JP2557985B2 - Curl-shaped pitch-based carbon fiber and method for producing the same - Google Patents
Curl-shaped pitch-based carbon fiber and method for producing the sameInfo
- Publication number
- JP2557985B2 JP2557985B2 JP1226511A JP22651189A JP2557985B2 JP 2557985 B2 JP2557985 B2 JP 2557985B2 JP 1226511 A JP1226511 A JP 1226511A JP 22651189 A JP22651189 A JP 22651189A JP 2557985 B2 JP2557985 B2 JP 2557985B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- pitch
- fiber
- based carbon
- producing
- 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 title claims description 73
- 239000004917 carbon fiber Substances 0.000 title claims description 73
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000835 fiber Substances 0.000 claims description 32
- 238000009987 spinning Methods 0.000 claims description 18
- 230000003287 optical effect Effects 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 5
- 238000002074 melt spinning Methods 0.000 claims 1
- 239000011295 pitch Substances 0.000 description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 4
- 239000011337 anisotropic pitch Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002303 thermal reforming Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Inorganic Fibers (AREA)
- Multicomponent Fibers (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はピッチ系炭素繊維及びその製造方法に関する
ものである。TECHNICAL FIELD The present invention relates to a pitch-based carbon fiber and a method for producing the same.
（従来の技術） 炭素繊維は、PAN系とピッチ系に大別される。現在、
工業的にはアクリロニトリルを特定条件下で焼成し製造
されているPAN系炭素繊維が主に高強度材料（HPタイ
プ）として利用されている。しかし、PAN系繊維は炭素
の含有量が低いため、焼成工程において分解ガスの発生
があり、また収率が50〜55％と低く、しかも高温におけ
る黒鉛構造が発達しにくいために、高強度品は作りやす
いが、弾性率の大きなものを作るのが困難である。(Prior Art) Carbon fibers are roughly classified into PAN type and pitch type. Current,
Industrially, PAN-based carbon fibers produced by firing acrylonitrile under specific conditions are mainly used as high-strength materials (HP type). However, since PAN fiber has a low carbon content, decomposition gas is generated in the firing process, the yield is low at 50 to 55%, and the graphite structure at high temperatures is hard to develop, so it is a high strength product. Is easy to make, but it is difficult to make one with a large elastic modulus.
一方、ピッチ系炭素繊維は、石炭、石油などのピッチ
を原料としているため、紡糸した繊維中の炭素含有量が
95％程度と高く、また収率も80〜85％と高く、しかも物
性面では大きな弾性率の発現に優れた特徴があるため、
急速に開発が進められて来た。On the other hand, pitch-based carbon fibers are made from pitch such as coal and petroleum, so the carbon content in the spun fiber is
High as high as 95%, yield as high as 80-85%, and in terms of physical properties, it has the characteristics of exhibiting a large elastic modulus.
Development has proceeded rapidly.
又ピッチ系炭素繊維でも、ピッチをそのまま溶融紡糸
し焼成すると、光学的等方性の炭素繊維が出来、いわゆ
る汎用系タイプ（GP品）の炭素繊維として安価で一定強
度が得られるとして構造物の補強材などに利用されてい
る。光学的異方性（メソフェース）をもつ炭素繊維は、
全面結晶性のピッチを紡糸することによって、紡糸時の
剪断応力場で液晶配列が繊維軸方向の配列となり、これ
を炭化することによって巨大黒鉛結晶が生成され、高弾
性率をもつ（HMタイプ）炭素繊維となるものである。Also for pitch-based carbon fibers, if the pitch is directly melt-spun and fired, optically isotropic carbon fibers can be produced, and it is possible to obtain a so-called general-purpose type (GP product) carbon fiber at a low cost and with a certain strength. It is used as a reinforcing material. Carbon fiber with optical anisotropy (mesoface) is
By spinning the pitch of all-crystallinity, the liquid crystal alignment becomes the alignment of the fiber axis direction in the shear stress field at the time of spinning, and by carbonizing this, a huge graphite crystal is generated and has a high elastic modulus (HM type) It becomes a carbon fiber.
したがって、これらのそれぞれの特徴に適合した製品
応用が進められ、炭素繊維単体としてはフィルター、触
媒、電磁遮蔽材などに用いられ、複合体としては樹脂、
金属、炭素、セラミックスなどのマトリックスに対して
補強材料として用いられ、宇宙、航空用、レジャー、ス
ポーツ用、産業用などに広範に利用されている。Therefore, application of products suitable for each of these characteristics is promoted, carbon fiber simple substance is used for filters, catalysts, electromagnetic shielding materials, etc.
It is used as a reinforcing material for matrices of metals, carbon, ceramics, etc., and is widely used for space, aviation, leisure, sports, industrial, and the like.
最近ではエンジニアリングプラスチックと複合して、
電子部品、自動車部品や構造材料にするための研究が進
められている。Recently, in combination with engineering plastics,
Research is progressing into electronic parts, automobile parts, and structural materials.
（発明が解決しようとする課題） しかし、これらの炭素繊維を複合材料として使用した
場合、熱可塑性プラスチックは延性材料であり、補強繊
維である炭素繊維は、引張強さ、弾性率は大きいが、延
伸性が低いため、脆性材料としての挙動を示すので、ク
ラックが一旦発生すると、そのまま最終破壊まで進んで
大きな事故につながりやすく、危険なため、破壊靭性を
いかに高めるかが大きな問題となっている。そして、こ
れらの炭素繊維強化プラスチックが破壊する要因は、マ
トリックスの破壊、マトリックスと繊維の剥離、繊維の
破断、繊維の引き抜け等があげられ、実際の破壊ではこ
れらの組み合わせによるものと考えられる。しかし、中
でも炭素繊維とプラスチックの間の剥離と繊維の引き抜
けが大きな要因をしめている。まして炭素繊維複合体と
して弾性体として使用することはほとんど不可能であっ
た。(Problems to be solved by the invention) However, when these carbon fibers are used as a composite material, the thermoplastic resin is a ductile material, and the carbon fibers as the reinforcing fibers have high tensile strength and elastic modulus, Since it exhibits a behavior as a brittle material due to its low stretchability, once cracks occur, it is easy to proceed to final fracture and lead to a major accident, which is dangerous. . The factors that cause the destruction of these carbon fiber reinforced plastics include the destruction of the matrix, the separation of the matrix and the fibers, the fracture of the fibers, the withdrawal of the fibers, and the like. However, the peeling between the carbon fiber and the plastic and the pulling out of the fiber are major factors. Furthermore, it was almost impossible to use as a carbon fiber composite as an elastic body.
その理由は、炭素繊維が直線性の高い材料であるこ
と、表面がなめらかで界面での接合性に問題があること
などが考えられる。It is considered that the reason is that the carbon fiber is a material having high linearity and that the surface is smooth and there is a problem in bondability at the interface.
又、炭素繊維を単体で使用する場合、フィルター、触
媒など一定体積内に、より多くの表面積と、より多くの
空間部を設ける必要がある。従来の炭素繊維は直線的な
ものであるため、網として織るか、マット状につみ上げ
て、空間部を作るためのバインダーを用いて成形してい
た。網は平面的に織られたものを重ね合わせても空間部
を一定に保つことがむずかしく、立体構造で一定のすき
まを設けた構造体にすることは大変困難であった。まし
て、弾力構造を必要とする用途においては全く利用する
ことが出来なかった。When using carbon fiber alone, it is necessary to provide more surface area and more space within a certain volume such as a filter and a catalyst. Since conventional carbon fibers are linear, they have been woven as a net or picked up in a mat shape and formed using a binder for forming a space. It was difficult to keep the space constant even when the nets were woven flatly, and it was very difficult to make a net structure with a constant gap. Furthermore, it could not be used at all in applications requiring an elastic structure.
そこで本発明は従来の炭素繊維のもつ断面構造とは異
なった構造を有し、従来の炭素繊維では解決できないか
さ高さや弾力性、伸縮性をもち、かつ複合体として柔軟
なマトリックス材との適合性の良いピッチ系炭素繊維及
びその製造方法を提供しようとするものである。Therefore, the present invention has a structure different from the cross-sectional structure of conventional carbon fibers, has bulkiness, elasticity and stretchability that cannot be solved by conventional carbon fibers, and is compatible with a matrix material that is flexible as a composite. It is intended to provide a pitch-based carbon fiber having good properties and a method for producing the same.
（課題を解決するための手段） 上記課題を解決するための本発明のピッチ系炭素繊維
は、繊維横断面において一部が気孔を有しない緻密な光
学的等方性の炭素繊維、残部が気孔を有しない緻密な光
学的異方性の炭素繊維で構成され、且つ繊維方向にカー
ルされていることを特徴とするものである。(Means for Solving the Problem) The pitch-based carbon fiber of the present invention for solving the above-mentioned problem is a dense optically isotropic carbon fiber in which a part of the fiber cross-section does not have pores, and the rest is pores. It is characterized in that it is composed of a dense and optically anisotropic carbon fiber that does not have a curl and is curled in the fiber direction.
また上記ピッチ系炭素繊維を作る本発明の製造方法
は、光学的等方性のピッチと光学的異方性のピッチとを
別々に紡糸装置に供給してシースコアー型紡糸孔より一
緒に溶融紡糸し、次に不融化処理し、次いで焼成するこ
とを特徴とするものである。Further, the production method of the present invention for producing the above pitch-based carbon fiber is such that an optically isotropic pitch and an optically anisotropic pitch are separately supplied to a spinning device and melt-spun together from a sheath core type spinning hole. Then, it is infusibilized and then fired.
（作用） 上述の如く本発明のピッチ系炭素繊維は、繊維横断面
において一部が気孔を有しない緻密な光学的等方性の炭
素繊維、残部が気孔を有しない緻密な光学的異方性の炭
素繊維で構成されていて、光学的等方性の炭素繊維の収
縮が大きく、光学的異方性の炭素繊維の収縮が小さい為
に、繊維方向に或る曲率でカールされている。従って、
かさ高さがあり、弾力性、伸縮性を備えているので、従
来のように網を編織するとか、マット状に積み上げるこ
となく、フィルター、触媒等を製作できる。また複合体
の製作に用いた際、柔軟なマトリックス材との適合性が
良いので、ピッチ系炭素繊維とマトリックス材との剥離
が起こりにくいものである。(Operation) As described above, the pitch-based carbon fiber of the present invention is a dense optically isotropic carbon fiber having a part of which has no pores in the cross section of the fiber, and the rest of which has a dense optical anisotropy. The optical isotropic carbon fiber has a large shrinkage and the optically anisotropic carbon fiber has a small shrinkage, so that it is curled with a certain curvature in the fiber direction. Therefore,
Since it is bulky and has elasticity and stretchability, it is possible to manufacture filters, catalysts, etc. without knitting or weaving nets or stacking them in a mat shape as in the past. Further, when it is used for producing a composite, it has good compatibility with a flexible matrix material, so that the peeling between the pitch-based carbon fiber and the matrix material does not easily occur.
また前述の本発明のピッチ系炭素繊維の製造方法によ
れば、上記特徴を有するピッチ系炭素繊維を容易に製造
でき、しかも繊維横断面における光学的等方性の炭素繊
維と光学的異方性の炭素繊維の比率及び配向の異なる種
々のピッチ系炭素繊維を製造することも容易である。Further, according to the method for producing a pitch-based carbon fiber of the present invention described above, the pitch-based carbon fiber having the above characteristics can be easily produced, and the optically isotropic carbon fiber and the optical anisotropy in the fiber cross section can be obtained. It is also easy to produce various pitch-based carbon fibers having different ratios and orientations of the carbon fibers.
（実施例） 以下本発明の実施例を説明する。(Examples) Examples of the present invention will be described below.
本発明による炭素繊維は、その出発原料に芳香族六員
環構造をその分子内に多くもった重質油、一般には石炭
タール、石油分解タールおよびスチームクラッカーター
ルなどが用いられる。これらの原料の中から純度、化学
組成の点で最適なものを選択するか、要求に合わない場
合は溶媒抽出や熱改質などの前処理を施す。次に一次熱
処理により、ピッチ中に含まれるフリーカーボン、鉱物
質の微粒、微小固形物が十分吸着されるだけのメソカー
ボン微小球体を生成せしめたあと、これを抽出濾過で除
去する。この濾液を濃縮して得られたピッチを、さらに
二次熱処理にかけ重縮合化させると同時に、軽質分を除
いて、光学的に等方性のピッチを得る。The starting material of the carbon fiber according to the present invention is a heavy oil having a large amount of aromatic six-membered ring structure in its molecule, such as coal tar, petroleum cracking tar and steam cracker tar. From these raw materials, the optimum one in terms of purity and chemical composition is selected, or if it does not meet the requirements, pretreatment such as solvent extraction or thermal reforming is performed. Next, a primary heat treatment is performed to generate mesocarbon microspheres that are sufficient to adsorb free carbon, fine particles of minerals, and fine solids contained in the pitch, and then these are removed by extraction filtration. The pitch obtained by concentrating the filtrate is further subjected to a secondary heat treatment for polycondensation, and at the same time, a light component is removed to obtain an optically isotropic pitch.
一方、光学的異方性ピッチは、ピッチを２〜３倍量に
テトラヒドロキノリンで稀釈し、400〜450℃の温度で、
10〜30kgf/cm2の自生圧下で溶媒水添する。これを濾過
して、フリーカーボンなどを十分除いたあと、脱溶媒す
る。最後に450〜500℃の温度で熱処理して光学的異方性
（メソフェース）のピッチを得る。On the other hand, the optically anisotropic pitch is prepared by diluting the pitch with tetrahydroquinoline in an amount of 2 to 3 times, and at a temperature of 400 to 450 ° C.
Hydrogenate the solvent under autogenous pressure of 10 to 30 kgf / cm 2 . This is filtered to sufficiently remove free carbon and the like, and then the solvent is removed. Finally, heat treatment is performed at a temperature of 450 to 500 ° C. to obtain an optically anisotropic (mesophase) pitch.
こうして得た光学的等方性ピッチと、光学的異方性ピ
ッチでは炭素繊維化した場合の性質が異なっている。一
般に光学的等方性ピッチを紡糸し、炭素繊維化すると、
炭化後の繊維内黒鉛結晶は微細なものとなり、繊維軸方
向配列が悪くなるため、汎用タイプ（GP品）と呼ばれ、
引張強さは100kg/mm2、弾性率5ton/mm2前後が一般的で
ある。光学的異方性の場合、原料ピッチの調製はもちろ
んであるが、特に高強度高弾性炭素繊維を得るために
は、分子の配向制御が重要であり、紡糸時の温度、ノズ
ル形状、液晶ピッチ特有の分子配向制御が影響する。よ
ってその条件で機械的特性も幅があり、現在得られてい
る炭素繊維の引張強さは300〜500kg/mm2、弾性率30〜70
ton/mm2である。The optically isotropic pitch thus obtained and the optically anisotropic pitch have different properties when made into carbon fiber. Generally, when an optically isotropic pitch is spun into carbon fiber,
It is called a general-purpose type (GP product) because the graphite crystals in the fiber after carbonization become fine and the alignment in the fiber axis direction deteriorates.
Tensile strength is generally 100 kg / mm 2 and elastic modulus is around 5 ton / mm 2 . In the case of optical anisotropy, it is of course necessary to adjust the raw material pitch, but in order to obtain high-strength and high-elasticity carbon fiber, it is important to control the molecular orientation, and the temperature during spinning, the nozzle shape, the liquid crystal pitch The specific molecular orientation control has an effect. Therefore, the mechanical properties have a wide range under that condition, and the tensile strength of the carbon fiber currently obtained is 300 to 500 kg / mm 2 , and the elastic modulus is 30 to 70.
It is ton / mm 2 .
又、光学的等方性の炭素繊維は熱膨脹率は1000℃で４
×10-6／Koに対して、光学的異方性の炭素繊維は２×10
-6／Koと半分の熱膨脹係数である。Also, the optical expansion coefficient of optically isotropic carbon fiber is 4 at 1000 ℃.
Carbon fiber with optical anisotropy is 2 × 10 with respect to × 10 -6 / K o
The coefficient of thermal expansion is half that of -6 / K o .
本発明は上述のように著しく異なる双方のピッチを組
み合わせることによって全く新しい特性をもったカール
状炭素繊維を作り出したものである。The present invention creates curled carbon fibers with entirely new properties by combining both pitches which are significantly different as described above.
以下本発明の具体的な実施例について説明する。 Specific examples of the present invention will be described below.
炭素繊維の出発原料として、コールタールピッチを用
い、不活性ガス雰囲気下で400℃の温度で加熱し、フリ
ーカーボン、微小固形物を濾過して、この炉液をさらに
濃縮して得られたピッチを400℃で二次熱処理をして重
縮合化させると同時に、軽質分を除いて得た光学的等方
性ピッチ（軟化点232℃）と、この光学的等方性ピッチ
を約３倍量にテトラヒドロキノリンで稀釈し、430℃の
温度、20kgf/cm2の圧力下で水添し、これを濾過してフ
リーカーボンなど除いたあと脱溶媒し、さらに470℃の
温度で熱処理して得られた光学的異方性ピッチ（軟化点
267℃）を、それぞれ別々に第１図に示す紡糸装置に供
給して、光学的等方性ピッチを流路１の外周側の流路２
に通しそれぞれの導入路３、４を通じて吐出孔５、６に
流入して溶融紡糸し、巻取速度100m/minで紡糸ドラムに
巻き取った。Pitch obtained by using coal tar pitch as a starting material for carbon fiber, heating it at a temperature of 400 ° C. in an inert gas atmosphere, filtering free carbon and fine solids, and further concentrating the furnace liquid. Is subjected to a second heat treatment at 400 ° C for polycondensation, and at the same time, the optical isotropic pitch (softening point 232 ° C) obtained by removing light components and this optical isotropic pitch are about three times as much. Is diluted with tetrahydroquinoline, hydrogenated at a temperature of 430 ° C and a pressure of 20 kgf / cm 2 , filtered to remove free carbon, desolvated, and then heat treated at a temperature of 470 ° C. Optically anisotropic pitch (softening point
267 ° C.) separately to the spinning device shown in FIG.
The melt was spun into the discharge holes 5 and 6 through the respective introduction passages 3 and 4 and was wound on a spinning drum at a winding speed of 100 m / min.
その後320℃×10minで不融化処理を施した上、焼成炉
にて1000℃、及び2600℃にて焼成した。Then, after infusibilizing treatment was performed at 320 ° C. for 10 minutes, firing was performed at 1000 ° C. and 2600 ° C. in a firing furnace.
この状態での横断面は第２図に示す如く光学的等方性
の炭素繊維７の周囲から半周ほどつつむように光学的異
方性の炭素繊維８が接合されて一本の炭素繊維９を構成
している。そして直径10μｍで、カールした曲率約3mm
φ〜5mmφ程度で、繊維軸方向にあみ上げられた状態に
なった繊維の束は、繊維軸方向に対して約200％の伸縮
性を示し、又、ランダムにまるめられた状態でその体積
を90％圧縮したときの圧縮復元率は100％であることが
確認出来た。As shown in FIG. 2, the cross section in this state is composed of a single carbon fiber 9 by joining the optically anisotropic carbon fiber 7 and the optically anisotropic carbon fiber 8 so as to wrap around the circumference about half way. are doing. And with a diameter of 10 μm, a curled curvature of about 3 mm
A bundle of fibers that has been rolled up in the fiber axis direction at about φ to 5 mmφ shows elasticity of about 200% in the fiber axis direction, and the volume of the bundle is randomly rounded. It was confirmed that the compression decompression rate at 90% compression was 100%.
又、ランダムにまとめた状態のものを容器内に入れる
と、網状又はマット状にしなくても、繊維の弾力性で固
定されるため濾過用フィルターなどにそのままの状態で
使用出来ることが確認出来た。In addition, it was confirmed that when the randomly packed state is put in a container, it can be used as it is for a filter for filtration because it is fixed by the elasticity of the fiber without forming a mesh or mat shape. .
又、弾力性のあるプラスチック材料との複合体を作る
ことによって従来不可能であったゴム状の炭素繊維複合
体が出来、耐摩耗性が強くかつ、弾力性のあるパッキン
等が製作できた。Further, by forming a composite with an elastic plastic material, a rubber-like carbon fiber composite, which has been impossible in the past, can be produced, and a packing having high abrasion resistance and elasticity can be manufactured.
尚、本発明のピッチ系炭素繊維の製造方法に於いて、
紡糸装置の紡糸孔先端の紡糸口断面形状を種々変えたも
のを用いてピッチ系炭素繊維を製造すれば、第３図ａ〜
ｇに示す如く繊維横断面における光学的等方性の炭素繊
維７と光学的異方性の炭素繊維８の比率及び配向の異な
る種々のピッチ系炭素繊維９が得られる。Incidentally, in the method for producing the pitch-based carbon fiber of the present invention,
When pitch-based carbon fibers are manufactured by using various spinning mouth cross-sectional shapes at the tip of the spinning hole of the spinning device, FIG.
As shown in g, various pitch-based carbon fibers 9 having different ratios and orientations of the optically isotropic carbon fibers 7 and the optically anisotropic carbon fibers 8 in the fiber cross section can be obtained.
（発明の効果） 以上の説明で判るように本発明のピッチ系炭素繊維
は、繊維横断面において一部が気孔を有しない緻密な光
学的等方性の炭素繊維、残部が気孔を有しない緻密な光
学的異方性の炭素繊維で構成されて繊維方向にカールさ
れているので、かさ高さがあり、弾力性、伸縮性を備え
ていて、従来のように網を編織するとか、マット状に積
み上げることなく、フィルター、触媒等を製作できる。
また複合材の製作に用いた際、柔軟なマトリックス材と
の適合性が良いので、ピッチ系炭素繊維とマトリックス
材との剥離が起こりにくいものである。従って伸縮性電
導材、弾力性パッキン及びプラスチック、金属、カーボ
ンなどと複合材を作るのに極めて有用な材料となる。(Effects of the Invention) As can be seen from the above description, the pitch-based carbon fiber of the present invention is a dense optically isotropic carbon fiber in which a part of the fiber does not have pores in the cross section of the fiber, and the rest is dense without pores. As it is made of carbon fiber with optical anisotropy and curled in the fiber direction, it has bulkiness, elasticity and stretchability, and weaving a mesh as in the past, or mat-like. You can fabricate filters, catalysts, etc.
Further, when used in the production of the composite material, the compatibility with the flexible matrix material is good, and therefore the peeling between the pitch-based carbon fiber and the matrix material does not easily occur. Therefore, it is a very useful material for making a composite material with a stretchable conductive material, an elastic packing and plastic, metal, carbon and the like.
また本発明のピッチ系炭素繊維の製造方法によれば、
上記の優れた効果を有するピッチ系炭素繊維を容易に製
造でき、しかも紡糸装置の紡糸孔先端の紡糸口断面形状
を種々変えたものを用いて製造することにより、繊維横
断面における光学的等方性の炭素繊維と光学的異方性の
炭素繊維の比率及び配向の異なる種々のピッチ系炭素繊
維を適宜製造できる。According to the pitch-based carbon fiber manufacturing method of the present invention,
The pitch-based carbon fiber having the above-mentioned excellent effects can be easily produced, and further, the optical fiber in the fiber cross section can be optically Various pitch-based carbon fibers having different ratios and orientations of the functional carbon fiber and the optically anisotropic carbon fiber can be appropriately produced.
尚、本実施例は長繊維の紡糸例を示したが、スピニン
グ法やガス圧による短繊維紡糸法によって紡糸すること
により多量に安くカールした繊維を製造することも出来
る。Although the present example shows an example of spinning a long fiber, a large amount of curled fiber can be produced at low cost by spinning by a spinning method or a short fiber spinning method by gas pressure.
第１図は本発明のピッチ系炭素繊維を製造する際に用い
られる紡糸装置を示す破断斜視図、第２図は本発明のピ
ッチ系炭素繊維の一例の横断面図、第３図ａ〜ｇは本発
明のピッチ系炭素繊維の横断面形状の種々の例を示す図
である。FIG. 1 is a cutaway perspective view showing a spinning apparatus used for producing the pitch-based carbon fiber of the present invention, FIG. 2 is a cross-sectional view of an example of the pitch-based carbon fiber of the present invention, and FIGS. FIG. 4 is a diagram showing various examples of the cross-sectional shape of the pitch-based carbon fiber of the present invention.
フロントページの続き (72)発明者 清水 進 東京都中央区日本橋茅場町２丁目６番６ 号 田中貴金属工業株式会社内 合議体 審判長 宮本 晴視 審判官 河合 厚夫 審判官 平田 和男 (56)参考文献 特開 平２−259117（ＪＰ，Ａ)Front Page Continuation (72) Inventor Susumu Shimizu 2-6-6 Nihonbashi Kayabacho, Chuo-ku, Tokyo Tanaka Kikinzoku K.K. JP-A-2-259117 (JP, A)
Claims (2)
ない緻密な光学的等方性の炭素繊維からなり、残部が気
孔を有さない緻密な光学的異方性の炭素繊維からなり、
前記繊維横断面において前記光学的異方性の部分が前記
等方性の部分の周囲を少なくとも三日月状に囲むように
して構成され、かつ、炭素繊維が繊維方向にカールされ
ていることを特徴とする、カール状ピッチ系炭素繊維。1. A cross-section of a fiber is made of a dense optically isotropic carbon fiber having no pores, and the rest is made of a dense optically anisotropic carbon fiber having no pores. ,
In the fiber cross section, the optically anisotropic portion is configured so as to surround at least a crescent shape around the isotropic portion, and the carbon fiber is curled in the fiber direction, Curl pitch carbon fiber.
性の生じるピッチとを別々に紡糸装置に供給してシース
コア型紡糸孔より一緒に溶融紡糸するに際し、前記光学
的異方性の生じるピッチを前記シースコア型紡糸孔のシ
ース部の流路に供給し前記光学的等方性の生じるピッチ
をコア部の流路に供給して溶融紡糸を行い、次にこれを
不融化処理し、次いで焼成することによって、繊維横断
面においてその一部が気孔を有さない緻密な光学的等方
性の炭素繊維からなり、残部が気孔を有さない緻密な光
学的異方性の炭素繊維からなり、前記繊維横断面におい
て前記光学的異方性の部分が前記等方性の部分の周囲を
少なくとも三日月状に囲むようにして構成され、かつ、
繊維方向にカールされてなるカール状ピッチ系炭素繊維
を得ることを特徴とする、カール状ピッチ系炭素繊維の
製造方法。2. Optically anisotropic when the pitch producing optical isotropy and the pitch producing optical anisotropy are separately supplied to a spinning device and melt-spun together through a sheath core type spinning hole. Of the sheath core of the sheath core type spinning hole is supplied to the flow path of the sheath, and the pitch of the optical isotropy is supplied to the flow path of the core to perform melt spinning. By treating and then firing, a part of the cross-section of the fiber is made of dense optically isotropic carbon fiber having no pores, and the rest is made of dense optical anisotropy having no pores. Made of carbon fiber, the optical anisotropic portion in the fiber cross section is configured to surround at least a crescent shape around the isotropic portion, and,
A method for producing a curled pitch-based carbon fiber, characterized in that a curled pitch-based carbon fiber curled in the fiber direction is obtained.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1226511A JP2557985B2 (en) | 1989-08-31 | 1989-08-31 | Curl-shaped pitch-based carbon fiber and method for producing the same |
| EP19900830386 EP0421944A3 (en) | 1989-08-31 | 1990-08-30 | Composite carbon fibre and process for preparing same |
| US07/575,955 US5188894A (en) | 1989-08-31 | 1990-08-31 | Composite carbon fiber and process for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1226511A JP2557985B2 (en) | 1989-08-31 | 1989-08-31 | Curl-shaped pitch-based carbon fiber and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0390626A JPH0390626A (en) | 1991-04-16 |
| JP2557985B2 true JP2557985B2 (en) | 1996-11-27 |
Family
ID=16846272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1226511A Expired - Lifetime JP2557985B2 (en) | 1989-08-31 | 1989-08-31 | Curl-shaped pitch-based carbon fiber and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2557985B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2951079B2 (en) | 1990-10-24 | 1999-09-20 | 興亜石油株式会社 | Method for producing coiled carbon fiber bundle |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5183603A (en) * | 1990-10-24 | 1993-02-02 | Koa Oil Company Limited | Process for producing a coil-shaped carbon fiber bundle |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2565769B2 (en) * | 1988-12-02 | 1996-12-18 | 株式会社ペトカ | Activated carbon fiber and manufacturing method thereof |
-
1989
- 1989-08-31 JP JP1226511A patent/JP2557985B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2951079B2 (en) | 1990-10-24 | 1999-09-20 | 興亜石油株式会社 | Method for producing coiled carbon fiber bundle |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0390626A (en) | 1991-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5188894A (en) | Composite carbon fiber and process for preparing same | |
| JP2557985B2 (en) | Curl-shaped pitch-based carbon fiber and method for producing the same | |
| JP2519042B2 (en) | Carbon-carbon composite material manufacturing method | |
| JPH0791372B2 (en) | Method for manufacturing raw material pitch for carbon material | |
| JPH0718058B2 (en) | Carbon fiber manufacturing method | |
| JPH0434019A (en) | Carbon short fiber and preparation thereof | |
| JPH0816032B2 (en) | High-strength carbon-carbon composite manufacturing method | |
| JPH0718057B2 (en) | Pitch-based fiber manufacturing method | |
| JPH0788604B2 (en) | Method for manufacturing pitch-based carbon fiber | |
| JP2786519B2 (en) | Short carbon fiber spinning device | |
| JP4601875B2 (en) | Carbon fiber manufacturing method | |
| JPS59223316A (en) | Preparation of carbon yarn having high strength and high elasticity | |
| JPH03152218A (en) | Pitch conjugate carbon fiber and production thereof | |
| EP0172955B1 (en) | A method for producing a precursor pitch for carbon fiber | |
| JPS6264889A (en) | Purification of pitch | |
| JPS6175820A (en) | Manufacturing method of pitch carbon fiber | |
| JP2594907B2 (en) | Method for producing pitch carbon fiber | |
| KR100407804B1 (en) | Multi-hollow pitch carbon fiber and preparation method of the same | |
| JPH1025624A (en) | Carbon fiber and carbon fiber aggregate | |
| JPH04305060A (en) | Production of carbon fiber reinforced carbon composite material | |
| JPH1025626A (en) | Carbon fiber production method | |
| JPH0380888B2 (en) | ||
| JPH08109076A (en) | Manufacture of carbon fiber-carbon conjugate material | |
| JPS60259631A (en) | Production of pitch carbon fiber | |
| JPH1025625A (en) | Carbon fiber and carbon fiber aggregate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |