JPH0122289B2 - - Google Patents
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- Publication number
- JPH0122289B2 JPH0122289B2 JP11715782A JP11715782A JPH0122289B2 JP H0122289 B2 JPH0122289 B2 JP H0122289B2 JP 11715782 A JP11715782 A JP 11715782A JP 11715782 A JP11715782 A JP 11715782A JP H0122289 B2 JPH0122289 B2 JP H0122289B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- conductive
- solution
- conductive composition
- powder
- 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
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- 239000000203 mixture Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 239000004962 Polyamide-imide Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920002312 polyamide-imide Polymers 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 23
- 239000010408 film Substances 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229920005575 poly(amic acid) Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920003055 poly(ester-imide) Polymers 0.000 description 2
- 229920002577 polybenzoxazole Polymers 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-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
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- -1 polyparaphenylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Description
産業上の利用分野
本発明は耐熱性縮合系高分子に金属などの粉末
添加して、更に真空中あるいは不活性ガス中で熱
処理して得られる新規な電導性組成物の製造方法
に関する。
従来例の構成とその問題点
元来絶縁体として知られてきた有機材料に電導
性を付与し、無機の金属、半導体あるいは酸化物
では実現しなかつたユニークな性質を出現させよ
うという試みが最近活発に行なわれている。その
ような試みの流れとしてはいくつかあるが、特に
電荷移動型錯化合物は代表例である。この考え方
で低抵抗の有機材料が作られた例としては、テト
ラシアノキノジメタン、ポリアセチレン、ポリパ
ラフエニレン、ポリピロールなどがある。また、
黒鉛および黒鉛繊維なども同様の考え方で低抵抗
化することが可能である。ところが、これらの電
荷移動型錯化合物に共通して言える欠点は、電荷
移動相互作用が本来非常に弱い性質のため、安定
性の高い化合物を得ることが難しいことである。
これに代る第２の重要な方法として、熱分解高
分子の形成が挙げられる。これは、ある特殊な材
料から出発して熱分解により重縮合した、高度に
共役の広がつた化合物を得ようとするものであ
り、生成物は主に炭素質であるが、出発原料によ
りその電導度が制御されるところに特徴がある。
熱分解高分子の歴史は古く、1960年代前半に注目
を集めた材料である。例えばロシア学派によるポ
リアクリロニトリルの熱分解では2Scm-1の電導度
が得られている。（Ａ・Ｖ・Airapetjanc氏等、
Dokl Akad.Nank SSSR，148巻、605頁、1963
年）また、IBM社のS.D.Bruck氏は1964年にポリ
イミド（デユポン社のカプトンＨフイルム）を
800℃で熱分解することによつて20Scm-1の電導体
が得られることを発見している。このような熱分
解により高電導体となり得る高分子材料の種類は
限られているが、本発明者らの研究の結果、最近
の縮合系高分子化学の進歩により得られた耐熱性
高分子のいくつかがその可能性を有するものとし
て提唱されている。その高分子化合物の例は、芳
香族ポリアミド、ポリアミドイミド、ポリオキサ
チアゾール、ポリチアジアゾール、ポリベンズイ
ミダゾール、ポリベンズオキサゾール、ポリベン
ズチアゾールなどである。これらの材料は真空中
あるいは不活性気流中で400〜1100℃の温度で熱
分解され、100Scm-1以上、最高500Scm-1の電導度
を与える。本発明者らは、これらの発見に基づ
き、新規電導材料の製造方法、化学的あるいは物
理的方法による薄膜の製造方法、更には金、ニツ
ケル、銅、銀などの金属と混合して、バインダー
中に分散させた電導性組成物に関する提案をして
いる。このようにして得られた熱分解高分子の特
徴は、高電導性と化学的、熱安定性にあり、ま
た、これから得られる粉末は多くの高分子バイン
ダーおよび有機溶剤によく相容する。これらの特
徴は熱分解高分子が、粉末として高分子バインダ
ー中に分散させられた電導性組成物に於いて顕著
に発揮され、従来のカーボンブラツクあるいは黒
鉛では得られない電導性皮膜の出現を可能にす
る。
しかしながら、今日迄に開発された熱分解高分
子を単独であるいは銀などの金属粉末と混合して
電導性組成物を製造する場合、いくつか不満足な
点が挙げられる。それらは、(1)熱分解高分子の電
導度が500Scm-1以下であること。特に、比較的低
コストのポリアミドイミド、ポリエステルイミド
では100Scm-1以上の電導度が得られ難いこと。(2)
空気中での熱安定性に限界があり、850℃以上の
使用は難しいこと、(3)熱分解高分子は炭素質材料
であるため、これを多く含む電導性組成物はハン
ダ性に乏しいこと、(4)熱分解高分子の原料として
挙げられる縮合系高分子は現在の使用量では高コ
ストのものが多いこと、などである。
発明の目的
本発明の目的とする所はこれらの欠点特に電導
度およびコストを改良した、新規な熱分解高分子
を提案することにあり、更に詳しくは、熱分解高
分子中に金属を添加した電導性組成物を提案する
ことにある。すなわち、本発明では、熱分解高分
子の原料で、ポリアミド酸などの溶液として得ら
れるものを選択し、その溶液中に金属などの添加
物を分散させ、硬化処理を行つた後に熱分解し
て、上記欠点の改良された電導性熱分解組成物を
製造しようとするものである。
発明の構成
次に具体的に本発明の構成要素となる高分子材
料と添加物について説明する。高分子材料として
は、ポリアミドイミド樹脂またはポリイミド中間
体であるポリアミド酸等の窒素含有複素環を有す
るかこれが形成されるような縮合系高分子が使用
される。本発明の組成物を製造する第一ステツプ
は、上記の縮合系高分子の溶液に添加物を均一に
分散することから始まる。したがつて高分子材料
としては溶液として得られるものが使用され、上
記のような縮合系高分子の中間体溶液の形で使用
するとよい。たとえば、ポリイミド樹脂はジカル
ボン酸無水物とジアミンの反応で得られるが、中
間体として、たとえば、
などの式で表わされるポリアミツク酸が得られ、
アミド系溶媒に溶解した溶液として比較的安定に
取扱うことができる。
また、ポリアミドイミドは例えば塩化イソフタ
ロイルとｍ―フエニレンジアミンにピロメリト酸
無水物を反応させて得られるが、ポリイミドの場
合と同様に
のような構造のポリアミツク酸中間体が得られ、
アセトアミド、キシレン、クレゾールなどの溶液
として得られる。同様にポリエステルイミドの場
合ポリアミツク酸中間体溶液として取扱うことが
可能である。
また、
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing a novel conductive composition obtained by adding a powder of metal or the like to a heat-resistant condensation polymer and then heat-treating the mixture in a vacuum or an inert gas. Structures of conventional examples and their problems Recently, attempts have been made to impart conductivity to organic materials, which were originally known as insulators, and to create unique properties that could not be achieved with inorganic metals, semiconductors, or oxides. It is actively carried out. There are a number of such attempts, and charge transfer type complex compounds are a particularly representative example. Examples of low-resistance organic materials created using this idea include tetracyanoquinodimethane, polyacetylene, polyparaphenylene, and polypyrrole. Also,
Graphite and graphite fibers can also be made to have lower resistance using the same concept. However, a common drawback of these charge transfer type complex compounds is that the charge transfer interaction is inherently very weak, making it difficult to obtain highly stable compounds. A second important alternative method involves the formation of pyrolytic polymers. This is an attempt to obtain a highly conjugated compound that is polycondensed by thermal decomposition starting from a certain special material.The product is mainly carbonaceous, but the starting material The feature is that the conductivity is controlled.
Pyrolytic polymers have a long history and are a material that attracted attention in the early 1960s. For example, in the thermal decomposition of polyacrylonitrile by the Russian school, an electrical conductivity of 2Scm -1 was obtained. (A.V. Airapejanc et al.
Dokl Akad.Nank SSSR, vol. 148, p. 605, 1963
In 1964, Mr. SDBruck of IBM introduced polyimide (DuPont's Kapton H film).
It has been discovered that a conductor of 20 Scm -1 can be obtained by thermal decomposition at 800°C. The types of polymer materials that can become highly conductive through such thermal decomposition are limited, but as a result of our research, we have developed heat-resistant polymers that have been obtained through recent advances in condensation polymer chemistry. Several have been proposed as having this possibility. Examples of the polymer compound include aromatic polyamide, polyamideimide, polyoxathiazole, polythiadiazole, polybenzimidazole, polybenzoxazole, polybenzthiazole, and the like. These materials are pyrolyzed at temperatures between 400 and 1100°C in vacuum or in an inert gas stream to give conductivities greater than 100 Scm -1 and up to 500 Scm -1 . Based on these discoveries, the present inventors have developed a new method for producing conductive materials, a method for producing thin films by chemical or physical methods, and a method for producing new conductive materials in binders by mixing them with metals such as gold, nickel, copper, and silver. proposed a conductive composition dispersed in The pyrolytic polymer thus obtained is characterized by high electrical conductivity and chemical and thermal stability, and the powder obtained from it is well compatible with many polymeric binders and organic solvents. These characteristics are clearly exhibited in conductive compositions in which pyrolytic polymers are dispersed as powders in polymeric binders, making it possible to form conductive films that cannot be obtained with conventional carbon black or graphite. Make it. However, when producing conductive compositions using the pyrolytic polymers developed to date either alone or by mixing them with metal powders such as silver, there are several unsatisfactory points. These are: (1) The electrical conductivity of the pyrolytic polymer is 500 Scm -1 or less. In particular, it is difficult to obtain an electrical conductivity of 100 Scm -1 or more with relatively low-cost polyamideimide and polyesterimide. (2)
(3) Pyrolytic polymers are carbonaceous materials, so conductive compositions containing a large amount of them have poor solderability. (4) Condensation polymers, which are cited as raw materials for pyrolytic polymers, are often expensive at current usage levels. OBJECTIVE OF THE INVENTION The purpose of the present invention is to propose a new pyrolytic polymer which improves these drawbacks, especially its electrical conductivity and cost. The purpose of this invention is to propose a conductive composition. That is, in the present invention, a raw material for the pyrolytic polymer is selected that can be obtained as a solution of polyamic acid, etc., additives such as metals are dispersed in the solution, and after a curing treatment, it is pyrolyzed. The present invention aims to produce an electrically conductive pyrolysis composition which is improved from the above-mentioned drawbacks. Structure of the Invention Next, the polymer materials and additives which are the constituent elements of the present invention will be specifically explained. As the polymer material, a condensed polymer having or formed with a nitrogen-containing heterocycle, such as polyamideimide resin or polyamic acid which is a polyimide intermediate, is used. The first step in producing the composition of the present invention begins with uniformly dispersing the additives in the solution of the condensation polymer described above. Therefore, as the polymer material, one obtained in the form of a solution is used, and it is preferable to use it in the form of an intermediate solution of the condensed polymer as described above. For example, polyimide resin is obtained by the reaction of dicarboxylic acid anhydride and diamine, but as an intermediate, for example, A polyamic acid represented by the formula is obtained,
It can be handled relatively stably as a solution dissolved in an amide solvent. In addition, polyamideimide can be obtained, for example, by reacting isophthaloyl chloride and m-phenylenediamine with pyromellitic anhydride, but as in the case of polyimide, A polyamic acid intermediate with the structure is obtained,
Obtained as a solution in acetamide, xylene, cresol, etc. Similarly, in the case of polyesterimide, it is possible to handle it as a polyamic acid intermediate solution. Also,
【式】はポリ
オキサジアゾールの中間体であり、
[Formula] is an intermediate of polyoxadiazole,
【式】なる単位を持つ化
合物はポリベンゾオキサゾールの中間体であり、
はポリベンズチアゾールの中間体であり、
A compound having a unit of [formula] is an intermediate of polybenzoxazole, is an intermediate of polybenzthiazole,
日立化成(株)製のポリアミイミド樹脂（商品名
HI―400；アセトアミドおよびキシレンを溶媒と
する30％の溶液状物質）をアセトアミドで２倍ま
で希釈して鉄、コバルト、ニツケルの325メツシ
ユ粉末を添加した。混練は羽根撹拌で、約２時間
行ない、完全な分散溶液が得られた後にガラス基
板上に溶液を広げ、オーブン中で180℃２時間の
熱処理を行なつた。得られた皮膜は黒〜緑色の光
沢を有するものであつた。この皮膜を石英管に充
填して、10-3Torrの真空中で熱分解を行なつた。
熱分解温度は600〜1100℃で行ない保持時間は１
時間としたが、生成物の電導度は温度に強く依存
し、保持時間にはわずかにしか依存しなかつた。
電導度は熱分解後銀ペーストおよび金線を用いて
４端子電極を施して、室温、空気中で測定した。
第１表に電導度のデータを示す。
Polyamide resin (product name) manufactured by Hitachi Chemical Co., Ltd.
HI-400 (a 30% solution containing acetamide and xylene as solvents) was diluted up to 2 times with acetamide, and 325 mesh powders of iron, cobalt, and nickel were added. Kneading was carried out using blade stirring for about 2 hours, and after a completely dispersed solution was obtained, the solution was spread on a glass substrate and heat-treated at 180° C. for 2 hours in an oven. The resulting film had a black to green luster. This film was filled into a quartz tube and thermally decomposed in a vacuum of 10 -3 Torr.
Thermal decomposition temperature is 600 to 1100℃ and the holding time is 1
The conductivity of the product was strongly dependent on temperature and only weakly on holding time.
The conductivity was measured at room temperature in air using a 4-terminal electrode using silver paste and gold wire after thermal decomposition.
Table 1 shows the conductivity data.
高分子として、ポリイミド中間体であるポリア
ミド酸のＮ―メチルピロリドンを用い、実施例１
と同様の実験を行なつた。金属の種類、添加量、
および熱分解温度の電導度に及ぼす効果の傾向は
実施例１の場合と同様であつたが、この高分子を
用いた場合は全体に更に高い電導度が得られるこ
とが特徴であつた。第２表にその例を示す。
Example 1 Using N-methylpyrrolidone of polyamic acid, which is a polyimide intermediate, as the polymer
conducted a similar experiment. Type of metal, amount added,
The tendency of the effect of thermal decomposition temperature on electrical conductivity was the same as in Example 1, but when this polymer was used, a higher electrical conductivity was obtained overall. Examples are shown in Table 2.
【表】
このようにして得られた高電導性の組成物は第
１図に示す構成のように電導性組成物１１に直接
電極１２を施して、半可撓性の電導体あるいは風
量センサーとして、あるいはボールミル等で粉砕
された粉末を高分子バインダー中に分散させた複
合電導電皮膜２１を第２図のように絶縁性基板２
３上に一対の銀電極２２を形成した上にまたがる
ように形成して、電子部品の配線用等に広く用い
ることが可能である。例えば、銀あるいは銅粉末
を55重量パーセント、本発明で得られる電導性組
成物の粉末を45パーセント含み、ポリビニルブチ
ラールをバインダーとする印刷皮膜の抵抗は約
0.02Ω／口となり、従来の銀ペーストとほとんど
同じ抵抗で、大幅なコスト低減を達成するもので
ある。更に、カーボン、グラフアイトなどの電導
性粉体と本発明の粉体とを混練して、低抗で低コ
ストの導電性ペーストを製造することが可能であ
つた。
発明の効果
以上のように、本発明は鉄、コバルト、ニツケ
ルいずれか１つまたはこれらの混合体の粉末を溶
剤に可溶な縮合系高分子中間体に分散し、先ず80
〜320℃の温度で空気中またはガス雰囲気中で高
分子の硬化処理を行なわせ、しかる後に700〜
1100℃の温度で真空中あるいは不活性気流中で熱
分解することにより新規な電導性組成物を提供す
るものであり、従来の単純な熱分解高分子の欠点
である電導性の制御およびコストを著しく改善す
るものである。本発明の方法により得られる組成
物は、可撓性を有する皮膜、化学蒸着あるいは物
理蒸着によつて得られる皮膜、あるいは粉末化し
て高分子バインダーあるいはガラスフリツトに分
散した複合皮膜など種々な形状で得られ、導電性
皮膜、太陽熱コレクタ用熱吸収膜、電極材料、磁
気記録媒体、センサ材料など広く用いられるもの
である。[Table] The highly conductive composition thus obtained can be used as a semi-flexible conductor or an airflow sensor by applying an electrode 12 directly to the conductive composition 11 as shown in FIG. Alternatively, a composite electrically conductive film 21 made by dispersing powder pulverized with a ball mill or the like in a polymer binder is applied to an insulating substrate 2 as shown in FIG.
It is possible to form a pair of silver electrodes 22 on the substrate 3 and to straddle the same, and to use it widely for wiring of electronic components and the like. For example, a printed film containing 55 percent by weight of silver or copper powder, 45 percent of the conductive composition powder obtained by the present invention, and polyvinyl butyral as a binder has a resistance of approximately
It has a resistance of 0.02Ω/hole, which is almost the same as conventional silver paste, and achieves a significant cost reduction. Furthermore, by kneading conductive powder such as carbon or graphite with the powder of the present invention, it was possible to produce a conductive paste with low resistance and low cost. Effects of the Invention As described above, the present invention first disperses powder of iron, cobalt, nickel, or a mixture thereof in a solvent-soluble condensation polymer intermediate, and
The polymer is cured in air or gas atmosphere at a temperature of ~320°C, and then heated to a temperature of ~700°C.
It provides a new conductive composition by thermally decomposing it at a temperature of 1100°C in vacuum or in an inert gas stream, and it solves the drawbacks of conventional simple thermally decomposed polymers, such as control of conductivity and cost. This is a significant improvement. The composition obtained by the method of the present invention can be obtained in various forms, such as a flexible film, a film obtained by chemical vapor deposition or physical vapor deposition, or a composite film obtained by powdering and dispersing in a polymeric binder or glass frit. It is widely used in conductive films, heat absorption films for solar collectors, electrode materials, magnetic recording media, sensor materials, etc.
第１図は本発明の電導性組成物を用いて構成し
た電導体の概念図、第２図ａ，ｂは本発明の電導
性組成物の粉末を高分子バインダーに分散させた
複合皮膜素子の構成を示す平面図および断面側面
図である。
１１……電導性組成物皮膜、１２……電極、２
１……複合導電皮膜、２２……銀電極、２３……
絶縁性基板。
Figure 1 is a conceptual diagram of a conductor constructed using the conductive composition of the present invention, and Figures 2a and b are diagrams of a composite film element in which the powder of the conductive composition of the present invention is dispersed in a polymer binder. FIG. 2 is a plan view and a cross-sectional side view showing the configuration. 11... Conductive composition film, 12... Electrode, 2
1...Composite conductive film, 22...Silver electrode, 23...
Insulating substrate.
Claims (1)
体であるポリアミド酸の溶液に、鉄、コバルトお
よびニツケルの少くとも１つの粉体を分散添加
し、空気中もしくはガス雰囲気中で80℃〜320℃
で熱処理を行ない、更に真空中もしくは不活性気
体中で700℃〜1100℃の温度で熱処理することを
特徴とする電導性組成物の製造方法。1 At least one powder of iron, cobalt, and nickel is dispersed and added to a solution of polyamide-imide resin or polyamide acid, which is a polyimide intermediate, and the mixture is heated at 80°C to 320°C in air or a gas atmosphere.
1. A method for producing a conductive composition, which comprises heat-treating the conductive composition at a temperature of 700°C to 1100°C in vacuum or in an inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11715782A JPS598731A (en) | 1982-07-06 | 1982-07-06 | Preparation of electrically-conductive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11715782A JPS598731A (en) | 1982-07-06 | 1982-07-06 | Preparation of electrically-conductive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS598731A JPS598731A (en) | 1984-01-18 |
| JPH0122289B2 true JPH0122289B2 (en) | 1989-04-26 |
Family
ID=14704863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11715782A Granted JPS598731A (en) | 1982-07-06 | 1982-07-06 | Preparation of electrically-conductive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS598731A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0230683Y2 (en) * | 1985-02-13 | 1990-08-17 | ||
| JPH0611860B2 (en) * | 1986-02-04 | 1994-02-16 | ニッポン高度紙工業株式会社 | Heat resistant flexible resin composition |
| KR100426344B1 (en) * | 2001-03-21 | 2004-04-06 | 이석현 | Soluble Self-orienting Materials and Conductive Polymer Composites having the same |
-
1982
- 1982-07-06 JP JP11715782A patent/JPS598731A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS598731A (en) | 1984-01-18 |
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