JP2812071B2 - Polymer thermosensor - Google Patents
Polymer thermosensorInfo
- Publication number
- JP2812071B2 JP2812071B2 JP4159193A JP15919392A JP2812071B2 JP 2812071 B2 JP2812071 B2 JP 2812071B2 JP 4159193 A JP4159193 A JP 4159193A JP 15919392 A JP15919392 A JP 15919392A JP 2812071 B2 JP2812071 B2 JP 2812071B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- polymer
- phosphite
- compound
- weight
- 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 - Lifetime
Links
- 229920000642 polymer Polymers 0.000 title claims description 18
- 239000004952 Polyamide Substances 0.000 claims description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 16
- 229920002647 polyamide Polymers 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- -1 imidazole compound Chemical class 0.000 claims description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 7
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- LZNWGSIDNAGRAJ-UHFFFAOYSA-N P(O)(O)OC(C(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(CCCCCCCCCCCCC)C1=CC=CC=C1 Chemical compound P(O)(O)OC(C(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(CCCCCCCCCCCCC)C1=CC=CC=C1 LZNWGSIDNAGRAJ-UHFFFAOYSA-N 0.000 claims description 4
- VMNKHSPZIGIPLL-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphite Chemical compound OCC(CO)(CO)COP(O)O VMNKHSPZIGIPLL-UHFFFAOYSA-N 0.000 claims description 4
- XZZWOTQMUOIIFX-UHFFFAOYSA-N 1-(2-diphenoxyphosphanyloxypropoxy)propan-2-yl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC(C)COCC(C)OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 XZZWOTQMUOIIFX-UHFFFAOYSA-N 0.000 claims description 3
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical class CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 2
- 230000000694 effects Effects 0.000 description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- HXZNHHUHZAMCET-UHFFFAOYSA-N 2-(2-heptadec-1-enyl-4,5-dihydroimidazol-1-yl)ethyl perchlorate Chemical compound CCCCCCCCCCCCCCCC=CC1=NCCN1CCOCl(=O)(=O)=O HXZNHHUHZAMCET-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UFYABLZSCAJYAX-UHFFFAOYSA-N 3-(1-hydroxypropan-2-yloxy)-1,1,1,2-tetraphenylpropan-2-ol;phosphorous acid Chemical compound OP(O)O.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C(O)(COC(CO)C)C1=CC=CC=C1 UFYABLZSCAJYAX-UHFFFAOYSA-N 0.000 description 1
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004959 Rilsan Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Thermistors And Varistors (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気採暖具等の可撓性
の温度センサや感温ヒータに用いる高分子感温体に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer thermosensor used for a flexible temperature sensor such as an electric heater or a thermosensor.
【０００２】[0002]
【従来の技術】従来、高分子感温体は、一般に一対の巻
き線電極間に配設され、可撓性線状の温度センサや感熱
ヒータとして用いられている。この高分子感温体として
は、ナイロン１２や特開昭５５−１００６９３号公報に
開示されている変性ナイロン１１（ＡＴＯ−ＣＨＩＭＩ
Ｅ社製、商品名「リルサンＮナイロン」）等のポリアミ
ド組成物が用いられ、その静電容量や抵抗値あるいはイ
ンピーダンス等の温度変化が利用され、温度センサの機
能を果たしている。さらに特公昭６０−４８０８１号公
報には亜リン酸エステルを熱劣化改良剤として添加した
ポリアミド組成物や特開昭６４−３０２０３号公報には
銅不活性化剤とフェノール系酸化防止剤を添加したイオ
ン伝導性感熱組成物の例が開示されている。2. Description of the Related Art Conventionally, a polymer thermosensor is generally disposed between a pair of winding electrodes and used as a flexible linear temperature sensor or a heat-sensitive heater. Examples of the polymer thermosensitive material include nylon 12 and modified nylon 11 (ATO-CHIMI) disclosed in JP-A-55-100693.
A polyamide composition such as "Rilsan N nylon" (trade name, manufactured by Company E) is used, and its temperature change such as capacitance, resistance value, or impedance is used to perform the function of a temperature sensor. Furthermore, Japanese Patent Publication No. 60-48081 discloses a polyamide composition containing a phosphite as a thermal deterioration improving agent, and Japanese Patent Application Laid-Open No. 64-30203 discloses a copper deactivator and a phenolic antioxidant. Examples of ionically conductive thermosensitive compositions are disclosed.
【０００３】[0003]
【発明が解決しようとする課題】しかし、ナイロン１２
は吸湿率が低い点は優れているが、温度センサとしては
湿度による感温特性の変動が大きいため、実用に供し難
い。また特開昭５５−１００６９３号公報に開示の変性
ポリアミドにおいては、インピーダンスの温度依存性が
小さいため温度検出感度が低く、耐熱安定性に劣る。こ
のため耐湿度性、感温性の改善のため、特公平３−５０
４０１号公報に開示されている様にフェノール系化合物
のアルデヒド重縮合体を配合した組成物が提案されてい
る。しかしこれらはいずれもインピーダンスの温度依存
性が低く、また長期間にわたる熱安定性が不十分である
等の問題点があった。However, nylon 12
Is excellent in that the moisture absorption rate is low, but it is difficult to use the temperature sensor as a temperature sensor because of its large fluctuation in temperature-sensitive characteristics due to humidity. Further, the modified polyamide disclosed in Japanese Patent Application Laid-Open No. 55-100693 has low temperature detection sensitivity due to small temperature dependence of impedance and is inferior in heat resistance stability. Therefore, in order to improve humidity resistance and temperature sensitivity, the Japanese Patent Publication No. 3-50
As disclosed in Japanese Patent Publication No. 401, a composition containing an aldehyde polycondensate of a phenolic compound has been proposed. However, all of them have problems such as low temperature dependence of impedance and insufficient thermal stability over a long period of time.
【０００４】本発明は、インピーダンスの温度依存性が
大きく、かつ熱安定性に優れた高分子感温体を提供する
ことを目的とする。[0004] It is an object of the present invention to provide a polymer thermosensor having a large impedance temperature dependence and excellent thermal stability.
【０００５】[0005]
【課題を解決するための手段】本発明は、ポリアミドに
イミダゾール系、またはアンモニウム塩系より選ばれた
少なくとも一種とリン濃度が３〜２０重量％で分子量２
００〜５,0００の亜リン酸エステル系化合物とを配合し
た組成物を感温体として用いる。According to the present invention, there is provided a polyamide comprising at least one selected from the group consisting of an imidazole type and an ammonium salt type, a phosphorus concentration of 3 to 20% by weight and a molecular weight of 2
A composition containing the phosphite-based compound of 5,000 to 5,000 is used as a temperature sensing element.
【０００６】[0006]
【作用】一般に、高分子感温体は、一対の銅あるいは銅
合金の巻き線電極間に配設されて、可撓性線状の温度セ
ンサや感熱ヒータとして用いられる。これら温度センサ
や感熱ヒータとしての耐熱安定性は、高分子感温体自体
の安定性と巻き線電極の表面状態により決まる。本発明
のポリアミド組成物を用いた場合、高分子感温体中のイ
ミダゾール系またはアンモニウム塩系の過塩素酸塩のも
つイオンキャリヤー性により著しくインピーダンスの温
度依存性を高めると共に、熱的にも安定なものとなる。
しかもテトラフェニル・ジプロピレングリコールジホス
ファイト、テトラフェニルテトラ（トリデシル）ペンタ
エリスリトールテトラホスファイトおよび水添フェノー
ルＡ・ペンタエリスリトールホスファイトポリマーの様
に高分子量でかつリン濃度の高いジホスファイトまたは
テトラホスファイトあるいはホスファイト系ポリマーの
もつ酸化防止性と還元防錆作用による効果により熱劣化
性が著しく相乗的に抑制される。リン濃度が低いとこの
効果は低く、また高すぎても実用的でない。リン濃度は
３〜２０重量％で効果があるが、望ましくは５〜１５重
量％で最も良い値を示す。また分子量が低いと高温で揮
発しやすく、効果の持続性に乏しい。また５,0００を越
えると分散が難しくなるので、望ましくは３００〜３,5
００が実用的である。本発明における過塩素酸塩と亜リ
ン酸エステル系化合物との組み合わせは作用が重複して
もお互いに疎外されるものでなく、加算されて相乗作用
を持つ。従って、高分子感温体の熱安定性を向上させ、
温度センサや感熱ヒータとして耐熱安定性を著しく増す
ものと考えられる。さらにフェノール化合物のアルデヒ
ド重縮合体の配合により強力な吸湿防止作用を付与する
ことができる。フェノール系化合物はポリアミドと相溶
性がよく、ポリアミド中で水素結合サイトに水分子の代
わりに配位して吸湿性を低減させ、湿度による感温特性
の変動を低減させる。またそのアミド基への作用により
感温性を増大する効果もある。In general, a polymer thermosensor is disposed between a pair of copper or copper alloy winding electrodes and used as a flexible linear temperature sensor or thermal heater. The heat stability of these temperature sensors and heat-sensitive heaters is determined by the stability of the polymer thermosensor itself and the surface condition of the winding electrode. When the polyamide composition of the present invention is used, the temperature dependence of impedance is remarkably enhanced by the ion carrier property of the imidazole-based or ammonium-based perchlorate in the polymer thermosensor, and it is also thermally stable. It becomes something.
Further, diphosphite or tetraphosphite having a high molecular weight and a high phosphorus concentration, such as tetraphenyl dipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite and hydrogenated phenol A / pentaerythritol phosphite polymer, or The effects of the phosphite-based polymer's antioxidant properties and reduction rust-preventive action significantly reduce synergistic thermal degradation. If the phosphorus concentration is low, this effect is low, and if it is too high, it is not practical. Although the phosphorus concentration is effective at 3 to 20% by weight, the best value is exhibited at 5 to 15% by weight. On the other hand, if the molecular weight is low, it tends to volatilize at high temperatures, and the effect is not persistent. If it exceeds 5,000, dispersion becomes difficult.
00 is practical. In the present invention, the combination of the perchlorate and the phosphite compound is not excluded from each other even if the actions overlap, but has a synergistic action when added. Therefore, the thermal stability of the polymer thermosensor is improved,
It is considered that the heat resistance of the temperature sensor or the heat-sensitive heater is remarkably increased. Further, by blending an aldehyde polycondensate of a phenol compound, a strong moisture absorption preventing action can be imparted. Phenolic compounds have good compatibility with polyamides, and coordinate with hydrogen bonding sites in polyamide instead of water molecules to reduce hygroscopicity and reduce fluctuations in temperature-sensitive characteristics due to humidity. There is also an effect of increasing the temperature sensitivity by acting on the amide group.
【０００７】[0007]
【実施例】本発明におけるポリアミドとしては、吸湿性
の少ないナイロン１２、Ｎ−アルキル置換ポリアミド１
１、ポリエーテルアミド、ダイマー酸含有アミドを選ん
だ。これらのポリマーのインピーダンスの温度依存性を
高める導電性付与剤として、熱安定性の高いイミダゾー
ル系およびアンモニウム塩系の過塩素酸塩が適する。イ
ミダゾール系化合物としては２−ヘプタデセニル−２−
イミダゾリン−１−エタノール過塩素酸塩を選び、また
アンモニウム塩としてはラウロイルアミノプロピルジメ
チルヒドロキシエチルパークロレート、オクチルジメチ
ルヒドロキシエチルアンモニウムパークロレートを選択
した。また上記過塩素酸塩と相乗作用をして酸化防止性
と還元防錆作用を高める構成として、亜リン酸エステル
としてテトラフェニル・ジプロピレングリコールジホス
ファイト（分子量５６６、リン濃度１０.9重量％）、テ
トラフェニルテトラ（トリデシル）ペンタエリスリトー
ルテトラホスファイト（分子量１,4２４、リン濃度８.7
重量％）、水添ビスフェノールＡ・ペンタエリスリトー
ルホスファイト（分子量２,5００〜３,1００、リン濃度
１３.8重量％）を選んだ。組成比は、ナイロン１００重
量部に対して添加剤は全て１重量部とした。フェノール
化合物のアルデヒド重縮合体を添加した例では、ポリア
ミドと相溶性の良いオキシ安息香酸オクチルエステル−
ホルムアルデヒド重縮合体を選び、１５重量部とした。
試料はこれらを配合し、押し出し機により混練りした
後、加熱プレスで約７０×７０mm、厚さ１mmのシートに
成形し、その両面に銀塗布面電極を設けて作成した。イ
ンピーダンスの温度依存性は、４０〜８０℃におけるサ
ーミスタＢ定数で表した。また耐熱安定性は１００℃に
おける初期のインピーダンスと１５０℃で１,0００時間
加熱空気老化をさせた後のインピーダンスとの温度差
（ΔＴz ）で表した。なお４０〜８０℃におけるサーミ
スタＢ定数は４０℃におけるインピーダンスＺ40および
８０℃におけるインピーダンスＺ80を測定した結果をも
とに算出した。The polyamides used in the present invention include nylon 12 and N-alkyl-substituted polyamide 1 having low hygroscopicity.
1. Polyether amide and dimer acid-containing amide were selected. As a conductivity-imparting agent for increasing the temperature dependence of the impedance of these polymers, imidazole-based and ammonium salt-based perchlorates having high thermal stability are suitable. As the imidazole compound, 2-heptadecenyl-2-
Imidazoline-1-ethanol perchlorate was selected, and as ammonium salts, lauroylaminopropyldimethylhydroxyethylperchlorate and octyldimethylhydroxyethylammonium perchlorate were selected. In order to enhance the antioxidant property and the reduction rust preventive action by synergistic action with the perchlorate, tetraphenyl dipropylene glycol diphosphite (molecular weight 566, phosphorus concentration 10.9% by weight) is used as a phosphite. ), Tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite (molecular weight 1,424, phosphorus concentration 8.7)
Wt.) And hydrogenated bisphenol A. pentaerythritol phosphite (molecular weight: 2,500-3,100, phosphorus concentration: 13.8% by weight). The composition ratio was 100 parts by weight of nylon and all additives were 1 part by weight. In an example in which an aldehyde polycondensate of a phenol compound is added, octyl oxybenzoate having good compatibility with polyamide is used.
A formaldehyde polycondensate was selected and adjusted to 15 parts by weight.
The sample was prepared by mixing these materials, kneading them with an extruder, forming them into a sheet of about 70 × 70 mm and a thickness of 1 mm by a heat press, and providing silver-coated electrodes on both surfaces. The temperature dependence of the impedance was represented by a thermistor B constant at 40 to 80 ° C. The thermal stability was represented by the temperature difference (ΔT z ) between the initial impedance at 100 ° C. and the impedance after heating air aging at 150 ° C. for 1,000 hours. Note the thermistor B constant at 40 to 80 ° C. was calculated based on the results of measurement of the impedance Z 80 of the impedance Z 40 and 80 ° C. at 40 ° C..
【０００８】これらの結果を（表１）、（表２）に示
す。The results are shown in (Table 1) and (Table 2).
【０００９】[0009]
【表１】 [Table 1]
【００１０】[0010]
【表２】 [Table 2]
【００１１】本発明の過塩素酸化合物には、ラウロイル
アミノ・プロピルジメチル・ヒドロキシエチルパークロ
レート、オクチルジメチルヒドロキシエチルアンモニウ
ムパークロレート、２−ヘプタデセニル−２−イミダゾ
リン−１−エタノール過塩素酸塩が用いられ、感温性と
耐熱性の向上に寄与している。また亜リン酸エステルと
しては、分子量が高く不揮発性に優れ、かつリン濃度が
適当なテトラフェニルジプロピレングリコールホスファ
イト、テトラフェニルテトラ（トリデシル）ペンタエリ
スリトールテトラフォスファイト、水添ビスフェノール
Ａ・ペンタエリスリトールホスファイトポリマーが用い
られ、耐熱安定性と防錆作用の向上に寄与している。こ
れらの組み合わせが、さらに相乗的効果を発揮してい
る。また、フェノール系化合物のアルデヒド重縮合体に
は、ｐ−オキシ安息香酸オクチルエステル−アルデヒド
重縮合体およびｐ−オキシ安息香酸イソステアリルエス
テル−ホルムアルデヒド重縮合体が相溶性および耐湿性
の点で優れているが、ｐ−オキシ安息香酸アルキルエス
テル以外にｐ−ドデシルフェノール、ｐ−クロロフェノ
ール、ｐ−オキシ安息香酸ノニルエステル等のアルデヒ
ド重縮合体であってもよい。これらは、ポリアミドに対
し、５〜３０重量部配合される。５重量部より少ないと
効果が低く、３０重量部より多いと組成物の性質を著し
く損なう。The perchloric acid compound of the present invention includes lauroylaminopropyldimethylhydroxyethylperchlorate, octyldimethylhydroxyethylammonium perchlorate, and 2-heptadecenyl-2-imidazoline-1-ethanol perchlorate. It contributes to the improvement of temperature sensitivity and heat resistance. Examples of the phosphite include tetraphenyldipropylene glycol phosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite having a high molecular weight, excellent non-volatility and an appropriate phosphorus concentration, and hydrogenated bisphenol A / pentaerythritol phosphite. A phytopolymer is used, which contributes to improvement in heat stability and rust prevention. These combinations have even more synergistic effects. In addition, aldehyde polycondensates of phenolic compounds include p-oxybenzoic acid octyl ester-aldehyde polycondensate and p-oxybenzoic acid isostearyl ester-formaldehyde polycondensate, which are excellent in compatibility and moisture resistance. However, in addition to the p-oxybenzoic acid alkyl ester, an aldehyde polycondensate such as p-dodecylphenol, p-chlorophenol, and nonyl p-oxybenzoate may be used. These are blended in an amount of 5 to 30 parts by weight with respect to the polyamide. If the amount is less than 5 parts by weight, the effect is low, and if it is more than 30 parts by weight, the properties of the composition are significantly impaired.
【００１２】[0012]
【発明の効果】以上のように本発明によれば、アンモニ
ウム塩およびイミダゾール系の過塩素酸塩及び分子量と
リン濃度が適当な値をもつ亜リン酸エステルとを併用す
るので、サーミスタＢ定数の向上と高温度に於ても、長
期に亘る機械的強度と電気特性を相乗的に安定なものと
して、多くの実用的な用途の信頼性を向上させることが
でき、温度検知感度が高く、かつ耐熱性の良い高分子感
温体が得られる。As described above, according to the present invention, an ammonium salt, an imidazole-based perchlorate, and a phosphite having an appropriate molecular weight and phosphorus concentration are used in combination, so that the thermistor B constant Even at high temperatures, the mechanical strength and electrical characteristics over a long period of time can be made synergistically stable to improve the reliability of many practical applications, and the temperature detection sensitivity is high, and A polymer thermosensor having good heat resistance can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 77/00 Ｃ０８Ｌ 77/00 Ｇ０１Ｋ 7/16 Ｇ０１Ｋ 7/16 Ｃ Ｈ０１Ｌ 51/00 Ｈ０１Ｌ 29/28 (72)発明者 柳田 直子 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 伊藤 雅彦 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 昭56−71211（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01C 7/02 - 7/22──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 77/00 C08L 77/00 G01K 7/16 G01K 7/16 C H01L 51/00 H01L 29/28 (72) Inventor Naoko Yanagida Matsushita Electric Industrial Co., Ltd., 1006, Kadoma, Kadoma, Osaka (72) Inventor Masahiko Ito 1006, Kadoma, Kadoma, Kadoma, Osaka, Japan Matsushita Electric Industrial Co., Ltd. (56) References , A) (58) Field surveyed (Int.Cl. 6 , DB name) H01C 7/02-7/22
Claims (4)
モニウム塩系より選ばれた少なくとも一種の過塩素酸塩
と、リン濃度が３〜２０重量％で分子量が２００〜５,0
００の亜リン酸エステル系化合物とを配合したポリアミ
ド組成物よりなる高分子感温体。1. A polyamide comprising at least one perchlorate selected from the group consisting of an imidazole compound and an ammonium salt compound, a phosphorus concentration of 3 to 20% by weight and a molecular weight of 200 to 5.0%.
A thermosensitive polymer made of a polyamide composition containing the phosphite-based compound of No. 00.
ル・ジプロピレングリコールジホスファイトまたはテト
ラフェニルテトラ（トリデシル）ペンタエリスリトール
テトラホスファイトまたは水添フェノールＡ・ペンタエ
リスリトールホスファイトポリマーより選ばれた少なく
とも一種である請求項１に記載の高分子感温体。2. The phosphite compound is at least one selected from tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetraphosphite, and hydrogenated phenol A pentaerythritol phosphite polymer. The polymer thermosensor according to claim 1, which is:
ル・ホルムアルデヒド重縮合体を含んでなる請求項１に
記載の高分子感温体。3. The polymer thermosensor according to claim 1, wherein the polyamide composition comprises a polycondensate of oxybenzoate and formaldehyde.
る群から選ばれた少なくとも１種である請求項１に記載
の高分子感温体。 （ａ）ポリウンデカンアミド （ｂ）ポリドデカンアミド （ｃ）ポリウンデカンアミドあるいはポリドデカンアミ
ドのＮ−アルキル置換アミド共重合体 （ｄ）ポリウンデカンアミドあるいはポリドデカンアミ
ドのエーテルアミド共重合体 （ｅ）ダイマー酸含有ポリアミド4. The polymer thermosensor according to claim 1, wherein the polyamide is at least one selected from the group consisting of the following (a) to (e). (A) Polyundecaneamide (b) Polydodecaneamide (c) Polyundecaneamide or N-alkyl substituted amide copolymer of polydodecaneamide (d) Polyundecaneamide or etheramide copolymer of polydodecaneamide (e) Polyamide containing dimer acid
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4159193A JP2812071B2 (en) | 1992-06-18 | 1992-06-18 | Polymer thermosensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4159193A JP2812071B2 (en) | 1992-06-18 | 1992-06-18 | Polymer thermosensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH063198A JPH063198A (en) | 1994-01-11 |
| JP2812071B2 true JP2812071B2 (en) | 1998-10-15 |
Family
ID=15688354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4159193A Expired - Lifetime JP2812071B2 (en) | 1992-06-18 | 1992-06-18 | Polymer thermosensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2812071B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6048081B2 (en) * | 1979-11-13 | 1985-10-25 | 松下電器産業株式会社 | polymer thermosensor |
-
1992
- 1992-06-18 JP JP4159193A patent/JP2812071B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH063198A (en) | 1994-01-11 |
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