JPH0656803B2 - Thermal element - Google Patents
Thermal elementInfo
- Publication number
- JPH0656803B2 JPH0656803B2 JP62254448A JP25444887A JPH0656803B2 JP H0656803 B2 JPH0656803 B2 JP H0656803B2 JP 62254448 A JP62254448 A JP 62254448A JP 25444887 A JP25444887 A JP 25444887A JP H0656803 B2 JPH0656803 B2 JP H0656803B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive element
- impedance
- plasticizer
- electric conductor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 claims description 30
- 239000004014 plasticizer Substances 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 19
- 230000008859 change Effects 0.000 claims description 18
- 239000004020 conductor Substances 0.000 claims description 18
- 238000004804 winding Methods 0.000 claims description 14
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 12
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 12
- 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 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 6
- 239000011162 core material Substances 0.000 claims description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims 1
- 238000005260 corrosion Methods 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 239000011347 resin Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- 239000003607 modifier Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- -1 trimellitic acid ester Chemical class 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003398 denaturant Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Landscapes
- Measuring Temperature Or Quantity Of Heat (AREA)
- Resistance Heating (AREA)
- Thermistors And Varistors (AREA)
Description
【発明の詳細な説明】 （技術分野） 本発明は感熱素子に係り、特に電気カーペット等に用い
られる線状，面状あるいは感熱素子部と発熱部とを一体
としたインピーダンス特性の優れた感熱素子に関するも
のである。Description: TECHNICAL FIELD The present invention relates to a heat-sensitive element, and more particularly to a heat-sensitive element used in an electric carpet or the like, which has a linear or planar shape or a heat-sensitive element unit and a heat-generating unit which are excellent in impedance characteristics. It is about.
（背景技術） 従来より電気カーペットにおいては第４図に示すように
感熱線が発熱線と一体になって使用されている。(Background Art) Conventionally, in an electric carpet, a heat-sensitive wire is used integrally with a heat-generating wire as shown in FIG.
すなわち、温度変化に応じてインピーダンスが変化する
管状の負特性高分子感温体（感熱樹脂材）３と、その外
面に巻き付けられた外巻電気導体線４と、芯材１に巻き
付けられて前記負特性高分子感温体３の内面に配された
内巻電気導体線２と、前記外巻電気導体線４の外面に設
けられた絶縁層５とにより構成された感熱素子が使用さ
れていた。That is, a tubular negative characteristic polymer temperature sensor (heat-sensitive resin material) 3 whose impedance changes according to a temperature change, an outer winding electric conductor wire 4 wound around the outer surface thereof, and a core material 1 wound around A heat sensitive element constituted by an inner winding electric conductor wire 2 arranged on the inner surface of the negative characteristic polymer temperature sensitive body 3 and an insulating layer 5 provided on the outer surface of the outer winding electric conductor wire 4 has been used. .
また、第５図は他の例であり、３は負特性高分子感温
体、12，14，116は電気導体線、５は絶縁層である。Further, FIG. 5 shows another example, 3 is a negative characteristic polymer temperature sensor, 12, 14, 116 are electric conductor wires, and 5 is an insulating layer.
ところで、この種の感熱素子には負特性高分子感温体３
としてＰＶＣ材に可塑剤，イオン性添加剤等を混練した
材料が使用され、外面の絶縁層５にも耐熱性のＰＶＣ材
が使用されている。その理由は、他の実用的な負特性高
分子感温体として知られているポリアミド系の材料に比
べて吸湿性が低く、インピーダンスの経時変化が少ない
ためである。By the way, this type of heat-sensitive element has a negative characteristic polymer temperature sensor 3
As the material, a material obtained by kneading a PVC material with a plasticizer, an ionic additive, etc. is used, and a heat-resistant PVC material is also used for the insulating layer 5 on the outer surface. The reason is that it has lower hygroscopicity and less change in impedance over time as compared with other polyamide-based materials known as other practical negative-characteristic polymer temperature sensitive materials.
しかし、近年、電気カーペットにあっては、表面材とし
て従来のニードルパンチ式の薄くて断熱性の小さいもの
から、タフト織等の厚くてソフト感のある断熱性の大き
い表面材が、カーペットライフの本物志向の高まりとと
もに広がってきており、それに対応するために、内部の
ヒータ温度を従来よりも高温にする必要が生じてきてい
る。それに対応して感熱線の温度も高くなる傾向が生じ
ている。However, in recent years, in electric carpets, from the conventional needle punch type thin and small heat insulating material as a surface material, a thick and soft heat insulating surface material such as tufted weave has been used for the carpet life. It is becoming more widespread with the increasing tendency toward genuine products, and in order to deal with it, it is necessary to raise the internal heater temperature higher than before. Correspondingly, the temperature of the heat sensitive wire tends to increase.
また、従来は感熱線の他に発熱線を一対にして使用する
ようにしたいわゆる２線式も採用されていたが、感熱線
の一方の電極を発熱線として使用するようないわゆる１
線式の検討も、コストダウンや安全性の向上の要求より
行われつつある。この場合にも前述と同様に負特性高分
子感温体の温度は発熱線と接しているために従来よりも
高温になる傾向が生じる。Further, conventionally, a so-called two-wire system in which a pair of heat generating wires is used in addition to the heat sensitive wire has also been adopted, but a so-called 1-wire type in which one electrode of the heat sensitive wire is used as a heat generating wire.
The examination of the wire system is also being conducted due to the demand for cost reduction and improvement of safety. In this case as well, the temperature of the negative-characteristic polymer temperature sensitive body tends to be higher than in the conventional case because it is in contact with the heating wire, as described above.
このように、負特性高分子感温体の温度が高くなるとＰ
ＶＣ材よりなる感熱素子は可塑剤のブリードアウト現象
が無視できない値となり、インピーダンスが大きくなる
方向に経時変化してしまい、最悪の場合には温度検知能
力の低下から危険温度になってしまうこともあった。In this way, when the temperature of the negative characteristic polymer temperature sensor becomes high, P
In a thermosensitive element made of a VC material, the bleed-out phenomenon of the plasticizer becomes a non-negligible value and changes with time in the direction of increasing impedance, and in the worst case, the temperature detection ability decreases and the temperature may reach a critical temperature. there were.
（発明の目的） 本発明は上記の点に鑑みて提案されたもので、その目的
とするところは、感熱素子のインピーダンス値が経時変
化しない限界温度を高め、この限界温度を超えて異常な
使用がなされたときには、感熱樹脂材がインピーダンス
が低下する方向に感熱樹脂材が分解して劣化し、安全性
を保つことができ、感熱線と発熱線とを一体化した発熱
機能を有する感熱素子を提供することにある。(Object of the Invention) The present invention has been proposed in view of the above points, and an object of the present invention is to raise the limit temperature at which the impedance value of the heat-sensitive element does not change with time, and to exceed the limit temperature for abnormal use. When the heat-sensitive resin material is released, the heat-sensitive resin material decomposes and deteriorates in the direction in which the impedance decreases, and safety can be maintained, and a heat-sensitive element having a heat-generating function that integrates the heat-sensitive wire and the heat-generating wire is provided. To provide.
（発明の開示） 本発明は、感熱素子を構成する負特性高分子感温体をＰ
ＶＣを主成分とする感熱樹脂から形成すると共に、この
主成分のＰＶＣ材に、トリメリット酸系及びピロメリッ
ト酸系の少なくとも一方の可塑剤を15〜40重量％、三塩
基性硫酸鉛を３〜10重量％、四級アンモニウム塩をサー
ミスタ特性（Ｂ定数）が最大となる限界の１〜２倍の添
加量、および前記可塑剤量の0.1 〜0.5 重量％のビスェ
ノールＡを添加して混練した材料で構成したことを特徴
としている。DISCLOSURE OF THE INVENTION The present invention provides a negative characteristic polymer temperature sensing element that constitutes a thermosensitive element.
In addition to being formed from a heat-sensitive resin containing VC as a main component, 15-40% by weight of at least one plasticizer of trimellitic acid type or pyromellitic acid type and 3 parts of tribasic lead sulfate are added to the PVC material of this main component. -10% by weight, quaternary ammonium salt was kneaded by adding 1 to 2 times the limit of maximum thermistor property (B constant) and 0.1 to 0.5% by weight of the plasticizer of Bishenol A. It is characterized by being composed of materials.
ＰＶＣ材は、この種の感熱素子の負特性高分子感温体材
として一般的に使用され、可塑性を保つために可塑剤の
添加が不可欠条件となっている。The PVC material is generally used as a negative characteristic polymer temperature sensitive material for this type of heat sensitive element, and the addition of a plasticizer is an essential condition for maintaining plasticity.
この可塑剤としては、トリメリット酸系の可塑剤および
ピロメリット酸系の可塑剤の少なくとも一方を添加する
ことが好ましい。As the plasticizer, it is preferable to add at least one of a trimellitic acid plasticizer and a pyromellitic acid plasticizer.
このトリメリット酸系の可塑剤としては、例えばトリメ
リット酸エステル可塑剤(TOTM)が挙げられ、その組成物
の構造式は次の通りである。Examples of the trimellitic acid plasticizer include trimellitic acid ester plasticizer (TOTM), and the structural formula of the composition is as follows.
一方、ピロメリット酸系の可塑剤としては、ピロメリッ
ト酸エステル可塑剤(TOPM)を挙げることができる。その
構造式は次の通りである。 On the other hand, examples of the pyromellitic acid plasticizer include pyromellitic acid ester plasticizer (TOPM). Its structural formula is:
可塑剤は、ＰＶＣ材からなる感熱樹脂の可塑性が低下す
ると、体積固有インピーダンスが大きくなり、インピー
ダンスの経時変化の原因となるということに着目しブリ
ードアウト現象を起し難く、かつ可塑剤の分解を少なく
する組成のものを選択することが好ましい。 The plasticizer is not likely to cause a bleed-out phenomenon, and it is difficult to cause the bleed-out phenomenon, because the volume specific impedance increases as the plasticity of the heat-sensitive resin made of PVC material decreases, which causes a change in the impedance over time. It is preferable to select a composition that reduces the amount.
ここで可塑剤の添加量を15〜40重量％の範囲としたの
は、15重量％以下では、サーミスタ定数が十分に大きく
する効果が少なく、逆に40重量％以上では、ＰＶＣへの
相応の溶解限界を超えてしまいブリードアウト現象が生
じるためである。Here, the amount of the plasticizer added is set in the range of 15 to 40% by weight because when the amount is 15% by weight or less, the effect of making the thermistor constant sufficiently large is small, and when it is 40% by weight or more, it is suitable for PVC. This is because the solubility limit is exceeded and a bleed-out phenomenon occurs.
三塩基性硫酸鉛は安定剤であって、ＰＶＣ材の遊離CL-
イオンを捕捉して安定物質を生成するものである。Tribasic lead sulfate is a stabilizer, the PVC material free CL -
It captures ions and produces stable substances.
四級アンモニウム塩は変性剤であって、負特性高分子感
温体のメカニズムとしてイオン伝導性のものを選び、サ
ーミスタ特性（Ｂ定数）の大きさが、その添加量によっ
て決まり、ブリードアウト現象によってＢ定数が減少す
るとインピーダンスの経時変化の原因となるので、四級
アンモニウム塩の添加量を過飽和状態とし、かつ四級ア
ンモニウム塩が、大きな境界活性効果に有することか
ら、過飽和状態であっても感熱樹脂の成形加工性を極端
に悪化することがない様にする必要がある。The quaternary ammonium salt is a denaturant, and an ion conductive one is selected as a mechanism of the negative characteristic polymer temperature sensor, and the size of the thermistor characteristic (B constant) is determined by its addition amount, and it depends on the bleed-out phenomenon. A decrease in the B constant causes a change in impedance over time. Therefore, the amount of the quaternary ammonium salt added is set to a supersaturated state, and the quaternary ammonium salt has a large boundary activation effect. It is necessary to prevent the moldability of the resin from being extremely deteriorated.
また第四級アンモニウム塩は、マイナスイオンとして過
塩素酸(ClO4 - )）又はリン酸(PO4 - )などを有している
塩である。The quaternary ammonium salts, perchloric acid as negative ions (ClO 4 -)) or phosphate (PO 4 -) is a salt having a like.
ここで、変性剤としてのイオン伝導性の四級アンモニウ
ム塩は、インピーダンスを経時的に安定させるのに有効
な成分であるが、変性剤の添加量を増すとＢ定数も次第
に増大する傾向があるが、Ｂ定数が最高値となる変性剤
量よりも過飽和状態に加えることが好ましい。感熱樹脂
中の変性剤が経時的に減少しても、予め過剰の変性剤が
添加されているので、定数の変化として現れることがな
い。Here, the ion conductive quaternary ammonium salt as a modifier is an effective component for stabilizing the impedance over time, but the B constant tends to gradually increase as the amount of the modifier added increases. However, it is preferable to add it in a supersaturated state rather than the amount of the modifier that maximizes the B constant. Even if the amount of the modifier in the heat-sensitive resin decreases with time, it does not appear as a change in the constant because the excess modifier is added in advance.
しかし、過度に変性剤の添加量を増すと、感熱樹脂が界
面活性化して感熱樹脂を押出し成形する時に、ゲル化が
促進されないために押出し成形が困難となり、そのため
樹脂の成形温度を上げたり、また押出し成形速度を落す
必要が生じて製造コスト上の問題がある一方、押出し成
形時に、可塑剤および変性剤のブリードアウト現象ある
いはＰＶＣの分解が起り易く感熱素子の品質のバラツキ
原因となる。However, if the amount of the modifier added is excessively increased, when the thermosensitive resin is surface-activated to extrude the thermosensitive resin, it becomes difficult to extrude the gel because gelation is not promoted, and therefore, the molding temperature of the resin is increased, Further, it is necessary to reduce the extrusion molding speed, which causes a problem in manufacturing cost. On the other hand, the bleed-out phenomenon of the plasticizer and the modifier or the decomposition of PVC is likely to occur during the extrusion molding, which causes variations in the quality of the heat sensitive element.
さらに樹脂の流動性が悪いため、押出し成形中に押出機
の内面に樹脂が残留し、この残留物が炭化して炭化物が
形成され、この炭化物が負特性高分子感温体の感熱樹脂
材中に混入して内巻電気導体線と外巻電気導体線との間
に短絡を生じることがある。Furthermore, since the resin has poor fluidity, the resin remains on the inner surface of the extruder during extrusion, and this residue is carbonized to form a carbide. May be mixed into the inner winding electric conductor wire to cause a short circuit between the inner winding electric conductor wire and the outer winding electric conductor wire.
したがって、第四級アンモニウム塩の添加量は押出し加
工性を考慮して、溶解飽和量の２倍が限度である。Therefore, the amount of the quaternary ammonium salt added is limited to twice the saturated saturation amount in consideration of extrusion processability.
ビスフェノールＡは、感熱樹脂中の可塑剤が高温で分解
するのを抑制する効果があり、インピーダンスの経時変
化を改良することができる。Bisphenol A has an effect of suppressing the decomposition of the plasticizer in the heat-sensitive resin at high temperatures, and can improve the change in impedance with time.
このビスフェノールＡは次の構造式である。This bisphenol A has the following structural formula.
アクリル系加工助剤は、ＰＶＣ材の加工性を改良するた
めに添加される助剤であって、メタクリル酸メチルを主
成分とし、ポリメチルメタクリレート(MMA) とアルキル
アクリレートの共重合体である。 The acrylic processing aid is an additive added to improve the workability of the PVC material, and is a copolymer of polymethylmethacrylate (MMA) and alkyl acrylate, which contains methyl methacrylate as a main component.
アクリル系加工助剤を樹脂に少量添加すると樹脂のゲル
化が短時間で進んで、押出し成形性を改善することがで
きる。When a small amount of the acrylic processing aid is added to the resin, gelation of the resin proceeds in a short time, and extrusion moldability can be improved.
また、このアクリル系加工助剤は、インピーダンス特性
やこのインピーダンスの経時変化に悪影響を及ぼすこと
がない。Further, this acrylic processing aid does not adversely affect the impedance characteristics and the change with time of the impedance.
次に、本発明の実施例を図によって説明する。Next, an embodiment of the present invention will be described with reference to the drawings.
負特性高分子感温度の素材となるＰＶＣ材の感熱樹脂
は、可塑剤の種類，添加量、安定剤及び変性剤の種類，
添加量を種々変えて、本発明No.１およびNo.２、従来例
No.１およびNo.２、さらに比較例No.１，No.２およびN
o.３の試料を製作した。Negative characteristic polymer Thermosensitive resin of PVC material, which is a temperature sensitive material, includes the types of plasticizers, the amount added, the types of stabilizers and modifiers,
No. 1 and No. 2 of the present invention, conventional examples with various addition amounts
No. 1 and No. 2, and comparative examples No. 1, No. 2 and N
A sample of o.3 was manufactured.
その各感熱樹脂の組成は、第１表に示す通りである。The composition of each heat-sensitive resin is as shown in Table 1.
なお、第１表に示した従来例（No.１，No.２）に用いた
可塑剤の構造式は、次の通りである。 The structural formulas of the plasticizers used in the conventional examples (No. 1 and No. 2) shown in Table 1 are as follows.
フタル酸エステル可塑剤 DTDP フタル酸エステル可塑剤 DDP 第１表に示した各々の感熱樹脂によって、負特性高分子
感温体を成形して、それぞれ感熱素子を組み立てて各試
験に供した。Phthalate plasticizer DTDP Phthalates Plasticizer DDP Negative characteristic polymer temperature sensitive bodies were molded from the respective heat sensitive resins shown in Table 1, and heat sensitive elements were assembled and subjected to each test.
この感熱素子は、第１図に示すように、芯材１と、その
外面に巻き付けられた内巻電導体線２と、その外面に配
された管状の負特性高分子感温体３と、その外面に巻き
付けられた外巻電気導体線４と、その外面に配された分
離層７，絶縁層５とから構成されるものである。As shown in FIG. 1, this heat-sensitive element includes a core material 1, an inner winding conductor wire 2 wound around the outer surface thereof, a tubular negative characteristic polymer temperature sensor 3 arranged on the outer surface thereof, The outer winding electric conductor wire 4 is wound around the outer surface, and the separation layer 7 and the insulating layer 5 are provided on the outer surface.
また、各部の寸法は以下のようにした。The dimensions of each part are as follows.
芯材１・・・・0.5mm φポリエステルより糸内巻電気導
体線２・・0.08mm×0.8mm の銅にNiメッキした箔を0.75
mmピッチ巻き負特性高分子感温体３・・感熱樹脂を0.3m
m 厚押出し 外巻電気導体線４・・0.08mm×0.8mm の銅にNiメッキし
た箔を1.05mmピッチ巻き 分離層７・・・ポリエステルテープ12μ２／３ラップ巻
き 絶縁層５・・・絶縁体を0.4mm 厚押出し 第２図は各感熱素子のインピーダンスの経時変化を示す
グラフであって、横軸に経過時間を、縦軸にインピーダ
ンス変化率(%) を表している。Core material 1 ... 0.5mm φ polyester twisted wire electrical conductor wire 2 ... 0.08mm × 0.8mm copper plated with Ni plated foil 0.75
mm Pitch winding Negative property Polymer temperature sensor 3 ... 0.3m of heat sensitive resin
m thick extruded outer conductor wire 4 .. 0.08 mm x 0.8 mm copper-plated Ni foil with 1.05 mm pitch Separation layer 7 ... Polyester tape 12μ 2/3 wrap Insulation layer 5 ... Insulator 0.4 mm thick extrusion FIG. 2 is a graph showing the time-dependent change in impedance of each heat-sensitive element, in which the horizontal axis represents elapsed time and the vertical axis represents impedance change rate (%).
インピーダンスの経時安定性については、 120℃の雰囲
気中でＡＣ 100Ｖ 60Hzの電圧をＯＮ−ＯＦＦサイクル
で印加し、電圧降下法で測定した各試料のインピーダン
ス変化を経過時間毎に測定し、初期値と比べてインピー
ダンス値がどの程度変化したかを各々比較した。Regarding the stability of impedance over time, the voltage of AC 100V 60Hz was applied in an ON-OFF cycle in an atmosphere of 120 ° C, and the impedance change of each sample measured by the voltage drop method was measured at each elapsed time. In comparison, how much the impedance value changed was compared.
本発明No.１，No.２は、第２図に示すように、比較例N
o.１，No.２に比べても、インピーダンスの経時変化が
著しく改善されていることが分かる。特に比較例No.１
にあっては、第１表に示したように変性剤としての第四
級アンモニウム塩の添加量が少ないために、ブリードア
ウト現象を起こすか、ＰＶＣよりの遊離Cl- イオンを捕
捉して安定物質を作る安定剤の三塩基性硫酸鉛が、主と
してイオン伝導に寄与している第四級アンモニウム塩の
マイナスイオンをも捕捉してしまいイオンキャリアーが
不足するためと考えられる。比較例No.２にあっては、
ビスフェノールＡを添加していないので、可塑剤が高温
で分解して可塑効果が減少してインピーダンスの経時変
化が生じている。The present invention No. 1 and No. 2 are, as shown in FIG.
Compared with o.1 and No.2, it can be seen that the change in impedance with time is significantly improved. Especially Comparative Example No. 1
In that case, as shown in Table 1, since the amount of the quaternary ammonium salt as a modifier added is small, a bleed-out phenomenon occurs or a stable substance by trapping free Cl − ions from PVC is obtained. It is considered that the tribasic lead sulfate, which is a stabilizer that makes a salt, captures even the negative ions of the quaternary ammonium salt, which mainly contributes to ion conduction, and the ion carrier is insufficient. In Comparative Example No. 2,
Since bisphenol A is not added, the plasticizer decomposes at high temperature, the plasticizing effect decreases, and the impedance changes with time.
一方、本発明No.１，No.２では、従来例No.１，No.２に
比べてインピーダンスの経時変化が著しく改善されてお
り、さらに図示しないが、温度 100℃におけるインピー
ダンス変化は、従来例に比して更に小さく、20 deg以上
の使用が可能な限界温度を高くすることができる。この
原因としては、可塑剤の分子量を増したことにもよる
が、結合アルコール数が３のトリメリット酸エステル(T
OTM)，４のピロメリット酸エステル(TOPM)を選んだこと
により、ブリードアウト速度が著しく低下したものであ
る。On the other hand, in the present invention No. 1 and No. 2, the change in impedance with time is significantly improved as compared with the conventional examples No. 1 and No. 2, and although not shown, the impedance change at a temperature of 100 ° C. It is smaller than the example, and the limit temperature that allows use of 20 deg or more can be increased. This is due to the increase in the molecular weight of the plasticizer, but the trimellitic acid ester (T
OTM) and 4 pyromellitic acid ester (TOPM) were selected, and the bleed-out rate was significantly reduced.
第３図は各感熱素子における経過時間と異常温度設定の
部分断熱最高温度との関係を示したもので、感熱素子を
異常高温で使用する場合において、初期値 130℃ OFFで
温度制御動作を繰り返し、ＯＦＦ点が時間経過とともに
上昇していく速度と、感熱樹脂の分解劣化により短絡的
動作をする温度とを比較した。Fig. 3 shows the relationship between the elapsed time in each heat sensitive element and the partial insulation maximum temperature of the abnormal temperature setting. When the heat sensitive element is used at an abnormally high temperature, the temperature control operation is repeated with the initial value 130 ° C OFF. The speed at which the OFF point rises with time is compared with the temperature at which a short-circuiting operation is caused by decomposition and deterioration of the thermosensitive resin.
なお、ＯＦＦ点が時間の経過とともに上昇する過程で
は、感熱樹脂の体積固有インピーダンスも大きくなる方
向に変化している。In addition, in the process in which the OFF point rises with the passage of time, the volume specific impedance of the heat-sensitive resin also changes to increase.
図中の各線は、インピーダンス値の安定限界温度を越え
る温度領域で感熱素子が使用された場合、例えば具体的
に併用された他の暖房器等から熱を受けて、インピーダ
ンス値が経時的に安定する限界温度を越えてインピーダ
ンス値が経時変化を始めた場合を想定して、初期値 130
℃ OFFで温度制御動作を繰り返し、ＯＦＦ点が時間経過
とともに上昇していく様子を表したものである。本発明
No.１，No.２にあっては、 150℃程度で感熱樹脂の分解
劣化（炭化現象）が現れて短絡が発生し、安全動作をす
ることができるが、これに対し比較例No.３では、 200
℃程度まで短絡が発生しない。Each line in the figure shows a stable impedance value over time when the heat-sensitive element is used in a temperature range that exceeds the stability limit temperature of the impedance value, for example, receiving heat from another heating device that is also used in combination. Assuming that the impedance value starts to change over time, the initial value of 130
The figure shows how the OFF point rises with the lapse of time by repeating the temperature control operation at ℃ OFF. The present invention
In No. 1 and No. 2, decomposition and deterioration (carbonization phenomenon) of the thermosensitive resin appeared at about 150 ° C, and a short circuit occurred, allowing safe operation. In contrast, Comparative Example No. 3 Then 200
Short circuit does not occur up to about ℃.
比較例No.３では、多量（20部）の安定剤が添加されて
いるのでＰＶＣが劣化するスピードが遅くなり、可塑剤
および変性剤によるブリードアウト現象が発生し易くな
り、炭化よりもインピーダンスの増大の方が早く進行す
るためである。これに対して本発明No.１，No.２にあっ
ては、安定剤の量（10部）があまり多くないこと、過飽
和に添加されている変性剤もＰＶＣの劣化を促進するこ
とによりインピーダンスの増大に比べて比較的早く炭化
が進むことによる。In Comparative Example No. 3, a large amount (20 parts) of the stabilizer was added, so that the speed of PVC deterioration was slowed, the bleed-out phenomenon due to the plasticizer and the modifier was more likely to occur, and the impedance was lower than that of carbonization. This is because the increase proceeds faster. On the other hand, in No. 1 and No. 2 of the present invention, the amount of the stabilizer (10 parts) is not so large, and the denaturant added to supersaturation also promotes the deterioration of PVC, thereby improving the impedance. The reason is that carbonization proceeds relatively faster than the increase in.
なお、本発明の感熱素子を第１図に示す如き管状，ケー
ブル状の構造に限って説明したが、これらに限定される
ものではなく、第５図に示した線状の構造や面状の構造
にも適用できることは言うまでもない。Although the heat-sensitive element of the present invention has been described only in the tubular or cable-shaped structure as shown in FIG. 1, it is not limited to these, and the linear structure or the planar shape shown in FIG. It goes without saying that it can be applied to the structure.
（発明の効果） 以上のように、本発明に係る感熱素子によれば、負特性
高分子感温体は主成分のＰＶＣ材に、トリメリット酸系
及びピロメリット酸系の可塑剤の少なくとも一方の15〜
40重量％と、３〜10重量％の三塩基性硫酸鉛と、サーミ
スタ特性が最大となる限界の１〜２倍の四級アンモニウ
ム塩と、前期可塑剤量の0.1 〜0.5 重量％のビスフェノ
ールＡとを混練した材料で構成したので、次の効果を有
する。(Effects of the Invention) As described above, according to the heat-sensitive element of the present invention, the negative-characteristic polymer temperature-sensitive material is composed of the PVC material as the main component and at least one of the trimellitic acid-based and pyromellitic-acid-based plasticizers. Of 15 ~
40% by weight, 3 to 10% by weight of tribasic lead sulfate, 1 to 2 times the limit of maximum thermistor characteristics of quaternary ammonium salt, and 0.1 to 0.5% by weight of bisphenol A of the previous plasticizer amount. Since it is made of a kneaded material, it has the following effects.
（イ） 感熱素子のインピーダンス安定限界温度が著し
く向上し、電気カーペットに適用した場合、クッション
性の良い表面材を使用しても、表面温度を充分暖かい温
度設定にすることが可能となる。(A) The impedance stability limit temperature of the heat sensitive element is remarkably improved, and when applied to an electric carpet, the surface temperature can be set to a sufficiently warm temperature even if a surface material having a good cushioning property is used.
（ロ） 感熱素子の一方の電極を発熱線として使用する
１線式の実現が可能となる。(B) It is possible to realize a one-wire system in which one electrode of the heat-sensitive element is used as a heating wire.
（ハ） 特性の経時変化がなくサーミスタ特性（Ｂ定
数）の大きい感熱素子が安定して製造可能となる。(C) The thermosensitive element having a large thermistor characteristic (B constant) without change in characteristics with time can be stably manufactured.
（ニ） インピーダンスが経時変化しない限界温度を超
えた異常な使用がなされ、負特性感熱樹脂材のインピー
ダンス値が大きくなる方向に変化を始めた場合、比較的
安全な温度以下でインピーダンスが低下する方向に分解
劣化するので、安全性が高まり、他に過昇防止装置を必
要としない１線式の実現が可能となる。(D) When the impedance has changed abnormally beyond the limit temperature where it does not change over time, and the impedance value of the negative characteristic heat-sensitive resin material begins to increase, the impedance decreases below a relatively safe temperature. Since it is decomposed and deteriorated, the safety is improved, and it is possible to realize a one-wire system that does not require an overheat prevention device.
第１図は本発明の感熱素子の一例を示す展開斜視図、第
２図は本発明の感熱素子のインピーダンスの経時変化を
示す比較グラフ、第３図は本発明の感熱素子の断熱最高
温度と経過時間との関係を示す比較グラフ、第４図およ
び第５図は従来の感熱素子を示す説明図である。 １……芯材、２……内巻電気導体線、３……負特性高分
子感温体、４……外巻電気導体線、５……絶縁層、７…
…分離層FIG. 1 is a developed perspective view showing an example of the heat-sensitive element of the present invention, FIG. 2 is a comparative graph showing changes in impedance of the heat-sensitive element of the present invention with time, and FIG. 3 is a maximum adiabatic temperature of the heat-sensitive element of the present invention. Comparative graphs showing the relationship with the elapsed time, and FIGS. 4 and 5 are explanatory views showing a conventional thermosensitive element. 1 ... Core material, 2 ... Inner winding electric conductor wire, 3 ... Negative characteristic polymer temperature sensor, 4 ... Outer winding electric conductor wire, 5 ... Insulating layer, 7 ...
… Separation layer
Claims (4)
ピロメリット酸系の可塑剤の少なくとも一方と三塩基性
硫酸鉛および四級アンモニウム塩を混練した材料で構成
した温度変化に応じてインピーダンスが変化する管状の
負特性高分子感温体と、 その外面に巻き付けられた外巻電気導体線と、 芯材に巻き付けられて前記負特性高分子感温体の内面に
配された内巻電気導体線と、 前記外巻電気導体線の外面に配された絶縁層とからなる
感熱素子において、 前記負特性高分子感温体を構成する材料の割合を、前記
可塑剤を15〜40重量％，前記三塩基性硫酸鉛を３〜10重
量％，前記四級アンモニウム塩をサーミスタ特性（Ｂ定
数）が最大となる限界の１〜２倍の添加量とし、更に前
記可塑剤量の0.1 〜0.5 重量％のビスフェノールＡを添
加したことを特徴とする感熱素子。1. An impedance according to a temperature change which is composed of a material obtained by kneading at least one of a trimellitic acid-based and pyromellitic acid-based plasticizer, a tribasic lead sulfate and a quaternary ammonium salt in a PVC material as a main component. The tubular negative characteristic polymer temperature sensor with variable temperature, the outer winding electric conductor wire wound on the outer surface, and the inner winding electric wire wound on the core material and arranged on the inner surface of the negative characteristic polymer temperature sensor. In a heat-sensitive element consisting of a conductor wire and an insulating layer arranged on the outer surface of the outer-winding electric conductor wire, the proportion of the material constituting the negative characteristic polymer temperature sensor is 15 to 40% by weight of the plasticizer. The amount of the tribasic lead sulfate is 3 to 10% by weight, and the amount of the quaternary ammonium salt is 1 to 2 times the limit that maximizes the thermistor characteristics (B constant). Addition of wt% bisphenol A Sensitive element characterized.
添加したことを特徴とする特許請求の範囲第１項記載の
感熱素子。2. The heat-sensitive element according to claim 1, further comprising 1 to 5% by weight of an acrylic processing aid.
する特許請求の範囲第１項記載の感熱素子。3. The heat sensitive element according to claim 1, wherein one of the electric conductor wires also serves as a heating wire.
キを施したことを特徴とする特許請求の範囲第１項記載
の感熱素子。4. The heat-sensitive element according to claim 1, wherein the electric conductor wire is formed by applying corrosion-resistant plating to the surface of a copper material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62254448A JPH0656803B2 (en) | 1987-10-08 | 1987-10-08 | Thermal element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62254448A JPH0656803B2 (en) | 1987-10-08 | 1987-10-08 | Thermal element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0196902A JPH0196902A (en) | 1989-04-14 |
| JPH0656803B2 true JPH0656803B2 (en) | 1994-07-27 |
Family
ID=17265149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62254448A Expired - Fee Related JPH0656803B2 (en) | 1987-10-08 | 1987-10-08 | Thermal element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0656803B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2886333B2 (en) * | 1990-11-27 | 1999-04-26 | 古河電気工業株式会社 | Polymer thermosensitive material |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5436320B2 (en) * | 1971-12-14 | 1979-11-08 | ||
| JPS5137099B2 (en) * | 1972-11-22 | 1976-10-13 | ||
| JPS5145616A (en) * | 1974-10-18 | 1976-04-19 | Hitachi Metals Ltd | IMONOSUNA |
| JPS5380452A (en) * | 1976-12-27 | 1978-07-15 | Tokyo Tokushu Densen Kk | Thermosensitive high polymer composition |
| JPS5578489A (en) * | 1979-11-19 | 1980-06-13 | Matsushita Electric Industrial Co Ltd | Heat sensitive heater wire |
| JPS5694231A (en) * | 1979-12-28 | 1981-07-30 | Matsushita Electric Ind Co Ltd | Thermosensitive element |
| JPS5730258A (en) * | 1980-07-31 | 1982-02-18 | Mitsubishi Plastics Ind Ltd | Explosion-proof fluorescent lamp |
| JPS58157845A (en) * | 1982-03-15 | 1983-09-20 | Nissan Chem Ind Ltd | Vinyl chloride resin composition |
-
1987
- 1987-10-08 JP JP62254448A patent/JPH0656803B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0196902A (en) | 1989-04-14 |
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