JPS62170527A - Production of pitch-based carbon fiber - Google Patents
Production of pitch-based carbon fiberInfo
- Publication number
- JPS62170527A JPS62170527A JP1284886A JP1284886A JPS62170527A JP S62170527 A JPS62170527 A JP S62170527A JP 1284886 A JP1284886 A JP 1284886A JP 1284886 A JP1284886 A JP 1284886A JP S62170527 A JPS62170527 A JP S62170527A
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- shear stress
- nozzle hole
- cross
- final nozzle
- 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.)
- Granted
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 40
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 7
- 206010061592 cardiac fibrillation Diseases 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- 230000002600 fibrillogenic effect Effects 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 239000011295 pitch Substances 0.000 description 48
- 238000009987 spinning Methods 0.000 description 29
- 230000007547 defect Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 241000234282 Allium Species 0.000 description 4
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 4
- 239000011294 coal tar pitch Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- 239000011300 coal pitch Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、ピッチ系炭素繊維の製造方法に関する。[Detailed description of the invention] Industrial applications The present invention relates to a method for producing pitch-based carbon fiber.
従来技術及びその問題点
ピッチ系材わｌを原料とする炭素繊維は１．ポリアクリ
ロニトリル等の有機合成繊維をプリカーサ−とする炭素
繊維に比して、主に製造コストが低い、高弾性率の製品
が得られやすい等の理由により、より安価で高性能の素
材となり得るものと期待されている。しかしながら、市
販されているピッチ系炭素繊維は、引張り強度が２００
ＫＦｌ／ｓ２程度以下であり、又品質安定性に劣り、充
分満足すべきものとは言い難い。Prior art and its problems Carbon fiber made from pitch-based material has 1. Compared to carbon fibers whose precursors are organic synthetic fibers such as polyacrylonitrile, they can be made into cheaper, higher-performance materials mainly because they have lower manufacturing costs and can easily produce products with high elastic modulus. It is expected that However, commercially available pitch-based carbon fibers have a tensile strength of 200
It is about KFl/s2 or less, and the quality stability is poor, so it is difficult to say that it is completely satisfactory.
一般に、ピッチ系炭素繊維においては、繊維断面の分子
凝集状態（以下断面高次溝道という）が、紡糸条件によ
って種々異なっている。即ち、基本的には、分子が繊維
の同心円方向に結晶を構成したり（いわゆるオニオン型
）、繊維の中心から放射状方向に結晶を構成したり（ラ
ジアル型）、或いは方向性を示すことなく任意の方向に
分布したりする（ランダム型）形態に大別されるが、実
際の繊維においては、これ等が混在したものも存在する
。更に、たて割れ、クラック、ボイド等の欠陥が繊維の
一部又は全体に存在する場合もあり、欠陥の有無を含め
れば、ピッチ系炭素繊維の断面高次構造の形態は、複雑
多岐にわたる。そして、この様な各種の欠陥及び断面高
次構造の存在が、ピッチ系炭素繊維の品質安定性を低下
させる主な原因の一つとなっている。Generally, in pitch-based carbon fibers, the state of molecular aggregation in the cross section of the fiber (hereinafter referred to as cross-sectional higher-order grooves) varies depending on the spinning conditions. That is, basically, the molecules form crystals in the concentric direction of the fiber (so-called onion type), the crystals form in the radial direction from the center of the fiber (radial type), or the molecules form crystals in the direction of the concentric circles of the fiber (so-called onion type), or the molecules form crystals in the radial direction from the center of the fiber (radial type). It is roughly divided into two types (random type) in which fibers are distributed in the direction of , but in actual fibers, there are also fibers with a mixture of these types. Furthermore, defects such as vertical cracks, cracks, and voids may be present in part or all of the fibers, and if the presence or absence of defects is included, the morphology of the cross-sectional higher-order structure of pitch-based carbon fibers is complex and diverse. The existence of such various defects and cross-sectional higher-order structures is one of the main causes of deteriorating the quality stability of pitch-based carbon fibers.
上記の如き欠陥の発生及び断面高次構造の形成は、紡糸
用ピッチの物性によっても変化するが、紡糸条件によっ
て最も大きく影響を受け、変動する。従って、炭素繊維
の品質安定性を高める為には、紡糸用ピッチの物性が若
干ばらついたとしても、常に欠陥がほとんど無く、一定
の断面高次構造を備えた炭素繊維を製造し得る紡糸技術
を確立する必要がある。即ち、たて割れ、クランク、ボ
イド等の欠陥をほとんど発生させず、且つ高引張強度を
発現するに有効な高次断面構造であるオニオン型及び／
又はランダム型構造を安定して形成させる技術が必要で
ある。Although the occurrence of defects and the formation of a cross-sectional higher-order structure as described above vary depending on the physical properties of the spinning pitch, they are most greatly influenced and fluctuated by the spinning conditions. Therefore, in order to improve the quality stability of carbon fibers, it is necessary to develop a spinning technology that can always produce carbon fibers with almost no defects and a constant cross-sectional higher-order structure, even if the physical properties of the spinning pitch vary slightly. need to be established. In other words, onion-type and/or high-order cross-sectional structures that hardly cause defects such as vertical cracks, cranks, and voids, and are effective in developing high tensile strength.
Alternatively, a technique for stably forming a random structure is required.
問題点を解決するための手段
本発明者は、上記の如き技術の現状に鑑みて鋭意研究を
重ねた結果、ピッチ系材料の溶融紡糸時に、最終ノズル
孔にいたる前に溶融ピッチ系材料をして特定形状のキャ
ピラリー部を通過させることにより一定値以上の剪断応
力を加え、次いで溶融ピッチを実質的に剪断応力を加え
ない状態に一旦保持した後、ノズル孔を通過させて紡糸
を行なう場合には、従来技術の問題点を実質的に解消若
しくは大巾に軽減し得ることを見出した。即ち、本発明
は、ピッチ系材料を溶融紡糸し、不融化し、炭化するピ
ッチ系炭素繊維の製造方法において、最終ノズル孔にい
たる前に溶融ピッチを円形、異形又はスリット型のキャ
ピラリー部を通過させることにより最終ノズル孔でうけ
る剪断応力の１／２以上の剪断応力を加えた俊、該溶融
ピッチを一旦剪断応力を実質的に加えない状態に保持し
、次いでノズル孔を通過させて紡糸することを特徴とす
るピッチ系炭素繊維の製造方法に係る。Means for Solving the Problems As a result of intensive research in view of the current state of the technology as described above, the inventor of the present invention has developed a method for spinning a molten pitch-based material before reaching the final nozzle hole during melt-spinning of the pitch-based material. When the molten pitch is passed through a capillary part of a specific shape to apply a shear stress of a certain value or more, and then after holding the molten pitch in a state where no shear stress is applied, the pitch is passed through a nozzle hole for spinning. discovered that the problems of the prior art can be substantially eliminated or greatly reduced. That is, the present invention provides a method for producing pitch-based carbon fiber in which a pitch-based material is melt-spun, infusible, and carbonized, in which the molten pitch is passed through a circular, irregularly shaped, or slit-shaped capillary section before reaching the final nozzle hole. By applying a shear stress of 1/2 or more of the shear stress received at the final nozzle hole, the molten pitch is temporarily held in a state where no shear stress is applied substantially, and then passed through the nozzle hole for spinning. The present invention relates to a method for producing pitch-based carbon fiber characterized by the following.
本発明によると、上記炭化工程で黒鉛化すればピッチ系
黒鉛繊維を製造することもできる。従って、本願明細書
において、炭化は黒鉛化を含み、炭素繊維とは黒鉛繊維
をも含むものとして用いる。According to the present invention, pitch-based graphite fibers can also be produced by graphitizing in the carbonization step. Therefore, in this specification, carbonization includes graphitization, and carbon fiber is used to include graphite fiber.
本発明においては、溶融ピッチ系材料を最終ノズル孔の
前に設けた円形、異形又はスリット型のキャピラリー部
を通過させることにより最終ノズル孔でうける剪断応力
の１／２以上の剪断応力を加えた侵、これを一旦剪断応
力を実質的に加えない状態に保持し、次いで最終ノズル
孔を通過させて紡糸することを必須とする。キャピラリ
ー部において溶融ピッチ系材料が受ける剪断応力が、最
終ノズル部での剪断応力の１／２未満で必る場合には、
所望の効果が充分に発揮されない。また、キャピラリー
方式以外の方法で、例えば、緻密な充填剤の間隙を通し
て剪断応力を加える場合にも、所望の効果は得られない
。更に、キャピラリー部で溶融ピッチ系材料に剪断応力
を加えた後、剪断応力を実質的に加えない状態に保持す
ることなく、直ちに最終ノズル孔から紡糸を行なう場合
にも、本発明の効果は発揮されない。本発明で使用する
キャピラリー部の断面の形状は、円形、スリット型（或
い長方型）、又はその他の異型（正方形、十字形、７字
形その他）のいずれであっても良い。In the present invention, a shear stress of 1/2 or more of the shear stress experienced at the final nozzle hole is applied by passing the molten pitch-based material through a circular, irregularly shaped, or slit-shaped capillary section provided in front of the final nozzle hole. It is essential to hold the fiber in a state in which no shear stress is applied to it, and then pass it through the final nozzle hole for spinning. If the shear stress that the molten pitch-based material receives in the capillary part is necessarily less than 1/2 of the shear stress in the final nozzle part,
The desired effect is not fully exerted. Further, the desired effect cannot be obtained even when shear stress is applied through a gap in a dense filler using a method other than the capillary method, for example. Furthermore, the effects of the present invention are exhibited even when spinning is performed immediately from the final nozzle hole without maintaining a state in which no shear stress is applied after shear stress is applied to the molten pitch-based material in the capillary section. Not done. The cross-sectional shape of the capillary part used in the present invention may be circular, slit-shaped (or rectangular), or other irregular shapes (square, cross-shaped, 7-shaped, etc.).
キャピラリーの断面積及び長さも、必要な剪断応力を付
加し得るものであれば良く、特に限定はされないが、通
常断面積５Ｘ１０ 〜５Ｘ１０２＃程度、長さ０．１〜
３．０廐程度である。The cross-sectional area and length of the capillary are not particularly limited as long as they can apply the necessary shear stress, but usually have a cross-sectional area of about 5 x 10 - 5 x 102 #, and a length of about 0.1 -
It is about 3.0 km.
キャピラリー部と最終ノズル孔との間で溶融ピッチに実
質的に剪断応力を加えない状態でこれを保持する時間は
、使用するピッチの種類及び性質、紡糸温度、単位時間
当りのピッチ吐出量、キャピラリー部及びノズル孔の形
状等により異なり、特に制限されるものではないが、通
常溶融ピッチがキャピラリー部を通過する時間の１０３
〜１０”程度の時間か好ましい。キャピラリー部と最終
ノズル孔との間で溶融ピッチに剪断応力を加えない為に
は、当該部分（以下応力緩和部という）をパンク外壁及
び／もしくはノズルの導入孔を除けば何ら剪断応力が働
かない様に空洞化したものとする。The time required to maintain the molten pitch in a state where no shear stress is applied to it between the capillary section and the final nozzle hole depends on the type and nature of the pitch used, the spinning temperature, the amount of pitch discharged per unit time, and the capillary. Although it is not particularly limited and varies depending on the capillary section and the shape of the nozzle hole, the time taken for the melt pitch to pass through the capillary section is usually 103
~10" is preferable. In order to avoid applying shear stress to the molten pitch between the capillary part and the final nozzle hole, the said part (hereinafter referred to as stress relaxation part) should be connected to the punctured outer wall and/or the nozzle introduction hole. It is assumed that it is hollowed out so that no shear stress is applied except for.
本発明で使用する紡糸用ピッチは、ピッチ状物質を不活
性ガス流通下に熱重縮合させることにより得られる。ピ
ッチ状物質としては、石油系ピッチ、石炭系ピッチ及び
有機化合物からの熱分解残渣ピッチのいずれであっても
良い。特にコールタールやコールタールピッチの様な石
炭系ピッチを原料とする場合には、熱重縮合に先立って
、特開昭５７−８８０１６号公報に記載の方法に従って
、予め原料ピッチを芳香族還元性溶剤により３５０〜５
００’Ｃで熱処理しておくことにより、紡糸性をより一
層改善することができるが、紡糸用ピッチとしては、紡
糸可能でおれば特に限定されない。The spinning pitch used in the present invention is obtained by thermally polycondensing a pitch-like substance under an inert gas flow. The pitch-like substance may be any of petroleum-based pitch, coal-based pitch, and pyrolysis residue pitch from organic compounds. In particular, when coal tar or coal-based pitch such as coal tar pitch is used as a raw material, the raw material pitch is subjected to aromatic reducing properties in advance according to the method described in JP-A-57-88016 prior to thermal polycondensation. 350-5 depending on solvent
The spinnability can be further improved by heat treatment at 00'C, but the pitch for spinning is not particularly limited as long as it can be spun.
本発明において使用する最終ノズル孔の断面積について
は特に制限はないが、通常５Ｘ１０−３〜１０−１ｍ！
１１２程度である。There is no particular restriction on the cross-sectional area of the final nozzle hole used in the present invention, but it is usually 5 x 10-3 to 10-1 m!
It is about 112.
本発明においては、上記の様にして得られたピンチ繊維
を常法に従って、例えば酸素雰囲気中３００〜３４０’
Ｃ程度で不融化した後、不活性ガス雰囲気中１０００〜
３０００’Ｃ程度で加熱することにより炭素繊維化する
。In the present invention, the pinch fibers obtained as described above are processed in accordance with a conventional method, for example, in an oxygen atmosphere with a length of 300 to 340'.
After infusibility at about C, 1000 ~
It is turned into carbon fiber by heating at about 3000'C.
本発明により得られる炭素繊維の断面高次構造は、その
一部もしくは全部がオニオン型構造をヱする（第１図及
び第２図参照）。一部がオニオン型構造である場合には
、内層部にオニオン型構造が存在して、外層部にランダ
ム型構造（第１図（ａ））又はラジアル型構造（第１図
（ｂ））が存在する。The cross-sectional higher-order structure of the carbon fiber obtained by the present invention has an onion-type structure in part or in whole (see FIGS. 1 and 2). If a portion has an onion-type structure, the onion-type structure exists in the inner layer and the random-type structure (Figure 1 (a)) or radial type structure (Figure 1 (b)) exists in the outer layer. exist.
発明の効果 本発明によれば以下の如き効果が奏される。Effect of the invention According to the present invention, the following effects are achieved.
（ｉ＞最終的に得られる炭素繊維は、その内部にたて割
れ、クラック、ボイド等のミクロ的欠陥をほとんど有し
ない。(i> The carbon fiber finally obtained has almost no microscopic defects such as vertical cracks, cracks, and voids inside it.
（ｉｉ）品質安定性に優れているので、原料たるピッチ
系材料の物性が若干変動したとしても、繊維断面の少な
くとも一部がオニオン型である安定した断面高次構造を
有する炭素繊維が得られる。(ii) It has excellent quality stability, so even if the physical properties of the pitch-based material used as the raw material change slightly, carbon fibers with a stable cross-sectional higher-order structure in which at least a portion of the fiber cross section is onion-shaped can be obtained. .
（ｉｉｉ ）上記（ｉ）及び（ｉｉ）の結果として、炭
素繊維の引張り強度が大巾に向上する。(iii) As a result of (i) and (ii) above, the tensile strength of carbon fibers is greatly improved.
（ｉｖ）更に、多ホールノズルを使用する紡糸時の糸切
れ頻度が低くなり、安定した連続紡糸が可能となる。(iv) Furthermore, the frequency of yarn breakage during spinning using a multi-hole nozzle is reduced, making stable continuous spinning possible.
（ｖｉ）炭素繊維の内部をオニオン構造としたまま表面
をオニオン、ランダム、ラジアルと変えることかできる
ので、安定した炭素繊維の力学物性を保持したまま、樹
脂複合体及び炭素複合体において樹脂及び炭素と良好な
接着性を待つ各種表面分子配列を選択することが出来る
。(vi) Since the surface of the carbon fiber can be changed to onion, random, or radial while keeping the inside of the carbon fiber in an onion structure, the resin and carbon Various surface molecular arrangements can be selected that provide good adhesion.
実施例
以下に参考例及び比較例と共に実施例を示し、本発明の
特徴とするところをより一層明らかにする。EXAMPLES Below, Examples will be shown together with Reference Examples and Comparative Examples to further clarify the characteristics of the present invention.
参考例１
軟化点１１０’Ｃ、キノリンネ溶分０．１８％、ベンゼ
ン不溶分３５％のコールタールピッチ１璽量部と水素化
型アンｌ−ラセン油２重用部との混合溶液をオートクレ
ーブ中で４３０’Ｃで６０分間撹拌下加熱した後、加圧
式フィルターで熱時ン濾過し、更に減圧下３００’Ｃて
水素化型アンドランセン油を除去して、還元ピッチを得
た。Reference Example 1 A mixed solution of 1 part of coal tar pitch with a softening point of 110'C, 0.18% of quinoline soluble content, and 35% of benzene insoluble content and 2 parts of hydrogenated anthracene oil was placed in an autoclave. After heating at 430'C for 60 minutes with stirring, the mixture was filtered while hot using a pressure filter, and the hydrogenated andranthene oil was removed at 300'C under reduced pressure to obtain reduced pitch.
ガス導入管、熱電対、撹拌機及び留出分除去管を備えた
反応器に上記で得られた還元ピッチ５０Ｋｇを入れ、１
覚拌下窒素ガスを導入しつつ４１０〜４８０’Ｃで低分
子生成分の除去及び熱重縮合を行なった。反応時間及び
温度の選択により得られた２種の熱重縮合ピッチの性状
を第１表にＮｏ、 １〜２として示す。50 kg of the reduced pitch obtained above was placed in a reactor equipped with a gas introduction tube, a thermocouple, a stirrer, and a distillate removal tube, and 1
Removal of low molecular weight components and thermal polycondensation were carried out at 410 to 480'C while introducing nitrogen gas under careful stirring. The properties of two types of thermally polycondensed pitches obtained by selecting reaction times and temperatures are shown in Table 1 as Nos. 1 and 2.
参考例２
水素化型アントラセン油との混合下における加熱処理を
経ることなく、参考例１と同様のコールタールピッチを
参考例１と同様にして熱重縮合反応に供した。得られた
熱重縮合ピッチの性状をＮ。Reference Example 2 The same coal tar pitch as in Reference Example 1 was subjected to a thermal polycondensation reaction in the same manner as in Reference Example 1 without undergoing heat treatment while mixing with hydrogenated anthracene oil. The properties of the obtained thermal polycondensation pitch are N.
３として第１表に示す。3 in Table 1.
第 １ 表
注：軟化点は、スイス メトラー社製軟化点測定装置に
より測定した。Table 1 Note: Softening points were measured using a softening point measuring device manufactured by Swiss Mettler.
実施例１〜３
直径０．１５ｍ、長さ０．４Ｍの細管１００本からなる
キャピラリー部、容積的１５０ｍ３の応力緩和部及び直
径０．２＃、長さ０．４Ｍのノズル（ノズル孔数１００
個）を備えた紡糸装置を使用して、参考例１及び２で得
た熱重縮合ピッチＮｏ、 １〜３を紡糸した。この紡糸
過程において、ピッチはキャピラリー部において最終ノ
ズル孔かうける剪断応力の約２５０％の剪断応力を加え
られ、次いで応力緩和で剪断応力を受けない状態におか
れ、最終ノズル孔で再び剪断応力を加えられた。Examples 1 to 3 A capillary part consisting of 100 thin tubes with a diameter of 0.15 m and a length of 0.4 M, a stress relaxation part with a volume of 150 m3, and a nozzle with a diameter of 0.2# and a length of 0.4 M (number of nozzle holes: 100).
Thermal polycondensation pitch Nos. 1 to 3 obtained in Reference Examples 1 and 2 were spun using a spinning device equipped with a spinning device. In this spinning process, the pitch is subjected to a shear stress of approximately 250% of the shear stress applied to the final nozzle hole in the capillary section, then left in a state where it is not subjected to shear stress by stress relaxation, and then subjected to shear stress again at the final nozzle hole. Added.
かくして得たピッチ繊維を空気中３００’Ｃで３０分間
不融化処理し、次いでＮ２ガス雰囲気中で１２００″Ｃ
まで加熱して炭素繊維を得た。The pitch fiber thus obtained was infusible at 300'C in air for 30 minutes, and then heated at 1200'C in N2 gas atmosphere.
Carbon fibers were obtained by heating to .
第２表に直径１０μｍのピッチ繊維を糸切れを生ずるこ
となく連続して紡糸し得る平均時間（ｈｒ）、上記で得
た炭素繊維の断面高次構造及び欠陥含有率を示す。Table 2 shows the average time (hr) in which pitch fibers with a diameter of 10 μm can be continuously spun without yarn breakage, the cross-sectional higher-order structure of the carbon fibers obtained above, and the defect content.
第 ２ 表
■
又、実施例１．２及び３で得られた炭素繊維の断面高次
構造を示す走査型電子顕微鏡写真をそれぞれ第３図（約
２６００倍）、第４図（約８０００倍）及び第５図（約
１７００倍）として示す。Table 2■ Also, scanning electron micrographs showing the cross-sectional higher-order structures of the carbon fibers obtained in Examples 1.2 and 3 are shown in Figure 3 (approximately 2600 times) and Figure 4 (approximately 8000 times), respectively. and FIG. 5 (approximately 1700 times magnification).
実施例４〜６
第３表に示す形状及び本数のキャピラリー部、容積的１
８０ｍ３の応力緩和部及び直径０．２ｍｔｎ、長さ０．
４ＩＩＩＩｎのノズル（ノズル孔数１００個）を備えた
紡糸装置を使用して、参考例って得た熱重縮合ピンチＮ
ｏ、 １を紡糸し、得られたピッチ繊維を実施例１〜３
と同様にして不融化及び炭化処理して炭素繊維を得た。Examples 4 to 6 Capillary parts having the shape and number shown in Table 3, volumetric 1
Stress relief section of 80m3, diameter 0.2mtn, length 0.
Thermal polycondensation pinch N obtained as a reference example using a spinning device equipped with a 4IIIn nozzle (100 nozzle holes)
o, 1 was spun, and the resulting pitch fibers were used in Examples 1 to 3.
Carbon fibers were obtained by infusibility and carbonization treatment in the same manner as above.
得られた炭素繊維の断面高次構造及び欠陥含有率を第３
表に示す。The cross-sectional higher-order structure and defect content of the obtained carbon fiber were
Shown in the table.
第 ３ 表
異型断面のキャピラリー部を有する紡糸装置を使用する
場合にも、欠陥がほとんど無く、内層オニオン型の断面
高次構造を有する炭素繊維が得られることが明らかであ
る。Table 3 It is clear that even when a spinning device having a capillary portion with an irregular cross section is used, carbon fibers with almost no defects and an inner layer having an onion-type cross-sectional higher-order structure can be obtained.
比較例１〜３
直径０．２簡、長ざ０．４＃のノズル（ノズル孔数１０
０個）を備えた紡糸装置を使用して、参考例１及び２で
得た熱重縮合ピッチＮｏ、 １〜３を紡糸した後、実施
例１〜３と同一条件下に不融化及び炭化処理を行なって
炭素繊維を得た。Comparative Examples 1 to 3 A nozzle with a diameter of 0.2 and a length of 0.4# (number of nozzle holes: 10)
After spinning the thermal polycondensation pitch Nos. 1 to 3 obtained in Reference Examples 1 and 2 using a spinning device equipped with Carbon fibers were obtained.
得られた炭素繊維の断面高次構造及び欠陥含有率、並び
に直径１０μｍのピッチ繊維を糸切れを生ずることなく
連続して紡糸し得る平均時間（ｈｒ）を第４表に示す。Table 4 shows the cross-sectional higher-order structure and defect content of the obtained carbon fibers, as well as the average time (hr) in which pitch fibers with a diameter of 10 μm can be continuously spun without yarn breakage.
比較例４
キャピラリー部の大きざが直径０．３＃、艮ざ０．６ｍ
ｍ（本数１００本）である以外は実施例１と同じ紡糸装
置を用いて、参考例１で得た熱重縮合ピッチＮｏ、 １
を紡糸した。この紡糸過程では、ピッチはキャピラリー
部において最終ノズル孔でうける剪断応力の約３０％の
剪断応力を加えられた。Comparative Example 4 The size of the capillary part is 0.3 # in diameter, and the width is 0.6 m.
Thermal polycondensation pitch No. 1 obtained in Reference Example 1 using the same spinning device as in Example 1 except that m (number of threads: 100)
was spun. During this spinning process, the pitch was subjected to a shear stress in the capillary section that was about 30% of the shear stress experienced at the final nozzle hole.
得られたピッチ繊維を実施例１と同一条件下に不融化及
び炭化処理を行なって炭素繊維を１ｑた。The obtained pitch fibers were subjected to infusibility and carbonization treatment under the same conditions as in Example 1 to obtain 1 q of carbon fibers.
炭素繊維の断面高次構造及び欠陥含有率を第４表に示す
。Table 4 shows the cross-sectional higher-order structure and defect content of the carbon fibers.
又本比較例で得られた炭素繊維の断面高次構造を示す走
査型電子顕微鏡写真（約２８００倍）を第６図として示
す。FIG. 6 shows a scanning electron micrograph (approximately 2800 times magnification) showing the cross-sectional higher-order structure of the carbon fiber obtained in this comparative example.
比較例５
直径０．１５ｍ、長さ０．４％の細管１００本からなる
キャピラリー部と直径０．２順、長さ０．４８のノズル
部（ノズル孔数１００個）とが実質的に直結されている
紡糸装置を使用して、参考例１で得た熱重縮合ピッチＮ
ｏ、 １を紡糸した。この紡糸過程においては、ピッチ
は、キャピラリー部において最終ノズル孔でうける剪断
応力の約２５０％の剪断応力を加えられ、次いで直ちに
最終ノズル孔で剪断応力を加えられた。Comparative Example 5 A capillary section consisting of 100 thin tubes with a diameter of 0.15 m and a length of 0.4% is substantially directly connected to a nozzle section (100 nozzle holes) with a diameter of 0.2 and a length of 0.48. Thermal polycondensation pitch N obtained in Reference Example 1 using the spinning device
o, 1 was spun. In this spinning process, the pitch was subjected to a shear stress of about 250% of the shear stress experienced at the final nozzle hole in the capillary section, and then immediately sheared at the final nozzle hole.
１ｑられたピンチ繊維を実施例１〜３と同一条件下に不
融化及び炭化処理に供して炭素繊維を得た。1 q of pinched fibers were subjected to infusibility and carbonization treatment under the same conditions as in Examples 1 to 3 to obtain carbon fibers.
炭素繊維の断面高次構造及び欠陥含有率を第４表に示す
。Table 4 shows the cross-sectional higher-order structure and defect content of the carbon fibers.
又、本比較例で得られた炭素繊維の断面高次構造を示す
走査型電子顕微鏡写真（約４０００倍）を第７図として
示す。Further, FIG. 7 shows a scanning electron micrograph (approximately 4000 times magnification) showing the cross-sectional higher-order structure of the carbon fiber obtained in this comparative example.
第 ４ 表
□□□；
第２表に示す実施例１〜３の結果と第４表に示す比較例
１〜３の結果との対比から明らかな如く、キャピラリー
部と応力緩和部とを有しない紡糸装置を使用する場合に
は、原料ピンチが同一であっても、連続紡糸性に劣り、
断面高次構造はラジアル型で且つ欠陥含有率が高い。Table 4 □□□; As is clear from the comparison between the results of Examples 1 to 3 shown in Table 2 and the results of Comparative Examples 1 to 3 shown in Table 4, there is no capillary part and stress relaxation part. When using spinning equipment, even if the raw material pinch is the same, continuous spinning performance is inferior,
The cross-sectional higher order structure is radial type and has a high defect content.
第２表に示す実施例１の結果と、第４表に示す比較例４
の結果との対比から明らかな如く、キャピラリー部にて
、最終ノズル孔でうける１／２以下の剪断応力を加えた
場合には、たて割れ、クラック等の欠陥含有率が高い。Results of Example 1 shown in Table 2 and Comparative Example 4 shown in Table 4
As is clear from the comparison with the results, when a shear stress of 1/2 or less of that at the final nozzle hole is applied to the capillary part, the content of defects such as vertical cracks and cracks is high.
更に、第２表に示す実施例１の結果と第４表に比較例５
の結果との対比から明らかな如く、キャピラリー部と最
終ノズル部との間に応力緩和部を有しない紡糸装置を使
用する場合にも、断面高次構造はラジアル型であり、欠
陥含有率も高い。Furthermore, the results of Example 1 shown in Table 2 and Comparative Example 5 shown in Table 4
As is clear from the comparison with the results, even when using a spinning device that does not have a stress relaxation section between the capillary section and the final nozzle section, the cross-sectional higher-order structure is radial, and the defect content is high. .
第１図及び第２図は、本発明方法により得られる炭素繊
維の断面高次構造を示す模式図、第３図乃至第５図は、
実施例１．２及び３で得られた炭素繊維の断面高次構造
を示す走査型電子顕微鏡写真であり、第６図及び第７図
は、比較例４及び５で得られた炭素繊維の断面高次構造
を示す走査型電子顕微鏡写真である。
（以 上）
第１図
（ａ）（ｂ）
第２図
第３図
第４図
第５ 図
第６図FIGS. 1 and 2 are schematic diagrams showing the cross-sectional higher-order structure of carbon fibers obtained by the method of the present invention, and FIGS. 3 to 5 are
FIGS. 6 and 7 are scanning electron micrographs showing cross-sectional higher-order structures of carbon fibers obtained in Examples 1.2 and 3, and FIGS. 6 and 7 show cross-sections of carbon fibers obtained in Comparative Examples 4 and 5. This is a scanning electron micrograph showing a higher-order structure. (Above) Figure 1 (a) (b) Figure 2 Figure 3 Figure 4 Figure 5 Figure 6
Claims (1)
ピッチ系炭素繊維の製造方法において、最終ノズル孔に
いたる前に溶融ピッチを円形、異形又はスリット型のキ
ャピラリー部を通過させることにより最終ノズル孔で受
ける剪断応力の１／２以上の剪断応力を加えた後、該溶
融ピッチを一旦剪断応力を実質的に加えない状態に保持
し、次いでノズル孔を通過させて紡糸することを特徴と
するピッチ系炭素繊維の製造方法。[1] In a method for producing pitch-based carbon fiber in which pitch-based material is melt-spun, infusible, and carbonized, by passing the molten pitch through a circular, irregularly shaped, or slit-shaped capillary part before reaching the final nozzle hole. After applying a shear stress of 1/2 or more of the shear stress received at the final nozzle hole, the molten pitch is temporarily held in a state where no shear stress is applied substantially, and then passed through the nozzle hole to be spun. A method for producing pitch-based carbon fiber.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1284886A JPS62170527A (en) | 1986-01-22 | 1986-01-22 | Production of pitch-based carbon fiber |
| PCT/JP1987/000041 WO1990007594A1 (en) | 1986-01-22 | 1987-01-22 | Process for producing pitch-base carbon fiber |
| US07/105,428 US4859381A (en) | 1986-01-22 | 1987-01-22 | Process for preparing pitch-type carbon fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1284886A JPS62170527A (en) | 1986-01-22 | 1986-01-22 | Production of pitch-based carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62170527A true JPS62170527A (en) | 1987-07-27 |
| JPH0413450B2 JPH0413450B2 (en) | 1992-03-09 |
Family
ID=11816814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1284886A Granted JPS62170527A (en) | 1986-01-22 | 1986-01-22 | Production of pitch-based carbon fiber |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS62170527A (en) |
| WO (1) | WO1990007594A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100194094A1 (en) | 2007-09-03 | 2010-08-05 | Susumu Kiuchi | Anti-counterfeit printed matter |
| US8985634B2 (en) | 2008-09-16 | 2015-03-24 | National Printing Bureau, Incorporated Administrative Agency | Anti-counterfeit printed matter, method of manufacturing the same, and recording medium storing halftone dot data creation software |
| EP2343194A4 (en) | 2008-10-03 | 2015-11-04 | Nat Printing Bureau Incorporated Administrative Ag | Forgery preventive printed matter |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59168127A (en) * | 1983-03-15 | 1984-09-21 | Toray Ind Inc | Production of carbon fiber |
| JPS60194120A (en) * | 1984-03-08 | 1985-10-02 | Mitsubishi Chem Ind Ltd | Production of pitch fiber |
| JPS60239520A (en) * | 1984-05-11 | 1985-11-28 | Mitsubishi Chem Ind Ltd | Carbon fiber |
| JPS60252723A (en) * | 1984-05-30 | 1985-12-13 | Mitsubishi Chem Ind Ltd | Production of pitch based carbon fiber |
-
1986
- 1986-01-22 JP JP1284886A patent/JPS62170527A/en active Granted
-
1987
- 1987-01-22 WO PCT/JP1987/000041 patent/WO1990007594A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59168127A (en) * | 1983-03-15 | 1984-09-21 | Toray Ind Inc | Production of carbon fiber |
| JPS60194120A (en) * | 1984-03-08 | 1985-10-02 | Mitsubishi Chem Ind Ltd | Production of pitch fiber |
| JPS60239520A (en) * | 1984-05-11 | 1985-11-28 | Mitsubishi Chem Ind Ltd | Carbon fiber |
| JPS60252723A (en) * | 1984-05-30 | 1985-12-13 | Mitsubishi Chem Ind Ltd | Production of pitch based carbon fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0413450B2 (en) | 1992-03-09 |
| WO1990007594A1 (en) | 1990-07-12 |
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