JPS63173302A - Polymer temperature sensitive unit - Google Patents
Polymer temperature sensitive unitInfo
- Publication number
- JPS63173302A JPS63173302A JP409287A JP409287A JPS63173302A JP S63173302 A JPS63173302 A JP S63173302A JP 409287 A JP409287 A JP 409287A JP 409287 A JP409287 A JP 409287A JP S63173302 A JPS63173302 A JP S63173302A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- nylon
- polyamide elastomer
- thermistor
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 26
- 229920002647 polyamide Polymers 0.000 claims description 26
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000000806 elastomer Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 229920000299 Nylon 12 Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920006122 polyamide resin Polymers 0.000 description 5
- 229920000571 Nylon 11 Polymers 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- -1 cyclic lactam Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、ポリアミドエラストマーを主成分として成る
高分子感温体、特に電気容量成分を一つの制御因子とし
て温度制御する装置における熱感応性材料の温度に対す
る抵抗値やインピーダンスまたはキャパシタンスの挙動
が改善された高分子感湿体に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a polymeric temperature sensitive body made of polyamide elastomer as a main component, particularly a heat-sensitive material used in a device that controls temperature using a capacitance component as one of the control factors. The present invention relates to a polymer moisture-sensitive material that has improved resistance value, impedance, or capacitance behavior with respect to temperature.
〈従来の技術と問題点〉
高分子感温体は土として電気毛布、電気カーペットなど
の発熱体の温度検知に用いられ、その為の材料としては
、ポリ塩化ビニル、セルロースエステル、ポリアミド、
アクリル酸エステルとアクリロニトリルの共重合物（特
公昭２６−１６２７、特公昭３５−７６３５、特公昭３
５−１４１７９）などが知られている。これら高分子材
料の中で、ポリアミドはその電気的性質、機械的性質、
耐熱性、成形加工性などの点で優れているため、高分子
感温体として最も多く使用されている。<Conventional technology and problems> Polymer thermosensitive materials are used as soil to detect the temperature of heating elements such as electric blankets and electric carpets.Materials for this purpose include polyvinyl chloride, cellulose ester, polyamide,
Copolymer of acrylic acid ester and acrylonitrile (Special Publication No. 26-1627, Special Publication No. 35-7635, Special Publication No. 3)
5-14179) and the like are known. Among these polymer materials, polyamide has excellent electrical and mechanical properties.
Because it has excellent heat resistance and moldability, it is most commonly used as a polymer thermosensitive material.
ただし、このポリアミドは一般に吸水性が大きく、吸水
率によって材料の電気容量が大きく変化してしまい、検
知温度が不正確になるという欠点を持っている。この欠
点を改良するため、吸水率の低いナイロン１１、ナイロ
ン１２、更に吸水率を低くしたポリエーテルエステルア
ミド（特開昭５５−１４５７５６）を使用することが公
知である。このうち、ナイロン１１、ナイロン１２など
は、単独では電気特性の温度変化が感温体としては小さ
すぎるためハロゲン化金属、界面活性剤などのイオン性
物質を添加しているが、この場合吸水率は増大してしま
う。However, this polyamide generally has a high water absorption property, and the capacitance of the material changes greatly depending on the water absorption rate, resulting in inaccurate temperature detection. In order to improve this drawback, it is known to use nylon 11, nylon 12, which have a low water absorption rate, and polyether ester amide (Japanese Patent Application Laid-Open No. 145756/1983), which has a lower water absorption rate. Among these, nylon 11, nylon 12, etc. have too small a temperature change in electrical properties to be used as a temperature sensor when used alone, so ionic substances such as metal halides and surfactants are added, but in this case, water absorption will increase.
−・方、ポリエーテルエステルアミドは、初期の電気特
性は高分子感温体として非常に侵れているが、経時的に
エステル結合部分が加水分解してしまい、電気的性質、
機械的強度伴に変化し、感温体としては信頼性に欠ける
ことが明らかになった。- On the other hand, the initial electrical properties of polyether ester amide are very good as a polymer thermosensitive material, but over time the ester bond part hydrolyzes and the electrical properties deteriorate.
It was revealed that the mechanical strength changed and that it lacked reliability as a temperature sensor.
〈問題点を解決するための手段〉
本発明者は、上記問題点に鑑み鋭意検討した結果、特定
のマルチブロックポリアミドエラストマーが優れた高分
子感温体であることを見出し、本発明に到達した。<Means for Solving the Problems> As a result of intensive studies in view of the above problems, the present inventors discovered that a specific multi-block polyamide elastomer is an excellent polymer thermosensitive material, and arrived at the present invention. .
即ち本発明は、ａ）ポリアミドからなるハードセグメン
ト、及びｂ）一般式
（ただしａ、ｃは１〜４、ｂは２〜３０）で示されるジ
アミンから成るソフトセグメントより製造されるマルチ
ブロックコポリマーであるポリアミドエラストマーを主
成分とする高分子感温体に関する。That is, the present invention is a multi-block copolymer produced from a) a hard segment made of polyamide, and b) a soft segment made of a diamine represented by the general formula (where a and c are 1 to 4, and b is 2 to 30). This invention relates to a polymeric thermosensitive material whose main component is a certain polyamide elastomer.
本発明におけるポリアミドエラストマーのハードセグメ
ントであるポリアミドとしては、ジカルボン酸とジアミ
ンとの重縮合、環状ラクタムの開環重合、アミノカルボ
ン酸の重縮合などにより製造され、その代表例としては
ナイロン６、ナイロン６・６、ナイロン１１、ナイロン
１２、ナイロン６・１２などを挙げることができる。The polyamide, which is the hard segment of the polyamide elastomer in the present invention, is produced by polycondensation of dicarboxylic acid and diamine, ring-opening polymerization of cyclic lactam, polycondensation of aminocarboxylic acid, etc. Typical examples thereof include nylon 6, nylon 6.6, nylon 11, nylon 12, nylon 6.12, etc.
また本発明におけるポリアミドエラストマーのソフトセ
グメントであるジアミンとしては、（ただしａ、Ｃは１
〜４、ｂは２〜３０）で示され、その代表例としては、
両末端アミノプロピル化ポリテトラヒドロフラン（’ａ
、ｃ＝３、ｂ＝６〜３０）などを挙げることができる。In addition, the diamine that is the soft segment of the polyamide elastomer in the present invention (where a and C are 1
~4, b is shown as 2 to 30), and representative examples thereof include:
Both ends aminopropylated polytetrahydrofuran ('a
, c=3, b=6-30).
これらハードセグメント、ソフトセグメントを用いたポ
リアミドエラストマーの製造は、公知のポリアミドの製
造方法で行うことができる（特開昭５５−１３３４２４
）。Polyamide elastomer using these hard segments and soft segments can be produced by a known polyamide production method (Japanese Patent Laid-Open No. 55-133424
).
また、本発明のポリアミドエラストマー重合の際は、上
記ハードセグメント成分、ソフトセグメント成分の他に
、ジカルボン酸、例えばドデカン二酸、テレスタル酸、
イソフタル酸などを一種またはそれ以上添加してもよい
。When polymerizing the polyamide elastomer of the present invention, in addition to the above-mentioned hard segment components and soft segment components, dicarboxylic acids such as dodecanedioic acid, teresteric acid,
One or more types of isophthalic acid or the like may be added.
また、本発明におけるポリアミドエラストマーとしては
、上記製造方法で製造したポリアミドエラストマーを単
独で用いると同時に、他のポリアミド樹脂と溶融ブレン
ドした材料を使用してもよい。ここで使用するポリアミ
ド樹脂としては、市販のポリアミド樹脂が使用可能であ
るが、特に低吸湿ナイロン、例えばナイロン１１、ナイ
ロン１２、ナイロン６・１２などが有利である。またポ
リアミドエラストマーと上記ポリアミド樹脂のブレンド
比は、ポリアミドエラストマー１００〜２０重量パーセ
ント、ポリアミド樹脂Ｏ〜８０重量パーセントが好適で
ある。Further, as the polyamide elastomer in the present invention, the polyamide elastomer produced by the above production method may be used alone, or a material obtained by melt-blending it with another polyamide resin may be used. As the polyamide resin used here, commercially available polyamide resins can be used, but low moisture absorption nylons such as nylon 11, nylon 12, nylon 6.12, etc. are particularly advantageous. The blend ratio of the polyamide elastomer and the polyamide resin is preferably 100 to 20 weight percent of the polyamide elastomer and O to 80 weight percent of the polyamide resin.
また、本発明におけるマルチブロックポリアミドエラス
トマーは、それ自体電気特性の温度依存性が大きく、高
分子感温体として充分使用可能であるが、更に温度制御
を正確にした高性能発熱体に用いるには、イオン性物質
を添加することが好ましい。添加イオン性物質としては
Ｋｌ、Ｃｕｒ、ＫＳＣＮなどハロゲン化金属、擬ハロゲ
ン化金属が適当で、その添加量としては０．１〜１重量
パーセントであることが望沫しい。これらイオン性物質
の添加方法としては、公知の種々の方法が採用できるが
、押出機による溶融ブレンドが特に有利である。Furthermore, the multi-block polyamide elastomer used in the present invention has electrical properties that are highly temperature-dependent and can be used satisfactorily as a polymeric temperature sensor, but cannot be used in a high-performance heating element with more accurate temperature control. , it is preferable to add an ionic substance. Suitable ionic substances to be added include metal halides and metal pseudohalides such as Kl, Cur, and KSCN, and the amount added is preferably 0.1 to 1 percent by weight. Various known methods can be used to add these ionic substances, but melt blending using an extruder is particularly advantageous.
本発明で使用するポリアミドエラストマーには、通常の
耐熱安定剤、滑剤等の添加剤を添加することも可能であ
る。It is also possible to add conventional additives such as heat stabilizers and lubricants to the polyamide elastomer used in the present invention.
〈発明の効果〉
、本発明から成る高分子感温体は、従来公知の高分子感
温体よりも電気特性の温度係数が大きく、しかも従来公
知のものよりも、吸水による電気特性の変化が小さい。<Effects of the Invention> The polymer thermosensitive material of the present invention has a larger temperature coefficient of electrical properties than conventionally known polymeric thermosensitive materials, and is also less susceptible to changes in electrical properties due to water absorption than conventionally known polymeric thermosensitive materials. small.
従って本発明品は非常に温度制御精度の高い高分子感温
体である。Therefore, the product of the present invention is a polymer thermosensitive material with extremely high temperature control accuracy.
〈実施例〉 以下に実施例を示し、本発明を詳述する。<Example> The present invention will be explained in detail with reference to Examples below.
実施例１
ラウリンラクタム７０重量部、両末端アミノプロピル化
ポリテトラヒドロフラン（平均分子量２０００）３０重
量部から得られたポリアミドエラストマーを約５０μの
アルミニウム箔の間にプレス法により約６０μのフィル
ムを成形し、高分子感湿体性能測定用試料とし、３０〜
６０℃の間で１ ＫＨｚにおけるインピーダンスを測定
し、サーミスタＢ定数を求めた。同時に、４０℃、９０
％ＲＨの条件で上記ポリアミドエラストマーフィルムを
飽和するまで吸湿処理した後のナーミスタ特性のズレを
測定した。このサーミスタ特性のズレは、乾燥時の５０
℃相当のインピーダンス値が、吸湿処理により何度相当
低温側にズしたかで表わした。結果は表１に示す。Example 1 A polyamide elastomer obtained from 70 parts by weight of laurin lactam and 30 parts by weight of polytetrahydrofuran (average molecular weight 2000) with aminopropylation at both terminals was formed into a film of about 60 μm by pressing between about 50 μm aluminum foil, As a sample for measuring polymer moisture-sensitive body performance, 30~
The impedance at 1 KHz was measured at 60° C., and the thermistor B constant was determined. At the same time, 40℃, 90℃
% RH, the polyamide elastomer film was subjected to moisture absorption treatment until it was saturated, and then the deviation in the nermistor characteristics was measured. This difference in thermistor characteristics is 50% when dry.
It was expressed as how many times the impedance value equivalent to ℃ shifted to the considerably lower temperature side due to moisture absorption treatment. The results are shown in Table 1.
実施例２
実施例１において、ラウリンラクタムのかわりにカプロ
ラクタムを用いること以外は実施例１と全く同様にして
サーミスタＢ定数とサーミスタ特性のズレを測定した。Example 2 The deviation between the thermistor B constant and thermistor characteristics was measured in exactly the same manner as in Example 1 except that caprolactam was used instead of laurinlactam.
結果を表１に示す。The results are shown in Table 1.
実施例３
実施例１において、ラウリンラクタムのかわりにアミノ
ウンデカン酸を用いること以外は実施例１と全く同様に
してサーミスタＢ定数とサーミスタ特性のズレを測定し
た。結果を表１に示す。Example 3 The deviation between the thermistor B constant and thermistor characteristics was measured in exactly the same manner as in Example 1 except that aminoundecanoic acid was used instead of laurinlactam. The results are shown in Table 1.
実施例４
実施例１で得られたポリアミドエラストマーを６０重組
部と、ナイロン１２を４０重量部を押出機中で溶融混合
し、次いで実施例１と全く同様にして高分子感湿体性能
測定用試料を作製し、サーミスタＢ定数、サーミスタ特
性のズレを測定した。Example 4 60 parts by weight of the polyamide elastomer obtained in Example 1 and 40 parts by weight of nylon 12 were melt-mixed in an extruder, and then prepared in the same manner as in Example 1 for measuring the performance of a polymer moisture sensitive material. A sample was prepared and the thermistor B constant and deviation in thermistor characteristics were measured.
結果を表１に示す。The results are shown in Table 1.
比較例１
ナイロン１２を使い、実施例１と同様の方法で高分子感
湿体性能測定用試料を作製し、サーミスタＢ定数、サー
ミスタ特性のズレを測定した。結果を表１に示す。Comparative Example 1 Using nylon 12, a sample for measuring the performance of a polymer moisture sensitive body was prepared in the same manner as in Example 1, and the thermistor B constant and deviation in thermistor characteristics were measured. The results are shown in Table 1.
実施例５
実施例１において、ポリアミドエラストマーにＫＩを０
．５重量部添加すること以外は実施例１と全く同様にし
てサーミスタＢ定数、サーミスタ特性のズレを測定した
。結果を表１に示す。Example 5 In Example 1, KI was 0 for the polyamide elastomer.
．． The thermistor B constant and the difference in thermistor characteristics were measured in the same manner as in Example 1 except that 5 parts by weight were added. The results are shown in Table 1.
比較例２
実施例４において、ポリアミドエラストマーを４重量部
、ナイロン１２を９６重量部とすること以外は実施例４
と全く同様にして高分子感湿体性能測定用試料を作製し
、サーミスタＢ定数、サーミスタ特性のズレを測定した
。結果を表１に示す。Comparative Example 2 Example 4 except that the polyamide elastomer was 4 parts by weight and the nylon 12 was 96 parts by weight.
A sample for measuring the performance of a polymeric moisture sensitive body was prepared in exactly the same manner as described above, and the deviation in the thermistor B constant and thermistor characteristics was measured. The results are shown in Table 1.
Claims (1)
般式 ▲数式、化学式、表等があります▼ （ただしａ、ｃは１〜４、ｂは２〜３０）で示されるジ
アミンから成るソフトセグメントより製造されるマルチ
ブロックコポリマーであるポリアミドエラストマーを主
成分とする高分子感温体[Claims] From a) a hard segment made of polyamide, and b) a diamine represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where a, c are 1 to 4, b is 2 to 30) A polymer thermosensitive material whose main component is polyamide elastomer, which is a multi-block copolymer made from soft segments.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP409287A JPS63173302A (en) | 1987-01-13 | 1987-01-13 | Polymer temperature sensitive unit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP409287A JPS63173302A (en) | 1987-01-13 | 1987-01-13 | Polymer temperature sensitive unit |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63173302A true JPS63173302A (en) | 1988-07-16 |
Family
ID=11575152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP409287A Pending JPS63173302A (en) | 1987-01-13 | 1987-01-13 | Polymer temperature sensitive unit |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63173302A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003286341A (en) * | 2002-01-28 | 2003-10-10 | Ube Ind Ltd | Polyamide elastomer |
| JP2004161964A (en) * | 2001-11-27 | 2004-06-10 | Ube Ind Ltd | Polyetherpolyamide elastomer having low water-absorbing property |
| JP2004351678A (en) * | 2003-05-27 | 2004-12-16 | Ube Ind Ltd | Corrugated tube |
| WO2008123450A1 (en) * | 2007-03-30 | 2008-10-16 | Ube Industries, Ltd. | Resin composition and molded article |
-
1987
- 1987-01-13 JP JP409287A patent/JPS63173302A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004161964A (en) * | 2001-11-27 | 2004-06-10 | Ube Ind Ltd | Polyetherpolyamide elastomer having low water-absorbing property |
| JP2003286341A (en) * | 2002-01-28 | 2003-10-10 | Ube Ind Ltd | Polyamide elastomer |
| JP2004351678A (en) * | 2003-05-27 | 2004-12-16 | Ube Ind Ltd | Corrugated tube |
| WO2008123450A1 (en) * | 2007-03-30 | 2008-10-16 | Ube Industries, Ltd. | Resin composition and molded article |
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