JPH0741684A - Heat-sensitive material, heat-sensitive unit and heat-sensitive heater element - Google Patents
Heat-sensitive material, heat-sensitive unit and heat-sensitive heater elementInfo
- Publication number
- JPH0741684A JPH0741684A JP18530493A JP18530493A JPH0741684A JP H0741684 A JPH0741684 A JP H0741684A JP 18530493 A JP18530493 A JP 18530493A JP 18530493 A JP18530493 A JP 18530493A JP H0741684 A JPH0741684 A JP H0741684A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- weight
- sensitive
- resin material
- conductive electrolyte
- 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
- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 75
- 229920005989 resin Polymers 0.000 claims abstract description 75
- 229920000642 polymer Polymers 0.000 claims abstract description 53
- 239000003792 electrolyte Substances 0.000 claims abstract description 41
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 36
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 36
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 23
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 17
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000004800 polyvinyl chloride Substances 0.000 claims description 18
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 18
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 8
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910000464 lead oxide Inorganic materials 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 238000004804 winding Methods 0.000 description 15
- 230000008859 change Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 9
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 6
- 229910020366 ClO 4 Inorganic materials 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Resistance Heating (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気カーペット等に用
いられる感熱樹脂材料及び感熱体、感熱発熱体に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive resin material, a heat-sensitive material, and a heat-sensitive heating element used for electric carpets and the like.
【０００２】[0002]
【従来の技術】電気カーペット等の広面積暖房器具に
は、従来よりポリ塩化ビニル樹脂を主成分とする感熱樹
脂材料をサーミスタとして用いた面状の感熱発熱体やコ
ード状の感熱体あるいは感熱発熱体が使用されている。
そして近年の電気カーペットにあっては、カーペット地
からなる表面材や、電気カーペットに被せて使用するカ
バー材として、本物志向や高級志向から分厚いものが好
まれる傾向にあり、発熱体の温度を従来よりも高くする
必要が生じてきている。2. Description of the Related Art A wide area heater such as an electric carpet has heretofore been used as a thermistor with a heat sensitive resin material containing polyvinyl chloride resin as a main component, for a sheet-like heat-generating element or a cord-like heat-generating element or heat-generating element. The body is being used.
In recent years, for electric carpets, there is a tendency that a thick material is used as a surface material made of a carpet material or as a cover material to be used by covering the electric carpet from a genuine or high-class orientation. There is a growing need for higher prices.
【０００３】[0003]
【発明が解決しようとする課題】しかし、発熱体の温度
を従来よりも高温にすると、部分的に断熱状態になると
きに生じる部分断熱高温部の温度が非常に高くなり、高
分子マトリクスポリマーとしてポリ塩化ビニル系樹脂を
主成分とするものを用いる従来の感熱樹脂材料では、高
温での熱老化のために温度センサーとしての固有インピ
ーダンス（以下｜Ｚ｜と略記）と温度との関係の特性が
経時変化し、｜Ｚ｜の変化によって感知する温度が危険
な高温になってしまうおそれがあった。この現象は、
ポリ塩化ビニル系樹脂中の可塑剤が高温の作用でブリー
ドアウトしてポリ塩化ビニル系樹脂のガラス転移点が高
温側にシフトしてしまう、ポリ塩化ビニル系樹脂が高
温にさらされると脱塩素反応を起こして熱老化してしま
う、等が原因になっていると考えられる。However, when the temperature of the heating element is made higher than that of the conventional one, the temperature of the high temperature part of the partially adiabatic state, which occurs when the part is in the adiabatic state, becomes extremely high, and as a polymer matrix polymer. In a conventional heat-sensitive resin material using a polyvinyl chloride-based resin as a main component, the characteristic of the relationship between the intrinsic impedance (hereinafter abbreviated as | Z |) as a temperature sensor and the temperature is due to heat aging at high temperature. There is a risk that the temperature sensed may become dangerously high due to the change over time and the change in | Z |. This phenomenon is
The plasticizer in polyvinyl chloride resin bleeds out due to the action of high temperature and the glass transition point of polyvinyl chloride resin shifts to the high temperature side. Dechlorination reaction when polyvinyl chloride resin is exposed to high temperature It is thought that the cause is heat aging caused by heat.
【０００４】また、ポリ塩化ビニル系樹脂の安定剤とし
て、分子中の鉛成分がリッチである酸化鉛（ＰｂＯ）と
二酸化珪素（ＳｉＯ2 ）からなる珪酸鉛を用いられてい
るが、この珪酸鉛は吸湿性が高いため感熱樹脂材料の｜
Ｚ｜と温度との関係の特性が湿度の影響を受けてしまう
という問題があった。さらに、感熱樹脂材料における｜
Ｚ｜と温度との関係の特性の安定性を増すために、イオ
ン伝導性電解質の添加量を多くしているが、イオン伝導
性電解質の高分子マトリクスポリマーに対する添加量が
多い場合、感熱樹脂材料に印加される交流電圧の電圧が
高くなると、イオンの移動距離が大きくなり、電極付近
で消耗されてしまうサーミスタブレーク現象によって｜
Ｚ｜と温度との関係の特性が経時変化してしまうという
問題があった。As a stabilizer for polyvinyl chloride resin, lead silicate composed of lead oxide (PbO) and silicon dioxide (SiO 2 ) whose lead component is rich in the molecule is used. Is a heat-sensitive resin material because it has high hygroscopicity.
There is a problem that the characteristic of the relationship between Z | and temperature is affected by humidity. Furthermore, in heat-sensitive resin materials
In order to increase the stability of the characteristic of the relationship between Z | and temperature, the amount of the ion conductive electrolyte is increased. However, when the amount of the ion conductive electrolyte added to the polymer matrix polymer is large, the heat-sensitive resin material is used. When the voltage of the AC voltage applied to the electrode increases, the migration distance of the ions increases and the thermistor break phenomenon is consumed near the electrodes.
There is a problem that the characteristic of the relationship between Z | and temperature changes with time.
【０００５】本発明は上記の点に鑑みてなされたもので
あり、熱老化や吸湿、電圧印加による｜Ｚ｜と温度との
関係の特性の変動を抑えることができると共に高感度化
することができる感熱樹脂材料及び感熱体、感熱発熱体
を提供することを目的とするものである。The present invention has been made in view of the above points, and it is possible to suppress the characteristic variation of the relationship between | Z | and temperature due to heat aging, moisture absorption, and voltage application, and to improve the sensitivity. It is an object of the present invention to provide a heat-sensitive resin material, a heat-sensitive body, and a heat-sensitive heating element that can be used.
【０００６】[0006]
【課題を解決するための手段】本発明に係る感熱樹脂材
料は、高分子マトリクスポリマーに、ポリエチレングリ
コールとポリプロピレングリコールの共重合体からなる
副ポリマー中にイオン性物質として過塩素酸金属塩を添
加して調製したイオン伝導性電解質を混練して成る感熱
樹脂材料であって、副ポリマーにおけるポリエチレング
リコールの比率が３０〜６０重量％であり、かつイオン
伝導性電解質における過塩素酸金属塩の比率が５〜２０
重量％であり、かつ高分子マトリクスポリマー１００重
量部に対するイオン伝導性電解質の添加量が０．５〜
１．５重量部であることを特徴とするものである。The heat-sensitive resin material according to the present invention comprises a high-molecular matrix polymer containing a metal perchlorate as an ionic substance in a subpolymer composed of a copolymer of polyethylene glycol and polypropylene glycol. A heat-sensitive resin material prepared by kneading the ion-conductive electrolyte prepared as above, wherein the proportion of polyethylene glycol in the subpolymer is 30 to 60% by weight, and the proportion of metal perchlorate salt in the ion-conductive electrolyte is 5-20
% By weight, and the addition amount of the ion conductive electrolyte is 0.5 to 100 parts by weight of the high molecular matrix polymer.
It is characterized by being 1.5 parts by weight.
【０００７】また本発明は、高分子マトリクスポリマー
としてポリ塩化ビニル系樹脂を用い、安定剤として酸化
鉛と二酸化珪素からなる珪酸鉛を添加したものである。
また本発明に係る感熱体及び感熱発熱体は、上記感熱樹
脂材料を使用して成ることを特徴とするものである。以
下、本発明を詳細に説明する。In the present invention, a polyvinyl chloride resin is used as the high molecular matrix polymer, and lead silicate composed of lead oxide and silicon dioxide is added as a stabilizer.
Further, the heat-sensitive body and the heat-sensitive heat-generating body according to the present invention are characterized by using the above-mentioned heat-sensitive resin material. Hereinafter, the present invention will be described in detail.
【０００８】本発明に係る感熱樹脂材料は、ポリエチレ
ングリコール（ポリエチレンオキサイド）とポリプロピ
レングリコール（ポリプロピレンオキサイド）の共重合
体よりなる副ポリマー中にイオン性物質を添加してイオ
ン伝導性電解質を調製し、このイオン伝導性電解質や安
定剤等を高分子マトリクスポリマー中に混練することに
よって作成することができる。The heat-sensitive resin material according to the present invention is prepared by adding an ionic substance to a subpolymer composed of a copolymer of polyethylene glycol (polyethylene oxide) and polypropylene glycol (polypropylene oxide) to prepare an ion conductive electrolyte, It can be prepared by kneading the ion conductive electrolyte, the stabilizer and the like into a polymer matrix polymer.
【０００９】ここで、ポリエチレングリコール、ポリプ
ロピレングリコールはそれぞれ次の化学式１、化学式２
で示される樹脂である。Polyethylene glycol and polypropylene glycol are represented by the following chemical formulas 1 and 2, respectively.
Is a resin represented by.
【００１０】[0010]
【化１】 [Chemical 1]
【００１１】本発明はこれらポリエチレングリコールと
ポリプロピレングリコールの共重合体を感熱樹脂材料の
主成分（主ポリマー）である高分子マトリクスポリマー
に対する副ポリマーとして用いるものである。この副ポ
リマーにイオン性物質を添加することによってイオン伝
導性電解質を得ることができる。本発明ではイオン性物
質として過塩素酸金属塩を用いる。過塩素酸金属塩とし
ては次に示すものを用いることができるが、勿論これら
に限定されるものではない。In the present invention, the copolymer of polyethylene glycol and polypropylene glycol is used as an auxiliary polymer for the polymer matrix polymer which is the main component (main polymer) of the thermosensitive resin material. An ionic conductive electrolyte can be obtained by adding an ionic substance to this sub-polymer. In the present invention, a metal salt of perchloric acid is used as the ionic substance. The following salts can be used as the metal salt of perchloric acid, but are not limited thereto.
【００１２】過塩素酸リチウム塩（ＬｉＣｌＯ4 ） 過塩素酸カリウム塩（ＫＣｌＯ4 ） 過塩素酸マグネシウム塩（Ｍｇ（ＣｌＯ4 ）2 ） 過塩素酸金属塩は有機の過塩素酸塩に比べて分子量が小
さく、主なイオン伝導媒体である副ポリマー中における
移動速度が大きくなるため、有機の過塩素酸塩に比べて
副ポリマーに対する添加量を少なくすることができるも
のである。また、この過塩素酸金属塩をイオン性物質と
して副ポリマーに添加すると、Ｌｉ+ ，Ｋ+ ，Ｍｇ2+な
ど金属元素の陽イオンとＣｌＯ4 - の陰イオンとに解離
するが、ＣｌＯ4 - の陰イオンは耐熱性が高く容易に分
解しないために、感熱樹脂材料が高温に長時間さらされ
た場合でも固有インピーダンス｜Ｚ｜の変動を小さくす
ることができるものである。Lithium perchlorate (LiClO 4 ) Potassium perchlorate (KClO 4 ) Magnesium perchlorate (Mg (ClO 4 ) 2 ) Metal perchlorate has a molecular weight higher than that of organic perchlorate. Is small and the moving speed in the subpolymer, which is the main ion-conducting medium, is high, so that the addition amount to the subpolymer can be reduced as compared with the organic perchlorate. When this metal salt of perchlorate is added to the subpolymer as an ionic substance, it dissociates into cations of metal elements such as Li + , K + and Mg 2+ and anions of ClO 4 − , but ClO 4 − Since the anion of 1 has high heat resistance and is not easily decomposed, the fluctuation of the specific impedance | Z | can be reduced even when the heat-sensitive resin material is exposed to a high temperature for a long time.
【００１３】また本発明では高分子マトリクスポリマー
に配合する安定剤として、酸化鉛（ＰｂＯ）と二酸化珪
素（ＳｉＯ2 ）からなる珪酸鉛を用いる。従来から安定
剤としては三塩基性硫酸鉛などの塩基性鉛が使用されて
いるが、塩基性の安定剤は高分子マトリクスポリマーに
配合されている可塑剤を分解させることがあるために熱
安定性を大きく高めることができない。これに対して珪
酸鉛は可塑剤を分解させることがなく、しかも分子中の
鉛成分がリッチであるために、熱安定性を大きく高める
ことができるものである。Further, in the present invention, lead silicate composed of lead oxide (PbO) and silicon dioxide (SiO 2 ) is used as a stabilizer to be added to the polymer matrix polymer. Conventionally, basic lead such as tribasic lead sulfate has been used as a stabilizer, but since the basic stabilizer may decompose the plasticizer compounded in the polymer matrix polymer, it is thermally stable. You can't significantly improve your sex. On the other hand, lead silicate does not decompose the plasticizer, and since the lead component in the molecule is rich, the thermal stability can be greatly improved.
【００１４】ここで、上記過塩素酸金属塩や珪酸鉛は一
般的に吸湿性が大きいため、高湿度雰囲気に感熱樹脂材
料が置かれた場合、感熱樹脂材料の｜Ｚ｜は小さくなる
方向に変動することになる。そこで、本発明ではポリエ
チレングリコールとポリプロピレングリコールの共重合
体からなる副ポリマーを用いることによって、感熱樹脂
材料の温度と｜Ｚ｜との関係の特性が吸湿の影響を受け
難くなるようにしている。すなわち、ポリエチレングリ
コールは吸湿すると粘度が増してイオンが移動し難くな
るように作用するために、感熱樹脂材料の｜Ｚ｜は大き
くなる方向に変化し、その程度は副ポリマーの共重合体
におけるポリエチレングリコールの重量比率によって変
わるものであり、珪酸鉛や過塩素酸金属塩の吸湿によっ
て｜Ｚ｜が小さくなる方向に変化する量とバランスをと
ることによって、感熱樹脂材料の｜Ｚ｜の変動を見掛け
上小さくすることができるものである。このバランスを
とるために本発明では、ポリエチレングリコールとポリ
プロピレングリコールの共重合体として、ポリエチレン
グリコールの比率が３０〜６０重量％の範囲のものを用
いるようにしている。副ポリマーにおけるポリエチレン
グリコールの比率が６０重量％を超えると感熱樹脂材料
の｜Ｚ｜変動率が正の大きな値となり、逆にポリエチレ
ングリコールの比率が３０重量％未満であると感熱樹脂
材料の｜Ｚ｜変動率が負の大きな値となるものであり、
このためにポリエチレングリコールの比率を３０〜６０
重量％の範囲に調整する必要がある。Since the metal salts of perchlorate and lead silicate generally have high hygroscopicity, when the thermosensitive resin material is placed in a high humidity atmosphere, | Z | of the thermosensitive resin material tends to decrease. It will fluctuate. Therefore, in the present invention, by using a sub-polymer composed of a copolymer of polyethylene glycol and polypropylene glycol, the characteristics of the relationship between the temperature and | Z | of the heat-sensitive resin material are less likely to be affected by moisture absorption. That is, when polyethylene glycol absorbs moisture, it acts to increase the viscosity and make it difficult for ions to move. Therefore, | Z | of the heat-sensitive resin material changes in the direction of increasing, and the degree thereof changes to polyethylene in the copolymer of the subpolymer. It varies depending on the weight ratio of glycol. By balancing with the amount of change in the direction of decreasing | Z | due to moisture absorption of lead silicate or metal salt of perchlorate, the variation of | Z | It can be made smaller. In order to achieve this balance, in the present invention, a polyethylene glycol / polypropylene glycol copolymer having a polyethylene glycol ratio of 30 to 60% by weight is used. If the proportion of polyethylene glycol in the sub-polymer exceeds 60% by weight, the | Z | fluctuation rate of the heat-sensitive resin material becomes a large positive value, and conversely if the proportion of polyethylene glycol is less than 30% by weight, the | Z | ｜ The fluctuation rate is a large negative value,
For this reason, the ratio of polyethylene glycol should be 30-60.
It is necessary to adjust to the range of weight%.
【００１５】しかし、高分子マトリクスポリマーに対す
るイオン伝導性電解質の添加量が多いと、ポリエチレン
グリコールの吸湿による増粘作用が大きくなり過ぎて、
感熱樹脂材料の｜Ｚ｜は大きくなる方向に変動すること
になり、また感熱樹脂材料中のイオン濃度が大きくなり
過ぎて、商用電源（１００Ｖ程度）の交流電圧が０．３
ｍｍ程度の厚みの感熱樹脂材料に印加された場合にサー
ミスタブレーク現象によりイオンが消耗されてしまい、
感熱樹脂材料の｜Ｚ｜が大きく変動するおそれがある。
このために、本発明ではイオン伝導性電解質の添加量
を、高分子マトリクスポリマー１００重量部に対して
１．５重量部以下に設定しているものである。イオン伝
導性電解質の添加量が高分子マトリクスポリマー１００
重量部に対して０．５重量部未満であるとイオン伝導性
電解質を高分子マトリクスポリマー中に均一に分散させ
ることが困難であるために実用性に乏しい。従って本発
明では高分子マトリクスポリマー１００重量部に対する
イオン伝導性電解質の添加量を０．５〜１．５重量部の
範囲に設定しているものである。However, if the amount of the ion conductive electrolyte added to the polymer matrix polymer is large, the thickening effect of polyethylene glycol due to moisture absorption becomes too large,
The | Z | of the heat-sensitive resin material fluctuates in the increasing direction, and the ion concentration in the heat-sensitive resin material becomes too high, so that the AC voltage of the commercial power source (about 100 V) is 0.3.
Ions are consumed by the thermistor break phenomenon when applied to a thermosensitive resin material with a thickness of about mm,
The | Z | of the heat-sensitive resin material may vary greatly.
Therefore, in the present invention, the amount of the ion conductive electrolyte added is set to 1.5 parts by weight or less with respect to 100 parts by weight of the polymer matrix polymer. The addition amount of the ion conductive electrolyte is 100 as the polymer matrix polymer.
If the amount is less than 0.5 parts by weight based on parts by weight, it is difficult to uniformly disperse the ion conductive electrolyte in the polymer matrix polymer, resulting in poor practicability. Therefore, in the present invention, the amount of the ion conductive electrolyte added to 100 parts by weight of the polymer matrix polymer is set in the range of 0.5 to 1.5 parts by weight.
【００１６】また本発明では、副ポリマーに過塩素酸金
属塩を添加して調整されるイオン伝導性電解質における
過塩素酸金属塩の比率は５重量％〜２０重量％の範囲に
設定している。イオン伝導性電解質における過塩素酸金
属塩の比率が５重量％未満であると、過塩素酸金属塩を
副ポリマーに均一に分散させることが困難であり、しか
も８０℃〜１００℃の高温領域における｜Ｚ｜と温度の
関係の特性のＢ定数が小さくなるために好ましくない。
ここで、Ｂ定数は｜Ｚ｜〜温度特性の変化率の大きさを
示すものであり（図４のような｜Ｚ｜〜温度曲線の傾き
度としてあらわれる）、サーミスタ特性の感度が高くな
るとＢ定数は大きくなる。逆にイオン伝導性電解質にお
ける過塩素酸金属塩の比率が２０重量％を超えると、吸
湿によるポリエチレングリコールの増粘によってイオン
伝導性電解質の粘度が高くなり過ぎ、高分子マトリクス
ポリマーにイオン伝導性電解質を均一に分散させ難くな
り、また活性が強くなり過ぎて危険が大きくなる。Further, in the present invention, the ratio of the metal perchlorate in the ion conductive electrolyte prepared by adding the metal perchlorate to the sub-polymer is set in the range of 5% by weight to 20% by weight. . When the ratio of the metal salt of perchlorate in the ion conductive electrolyte is less than 5% by weight, it is difficult to uniformly disperse the metal salt of perchlorate in the subpolymer, and in a high temperature range of 80 ° C to 100 ° C. It is not preferable because the B constant of the characteristic of the relationship between | Z | and temperature becomes small.
Here, the B constant represents the magnitude of the change rate of | Z | to temperature characteristics (which appears as | Z | to the slope of the temperature curve as shown in FIG. 4), and the higher the sensitivity of the thermistor characteristic, the higher the B The constant increases. On the contrary, when the ratio of the metal salt of perchlorate in the ion conductive electrolyte exceeds 20% by weight, the viscosity of the polyethylene glycol increases due to moisture absorption and the viscosity of the ion conductive electrolyte becomes too high, and the ion conductive electrolyte becomes high in the polymer matrix polymer. It becomes difficult to disperse evenly, and the activity becomes too strong and the danger increases.
【００１７】一方、感熱樹脂材料の主成分となる高分子
マトリクスポリマーとしては、ポリ塩化ビニル樹脂やそ
の誘導体などポリ塩化ビニル系樹脂を用いることができ
る。そして上記のイオン伝導性電解質や安定剤としての
珪酸鉛を、可塑剤を配合した高分子マトリクスポリマー
に添加して混練することによって、イオン伝導性プラス
チックサーミスタ特性を示す感熱樹脂材料を得ることが
できるものである。On the other hand, as the polymer matrix polymer which is the main component of the heat-sensitive resin material, polyvinyl chloride resin such as polyvinyl chloride resin or its derivative can be used. Then, by adding the above-mentioned ion conductive electrolyte or lead silicate as a stabilizer to a polymer matrix polymer containing a plasticizer and kneading, a heat-sensitive resin material exhibiting ion conductive plastic thermistor characteristics can be obtained. It is a thing.
【００１８】また本発明に係る感熱体は、図６に示すよ
うに、絶縁性の芯糸１に金属線を巻いて内巻電極２と
し、上記のように調製した感熱樹脂材料３を内巻電極２
の外側に被覆し、その外側に金属線を巻いて外巻電極４
とすることによって作成することができる。感熱樹脂材
料３は上記のように温度変化に伴って｜Ｚ｜が変化する
ので、内巻電極２と外巻電極３の間の電位差を測定して
インピーダンスを検出することによって発熱温度を検知
することができるものである。As shown in FIG. 6, the heat-sensitive material according to the present invention has an insulative core yarn 1 wound with a metal wire to form an inwardly wound electrode 2, and an inwardly wound thermosensitive resin material 3 prepared as described above. Electrode 2
The outer winding electrode 4 is coated on the outside of the
It can be created by Since | Z | changes with the temperature change in the heat-sensitive resin material 3 as described above, the heat generation temperature is detected by measuring the potential difference between the inner winding electrode 2 and the outer winding electrode 3 to detect the impedance. Is something that can be done.
【００１９】さらに、本発明に係る感熱発熱体Ａは、こ
の感熱体の内巻電極２と外巻電極３の少なくとも一方を
発熱抵抗体として通電によって発熱させるようにし、こ
れらを絶縁体５で被覆することによって作成することが
できる。図６において１０は外巻電極３の外側に樹脂フ
ィルムを巻いて形成した分離層である。Further, in the heat-sensitive heating element A according to the present invention, at least one of the inner wound electrode 2 and the outer wound electrode 3 of the heat sensitive body is used as a heating resistor to generate heat by energization, and these are covered with the insulator 5. Can be created by doing. In FIG. 6, reference numeral 10 denotes a separation layer formed by winding a resin film around the outer winding electrode 3.
【００２０】[0020]
【実施例】次に、本発明を実施例によって具体的に説明
する。 （実施例１）ポリ塩化ビニル樹脂１００重量部にトリメ
リット酸系の可塑剤を４５重量部、珪酸鉛を安定剤とし
て２５重量部配合し、さらに、ポリエチレングリコール
とポリプロピレングリコールを約１：１の重量比で共重
合させた平均分子量３５００のブロック共重合体を副ポ
リマーとして用い、過塩素酸金属塩として過塩素酸リチ
ウム塩（ＬｉＣｌＯ4 ）をこの副ポリマーに対して１５
重量％添加してイオン伝導性電解質を調製した。そして
このイオン伝導性電解質を上記配合物にポリ塩化ビニル
樹脂１００重量部に対して１．４重量部の配合量で添加
し、混練することによって感熱樹脂材料を得た。EXAMPLES Next, the present invention will be specifically described with reference to examples. (Example 1) 100 parts by weight of polyvinyl chloride resin was mixed with 45 parts by weight of a trimellitic acid-based plasticizer and 25 parts by weight of lead silicate as a stabilizer, and polyethylene glycol and polypropylene glycol were mixed in an amount of about 1: 1. A block copolymer having an average molecular weight of 3500 copolymerized in a weight ratio is used as a subpolymer, and lithium perchlorate (LiClO 4 ) as a metal salt of perchlorate is added to the subpolymer.
An ion-conducting electrolyte was prepared by adding it in a weight percentage. Then, this ion conductive electrolyte was added to the above-mentioned composition in an amount of 1.4 parts by weight based on 100 parts by weight of the polyvinyl chloride resin, and kneaded to obtain a heat-sensitive resin material.
【００２１】（比較例１）イオン伝導性電解質をポリ塩
化ビニル樹脂１００重量部に対して１．８重量部の配合
量で添加するようにした他は、実施例１と同様にして感
熱樹脂材料を得た。図１に、実施例１と比較例１の感熱
樹脂材料を６０℃×９５％ＲＨの高温高湿雰囲気下に放
置したときの、｜Ｚ｜の変化率と放置時間との関係を示
す。放置開始後３６時間経過時点での｜Ｚ｜の変化率
は、実施例１のものが３．９％であるのに対して、イオ
ン伝導性電解質の添加量が多い比較例１のものは１２．
７％であり、実施例１は比較例１の約１／３の変化率に
収まっていることが確認される。Comparative Example 1 A heat-sensitive resin material was prepared in the same manner as in Example 1 except that the ion conductive electrolyte was added in an amount of 1.8 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. Got FIG. 1 shows the relationship between the change rate of | Z | and the standing time when the thermosensitive resin materials of Example 1 and Comparative Example 1 were allowed to stand in a high temperature and high humidity atmosphere of 60 ° C. × 95% RH. The change rate of | Z | at 36 hours after the start of standing was 3.9% in Example 1 and was 12 in Comparative Example 1 in which the amount of the ion conductive electrolyte added was large. ．
It is 7%, and it is confirmed that the rate of change in Example 1 is about 1/3 of that in Comparative Example 1.
【００２２】（実施例２）実施例１で得た感熱樹脂材料
を用い、図６に示す構造の感熱発熱体を製作した。ここ
で、感熱発熱体３の厚みを０．３ｍｍに設定して内巻電
極２と外巻電極４の両間距離は０．３ｍｍにした。 （比較例２）比較例１で得た感熱樹脂材料を用い、図６
に示す構造の感熱発熱体を製作した。ここで、感熱発熱
体３の厚みを０．３ｍｍに設定して内巻電極２と外巻電
極４の両間距離は０．３ｍｍにした。Example 2 Using the thermosensitive resin material obtained in Example 1, a thermosensitive heating element having a structure shown in FIG. 6 was manufactured. Here, the thickness of the heat-sensitive heating element 3 was set to 0.3 mm, and the distance between the inner winding electrode 2 and the outer winding electrode 4 was 0.3 mm. Comparative Example 2 Using the thermosensitive resin material obtained in Comparative Example 1, FIG.
A heat-sensitive heating element having the structure shown in was produced. Here, the thickness of the heat-sensitive heating element 3 was set to 0.3 mm, and the distance between the inner winding electrode 2 and the outer winding electrode 4 was 0.3 mm.
【００２３】図２に、実施例２と比較例２の感熱発熱体
（長さ３ｍ）の内巻電極２と外巻電極４の極間（極間距
離０．３ｍｍ）に商用交流電圧（ＡＣ１００Ｖ６０Ｈ
ｚ）を定期的に繰り返して一定時間印加しつつ、この感
熱発熱体を１３６℃の高温雰囲気中に放置したときの、
｜Ｚ｜の変化率と放置時間との関係を示す。図２にみら
れるように、放置時間が１００時間経過後、比較例２の
ものは｜Ｚ｜の変化率が１６０％であるのに対して、実
施例２のものは｜Ｚ｜の変化率が１００％以下に低減さ
れているものであった。In FIG. 2, a commercial AC voltage (AC100V60H) is applied between the inner winding electrode 2 and the outer winding electrode 4 of the heat-sensitive heating elements (length 3 m) of Example 2 and Comparative Example 2 (distance between electrodes is 0.3 mm).
z) is periodically applied for a certain period of time, and when this heat-sensitive heating element is left in a high temperature atmosphere of 136 ° C.,
The relationship between the change rate of | Z | and the standing time is shown. As shown in FIG. 2, after 100 hours of standing time, the change rate of | Z | of Comparative Example 2 is 160%, whereas the change rate of | Z | Was reduced to 100% or less.
【００２４】（実施例３）副ポリマーとして、ポリエチ
レングリコールとポリプロピレングリコールのブロック
共重合体であって平均分子量が３３００でポリエチレン
グリコールの比率が２５重量％のもの、及び平均分子量
が４１００でポリエチレングリコールの比率が５０重量
％のもの、ポリエチレングリコール単体であって平均分
子量が１０００のもの、ポリプロピレングリコール単体
であって平均分子量が２０００のものをそれぞれ用い、
イオン性物質として過塩素酸リチウム塩をこの各副ポリ
マーに対して一律１５重量％添加してイオン伝導性電解
質を調製した。またポリ塩化ビニル樹脂１００重量部に
トリメリット酸系の可塑剤を４５重量部、安定剤として
珪酸鉛を２５重量部配合し、さらにこれに上記イオン伝
導性電解質を一律１．４重量％の割合で添加して混練す
ることによって感熱樹脂材料を得た。そしてこの感熱樹
脂材料を６０℃×９５％ＲＨの高温多湿雰囲気に１６８
時間放置する前後での６０℃における｜Ｚ｜変動率を測
定し、｜Ｚ｜変動率と副ポリマーにおけるポリエチレン
グリコールの重量比率との関係を図３に示した。(Example 3) As a subpolymer, a block copolymer of polyethylene glycol and polypropylene glycol having an average molecular weight of 3300 and a polyethylene glycol ratio of 25% by weight, and an average molecular weight of 4100 and polyethylene glycol were used. A ratio of 50% by weight, a polyethylene glycol simple substance having an average molecular weight of 1000, and a polypropylene glycol simple substance having an average molecular weight of 2000 are used.
A lithium perchlorate salt as an ionic substance was uniformly added to the respective subpolymers in an amount of 15% by weight to prepare an ion conductive electrolyte. In addition, 100 parts by weight of polyvinyl chloride resin was mixed with 45 parts by weight of a trimellitic acid-based plasticizer and 25 parts by weight of lead silicate as a stabilizer, and the above ion conductive electrolyte was uniformly mixed in a ratio of 1.4% by weight. A thermosensitive resin material was obtained by adding and kneading. Then, this heat-sensitive resin material is exposed to a high temperature and high humidity atmosphere of 168 ° C. × 95% 168
The | Z | fluctuation ratio at 60 ° C. was measured before and after standing for a period of time, and the relationship between the | Z | fluctuation ratio and the weight ratio of polyethylene glycol in the subpolymer is shown in FIG.
【００２５】図３にみられるように、副ポリマーにおけ
るポリエチレングリコールの比率が１００重量％のもの
は｜Ｚ｜変動率は正の大きな値となり、逆にポリエチレ
ングリコールの比率が０重量％のものは｜Ｚ｜変動率は
負の大きな値となるものであり、またポリエチレングリ
コールの比率が３０〜６０重量％の場合は｜Ｚ｜変動率
の絶対値は小さな値となるものであった。副ポリマーを
ポリエチレングリコールとポリプロピレングリコールの
ブロック共重合体で形成すると、ポリエチレングリコー
ルとポリプロピレングリコールの両者の特性を併せ持つ
が、ポリエチレングリコールは吸湿すると粘度が増して
イオンが移動し難くなるために、｜Ｚ｜は大きくなる方
向に変動し、その程度はブロック共重合体におけるポリ
エチレングリコールの重量比率によって変えることがで
きるのである。As shown in FIG. 3, when the proportion of polyethylene glycol in the subpolymer is 100% by weight, the | Z | fluctuation rate becomes a large positive value, and conversely, when the proportion of polyethylene glycol is 0% by weight. The | Z | fluctuation ratio has a large negative value, and the absolute value of the | Z | fluctuation ratio has a small value when the proportion of polyethylene glycol is 30 to 60% by weight. When the sub-polymer is formed of a block copolymer of polyethylene glycol and polypropylene glycol, it has the characteristics of both polyethylene glycol and polypropylene glycol, but polyethylene glycol has a viscosity that increases when moisture is absorbed, making it difficult for ions to move. | Fluctuates in the direction of increasing, and the degree thereof can be changed by the weight ratio of polyethylene glycol in the block copolymer.
【００２６】（実施例４）副ポリマーとして平均分子量
３６５０のポリエチレングリコールとポリプロピレング
リコールのブロック共重合体を用い、イオン性物質とし
て過塩素酸リチウム塩を副ポリマーに対して１０重量
％、１５重量％添加して２種類のイオン伝導性電解質を
調製した。またポリ塩化ビニル樹脂１００重量部にトリ
メリット酸系の可塑剤を４５重量部、安定剤として珪酸
鉛を２５重量部配合し、これに各イオン伝導性電解質を
一律１．５重量％の割合で添加して混練することによっ
て感熱樹脂材料を得た。この各感熱樹脂材料の固有イン
ピーダンス｜Ｚ｜〜温度曲線を図４に示す。Example 4 A block copolymer of polyethylene glycol and polypropylene glycol having an average molecular weight of 3650 was used as a subpolymer, and lithium perchlorate was used as an ionic substance in an amount of 10% by weight and 15% by weight based on the subpolymer. Two kinds of ion conductive electrolytes were prepared by adding. Further, 45 parts by weight of trimellitic acid-based plasticizer and 25 parts by weight of lead silicate as a stabilizer were mixed with 100 parts by weight of polyvinyl chloride resin, and each of these ion conductive electrolytes was uniformly mixed at a ratio of 1.5% by weight. A thermosensitive resin material was obtained by adding and kneading. FIG. 4 shows the characteristic impedance | Z | -temperature curve of each heat-sensitive resin material.
【００２７】図４にみられるように、８０℃〜１００℃
におけるＢ定数はイオン性物質の副ポリマーに対する添
加量を多くする程、大きくすることができる。また｜Ｚ
｜の絶対値もイオン性物質の副ポリマーに対する添加量
によって変化することがみられる。尚、図４において過
塩素酸リチウム塩を副ポリマーに対して１０重量％添加
したものをＲ＝１０重量％、１５重量％添加したものを
Ｒ＝１５重量％として示す。As seen in FIG. 4, 80 ° C. to 100 ° C.
B constant can be increased as the amount of the ionic substance added to the subpolymer is increased. Also | Z
It can be seen that the absolute value of | also changes depending on the amount of the ionic substance added to the subpolymer. In FIG. 4, 10% by weight of the perchloric acid lithium salt with respect to the sub-polymer is shown as R = 10% by weight, and 15% by weight is shown as R = 15% by weight.
【００２８】（実施例５）副ポリマーとして平均分子量
２２２０のポリエチレングリコールとポリプロピレング
リコールの約１：１重量比率のブロック共重合体を用
い、イオン性物質として過塩素酸リチウム塩を副ポリマ
ーに対して１０重量％添加してイオン伝導性電解質を調
製した。またポリ塩化ビニル樹脂１００重量部にトリメ
リット酸系の可塑剤を４５重量部、安定剤として珪酸鉛
を２５重量部配合し、これに上記イオン伝導性電解質を
１重量％、１．５重量％、２重量％の割合で添加して混
練することによって、３種類の感熱樹脂材料を得た。こ
の各感熱樹脂材料の固有インピーダンス｜Ｚ｜〜温度曲
線を図５に示す。Example 5 As a subpolymer, a block copolymer of polyethylene glycol and polypropylene glycol having an average molecular weight of 2220 in a weight ratio of about 1: 1 was used, and lithium perchlorate salt was used as an ionic substance with respect to the subpolymer. An ion conductive electrolyte was prepared by adding 10% by weight. Further, 45 parts by weight of a trimellitic acid-based plasticizer and 25 parts by weight of lead silicate as a stabilizer were mixed with 100 parts by weight of polyvinyl chloride resin, and 1% by weight and 1.5% by weight of the above-mentioned ion conductive electrolyte were added thereto. By adding 2% by weight and kneading, three kinds of heat-sensitive resin materials were obtained. The characteristic impedance | Z | of the heat-sensitive resin materials to temperature curves are shown in FIG.
【００２９】図６にみられるように、イオン伝導性電解
質の添加量を多くする程、｜Ｚ｜の絶対値は小さくなる
傾向がある。尚、図５においてイオン伝導性電解質を１
重量％添加したものをＶ＝１重量％、１．５重量％添加
したものをＶ＝１．５重量％、２重量％添加したものを
Ｖ＝２重量％として示す。 （実施例６）本発明に係る感熱性樹脂材料を用いて、図
６に示すようなコード状の感熱発熱体Ａを製造した。こ
の感熱発熱体Ａは、絶縁性の芯糸１に金属線をスパイラ
ル状に巻いて内巻電極２とし、上記各実施例のように調
製した感熱樹脂材料３を例えば押し出し成形して内巻電
極２の外側に被覆し、その外側に金属線を巻いて外巻電
極４とし、さらにその外側に樹脂フィルムを巻いて分離
層１０を形成した後に、その外側に絶縁体５を被覆する
ことによって製造したものである。As shown in FIG. 6, the absolute value of | Z | tends to decrease as the amount of the ion conductive electrolyte added increases. In FIG. 5, the ion conductive electrolyte is 1
The amount added with V% is V = 1% by weight, the amount added with 1.5% by weight is V = 1.5% by weight, and the amount added with 2% by weight is V = 2% by weight. Example 6 A cord-shaped heat-sensitive heating element A as shown in FIG. 6 was manufactured using the heat-sensitive resin material according to the present invention. In this heat-sensitive heating element A, a metal wire is spirally wound around an insulative core yarn 1 to form an inner wound electrode 2, and the heat-sensitive resin material 3 prepared as in each of the above embodiments is extruded to form an inner wound electrode. 2 is coated on the outside, a metal wire is wound on the outside to form the outer wound electrode 4, a resin film is further wound on the outside to form the separation layer 10, and then the outside is covered with the insulator 5. It was done.
【００３０】この感熱発熱体Ａは、内巻電極２と外巻電
極４の少なくとも一方を発熱抵抗体（ヒータ）として通
電することによって発熱させることができる。そしてこ
の感熱発熱体Ａにあって、電極２，４の一方を発熱させ
ると感熱樹脂材料３は温度変化に伴って｜Ｚ｜が変化す
るために、電極２，４間の電位差を検出することによっ
て発熱温度を検知することができる。The heat-sensitive heating element A can generate heat by energizing at least one of the inner winding electrode 2 and the outer winding electrode 4 as a heating resistor (heater). In this heat-sensitive heating element A, when one of the electrodes 2 and 4 is heated, | Z | of the heat-sensitive resin material 3 changes with a temperature change. Therefore, the potential difference between the electrodes 2 and 4 must be detected. The heat generation temperature can be detected by.
【００３１】このように作成される感熱発熱体Ａを、例
えば図７（ａ）（ｂ）に示すように、ポリエステル繊維
等の厚さ１０ｍｍ程度の裏面布１１と厚さ９μ程度の均
熱アルミニウム平面体１２との間に挟んでジグザグ状に
配置し、そして均熱アルミニウム平面体１２の上にポリ
エステル繊維等の厚さ５ｍｍ程度の表面布１３を積層す
ることによって電気カーペットＢを作成することができ
る。図７（ａ）において１４は電源コード、１５は温度
コントローラである。As shown in FIGS. 7 (a) and 7 (b), for example, the heat-sensitive heating element A thus produced is made of polyester fiber or the like with a back cloth 11 having a thickness of about 10 mm and a soaking aluminum having a thickness of about 9 μ. The electric carpet B can be produced by arranging the surface cloth 13 in a zigzag shape by sandwiching it between the flat body 12 and the surface cloth 13 having a thickness of about 5 mm, such as polyester fiber, on the soaking aluminum flat body 12. it can. In FIG. 7A, 14 is a power cord and 15 is a temperature controller.
【００３２】[0032]
【発明の効果】上記のように本発明は、高分子マトリク
スポリマーに、ポリエチレングリコールとポリプロピレ
ングリコールの共重合体からなる副ポリマー中にイオン
性物質として過塩素酸金属塩を添加して調製したイオン
伝導性電解質を混練して感熱樹脂材料を調製するにあた
って、副ポリマーにおけるポリエチレングリコールの比
率を３０〜６０重量％、イオン伝導性電解質における過
塩素酸金属塩の比率を５〜２０重量％、高分子マトリク
スポリマー１００重量部に対するイオン伝導性電解質の
添加量を０．５〜１．５重量部に設定したので、配合を
これらの範囲に設定することによって熱老化、吸湿、商
用交流電圧印加によって感熱樹脂材料の｜Ｚ｜と温度と
の関係の特性が変化するのを防止することができるもの
であり、またこの結果｜Ｚ｜〜温度特性を高感度化する
ことができるものである。INDUSTRIAL APPLICABILITY As described above, according to the present invention, an ion prepared by adding a metal perchlorate as an ionic substance to a high molecular matrix polymer in a subpolymer composed of a copolymer of polyethylene glycol and polypropylene glycol. In preparing the thermosensitive resin material by kneading the conductive electrolyte, the ratio of polyethylene glycol in the sub-polymer is 30 to 60% by weight, the ratio of metal perchlorate salt in the ion conductive electrolyte is 5 to 20% by weight, and the polymer Since the amount of the ion conductive electrolyte added was set to 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the matrix polymer, heat aging, moisture absorption, and application of a commercial AC voltage to the heat-sensitive resin by setting the blending range to these ranges. It is possible to prevent the characteristic of the relation between | Z | and temperature of the material from changing, and Fruit | Z | is capable of high sensitivity to ~ temperature characteristics.
【００３３】また本発明は、高分子マトリクスポリマー
としてポリ塩化ビニル系樹脂を用い、安定剤として酸化
鉛と二酸化珪素からなる珪酸鉛を添加するようにしたの
で、珪酸鉛はポリ塩化ビニル樹脂に配合される可塑剤を
分解することがなく熱安定性を高く得ることができるも
のであり、熱老化で感熱樹脂材料の｜Ｚ｜と温度との関
係の特性が経時変化するのを防止することができるもの
である。Further, in the present invention, a polyvinyl chloride resin is used as the polymer matrix polymer, and lead silicate consisting of lead oxide and silicon dioxide is added as a stabilizer. Therefore, lead silicate is blended with the polyvinyl chloride resin. It is possible to obtain high thermal stability without decomposing the plasticizer to be used, and to prevent the characteristics of the relationship between | Z | and temperature of the heat-sensitive resin material from changing with time due to heat aging. It is possible.
【図１】実施例１及び比較例１の感熱樹脂材料を６０℃
×９５％ＲＨの高温高湿雰囲気下に放置したときの、｜
Ｚ｜変化率と放置時間との関係を示すグラフである。FIG. 1 shows the thermosensitive resin materials of Example 1 and Comparative Example 1 at 60 ° C.
When left in a high temperature and high humidity atmosphere of × 95% RH,
It is a graph which shows the relationship of Z | change rate and leaving time.
【図２】実施例２と比較例２の感熱発熱体に商用交流電
圧を印加しつつ１３６℃雰囲気中に放置したときの｜Ｚ
｜変化率と放置時間との関係を示すグラフである。FIG. 2 shows | Z when the commercial heat-generating elements of Example 2 and Comparative Example 2 were left in a 136 ° C. atmosphere while applying a commercial AC voltage.
| Is a graph showing the relationship between the change rate and the standing time.
【図３】実施例３の感熱樹脂材料の｜Ｚ｜変動率と副ポ
リマー中のポリエチレングリコールの重量比率との関係
を示すグラフである。FIG. 3 is a graph showing the relationship between the | Z | fluctuation rate of the thermosensitive resin material of Example 3 and the weight ratio of polyethylene glycol in the subpolymer.
【図４】実施例４の感熱樹脂材料の固有インピーダンス
〜温度曲線のグラフである。FIG. 4 is a graph of the characteristic impedance-temperature curve of the thermosensitive resin material of Example 4.
【図５】実施例５の感熱樹脂材料の固有インピーダンス
〜温度曲線のグラフである。FIG. 5 is a graph of intrinsic impedance-temperature curve of the thermosensitive resin material of Example 5.
【図６】感熱発熱体の一実施例の一部の正面図である。FIG. 6 is a partial front view of an embodiment of the heat-sensitive heating element.
【図７】電気カーペットを示すものであり、（ａ）は斜
視図、（ｂ）は一部の拡大した断面図である。7A and 7B are views showing an electric carpet, in which FIG. 7A is a perspective view and FIG. 7B is a partially enlarged sectional view.
１ 芯糸 ２ 内巻電極 ３ 感熱樹脂材料 ４ 外巻電極 ５ 絶縁体 1 core thread 2 inner winding electrode 3 thermosensitive resin material 4 outer winding electrode 5 insulator
Claims (4)
レングリコールとポリプロピレングリコールの共重合体
からなる副ポリマー中にイオン性物質として過塩素酸金
属塩を添加して調製したイオン伝導性電解質を混練して
成る感熱樹脂材料であって、副ポリマーにおけるポリエ
チレングリコールの比率が３０〜６０重量％であり、か
つイオン伝導性電解質における過塩素酸金属塩の比率が
５〜２０重量％であり、かつ高分子マトリクスポリマー
１００重量部に対するイオン伝導性電解質の添加量が
０．５〜１．５重量部であることを特徴とする感熱樹脂
材料。1. A high-molecular matrix polymer prepared by kneading an ion-conductive electrolyte prepared by adding a metal salt of perchloric acid as an ionic substance in a sub-polymer composed of a copolymer of polyethylene glycol and polypropylene glycol. A heat-sensitive resin material, wherein the proportion of polyethylene glycol in the sub-polymer is 30 to 60% by weight, the proportion of metal perchlorate in the ion conductive electrolyte is 5 to 20% by weight, and a high molecular matrix polymer A heat-sensitive resin material, wherein the amount of the ion conductive electrolyte added is 100 parts by weight of 0.5 to 1.5 parts by weight.
化ビニル系樹脂を用い、安定剤として酸化鉛と二酸化珪
素からなる珪酸鉛を添加して成ることを特徴とする請求
項１に記載の感熱樹脂材料。2. The heat-sensitive resin material according to claim 1, wherein a polyvinyl chloride resin is used as the polymer matrix polymer, and lead silicate consisting of lead oxide and silicon dioxide is added as a stabilizer.
使用して成ることを特徴とする感熱体。3. A heat-sensitive body comprising the heat-sensitive resin material according to claim 1 or 2.
使用して成ることを特徴とする感熱発熱体。4. A heat-sensitive heating element comprising the heat-sensitive resin material according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18530493A JP3493690B2 (en) | 1993-07-27 | 1993-07-27 | Heat-sensitive resin material and heat-sensitive body, heat-sensitive heat generator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18530493A JP3493690B2 (en) | 1993-07-27 | 1993-07-27 | Heat-sensitive resin material and heat-sensitive body, heat-sensitive heat generator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0741684A true JPH0741684A (en) | 1995-02-10 |
| JP3493690B2 JP3493690B2 (en) | 2004-02-03 |
Family
ID=16168521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18530493A Expired - Lifetime JP3493690B2 (en) | 1993-07-27 | 1993-07-27 | Heat-sensitive resin material and heat-sensitive body, heat-sensitive heat generator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3493690B2 (en) |
-
1993
- 1993-07-27 JP JP18530493A patent/JP3493690B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3493690B2 (en) | 2004-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0342681B2 (en) | ||
| KR900007569B1 (en) | Flexible thermal wire | |
| JP3493690B2 (en) | Heat-sensitive resin material and heat-sensitive body, heat-sensitive heat generator | |
| SE8304042L (en) | TAPE HEATER WITH ELECTRICAL DEVICES INCLUDING LEADING POLYMER COMPOSITIONS | |
| JP3381963B2 (en) | Heat-sensitive resin material and heat-sensitive body, heat-sensitive heat generator | |
| Strong | Aqueous hydrochloric acid conductance from 0 to 100. degree. C | |
| Bac et al. | The effect of type of the inorganic filler and dopant salt concentration on the PEO–LiClO4 based composite electrolyte–lithium electrode interfacial resistivity | |
| JPH076903A (en) | Heat sensitive resin material and heat sensitive heating element | |
| JPH07216174A (en) | Heat-sensitive resin material, heat-sensitive body and heat-sensitive heat-generating body | |
| JP3430536B2 (en) | Thermal element and thermal element | |
| JP2955029B2 (en) | Thermosensitive resin material and thermosensitive heating element | |
| JPH11144848A (en) | Ptc heating element and its manufacture | |
| Dias et al. | Phosphonium ionic liquids as greener electrolytes for poly (vinyl chloride)-based ionic conducting polymers | |
| JPH07216173A (en) | Heat-sensitive resin material, heat-sensitive body and heat-sensitive heat-generating body | |
| JPH0657075A (en) | Heat-sensitive resin material and heat-sensitive heater | |
| JPS59132352A (en) | Moisture sensitive material | |
| JP2955028B2 (en) | Thermosensitive resin material and thermosensitive heating element | |
| JPH0532696B2 (en) | ||
| JP2882717B2 (en) | High temperature durability polymer semiconductor | |
| JP2630884B2 (en) | Polymer thermosensor | |
| JPS6248751A (en) | Solvent-resistant polyvinyl chloride composition and flexible electric wire using the same | |
| JPS63132965A (en) | Low temperature heating element and its manufacturing method | |
| JP3032441B2 (en) | Ozone sensor | |
| JP2010135575A (en) | Polymer thermal detector | |
| JPS61239585A (en) | Heat sensitive wire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20031021 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081121 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081121 Year of fee payment: 5 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091121 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091121 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101121 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111121 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121121 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121121 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131121 Year of fee payment: 10 |
|
| EXPY | Cancellation because of completion of term |