JPH0363571B2 - - Google Patents
Info
- Publication number
- JPH0363571B2 JPH0363571B2 JP1763682A JP1763682A JPH0363571B2 JP H0363571 B2 JPH0363571 B2 JP H0363571B2 JP 1763682 A JP1763682 A JP 1763682A JP 1763682 A JP1763682 A JP 1763682A JP H0363571 B2 JPH0363571 B2 JP H0363571B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- heat
- resistance
- sensitive
- wire
- 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
Links
- 239000004952 Polyamide Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 description 10
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 7
- 229920000299 Nylon 12 Polymers 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 4
- 229920000571 Nylon 11 Polymers 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical group CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 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
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- 239000004677 Nylon Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- FKVMWDZRDMCIAJ-UHFFFAOYSA-N undecanamide Chemical compound CCCCCCCCCCC(N)=O FKVMWDZRDMCIAJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Measuring Temperature Or Quantity Of Heat (AREA)
- Thermistors And Varistors (AREA)
- Organic Insulating Materials (AREA)
Description
【発明の詳細な説明】
本発明は特定のポリエステルアミドから成る感
熱性素子に関するものである。更に詳しくは電気
毛布、電気カーペツトなどにおいて温度制御のた
めの温度検知材料として用いられる感温体に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to heat-sensitive elements made of certain polyesteramides. More specifically, the present invention relates to a temperature sensitive body used as a temperature sensing material for temperature control in electric blankets, electric carpets, etc.
高分子材料の持つ電気的な性質の温度依存性を
利用してこれを温度検知体として用いることは、
例えば電気毛布やで電気カーペツトの場合に見ら
れるように従来からよく知られている。 Utilizing the temperature dependence of the electrical properties of polymeric materials and using them as temperature detectors,
This is well known in the art, for example in the case of electric blankets and electric carpets.
これらの暖房器具用途における感熱温度制御線
は、第１図に示すように本質的にはヒーター線
２、感熱性素子３、信号機４、外被５および芯線
６から構成されている。 The heat-sensitive temperature control wire for use in these heating appliances essentially consists of a heater wire 2, a heat-sensitive element 3, a signal 4, a jacket 5, and a core wire 6, as shown in FIG.
いまヒーター線２に電源をつなぐと、該制御線
または面が低温であればヒーター線２自体が発熱
し、感熱温度制御線または面１全体が昇温する。
ここで昇温の程度とともに供給される電気エネル
ギーの減少または供給停止がなされなければ、そ
の供給エネルギーに見合うエネルギーの発熱がヒ
ーター線２に起こる。しかし感熱温度制御線１は
適度の温度に保たれることが要求されるので、そ
の温度をヒーター線２の供給源に知らせて供給さ
れる電気エネルギーの制御に役立たせるものがい
る。この役目をするのが信号線４である。そして
信号線４はヒーター線２の発熱量を何らかの形で
感知しなければならない。 Now, when power is connected to the heater wire 2, if the control wire or surface is at a low temperature, the heater wire 2 itself generates heat, and the temperature of the thermosensitive temperature control wire or surface 1 as a whole rises.
If the electrical energy supplied is not reduced or stopped as the temperature rises, the heater wire 2 generates heat corresponding to the supplied energy. However, since the heat-sensitive temperature control line 1 is required to be maintained at an appropriate temperature, there are some who inform the supply source of the heater line 2 of its temperature to help control the supplied electrical energy. The signal line 4 plays this role. The signal line 4 must sense the amount of heat generated by the heater line 2 in some way.
通常このヒーター線２の発熱量はヒーター線と
信号線の間に介在する感温体の電気的特性に変換
させて信号線４に伝える。この感温物体が感熱性
素子３であり、温度による自己の電気特性の変化
によつて温度検知機能を発揮する。従つてこのよ
うな感熱素子材料として要求される特性は、誘電
率、直流抵抗、交流インピーダンス等の電気特性
の温度依存性が大きいことである。ポリアミドは
一般に電気特性の温度による変化が大きく、機械
物性、成形加工性、耐熱性にも優れた好適な感熱
素子材料であり、なかでもとくに吸湿性の低いナ
イロン11、ナイロン12が電気毛布、電気カーペツ
トの感熱体として実用に供されている。実際の温
度制御回路においてはその制御因子として用いら
れる電気特性にはいくつかの可能性があり、従来
ナイロン11、ナイロン12を感熱素子材料とする場
合主に誘電率或いは交流インピーダンスが制御因
子とされてきており、これらの電気特性の温度依
存性を改良する試みも数多く成されてきた（例え
ば特公昭48−10978号公報、特開昭56−104938号
など）。しかし電気毛布、電気カーペツトの温度
制御回路が多様化するのにともない感熱体高分子
の直流抵抗を制御因子とする温度制御回路も開発
されている。ナイロン11、ナイロン12は直流抵抗
の温度変化は非常に大きく、このような制御回路
にも適した材料であるが、本来絶縁体であるた
め、室温付近の抵抗が高過ぎるという欠点があ
る。室温付近の抵抗が大きいと、制御回路を設計
する際に抵抗を検知する抵抗計として大容量のも
のを用いなければならず、大容量の抵抗計を使え
ばその分感度が低下し温度制御の精密性に欠ける
結果となる。実用的な温度制御範囲内において精
密な温度制御ができるようにするためには、感熱
素子材料の室温の体積固有抵抗をナイロン11、ナ
イロン12の1/50以上程度にすることが必要であ
る。ナイロンの導電性を増すために炭素粉末、
Al粉末等の導電性充填材を混入させることは従
来公知の技術であるが、このような充填材を用い
る処方は本用途においては非常に薄い感熱相
（200〜300μ）中に異物が入ることになり、均一
性が損われまた絶縁不良の原因ともなり得るので
好ましくない。またイオン性物質を添加して導電
性を付与すると、直流印加下で使用中に電気泳動
によつて添加剤が流失し、電気特性が経時変化す
るためこの方法も不適当である。 Normally, the amount of heat generated by the heater wire 2 is converted into the electrical characteristics of a temperature sensing element interposed between the heater wire and the signal wire, and is transmitted to the signal wire 4. This temperature-sensitive object is the heat-sensitive element 3, which exhibits a temperature detection function by changing its own electrical characteristics due to temperature. Therefore, the characteristics required of such a heat-sensitive element material are that electrical properties such as dielectric constant, DC resistance, AC impedance, etc. have a large temperature dependence. Polyamide generally exhibits large changes in electrical properties with temperature, and is a suitable material for heat-sensitive elements with excellent mechanical properties, moldability, and heat resistance. Among them, nylon 11 and nylon 12, which have particularly low moisture absorption, are used in electric blankets and electric It is put into practical use as a heat susceptor for carpets. In an actual temperature control circuit, there are several possibilities for the electrical properties that can be used as control factors. Conventionally, when nylon 11 and nylon 12 are used as heat-sensitive element materials, the main control factors are dielectric constant or AC impedance. Many attempts have been made to improve the temperature dependence of these electrical characteristics (for example, Japanese Patent Publication No. 10978/1982, Japanese Patent Application Laid-Open No. 104938/1982). However, with the diversification of temperature control circuits for electric blankets and electric carpets, temperature control circuits that use the direct current resistance of a thermosensitive polymer as a control factor have also been developed. Nylon 11 and nylon 12 have a very large change in direct current resistance with temperature, making them suitable materials for such control circuits, but since they are originally insulators, they have the disadvantage that their resistance near room temperature is too high. If the resistance near room temperature is large, it is necessary to use a high-capacity resistance meter to detect resistance when designing a control circuit, and if a high-capacity resistance meter is used, the sensitivity will decrease accordingly, making temperature control This results in a lack of precision. In order to enable precise temperature control within a practical temperature control range, the volume resistivity of the heat-sensitive element material at room temperature must be approximately 1/50 or more of that of nylon 11 and nylon 12. Carbon powder, to increase the conductivity of nylon
Mixing conductive fillers such as Al powder is a conventionally known technique, but formulations using such fillers may cause foreign matter to enter the extremely thin heat-sensitive phase (200 to 300μ) in this application. This is undesirable because it impairs uniformity and may cause poor insulation. Furthermore, if an ionic substance is added to impart conductivity, the additive will be washed away by electrophoresis during use under direct current application, and the electrical properties will change over time, so this method is also inappropriate.
そこで本発明者らは充填材、添加剤処方などに
よらず、室温付近の抵抗値が小さく、精密な温度
制御のできる高性能感熱素子を開発すべく鋭意検
討した結果、特定の脂肪族成分からなるポリエス
テルアミドが室温付近の抵抗値が低く、且つ温度
による抵抗の変化も大きい優れた感熱素子材料で
あることを見出し本発明に到達した。 Therefore, the present inventors conducted intensive studies to develop a high-performance heat-sensitive element that has a low resistance near room temperature and is capable of precise temperature control without depending on fillers or additive formulations. The present inventors have discovered that polyesteramide is an excellent thermosensitive element material that has a low resistance value near room temperature and a large change in resistance depending on temperature.
すなわち本発明は(A)下記（）式で示されるポ
リアミド単位90〜60重量部、および(B)下記（）
および／または（）式で示されるポリエステル
単位10〜40重量部より構成されるポリエステルア
ミドより成ることを特徴とする感熱性素子を提供
するものである。 That is, the present invention comprises (A) 90 to 60 parts by weight of polyamide units represented by the following formula (), and (B) the following ()
The present invention provides a heat-sensitive element characterized by being made of a polyesteramide comprising 10 to 40 parts by weight of polyester units represented by formula () and/or ().
（ここでｋは10または11、ｌは３〜11の整数、Ｒ
は二価の脂肪族、脂環族の基、ｎは４〜10の整数
を表わす。）
本発明のポリエステルアミドのポリアミド単位
はウンデカンアミドまたはドデカンアミド単位で
あり、各々相当するアミノ酸、ラクタムから誘導
される。一方ポリエステル単位の内（）式で示
されるものは、ラクトン類から誘導されるもので
あり、モノマ原料の例としてブチロラクトン、カ
プロラクトン等を挙げることができる。また
（）式で表わされるポリエステル単位を形成す
るジオール成分としてはエチレングリコール、
１，３−プロパンジオール、２，２−ジメチル−
１，３−プロパンジオール、１，４−ブタンジオ
ール、１，５−ペンタンジオール、１，６−ヘキ
サンジオール、１，４−シクロヘキサンジメタノ
ール等を挙げることができ、ジカルボン酸として
はアジピン酸、アゼライン酸、セバシン酸、ドデ
カン二酸等が挙げられる。 (Here, k is 10 or 11, l is an integer from 3 to 11, R
represents a divalent aliphatic or alicyclic group, and n represents an integer of 4 to 10. ) The polyamide units of the polyesteramides of the present invention are undecaneamide or dodecanamide units, each derived from the corresponding amino acid or lactam. On the other hand, among the polyester units, those represented by the formula () are derived from lactones, and examples of monomer raw materials include butyrolactone, caprolactone, and the like. In addition, as the diol component forming the polyester unit represented by the formula (), ethylene glycol,
1,3-propanediol, 2,2-dimethyl-
Examples of dicarboxylic acids include adipic acid and azelain. Examples include sebacic acid, dodecanedioic acid, and the like.
本発明のポリエステルアミドの代表的な製造方
法としてはアミド成分原料のアミノ酸またはラク
タム、エステル成分のラクトンまたはジオールと
ジカルボン酸を混合し、触媒の存在下に加熱減圧
縮重合させる方法を挙げることができるが、製造
方法はこれらに限られるものでなく、例えばアミ
ド成分、エステル成分のいずれか一方又は両方を
適当な分子量を持つオリゴマとした後これを原料
として用いる方法も採用できる。またポリエステ
ルアミドの共重合比は(A)ポリアミド単位90〜60重
量部に対し、(B)ポリエステル単位10〜40重量部が
適当であり、(A)ポリアミド単位が90重量部を越え
ると室温における体積固有抵抗特性の改良効果が
不十分であり、また(A)ポリアミド単位が60重量部
以下の場合にはポリマ融点が低くなりすぎて暖房
器具の発熱部分で使用される感熱素子としての実
用に耐えない。 A typical method for producing the polyester amide of the present invention is a method in which an amino acid or lactam as a raw material for the amide component, a lactone or diol as an ester component, and a dicarboxylic acid are mixed, and the mixture is heated and subjected to compression polymerization in the presence of a catalyst. However, the manufacturing method is not limited to these, and for example, a method can also be adopted in which one or both of the amide component and the ester component is made into an oligomer having an appropriate molecular weight, and then this is used as a raw material. The appropriate copolymerization ratio of polyester amide is 10 to 40 parts by weight of (B) polyester units to 90 to 60 parts by weight of (A) polyamide units. The effect of improving volume resistivity characteristics is insufficient, and if the (A) polyamide unit is less than 60 parts by weight, the polymer melting point will be too low to be practical as a heat-sensitive element used in the heat-generating part of a heating appliance. I can't stand it.
本発明のポリエステルアミドにはその物性をそ
こなわない限りにおいて重合時もしくは重合後成
形前に酸化防止剤、熱分解安定剤、耐光剤、耐加
水分解性向上剤、着色剤、難燃剤、各種成形助剤
などを適宜用いることができる。 The polyester amide of the present invention may contain antioxidants, thermal decomposition stabilizers, light resistance agents, hydrolysis resistance improvers, colorants, flame retardants, various molding agents, etc. during polymerization or after polymerization and before molding, as long as the physical properties are not impaired. Auxiliary agents and the like can be used as appropriate.
上記ポリエステルアミドを通常の押出機などに
供給し、電熱線またはシートなどの形状に成形す
ることにより、感熱性素子が得られる。 A heat-sensitive element can be obtained by supplying the above polyesteramide to a conventional extruder or the like and molding it into a shape such as a heating wire or a sheet.
以下に実施例を挙げて本発明を更に詳しく述べ
る。実施例および比較例中の諸特性の評価は次の
ように行なつた。 The present invention will be described in more detail with reference to Examples below. Evaluation of various properties in Examples and Comparative Examples was performed as follows.
(1) 溶液相対粘度：ポリマ0.5ｇを100mlのオルト
クロロフエノールに溶解した溶液の25℃におけ
る相対粘度。(1) Relative viscosity of solution: Relative viscosity at 25°C of a solution of 0.5 g of polymer dissolved in 100 ml of orthochlorophenol.
(2) 融点：Perkin−Elmer製DSC−1B型示差差
動熱量計を用いて20℃／分の昇温速度で測定し
た際の融解ピーク温度。(2) Melting point: Melting peak temperature measured using a Perkin-Elmer DSC-1B differential calorimeter at a heating rate of 20°C/min.
(3) 体積固有抵抗：ポリマを乾燥後、溶融プレス
によつて厚さ約0.2mmのシート状に成形し、こ
のシートの両面に導電性塗料を円状に塗布して
電極とし、電極間の直流抵抗を測定した後、電
極面積とシート厚とから体積固有抵抗を算出し
た。(3) Volume resistivity: After drying the polymer, it is formed into a sheet approximately 0.2 mm thick using a melt press, and conductive paint is applied circularly on both sides of this sheet to form an electrode. After measuring the direct current resistance, the volume resistivity was calculated from the electrode area and sheet thickness.
実施例 １
12−アミノドデカン酸76.4部、ドデカン二酸
24.3部、１，４−ブタンジオール17.1部を混合し
加熱均一化した後、触媒の存在下に250〜270℃で
３〜４時間減圧縮重合することによつて溶液相対
粘度1.63の溶融時均一透明なポリマが得られた。
このポリマはドデカンアミド単位とブチレンドデ
カジオエート単位との重量比が70／30であり、そ
の融点は150℃であつた。このポリマの体積固有
抵抗の温度依存性は第２図に示す通りであり、30
℃付近の体積固有抵抗が4.2×1011Ω・cmでナイロ
ン12より低く、且つ温度依存性の大きい極めて優
れた感熱素子材料であることが判明した。Example 1 76.4 parts of 12-aminododecanoic acid, dodecanedioic acid
After mixing 24.3 parts of 1,4-butanediol and 17.1 parts of 1,4-butanediol and homogenizing by heating, polymerization was carried out under reduced compression at 250 to 270°C for 3 to 4 hours in the presence of a catalyst, resulting in a uniform melting temperature with a relative viscosity of 1.63. A transparent polymer was obtained.
This polymer had a weight ratio of dodecane amide units to butylene dodecadiate units of 70/30, and a melting point of 150°C. The temperature dependence of the volume resistivity of this polymer is shown in Figure 2, and 30
It was found that the volume resistivity near ℃ was 4.2×10 11 Ω·cm, which is lower than nylon 12, and it is an extremely excellent heat-sensitive element material with large temperature dependence.
比較例 １
ω−ラウロラクタムを原料として通常の加圧溶
融重合を行なつて得られたナイロン12の体積固有
抵抗を実施例１と同様の方法で測定しその温度変
化を第２図に示した。30℃付近の体積固有抵抗値
が2.6×1014Ω・cmと高過ぎ、特性が不十分であつ
た。Comparative Example 1 The volume resistivity of nylon 12 obtained by normal pressure melt polymerization using ω-laurolactam as a raw material was measured in the same manner as in Example 1, and the temperature change is shown in Figure 2. . The volume resistivity value near 30°C was 2.6×10 14 Ω·cm, which was too high, and the characteristics were insufficient.
実施例 ２
12−アミノドデカン酸39.3部、分子量3000〜
4000のポリカプロラクトン9.0部を触媒と共に混
合し、以下実施例１と同様に縮重合反応を行な
い、ドデカンアミド単位とカプロラクトン単位の
重量比が80／20の溶融時均一透明なポリエステル
アミドを得た（相対粘度1.55、融点163℃）。この
ポリマの体積固有抵抗の温度依存性を実施例１と
同様に測定し、結果を第２図に示した。本ポリマ
も低温部特性、温度依存性共に極めて良好な感熱
素子材料であることが判明した。Example 2 39.3 parts of 12-aminododecanoic acid, molecular weight 3000~
4000 polycaprolactone was mixed with a catalyst, and a polycondensation reaction was carried out in the same manner as in Example 1 to obtain a polyester amide that was uniformly transparent when melted and had a weight ratio of dodecanamide units to caprolactone units of 80/20 ( Relative viscosity 1.55, melting point 163℃). The temperature dependence of the volume resistivity of this polymer was measured in the same manner as in Example 1, and the results are shown in FIG. This polymer was also found to be a heat-sensitive element material with extremely good low-temperature properties and temperature dependence.
第１図は有機高分子材料からなる感熱性素子を
使用した感熱ヒーター線の一例を示す側面図であ
る。
１：感熱ヒーター線、２：発熱線、３：感熱性
素子、４：信号線、５：絶縁材、６：芯線、
第２図は本発明のポリエステルアミドおよび比
較材料の直流体積固有抵抗の温度依存性を示すグ
ラフである。
FIG. 1 is a side view showing an example of a heat-sensitive heater wire using a heat-sensitive element made of an organic polymer material. 1: Heat-sensitive heater wire, 2: Heat-generating wire, 3: Heat-sensitive element, 4: Signal wire, 5: Insulating material, 6: Core wire, Figure 2 shows the temperature of the DC volume resistivity of the polyesteramide of the present invention and the comparative material. It is a graph showing dependence.
Claims (1)
〜60重量部および(B)下記（）式および／または
（）式で示されるポリエステル単位10〜40重量
部より構成されるポリエステルアミドより成るこ
とを特徴とする感熱性素子。 （ここでｋは10または11、ｌは３〜11の整数、Ｒ
は二価の脂肪族、脂環族の基、ｎは４〜10の整数
を表わす。）[Claims] 1 (A) Polyamide unit 90 represented by the following formula ()
60 parts by weight and (B) 10 to 40 parts by weight of polyester units represented by the following formula () and/or (). (Here, k is 10 or 11, l is an integer from 3 to 11, R
represents a divalent aliphatic or alicyclic group, and n represents an integer of 4 to 10. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1763682A JPS58136624A (en) | 1982-02-08 | 1982-02-08 | Heat-sensitive element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1763682A JPS58136624A (en) | 1982-02-08 | 1982-02-08 | Heat-sensitive element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58136624A JPS58136624A (en) | 1983-08-13 |
| JPH0363571B2 true JPH0363571B2 (en) | 1991-10-01 |
Family
ID=11949347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1763682A Granted JPS58136624A (en) | 1982-02-08 | 1982-02-08 | Heat-sensitive element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58136624A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58196231A (en) * | 1982-05-12 | 1983-11-15 | Toray Ind Inc | Polymer fuse |
| US4617356A (en) * | 1984-06-15 | 1986-10-14 | Matsushita Electric Industrial Co., Ltd. | Temperature sensitive polymer compositions |
-
1982
- 1982-02-08 JP JP1763682A patent/JPS58136624A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58136624A (en) | 1983-08-13 |
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