JPH0536533B2 - - Google Patents
Info
- Publication number
- JPH0536533B2 JPH0536533B2 JP60139130A JP13913085A JPH0536533B2 JP H0536533 B2 JPH0536533 B2 JP H0536533B2 JP 60139130 A JP60139130 A JP 60139130A JP 13913085 A JP13913085 A JP 13913085A JP H0536533 B2 JPH0536533 B2 JP H0536533B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- fibers
- highly conductive
- fiber
- package
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 55
- 239000004917 carbon fiber Substances 0.000 claims description 55
- 239000000835 fiber Substances 0.000 claims description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011247 coating layer Substances 0.000 claims description 14
- 238000005229 chemical vapour deposition Methods 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- LNDJVIYUJOJFSO-UHFFFAOYSA-N cyanoacetylene Chemical group C#CC#N LNDJVIYUJOJFSO-UHFFFAOYSA-N 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 238000005979 thermal decomposition reaction Methods 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 alicyclic hydrocarbons Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- PCTCNWZFDASPLA-UHFFFAOYSA-N hexa-2,4-diyne Chemical compound CC#CC#CC PCTCNWZFDASPLA-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- UMIPWJGWASORKV-UHFFFAOYSA-N oct-1-yne Chemical compound CCCCCCC#C UMIPWJGWASORKV-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は高導電性繊維の製造方法に関し、さ
らに詳しくは、化学気相蒸着法（CVD法：
Chemical Vapor Deposition）を用いて、炭素
を基質とし、グラフアイトを外皮層とする高導電
性繊維を製造する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing highly conductive fibers, and more specifically, to a method for producing highly conductive fibers, and more specifically, a chemical vapor deposition method (CVD method:
The present invention relates to a method for producing highly conductive fibers using carbon as a substrate and graphite as an outer layer using chemical vapor deposition.
［従来の技術］
炭素を基質とし、グラフアイトを外皮層とする
高導電性繊維を製造する方法としては、特願昭58
−58734号明細書に記載された方法がある。この
方法は、炭素繊維に直接通電することによつてそ
れを加熱するとともに、その炭素繊維にCVD法
により易グラフアイト化炭素の被覆層を形成し、
次いでその被覆炭素繊維を2500℃以上の温度に加
熱して上記易グラフアイト化炭素（前駆体）をグ
ラフアイト化するものである。しかしながら、か
かる従来の方法は、炭素繊維の切断が起こりやす
いという欠点をもつている。[Prior art] A method for producing highly conductive fibers using carbon as a substrate and graphite as an outer layer is disclosed in Japanese Patent Application No. 1983.
There is a method described in the specification of No.-58734. This method heats the carbon fibers by directly applying electricity to them, and forms a coating layer of easily graphitized carbon on the carbon fibers using the CVD method.
Next, the coated carbon fiber is heated to a temperature of 2500°C or higher to graphitize the easily graphitable carbon (precursor). However, such conventional methods have the disadvantage that carbon fibers are easily cut.
すなわち、上述した従来の方法は、炭素繊維の
加熱を、それに直接通電することによつて生ずる
ジユール熱を利用して行うものである。しかる
に、炭素繊維に易グラフアイト化炭素の被覆層が
形成されてくると、それに伴つて被覆炭素繊維と
してみた熱容量や抵抗値が連続的に変化してく
る。そのため、繊維軸方向において大きな温度分
布ができ、局部的加熱が起こつて炭素繊維が切れ
てしまうのである。 That is, in the conventional method described above, carbon fibers are heated using Joule heat generated by directly applying electricity to the carbon fibers. However, when a coating layer of easily graphitized carbon is formed on carbon fibers, the heat capacity and resistance value of the coated carbon fibers change continuously. Therefore, a large temperature distribution occurs in the fiber axial direction, causing localized heating and causing the carbon fiber to break.
さらに別の公知例として特開昭59−187622号公
報、特公昭43−27552号公報があるが、これらは
いずれも熱分解させて被覆させる反応装置が適切
でなかつたため、効率よく高導電性繊維を作るこ
とが困難であつた。さらに別の公知例として赤外
線集光炉があるが（実公昭56−53278号公報）、こ
の公知例を化学気相蒸着法（CVD法）に用いて
も、赤外線ランプがすぐに汚れて使用できないも
のであつた。 Further known examples include JP-A No. 59-187622 and JP-A No. 43-27552, but in both cases, because the reaction equipment for thermal decomposition and coating was not appropriate, highly conductive fibers could not be efficiently coated. It was difficult to make. Another known example is an infrared concentrator (Japanese Utility Model Publication No. 56-53278), but even if this known example is used in chemical vapor deposition (CVD), the infrared lamp becomes dirty quickly and cannot be used. It was hot.
［発明が解決しようとする問題点］
この発明の目的は、易グラフアイト化炭素の被
覆を特定の反応装置を用いることにより、従来の
方法の上記欠点を解決し、炭素繊維の加熱に際し
てその切断を防止することができる高導電性繊維
の製造方法を提供するにある。[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned drawbacks of the conventional method by coating easily graphitized carbon using a specific reaction device, and to solve the problem of cutting carbon fibers when heating them. An object of the present invention is to provide a method for producing highly conductive fibers that can prevent the above.
［問題点を解決するための手段］
上記目的を達成するため本発明は下記の構成か
らなる。[Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration.
「炭素繊維を基質とし、グラフアイトを外皮層
とする高導電性繊維の製造方法において、第１段
処理として、供給繊維パツケージ、および巻き取
り繊維パツケージを含む系全体を密閉系に保ち、
加熱部分を石英管とし、輻射エネルギーを集光す
る加熱手段を設けた反応装置を用いて、第１段処
理として、炭素繊維を、モーターを用いて繰り出
して、ベンゼンまたはシアノアセチレンを1100〜
1500℃で熱分解することによつて化学気相蒸着法
により易グラフアイト化炭素の被覆層を形成して
巻き取り、次いで第２段処理として、パツケージ
の巻き戻しを行い、前記被覆炭素繊維を2500℃以
上の温度に加熱することを特徴とする高導電性繊
維の製造方法。」
この発明をさらに詳細に説明すると、この発明
においては、まず、いわゆる基材として炭素繊維
を連続繊維の形態で用意する。炭素繊維は、ポリ
アクリルニトリル系、ピツチ系、セルローズ系、
ビニロン系、リグニン／ポバール系など、どのよ
うなものであつてもよい。しかして、炭素繊維
は、通常、５〜10μｍ程度の単糸径を有するもの
を使用する。なお、形態は、モノフイラメントで
あつてもよいし、マルチフイラメントであつても
よい。 "In a method for producing highly conductive fibers using carbon fiber as a substrate and graphite as an outer layer, the first step is to keep the entire system including the supplied fiber package and the wound fiber package in a closed system,
Using a reaction device with a quartz tube as the heating part and a heating means for concentrating radiant energy, in the first stage of treatment, carbon fibers are fed out using a motor to produce benzene or cyanoacetylene at 1100~
A coating layer of easily graphitized carbon is formed by thermal decomposition at 1500° C. by chemical vapor deposition and then wound.Then, as a second stage treatment, the package is unwound to remove the coated carbon fiber. A method for producing highly conductive fibers, which comprises heating to a temperature of 2500°C or higher. ” To explain this invention in more detail, in this invention, carbon fibers are first prepared in the form of continuous fibers as a so-called base material. Carbon fibers include polyacrylonitrile, pitch, cellulose,
It may be of any type, such as vinylon type or lignin/poval type. Therefore, the carbon fiber used usually has a single yarn diameter of about 5 to 10 μm. Note that the shape may be monofilament or multifilament.
次に、この発明においては、上記炭素繊維を連
続的に走行させながら、その炭素繊維に輻射エネ
ルギーを集束して加熱する。と同時に、その炭素
繊維にCVD法により易グラフアイト化炭素の被
覆層を形成する。 Next, in the present invention, while the carbon fibers are continuously running, radiant energy is focused on the carbon fibers to heat them. At the same time, a coating layer of easily graphitized carbon is formed on the carbon fiber by CVD method.
輻射エネルギー源としては、たとえば炭酸ガス
レーザーのように、大容量で、かつ赤外ないし近
赤外領域に非連続的なスペクトルをもつものや、
赤外線ランプのように、赤外から近赤外領域にか
けて連続したスペクトルをもつもの、あるいはハ
ロゲンランプやキセノンアークランブなどを用い
ることができる。また、これらの輻射エネルギー
源から輻射される光エネルギーを炭素繊維上に集
束する手段としては、回転楕円面鏡や光学レンズ
などを使用することができる。好ましくは、炭素
繊維を囲むように回転楕円面鏡を配置し、炭素繊
維にその繊維軸方向と直交する平面内において全
方向から光エネルギー（たとえば赤外線）が集束
されるようにする。 Examples of radiant energy sources include those that have a large capacity and have a discontinuous spectrum in the infrared or near-infrared region, such as carbon dioxide lasers,
An infrared lamp with a continuous spectrum from infrared to near-infrared, a halogen lamp, a xenon arc lamp, etc. can be used. Furthermore, as a means for focusing the optical energy radiated from these radiant energy sources onto the carbon fibers, a spheroidal mirror, an optical lens, or the like can be used. Preferably, a spheroidal mirror is arranged to surround the carbon fibers so that light energy (for example, infrared rays) is focused on the carbon fibers from all directions within a plane orthogonal to the fiber axis direction.
上記のとおり、輻射エネルギーの集光手段を用
いることにより、目的とする炭素繊維のみを加熱
でき、ほかの部分、たとえば加熱炉の壁など不要
な部分は加熱しないので、効率よく被覆層を沈着
できる。さらに、加熱炉の汚染を防止できるの
で、長期間、連続的に第１段の反応を続けること
ができる。 As mentioned above, by using a radiant energy condensing means, it is possible to heat only the target carbon fibers, and other parts, such as unnecessary parts such as the walls of the heating furnace, are not heated, so the coating layer can be deposited efficiently. . Furthermore, since contamination of the heating furnace can be prevented, the first stage reaction can be continued continuously for a long period of time.
CVD法は、炭化水素を気相状態で熱分解する
ことにより、易グラフアイト化炭素となる、いろ
いろな縮合環をもつ化合物を基材上に堆積させる
方法である。この発明においては、上述したよう
にこのCVD法を利用して炭素繊維に易グラフア
イト化炭素の被覆層を形成する。 The CVD method is a method in which compounds with various condensed rings, which become easily graphitized carbon, are deposited on a substrate by thermally decomposing hydrocarbons in a gaseous state. In this invention, as described above, the CVD method is utilized to form a coating layer of easily graphitized carbon on carbon fibers.
熱分解させる炭化水素としては、ベンゼンとシ
アノアセチレンが必要である。これらのものは易
グラフアイト化炭素となりやすいからである。そ
のほか芳香族炭化水素、脂環族炭化水素、脂肪族
炭化水素や、これら炭化水素の誘導体を併用して
もよい。具体的には、ベンゼン、シアノアセチレ
ン、トルエン、キシレン、ナフタリン、１−オク
チン、２，４−ヘキサジイン、アセトニトリル、
テトラシアノエチレン、フエニルアセチレン、ヘ
プタン、シクロヘキサン、プロパギルアルコー
ル、アセチレン、メチルアセチレン、メタンなど
である。 Benzene and cyanoacetylene are required as hydrocarbons to be thermally decomposed. This is because these materials tend to become easily graphitized carbon. In addition, aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, and derivatives of these hydrocarbons may be used in combination. Specifically, benzene, cyanoacetylene, toluene, xylene, naphthalene, 1-octyne, 2,4-hexadiyne, acetonitrile,
These include tetracyanoethylene, phenylacetylene, heptane, cyclohexane, propargyl alcohol, acetylene, methylacetylene, and methane.
炭化水素の熱分解は、上述した輻射エネルギー
によつて行う。熱分解温度は、1100〜1500℃であ
る。すなわち、1100℃未満では易グラフアイト化
炭素の被覆層の形成速度が遅くなる。また、1500
℃を越えると、難グラフアイト化炭素の生成量が
多くなるので好ましくない。換言すれば、炭素繊
維上に集束する輻射エネルギーは、その炭素繊維
が1100〜1500℃に加熱されるように調節される。 Thermal decomposition of hydrocarbons is performed using the above-mentioned radiant energy. The thermal decomposition temperature is 1100-1500°C. That is, if the temperature is lower than 1100°C, the formation rate of the coating layer of easily graphitized carbon becomes slow. Also, 1500
If the temperature exceeds .degree. C., the amount of hard-to-graphite carbon increases, which is not preferable. In other words, the radiant energy focused onto the carbon fiber is adjusted so that the carbon fiber is heated to 1100-1500°C.
第１段の反応装置の系は密閉系であることが必
要である。系全体の減圧系に保つたり、ベンゼン
やシアノアセチレンモノマーの洩れを防ぎ安全性
を保つためである。 The system of the first stage reactor needs to be a closed system. This is to maintain safety by keeping the entire system under reduced pressure and preventing leakage of benzene and cyanoacetylene monomers.
ベンゼンやシアノアセチレンモノマーの熱分解
は、分圧としてみた炭化水素の濃度が、0.5〜100
mmHgである範囲で行うのが好ましい。さらに好
ましいのは、１〜30mmHgである。もつとも、熱
分解は、窒素やアルゴンの共存下で、必要に応じ
てさらに水素の共存下で行うこともできる。この
場合は、炭化水素濃度を0.1〜20体積％程度にす
るのが好ましい。 Thermal decomposition of benzene and cyanoacetylene monomers occurs when the concentration of hydrocarbons in terms of partial pressure is between 0.5 and 100.
It is preferable to carry out the treatment within a certain range of mmHg. More preferred is 1 to 30 mmHg. However, thermal decomposition can also be carried out in the coexistence of nitrogen or argon, and if necessary, in the coexistence of hydrogen. In this case, the hydrocarbon concentration is preferably about 0.1 to 20% by volume.
熱分解時間は、通常、数分から数十分程度であ
る。より均質な易グラフアイト化炭素の被覆層を
形成するためには、熱分解温度やモノマー濃度を
低くし、熱分解時間を長くするのが好ましい。 The thermal decomposition time is usually about several minutes to several tens of minutes. In order to form a more homogeneous coating layer of easily graphitized carbon, it is preferable to lower the thermal decomposition temperature and monomer concentration and to lengthen the thermal decomposition time.
易グラフアイト化炭素の被覆層の厚みは、炭化
水素の濃度、熱分解温度、熱分解時間などによつ
て調節できるが、最終的に得られる高導電性繊維
の可撓性が著しく損われないように、また電気伝
導度（以下、電導度という）の低い基材炭素繊維
の割合が極端に大きくならないように、10〜
200μｍ程度であるのが好ましい。なお、炭素繊
維をマルチフイラメントの形態で供する場合に
は、堆積した易グラフアイト化炭素によつて単繊
維同士が結着され、被覆炭素繊維、ひいては最終
的に得られる高導電性繊維の可とう性が失われが
ちになるので、被覆の形成速度を極力遅くするの
が好ましい。 The thickness of the coating layer of easily graphitized carbon can be adjusted by adjusting the hydrocarbon concentration, thermal decomposition temperature, thermal decomposition time, etc., but the flexibility of the final highly conductive fiber is not significantly impaired. In order to prevent the proportion of base material carbon fiber with low electrical conductivity (hereinafter referred to as electrical conductivity) from becoming extremely large,
The thickness is preferably about 200 μm. Note that when carbon fibers are provided in the form of multifilaments, the deposited easily graphitized carbon binds the single fibers to each other, resulting in the formation of coated carbon fibers and, ultimately, the flexible highly conductive fibers obtained. Since this tends to result in a loss of properties, it is preferable to slow down the rate of coating formation as much as possible.
さて、この発明においては、次いで、上述し
た、易グラフアイト化炭素被覆炭素繊維を加熱し
てその易グラフアイト化炭素をグラフアイト化
し、炭素を基質とし、グラフアイトを外皮層に有
する高導電性繊維を得る。外皮層を形成するグラ
フアイトが、主として電導度の向上効果を受け持
つ。 Now, in this invention, next, the above-mentioned easily graphitable carbon-coated carbon fiber is heated to graphitize the easily graphitized carbon to form a highly conductive carbon fiber having carbon as a substrate and graphite as an outer layer. Get fiber. Graphite, which forms the outer skin layer, is mainly responsible for the effect of improving electrical conductivity.
この発明においてグラフアイトとは、SP2結合
によつて結合した６員環炭素で構成される面がπ
結合により結合してなる構造が発達してできた炭
素を主成分とする化合物である。そのような化合
物は、Cu−Kα線を使用したＸ線回折によつて
002面から求めた面間隔が3.363Å以下であるとい
うことによつて特徴付けられる。また、高導電性
とは、４端子法により室温かつ空気中で測定した
電導度が１×104S／cm以上であるものとして定義
される。 In this invention, graphite refers to a surface composed of 6-membered ring carbons bonded by SP 2 bonds.
It is a compound whose main component is carbon, resulting from the development of a bonded structure. Such compounds can be identified by X-ray diffraction using Cu-Kα radiation.
It is characterized by the interplanar spacing determined from the 002 plane being 3.363 Å or less. Moreover, high conductivity is defined as having an electrical conductivity of 1×10 4 S/cm or more when measured in air at room temperature using a four-terminal method.
さて、第２段目の処理である被覆炭素繊維の加
熱は、CVD法と同様に輻射エネルギーにより、
あるいはタンマン炉などの外部加熱式の加熱装置
によつて行う。加熱温度は2500℃以上である。
2500℃未満では易グラフアイト化炭素のグラフア
イト化が進行せず、高導電性繊維を得ることがで
きない。たとえば、2000℃に加熱することによつ
て得られた繊維の電導度は、1.4×103程度と大変
低い。また、002面の面間隔は3.426Åと広い。な
お、加熱温度が3500℃を越えると、グラフアイト
の蒸気圧が増大して炭素繊維から炭素が揮発しが
ちになる。そのため、加熱温度の上限は3500℃と
するのが好ましい。 Now, the second stage of treatment, the heating of the coated carbon fiber, uses radiant energy, similar to the CVD method.
Alternatively, it is carried out using an external heating device such as a Tammann furnace. The heating temperature is 2500°C or higher.
If the temperature is lower than 2500°C, graphitization of easily graphitized carbon does not proceed, making it impossible to obtain highly conductive fibers. For example, the electrical conductivity of fibers obtained by heating to 2000°C is as low as 1.4×10 3 . Furthermore, the interplanar spacing of the 002 plane is as wide as 3.426 Å. Note that when the heating temperature exceeds 3500°C, the vapor pressure of graphite increases and carbon tends to volatilize from the carbon fibers. Therefore, the upper limit of the heating temperature is preferably 3500°C.
グラフアイト化に要する時間は、通常、10〜60
分である。また、グラフアイト化に際して、電子
供与性または電子受容性の物質をグラフアイトの
層間に挿入（Intercalation）すると、より導電
性の高い繊維が得られるようになるので好まし
い。そのような、いわゆるインターカレーシヨン
法は、たとえば炭素材料学会刊、雑誌「炭素」、
第111巻、第171頁（1982年）に記載されている。
電子供与性または電子受容性の物質としては、た
とえばリチウム、ナトリウム等のアルカリ金属、
塩素、臭素等のハロゲンガス、IF5などのハロゲ
ン化合物、MgCl5、WCl6等の金属ハロゲン化物、
硝酸、硫酸、AsF5等の酸、Na−NH3等の金属−
分子化合物、Ｋ−ナフタレン等の有機金属化合物
など、いろいろ知られているが、安価かつ無毒で
あり、しかも生成物が安定している硝酸が最も好
ましい。 The time required for graphiteization is usually 10 to 60 minutes.
It's a minute. In addition, it is preferable to intercalate an electron-donating or electron-accepting substance between the layers of graphite during graphite formation, since a fiber with higher conductivity can be obtained. Such a so-called intercalation method is described, for example, in the magazine "Carbon" published by the Carbon Materials Society,
Described in Volume 111, Page 171 (1982).
Examples of electron-donating or electron-accepting substances include alkali metals such as lithium and sodium;
Halogen gases such as chlorine and bromine, halogen compounds such as IF 5 , metal halides such as MgCl 5 and WCl 6 ,
Acids such as nitric acid, sulfuric acid, AsF 5 , etc., metals such as Na-NH 3 -
Various molecular compounds and organometallic compounds such as K-naphthalene are known, but nitric acid is the most preferred because it is inexpensive, non-toxic, and produces a stable product.
［実施例］
以下、実施例に基いてこの発明をさらに詳細に
説明する。[Examples] Hereinafter, the present invention will be explained in more detail based on Examples.
実施例 １
図面に示すこの発明の方法により、高導電性繊
維を得た。Example 1 Highly conductive fibers were obtained by the method of the present invention shown in the drawings.
すなわち、炭素繊維として、米国ユニオンカー
バイド社製ピツチ系炭素繊維“Thornel”P75（モ
ノフイラメント、直径：10μｍ）を使用し、その
炭素繊維をモーター１によつて駆動される供給パ
ツケージ２から繰り出し、反応管３内に通し、モ
ーター４によつて駆動されるボビンに巻き取り、
パツケージ５を形成するようにした。なお、反応
管３は、内径45mm、長さ350mmの石英管で作られ
ている。石英管を用いるのは耐熱性が要求される
ためである。また、反応管３の周りには、その反
応管３を取り囲むように回転楕円面鏡６を設け、
その内部にはハロゲンランプ７を収容し、そのハ
ロゲンランプ７の輻射エネルギーが、炭素繊維上
にその繊維軸方向と直交する面内において全方向
から集光されるようにした。一方、真空源に接続
された弁８を調節し、また炭化水素源に接続され
た弁９を調節して、炭化水素が弁９を介して反応
管３内に所望の速度で導入され、同時にその濃度
が所望の値に維持できるようにした。 That is, as the carbon fiber, Pitch-based carbon fiber "Thornel" P75 (monofilament, diameter: 10 μm) manufactured by Union Carbide Company, USA is used, and the carbon fiber is fed out from a supply package 2 driven by a motor 1 and reacted. passed through a tube 3 and wound onto a bobbin driven by a motor 4;
A package 5 was formed. Note that the reaction tube 3 is made of a quartz tube with an inner diameter of 45 mm and a length of 350 mm. The reason why a quartz tube is used is because heat resistance is required. Further, a spheroidal mirror 6 is provided around the reaction tube 3 so as to surround the reaction tube 3,
A halogen lamp 7 was housed inside the carbon fiber, and the radiant energy of the halogen lamp 7 was focused onto the carbon fiber from all directions in a plane perpendicular to the fiber axis direction. Meanwhile, by adjusting the valve 8 connected to the vacuum source and also adjusting the valve 9 connected to the hydrocarbon source, hydrocarbons are introduced into the reaction tube 3 through the valve 9 at the desired rate, and at the same time The concentration was maintained at the desired value.
さて、供給パツケージ２から炭素繊維を150
mm／時の速度で連続的に繰り出し、またハロゲン
ランプ７を点灯して炭素繊維を約1300℃に加熱し
た。同時に、弁８および弁９を調節し、反応管３
内に弁９を介してベンゼンが５c.c.／分の速度で連
続的に流れ込むように、かつ反応管３内が約３mm
Hgになるようにし、ベンゼンを熱分解して炭素
繊維に易グラフアイト化炭素の被覆層を形成した
後ボビンに巻き取り、パツケージ５を形成した。 Now, take 150 carbon fibers from supply package 2.
The carbon fibers were continuously fed out at a speed of mm/hour, and the halogen lamp 7 was turned on to heat the carbon fibers to about 1300°C. At the same time, adjust valves 8 and 9 to
so that benzene continuously flows into the reactor tube 3 through valve 9 at a rate of 5 c.c./min, and the inner diameter of reaction tube 3 is approximately 3 mm.
A coating layer of easily graphitized carbon was formed on the carbon fiber by thermally decomposing benzene and then wound around a bobbin to form a package 5.
パツケージ２の炭素繊維が全部繰り出された
後、ハロゲンランプ７をキセノンアークランプに
取り替え、また反応管３内をアルゴン雰囲気に変
換した後、こんどはモーター４を逆転させてパツ
ケージ５を形成している被覆炭素繊維を40mm／時
の速度で連続的に繰り出し、同様に逆転させたモ
ーター１によつてパツケージ２を形成していたボ
ビンに巻き取りながらキセノンアークランプの輻
射エネルギーを利用して被覆輻射エネルギーを約
3000℃に加熱し、前工程で炭素繊維に被覆した易
グラフアイト化炭素をグラフアイト化した。 After all the carbon fibers in the package 2 have been unwound, the halogen lamp 7 has been replaced with a xenon arc lamp, and the inside of the reaction tube 3 has been changed to an argon atmosphere, and then the motor 4 is reversed to form the package 5. The coated carbon fibers are continuously fed out at a speed of 40 mm/hour, and coated with radiant energy using the radiant energy of the xenon arc lamp while being wound around the bobbin forming the package 2 by the motor 1 which is also reversed. Approximately
The easily graphitized carbon coated on the carbon fibers in the previous step was heated to 3000°C to graphitize it.
かくして得られた高導電性繊維は約45μｍの直
径をもち、電導度は約1.5×104S／cmであつた。
また、002面の面間隔は約3.362Åであつた。ちな
みに、基材として使用した上記炭素繊維の電導度
は約1.1×103S／cmであり、また002面の面間隔は
約3.392Åである。 The highly conductive fiber thus obtained had a diameter of about 45 μm and an electrical conductivity of about 1.5×10 4 S/cm.
Furthermore, the interplanar spacing of the 002 plane was approximately 3.362 Å. Incidentally, the electrical conductivity of the carbon fiber used as the base material is approximately 1.1×10 3 S/cm, and the spacing between the 002 planes is approximately 3.392 Å.
実施例 ２
炭化水素としてシアノアセチレンを使用したほ
かは実施例１と全く同様にして、この発明の方法
による高導電性繊維を得た。得られた高導電性繊
維の直径は約62μｍであり、電導度は約1.7×104
であつた。また、002面の面間隔は約3.357Åであ
つた。Example 2 Highly conductive fibers were obtained by the method of the present invention in exactly the same manner as in Example 1, except that cyanoacetylene was used as the hydrocarbon. The diameter of the obtained highly conductive fibers is approximately 62 μm, and the electrical conductivity is approximately 1.7×10 4
It was hot. Furthermore, the interplanar spacing of the 002 plane was approximately 3.357 Å.
実施例 ３
実施例１で得られた高導電性繊維を発煙硝酸に
約60分間晒し、硝酸をインターカレーシヨンした
ところ、電導度が約1.7×105と大きく向上した。Example 3 When the highly conductive fiber obtained in Example 1 was exposed to fuming nitric acid for about 60 minutes to intercalate the nitric acid, the electrical conductivity was greatly improved to about 1.7×10 5 .
実施例 ４
実施例２で得られた高導電性繊維を実施例３と
同様にインターカレーシヨンしたところ、電導度
が約1.9×105になつた。Example 4 When the highly conductive fiber obtained in Example 2 was intercalated in the same manner as in Example 3, the conductivity was approximately 1.9×10 5 .
実施例 ５
炭素繊維として東レ株式会社製炭素繊維“トレ
カ”Ｔ−300（マルチフイラメント、フイラメント
数：600本、平均単糸径：約6μｍ）を使用し、ま
たその繰出速度を300mm／時とし、反応管３内の
真空度を約１mmHgとし、易グラフアイト化炭素
の被覆層の形成を繰り返し４回行つたほかは実施
例２と同様にして高導電性繊維を得た。この高導
電性繊維は、約43μｍの単糸径をもち、電導度は
約1.8×104S／cmであつた。また、002面の面間隔
は約3.356Åであつた。単糸同士の結着はほとん
ど認められなかつた。Example 5 Carbon fiber "Torayca" T-300 manufactured by Toray Industries, Inc. (multifilament, number of filaments: 600, average single fiber diameter: approximately 6 μm) was used as the carbon fiber, and the feeding speed was 300 mm/hour. Highly conductive fibers were obtained in the same manner as in Example 2, except that the degree of vacuum in the reaction tube 3 was set to about 1 mmHg, and the coating layer of easily graphitized carbon was repeatedly formed four times. This highly conductive fiber had a single thread diameter of about 43 μm and an electrical conductivity of about 1.8×10 4 S/cm. Furthermore, the interplanar spacing of the 002 plane was approximately 3.356 Å. Almost no binding between single yarns was observed.
実施例 ６
実施例５による高導電性繊維を実施例３，４と
同様にインターカレーシヨンしたところ、電導度
が約2.0×105S／cmと大きく向上した。Example 6 When the highly conductive fiber according to Example 5 was intercalated in the same manner as in Examples 3 and 4, the conductivity was greatly improved to about 2.0×10 5 S/cm.
実施例 ７
図面において、反応管３内に、弁９を介してシ
アノアセチレンを10c.c.／分の速度で、また弁１０
を介して水素を40c.c.／分の速度で、さらに弁１１
を介してアルゴンを950c.c.／分の速度でそれぞれ
導入しながら、反応管３内を常圧に保ち、易グラ
フアイト化炭素の被覆層形成時の加熱温度を約
1500℃としたほかは実施例２と全く同様にして高
導電性繊維を得た。Example 7 In the drawing, cyanoacetylene is introduced into reaction tube 3 through valve 9 at a rate of 10 c.c./min and through valve 10.
through valve 11 at a rate of 40 c.c./min.
While introducing argon at a rate of 950 c.c./min through the tubes, the inside of the reaction tube 3 was kept at normal pressure, and the heating temperature for forming the coating layer of easily graphitized carbon was set to about
Highly conductive fibers were obtained in exactly the same manner as in Example 2 except that the temperature was 1500°C.
この高導電性繊維は、約49μｍの直径をもち、
電導度は約1.8×104S／cmであつた。また、002面
の面間隔は約3.356Åであつた。 This highly conductive fiber has a diameter of approximately 49 μm,
The conductivity was approximately 1.8×10 4 S/cm. Furthermore, the interplanar spacing of the 002 plane was approximately 3.356 Å.
比較例 １
第１段処理のモノマー堆積時の温度を1700℃と
した以外は、実施例１と同様の方法を用いてグラ
フアイト繊維を作成した。Comparative Example 1 Graphite fibers were produced using the same method as in Example 1, except that the temperature during monomer deposition in the first stage treatment was 1700°C.
得られた繊維の電導度は6.8×103S／cmであつ
た。すなわちこの電導度は実施例１と比較すると
約半分であり、これは堆積時の温度が高過ぎるた
めと考えられる。 The electrical conductivity of the obtained fiber was 6.8×10 3 S/cm. That is, this electrical conductivity is about half that of Example 1, and this is thought to be due to the temperature during deposition being too high.
比較例 ２
第１段処理のモノマー堆積時の温度を2000℃と
した以外は、実施例２と同様の方法を用いてグラ
フアイト繊維を作成した。Comparative Example 2 Graphite fibers were produced using the same method as in Example 2, except that the temperature during monomer deposition in the first stage treatment was 2000°C.
得られた繊維の電導度は7.9×103S／cmであつ
た。すなわちこの電導度は実施例２と比較すると
約半分であり、これは堆積時の温度が高過ぎるた
めと考えられる。 The electrical conductivity of the obtained fiber was 7.9×10 3 S/cm. That is, this conductivity is about half that of Example 2, and this is thought to be due to the temperature during deposition being too high.
［発明の効果］
この発明は、炭素繊維に対するCVD法による
易グラフアイト化炭素の被覆層の形成に輻射エネ
ルギーを使用するものであるからして、炭素繊維
に直接通電してそれを加熱する従来の方法の欠点
であつた、繊維軸方向における温度分布の発生を
防止することができ、局部的な加熱による炭素繊
維の切断を防止することができる。しかも、輻射
エネルギーの利用により炭素繊維のみを選択的に
加熱することができるようになり、電熱加熱炉等
による外部加熱による方法のように炉壁などに易
グラフアイト化炭素が付着して炉を汚す心配がな
い。またはまた、炭化水素の効率的使用が可能で
あるということでもある。[Effects of the Invention] Since the present invention uses radiant energy to form a coating layer of easily graphitized carbon on carbon fibers by the CVD method, it is different from the conventional method of heating carbon fibers by directly applying electricity to them. It is possible to prevent the occurrence of temperature distribution in the fiber axis direction, which was a drawback of the method described above, and it is possible to prevent carbon fibers from being cut due to localized heating. Furthermore, by using radiant energy, it is now possible to selectively heat only the carbon fibers, and unlike external heating methods such as electric heating furnaces, easily graphitized carbon adheres to the furnace walls, causing the furnace to deteriorate. No need to worry about getting it dirty. Alternatively, it also means that hydrocarbons can be used efficiently.
また、この発明の方法によれば、電導度が高
く、しかも軽量な高導電性繊維を得ることができ
る。そのため、これを、たとえば送電線として使
用すれば、支柱の荷重が軽減され、架設費が低減
できる。そればかりか、特に外皮層の電導度が高
いことから、表皮効果が現われる交流用送電線と
して使用してもエネルギー損失が少ない。また、
軽量であることは、重量軽減効果の大きい航空機
用電線としても好適である。 Further, according to the method of the present invention, it is possible to obtain highly conductive fibers that have high conductivity and are lightweight. Therefore, if this is used, for example, as a power transmission line, the load on the support can be reduced and construction costs can be reduced. Moreover, since the conductivity of the outer skin layer is particularly high, there is little energy loss even when used as an AC power transmission line where the skin effect appears. Also,
Being lightweight, it is also suitable as an aircraft electric wire, which has a large weight reduction effect.
さらに、この発明の方法によつて得られる高導
電性繊維は、本質的に炭素からなるものであるか
ら、高温に耐え、しかも耐食性が高い。したがつ
て、たとえば蓄電池や燃料電池の極板材料として
も適している。 Furthermore, since the highly conductive fibers obtained by the method of the present invention are essentially composed of carbon, they can withstand high temperatures and have high corrosion resistance. Therefore, it is also suitable as an electrode plate material for storage batteries and fuel cells, for example.
図面は、この発明の方法を実施している様子を
示す概略工程図である。
１：モーター、２：パツケージ、３：反応管、
４：モーター、５：パツケージ、６：回転楕円面
鏡、７：ハロゲンランプ（輻射エネルギー源）、
８：弁、９：弁、１０：弁、１１：弁。
The drawings are schematic process diagrams showing how the method of the present invention is carried out. 1: Motor, 2: Package, 3: Reaction tube,
4: Motor, 5: Package, 6: Spheroidal mirror, 7: Halogen lamp (radiant energy source),
8: Valve, 9: Valve, 10: Valve, 11: Valve.
Claims (1)
とする高導電性繊維の製造方法において、供給繊
維パツケージ、および巻き取り繊維パツケージを
含む系全体を密閉系に保ち、加熱部分を石英管と
し、輻射エネルギーを集光する加熱手段を設けた
反応装置を用いて、第１段処理として、炭素繊維
を、モーターを用いて繰り出して、ベンゼンまた
はシアノアセチレンを1100〜1500℃で熱分解する
ことによつて化学気相蒸着法により易グラフアイ
ト化炭素の被覆層を形成して巻き取り、次いで第
２段処理として、パツケージの巻き戻しを行い、
前記被覆炭素繊維を2500℃以上の温度に加熱する
ことを特徴とする高導電性繊維の製造方法。 ２ 第１段処理のベンゼンまたはシアノアセチレ
ンの圧力が、0.5〜100mmHgの範囲であることを
特徴とする特許請求の範囲第１項記載の高導電性
繊維の製造方法。[Claims] 1. In a method for producing highly conductive fibers using carbon fiber as a substrate and graphite as an outer skin layer, the entire system including a supply fiber package and a wound fiber package is kept in a closed system, and the heated part Using a reaction device equipped with a quartz tube and a heating means for concentrating radiant energy, in the first stage of treatment, carbon fibers are fed out using a motor and heated with benzene or cyanoacetylene at 1100 to 1500°C. By decomposition, a coating layer of easily graphitized carbon is formed by chemical vapor deposition and then wound, and as a second stage process, the package is unwound.
A method for producing highly conductive fibers, comprising heating the coated carbon fibers to a temperature of 2500°C or higher. 2. The method for producing highly conductive fibers according to claim 1, wherein the pressure of benzene or cyanoacetylene in the first stage treatment is in the range of 0.5 to 100 mmHg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13913085A JPS626973A (en) | 1985-06-27 | 1985-06-27 | Production of highly conductive fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13913085A JPS626973A (en) | 1985-06-27 | 1985-06-27 | Production of highly conductive fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS626973A JPS626973A (en) | 1987-01-13 |
| JPH0536533B2 true JPH0536533B2 (en) | 1993-05-31 |
Family
ID=15238223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13913085A Granted JPS626973A (en) | 1985-06-27 | 1985-06-27 | Production of highly conductive fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS626973A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09218856A (en) * | 1996-02-09 | 1997-08-19 | Nec Corp | Portable input/output device |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07111028B2 (en) * | 1986-07-01 | 1995-11-29 | 大塚化学株式会社 | Conductive fiber and manufacturing method thereof |
| JPH07111027B2 (en) * | 1986-07-01 | 1995-11-29 | 大塚化学株式会社 | Highly conductive fiber manufacturing method |
| JPH01272866A (en) * | 1987-07-17 | 1989-10-31 | Mitsubishi Corp | Production of graphite fiber treated with bromine |
| JPH02210060A (en) * | 1988-03-30 | 1990-08-21 | Agency Of Ind Science & Technol | Production of highly graphitized yarn |
| JPH05125660A (en) * | 1991-10-29 | 1993-05-21 | Shin Etsu Chem Co Ltd | Thermally decomposed carbon composite material and heat insulating material for high-temperature furnace |
| JP2011138703A (en) * | 2009-12-28 | 2011-07-14 | Denso Corp | Electric conduction wire and its manufacturing method |
| CN106128608B (en) * | 2016-08-24 | 2017-10-20 | 宁波华众和创工业设计有限公司 | A kind of high-strength flexible fireproof cable and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59187622A (en) * | 1983-04-05 | 1984-10-24 | Agency Of Ind Science & Technol | Graphite filament having high electrical conductivity and its preparation |
-
1985
- 1985-06-27 JP JP13913085A patent/JPS626973A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59187622A (en) * | 1983-04-05 | 1984-10-24 | Agency Of Ind Science & Technol | Graphite filament having high electrical conductivity and its preparation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09218856A (en) * | 1996-02-09 | 1997-08-19 | Nec Corp | Portable input/output device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS626973A (en) | 1987-01-13 |
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