JP2001326393A - Polyaniline, thermoelectric material using it, and manufacturing method thereof - Google Patents
Polyaniline, thermoelectric material using it, and manufacturing method thereofInfo
- Publication number
- JP2001326393A JP2001326393A JP2000140831A JP2000140831A JP2001326393A JP 2001326393 A JP2001326393 A JP 2001326393A JP 2000140831 A JP2000140831 A JP 2000140831A JP 2000140831 A JP2000140831 A JP 2000140831A JP 2001326393 A JP2001326393 A JP 2001326393A
- Authority
- JP
- Japan
- Prior art keywords
- polyaniline
- doped
- type conductive
- emeraldine
- thermoelectric
- 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
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 229920000775 emeraldine polymer Polymers 0.000 claims abstract description 4
- 239000002019 doping agent Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 9
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 230000000704 physical effect Effects 0.000 claims description 4
- 230000005619 thermoelectricity Effects 0.000 claims 1
- 229920001940 conductive polymer Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910005329 FeSi 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910018967 Pt—Rh Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 241000579895 Chlorostilbon Species 0.000 description 1
- -1 N-substituted aniline Chemical class 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 229910052876 emerald Inorganic materials 0.000 description 1
- 239000010976 emerald Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000000960 laser cooling Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱電材料として有
用な導電性ポリアニリン類とその製造方法に関する。The present invention relates to a conductive polyaniline useful as a thermoelectric material and a method for producing the same.
【０００２】[0002]
【従来の技術】本発明者らは、先にカンファースルホン
酸（ＣＳＡ）でドープした高導電性ポリアニリン膜が初
の有機材料として熱電変換材料として使用できる可能性
があることを見出し、特願平１１−１２６３０１号発明
として出願した。しかし、さらに研究を進めたところ、
実用的熱電材料としては、まだその熱電特性が充分でな
いことが判った。BACKGROUND OF THE INVENTION The present inventors have found that a highly conductive polyaniline film doped with camphorsulfonic acid (CSA) may be used as a thermoelectric conversion material as the first organic material. An application was filed as the invention of No. 11-126301. However, after further research,
It has been found that the thermoelectric properties are not yet sufficient as a practical thermoelectric material.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、従来
導電性高分子材料では達成できなかった、実用化可能レ
ベルの高い熱電特性における物理的内部因子（ＴＰＦ）
を有する導電性ポリアニリン類とその製造方法を提供す
る点にある。SUMMARY OF THE INVENTION The object of the present invention is to achieve a physical internal factor (TPF) in thermoelectric properties at a practically high level, which has not been achieved with conventional conductive polymer materials.
And a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明の第一は、耐熱温
度が１８０〜２０５℃、熱電特性における物理的内部因
子（ＴＰＦ）が１０−７〜１０−４Ｗｍ−１Κ−２、好
ましくは１０−６〜１０−４Ｗｍ−１Κ−２、とくに好
ましくは１０−５〜１０−４Ｗｍ−１Κ−２であり、か
つ分子配向していることを特徴とするドープしたエメラ
ルジン型導電性ポリアニリン類に関する。Means for Solving the Problems The first aspect of the present invention is that the heat resistance temperature is 180 to 205 ° C., and the physical internal factor (TPF) in thermoelectric properties is 10 −7 to 10 −4 Wm −1 −２ −2 , preferably. Is 10 −6 to 10 −4 Wm −1 −２ −2 , particularly preferably 10 −5 to 10 −4 Wm -1 −２ −2 , and is a doped emeraldine-type conductive material characterized by being molecularly oriented. Polyanilines.
【０００５】本発明のポリアニリン類は、非延伸の同一
ポリアニリン類と比較して、その熱電特性における物理
的内部因子が２倍以上、好ましくは３倍以上向上してい
る点も特徴的である。[0005] The polyaniline of the present invention is also characterized in that the physical internal factor in the thermoelectric properties is improved by a factor of 2 or more, preferably by a factor of 3 or more, as compared with the same non-stretched polyaniline.
【０００６】本発明の第二は、前記ドープしたエメラル
ジン型導電性ポリアニリン類よりなることを特徴とする
熱電材料とくに冷却材料に関する。A second aspect of the present invention relates to a thermoelectric material, particularly a cooling material, comprising the doped emeraldine-type conductive polyaniline.
【０００７】本発明の第三は、ドーパントをポリアニリ
ン類のアニリン単位に対してモル比で０．３〜０．７含
有し、かつ溶媒をポリアニリン類に対して３〜２０重量
％含有しているポリアニリン類を、ドーパントと溶媒の
いずれか低い方の沸点（沸点がないものについては分解
温度）以下（通常下限は１５〜２０℃の室温である）
で、所期の物性を示すのに充分な延伸を行うことを特徴
とする請求項１〜３いずれか記載のドープしたエメラル
ジン型導電性ポリアニリン類の製造方法に関する。A third aspect of the present invention is that the dopant is contained in a molar ratio of 0.3 to 0.7 with respect to the aniline unit of the polyaniline, and the solvent is contained in a content of 3 to 20% by weight with respect to the polyaniline. The polyaniline is prepared by lowering the boiling point of the lower of the dopant and the solvent (decomposition temperature for those having no boiling point) or less (the lower limit is usually room temperature of 15 to 20 ° C).
4. A method for producing a doped emeraldine-type conductive polyaniline according to any one of claims 1 to 3, wherein the film is stretched sufficiently to exhibit desired physical properties.
【０００８】延伸率についてはとくに制限するものでは
ないが、通常少なくとも４０％以上、好ましくは６０％
以上、とくに好ましくは７０％以上であり、ほゞ５００
％までの延伸が可能である。The stretching ratio is not particularly limited, but is usually at least 40% or more, preferably 60% or more.
Above, particularly preferably 70% or more, and about 500%.
% Stretching is possible.
【０００９】延伸後、配向したポリアニリンフィルムま
たは繊維は、減圧下（２０〜１０− ４Ｔｏｒｒ、好まし
くは５〜１０−４Ｔｏｒｒ）で、１００〜１９０℃で
０．５〜８時間処理する。これにより、１８０〜２０５
℃までの高い耐熱性を有する材料が得られる。[0009] After stretching, oriented polyaniline films or fibers, under reduced pressure (20 to 10 - 4 Torr, preferably 5 to 10 -4 Torr), the processing 0.5-8 hours at 100 to 190 ° C.. As a result, 180 to 205
A material having high heat resistance up to ° C is obtained.
【００１０】本発明において、改善を狙っている熱電特
性とは、セーベック係数Ｓ、導電率σ、熱伝導率κ、物
理的内部因子ＴＰＦ、熱電性能指数Ｚ、無次元熱電性能
指数ＺＴなどがある。熱電特性がよいと熱（温度差）を
電気に換える効率や電気を用いて冷却する効率を高める
ことができる。なお、前記物理的内部因子ＴＰＦは、In the present invention, the thermoelectric properties to be improved include the Savebeck coefficient S, conductivity σ, thermal conductivity κ, physical internal factor TPF, thermoelectric figure of merit Z, dimensionless thermoelectric figure of merit ZT, and the like. . Good thermoelectric properties can increase the efficiency of converting heat (temperature difference) to electricity and the efficiency of cooling using electricity. The physical internal factor TPF is:
【数１】ＴＰＦ＝Ｓ２σ Ｓはセーベック係数（ＶΚ−１）（絶対温度差１°当り
の起電力） σは導電率（Ω−１ｍ−１） ＴＰＦの単位はＷｍ−１Κ−２ で示すことができ、また、無次元熱電性能指数ＺＴは、## EQU1 ## TPF = S2σ S is the Söbeck coefficient (VΚ-1) (Per 1 ° absolute temperature difference)
Σ is the conductivity (Ω-1m-1The unit of TPF is Wm-1Κ-2 And the dimensionless thermoelectric figure of merit ZT is
【数２】ＺＴ＝（ＴＰＦ／κ）×Ｔ Ｔは絶対温度 κは熱伝導率（Ｗｍ−１Κ−１） で示すことができる。[Number 2] ZT = (TPF / κ) × T T is the absolute temperature kappa can be indicated by the thermal conductivity (Wm -1 Κ -1).
【００１１】本発明において、前記熱電特性の測定は、
１０〜１０−４ｍＡの定電流を流すことのできる定電流
発生装置、温度制御が室温から１０００℃まで可能な電
気炉、小型ヒータおよび図６に示す精密電位差測定装置
（０．１μＶまで測定可能）を用い、ポリアニリン類の
膜を図のようにセットし、温度毎のセーベック係数Ｓや
導電率σを測定することなどにより求めることができ
る。具体的に説明するとＰｔ→の部分は白金線であり、
左から右に電流を流す。またポリアニリン膜上にはＰｔ
／Ｐｔ−Ｒｈ／Ｐｔよりなる熱電対を設け、Ｐｔ−Ｐｔ
間で電位を測定し，Ｐｔ／Ｐｔ−Ｒｈ熱電対で温度を測
定する。[0011] In the present invention, the measurement of the thermoelectric properties is performed by:
A constant current generator capable of flowing a constant current of 10 to 10 -4 mA, an electric furnace capable of controlling the temperature from room temperature to 1000 ° C., a small heater, and a precise potential difference measuring device shown in FIG. ), A polyaniline film is set as shown in the figure, and the temperature can be determined by measuring the Söbeck coefficient S and the conductivity σ at each temperature. Specifically, the Pt → part is a platinum wire,
Apply current from left to right. Also, Pt is formed on the polyaniline film.
/ Pt-Rh / Pt thermocouple is provided, and Pt-Pt
The potential is measured and the temperature is measured with a Pt / Pt-Rh thermocouple.
【００１２】本発明に用いるドーピング剤は、ポリアニ
リン類に対する機能性酸とくに、カンファースルホン酸
（ＣＳＡ）、ドデシルベンゼンスルホン酸（ＤＢＳ）、
２−ナフタレンスルホン酸、リン酸などを挙げることが
できる。The doping agent used in the present invention is a functional acid for polyanilines, in particular, camphorsulfonic acid (CSA), dodecylbenzenesulfonic acid (DBS),
Examples thereof include 2-naphthalenesulfonic acid and phosphoric acid.
【００１３】本発明で用いる溶剤は、とくに制限はない
が、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルスルホ
キシド（ＤＭＳＯ）、ｍ−クレゾール、ジメチルフラン
（ＤＭＦ）、Ｎ，Ｎ′−ジメチルプロピレン尿素（ＤＭ
ＰＵ）、クロロホルム、トルエン、キシレンなどを例示
することができる。Although the solvent used in the present invention is not particularly limited, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), m-cresol, dimethylfuran (DMF), N, N'-dimethylpropylene urea (DM
PU), chloroform, toluene, xylene and the like.
【００１４】本発明のドープしたエメラルジン型導電性
ポリアニリン類としては、Ｎ−置換アニリン以外のもの
であれば何でもよく、それ以外に特別の制限はないが、
一つの代表グループとしては下記反応式で得られるもの
を例示することができる。また、分子量は通常１万〜１
００万のものを使用する。The doped emeraldine-type conductive polyaniline of the present invention may be any other than N-substituted aniline, and is not particularly limited.
As one representative group, those obtained by the following reaction formula can be exemplified. The molecular weight is usually 10,000 to 1
Use one million.
【００１５】[0015]
【化１】 （式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は、水素、アルキル
基、アリール基、ハロゲン、スルホン酸基、カルボキシ
ル基、ニトリル基よりなる群からそれぞれ独立して選ば
れた基であり、Ａはドーピング剤である酸基であり、ｙ
は全ポリアニリン類中におけるキノイド型構造の割合を
示し、ｎはアニリン単位の数を示す。）Embedded image (Wherein, R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of hydrogen, an alkyl group, an aryl group, a halogen, a sulfonic acid group, a carboxyl group, and a nitrile group. , A is an acid group as a doping agent, and y
Represents the ratio of the quinoid structure in all polyanilines, and n represents the number of aniline units. )
【００１６】延伸処理に適したポリアニリン膜調製用の
混合溶液におけるポリアニリン類とドーパントの割合
は、ポリアニリン類のアニリン単位に対してのモル比で
通常０．２〜２．０、好ましくは０．３〜１．０、とく
に好ましくは０．３５〜０．５５であり、ポリアニリン
類とドーパントの総量の溶媒に対する重量含有率は、通
常１〜１０重量％、好ましくは３〜８重量％、とくに好
ましくは４〜５重量％である。The proportion of the polyaniline and the dopant in the mixed solution for preparing the polyaniline film suitable for the stretching treatment is usually 0.2 to 2.0, preferably 0.3 to 2.0 in terms of the molar ratio of the polyaniline to the aniline unit. 1.0 to 1.0, particularly preferably 0.35 to 0.55, and the weight content of the total amount of the polyaniline and the dopant to the solvent is usually 1 to 10% by weight, preferably 3 to 8% by weight, particularly preferably It is 4 to 5% by weight.
【００１７】前記ポリアニリン類とドーパントおよび溶
媒との混合溶液に、その溶解状態を向上させる目的で超
音波処理を行うことが望ましい。超音波処理機の出力は
１１０〜９３０Ｗ、液温は２０〜５５℃、処理時間は１
〜１０時間程度であるが、液温はドーパントや溶媒の沸
点によって変化する。このようにして得られた溶液は遠
心分離などの手段によって不溶分を完全に除去すること
が好ましい。It is desirable that the mixed solution of the polyaniline, the dopant and the solvent is subjected to ultrasonic treatment for the purpose of improving the dissolved state. The output of the ultrasonic processor is 110-930W, the liquid temperature is 20-55 ° C, and the processing time is 1
The liquid temperature varies depending on the dopant and the boiling point of the solvent. It is preferable that the solution thus obtained is completely removed of insoluble components by means such as centrifugation.
【００１８】不溶分を除去したポリアニリン類溶液は、
流延成形などの手段でフィルムに成形したり、紡糸によ
り糸状に成形する。フィルムの場合の膜厚は、１０〜１
０００μｍ、好ましくは５０〜２００μｍ程度のものが
延伸処理に適している。The polyaniline solution from which insolubles have been removed is
It is formed into a film by means such as casting, or formed into a thread by spinning. The thickness of the film is 10 to 1
Those having a size of about 000 μm, preferably about 50 to 200 μm are suitable for the stretching treatment.
【００１９】本発明においては、ドーパントをポリアニ
リン類のアニリン単位に対してモル比で０．３〜０．７
含有し、かつ溶媒をポリアニリン類に対して３〜２０重
量％含有しているポリアニリン類（例えばフィルムや繊
維の形のもの）を、ドーパントと溶媒のいずれか低い方
の沸点（沸点がないものについては分解温度）以下で、
所期の物性を示すのに充分な延伸を行い、ドープしたエ
メラルジン型導電性ポリアニリン類の膜類を製造する。In the present invention, the dopant is used in a molar ratio of 0.3 to 0.7 with respect to the aniline unit of the polyaniline.
Containing polyaniline (for example, in the form of a film or fiber) containing a solvent in an amount of 3 to 20% by weight based on the polyaniline, the lower boiling point of the dopant and the solvent (for those having no boiling point) Below the decomposition temperature)
The film is stretched sufficiently to exhibit the desired physical properties to produce doped emeraldine-type conductive polyaniline films.
【００２０】さらに、前記延伸されたポリアニリン類
は、ひきつづいて、２０〜１０−４Ｔｏｒｒの減圧下に
１００〜１９０℃で熱処理することが好ましい。Further, it is preferable that the stretched polyaniline is subsequently heat-treated at 100 to 190 ° C. under a reduced pressure of 20 to 10 -4 Torr.
【００２１】延伸率（％）は、延伸の前と後での延伸方
向の長さの差が延伸前の長さに対してどの程度になって
いるかを百分率（％）で示すものである。延伸率が高い
ほど分子配列の程度が向上する傾向にあり、一軸延伸を
すると、延伸率が８０％のとき、その熱電特性における
物理的内部因子（ＴＰＦ）は延伸方向に平行な方向にお
いては非延伸フィルムの約４倍、延伸方向に垂直な方向
においては非延伸フィルムの約２倍という優れた結果が
得られた。したがって、本発明においては、ポリアニリ
ン類フィルムの熱電特性における物理的内部因子（ＴＰ
Ｆ）が非延伸フィルムの２倍以上のものとすることは極
めて容易である。The stretching ratio (%) indicates, as a percentage (%), how much the difference between the length in the stretching direction before and after stretching is relative to the length before stretching. When the stretching ratio is higher, the degree of molecular arrangement tends to be improved. When uniaxial stretching is performed, when the stretching ratio is 80%, the physical internal factor (TPF) in the thermoelectric properties is non-linear in the direction parallel to the stretching direction. Excellent results were obtained, about four times the stretched film and about twice the unstretched film in the direction perpendicular to the stretching direction. Therefore, in the present invention, a physical internal factor (TP) in the thermoelectric properties of the polyaniline film is used.
It is very easy to make F) twice or more that of the unstretched film.
【００２２】本発明における熱電材料とは、温度差を直
接電力に変換したり、反対に電力を直接温度差に変換す
る材料であり、可動部がなく直接変換できる点が特徴的
である。具体的には体温で動く時計、振動のない冷蔵庫
（ワイン冷却保存用）、レーザの冷却、人工衛星での温
度差利用発電、自動車などの廃熱利用発電、小さい温度
差を利用した発電、液化天然ガスなどの冷廃熱を利用し
た発電、ペルチエ効果を利用して電力を用いた電子冷却
材などがある。The thermoelectric material in the present invention is a material that directly converts a temperature difference into electric power or vice versa, and is characterized by a direct conversion without a movable part. Specifically, a clock that moves at body temperature, a refrigerator that does not vibrate (for cooling and storing wine), laser cooling, power generation using a temperature difference using satellites, power generation using waste heat from cars, power generation using a small temperature difference, liquefaction There are power generation using cold waste heat such as natural gas, and electronic coolant using electric power using the Peltier effect.
【００２３】[0023]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれにより何等限定されるものではない。EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited in any way by this.
【００２４】実施例１ アニリンを重合温度−８℃〜−６℃で化学酸化重合する
ことにより得られた重量平均分子量（Ｍｗ）９９００
０、分散度（Ｍｗ／Ｍｎ）＝３．２０のポリアニリン
１．０ｇを（±）−１０−カンファースルホン酸１．２
ｇ、ｍ−クレゾール２４．９ｇの混合液に溶解し、液温
２０〜５５℃において、１１０〜９３０Ｗ、３８ＫＨｚ
の超音波処理を４時間行い、溶解とドーピングを充分に
進行させた後、遠心分離を行って不溶解分を除去した。
得られた導電性ポリアニリン溶液を基板上に流延成形
し、８０℃で２４時間加熱して、１００μｍ程度の膜厚
の導電性ポリアニリンフィルムを得、このフィルムを８
０〜１００℃に加熱しながら延伸率７８％で一軸延伸を
行った。この延伸膜を２０Ｔｏｒｒ〜１０−４Ｔｏｒｒ
の減圧下、１９０℃で３０分間熱処理して熱電特性測定
用サンプルとした。Example 1 Weight average molecular weight (Mw) 9900 obtained by subjecting aniline to chemical oxidative polymerization at a polymerization temperature of -8 ° C. to -6 ° C.
0, 1.0 g of polyaniline having a dispersity (Mw / Mn) of 3.20 was added to (±) -10-camphorsulfonic acid 1.2.
g and m-cresol in a mixed solution of 24.9 g, and at a liquid temperature of 20 to 55 ° C., 110 to 930 W and 38 KHz.
Was carried out for 4 hours to sufficiently advance dissolution and doping, and then centrifuged to remove insoluble components.
The obtained conductive polyaniline solution was cast on a substrate and heated at 80 ° C. for 24 hours to obtain a conductive polyaniline film having a thickness of about 100 μm.
Uniaxial stretching was performed at a stretching ratio of 78% while heating to 0 to 100 ° C. This stretched film is subjected to 20 Torr to 10 −4 Torr.
The sample was heat-treated at 190 ° C. for 30 minutes under reduced pressure to obtain a sample for measuring thermoelectric properties.
【００２５】得られた延伸ポリアニリン膜の耐熱性は、
図１に示すように２０６℃までは重量変化がほとんど起
らず、すばらしい耐熱性を示す。なお延伸前のポリアニ
リン膜は１５０℃から重量変化がおきはじめているか
ら、この耐熱性の向上効果は実に驚くべき大きさと言え
る。The heat resistance of the obtained stretched polyaniline film is as follows:
As shown in FIG. 1, there is almost no change in weight up to 206 ° C., showing excellent heat resistance. Since the weight of the polyaniline film before stretching starts to change from 150 ° C., the effect of improving the heat resistance can be said to be a surprising magnitude.
【００２６】図２は、下から（イ）ドーピング処理をし
ていないポリアニリンフィルム（ＥＢ＝Ｅｍｅｒａｌｄ
ｉｎｅ Ｂａｓｅ）、（ロ）本実施例のドーピング処理
した未延伸ポリアニリンフィルム（ＥＳ＝Ｅｍｅｒａｌ
ｄｉｎｅ Ｓａｌｔ）、（ハ）１９０℃で３０分間減圧
乾燥（２０Ｔｏｒｒ〜１０−４Ｔｏｒｒ）した実施例１
の延伸ポリアニリンフィルムおよび（ニ）室温から４０
０℃にまで昇温速度毎分１０℃で加熱した実施例１の延
伸ポリアニリンフィルムのそれぞれのＩＲ吸収スペクト
ルを示す。このように減圧乾燥してもドーピングしたポ
リアニリンの化学構造はほとんど変化せず、組成的に高
い耐熱性をもつことが判る。FIG. 2 shows, from the bottom, (a) a polyaniline film (EB = Emerald) not doped.
Ine Base), (b) Doped unstretched polyaniline film of this example (ES = Emeral
Dine Salt), (c) Example 1 dried under reduced pressure (20 Torr to 10 −4 Torr) at 190 ° C. for 30 minutes.
Stretched polyaniline film and (d) room temperature to 40
2 shows the IR absorption spectrum of each of the stretched polyaniline films of Example 1 heated at a heating rate of 10 ° C. per minute to 0 ° C. Thus, even when dried under reduced pressure, the chemical structure of the doped polyaniline hardly changes, indicating that the polyaniline has high heat resistance in terms of composition.
【００２７】図３に、本発明による熱電特性における物
理的内部因子（ＴＰＦ）の向上効果を示す。黒丸印は実
施例１の延伸ポリアニリンフィルム（延伸率７８％）の
延伸方向に平行な方向の物理的内部因子（ＴＰＦ）を示
し、白丸印は実施例１の延伸ポリアニリンフィルム（延
伸率７８％）の延伸方向に垂直な方向の物理的内部因子
（ＴＰＦ）を示し、内十字白丸印は実施例１で延伸する
前のポリアニリンフィルムの物理的内部因子（ＴＰＦ）
を示す。このように、延伸率７８％の延伸処理により、
未延伸フィルムに比べ、延伸方向に平行な方向では約４
倍、延伸方向に垂直な方向では約２倍と物理的内部因子
（ＴＰＦ）が向上していることが判る。FIG. 3 shows the effect of improving the physical internal factor (TPF) in the thermoelectric characteristics according to the present invention. The black circles indicate the physical internal factor (TPF) in the direction parallel to the stretching direction of the stretched polyaniline film of Example 1 (78% stretch ratio), and the white circles indicate the stretched polyaniline film of Example 1 (78% stretch ratio). Indicates the physical internal factor (TPF) in the direction perpendicular to the stretching direction of the polyaniline film before stretching in Example 1.
Is shown. Thus, by the stretching treatment at a stretching ratio of 78%,
Approximately 4 in the direction parallel to the stretching direction compared to the unstretched film
In the direction perpendicular to the stretching direction, the physical internal factor (TPF) is improved by about twice.
【００２８】実施例２ 延伸率を０％、１３％、４２％、７８％と変化させた以
外は実施例１と同様にして延伸ポリアニリンフィルムを
つくり、絶対温度３４５°Ｋにおける物理的内部因子
（ＴＰＦ）と絶対温度４２６°Ｋの物理的内部因子（Ｔ
ＰＦ）をそれぞれ求め、図４に前者を白丸印で、後者を
黒丸印で示した。６０〜７０％の延伸率のあたりから急
激にＴＰＦが向上していることが判る。Example 2 A stretched polyaniline film was prepared in the same manner as in Example 1 except that the stretching ratio was changed to 0%, 13%, 42%, and 78%, and physical internal factors at an absolute temperature of 345 ° K ( TPF) and a physical internal factor (T
PF) was determined, and the former is shown by a white circle and the latter by a black circle in FIG. It can be seen that the TPF is sharply improved around the stretch ratio of 60 to 70%.
【００２９】実施例３ 延伸率を０％、３０％、４０％、５０％とした以外は実
施例１を繰り返した。得られたポリアニリンフィルムの
分子配向状態を調べたところ、図５に示すように延伸率
が４０％以上になると、延伸により結晶化によるピーク
が一層鋭くなってくるのが判る。なお、図５における縦
軸は回折強度Ｉ（単位ｃｐｓ）で、横軸は回折角度（単
位は２θ）である。Example 3 Example 1 was repeated except that the stretching ratio was 0%, 30%, 40% and 50%. When the molecular orientation state of the obtained polyaniline film was examined, it was found that the peak due to crystallization became sharper due to the stretching when the stretching ratio was 40% or more as shown in FIG. The vertical axis in FIG. 5 is the diffraction intensity I (unit: cps), and the horizontal axis is the diffraction angle (unit: 2θ).
【００３０】[0030]
【発明の効果】（１）ドーピング剤で処理したエメラル
ジン型の導電性ポリアニリン類は、延伸により著しく熱
電特性が改善され、ＦｅＳｉ２などの無機半導体の熱電
材料に対抗できる新規な熱電材料を提供することができ
た。 （２）熱電特性の程度は延伸率によって制御できる。 （３）図２にみられるように、延伸、熱処理により耐熱
性も著しく向上する。 （４）本発明のポリアニリン類は、その熱電特性が大き
く改善されているので、無機材料のＦｅＳｉ２の対抗品
として有用である。とくに無機材料はそれ自体は粉末や
結晶体の形としてしか使用できないが、本発明のものは
高分子材料であるから、それ自体自己支持性があり、フ
ィルムや繊維、あるいは不織布、織物あるいはこれらの
積層体として用いることができるので、本発明のものを
例えば発熱するのが避けられないような材料、たとえば
ＥＬ素子や超ＬＳＩなどに本発明のフィルムなどを積層
し、これに電気を流してペルチエ効果を利用した冷却材
として使用することができる。EFFECTS OF THE INVENTION (1) The emeraldine-type conductive polyaniline treated with a doping agent has a significantly improved thermoelectric property by stretching, and provides a novel thermoelectric material which can compete with thermoelectric materials of inorganic semiconductors such as FeSi 2. I was able to. (2) The degree of thermoelectric properties can be controlled by the stretching ratio. (3) As shown in FIG. 2, the heat resistance is significantly improved by stretching and heat treatment. (4) Since the polyaniline of the present invention has greatly improved thermoelectric properties, it is useful as a counterpart to the inorganic material FeSi 2 . In particular, inorganic materials themselves can be used only in the form of powders or crystals, but since the materials of the present invention are polymeric materials, they have self-supporting properties themselves, and can be films, fibers, nonwoven fabrics, woven fabrics or these. Since the film of the present invention can be used as a laminate, for example, the film of the present invention is laminated on a material which cannot avoid generation of heat, for example, an EL element or a super LSI, and electricity is passed through the film to make the Peltier. It can be used as a coolant utilizing the effect.
【図１】実施例１における延伸、熱処理により耐熱性が
著しく向上したことを示すための耐熱性（ＴＧ）曲線で
あり、縦軸は重量変化の割合（％）、横軸は温度（℃）
である。FIG. 1 is a heat resistance (TG) curve showing that the heat resistance was significantly improved by stretching and heat treatment in Example 1, in which the vertical axis represents the rate of weight change (%), and the horizontal axis represents temperature (° C.).
It is.
【図２】非導電性ポリアニリンフィルム（ＥＢ）、ドー
ピング処理した未延伸ポリアニリンフィルム（ＥＳ）、
延伸ＥＳフィルムを減圧下１９０℃で３０分保持したフ
ィルム、さらに延伸ＥＳフィルムを室温から４００℃ま
で昇温速度毎分１０℃で加熱したフィルムの四者につい
てのＩＲスペクトルを示す。FIG. 2. Non-conductive polyaniline film (EB), doped unstretched polyaniline film (ES),
4 shows IR spectra of a film obtained by holding a stretched ES film under reduced pressure at 190 ° C. for 30 minutes and a film obtained by heating a stretched ES film from room temperature to 400 ° C. at a heating rate of 10 ° C. per minute.
【図３】実施例１の延伸配向によるポリアニリンフィル
ムの熱電特性ＴＰＦの向上効果を示すグラフであり、縦
軸はＴＰＦ（１０−６Ｗｍ−１Ｋ−２）、横軸は絶対温
度（Ｋ）である。FIG. 3 is a graph showing the effect of improving the thermoelectric characteristic TPF of the polyaniline film by the stretching orientation in Example 1, wherein the vertical axis is TPF (10 −6 Wm −1 K −2 ), and the horizontal axis is the absolute temperature (K). It is.
【図４】実施例２に示すように、熱電特性ＴＰＦの延伸
率依存性を示すグラフであり、縦軸はＴＰＦ（１０−６
Ｗｍ−１Ｋ−２）、横軸は延伸率（％）を示す。FIG. 4 is a graph showing the elongation rate dependence of thermoelectric characteristics TPF as shown in Example 2, where the vertical axis is TPF (10 −6).
Wm −1 K −2 ), and the horizontal axis indicates the stretching ratio (%).
【図５】延伸率とポリアニリンフィルムの分子配向の状
態との関係を示すグラフである。FIG. 5 is a graph showing a relationship between a stretching ratio and a state of molecular orientation of a polyaniline film.
【図６】本発明の熱電特性測定のための装置を示す。FIG. 6 shows an apparatus for measuring thermoelectric properties according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大野 尚典 山口県小野田市大字須恵西2593−１ (72)発明者 福岡 直彦 兵庫県神戸市中央区東川崎町１丁目３番３ 号 ケミプロ化成株式会社内 Ｆターム(参考） 4F071 AA58 AC14 AF37 BB02 BB07 BC01 4J002 CM051 EV236 GQ02 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor, Naoori Onoda, Yamaguchi Prefecture, Onoda City, 259-1-1, Suenishi (72) Inventor, Naohiko Fukuoka F term (reference) 4F071 AA58 AC14 AF37 BB02 BB07 BC01 4J002 CM051 EV236 GQ02
Claims (8)
における物理的内部因子（Ｔｈｅｒｍｏｅｌｅｃｔｒｉ
ｃ Ｐｏｗｅｒ Ｆａｃｔｏｒ，以下ＴＰＦと略す）が
１０−７〜１０−４Ｗｍ−１Κ−２であり、かつ分子配
向していることを特徴とするドープしたエメラルジン型
導電性ポリアニリン類。1. A heat resistant temperature of 180 to 205 ° C., a physical internal factor in thermoelectric properties (Thermoelectricity).
c Power Factor, hereinafter referred to as TPF) is 10 -7 to 10 a -4 Wm -1 Κ -2, and emeraldine type conductive polyanilines doped, characterized in that the molecularly oriented.
（ＴＰＦ）が１０−６〜１０−４Ｗｍ−１Κ−２である
請求項1記載のドープしたエメラルジン型導電性ポリア
ニリン類。2. Physical internal factor (TPF) is emeraldine type conductive polyanilines doped according to claim 1, wherein a 10 -6 ~10 -4 Wm -1 Κ -2 in the thermoelectric properties.
性における物理的内部因子（ＴＰＦ）の少なくとも２倍
の熱電特性における物理的内部因子（ＴＰＦ）をもつこ
とを特徴とする請求項１または２記載のドープしたエメ
ラルジン型導電性ポリアニリン類。3. The non-stretched polyaniline according to claim 1, which has a physical internal factor (TPF) in thermoelectric properties at least twice that of the thermoelectric properties of the corresponding unstretched polyanilines. Emeraldine-type conductive polyanilines doped with:
エメラルジン型導電性ポリアニリン類よりなることを特
徴とする熱電材料。4. A thermoelectric material comprising the doped emeraldine-type conductive polyaniline according to claim 1.
エメラルジン型導電性ポリアニリン類よりなることを特
徴とする冷却材料。5. A cooling material comprising the doped emeraldine-type conductive polyaniline according to claim 1.
単位に対してモル比で０．３〜０．７含有し、かつ溶媒
をポリアニリン類に対して３〜２０重量％含有している
ポリアニリン類を、ドーパントと溶媒のいずれか低い方
の沸点（沸点がないものについては分解温度）以下で、
所期の物性を示すのに充分な延伸を行うことを特徴とす
る請求項１〜３いずれか記載のドープしたエメラルジン
型導電性ポリアニリン類の製造方法。6. A polyaniline containing a dopant in a molar ratio of 0.3 to 0.7 with respect to the aniline unit of the polyaniline, and a solvent containing 3 to 20% by weight of the polyaniline with the dopant. And the solvent below the lower boiling point (decomposition temperature for those without a boiling point)
The method for producing a doped emeraldine-type conductive polyaniline according to any one of claims 1 to 3, wherein the film is stretched sufficiently to exhibit desired physical properties.
単位に対してモル比で０．３〜０．７含有し、かつ溶媒
をポリアニリン類に対して３〜２０重量％含有している
ポリアニリン類を、ドーパントと溶媒のいずれか低い方
の沸点（沸点がないものについては分解温度）以下で、
所期の物性を示すのに充分な延伸を行い、ついで２０〜
１０−４Ｔｏｒｒの減圧下に１００〜１９０℃で熱処理
することを特徴とするドープしたエメラルジン型導電性
ポリアニリン類の製造方法。7. A polyaniline containing a dopant in a molar ratio of 0.3 to 0.7 with respect to the aniline unit of the polyaniline and a solvent in an amount of 3 to 20% by weight with respect to the polyaniline is used as a dopant. And the solvent below the lower boiling point (decomposition temperature for those without a boiling point)
Stretching sufficient to show the desired physical properties is performed.
A method for producing a doped emeraldine-type conductive polyaniline, which is heat-treated at 100 to 190 ° C. under a reduced pressure of 10 −4 Torr.
は７記載のドープしたエメラルジン型導電性ポリアニリ
ン類の製造方法。8. The method for producing a doped emeraldine-type conductive polyaniline according to claim 6, wherein the stretching is uniaxial stretching.
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|---|---|---|---|
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|---|---|---|---|---|
| JP2006114793A (en) * | 2004-10-18 | 2006-04-27 | Toyota Central Res & Dev Lab Inc | Thermoelement |
| US8287768B2 (en) | 2007-09-14 | 2012-10-16 | 3M Innovative Properties Company | Polythienylenevinylene thermoelectric conversion material |
| WO2013047730A1 (en) | 2011-09-28 | 2013-04-04 | 富士フイルム株式会社 | Thermoelectric conversion material and thermoelectric conversion element |
| WO2014126211A1 (en) * | 2013-02-15 | 2014-08-21 | 国立大学法人奈良先端科学技術大学院大学 | N-type thermoelectric conversion material, thermoelectric conversion component, and manufacturing method for n-type thermoelectric conversion material |
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| WO2015178793A1 (en) * | 2014-05-23 | 2015-11-26 | Открытое акционерное общество "Инфотэк Груп" | Method for manufacturing a thermoelectric cooling element |
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