JPH0967462A - Organic resistor having positive temperature characteristic - Google Patents
Organic resistor having positive temperature characteristicInfo
- Publication number
- JPH0967462A JPH0967462A JP24882395A JP24882395A JPH0967462A JP H0967462 A JPH0967462 A JP H0967462A JP 24882395 A JP24882395 A JP 24882395A JP 24882395 A JP24882395 A JP 24882395A JP H0967462 A JPH0967462 A JP H0967462A
- Authority
- JP
- Japan
- Prior art keywords
- resistance
- volume
- carbon black
- powder
- rate
- 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.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000006229 carbon black Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000004438 BET method Methods 0.000 claims abstract description 5
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 5
- 229910021543 Nickel dioxide Inorganic materials 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000011231 conductive filler Substances 0.000 description 19
- 239000002033 PVDF binder Substances 0.000 description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 241000872198 Serjania polyphylla Species 0.000 description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 108010013381 Porins Proteins 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- NPURPEXKKDAKIH-UHFFFAOYSA-N iodoimino(oxo)methane Chemical compound IN=C=O NPURPEXKKDAKIH-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 102000007739 porin activity proteins Human genes 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、正の温度特性（ＰＴ
Ｃ）を有する有機抵抗体に関する。BACKGROUND OF THE INVENTION The present invention has a positive temperature characteristic (PT
C) with an organic resistor.
【０００２】[0002]
【従来の技術】一般に、結晶性の熱可塑性重合体中に１
種またはそれ以上の導電性充填剤、例えばカーボンブラ
ックまたは微粉化された金属を分散させた抵抗体は正の
抵抗温度係数を有する。良く知られたものとしては、高
密度ポリエチレンにカーボンブラックを導電性フィラー
として添加したものがある（特公昭６４−３３２２号公
報）。また、本発明者等は、大電流用途でしかも経年劣
化を起こしにくいものとして、すでに金属粉の表面を炭
化、ホウ化、あるいは窒化したものを開発し、特願平６
−７９３９０号として提案している。2. Description of the Prior Art Generally, 1 in a crystalline thermoplastic polymer.
Resistors dispersed with one or more conductive fillers, such as carbon black or finely divided metal, have a positive temperature coefficient of resistance. A well-known one is one in which carbon black is added as a conductive filler to high-density polyethylene (Japanese Patent Publication No. 64-3322). Further, the present inventors have developed a metal powder whose surface has been carbonized, borated, or nitrided, as a material that is resistant to deterioration over time even in a large current application.
-79390 is proposed.
【０００３】[0003]
【発明が解決しようとする課題】前記特公昭６４−３３
２２号公報に記載の導電フィラーとしてカーボンブラッ
クのみを用いた正の温度特性の有機抵抗体には下記のよ
うな問題点がある。 前述のように、カーボンブラックを導電性フィラーと
して用いた実用可能な有機抵抗体では、せいぜい室温比
抵抗が２Ωｃｍ程度にしか低くすることはできず、大電
流用途には不向きであった。また、ＰＴＣ特性の有機抵
抗体を低抵抗化できれば、小型化が可能であり、例えば
電池等における過大電流による放電あるいは充電を防止
するものとして、電池内収容あるいは電池外への取付け
に至便な小型のものが提供できるが、前述のように、従
来のカーボンブラック使用のものでは低抵抗化に制限が
あるため、小型化が達成できず、取付け上、省スペース
化されたものの提供が困難である。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The organic resistor having positive temperature characteristics, which uses only carbon black as the conductive filler described in Japanese Patent No. 22 has the following problems. As described above, a practical organic resistor using carbon black as a conductive filler can have a room temperature resistivity of at most about 2 Ωcm, which is unsuitable for high current applications. Further, if the resistance of the organic resistor having the PTC characteristic can be reduced, the size can be reduced. For example, as a device for preventing discharge or charge due to an excessive current in a battery or the like, a compact size convenient for accommodating inside the battery or mounting outside the battery. However, as described above, conventional carbon black products are limited in low resistance, so miniaturization cannot be achieved, and it is difficult to provide space-saving products in terms of mounting. .
【０００４】また、低抵抗化できれば、同じ電流でも発
熱が押えられ、ＰＴＣとして動作しないが、大電流で使
用すれば発熱するため、大電流での使用が可能となる
が、前述したカーボンブラック使用のものでは、低抵抗
化に制限があるため、大電流での使用ができない。も
し、低抵抗化を図るために、導電性フィラーの量を増や
すと、抵抗変化率が小さくなり、異常時の電流遮断がし
にくくなるという欠点がでてくる。Further, if the resistance can be reduced, heat generation is suppressed even with the same current, and it does not operate as a PTC, but if it is used with a large current, it will generate heat, so that it can be used with a large current. However, it is not possible to use it with a large current because it has a limitation in reducing the resistance. If the amount of the conductive filler is increased in order to reduce the resistance, the rate of change in resistance becomes small, which makes it difficult to interrupt the current in the event of an abnormality.
【０００５】例えば自動車ドアロック装置用あるいは
電池等の過電流防止用途の有機抵抗体としては、室温比
抵抗が１０Ωｃｍ以下、抵抗変化率が５桁以上であるこ
とが望ましいが、金属粒子を導電性フィラーとして用い
た場合には、室温比抵抗は低くできるものの、抵抗変化
率が小さく、前記使用に耐えられることができなかっ
た。For example, as an organic resistor for an automobile door lock device or an overcurrent preventing device such as a battery, it is desirable that the room temperature resistivity is 10 Ωcm or less and the rate of resistance change is 5 digits or more. When it was used as a filler, the room temperature resistivity could be lowered, but the rate of change in resistance was small and it was not possible to withstand the above use.
【０００６】本発明は、上記した問題点に鑑み、室温比
抵抗が低く、かつ抵抗変化率が大きな正の温度特性の有
機抵抗体を提供することを目的とする。In view of the above problems, it is an object of the present invention to provide an organic resistor having a positive temperature characteristic which has a low room temperature specific resistance and a large rate of resistance change.
【０００７】[0007]
【課題を解決するための手段】この目的を達成するた
め、本発明は、金属粉末とウイスカ状導電酸化物および
カーボンブラックを結晶性の熱可塑性重合体に分散、混
合してＰＴＣ有機抵抗体を構成したことを特徴とする。In order to achieve this object, the present invention provides a PTC organic resistor by dispersing and mixing a metal powder, a whisker-like conductive oxide and carbon black in a crystalline thermoplastic polymer. It is characterized by being configured.
【０００８】本発明において、前記金属粉末はスパイク
状のニッケル粉末で構成し、またその平均粒径を１．０
μｍ〜４．０μｍ、見掛密度を０．５ｇ／ｃｍ3〜０．
８ｇ／ｃｍ3とし、金属粉末の重合体に対する充填率は
１０体積％〜２５体積％とすることが好ましい。またウ
イスカ状導電酸化物は、チタン酸カリウムの粉末の表面
を銀、ニッケル、炭素、二酸化錫のうちの一種以上の導
電物で被覆したものとし、また、ウイスカ状導電酸化物
の重合体に対する充填率は５体積％〜２０体積％とする
ことが好ましい。また、カーボンブラックは、ＢＥＴ法
による比表面積が８００ｍ2／ｇ以上、１３００ｍ2／ｇ
以下の高比表面積を持ち、また、カーボンブラックの重
合体に対する充填率は１体積％〜５体積％とすることが
好ましい。In the present invention, the metal powder is composed of spiked nickel powder and has an average particle size of 1.0.
μm to 4.0 μm, and an apparent density of 0.5 g / cm 3 to 0.
It is preferably 8 g / cm 3 and the filling rate of the metal powder with respect to the polymer is preferably 10% by volume to 25% by volume. The whisker-like conductive oxide shall be the surface of potassium titanate powder coated with one or more conductors of silver, nickel, carbon and tin dioxide. The rate is preferably 5% by volume to 20% by volume. Further, carbon black has a specific surface area of 800 m 2 / g or more by BET method of 1300 m 2 / g.
It has the following high specific surface area, and the filling rate of carbon black with respect to the polymer is preferably 1% by volume to 5% by volume.
【０００９】[0009]
【作用】本発明においては、導電性フィラーとしてカー
ボンブラックのみの単一導電性フィラーを用いたものと
比較し、室温比抵抗（初期比抵抗）を１／２以下に低く
でき、なおかつ抵抗変化率も５桁以上のものが得られ
る。In the present invention, the room temperature specific resistance (initial specific resistance) can be reduced to 1/2 or less and the rate of change in resistance can be reduced as compared with the case where a single conductive filler containing only carbon black is used as the conductive filler. Also, you can get more than 5 digits.
【００１０】[0010]
【実施例】図１は本発明による有機抵抗体の一実施例を
示す断面図であり、この有機抵抗体は、ＰＴＣ素体１の
両面に電極２を固着し、該各電極２にそれぞれリード線
３を固着し、このような電極２およびリード線３を設け
た素体１全体を、モールド重合体４によりリード線３の
先端部を除いて一体にモールドしたものである。ＰＴＣ
素体１は、導電性フィラー主剤としての金属粉末と、室
温比抵抗を低下させるための導電助剤としてのカーボン
ブラックと、抵抗変化率を上げるための導電助剤として
のウイスカ状導電酸化物とを混合し、結晶性の熱可塑性
重合体に分散、混合してなるものである。1 is a cross-sectional view showing an embodiment of an organic resistor according to the present invention. In this organic resistor, electrodes 2 are fixed on both sides of a PTC element body 1 and lead electrodes are respectively attached to the electrodes 2. The wire 3 is fixed, and the entire element body 1 provided with the electrodes 2 and the lead wires 3 is integrally molded with the mold polymer 4 except for the tip portions of the lead wires 3. PTC
The element body 1 is composed of a metal powder as a conductive filler main agent, carbon black as a conductive auxiliary agent for lowering the room temperature specific resistance, and a whisker-like conductive oxide as a conductive auxiliary agent for increasing the resistance change rate. Are mixed, dispersed and mixed in a crystalline thermoplastic polymer.
【００１１】図２は該実施例の有機抵抗体の製造工程の
一例を示す工程図であり、結晶性の熱可塑性重合体の一
例であるポリフッ化ビニリデンと、金属粉末としてのス
パイク状のニッケル粉末（粒体の周囲に多数の突起を有
する粉末）と、カーボンブラックと、ウイスカ状のチタ
ン酸カリウムのような酸化物粉末の表面を、銀、ニッケ
ル、炭素、二酸化錫（ＳｎＯ2）等の導電物で被覆した
ウイスカ状導電酸化物と、架橋剤とを２００℃で１時間
混練し（Ｓ１）、このように混練した材料を押出機によ
りもしくはプレスによりシート状に形成し（Ｓ２）、電
子線等により架橋処理し（Ｓ３）、その後、シートの両
面にニッケル、金、銅、アルミニウム等の箔を２００℃
の加熱状態において加圧して付けるか、あるいはこれら
の金属でなる導電ペーストを塗布して電極２を形成し
（Ｓ４）、このように電極２を付けたシート状の素材を
所定形状に打ち抜いた（Ｓ５）後、リード線３を電極２
に加熱加圧状態で固着し（Ｓ６）、リード線３の先端を
除いてエポキシ重合体等によりモールドして製品とする
（Ｓ７）。なお、リード線３は付けず、電極２の一部を
露出する場合もある。FIG. 2 is a process chart showing an example of a process for producing the organic resistor of the embodiment, which is polyvinylidene fluoride which is an example of a crystalline thermoplastic polymer, and spike-shaped nickel powder which is a metal powder. (The powder having a large number of protrusions around the particles), carbon black, and the surface of the oxide powder such as whisker-like potassium titanate is electrically conductive with silver, nickel, carbon, tin dioxide (SnO 2 ) or the like. The whisker-like conductive oxide coated with the substance and the cross-linking agent are kneaded at 200 ° C. for 1 hour (S1), and the material thus kneaded is formed into a sheet by an extruder or a press (S2). (S3), and then a nickel, gold, copper, aluminum foil at 200 ° C on both sides of the sheet.
In the heated state, the electrode 2 is formed by applying pressure or applying a conductive paste made of these metals (S4), and the sheet-like material to which the electrode 2 is thus attached is punched into a predetermined shape ( After S5), the lead wire 3 is connected to the electrode 2
Then, the lead wire 3 is fixed under heat and pressure (S6), and the tip of the lead wire 3 is removed and molded with an epoxy polymer or the like to obtain a product (S7). The lead wire 3 may not be attached and a part of the electrode 2 may be exposed.
【００１２】上述のように製造された有機抵抗体におい
て、ポリフッ化ビニリデンとして呉羽化学社製ＫＦ１０
００、ニッケル粉末としてインコ（ＩＮＣＯ）社製＃２
５５、カーボンブラックとしてケッチェンブラック・イ
ンターナショナル社製ＥＣ６００ＪＤ、カーボンコート
チタン酸カリウムとして大塚化学社製デントールＢＫ３
００を用い、それぞれの体積％を表１の組成（なお、表
１ないし以降の表中に示す％は体積％を表す）として素
体を構成した場合、２５℃における初期比抵抗は０．８
２Ωｃｍとなり、従来のカーボンブラックを導電性フィ
ラーとして充填した有機抵抗体に比較し、かなり低い初
期比抵抗が得られた。また、温度変化に対する比抵抗の
変化は図３に示す通りとなり、抵抗変化率［＝log（最
大抵抗値／初期抵抗値）］は８．６、すなわち６桁以上
となり、十分実用可能な値となった。なお、図３に示す
比較例１、２は、それぞれ表１にも示す下記の組成から
なる。 比較例１：ポリフッ化ビニリデン（前記ＫＦ１０００）
７５体積％、カーボンブラック（東海カーボン社製＃４
５００）２５体積％ 比較例２：ポリフッ化ビニリデン（前記ＫＦ１０００）
７５体積％、ニッケル粉末（前記＃２５５）１５体積
％、カーボンブラック（前記ＥＣ６００ＪＤ）１０体積
％In the organic resistor manufactured as described above, KF10 manufactured by Kureha Chemical Co. is used as polyvinylidene fluoride.
00, nickel powder # 2 manufactured by INCO
55, carbon black EC600JD made by Ketjen Black International, carbon coated potassium titanate Dentsu BK3 made by Otsuka Chemical
No. 00 is used to form an element body in which the volume% of each is the composition of Table 1 (the% shown in Table 1 to the following tables represents the volume%), the initial specific resistance at 25 ° C. is 0.8.
The resistance was 2 Ωcm, which was considerably lower than that of the conventional organic resistor filled with carbon black as a conductive filler. Further, the change in the specific resistance with respect to the temperature change is as shown in FIG. 3, and the resistance change rate [= log (maximum resistance value / initial resistance value)] is 8.6, that is, 6 digits or more, which is a sufficiently practical value. became. In addition, Comparative Examples 1 and 2 shown in FIG. 3 have the following compositions shown in Table 1, respectively. Comparative Example 1: Polyvinylidene fluoride (KF1000 above)
75% by volume, carbon black (# 4 manufactured by Tokai Carbon Co., Ltd.
500) 25% by volume Comparative Example 2: Polyvinylidene fluoride (KF1000 described above)
75% by volume, nickel powder (# 255) 15% by volume, carbon black (EC600JD) 10% by volume
【００１３】図３から分かるように、本発明によれば、
比較例１、２、すなわちカーボンブラック単独、あるい
はカーボンブラックとニッケルを混入した抵抗体に比較
して、大きな抵抗変化率が得られた。また、前記特願平
６−７９３９０号のように、金属粉末のみを用いた場合
には、抵抗変化率が最大６．０程度であったが、本発明
によれば、この金属粉末だけの場合よりも大きな抵抗変
化率が得られた。As can be seen from FIG. 3, according to the invention,
A large rate of change in resistance was obtained as compared with Comparative Examples 1 and 2, that is, carbon black alone or a resistor in which carbon black and nickel were mixed. Further, as in the above-mentioned Japanese Patent Application No. 6-79390, when only the metal powder was used, the resistance change rate was about 6.0 at maximum, but according to the present invention, in the case of only this metal powder. A larger rate of resistance change was obtained.
【００１４】本発明において、金属粉末として用いられ
る材料としては、比較的酸化しにくいものが好ましく、
この酸化しにくい化合物としては、炭化物、窒化物、ホ
ウ化物等がある。また、酸化しにくい金属としては、
銀、ニッケルがある。その中から、比較的安価で比抵抗
も低い前記ニッケル粉末と、炭化チタンと炭化タングス
テンを導電性フィラーに用いた場合の初期比抵抗と抵抗
変化率を比較した。In the present invention, the material used as the metal powder is preferably one that is relatively difficult to oxidize,
Examples of compounds that are difficult to oxidize include carbides, nitrides and borides. Also, as a metal that is difficult to oxidize,
There are silver and nickel. Among them, the nickel powder, which is relatively inexpensive and has a low specific resistance, was compared with the initial specific resistance and the rate of resistance change when titanium carbide and tungsten carbide were used as the conductive filler.
【００１５】試作品は、表２に示すように、重合体に前
記ポリフッ化ビニリデンを用い、これらの金属粉末の重
合体に対する充填率をほぼ同じ（１５．２体積％または
１６．８体積％）、カーボンブラックの重合体に対する
充填率を３．０体積％、カーボンコートチタン酸カリウ
ムの重合体に対する充填率を１１．１体積％〜１１．２
体積％とした。これらの金属粉末を用いた素体の初期比
抵抗と抵抗変化率は表２に示す通りであり、表２から分
かるように、スパイク状のニッケル粉末を用いれば、初
期比抵抗を大幅に低減でき、抵抗変化率も６桁以上の値
が得られ、金属粉末としてスパイク状のニッケル粉末を
用いることが好ましいことが分かる。なお、導電性フィ
ラー充填率とは、例えば導電性フィラー（ニッケルまた
はカーボンブラックもしくはチタン酸カリウム）の体積
をａ、重合体の体積をｂとすると、重合体に対する充填
率（％）＝｛ａ／（ａ＋ｂ）｝×１００である。As shown in Table 2, in the prototype, the polyvinylidene fluoride was used as the polymer, and the packing ratio of these metal powders to the polymer was almost the same (15.2% by volume or 16.8% by volume). The filling ratio of carbon black to the polymer is 3.0% by volume, and the filling ratio of carbon-coated potassium titanate to the polymer is 11.1% to 11.2%.
% By volume. The initial resistivity and resistance change rate of the element body using these metal powders are as shown in Table 2. As can be seen from Table 2, the spike-shaped nickel powder can significantly reduce the initial resistivity. A resistance change rate of 6 digits or more is obtained, and it is understood that it is preferable to use spike-shaped nickel powder as the metal powder. The conductive filler filling rate means, for example, that the volume of the conductive filler (nickel, carbon black or potassium titanate) is a and the volume of the polymer is b, the filling rate (%) of the polymer = {a / (A + b)} × 100.
【００１６】なおこのようにスパイク状のニッケル粉末
を用いた場合、ニッケル粉末の平均粒径を１．０μｍ〜
４．０μｍとし、見掛密度を０．５ｇ／ｃｍ3〜０．８
ｇ／ｃｍ3とすることが好ましい。平均粒径が１．０μ
ｍ未満であると、酸化しやすくなって経年変化を起こし
易くなり、また、４．０μｍを超えると、抵抗値が高く
なる。また、見掛密度が０．５ｇ／ｃｍ3未満であると
抵抗値が上り、見掛密度が０．８ｇ／ｃｍ3を超えると
抵抗変化率が低くなる。When the spike-shaped nickel powder is used as described above, the average particle diameter of the nickel powder is 1.0 μm to
4.0 μm and an apparent density of 0.5 g / cm 3 to 0.8
It is preferably g / cm 3 . Average particle size is 1.0μ
When it is less than m, it is easy to oxidize and secular change easily occurs, and when it exceeds 4.0 μm, the resistance value becomes high. Further, when the apparent density is less than 0.5 g / cm 3 , the resistance value increases, and when the apparent density exceeds 0.8 g / cm 3 , the rate of resistance change decreases.
【００１７】一方、前記ウイスカ状導電酸化物は、これ
を導電性フィラーとして添加することにより、抵抗変化
率を上げることができるが、無処理のまま使用すると、
抵抗値が高くなってしまう。そこでウイスカ状導電酸化
物の表面を導電物で被覆して抵抗値を下げることが好ま
しく、抵抗値を下げるため、炭素、銀、酸化錫、ニッケ
ルでチタン酸カリウムのウイスカ状粉末をコートしたと
ころ、初期比抵抗、抵抗変化率共に十分な値が得られ
た。表３は炭素、銀、酸化錫でコートしたウイスカ状導
電酸化物を導電性フィラーの一部に用い、他の導電性フ
ィラーや重合体を前記同様とした場合の初期比抵抗と抵
抗変化率とを示す。銀をウイスカ状導電酸化物のコート
材に用いると高価になるため、実用的には炭素コートで
十分である。On the other hand, the whisker-like conductive oxide can increase the rate of resistance change by adding it as a conductive filler, but if it is used without treatment,
The resistance value becomes high. Therefore, it is preferable to coat the surface of the whisker-like conductive oxide with a conductive material to reduce the resistance value.To reduce the resistance value, carbon, silver, tin oxide, nickel was coated with whisker-like powder of potassium titanate, Sufficient values were obtained for both the initial resistivity and the rate of resistance change. Table 3 shows the initial specific resistance and the rate of change in resistance when the whisker-like conductive oxide coated with carbon, silver and tin oxide was used as a part of the conductive filler, and other conductive fillers and polymers were used as described above. Indicates. If silver is used as a coating material for the whisker-like conductive oxide, it becomes expensive, so carbon coating is sufficient for practical use.
【００１８】本発明において、抵抗値を低くする導電助
剤として用いるカーボンブラックは、比表面積が大きい
程、抵抗値を下げる効果が大きかった。比表面積の小さ
なカーボンブラックを増すと抵抗値は下がるが、添加量
が増えると、抵抗変化率が低くなる。そこで、いかに少
ない添加量で抵抗値を下げるかがポイントであり、カー
ボンブラックの比表面積と初期比抵抗および抵抗変化率
について検討した。表４はその結果を示す表であり、表
４の試料において、ニッケル粉末およびカーボンコート
チタン酸カリウムは表１について説明したものと同じも
のを用いた。また、表４の比表面積はＢＥＴ法によるも
のであり、Ｎｏ．１の試料のカーボンブラックは、東海
カーボン社製＃４５００、Ｎｏ．２はキャボット（Ｃａ
ｂｏｔ）社製ブルカン（Ｖｕｌｃａｎ）ＸＣ−７２、Ｎ
ｏ．３はケッチェンブラック・インターナショナル社製
ＥＣ、Ｎｏ．４はケッチェンブラック・インターナショ
ナル社製ＥＣ６００ＪＤを用いた。In the present invention, the larger the specific surface area of the carbon black used as the conductive additive for lowering the resistance value, the greater the effect of lowering the resistance value. The resistance value decreases as the carbon black having a small specific surface area increases, but the resistance change rate decreases as the addition amount increases. Therefore, the point is how to reduce the resistance value with a small addition amount, and the specific surface area of carbon black, the initial specific resistance, and the rate of resistance change were examined. Table 4 is a table showing the results. In the sample of Table 4, the same nickel powder and carbon-coated potassium titanate as those described in Table 1 were used. Further, the specific surface area in Table 4 is based on the BET method, and No. The carbon black of the sample No. 1 was No. 4500, No. 4 manufactured by Tokai Carbon Co., Ltd. 2 is Cabot (Ca
Bot) Vulcan XC-72, N
o. No. 3 is EC, No. 3 manufactured by Ketjen Black International. 4 used EC600JD manufactured by Ketjen Black International.
【００１９】表４に示すように、比表面積が５８ｍ2／
ｇ以上のカーボンブラックを用いたものにおいて、５桁
以上の抵抗変化率が得られるものの、初期比抵抗が高く
なる。表４に示す組成において、比表面積と初期比抵抗
との関係から、おおよそ８００ｍ2／ｇ以上であれば、
初期比抵抗を２Ωｃｍ以下に押えることができることが
判明した。また、この比表面積の上限は、５桁以上の抵
抗変化率を得るためには、１３００ｍ2／ｇ以下とする
ことが好ましい。As shown in Table 4, the specific surface area is 58 m 2 /
In the case of using carbon black of g or more, although the resistance change rate of five digits or more can be obtained, the initial specific resistance becomes high. In the composition shown in Table 4, from the relationship between the specific surface area and the initial specific resistance, if approximately 800 m 2 / g or more,
It was found that the initial specific resistance can be suppressed to 2 Ωcm or less. The upper limit of the specific surface area is preferably 1300 m 2 / g or less in order to obtain a resistance change rate of 5 digits or more.
【００２０】次に導電粉末としてのニッケル粉末の充填
量について検討した結果を説明する。比抵抗を下げるに
は、重合体中に導電性フィラーを多く添加すればよいわ
けであるが、あまり添加量が多過ぎると、重合体が膨張
した後も導電性フィラー間の接触が解けずに抵抗が上が
らず、抵抗変化率が小さいため、ＰＴＣ抵抗体として実
用に耐えない。そこで、表５に示すように、カーボンブ
ラックのポリフッ化ビニリデンに対する充填率を３．０
体積％、カーボンブラックのポリフッ化ビニリデンに対
する充填率を１１．１体積％といずれもほぼ一定にし、
ポリフッ化ビニリデンとニッケル粉末の割合、すなわち
ニッケル粉末の充填率を種々に変え、初期比抵抗と抵抗
変化率とを測定した。その結果、重合体に対するニッケ
ル粉末の充填率が１０体積％を下まわると、抵抗が大き
過ぎ、２５体積％を上まわると抵抗変化率も５桁以下に
なり、実用に耐えないことが判明した。Next, the result of studying the filling amount of the nickel powder as the conductive powder will be described. In order to reduce the specific resistance, it is sufficient to add a large amount of conductive filler in the polymer, but if the addition amount is too large, the contact between the conductive fillers cannot be broken even after the polymer expands. Since the resistance does not increase and the resistance change rate is small, it cannot be practically used as a PTC resistor. Therefore, as shown in Table 5, the filling ratio of carbon black to polyvinylidene fluoride is 3.0.
%, The filling rate of carbon black to polyvinylidene fluoride is 11.1% by volume, which is almost constant.
The initial specific resistance and the rate of resistance change were measured while changing the ratio of polyvinylidene fluoride and nickel powder, that is, the filling rate of nickel powder. As a result, it was found that when the filling rate of the nickel powder with respect to the polymer was less than 10% by volume, the resistance was too large, and when it exceeded 25% by volume, the rate of change in resistance was 5 digits or less, which was not practical. .
【００２１】ウィスカー状のチタン酸カリウムの添加の
目的は、ニッケル単体の添加に比べ、抵抗変化率を大き
くすることにある。しかしながら、チタン酸カリウムが
少な過ぎたり、多過ぎたりすると、抵抗変化率が小さく
なってしまう。よってその適正な添加量について検討し
た。表６はポリフッ化ビニリデンに対するニッケル粉
末、カーボンブラックの充填率をそれぞれ１５．０体積
％〜１５．１体積％、３．０体積％とほぼ一定にし、ポ
リフッ化ビニリデンとカーボンコートチタン酸カリウム
との充填率を種々に変化させて初期比抵抗と抵抗変化率
とを測定した結果を示す。表６の結果から、チタン酸カ
リウムは重合体に対する充填率が５体積％〜２０体積％
が適当な量であれば初期比抵抗としてほぼ４Ωｃｍ以下
の値が得られ、抵抗変化率も５桁以上の値が得られるこ
とが判った。The purpose of adding whisker-like potassium titanate is to increase the rate of change in resistance as compared with the addition of nickel alone. However, if the amount of potassium titanate is too small or too large, the rate of resistance change becomes small. Therefore, the proper addition amount was examined. Table 6 shows that the filling ratios of nickel powder and carbon black with respect to polyvinylidene fluoride were almost constant at 15.0% by volume to 15.1% by volume and 3.0% by volume, respectively, and that polyvinylidene fluoride and carbon-coated potassium titanate were mixed. The results of measuring the initial specific resistance and the rate of resistance change by varying the filling rate are shown below. From the results of Table 6, the packing ratio of potassium titanate to the polymer is 5% by volume to 20% by volume.
It has been found that when the value is an appropriate amount, a value of about 4 Ωcm or less can be obtained as the initial specific resistance and a rate of resistance change of 5 digits or more can be obtained.
【００２２】また、カーボンブラックの添加により、少
量の添加量であっても比抵抗を低くできるため、ニッケ
ル粉末の助剤として、その添加量を検討した。このカー
ボンブラックの充填量は、ニッケル粉末の場合と同様
に、あまり多過ぎると抵抗変化率が小さくなってしま
う。表７は重合体に対するニッケル粉末とカーボンコー
トチタン酸カリウムの充填率を、それぞれ１５．０体積
％〜１５．１体積％、１１．０体積％〜１１．１体積％
とほぼ一定にし、カーボンブラックの重合体に対する充
填率を変えて初期比抵抗と抵抗変化率を測定した結果を
示すものであり、重合体に対するカーボンブラックの充
填率が１体積％〜５体積％であれば、初期比抵抗が約２
Ωｃｍより低くすることができ、抵抗変化率も５桁以上
の値を得ることができることが判明した。Further, by adding carbon black, the specific resistance can be lowered even with a small amount of addition, so that the addition amount was investigated as an auxiliary agent of nickel powder. As in the case of nickel powder, if the carbon black filling amount is too large, the resistance change rate will be small. Table 7 shows the filling rates of nickel powder and carbon-coated potassium titanate with respect to the polymer, respectively, from 15.0% by volume to 15.1% by volume and 11.0% by volume to 11.1% by volume.
The results show that the initial specific resistance and the rate of change in resistance were measured by changing the filling rate of carbon black with respect to the polymer, and the filling rate of carbon black with respect to the polymer was 1% by volume to 5% by volume. If so, the initial resistivity is about 2
It was found that the value can be made lower than Ωcm and the rate of change in resistance can be obtained in a value of 5 digits or more.
【００２３】本発明において用いる熱可塑性重合体とし
ては、ポリフッ化ビニリデン以外に高密度ポリエチレ
ン、ポリプロピレン、ポリアミド樹脂、ポリアセター
ル、ポリン塩化ビニリデン、ポリ四フッ化エチレン等が
挙げられる。Examples of the thermoplastic polymer used in the present invention include high density polyethylene, polypropylene, polyamide resin, polyacetal, porin vinylidene chloride, and polytetrafluoroethylene in addition to polyvinylidene fluoride.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【表３】 [Table 3]
【００２７】[0027]
【表４】 [Table 4]
【００２８】[0028]
【表５】 [Table 5]
【００２９】[0029]
【表６】 [Table 6]
【００３０】[0030]
【表７】 [Table 7]
【００３１】[0031]
【発明の効果】請求項１によれば、金属粉末とウイスカ
状導電酸化物およびカーボンブラックを結晶性の熱可塑
性重合体に分散、混合してＰＴＣ特性の有機抵抗体を構
成したので、カーボンブラックからなる単一の導電性フ
ィラーのものに比較し、室温比抵抗を１／２以下に低く
押えることができ、しかも金属粉末単独あるいは金属粉
末とカーボンブラックとからなる導電性フィラーを用い
たものよりも大きな抵抗変化率が得られ、実用可能な大
電流用途への使用可能なＰＴＣ特性の有機抵抗体が得ら
れる。また、小型化が達成できるので、取付け上有利な
ＰＴＣ特性の有機抵抗体を提供できる。According to the first aspect of the present invention, metal powder, whisker-like conductive oxide and carbon black are dispersed and mixed in a crystalline thermoplastic polymer to form an organic resistor having a PTC characteristic. Comparing with a single conductive filler consisting of, it is possible to suppress the room temperature specific resistance to 1/2 or lower, and moreover than the one using the conductive filler consisting of the metal powder alone or the metal powder and carbon black. A large resistance change rate can be obtained, and an organic resistor having a PTC characteristic that can be used for a practically large current application can be obtained. Further, since miniaturization can be achieved, it is possible to provide an organic resistor having a PTC characteristic which is advantageous in mounting.
【００３２】請求項２によれば、金属粉末としてスパイ
ク状のニッケル粉末を用い、その平均粒径を１．０μｍ
〜４．０μｍとしたので、小粒化による酸化防止と、大
粒化による抵抗値の増大を防止できる。また、ニッケル
粉末の見掛密度を０．５ｇ／ｃｍ3〜０．８ｇ／ｃｍ3と
したので、密度低下による抵抗値の増大と、見掛密度が
過大になることによる抵抗変化率の低下を防止できる。According to claim 2, spike-shaped nickel powder is used as the metal powder, and the average particle size is 1.0 μm.
.About.4.0 .mu.m, it is possible to prevent the oxidation due to the grain size reduction and the increase in the resistance value due to the grain size increase. Further, since the apparent density of the nickel powder was 0.5g / cm 3 ~0.8g / cm 3 , an increase in resistance due to decrease in density, a reduction in the resistance change rate due to the apparent density becomes excessive It can be prevented.
【００３３】請求項３によれば、ウイスカ状導電酸化物
として、ウイスカ状のチタン酸カリウムの表面を銀、ニ
ッケル、炭素、二酸化錫のうちの一種以上の導電物で被
覆したものを用いたので、抵抗変化率を下げることな
く、初期比抵抗を下げることが可能となる。According to the third aspect of the present invention, the whisker-like conductive oxide used is a whisker-like potassium titanate whose surface is coated with one or more conductors of silver, nickel, carbon and tin dioxide. The initial specific resistance can be lowered without lowering the resistance change rate.
【００３４】請求項４によれば、ＢＥＴ法による比表面
積が８００ｍ2／ｇ以上の比表面積を持つカーボンブラ
ックを用いたので、抵抗変化率を下げることなく、初期
比抵抗を下げることが可能となる。According to claim 4, since carbon black having a specific surface area of 800 m 2 / g or more by the BET method is used, the initial specific resistance can be lowered without lowering the rate of change in resistance. Become.
【００３５】請求項５によれば、金属粉末の重合体に対
する充填率を１０体積％〜２５体積％としたので、初期
比抵抗を低くすることができ、なおかつ抵抗変化率を５
桁以上とすることができる。According to the fifth aspect, since the filling rate of the metal powder with respect to the polymer is set to 10% by volume to 25% by volume, the initial specific resistance can be lowered and the rate of change in resistance can be 5%.
It can be more than one digit.
【００３６】請求項６によれば、ウイスカ状導電酸化物
の重合体に対する充填率を５体積％〜２０体積％とした
ので、初期比抵抗を低くすることができ、なおかつ抵抗
変化率を５桁以上とすることができる。According to the sixth aspect, since the filling rate of the whisker-like conductive oxide with respect to the polymer is set to 5% by volume to 20% by volume, the initial specific resistance can be lowered, and the rate of change in resistance is 5 digits. The above can be done.
【００３７】請求項７によれば、カーボンブラックの重
合体に対する充填率を１体積％〜５体積％としたので、
初期比抵抗を低くすることができ、なおかつ抵抗変化率
を５桁以上とすることができる。According to claim 7, since the filling rate of the carbon black with respect to the polymer is set to 1% by volume to 5% by volume,
The initial specific resistance can be lowered, and the rate of resistance change can be set to 5 digits or more.
【図１】本発明によるＰＴＣ特性の有機抵抗体の一実施
例を示す断面図である。FIG. 1 is a cross-sectional view showing an example of an organic resistor having PTC characteristics according to the present invention.
【図２】本実施例の製造工程図である。FIG. 2 is a manufacturing process diagram of the present embodiment.
【図３】本実施例の温度に対する抵抗値の変化を示すグ
ラフである。FIG. 3 is a graph showing changes in resistance value with respect to temperature in this example.
１：ＰＴＣ素体、２：電極、３：リード線、４：モール
ド重合体1: PTC element body, 2: Electrode, 3: Lead wire, 4: Mold polymer
Claims (7)
ーボンブラックを結晶性の熱可塑性重合体に分散、混合
してなることを特徴とする正の温度特性を持つ有機抵抗
体。1. An organic resistor having a positive temperature characteristic, which is obtained by dispersing and mixing a metal powder, a whisker-like conductive oxide and carbon black in a crystalline thermoplastic polymer.
ク状のニッケル粉末であり、かつ平均粒径が１．０μｍ
〜４．０μｍ、見掛密度が０．５ｇ／ｃｍ3〜０．８ｇ
／ｃｍ3であることを特徴とする正の温度特性を持つ有
機抵抗体。2. The metal powder according to claim 1, wherein the metal powder is a spiked nickel powder and has an average particle size of 1.0 μm.
~ 4.0 μm, apparent density 0.5 g / cm 3 ~ 0.8 g
/ Cm 3 is an organic resistor having a positive temperature characteristic.
電酸化物が、チタン酸カリウムの粉末の表面を銀、ニッ
ケル、炭素、二酸化錫のうちの一種以上の導電物で被覆
したものでなることを特徴とする正の温度特性を持つ有
機抵抗体。3. The whisker-like conductive oxide according to claim 1 or 2, wherein the surface of the powder of potassium titanate is coated with at least one conductive material selected from silver, nickel, carbon and tin dioxide. An organic resistor with positive temperature characteristics.
カーボンブラックのＢＥＴ法による比表面積が８００ｍ
2／ｇ〜１３００ｍ2／ｇであることを特徴とする正の温
度特性を持つ有機抵抗体。4. The method according to any one of claims 1 to 3,
Specific surface area of carbon black by BET method is 800m
An organic resistor having a positive temperature characteristic, characterized in that it is 2 / g to 1300 m 2 / g.
金属粉末の重合体に対する充填率が１０体積％〜２５体
積％であることを特徴とする正の温度特性を持つ有機抵
抗体。5. The method according to any one of claims 1 to 4,
An organic resistor having a positive temperature characteristic, wherein the filling rate of the metal powder with respect to the polymer is 10% by volume to 25% by volume.
ウイスカ状導電酸化物の重合体に対する充填率が５体積
％〜２０体積％であることを特徴とする正の温度特性を
持つ有機抵抗体。6. The method according to any one of claims 1 to 5,
An organic resistor having a positive temperature characteristic, wherein the filling rate of the whisker-like conductive oxide with respect to the polymer is 5% by volume to 20% by volume.
カーボンブラックの重合体に対する充填率が１体積％〜
５体積％であることを特徴とする正の温度特性を持つ有
機抵抗体。7. The method according to any one of claims 1 to 6,
The filling rate of carbon black to the polymer is 1% by volume to
An organic resistor having a positive temperature characteristic characterized by being 5% by volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24882395A JPH0967462A (en) | 1995-08-31 | 1995-08-31 | Organic resistor having positive temperature characteristic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24882395A JPH0967462A (en) | 1995-08-31 | 1995-08-31 | Organic resistor having positive temperature characteristic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0967462A true JPH0967462A (en) | 1997-03-11 |
Family
ID=17183956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24882395A Pending JPH0967462A (en) | 1995-08-31 | 1995-08-31 | Organic resistor having positive temperature characteristic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0967462A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1205514A1 (en) * | 2000-11-13 | 2002-05-15 | Atofina | Polymeric conducting composite material whose resistance is automatically controlled by the temperature |
| FR2816625A1 (en) * | 2000-11-13 | 2002-05-17 | Atofina | Composite material with a positive temperature coefficient, useful in heating devices, comprises a vinylidene fluoride (co)polymer in beta crystal form and a conductive filler |
| KR100395693B1 (en) * | 2000-08-02 | 2003-08-25 | 삼성종합화학주식회사 | Method for conductive polymer |
| CN116948286A (en) * | 2023-07-28 | 2023-10-27 | 厦门敦特电子科技有限公司 | High-voltage-resistant PPTC (Polypropylene-based) polymer composition and preparation method thereof |
-
1995
- 1995-08-31 JP JP24882395A patent/JPH0967462A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100395693B1 (en) * | 2000-08-02 | 2003-08-25 | 삼성종합화학주식회사 | Method for conductive polymer |
| EP1205514A1 (en) * | 2000-11-13 | 2002-05-15 | Atofina | Polymeric conducting composite material whose resistance is automatically controlled by the temperature |
| FR2816625A1 (en) * | 2000-11-13 | 2002-05-17 | Atofina | Composite material with a positive temperature coefficient, useful in heating devices, comprises a vinylidene fluoride (co)polymer in beta crystal form and a conductive filler |
| CN116948286A (en) * | 2023-07-28 | 2023-10-27 | 厦门敦特电子科技有限公司 | High-voltage-resistant PPTC (Polypropylene-based) polymer composition and preparation method thereof |
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