0.25 mm thick flat plate with electrodes. Next, the flat plate with electrodes is irradiated with 1 OMrad from one surface in the electron beam irradiation apparatus, and then irradiated with 1 OMrad from the other surface, and high-density poly: radiation crosslinking is performed. Then, a 5 x 5 mm sample is cut out. A lead wire is soldered to each of the nickel foils on the front and back of the sample to create a PTC element.
  • Fig. 1 shows the resistance-temperature characteristics measured in a constant temperature test tank.
  • Table 1 shows the number of digits of resistance rise.
  • the “number of digits in which the resistance rises” shown in Table 1 is defined as the logarithm of the numerical value obtained by dividing the resistance of the PTC element at each temperature by the initial (25 ° C) resistance.
  • the use of a surface treatment agent can improve the number of digits in which the resistance value of the PTC element increases.
  • the measurement method is as follows. After applying a current of 20 A at an interval of OFF for 1 minute ⁇ N and 5 minutes, increase the imprinting current by 20 A in each step and finally apply a current of 200 A. After measuring the dynamic characteristics, abnormalities in the conductive polymer (crack formation and coupling agent No bleeding or ignition, and the resistance at room temperature changed more than twice). Table 1 shows the presence or absence of bleeding of this surface treatment agent.
  • Table 1 shows the results of measuring the number of digits of increase in the resistance value using this PTC element as sample No. 2. From comparison with a comparative example described later, it is understood that the number of digits in which the resistance value increases can be improved by using the surface treatment agent in this manner.
  • CB Power Bon Black
  • AC Aluminum-based coupling agent
  • Comparative Example 1 In the comparative example, the same conductive particles were used without surface treatment in the first embodiment, and a PTC element was produced with the same mixing amount as in the first embodiment.
  • a PTC is produced in the same manner as in the first embodiment.
  • a device was created.
  • Figure 1 shows the resistance-temperature curve of the PTC element sample No. 7 obtained here measured in a constant temperature test tank.
  • Table 2 shows the results of measuring the number of digits of increase in the resistance value using this PTC element as sample No. 7. In this comparative example, the number of digits in which the resistance value increased was about one digit smaller than that of the sample No. 1 in which the surface of the force pump rack was treated.
  • the amount of the surface treatment agent even 0.1 part by weight of the conductive particles, was effective in improving the rate of increase in the resistance value.
  • the amount of the surface treatment agent exceeded 1 part by weight, the surface of the conductive polymer was blurred.
  • the conductive polymer according to the present invention even when the mixed weight of the conductive particles in the conductive polymer is the same as the conventional amount, the resistance value increase rate is large, and excessive surface treatment agent flows out to the surface due to heat. It does not degrade the appearance of the product and does not change its characteristics such as resistance. For this reason, the conductive polymer according to the present invention is excellent as a component of a PTC element used in electronic equipment.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un polymère électro-conducteur fait d"un polymère cristallin dans lequel est dispersé un mélange de particules électro-conductrices et d"un agent de finition à raison de 0,1 à 1 parties en masse pour 100 parties en masse de particules électro-conductrices. Cette construction réduit la résistance du polymère électro-conducteur et améliore le coefficient d"augmentation de la résistance lorsqu"on fait varier le coefficient de température positif. Ce polymère électro-conducteur stable évite au chauffage la remontée en surface de l"agent de finition. Il convient donc à la production d"un élément à coefficient de température positif aux caractéristiques stabilisées.
PCT/JP2001/009403 2000-10-26 2001-10-25 Polymère électro-conducteur, élément de protection anti-surintensité et procédés de production correspondants WO2002035557A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000-326591 2000-10-26
JP2000326591A JP2002134303A (ja) 2000-10-26 2000-10-26 導電性ポリマ及びその製造方法と過電流保護素子及びその製造方法

Publications (1)

Publication Number Publication Date
WO2002035557A1 true WO2002035557A1 (fr) 2002-05-02

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WO (1) WO2002035557A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4240961B2 (ja) 2002-09-04 2009-03-18 チッソ株式会社 改質された導電性ポリマーフイルム及びその製造方法
JP2006228760A (ja) * 2005-01-21 2006-08-31 Shin Etsu Polymer Co Ltd 過電流保護素子及びその製造方法
CN103971870A (zh) * 2014-02-19 2014-08-06 贵州凯里经济开发区中昊电子有限公司 高分子热敏电阻器芯材及其产品的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09246012A (ja) * 1996-03-08 1997-09-19 Matsushita Electric Ind Co Ltd 導電性ポリマおよびこれを用いた過電流保護素子
JPH10303003A (ja) * 1997-02-28 1998-11-13 Mitsubishi Electric Corp 有機ｐｔｃ組成物及びそれを用いた回路保護装置
JP2000001618A (ja) * 1998-06-15 2000-01-07 Matsushita Electric Ind Co Ltd 過電流保護素子用ポリマーｐｔｃ組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09246012A (ja) * 1996-03-08 1997-09-19 Matsushita Electric Ind Co Ltd 導電性ポリマおよびこれを用いた過電流保護素子
JPH10303003A (ja) * 1997-02-28 1998-11-13 Mitsubishi Electric Corp 有機ｐｔｃ組成物及びそれを用いた回路保護装置
JP2000001618A (ja) * 1998-06-15 2000-01-07 Matsushita Electric Ind Co Ltd 過電流保護素子用ポリマーｐｔｃ組成物

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