JPH03187201A - Thermosensible electric resistance composition body - Google Patents
Thermosensible electric resistance composition bodyInfo
- Publication number
- JPH03187201A JPH03187201A JP32662189A JP32662189A JPH03187201A JP H03187201 A JPH03187201 A JP H03187201A JP 32662189 A JP32662189 A JP 32662189A JP 32662189 A JP32662189 A JP 32662189A JP H03187201 A JPH03187201 A JP H03187201A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- electric resistance
- metal
- resistance composition
- thermosensible
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 8
- 239000011888 foil Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 5
- 239000004065 semiconductor Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000012212 insulator Substances 0.000 claims description 3
- 239000003086 colorant Substances 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 abstract description 2
- 229920000914 Metallic fiber Polymers 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 230000020169 heat generation Effects 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 229910001887 tin oxide Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002359 Tetronic® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass 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
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
- Resistance Heating (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
［産業上の利用分野］
本発明は、ポリエチレングリコール、ポリエチレンオキ
シド、クラウンエーテルのようなアルキレンオキシドを
単位構造として持つ化合物に、カーボン以外の導電性粒
子を添加して、スイッチング特性を発現せしめる感熱電
気抵抗組成物であって、かつ自己温度調節発熱体となる
ものに関するものである。
ここで、スイッチング特性とは、次のように定義する。
該当する系の温度と電気抵抗の関係において、系の温度
を増加せしめて行くとある温度から抵抗値が急増し、温
度がこれより下ると再び抵抗値が低下することをいう。
すなわち、温度−抵抗曲線を描くと変曲点が出ることが
重要である。[Industrial Field of Application] The present invention is a thermosensitive electrical device that develops switching characteristics by adding conductive particles other than carbon to a compound having an alkylene oxide unit structure such as polyethylene glycol, polyethylene oxide, or crown ether. The present invention relates to a resistive composition that is a self-temperature heating element. Here, the switching characteristics are defined as follows. In the relationship between the temperature and electrical resistance of the relevant system, as the temperature of the system is increased, the resistance value increases rapidly from a certain temperature, and when the temperature falls below this value, the resistance value decreases again. That is, it is important that an inflection point appears when drawing a temperature-resistance curve.
【従来の技術１
本発明に関連する従来の技術としては１次の２種が知ら
れている。
■チタン酸バリウム・セラミックス系の熱膨張を利用し
た自己温度調節発熱体が公知である。
■カーボンとアルキレンオキシドを単位構造にもつ化合
物との組成物による感熱電気抵抗組成物・自己温度調節
発熱体は本発明者が提案（特開昭６０−１４０６９２号
）している。
【発明が解決しようとする課題】
アルキレンオキシドを単位構造として持つ化合物と黒鉛
・カーボンブラック等のカーボン充填系については、こ
れまでに詳細に検討してきた。これらの系は、電気的性
能は申し分がないが、力一ボンを充填しているので、外
観は黒色を呈している。これらの系をヒーターとして用
いる場合、黒色以外のものが望まれる場合がある０時と
しては。
透明なヒーターが望ましい場合もある。
例えば、窓に付着する雪や氷を溶かすためのヒーターと
しては、ヒーター面積を少なくすることは勿論大事であ
るが、出来れば透明なヒーターが望ましい、その他、装
飾をも兼ねるヒーターの場合は、黒色のみでは困ること
もある。そこで、黒色から抜は出すことが出来ないカー
ボンを避けて、他の導電性粒子を用いることを試み、本
発明に至った。金属粒子を充填する場合、用いる金属に
よって金色、銀色等の外観を呈するヒーターを得ること
が出来る。 また、いわゆるＩＴｏ（インジウムをドー
プしたスズの酸化物）を透明な粒子等にコートしたもの
を用いれば、透明なヒーターが得られる。[Prior art 1] Two types of prior art related to the present invention are known: primary. ■A self-temperature-regulating heating element that utilizes the thermal expansion of barium titanate ceramics is well known. (2) The present inventor has proposed a heat-sensitive electrical resistance composition/self-temperature-regulating heating element made of a composition of carbon and a compound having an alkylene oxide unit structure (Japanese Patent Application Laid-open No. 140692/1982). [Problems to be Solved by the Invention] Compounds having alkylene oxide as a unit structure and carbon filling systems such as graphite and carbon black have been studied in detail so far. Although these systems have satisfactory electrical performance, they have a black appearance because they are filled with power. When using these systems as heaters, a color other than black may be desired. Transparent heaters may be desirable. For example, when using a heater to melt snow and ice that adheres to a window, it is of course important to reduce the area of the heater, but if possible, a transparent heater is preferable, and if the heater also serves as a decoration, a black heater is recommended. Sometimes it is difficult to do it alone. Therefore, an attempt was made to avoid carbon, which cannot be extracted from the black color, and to use other conductive particles, resulting in the present invention. When filled with metal particles, it is possible to obtain a heater that has a golden, silvery, etc. appearance depending on the metal used. Furthermore, if transparent particles or the like are coated with so-called ITo (tin oxide doped with indium), a transparent heater can be obtained.
そこで、導電性粒子としての金属粉、金属箔片、金属繊
維、あるいは絶縁物や半導体又は金属酸化物の粒子、箔
、繊維等であってもその表面を金属又は金属酸化物でコ
ートして導電性としたものと、アルキレンオキシドを単
位構造に持つ化合物との組成物よりなる感熱電気抵抗組
成物を開発したのである。
マトリックスとしてのアルキレンオキシドを単位構造に
持つ化合物とは１分子中に複数のアルキレンオキシドを
単位構造として含有する有機化合物ポリアルキレンオキ
シドであり、とりわけ、ポリエチレングリコールが良好
で、その他、ポリプロピレングリコール、ポリエチレン
オキシドとポリプロピレンオキシドとのブロック共重合
体（プルロニック、あるいはテトロニック）、 クラウ
ンエーテル類が有用である。
導電性粒子の具体例は次の通りである。
金属粉、金属箔片、金属繊維としての金属は、金、銀、
銅、鉛、錫、アンチモン、鉄、ニッケル。
コバルト、インジウム等であり、粉の粒子径はおよそ０
．１〜５０１ｊｊＩ程度、金属箔片は厚さ０．１〜２０
−。
アスペクト比５〜２００程度のものがよい。
金属繊維としては、太さ０．０５〜５０−２長さ１〜２
ｍ＋程度のものが好ましい。
絶縁物としては、アルミナ、ゼオライト、ガラス材など
があり、半導体としては、ＺｎＯ，ＳＬ。
ＧａＡｓ、Ｃ：ｄＳ、Ｚｎ５ｅ、Ｃｒ２Ｏ３など力１．
金属酸化物としては、 ＴｉＯ，ＣｒＯ，、ＭｏＯ２，
ＣａＮｉＯ３などである。
これらは、上記マトリックスに対して１．５〜７０重量
％、好ましくは２〜３０重量％である。
混合に際しては、粒子が媒体中に均−１二分散するよう
に注意する。
（作用］
充填剤がカーボン以外の場合でも、エーテル結合の酸素
の孤立電子対が、充填剤の分散等４こ対してやはり重要
な役割を演じてｂすると思われる。マトリックスとして
ポリエチレングリコール（ＰＥＧ）を例にとって説明す
る。
上記のマトリックスに導電性粒子を充填した場合の電気
抵抗は、パーコレーション理論で説明できる。
すなわち、導電性粒子の充填濃度が低い場合は、各粒子
が孤立しているので、系全体の抵抗値はマトリックス単
独の系の抵抗値とほぼ同じである。
粒子の濃度が増加するにつれて、粒子同士の接触が始ま
り、遂には一方の電極から他方の電極まで、粒子の連結
による伝導性の回路が形成されるようになる。この回路
が電極間でただ一個のみ形成されただけでは、系全体の
抵抗値はそれほど減少しない、充填濃度を更に増加せし
めていくと、形成される伝導性回路の数が急激に多くな
る充填濃度に到達する。パーコレーション理論によれば
、この濃度は大体３０容量％とのことである。
しかし、この伝導性回路の数が急激に増加し始める濃度
は、充填粒子の形状に大きく依存することは、よく知ら
れている。一般にアスペクト比が大きいほど、低い充填
濃度で、目的とする抵抗値に到達できる。すなわち１球
形よりも箔片状、針状の方が、低い充填濃度で、目的の
抵抗値が得られる。
したがって、充填濃度の実用上の下限は、この充填粒子
の形状に依存する。また、たとえ抵抗値が高い状態に留
まっていても、電極間距離、電流に対する断面積を適当
に調節して、実用に供することができる発熱体の作製が
可能である。よって導電性粒子の実用濃度の下限として
は、２ｗｔ％程度である。
導電性粒子として、箔状の銀の粒子（平均粒径：０．２
２．）をＩ） Ｅ Ｇ ＃ ６０００に充填した場合の
、体積抵抗と充填濃度との関係を第１図に示す、ｍ度が
１０ｗｔ％までの抵抗値の減少は穏やかであるが、１２
ｗｔ％あたりから減少が急激となり、前述の電極の一方
から他方への伝導性の回路の形成が進んでいることを示
す、このＰＥＧと銀粒子の組成物の外観はもちろん銀色
を呈している。
次に、前述の銀粒子２１ｗｔ％を、Ｐ Ｅ Ｇ ＃６０
００に充填した組成物で面状発熱体を作製し、その温度
抵抗−特性を測定して第２図に示した。この図から分か
るように、 温度が５０℃より低い領域では、抵抗値は
殆ど変化しないが、５０℃を越えると抵抗値の急激な上
昇が見られ、この系がスイッチング特性を有することが
確認できる。このような系に電力を供給すると、温度が
５０℃以下では低抵抗のため系の温度が速やかに上昇し
、系の温度が５０℃を越えると、抵抗値が急増するため
に系に流入する電力が低下し、一定温度を維持するよう
になる。
温度抵抗曲線のシャープな折れ曲がりのため、定常恒温
度に短時間で到達する。定常温度で通電中の発熱体に対
して外部から冷却することを試みると、冷却により発熱
体温度が低下すれば、系の抵抗値も減少するので、供給
される電力がそれに追従して増加し、その結果やはり一
定温度が持続される。もちろん、電力の最大供給量は発
熱体の抵抗値に依存するので、この電力最大供給量を上
回る冷却速度で冷やした場合は恒温は維持できない。
しかしながら冷却速度に見合った電力供給量の発熱体に
設計しておけば、問題は解決する。
導電性金属酸化物粒子の一例として、少量のアンチモン
をドープした酸化錫粒子（粒径： ０．１．）をＰ Ｅ
Ｇ ＃ ６０００充填した系の温度と体積抵抗の関係
を第３図に示した。この充填物そのものの固有抵抗が金
属、グラファイトと比較すると高抵抗であり、粒子の形
状も球形に近いため、抵抗値が低下し始める充填濃度は
第１図と比べると高濃度である。すなわち２０ｗｔ％か
ら抵抗値が減少し始め、３０ｗｔ％で減少は飽和に近づ
く。また、この飽和に達した抵抗値も第１図より高い。
これも酸化物自身の抵抗と粒子の形状に起因すると考え
られる。
上記のアンチモンドープ酸化錫粒子４０ｗｔ％をＰＥ
Ｇ ＃ ６０００に充填した系より面状発熱体を作製し
、その温度−抵抗特性を測定して第４図に示した。
この図から分かるように、２０から５４℃の温度領域で
は抵抗値の温度変化は少ないが、５６℃を越えると抵抗
値が急増し、この系においてもスイッチング特性が発現
することが確認できた。
金属酸化物導電体は、一般に金属よりも高抵抗である。
この抵抗値の高さは、充填粒子の形状、発熱体にした
ときの電極間距離等の適切な設計で補うことができる。
この金属酸化物導電体の特質は、上で述べたように、透
明な充填物が得られることである。また、マトリックス
に対して、電気的性質を損なうことのない範囲で、着色
剤を求めることもできる。その結果、カラフルなヒータ
ーを作製することも可能である。Therefore, even if the conductive particles are metal powder, metal foil pieces, metal fibers, or particles, foils, or fibers of insulators, semiconductors, or metal oxides, their surfaces are coated with metals or metal oxides to make them conductive. They developed a heat-sensitive electrical resistance composition consisting of a chemical compound having an alkylene oxide as a unit structure and a compound having alkylene oxide as a unit structure. A compound having an alkylene oxide unit structure as a matrix is an organic compound polyalkylene oxide containing multiple alkylene oxides as a unit structure in one molecule, and polyethylene glycol is particularly good, and other compounds include polypropylene glycol and polyethylene oxide. Block copolymers of polypropylene oxide and polypropylene oxide (Pluronic or Tetronic) and crown ethers are useful. Specific examples of the conductive particles are as follows. Metals such as metal powder, metal foil pieces, and metal fibers include gold, silver,
Copper, lead, tin, antimony, iron, nickel. Cobalt, indium, etc., and the particle size of the powder is approximately 0.
．． 1 to 501jjI, metal foil piece thickness 0.1 to 20
−. An aspect ratio of about 5 to 200 is preferable. The metal fiber has a thickness of 0.05 to 50-2 and a length of 1 to 2.
It is preferable to have a value of around m+. Insulators include alumina, zeolite, glass, etc., and semiconductors include ZnO and SL. GaAs, C:dS, Zn5e, Cr2O3, etc. Force 1.
Examples of metal oxides include TiO, CrO, MoO2,
Such as CaNiO3. These amount to 1.5 to 70% by weight, preferably 2 to 30% by weight, based on the matrix. When mixing, care is taken to ensure that the particles are uniformly dispersed in the medium. (Function) Even when the filler is other than carbon, the lone pair of oxygen in the ether bond still seems to play an important role in the dispersion of the filler.Polyethylene glycol (PEG) is used as the matrix. Let's take this as an example.The electrical resistance when the matrix above is filled with conductive particles can be explained using percolation theory.In other words, when the filling concentration of conductive particles is low, each particle is isolated, so The resistance of the entire system is approximately the same as that of the matrix alone. As the concentration of particles increases, they begin to come into contact with each other, and eventually conduction from one electrode to the other through the coupling of particles. If only one circuit is formed between the electrodes, the resistance value of the entire system will not decrease significantly.If the filling concentration is further increased, the conduction circuit formed will increase. A filling concentration is reached at which the number of conductive circuits rapidly increases.According to percolation theory, this concentration is approximately 30% by volume.However, the concentration at which the number of conductive circuits begins to increase rapidly is It is well known that this greatly depends on the shape of the filled particles.In general, the larger the aspect ratio, the lower the filling concentration can reach the desired resistance value. The desired resistance value can be obtained with a lower filling concentration.Therefore, the practical lower limit of the filling concentration depends on the shape of the filled particles.Also, even if the resistance value remains high, By appropriately adjusting the distance between the electrodes and the cross-sectional area for the current, it is possible to produce a heating element that can be put to practical use.Therefore, the lower limit of the practical concentration of conductive particles is about 2 wt%. Foil-shaped silver particles (average particle size: 0.2
2. ) is filled in I) E G # 6000, and the relationship between volume resistance and filling concentration is shown in Figure 1.The decrease in resistance value is moderate when m degree reaches 10 wt%, but 12
The decrease becomes rapid from around wt%, and the appearance of this composition of PEG and silver particles is of course silvery, indicating that the formation of the conductive circuit from one side of the electrode to the other is proceeding. Next, 21 wt% of the above-mentioned silver particles were added to PEG #60.
A planar heating element was prepared using the composition filled with 0.00%, and its temperature resistance characteristics were measured and are shown in FIG. As can be seen from this figure, when the temperature is lower than 50°C, the resistance value hardly changes, but when the temperature exceeds 50°C, there is a rapid increase in the resistance value, confirming that this system has switching characteristics. . When power is supplied to such a system, when the temperature is below 50°C, the temperature of the system rises quickly due to low resistance, and when the temperature of the system exceeds 50°C, the resistance value increases rapidly and flows into the system. Power is reduced to maintain a constant temperature. Because of the sharp bend in the temperature resistance curve, steady constant temperature is reached in a short time. When an attempt is made to externally cool a heating element that is energized at a steady temperature, as the temperature of the heating element decreases due to cooling, the resistance value of the system also decreases, so the supplied power increases accordingly. As a result, a constant temperature is maintained. Of course, the maximum amount of power supplied depends on the resistance value of the heating element, so if cooling is performed at a cooling rate that exceeds this maximum amount of power supplied, constant temperature cannot be maintained. However, if the heating element is designed with an amount of power supplied commensurate with the cooling rate, the problem can be solved. As an example of conductive metal oxide particles, tin oxide particles (particle size: 0.1.) doped with a small amount of antimony are used as PE.
Figure 3 shows the relationship between temperature and volume resistance of a system filled with G#6000. The specific resistance of this filling itself is high compared to metals and graphite, and the shape of the particles is also close to spherical, so the filling concentration at which the resistance value starts to decrease is higher than that shown in FIG. That is, the resistance value begins to decrease from 20 wt%, and the decrease approaches saturation at 30 wt%. Furthermore, the resistance value that reached this saturation is also higher than in FIG. This is also considered to be due to the resistance of the oxide itself and the shape of the particles. 40 wt% of the above antimony-doped tin oxide particles were
A planar heating element was prepared from the system filled in G#6000, and its temperature-resistance characteristics were measured and are shown in FIG. As can be seen from this figure, in the temperature range from 20 to 54°C, there is little change in the resistance value with temperature, but when the temperature exceeds 56°C, the resistance value increases rapidly, confirming that switching characteristics are developed in this system as well. Metal oxide conductors generally have higher resistance than metals. This high resistance value can be compensated for by appropriate design such as the shape of the filled particles and the distance between electrodes when used as a heating element. A feature of this metal oxide conductor is that, as mentioned above, transparent fillings are obtained. Further, a coloring agent can be added to the matrix within a range that does not impair the electrical properties. As a result, it is also possible to produce colorful heaters.
実施例１
ポリエチレングリコール（＃ ６０００：分子量＝ ８
２００）を加熱溶融し、これに箔状の銀の粒子（平均粒
径：０．２２．）を混合し、均一分散するように撹拌し
た。
これを直径２０ｍ、厚さ２ｍｍのディスク状に成形し。
上下の円の面を導電性銀ペイントで塗布して電極とした
。所定量の銀粒子の充填濃度の試料を作製し、これらの
体積抵抗を２０℃で測定したのが前述した第１図である
。電気抵抗の測定は、デジタルマルチメーター（タケダ
リケンＴＲ６８４１）、またはピコアンペアメーター（
タケダリケンＴＲ６８４１）と直流電源（菊水電気Ｐ
Ａ Ｂ ２５０）の組合せを用いて行なった。なお、Ｓ
定は全て空気恒温槽（コマッ・ヤマトークールニクスＣ
ＴＧ、ＣＴＲ−５２０）内で温度制御のもとに行なった
。
実施例２
ポリエチレングリコールｘ ６０００に対して少量のア
ンチモンをドープした酸化錫の粒子（粒径：０．１ＩＬ
ＩＩ＋）を実施例１と同様な方法で、直径２０ａ＋＋、
厚さ２ｍのディスク状に成形し、銀ペイント電極を付け
、各充填濃度の試料に対して２０℃における体積抵抗を
測定し、この結果を前述した第３図に示した。測定方法
は実施例１と同様である。
実施例３
ポリエチレングリコール（＃６０００）７９重量部を加
熱溶融し、 これに対して箔状の銀の粒子（平均粒径：
０．２２．）２１重量部を混合し、 これが均一に分
散するまで混合して感熱電気抵抗組成物（１）とした。
これを２枚のポリエステルの不織布（２）の付いたポ
リエステルフィルム（３）（一方のフィルムに予め電極
（４）（４）をセットしである）の間にはさんで面状発
熱体とした。この面状発熱体の構成は第５図に示しであ
る。この面状発熱体の温度−抵抗特性を測定し、図示し
たのが第２図である。
この面状発熱体を２枚の厚さ５０ｍａ＋の発泡ポリウレ
タン断熱材の間にはさんだ状態でＡＣｌｏｏＶを印加し
、印加機番時間における発熱温度を測定し。
第６図（ａ）に示した。電圧印加機温度が速やかに上昇
して短時間内で一定の恒温に到達し、その後この温度を
持続して、自己温度調節機能を有していることが確認で
きた。
実施例４
ポリエチレングリコール（＃ ６０００：分子量＝ ８
２００）６０重量部を加熱溶融し、これに実施例２で述
べたアンチモンドープの酸化錫粒子４０ｇ量部を混合し
、実施例３と同様な方法で面状発熱体とした。ただし、
この場合は電極間距離を５Ｗｎ、面状発熱体の厚みを２
＋ｎ＋＋＋とじた。この面状発熱体の温度−抵抗特性を
測定し、第４図に示した。測定方法は実施例１と同様で
ある。
実施例３と同様に、この面状発熱体を２枚の厚さ５０＋
ｎｎ＋の発泡ポリウレタン断熱材の間にはさんだ状態で
Ａ Ｃ１００Ｖを印加し、印加機番時間における発熱温
度を測定し、第６図（ｂ）に示した。 この場合も同様
に、電圧印加機温度が速やかに上昇して短時間内で一定
の恒温に到達し、その後この温度を持続して、自己温度
調節機能を有していることが確認できた。
実施例５
７５重量部のベンゾ−１５−クラウン−５を加熱熔融し
、 これに２５重量部の箔状銀粒子（平均粒径：０．２
２．）を混合し、均一分散するように撹拌した。
これを直径２０ＩＩＯ１厚さ２ｍのディスク状に成形し
、上下の円の面を導電性銀ペイントで塗布して電極とし
て試料を作製した。この試料の温度変化に伴う抵抗値を
測定し、第７図に示した。測定方法は実施例１と同様で
ある。
実施例６
７５重量部のベンゾ−１５−クラウン−５を加熱溶融し
、 これに対して２５重量部の箔状銀粒子（平均粒径：
０．２２ｕ）を混合し、 これが均一に分散するまで混
合して、２枚のポリエステルの不織布の付いたポリエス
テルフィルム（一方のフィルムに予め電極をセットしで
ある）の間に挟んで面状発熱体とした。
この面状発熱体を２枚の厚さ５０ｍの発泡ポリウレタン
断熱材の間にはさんだ状態でＡ Ｃ１００Ｖを印加し、
印加機番時間における発熱温度を測定し、第８図にその
結果を示した。この図から明らかなように、電圧印加後
に温度が速やかに上昇して短時間内で一定の恒温に到達
し、その後この温度を持続して、自己温度調節機能を有
していることが確認できた。
【発明の効果１
本発明の感熱電気抵抗組成物は、これを面状発熱体とす
ることによりスイッチング特性を持つ、自己温度調節機
能を有し、センサーのいらない暖房用のマット、パネル
テープ等各種用途に応じた形状の製品とすることができ
、しかも、従来のカーボングラファイト系では得られな
い透明あるいは半透明でかつカラフルな面状発熱体を得
ることができる有用なものである。Example 1 Polyethylene glycol (#6000: molecular weight = 8
200) was heated and melted, and foil-shaped silver particles (average particle size: 0.22.) were mixed therein and stirred to uniformly disperse the mixture. This was formed into a disk shape with a diameter of 20 m and a thickness of 2 mm. The upper and lower circular surfaces were coated with conductive silver paint to form electrodes. As shown in FIG. 1, samples having a predetermined amount of silver particles were prepared and their volume resistivities were measured at 20°C. Electrical resistance can be measured using a digital multimeter (Takedariken TR6841) or a picoamp meter (
Takedariken TR6841) and DC power supply (Kikusui Electric P
A combination of A B 250) was used. In addition, S
All temperatures are controlled using an air temperature chamber (Komat Yamato Coolnics C).
It was carried out under temperature control in a TG, CTR-520). Example 2 Particles of tin oxide doped with a small amount of antimony to polyethylene glycol x 6000 (particle size: 0.1IL)
II+) in the same manner as in Example 1, with a diameter of 20a++,
The sample was molded into a disk shape with a thickness of 2 m, silver paint electrodes were attached, and the volume resistivity at 20° C. was measured for each sample with each filling concentration. The results are shown in FIG. 3 described above. The measurement method is the same as in Example 1. Example 3 79 parts by weight of polyethylene glycol (#6000) was heated and melted, and foil-shaped silver particles (average particle size:
0.22. ) and mixed until uniformly dispersed to obtain a heat-sensitive electrical resistance composition (1). This was sandwiched between two polyester films (3) attached to polyester nonwoven fabric (2) (electrodes (4) (4) were set in advance on one of the films) to form a planar heating element. . The structure of this planar heating element is shown in FIG. FIG. 2 shows the measured temperature-resistance characteristics of this sheet heating element. AClooV was applied to this planar heating element sandwiched between two sheets of polyurethane foam insulation with a thickness of 50 m, and the heat generation temperature during the application time was measured. It is shown in FIG. 6(a). It was confirmed that the temperature of the voltage application device rose rapidly, reached a constant constant temperature within a short time, and then maintained this temperature, confirming that the device had a self-temperature regulation function. Example 4 Polyethylene glycol (#6000: molecular weight = 8
200) was heated and melted, and 40 g of the antimony-doped tin oxide particles described in Example 2 were mixed therewith to prepare a planar heating element in the same manner as in Example 3. however,
In this case, the distance between the electrodes is 5Wn, and the thickness of the sheet heating element is 2
+n+++ closed. The temperature-resistance characteristics of this planar heating element were measured and are shown in FIG. The measurement method is the same as in Example 1. As in Example 3, this sheet heating element was formed into two sheets with a thickness of 50+.
AC 100V was applied while sandwiched between nn+ foamed polyurethane heat insulating materials, and the heat generation temperature during the application time was measured, and is shown in FIG. 6(b). In this case as well, the temperature of the voltage applier rose rapidly, reached a constant constant temperature within a short time, and then maintained this temperature, confirming that it had a self-temperature regulating function. Example 5 75 parts by weight of benzo-15-crown-5 was heated and melted, and 25 parts by weight of foil-like silver particles (average particle size: 0.2
2. ) and stirred to ensure uniform dispersion. This was molded into a disk shape with a diameter of 20 IIO and a thickness of 2 m, and the upper and lower circular surfaces were coated with conductive silver paint to prepare a sample as an electrode. The resistance value of this sample as a result of temperature changes was measured and is shown in FIG. The measurement method is the same as in Example 1. Example 6 75 parts by weight of benzo-15-crown-5 was heated and melted, and 25 parts by weight of foil-like silver particles (average particle size:
0.22u), mix until uniformly dispersed, and sandwich it between two polyester films with a polyester nonwoven fabric (one film has an electrode set in advance) to generate a sheet of heat. As a body. This sheet heating element was sandwiched between two sheets of polyurethane foam insulation material with a thickness of 50 m, and 100 V of AC was applied.
The heat generation temperature during the application time was measured, and the results are shown in FIG. As is clear from this figure, the temperature rises quickly after voltage application, reaches a constant constant temperature within a short time, and then maintains this temperature, confirming that it has a self-temperature regulation function. Ta. Effects of the Invention 1 The heat-sensitive electrical resistance composition of the present invention has a switching characteristic and self-temperature adjustment function by using it as a planar heating element, and can be used in various applications such as heating mats and panel tapes that do not require sensors. It is useful because it can be made into a product with a shape depending on the application, and it can also produce a transparent or translucent and colorful planar heating element, which cannot be obtained with conventional carbon graphite systems.
第１図は、実施例１の組成物系の体積抵抗と粒子の充填
濃度との関係を示すグラフである。
第２図は、実施例１の組成物より作製した面状発熱体の
、温度と抵抗値の関係を示すグラフである。
第３図は、実施例２の組成物系の体積抵抗と充填濃度と
の関係を示すグラフである。
第４図は、実施例２の組成物より作製した面状発熱体の
、温度と抵抗値の関係を示すグラフである。
第５図は、面状発熱体の基本構成を示す斜視図である。
第６図は、実施例３及び４の面状発熱体の通電時間と発
熱温度の関係を示すグラフである。
第７図は、実施例５の面状発熱体の温度と抵抗値の関係
を示すグラフである。
第８図は、実施例６の面状発熱体の通電時間と発熱温度
を示すグラフである。
（＋）感熱電気抵抗組成物（２）不織布（３）ポリエス
テル （４）電極
以上FIG. 1 is a graph showing the relationship between the volume resistance of the composition system of Example 1 and the filling concentration of particles. FIG. 2 is a graph showing the relationship between temperature and resistance value of the sheet heating element produced from the composition of Example 1. FIG. 3 is a graph showing the relationship between volume resistance and filling concentration of the composition system of Example 2. FIG. 4 is a graph showing the relationship between temperature and resistance value of the planar heating element produced from the composition of Example 2. FIG. 5 is a perspective view showing the basic structure of the planar heating element. FIG. 6 is a graph showing the relationship between the energization time and the heat generation temperature of the planar heating elements of Examples 3 and 4. FIG. 7 is a graph showing the relationship between temperature and resistance value of the planar heating element of Example 5. FIG. 8 is a graph showing the energization time and heat generation temperature of the planar heating element of Example 6. (+) Heat-sensitive electrical resistance composition (2) Nonwoven fabric (3) Polyester (4) Electrode or more
Claims (1)
あるいは絶縁物、半導体又は金属酸化物の粒子、箔、繊
維等の表面を金属又は金属酸化物でコートしたものから
選ばれた１種又は２種以上の混合物と、アルキレンオキ
シドを単位構造に持つ化合物との混合物よりなる感熱電
気抵抗組成物。1 Metal powder, metal foil pieces, metal fibers as conductive particles,
Or a mixture of one or more selected from insulators, semiconductors, metal oxide particles, foils, fibers, etc. whose surfaces are coated with metal or metal oxide, and a compound having an alkylene oxide as a unit structure. A heat-sensitive electrical resistance composition consisting of a mixture of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32662189A JP2852778B2 (en) | 1989-12-16 | 1989-12-16 | Heat-sensitive electrical resistance composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32662189A JP2852778B2 (en) | 1989-12-16 | 1989-12-16 | Heat-sensitive electrical resistance composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03187201A true JPH03187201A (en) | 1991-08-15 |
| JP2852778B2 JP2852778B2 (en) | 1999-02-03 |
Family
ID=18189849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32662189A Expired - Fee Related JP2852778B2 (en) | 1989-12-16 | 1989-12-16 | Heat-sensitive electrical resistance composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2852778B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0543494U (en) * | 1991-11-06 | 1993-06-11 | エヌオーケー株式会社 | Sheet heating device |
| JPH07318228A (en) * | 1994-05-26 | 1995-12-08 | Kajima Corp | Preventing method for dewing in pipeline member of cooling agent |
| US5982271A (en) * | 1996-11-28 | 1999-11-09 | Tdk Corporation | Organic positive temperature coefficient thermistor |
| JP2003109804A (en) * | 2001-09-28 | 2003-04-11 | Matsushita Electric Ind Co Ltd | Flexible ptc heating element |
| JP2003109803A (en) * | 2001-09-28 | 2003-04-11 | Matsushita Electric Ind Co Ltd | Flexible ptc sheetlike heating element and its manufacturing method |
| JP2006344872A (en) * | 2005-06-10 | 2006-12-21 | Matsushita Electric Ind Co Ltd | Polymer heating element |
-
1989
- 1989-12-16 JP JP32662189A patent/JP2852778B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0543494U (en) * | 1991-11-06 | 1993-06-11 | エヌオーケー株式会社 | Sheet heating device |
| JPH07318228A (en) * | 1994-05-26 | 1995-12-08 | Kajima Corp | Preventing method for dewing in pipeline member of cooling agent |
| US5982271A (en) * | 1996-11-28 | 1999-11-09 | Tdk Corporation | Organic positive temperature coefficient thermistor |
| JP2003109804A (en) * | 2001-09-28 | 2003-04-11 | Matsushita Electric Ind Co Ltd | Flexible ptc heating element |
| JP2003109803A (en) * | 2001-09-28 | 2003-04-11 | Matsushita Electric Ind Co Ltd | Flexible ptc sheetlike heating element and its manufacturing method |
| JP2006344872A (en) * | 2005-06-10 | 2006-12-21 | Matsushita Electric Ind Co Ltd | Polymer heating element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2852778B2 (en) | 1999-02-03 |
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