JPS62500600A - Carbonaceous fiber with spring-like reversible deflection and its manufacturing method - Google Patents
Carbonaceous fiber with spring-like reversible deflection and its manufacturing methodInfo
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- JPS62500600A JPS62500600A JP61502457A JP50245786A JPS62500600A JP S62500600 A JPS62500600 A JP S62500600A JP 61502457 A JP61502457 A JP 61502457A JP 50245786 A JP50245786 A JP 50245786A JP S62500600 A JPS62500600 A JP S62500600A
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- fibers
- fiber
- spring
- tow
- temperature
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- 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
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- 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
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- 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
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- 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
- D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
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- 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
- D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
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- 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
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 バネ状の可逆的偏向をもつ炭素質繊維とその製造方法 本発明は弛緩状態にあるときの繊維の長さの約１．２倍以上の可逆的偏向をなし うるバネ状構造の形態を付与した、安定化炭素質前駆体物質から誘導した弾力の ある繊維または繊維集合体に関する。[Detailed description of the invention] Carbonaceous fiber with spring-like reversible deflection and its manufacturing method The present invention provides a reversible deflection of approximately 1.2 times or more the fiber length in a relaxed state. elasticity derived from a stabilized carbonaceous precursor material that imparts the morphology of a flexible spring-like structure. Relating to a certain fiber or fiber aggregate.
本発明の炭素質繊維は実質的に永久の、非線状、弾力性の、伸ばしつる、バネ状 構造の形態たとえば繊維中に急々又は鋭角の曲が９のない形態を備えている。本 発明の繊維のバネ状構造の形態と弾力性の伸ばしうる特徴は弛緩状態（す々わち バネ状の状￥！４）から繊維が張力下におかれたときの伸ばされた、延伸された 、そして実質的に線状の状態までの、あるいはそれらの間の任意の程度までの繊 維の寸法変化を可能にする。張力下においたとき、この繊維はその弛緩した、非 偏向のバネ状形態の繊維の長さの少なくとも１．２倍、代表的には２〜４倍、に 伸ばすことができる。従ってこのバネ状繊維は実質的に線状の形状もしくは形態 にまで偏向（伸ばし又は延伸）することができる。繊維自体の弾性モジュラスに 到達しないか、あるいはこれを越えないならば、すなわ′Ｇ）繊維が実質的に線 状の形状にまでまっすぐにされるに必要な張力を越える張力下におかれていなけ れば、この繊維は繊維の寸法もしくは物理的構造を破壊もしくは実質的に変化さ せることなしに、応力による伸びと弛緩の多Ｖのサイクルにわたって線状からそ の弛緩バネ状の形状に戻ることができる。The carbonaceous fibers of the present invention are substantially permanent, non-linear, elastic, tendrils, spring-like fibers. The structure has a configuration, for example, one in which there are no abrupt or acute turns 9 in the fiber. Book The form of the spring-like structure and the stretchable characteristics of elasticity of the fibers of the invention result in a relaxed state. Spring-like shape! 4) Stretched, drawn when the fiber is placed under tension , and to a substantially linear state, or to any degree in between. allows for dimensional changes in fibers. When placed under tension, this fiber maintains its relaxed, non- at least 1.2 times, typically 2 to 4 times, the length of the fiber in the spring-like form of deflection. It can be stretched. Therefore, this spring-like fiber has a substantially linear shape or form. It can be deflected (stretched or stretched) up to The elastic modulus of the fiber itself If it does not reach or exceed this, that is 'G) the fiber is substantially a line. The material must be under tension in excess of that required to straighten it to the desired shape. if the fiber is destroyed or substantially altered in its dimensions or physical structure. from a line to a straight line over multiple V cycles of stress-induced elongation and relaxation without can return to its relaxed spring-like shape.
従来技術は組成物を溶融紡糸して連続フィラメントを製造し次いでこれを酸化に よって安定化させる通常技術によってピッチ基材の（石油および／またはコール タールの）組成物からフィラメントを製造することを一般的に教示している。こ のようなフィラメントはそれ自体で有用であると教示されている。あるいはまた 、この連続フィラメントは画業技術において「ステーブル」ファイバーと呼ばれ るものに切断または延伸破断してもよい。Prior art involves melt spinning the composition to produce continuous filaments, which are then subjected to oxidation. Therefore, the pitch base material (petroleum and/or coal) is stabilized by conventional techniques. generally teaches the production of filaments from tar) compositions. child Filaments such as are taught to be useful in their own right. Or again , this continuous filament is called a "stable" fiber in the art of painting. It may be cut or stretched to break.
このような「ステープル」ファイバーは（当該工業において紡糸と呼ばれる）ド ラフト、延伸および／または撚シによってヤーンに転化させることができる。連 続フィラメントはまた多数の連続モノフィラメントから形成されるトウにするこ ともできる。生成するヤーンまたは糸はそれ自体で使用され、あるいはまた布状 物品に織られそれ自体で使用される。あるいはまた、織られた物品は炭化させて グラファイトもしくはグラファイト状の布とすることもできる。また、トウそれ 自体を、このトウを布に織ることなしに、炭化してその後に合成樹脂質材料の補 強剤たとえば「プリプレグ」などとして使用することもできる。Such "staple" fibers (called spinning in the industry) It can be converted into yarn by rafting, drawing and/or twisting. Communicating Continuous filaments can also be made into tows formed from a number of continuous monofilaments. Can also be done. The resulting yarn or yarn can be used as such or can also be fabricated. Woven into articles and used by itself. Alternatively, woven articles can be carbonized. It can also be graphite or graphite-like cloth. Also, tow it The tow itself is carbonized and then supplemented with synthetic resin material without weaving it into cloth. It can also be used as a toughening agent, such as a "prepreg".
や＼類似の方法で、ポリアクリロニトリル（ＰＡＮ）をフィラメントに湿式紡糸 し、このフィラメントを集めてトウにし、このフィラメントまたはトウを酸化に より安走化させ、このフィラメントまたはトウを切断または延伸破断によってス テーブルにし、このステーブルを紡糸してヤーンにし、このヤーンｔ−ｍむか織 って布もしくは生地にし、そして所望ならば生成生地を１４００℃以上の温度で 炭化することが教示された。これらの材料は、その予備炭化繊物状態において、 メタライズ耐火服用の非燃焼性補強材として使用された。その織っていない炭化 形体において、これらの材料はまた合成樹脂質材料たとえばゴルフ・クラブのシ ャフトなどの補強剤として使用された。Wet-spun polyacrylonitrile (PAN) into filaments using a similar method. This filament is collected into a tow, and this filament or tow is subjected to oxidation. This filament or tow can be cut or stretched to make it safer to run. Make a table, spin this stable into yarn, and make this yarn t-m Mukaori. and, if desired, the resulting fabric at a temperature of 1400°C or higher. It was taught that carbonization occurs. These materials, in their pre-carbonized fiber state, Used as a non-combustible reinforcing material for metallized fireproof clothing. its unwoven carbonized In form, these materials can also be used in synthetic resinous materials such as golf club shells. Used as a reinforcing agent for shafts, etc.
編物、織物または他の繊維製品の製造用の炭化していない通常のポリマー繊維製 品ヤーンの製造において、繊維トウをピンチ・クリンプしてトウの個々の繊維を 鋭くクリンプ・セットする（繊維中に急な又は鋭角の曲がシを入れる）ことは当 該工業における通常の慣習である。Made of regular non-carbonized polymer fibers for the production of knitted, woven or other textile products In the production of yarn, the fiber tow is pinch-crimped to separate the individual fibers of the tow. Sharp crimp-setting (inserting sharp or sharp bends into the fibers) is prohibited. This is normal practice in the industry.
このような繊維製品の処理は安定化した炭素質前駆体のヤーンまたはトウに使用 すれば同じ効果をもつ。すなわち、強い鋭角のクリンプがヤーンに付与され、ヤ ーンの個々の繊維の間にもつれを生ぜしめ、ヤーン中の短いステーブル・ファイ バーを保持もしくは固定するのに、ならびにヤーンに嵩ばり性を付与するのに役 立つ。然しなから、Ｊ−θ常の繊維製品ヤーンの製造法を行ない、炭素質前駆体 材料から作ったヤーンをクリンプし次いで約１０００℃以上の温度で、もつと実 質的には１４００℃およびそれ以上の温度で炭化させると、生成する炭化ヤーン は非常に脆くなる。すなわち、とのヤーンは編み又は織シを非常な注意を払って 且つ高度に制御されたプロセス条件下で行なわない限り、苛酷な取扱いをしたり 又は鋭くひだを付けたりすること例えば編んだシ織ったりすることはできない。Such textile treatments are used to stabilize carbonaceous precursor yarns or tows. It will have the same effect. That is, a strong sharp crimp is imparted to the yarn and the It creates tangles between the individual fibers of the yarn and short stable fibers in the yarn. Helps hold or secure the bar and add bulk to the yarn. stand. However, we carried out the conventional J-θ textile yarn manufacturing method and used a carbonaceous precursor. The yarn made from the material is crimped and then dried at a temperature of about 1000°C or higher. Qualitatively, carbonized yarn produced when carbonized at temperatures of 1400°C and above becomes very brittle. That is, the yarn must be knitted or woven with great care. and harsh handling unless done under highly controlled process conditions. Or, it cannot be sharply pleated, for example, woven or woven.
同じ理由で、このような編んだ又は織ったヤーンはヤーン中の繊維を小断片に破 断することなしに容易に編みほぐし、再生処理、またはカーディングを行なうこ とはできない。このような脆弱性の結果として、編んだ編物は特別の注意なしに は編みほぐしをすることができず、そしてこのような編みほぐしをしたヤーンは その後にカーディングして繊維のひどい破壊すなわち破断を生せしめることなし にヤーン中の繊維をウール状のふわふわした材料に転化させることはできない。For the same reason, such knitted or woven yarns tend to break the fibers in the yarn into small pieces. Easy to unravel, recycle, or card without cutting. I can not do such a thing. As a result of such fragility, knitted fabrics can be worn without special care. cannot be loosened, and the yarn that has been loosened in this way is without subsequent carding resulting in severe destruction or breakage of the fibers It is not possible to convert the fibers in the yarn into a wool-like fluffy material.
従来技術はまた高い引張り強度または大きい表面積をもつ炭化フィラメントを一 般的に開示している。このようなフィラメントは高度に「グラファイト性」の性 質をもち、そして必然の結果として？ｉｌＪ温を使用して高度の炭化を得る。然 しなから、このような高温処理によって製造されたフィラメントは非常に脆弱で あって、フィラメントのくりかえしの曲げのような応力に耐えることができない 。このことはこれらのフィラメントが約１０００℃以上の温度にさらされたとき に特に真実であ夛、これらのフィラメントが約１４００℃以上の温度にさらされ たときになおさら真実である。安定化中間相ピッチから誘導されたフィラメント の高温処理の実例は米国特許第４．００５，１８３号に見出すことができ、そこ では（２５０〜４００℃の温度での）酸化安定化繊維が低い（通常の吸収性カー ・ボンより低い）表面積と１〜５５ミリオンア＃（（７ＧＰα〜３８００Ｐａ） の範囲内のヤング・モジュラスをもつ−ヤーンにされている。Prior art also uses carbonized filaments with high tensile strength or large surface area. Generally disclosed. Such filaments are highly “graphitic” in nature With quality and as a necessary result? A high degree of carbonization is obtained using ilJ temperature. Naturally Therefore, filaments produced through such high-temperature treatments are extremely brittle. Therefore, it cannot withstand the stress caused by repeated bending of the filament. . This means that when these filaments are exposed to temperatures above about 1000°C, This is especially true when these filaments are exposed to temperatures above about 1400°C. This is even more true when Filaments derived from stabilized mesophase pitch An example of high temperature processing can be found in U.S. Pat. (at temperatures between 250 and 400 °C) has low oxidation stabilization (at temperatures of 250 to 400 °C) ・Surface area (lower than Bonn) and 1 to 55 million a# ((7GPα to 3800Pa) - yarns with a Young's modulus within the range of .
繊物パネルの製造技術は米国特許第４，３４１，８３０号に記載されており、そ こではアクリル・フィラメントのトウが２００〜３００℃の温度で張力下に酸化 され、スタッファ−・ボックス中で捲縮され（ピンチ型クリンプを付与され）、 ステーブル・ファイバーにされ、ヤーンに紡糸され、次いで織物パネルに爾まれ 、そして１４００℃の温度で不活性雰囲気中で熱処理すなわ′ｃ）炭化処理され る。このようにして炭化された織物パネルは積み重ね物に集積され、そしてこの 積み重ね物が炭素蒸気炉に入れられて槓み重ね物の上とその中に炭素が析出せし められる。この処理は炭素質ガスすなわちメタンを積み重ね物中に通し、そのあ いだ積み重ね物を電気誘導的に２０００℃の温度にまで加熱して炭素を槓み重ね 物の上および中に析出させ、編んだパネルのマトリックスをもつ炭素質物体を製 造する。然しなから、この方法で作ったヤーンは後述の比較例で示すように非常 に脆弱であり、繊維のひどい破断なしには、織物パネルが描みほぐされてカーデ ィングを受ける場合に起るような、くりかえしの鋭角応力の曲げを受けることは できない。The fabric panel manufacturing technique is described in U.S. Pat. No. 4,341,830, which Here, acrylic filament tow is oxidized under tension at temperatures of 200-300°C. and crimped in a stuffer box (applied with a pinch crimp). Made into stable fibers, spun into yarn and then spun into woven panels. , and heat treated in an inert atmosphere at a temperature of 1400°C i.e.'c) carbonized. Ru. Carbonized textile panels are thus collected into stacks and this The stacks are placed in a carbon steam furnace and carbon is deposited on and within the stacks. I can't stand it. The process involves passing a carbonaceous gas, methane, through the stack. The stacked materials were electrically heated to a temperature of 2000℃ and the carbon was piled up. Precipitate on and into objects to produce carbonaceous objects with a matrix of woven panels. Build. However, the yarn made using this method is very poor as shown in the comparative example below. Fabric panels can be unraveled and carded without severe fiber breakage. Bending under repeated acute angle stresses, such as occurs when subjected to bending. Can not.
「繊維」または「フィラメント」は互換性のある用語として、通常の用途におけ る天然または合成の材料の微細な糸状体もしくは糸状構造物をいう。これに含ま れるのは石油またはコールタールのようなピッチ基材組成物を溶融紡糸すること によって製造されるフィラメント、あるいはＰＡＮまたはナイロンのような合成 樹脂物質を湿式紡糸することによって製造される繊維である。"Fiber" or "filament" are used interchangeably in common usage. A fine filament or filamentous structure of natural or synthetic material. Included in this The process involves melt spinning pitch base compositions such as petroleum or coal tar. filaments manufactured by or synthetics such as PAN or nylon A fiber produced by wet spinning a resin material.
ここに使用する「繊維集合体」なる用語はトウまたはヤーンのような繊維織物工 業でふつうにいう多数本のフィラメントをいう。繊維集合体は通常のポリマー織 物繊維もしくはフィラメントから作られるが、以下に述べる説明および実施例に より安定化および処理した炭素質繊維またはフィラメントにも適用される。As used herein, the term "fiber aggregate" refers to textile fabrics such as tow or yarn. Refers to a large number of filaments commonly used in the industry. The fiber aggregate is a normal polymer weave. made from fibers or filaments; It also applies to more stabilized and treated carbonaceous fibers or filaments.
「バネ状」、「バネ状構造」または「バネ状構造の形態」なる用語はここでは互 換性ある用語として使用され、実質的に線状の形態から鋭角の曲けをもたないコ イル状、シヌンイダル状（正弦波状）、または他の多重曲線の形体もしくは形態 に物理的に変形される繊維、ヤーンま九はトウを呼ぶのに使用される。The terms "spring-like", "spring-like structure" or "form of spring-like structure" are used interchangeably herein. A term used interchangeably to refer to a substantially linear form with no sharp bends. il-like, sinusoidal, or other multiple curved shapes or configurations Fibers that are physically transformed into yarns are used to call tow.
ここにいう「トウ」なる用語はフィラメントの数が定義ｓｆ（％は１０００本の フィラメントの増分の数値でちる）によって同定される多数本の連続フィラメン トの集合体をいう。The term "tow" used here is defined as the number of filaments sf (% is 1000 filaments). A large number of continuous filaments identified by the number of filament increments refers to a collection of objects.
「ステーブル」なる飴は織った及び／又は編んだ物品を製造する繊維織物工業に 使用されるヤーンもしくは糸に「紡糸」（ドラフト、延伸および／または懲り） しうる糸もしくは繊維の非連続ストランドをいう。"Stable" candy is used in the textile industry, which manufactures woven and/or knitted articles. The yarn or thread used is "spun" (drafted, drawn and/or disciplined) A non-continuous strand of flexible yarn or fiber.
ここにいう「安定化」なる用語は特定の温度、ＰＡＮについては代表的に約２５ ０℃未満の温度で酸化された繊維またはトウに適用される。ただし、ある場合に は繊維は化学酸化剤で低温で酸化されることが理解されるべきである。The term "stabilization" here refers to a specific temperature, typically about 25°C for PAN. Applicable to fibers or tows oxidized at temperatures below 0°C. However, in some cases It should be understood that the fibers are oxidized at low temperatures with chemical oxidizing agents.
ここにいう「ヤーン」なる用語は撚ったフィラメント、糸または繊維の連続スト ランドに適用される。「紡糸ヤーン」なる用語は糸またはヤーンにドラフト、延 伸および／または撚ったステープル・７アイパーの連続ストランドをいう。The term "yarn" as used herein refers to a continuous string of twisted filaments, threads or fibers. Applies to land. The term "spun yarn" refers to a thread or yarn that is drafted, drawn, Refers to a continuous strand of staples and 7-eyepers that are stretched and/or twisted.
ここにいう「カーディング」なる用語は歯の付いた装置たとえばワイヤ・ブラシ でヤーンを櫛入れ又はブラシ掛けしてもつれたウェブもしくはスライバー（梳き 毛）へのステープル・ファイバーの少なくとも部分的な整列を行なう操作をいう 。The term ``carding'' refers to toothed devices such as wire brushes. Comb or brush the yarn to create a tangled web or sliver. refers to the operation of at least partial alignment of staple fibers to .
ここにいう「再生（ガーネット）」なる用語はカードに似たガーネットと呼ぶ機 械に織物廃物を通すことによって種々の織物廃物を繊維に戻す方法をいう。The term "regeneration (garnet)" used here refers to a machine called garnet that resembles a card. A method of converting various textile wastes into fibers by passing the textile waste through a machine.
ここにいう「編み」には単純シャーシー・ニット、リブ・ニット、パール・ニッ ト、インターロック・ニット、ダブル・ニットならびに繊維、ヤーンまたはトウ を布に編む類似の方法が包含される。“Knitting” here includes simple chassis knitting, rib knitting, and purl knitting. interlock knits, double knits and fibers, yarns or tows Similar methods of knitting into cloth are included.
「可逆的偏向」または「加工偏向」はここではらせん状、シヌソイダル状（正弦 波状）の圧縮バネに適用されるものとして使用する。ｈｈｃんａｓｉａａｌ Ｄ ａｒｔｇｎ−Ｔ五−ｏｒｙａｎｄ ＰｒｃＬｃｔｉｃｍ （Ｍａｃ Ｍｉｌｌｃ Ｌｎ Ｐｗｂｌ、Ｃｏ、、 １９７５ ）第７１９〜７４８頁特にセクション１ ４−２、第７２１〜７２４頁参照。``Reversible deflection'' or ``processing deflection'' is defined here as spiral, sinusoidal (sinusoidal) It is used to apply to compression springs (wavy). hhc asiaal D artgn-T5-oryand PrcLcticm (Mac Millc Ln Pwbl, Co, 1975) pp. 719-748 especially section 1 4-2, pp. 721-724.
「フックの法則」とはここでは物体を引張り又は圧縮するために加える応力は、 弾性の限界を越えない限り、付与される歪み又は長さの変化に比例することをい う。``Hooke's Law'' states that the stress applied to pull or compress an object is It is meant to be proportional to the applied strain or change in length, as long as the elastic limit is not exceeded. cormorant.
本発明のバネ状構造形態の繊維を作る能力をもつ炭素質前駆体出発物質はピッチ （石油またはコールタール）、ポリアセチレン、ＰＡＮ（ＰＡＮＯＸまたはＧＲ ＡＦＩＬ）；ポリフェニレン、サラン（商標名）、などのような原料物質からえ らばれる。炭素質前駆体物質は若干の骨格配位をもつべきである、すなわち加熱 すると表面またはその近くで縮合ベンゾノイドに転化し５る実質的な濃度の配位 した縮合ベンゾノイド構造部分をもつべきである。The carbonaceous precursor starting material capable of making the spring-like structural morphology fibers of the present invention is pitch (petroleum or coal tar), polyacetylene, PAN (PANOX or GR AFIL); derived from raw materials such as polyphenylene, Saran (trade name), etc. It will be revealed. The carbonaceous precursor material should have some skeletal coordination, i.e. heating Thereupon, a substantial concentration of coordination at or near the surface converts to condensed benzonoids. It should have a fused benzonoid structure moiety.
好ましい前駆体物質はモノフィラメントまたはマルチフィラメントの集合体を生 ずるように溶融紡糸または湿式紡糸によって製造される。このフィラメントは酸 化または脱塩化水素化によって安定化され、次いで多数の商業的に利用しうる技 術のうちの任意の技術によってヤーン、トウ、または織った又は編んだ織物に転 化される。Preferred precursor materials produce monofilament or multifilament aggregates. It is manufactured by melt spinning or wet spinning. This filament is acid stabilized by oxidation or dehydrochlorination and then processed by a number of commercially available techniques. into yarn, tow, or woven or knitted fabric by any of the following techniques: be converted into
本発明によれば、このような炭素質前駆体物質から独特の物品が製造される。こ のよ５な炭素質前駆体物質は繊維、ヤーンまたは繊維のトウに形成され、酸化ま たは脱塩化水素化によって安定化され、次いでバネ状構造形態が与えられ、伸び と収縮の多くのサイクルにわたって繊維のバネ状構造形態を変えることなしに繊 維に柔軟性、弾力性、伸長性および偏向性が付与される。ＰＡＮから製造した繊 維は一般に２００〜２５０℃の温度で酸化により安定化され、代表的には１０〜 ２０ミクロンの公称直径をもつ。中間相ピッチから製造した繊維は米国特許第４ ．Ｕ Ｏ５，１８３号に記載されているように２５０〜４００℃のや＼高い温度 で、好ましくは３００〜３９０℃の温度で酸化によう安定化される。サランから 製造した繊維は脱塩化水素化により安定化され、繊維はその熱可塑性を弛るめ、 熱硬化状の挙動をと９始める。堅い繊維が所望の場合、上記の挙動および堅い繊 維を使用しよ５とする特定の最終用途に応じてたとえば３０ミクロンのや−大き い直径をもつ繊維を使用することができることが理解されるであろう。According to the present invention, unique articles are produced from such carbonaceous precursor materials. child Carbonaceous precursor materials are formed into fibers, yarns or fiber tows and are not oxidized or stabilized by dehydrochlorination or by dehydrochlorination, and then given a spring-like structural morphology and elongated. fibers without changing their spring-like structural morphology over many cycles of shrinkage and contraction. It imparts flexibility, elasticity, extensibility and deflection to the fibers. Fibers made from PAN Fibers are generally stabilized by oxidation at temperatures of 200-250°C, typically 10-250°C. It has a nominal diameter of 20 microns. Fibers made from mesophase pitch are disclosed in U.S. Pat. ．． A rather high temperature of 250 to 400℃ as described in U O5,183 It is preferably stabilized against oxidation at a temperature of 300 to 390°C. From Saran The produced fibers are stabilized by dehydrochlorination, which loosens their thermoplasticity and Thermosetting-like behavior begins at 9. If stiff fibers are desired, the above behavior and stiff fibers Depending on the specific end use for which the fiber will be used, for example 30 micron or larger It will be appreciated that fibers with larger diameters can be used.
多数の連続繊維を集めてトウを作り、次いでこれを通常の方法で酸化することに よって安定化させる。安定化したトウ（′−！たは切断もしくは延伸破断じた繊 維ステーブルから作ったステープル・ヤーン）はその後に、そして本発明に従い 、たとえばトウを円筒状ロッドまたはマンドレル上に巻きつけることによってコ イル状構造の形体にするか、またはトウまたはヤーンを織物または布に編むこと によってシヌンイダル形（正弦波形）または他の曲線形にする（他の織物形成法 およびコイル形成法も使用しうろことが認められる）。標準の織物編み機（たと えば千床編み機または管状編み機）上で、あるいは繊維に急な又は鋭角の曲げを 付与しない丸歯ギヤー−ボックス中でシヌソイダル構造を形成させるのが便利で ある。A large number of continuous fibers are assembled to form a tow, which is then oxidized using conventional methods. Therefore, it is stabilized. Stabilized tow (′-! or cut or stretch broken fibers) Staple yarn made from fiber stable is then produced and in accordance with the present invention. , for example by winding the tow onto a cylindrical rod or mandrel. to form a coil-like structure or to knit tow or yarn into a fabric or cloth Depending on the shape (sinusoidal shape) or other curved shape (other textile forming methods) and coil formation methods may also be used). Standard textile knitting machine (e.g. on a thousand floor or tubular knitting machine) or when the fibers are subjected to sharp or sharp bends. It is convenient to form a sinusoidal structure in the round tooth gear box. be.
コイル状の又はシヌンイダル形の繊維、トウまたは編み布をその後に１５０〜１ ５５０℃の温度で熱処理する。Coiled or woven fibers, tows or knitted fabrics are then added to 150-1 Heat treatment at a temperature of 550°C.
約２５０℃以上の温度において、繊維、トウまたは布を不活性雰囲気中で熱処理 する。所望の最終生成物が爾後の機械的処理すなわち織物のカーディングまたは 編みほぐしを必要とする場合、繊維、トウまたは布を不活性雰囲気中で約５５０ ℃以下の温度に加熱するのが好ましい。Heat treatment of fibers, tows or fabrics in an inert atmosphere at temperatures above about 250°C do. The desired end product is then subjected to mechanical processing i.e. carding of the fabric or If de-weaving is required, the fibers, tows or fabrics are dried in an inert atmosphere at approximately 550°C. Preferably, the heating is carried out to a temperature below .degree.
１５０〜５２５℃の温度において、繊維に仮のセットが与えられるが、「グラフ ァイト」繊維に伴なう高度の脆弱性は未だもっていない。然し、繊維がはじめに ５５０〜１０００℃の上限範囲の温度で処理されると、その繊維には「永久セッ ト」が付与される。このような永久セットは繊維の爾後の処理中に（特にその処 理が測度にもつれた短いステープル・ファイバーについて行なわれる場合に）若 干の繊維の破断に導きうる、ある程度の配位と脆弱性が付随する。バネ状繊維を 連続フィラメントから製造するとき、１５５０℃程度の高温を使用しうろことが 発見された。これらのフィラメントは（ステープル・ファイバーまたはステープ ル・ヤーンの場合のようには相互にもつれておらず、ウール状のふさふさした状 態を作るに必要な機械的処理はこのような連続フィラメントの分離の際にはひど くないからである。At temperatures between 150 and 525°C, the fibers are given a temporary set, but the graph It does not yet have the high degree of brittleness associated with "Hite" fibers. However, in the beginning, fiber When processed at temperatures in the upper range of 550-1000°C, the fibers have a “permanent set”. "To" will be given. Such permanent set occurs during the subsequent processing of the fibers, especially during (when the process is carried out on short staple fibers that are tangled) There is some degree of coordination and fragility involved that can lead to fracture of the dried fibers. spring-like fibers When manufacturing from continuous filament, high temperatures of around 1550°C are used to prevent scaling. It's been found. These filaments (staple fibers or staples) They are not intertwined with each other as in the case of le yarn, but have a woolly, fluffy appearance. The mechanical processing required to create the This is because there is no such thing.
丸歯ギア・クリンプによって又はロッドもしくはマンドレルのまわ〕への巻きつ けによって繊維または繊維トウにバネ状形態を付与する場合には、繊維は張力下 におきながら約２５０℃を越える温度にまで加熱しないことが特に重要である。by round gear crimp or around a rod or mandrel. When imparting a spring-like morphology to fibers or fiber tows by It is particularly important not to heat the product to temperatures above about 250° C. while still standing.
この温度を越えると、繊維は重量損失を開始してコイル径が収縮し、そしてこの ような収縮と重量損失から生ずる張力は非焼鈍性応力亀裂と弱点を繊維中に生せ しめる。Above this temperature, the fiber begins to lose weight and the coil diameter shrinks, and this Tension resulting from shrinkage and weight loss can cause non-annealing stress cracks and weaknesses in the fiber. Close.
繊維が弛緩状態（バネ状の形態）にある間に且つ不活性な非酸化性雰囲気下で熱 処理を行なう限シ、繊維、トウまたはヤーンは始めに高温（ステーブル・ヤーン の編んだ織物については５５０〜１０００℃、連続フィラメントのトウから作っ た−んだ織物については１５５０℃）で熱処理することができる。高温処理の結 果として、永久セットのバネ状構造の形態が繊維に付与される。このようなバネ 状構造の形態をもつ生成した繊維、トウまたはヤーンはそれ自体で使用すること ができ、あるいは編んだ布の場合にはシヌソイダル状の又は他の曲線状のヤーン またはトウに編みほぐしすることもできる。いづれの場合にも、ヤーン、トウま たは布はそれ自体で次にカーディングまたはガーネツテング（再生）の操作また は画業技術で知られている多数の他の機械的処理法のうちの任意の処理を受けて 、繊維がもつれた繊維の集塊に分離されている且つ個々の繊維がそのバネ状形態 を保持している、もつれたウール状のふわふわした物質にすることができる。Heat while the fibers are in a relaxed state (spring-like form) and under an inert, non-oxidizing atmosphere. For processing, the yarn, fiber, tow or yarn is initially heated to a high temperature (stable yarn 550-1000℃ for knitted fabrics made from continuous filament tows. The folded fabric can be heat treated at 1550°C. The result of high temperature treatment As a result, a permanently set spring-like structure is imparted to the fibers. A spring like this The resulting fibers, tows or yarns in the form of a similar structure may be used as such. or, in the case of knitted fabrics, sinusoidal or other curved yarns. Or you can unravel it into tows. In either case, the yarn and tow or the cloth itself is then subjected to carding or garnet tenging (reproduction) operations or has been subjected to any of the numerous other mechanical treatments known in the art of painting. , the fibers are separated into tangled fiber agglomerates and the individual fibers have their spring-like morphology It can become a tangled, wool-like, fluffy substance that holds together.
本発明の繊維は２．５ｆ／ω未満の密度をもち、そしである棟の用途については 好ましくは７〜３８０ ＧＰａのヤング・モジュラスヲモつ。The fibers of the present invention have a density of less than 2.5 f/ω, and for use in Preferably a Young modulus of 7 to 380 GPa.
弛緩状態で（繊維、ヤーン、トウまたは糸に仮のセットのバネ状形！１を与えた 状態で）約５２５℃以下の温度で熱処理することによって生成した繊維、トウ、 またはヤーン、あるいは編んだ布またはクール状のふわふわした物質は、次いで 弛緩状態で非酸化性雰囲気下に５５０〜１５５０℃の温度に更に熱処理して繊維 に永久セットのバネ状構造の形態を与える。約１５５０℃よシ高く約３０００ ′ｃまでの温度において、種々の低度の電気抵抗性が繊維に付与され、このよう な抵抗値は好ましくは約１０！０オーム・センナメートル未満である。これらの 高温における繊維の熱処理により、縮合共役（ベンゾノイド）構造形態が繊維に 、少なくとも繊維外面に、付与される。熱処理が高温で、特に１０００〜１５５ ０℃で行なわれると、縮合ベンゾノイド構造の更に高度の発達が起る。ＰＡＮ繊 維の場合、繊維の直径は約１５５０℃までの温度での処理により減少する。この ような高温処理は脆弱性を徐々に増大させるけれども、繊維は依然としてそのバ ネ状形態を保持する。炭素質前駆体物質は加熱の際にその非炭素部分を失なって 炭素−炭素の骨格内に共役結合構造を形成すると信ぜられる性質をもち、これが グラファイト性炭素の芳香族環状形体に転化するものと信ぜられる。In a relaxed state (a fiber, yarn, tow or yarn is given a temporary set spring-like shape!1) Fibers, tows, produced by heat treatment at temperatures below about 525°C or yarn, or knitted cloth or cool fluffy substance, then In the relaxed state, the fibers are further heat-treated at a temperature of 550 to 1550°C in a non-oxidizing atmosphere. gives the form of a permanently set spring-like structure. Approximately 1550℃ higher than 3000℃ At temperatures up to The resistance value is preferably less than about 10!0 ohms. these Heat treatment of the fibers at high temperatures imparts a condensed conjugate (benzonoid) structural morphology to the fibers. , applied to at least the outer surface of the fiber. Heat treatment at high temperature, especially 1000~155 When carried out at 0° C., a higher degree of development of the fused benzonoid structure occurs. PAN fiber In the case of fibers, the diameter of the fibers is reduced by treatment at temperatures up to about 1550°C. this Although high-temperature treatments such as Retains rod-like morphology. The carbonaceous precursor material loses its non-carbon portion upon heating. It has a property that is believed to form a conjugated bond structure within the carbon-carbon skeleton, and this is It is believed that the graphitic carbon is converted to an aromatic cyclic form.
好ましくは、繊維中のバネ状構造形態がステーブル紡糸ヤーンまたはトウを布に 編むことによって形成されるとき、編んだ布はウール状のふわふわした物質が望 まれるときカーディングの前に１０００℃を越えて加熱することのないように、 好ましくは５５０℃に越えて加熱することのないようにして繊維の破断を防ぐべ きである。Preferably, the spring-like structural form in the fibers allows the stable spun yarn or tow to form a fabric. When formed by knitting, the knitted fabric is a wool-like, fluffy substance. When processing, be careful not to heat it above 1000℃ before carding. Preferably, heating should not exceed 550°C to prevent fiber breakage. It is possible.
１０００℃をかなシ越える温度においては、繊維は脆くなシすぎてウール状のふ わふわした物質を製造するのに必要なもつれ解きの機械的な力に耐えられないか らである。然し、注意深い取扱いと改良された取扱い技術によれば、１０００℃ を越える高温で製造した脆い繊維は。At temperatures well above 1000°C, the fibers become too brittle and become wool-like. Can't withstand the mechanical forces of untangling required to produce fluffy materials? It is et al. However, with careful handling and improved handling techniques, Brittle fibers produced at high temperatures exceeding .
たとえば種々の合成樹脂物質の構造上の補強材として、合成樹脂物質に静電防止 性を付与する充てん材として、他として、依然有用である。For example, as a structural reinforcement for various synthetic resin materials. It remains useful, among other things, as a filler that imparts properties.
上記のバネ構造形態の形成中にステーブル・ヤーンおよび糸の熱処理を限定する ことは望ましいけれども、更なる機械的処理が提案されるときは、このことは連 続フィラメントのトウをバネ状構造形態にする際には重要なことではない。すな わち、連続フィラメントのトウは約１５５０℃の温度に熱処理することができ、 然もカーディングしてウール状のふわふわした生成物にすることができる。Limiting the heat treatment of stable yarns and threads during the formation of the above spring structure form Although desirable, this is not relevant when further mechanical processing is proposed. This is not critical when forming the tow of continuous filaments into a spring-like structural configuration. sand That is, the continuous filament tow can be heat treated to a temperature of about 1550°C, However, it can be carded into a woolly, fluffy product.
酸化安定化繊維、ヤーンまたはトウは、たとえば編み、そしてその後に５５０〜 １５５０℃の温度で加熱することによって所望のバネ状構造形態に熱固定（ヒー ト・セット）されるとき、フックの法則に従うその弾力性のある可逆的な偏向特 性を保持する。ヤーンまたはトウが編まれ、５５０〜１０００’ｃの間の温度で 熱処理されてヤーンまたはトウ中にバネ状形態が「予備セット」されたものであ るときは、このものは次いで編みほぐし、カーディング、ガーネット（再生）処 理あるいは他の機械的処理を行なって編みほぐしたヤーンまたはトウを、ウール 中に見出されるのと同様の弾力性を依然として保持する、もつれたウール状のふ わふわした物質にすることができる。The oxidation stabilized fibers, yarns or tows can be knitted and then 550~ Heat set into the desired spring-like structural form by heating at a temperature of 1550°C. Its elastic and reversible deflection properties obey Hooke's law when Retain your sexuality. The yarn or tow is knitted at a temperature between 550 and 1000'c. It is heat treated to "pre-set" a spring-like form into the yarn or tow. This material is then knitted, carded, and garnet (regenerated) treated. Yarn or tow that has been loosened by mechanical processing or other mechanical processing is A tangled wool-like fabric that still retains the same elasticity found in It can be made into fluffy substances.
上記のようにしてバネ状構造形態にした予め定めた長さの繊維、ヤーンまたはト ウは、その弛緩した、延伸されていない、バネ状形態のＬ２倍以上の一般には２ 倍以上の可逆的偏向を示す。換言すれば、永久セットされたバネ状構造を付与さ れた繊維、ヤーンまたはトウは、そのコイル状の、すなわち弛緩したバネ状構造 形態の長さの少なくとも１．２倍の長さに延伸または引伸ばしすることができる 。この構造形態を調節することによって、たとえば長さ当りのループの１！また はロッドもしくはマンドレル上の巻き数を調節することによって、バネ状の繊維 、ヤーンまたはトウのより大きな伸長もしくは伸びが可能であることが当然に理 解される。繊維中の非線状のコイル奄しくはカールの緊張または弛緩、たとえば 該繊維を編んだ布巾のセンナメートル当シのループ数はバネ状繊維、ヤーンまた はトウの伸びの程度を支配する。従って、可逆的偏向は弛緩状態のバネ状構造に あるときの繊維、ヤーンまたはトウの長さの２倍よシずつと大きくすることもで きる。Predetermined lengths of fibers, yarns or threads formed into a spring-like structural form as described above. C is generally 2 times more than L2 in its relaxed, unstretched, spring-like form. It shows a reversible deflection of more than twice as much. In other words, it has a permanently set spring-like structure. fibers, yarns or tows that have a coiled or relaxed spring-like structure Capable of being stretched or stretched to a length of at least 1.2 times the length of the form . By adjusting this construction form, for example 1! of loops per length! Also creates a spring-like fiber by adjusting the number of turns on a rod or mandrel. , it naturally stands to reason that greater elongation or elongation of the yarn or tow is possible. be understood. Tension or relaxation of non-linear coils or curls in the fiber, e.g. The number of loops in the dish cloth knitted from this fiber is determined by governs the extent of tow elongation. Therefore, the reversible deflection is caused by a spring-like structure in the relaxed state. The length of the fiber, yarn or tow can be increased by twice the length of the existing fiber, yarn or tow. Wear.
好ましい具体例において、集合体すなわち繊維の束は、炭素質前駆体物質を紡糸 して繊維となし、この繊維を酸維を集めてトウとなし、そしてこのトウを礪むこ とによってえられる。編んだ後に、布巾の繊維を、この編んだ布を１５０〜５５ ０℃で処理することによって、コイル状またはシヌソイダル構造に仮に「固定」 （セット）する、好ましくは纏んだ布巾の繊維は不活性雰囲気下、弛緩状態で５ ５０〜６５０℃の温度において、最も好ましくは約１０００℃未満の温度で永久 セットのコイル状構造にする。編んだ布中の繊維は次いで１０００℃を越える温 度で炭化させて上述のように他の望ましい性質を繊維に付与する。In a preferred embodiment, the aggregate or bundle of fibers is spun from a carbonaceous precursor material. The fibers are collected into fibers and made into tow, and this tow is made into It is obtained by After knitting, the fibers of the cloth are heated to 150 to 55 Temporarily “fixed” into a coiled or sinusoidal structure by treatment at 0°C (set), preferably the fibers of the wrapped cloth are in a relaxed state under an inert atmosphere. Permanent at temperatures between 50 and 650°C, most preferably at temperatures below about 1000°C. Make the set into a coiled structure. The fibers in the knitted fabric are then exposed to temperatures exceeding 1000°C. Carbonization at high temperatures imparts other desirable properties to the fibers as described above.
同様に、カール状のふわふわした物質が所望ならば、バネ状形態をもつ繊維のト ウを（あるいは編んだ織物でさえ）、１５５０℃未満の、好ましくは１０００℃ 未満の、そしてウール状のふわふわした物質の製造の際には最も好ましくは６５ ０未満の温度での処理後または処理前のいづれかにカーディング、ガーネット（ 再生）処理または他の機械的処理Ｋかけることができる。繊維中に更に高い電気 伝導度が望まれるならば、永久セット（ＳＯＯ〜１０００℃）した繊維を更に１ ０００℃より高い、たとえば３０００℃までの温度に熱処理することができる。Similarly, if a curly, fluffy material is desired, fibers with a spring-like morphology can be used. (or even knitted fabrics) at temperatures below 1550°C, preferably 1000°C. 65 and most preferably in the production of woolly fluffy materials. Carding, garnet ( It may be subjected to regeneration) treatment or other mechanical treatment. Higher electricity in fiber If conductivity is desired, add 1 more permanently set (SOO~1000°C) fibers. It can be heat treated to temperatures higher than 000°C, for example up to 3000°C.
前述のように、１５５０℃より高い温度で処理した繊維は非常に脆くな夛、容易 には編みほぐし、カーディング、ガーネット処理を行なうことができない。As mentioned above, fibers treated at temperatures higher than 1550°C become very brittle and easily Unraveling, carding, and garnet processing cannot be performed on this material.
それ故、このようなカーディングおよび／またはガーネット処理はステープル・ ヤーン、トウまたは糸については１０００℃を越える温度への熱処理前に１そし て連続繊維または繊維トウについては１５５０℃までの温度ぺの熱処理前に行な うべきである。Therefore, such carding and/or garnet treatment 1 for yarn, tow or yarn before heat treatment to temperatures exceeding 1000°C. Continuous fibers or fiber tows should be heat treated at temperatures up to 1550°C. should be.
炭素質前駆体物質から製造した繊維は、上記のような方法によシ製造したとき、 通常０．５〜１６００ 憔”／ ｆ。Fibers produced from carbonaceous precursor materials, when produced by the method described above, Usually 0.5-1600"/f.
好ましくは０．５〜１５ ｍ”／ ？の表面積をもつ、然し、繊維を高温に迅速 に加熱して非炭素質部分（＊維に残っていると表面を***させる）をガスに転化 させることによって上記よシ大きい表面積をこのような繊維に付与しうろことが 知られている。高い表面積、高い多孔性の繊維を製造するために画業技術におい て知られている他の技術として、繊維表面の酸化があげられる。このような扁い 多孔性の繊維は、バネ状構造形態を繊維に付与した後に同様の技術によって本発 明の物質から製造することができる。Preferably with a surface area of 0.5-15 m”/?, but the fibers can be brought to high temperatures quickly. Convert the non-carbonaceous part (*if it remains in the fibers, it will split the surface) into gas. It is possible to impart a larger surface area to such fibers by Are known. Painting techniques are used to produce high surface area, high porosity fibers. Another known technique is oxidation of the fiber surface. flat like this Porous fibers are produced using similar techniques after imparting a spring-like structural morphology to the fibers. It can be manufactured from light substances.
バネ状構造の形態を繊維中に形成させた後に、連続フィラメントあるいはステー ブル・ファイバーのヤーンもしくは糸を別々の長さのものに切断し、とれらを不 織布の製造について現在知られている技術を使用して不織布製品にすることがで きることも理解されるべきである。After forming a spring-like structure in the fiber, continuous filaments or staples are Cut the bull fiber yarn or thread into separate lengths and Non-woven products can be made using techniques currently known for the production of woven fabrics. It should also be understood that it is possible to
本発明の技術によって製造することのできる生成物の実例を下記の実施例におい て示す。Illustrative examples of products that can be produced by the technique of the invention are given in the examples below. Shown.
公称単一繊維直径が１２ミクロンである（約２５０℃の温度で）酸化安定化した ポリアクリロニトリルｐＡｙ−ＯＸ（Ｒ，に、ＴａｚｔｉＬａａ）連続３Ｋまた は６ｆｆ（３０００または６０００本の繊維）のトウを千床編み機で編んで１セ ンチメートル当り３〜４個のループをもつ布を作った。この布の部分を窒素の不 活性雰囲気下、第１表に示す温度で６時間にわたって熱処理した。この布を編＆ はぐしたとき、それは２：１よシも大きい伸びもしくは可逆性偏向をもつトウを 生じた。この編みほぐしたトウを５〜２５ｃｒＩＬの棟々の長さに切断してＰＬ ａｔｔａ ５ｈｔｒｌａｙＡ％（ｚｌｙｇｇデに供給した。このトウの繊維をカ ーディング処理によって分離してウール状のふわふわした物質をえた。すなわち 、えられた生成物はもつれたウール状の塊ま９又はふわふわした物質であυ、該 物質中の繊維は該繊維のコイル状およびバネ状の形態の結果として高度のすきま 間隔と高度の重なｐ合いをもっていた。このような処理のそれぞれの繊維の長さ を測定し、これらの結果を第１表に示した。Oxidation stabilized (at a temperature of about 250°C) with a nominal single fiber diameter of 12 microns Polyacrylonitrile pAy-OX (R, TaztiLaa) continuous 3K or is made by knitting 6ff (3000 or 6000 fibers) tow with a thousand floor knitting machine. Fabrics with 3-4 loops per inch were made. Place this piece of cloth in a nitrogen bath. Heat treatment was performed under an active atmosphere at the temperatures shown in Table 1 for 6 hours. Knit this cloth & When stripped, it has a tow with an elongation or reversible deflection greater than 2:1. occured. Cut this loosened tow into ridge lengths of 5 to 25 crIL and PL atta 5htrlayA% (supplied to zlygg de. The fibers of this tow were A fluffy, wool-like substance was obtained by separation during the wading process. i.e. , the product obtained is a tangled wool-like mass or fluffy substance, The fibers in the material have a high degree of clearance as a result of the coiled and spring-like morphology of the fibers. It had an overlapping p-match in spacing and altitude. The length of each fiber of such treatment were measured and the results are shown in Table 1.
実施例２゜ シンガー十床編み機上の３Ｋまたは６にのＰＡＮＯＸ（Ｒ，に、Ｔｇｚｔｉｌｇ ｚ）連続安定化フィラメントのトウから織物を編み、窒素の不活性雰囲気下で第 ８表に示す温度において熱処理した。この織物を次いで編みほぐし、バネ状構造 の形態をもつトウをカーディング機ＶＣ直接に供給した。えられたウール状集塊 を回転ドラム状に収集したが、容易に取扱いするのを可１ｉＱにするに十分な一 体性をもっていた。これらの繊維の長さは２〜１５αの範囲にあった。９５０℃ の温度で処理したウール状集塊は高度に１！専性であり、ウール状集塊中の６０ ｃｒｆＬまでの広く分離した距離においてとった任意の検査長において７５オー ム未溝の抵抗をもっていた。Example 2゜ 3K or 6 PANOX (R, Tgztilg on Singer ten-bed knitting machine) z) Knitting a fabric from a tow of continuous stabilized filaments and drying it under an inert atmosphere of nitrogen. Heat treatment was performed at the temperatures shown in Table 8. This fabric is then unwoven to form a spring-like structure. The tow having the form was fed directly to the carding machine VC. Woolly agglomerates obtained was collected in a rotating drum, with sufficient mass to make it easy to handle. It had physicality. The length of these fibers ranged from 2 to 15α. 950℃ Wool-like agglomerates treated at a temperature of 1! 60 in woolly agglomerates 75 ohms at any test length taken at widely separated distances to crfL. There was tremendous resistance.
一′−ｊ 実施例３゜ ３Ｋ（１）ＰＡＮＯＸの安定化トウをシンガー千床編み機上でα轟り４ｍみの割 合で編み、次いで窒素の不活性雰囲気下で９５０℃の温度において熱処理した。1'-j Example 3゜ 3K (1) PANOX stabilized tow was split into 4m pieces on a Singer Chitoko knitting machine. The fabric was then knitted in a single layer and then heat treated at a temperature of 950° C. under an inert atmosphere of nitrogen.
この布を編みほぐし、そしてトウ（２：１より大きい引張夛伸びま九は可逆的偏 向の比をもっていた）を７．５ｃｍの長さに切断した。切断したヤーンを次いで Ｆｌａｔｅｓｔ％ａｔ％ｒ＃Ｃａｒｄｉｎｇ 機上でカーディングして３．５〜 ６．５ａの範囲の長さ及び約５１の平均の長さをもつウール状のふわふわした繊 維を得た。このウール状のふわふわした物質は試験した６０ｃＩｒＬまでの長さ の任意の長さにわたって高い電気伝導度をもっていた。This cloth is unwoven and tow (tensile elongation greater than 2:1 is reversible). (which had a ratio of 3.5 cm) was cut into a length of 7.5 cm. The cut yarn is then Flatest%at%r#Carding 3.5～ by carding on the machine A wool-like fluffy fiber with lengths in the range of 6.5a and an average length of about 51 I got the answer. This woolly, fluffy substance has been tested in lengths up to 60 cIrL. It had high electrical conductivity over any length.
実施例４゜ 実施例３と同様にして、同じ編んだ布からの一部を窒素の不活性雰囲気下で１５ ５０℃の温度において熱処理した。この布自体およびこれを尚みほぐしたトウは 非常に高い電気伝導度をもっていた。切断したトウの１５ｃＩＬの長さのものを カーディングしたところ、２．５〜９．５はの範囲の繊維の長さをもち平均の長 さが５０であるふわふわした物質をえた。すなわち、１０００℃を越える温度に あてた堀４はぐした連続フィラメントのトウのカーディングは依然としてウール 状のふわふわした製品をしうろことがわかった。Example 4゜ Analogously to Example 3, a portion from the same knitted fabric was heated for 15 minutes under an inert atmosphere of nitrogen. Heat treatment was carried out at a temperature of 50°C. This cloth itself and the tow that loosened it It had extremely high electrical conductivity. The length of the cut tow is 15 cIL. When carded, the fiber length ranged from 2.5 to 9.5, with an average length of I got a fluffy substance with a size of 50. In other words, at temperatures exceeding 1000℃ The applied moat 4 removed continuous filament tow carding is still wool It was found that the product was fluffy and fluffy.
比較例Ａ ステーブル２層シングルの１０本の安定化ポリアクリロニトリルＰＡＮＯＸヤー ンを１ｃｍ当り４ループの割合で管状ンツクスに編み、その後ＶｃＮ累の不活性 雰囲気下で１５５０℃の温度において熱処理した。このヤーンを次いで１０工の 長さに切断した。切断したヤーンを次いでカーディング機中でカーディングしだ 。生成物を収集するのは困難であった。０．５〜１．２５ｃｍの長さの短い繊維 が多量の屑と共にえられた。繊維回収の困難性は紡糸ヤーンに代表的に見出され る高度の撚りと繊維のもつれから生じた。Ｈｙａｏｌ−Ｇｒａｆｔｌ Ｌｔｄ、 （英国コベントリー州）からえられたＧτａｆｉｌ−０１の同様の紡糸ヤーン を原料として上記の実施例をくりかえしたとき同様の結果かえられた。Comparative example A 10 stabilized polyacrylonitrile PANOX yarns in a stable 2-layer single layer knitted into a tubular mesh at a rate of 4 loops per cm, then inert with VcN Heat treatment was carried out at a temperature of 1550° C. under atmosphere. This yarn was then passed through 10 knits. Cut to length. The cut yarn is then carded in a carding machine. . The product was difficult to collect. Short fibers with a length of 0.5-1.25 cm was obtained along with a large amount of debris. Difficulties in fiber recovery are typically found in spun yarn. This results from the high degree of twist and entanglement of the fibers. Hyaol-Graftl Ltd. Similar spun yarn of Gτafil-01 obtained from Coventry, UK When the above example was repeated using as the raw material, similar results were obtained.
実施例５゜ 種々の熱処理温度が繊維に及ぼす＃響を調べるために一連の実験を行なった。有 意義な性質は繊維の比抵抗であった。このような性質を調べるために、１．３５ 〜１．３８２／α１の密度をもつ涜化女走化ＰＡＮヤーンの多くの試料を３にお よび６にのトウに集めた。このトウ（ｐｍｏｘと呼ばれ、英国ストックボート州 ヒートンーノリスのＲＫ Ｔｍｚｔｉｌａｍ によって製造されているもの）ｉ ｌｃ！Ｌ当りそれぞれ３個および５個の−４をもつ無地シャーシーの平らな７５ に編んだ。この布をその後に増分熱制御石英管炉中で散索を含まない窒素雰囲気 下に種々の温度で熱処理した。炉の温度を室温から約５５０℃Ｋｔで３時ｉ］］ にわたって徐々に上昇させ、これより高温は１０〜１５分毎に５０℃の割合で上 昇させた。試料を所望温度に約１時間保持し、炉を開放して窒素パージを行ない ながら冷却させた３、上記の昇温スケジュールでの炉の温度ｏ代ｉ値は６にのヤ ーンについてのものであり、次の第ｍ表に示す。Example 5゜ A series of experiments were conducted to investigate the effects of various heat treatment temperatures on fibers. Yes The significant property was the specific resistance of the fibers. In order to investigate such properties, 1.35 A large number of samples of PTFE PAN yarn with a density of ~1.382/α1 were It was collected in a tow of 6 and 6. This tow (called pmox, stockboat, UK) Manufactured by RK Tmztilam of Heaton Norris)i lc! Plain chassis flat 75 with 3 and 5 -4 per L respectively Knitted into. This cloth is then incrementally heated in a controlled quartz tube furnace in a nitrogen-free atmosphere. It was then heat treated at various temperatures. The temperature of the furnace was increased from room temperature to approximately 550°C Kt for 3 hours.] Raise the temperature gradually over a period of I raised it. Hold the sample at the desired temperature for approximately 1 hour, then open the furnace and perform a nitrogen purge. 3, the temperature of the furnace with the above heating schedule is 6. It is shown in Table m below.
第■表 繊維の比抵抗は６個の測定値の平均値を使用して各試料について行なった測定値 から計算した。６個の測定値は試料のそｆ′＋ぞれのコーナーにおいて除かれた 繊維から作られたもの及び試料のｌＬ神央において、それぞれの縁から除かれた 繊維から作られたものについての測定値である。これらの結果を次の第■表に示 す。Table ■ The specific resistance of the fiber is the value measured for each sample using the average value of 6 measurements. Calculated from. Six measurements were taken at each f′+ corner of the sample. made from fibers and specimens removed from each edge. This is a measurement value for items made from fiber. These results are shown in the following table. vinegar.
第 ■ 表 ５００ ４．８４９ ６０（Ｊ ２．０１０ ７５０ ３７ −１．２１ ８５０ ３８ −２．０２ ９００ ４２ −２．５４ ９５０ ４５ −２．８４ １０００ ４８ −３．０２６ １８００ ５１ −３．２９５ 本発明の炭化および水入セットのＮＲ維は、繊維に電気伝導性を付与するに十分 な温度で然も繊維が弾力性、柔軟性、可逆的偏向、および非脆弱性を依然として 示すに十分に低い温度で処理したとき、標準のカーペット繊維またはヤーンとま ぜて静電気消散性をもつヤーンを製造するのに特に好適である。このようなカー ペット／ヤーンのブレンドはカーペット・ヤーン中に少々くと４０．２５重量％ の炭化繊維を含むことができる。合成カーペット繊維二次化繊維の重賞比は好ま しくは１００：１より太きく２００ ： Ｉｔでの値である。本発明の炭化繊維 を使用するカーペットは１秒未満で印加静電荷を０％にする静電気放出性を示し た。■Table 500 4.849 60 (J 2.010 750 37 -1.21 850 38 -2.02 900 42 -2.54 950 45 -2.84 1000 48 -3.026 1800 51 -3.295 The carbonized and water-filled NR fibers of the present invention are sufficient to impart electrical conductivity to the fibers. Even at high temperatures, the fibers still retain their elasticity, flexibility, reversible deflection, and non-brittle properties. Standard carpet fibers or yarns and yarns when processed at temperatures low enough to show It is particularly suitable for producing yarns which also have static dissipative properties. A car like this The PET/yarn blend is 40.25% by weight when added to the carpet yarn. carbonized fibers. The major prize ratio of synthetic carpet fiber secondary fiber is favorable. In other words, the value is thicker than 100:1 and is 200:It. Carbonized fiber of the present invention Carpets using this material exhibit electrostatic discharge properties that reduce the applied static charge to 0% in less than 1 second. Ta.
実施例６゜ モンサンドの１８７９ナイロン（ｔｒＮｏｂａｌ ）ステーブルに本発明によ０ 製造した電気伝導性繊維を０．５重量％ブレンドした。この電気伝導性繊維は布 に編んだ酸化安定化ポリアクリロニトリル・マルチフィラメント繊維のトウを加 熱し、約１５００℃で熱処理し、編みほぐして長さ約１８ｃ＋ｘのステーブルに 切断して作ったものであった。ブレンドしたステーブルをカーディングし、えら れたスライバーを３回ピン・ドラフトした。組み換え比はそれぞれ１０：１．３ ：１、および５：１であった。えもれたドラフト・スライバーを約４．７５の平 均撚りをもつ単一ブライのヤーンに紡糸した。大部分の炭素質繊維はもとの１８ ｃｍの長さよりずつと小さい長さに破断され、単−紡糸法にはじめから含まれて いるものから大意の炭素質繊維の損失が生じた。卑−ヤーンを含む生成炭素質＃ ＆維を同様にして製造したが炭素質ｆ＆維を含まないナイロン・ヤーンに重ねた 。５ｓａｓｓｅ％熱固定装置上で熱固定し九３．００ ／ ２の重ねヤーンをそ の後にタフト化してｚグー’／、２７．（Ｊ３（７６℃Ｍ’）、９．５１パイル 高さのカーペット（カット・ループ型）で口当り約３個の編＾をもつカーペット を製造した。タフト化操作中の炭素質繊維／炭素質ヤーンを含まないヤーンの比 はそれぞれ１：５であった。このカーベントの一部を市販の非伝導性ラテックス ・カーペット裏打′Ｃ）利で裏打ちし７た。えられたカーペットを相対湿度２０ ％未満の雰囲気中で５０００ボルトに荷電することによってその静電気放出性を 試験した。静電荷は１秒未満でもとの電荷の０％にまで消散し、ある種の試料で は％秒未満で放電し念。工業用の規準は２秒以内で０％までの放出である。Example 6゜ According to the present invention, Monsando's 1879 nylon (trNobal) stable The produced electrically conductive fibers were blended at 0.5% by weight. This electrically conductive fiber is a cloth A tow of oxidation-stabilized polyacrylonitrile multifilament fibers woven into Heat it, heat treat it at about 1500℃, loosen it and make it into a stable with a length of about 18cm+x. It was made by cutting. Carding the blended stable and gills The sliver was pin-drafted three times. The recombination ratio is 10:1.3, respectively. :1 and 5:1. Cut the leaked draft sliver into approximately 4.75 square meters. It was spun into a single bray yarn with even twist. Most carbon fibers are original 18 It is broken into lengths smaller than cm, and is included in the single-spinning method from the beginning. Significant loss of carbon fibers occurred from those in use. Produced carbon material containing base yarn # F& fibers were produced in the same manner but layered on nylon yarns that did not contain carbonaceous F& fibers. . Heat set on a 5sasse% heat setting device and make a 93.00/2 layered yarn. After that, it becomes tufted and becomes z goo'/, 27. (J3 (76℃M’), 9.51 piles Carpet with a height of about 3 stitches (cut/loop type) was manufactured. Carbon fiber/yarn ratio without carbon yarn during tufting operation The ratio was 1:5, respectively. A part of this car vent is made of commercially available non-conductive latex. ・Carpet backing'C) Backing with carpet 7. The resulting carpet is kept at a relative humidity of 20 Its electrostatic discharge properties can be reduced by charging it to 5000 volts in an atmosphere of less than Tested. Static charges dissipate to 0% of the original charge in less than 1 second, and for some types of samples Make sure it discharges in less than % seconds. The industry standard is up to 0% release within 2 seconds.
この実施例は約１０００℃より高い温度がバネ状構造形態を炭素質繊維の一トウ に熱固定するのに使用できること、然し１０００℃より高い温度においては多く の脆弱化が起夕、生成繊維は非効率的に使用され、短繊維として失なわれ、そし て通常のカーペット・ステーブルと共にドラフトしてシングルス全作るときヤー ンに配合されないこと、を示している。This example shows that temperatures above about 1000° C. cause the spring-like structure to form in one tow of carbonaceous fibers. can be used for heat setting, but at temperatures higher than 1000°C The resulting fibers are used inefficiently, lost as short fibers, and When drafting with a regular carpet stable to make all singles, This indicates that it is not included in the product.
別の実施例において、実施例６に述べたものと同じ前駆体アクリロニトリル繊維 のトウ１００１を使用した。In another example, the same precursor acrylonitrile fibers as described in Example 6 Tow 1001 was used.
然し、前躯体繊維は編んだ後に９５０℃の温度で熱処理した。炭素質物質の取板 いについての他のすべての点は同じであった。炭化繊維を実施例６のノニうにし てモンサンドの１８７９ナイロン・ヤーン４５．３汀にブレンドした。えられた ヤーンは０．０２皇童％の炭化繊維を會んでおり、この炭化繊維はヤーン中にく まなく実質的に均一に分布していた。このヤーンを実施例６と同様にしてタフト 化してカーペットにした。すなわち、それぞれのタフト化端部は炭化繊維金倉ん でいた。結果は実施例６でえもれた結果と同様であった。However, the precursor fibers were heat treated at a temperature of 950° C. after knitting. Carbonaceous material removal plate All other respects were the same. Carbonized fibers were added to the noni sea urchin of Example 6. It was blended with Monsando's 1879 nylon yarn 45.3 mm. was given The yarn contains 0.02% carbonized fiber, and this carbonized fiber is incorporated into the yarn. It was almost evenly distributed. This yarn was tufted in the same manner as in Example 6. It was turned into a carpet. That is, each tufted end is covered with carbonized fiber Kanakura. It was. The results were similar to those obtained in Example 6.
１ｏｏｏ℃より高い温度に熱処理した、従って電気伝導性の付与された、―んだ ヤーンまたは繊維トウはまた、米国特許出願継続＠号笛５５８，２３９号（１９ ８３年１２月５日出願；発明者エフ・ビー・マツカロウおよびニー・エフ・ビー ル・ジュニア；発明の名称「エネルギー貯蔵装置」）ならびに同第６７８，１８ ６号（１９８４年１２月４日出願；発明の名称［二次電気工ネル貯蔵装置および そのための電極）に記載されているような非水系二次エネルギー貯蔵装置用の電 極の製造にも特別の用途が見出された。Heat-treated to a temperature higher than 100°C, thus imparting electrical conductivity. Yarns or fiber tows are also used in U.S. patent application Ser. No. 558,239 (19 Filed on December 5, 1983; inventors F.B. Matsukarou and N.F.B. Le Junior; title of invention "Energy storage device") and same No. 678, 18 No. 6 (filed on December 4, 1984; title of invention [Secondary electric channel storage device and Electrodes for non-aqueous secondary energy storage devices such as those described in It has also found special use in the production of poles.
実施例８゜ 別の実験において、平らなストック布を編みほぐしてトウを作った。このトウは −みほぐし前に指示温度において熱固定させた指示フィラメント数の安定化ポリ アクリロニ） ＩＪル前駆体であった。トウの部分に既知の荷重を加えることに よって弾性偏向を測定し、そして中間と最終の変形ならびに最終の非弾性伸びの 偏向を測定した。Example 8゜ In another experiment, flat stock cloth was knitted into tows. This toe is - Stabilized polyester with the indicated number of filaments heat-set at the indicated temperature before loosening Acryloni) was a precursor of IJ. Applying a known load to the toe Thus, the elastic deflection is measured and the intermediate and final deformations as well as the final inelastic elongation The deflection was measured.
これらの結果を第１表に示す。These results are shown in Table 1.
第 Ｖ 表 ℃ ｏ ｏｏｏｏｏｏｕ ｏ。Table V ℃ o ooooooo o.
Ｏ，２７５１６３３２５３１３８５５５１２２２９０，９Ｕ１ ５４ １０１ ７５ ７１ ６９ １１１ １３１ ５７ ８１１．５２６ ８３ １４０ ８ ７ ９８ ６６ １１６ １６７ ８２ １０８２．１０７ ９９ １６３ １ １６ １０５ ６６ １１５ １８７ ９４ １１９２．４６８ １１０ １７ ２ １２８ １１５ ６１ １１６ １９６ １０４ １２６２．９４３ １１ ９ １８６ １３３ １１９ ６０ １１８ ２０１ １１４ １３２試料 （α１３−４ｉい／ｃｌＬの無地シャーシーとしての０．４撚り／ａをもつＰａ ｎＯｓ ６１Ｋ ）つ。O, 2751633253138555122290, 9U1 54 101 75 71 69 111 131 57 811.526 83 140 8 7 98 66 116 167 82 1082.107 99 163 1 16 105 66 115 187 94 1192.468 110 17 2 128 115 61 116 196 104 1262.943 11 9 186 133 119 60 118 201 114 132 samples (Pa with 0.4 twist/a as a plain chassis of α13-4i/clL nOs 61K ).
（６１４−５縫い／σの無地シャーシー・ニットとしての撚シのないＰａ％ｏｚ ３にトウ◇ （ｃ）３縫い／ｃ！ＩＬの重ね合せ編みの、撚りのないＧデαｆ（ト０１ 、６ にトウ。(Untwisted Pa%oz as plain chassis knit of 614-5 stitches/σ Tow to 3◇ (c) 3 stitches/c! IL overlapping knitting, untwisted G de αf (to 01, 6 ni tow.
（ｄ）３縫い／１の重ね合せ胸みのＧｒａｆｉＬ、０１゜ｔ＊１３−４縫い７ｃ ｍの無地シャーシー編みの０．４撚り／ｃ１！ＬヲもつＰａｎｅｓ ６Ｋ）つ。(d) 3 stitches/1 overlapping chest GrafiL, 01°t*13-4 stitches 7c M plain chassis knit 0.4 twist/c1! Panes with L 6K).
＋７１３−４縫イ／ｃｒＩＬの無地シャーシー編みの０．４撚り／ｃ’ｉ ’、 （もつＰａｎｏｚ ６Ｋ）つ。+713-4 sewing i/crIL plain chassis knitting 0.4 twist/c'i', (Motsu Panoz 6K) One.
（ｇｔ ３−４縫い／ｃｒｆＬの無地シャーシー編みの帆４撚り／１ｔもつＰａ ｎｏｚ ６Ｋ トウ。(gt 3-4 stitches/crfL plain chassis knit sail 4 twists/1t Pa noz 6K tow.
（ルおよびｊ）４−５縫い／１の熱地ニットとしての撚りのないＰＡＮＯＸ ３ Ｋ）つ。(Le and j) 4-5 stitches/1 untwisted PANOX as a hot ground knit 3 K) One.
肴 構造物の長さに十分に引張られたもの。Appetizer: Something that has been stretched to the length of the structure.
畳骨 すべでの荷重が除かれ、コイルが弛緩状態に戻つバネ状形態の固定（セッ ト）中の繊維に及ぼす張力の効果を示すために、Ｐａｎｏｚｉ４続＃＆維の６に のトウを８期の水晶棒にロール状に巻きつけた。この巻いたトウを実施例５の第 ■表に示すスケジュールに従って、３００℃の最終温度に、巻きつげたトウの端 部をしっかりと保持しながら、熱処理した。この熱処理はトウにバネ状形態を固 定させた。然し繊維は非常に堅く、トウを禅から除くのは困難であった。繊維の 多くは除去の際に破断した。Tatami bone: Spring-like fixation (setup) that removes all loads and returns the coil to a relaxed state g) In order to show the effect of tension on the fibers in Panozzi 4 series # & 6 The tow was wrapped in a roll around an 8th period crystal rod. This rolled tow was ■The ends of the rolled tow are heated to a final temperature of 300°C according to the schedule shown in the table. Heat treatment was performed while holding the parts firmly. This heat treatment solidifies the spring-like morphology to the tow. established. However, the fibers were very stiff and it was difficult to remove the tow from the Zen. of fiber Many were broken during removal.
このトウは弛緩した編んだ形態で熱固定したトウと同じ弾力性はもっていなかっ た。バネ状のトウを３５０℃の温度に加熱する以外は同じ方法を使用した場合、 除去前でさえ更に多くの破断が生じた。This tow does not have the same elasticity as heat-set tow in its relaxed, braided form. Ta. Using the same method except heating the spring tow to a temperature of 350°C, More breaks occurred even before removal.
後者の方法をくりかえし、熱処理した物質（３５０℃）を偉から注意深く除いた 後に弛緩状態で徐々に約６５０℃の温度にまで加熱してアニーリングが起るか否 かを調べた。アニーリングは全く起らなかった。生成コイルは脆くて外性をもた なかった。The latter method was repeated and the heat-treated material (350°C) was carefully removed from the cage. Afterwards, it is gradually heated to a temperature of about 650°C in a relaxed state to see if annealing occurs. I looked into it. No annealing occurred. The generating coil is brittle and has external properties. There wasn't.
然し、巻きつけたコイル状のトウを２７５℃に到達する前に棒から除き、径の小 さいｍを挿入してバネ状形体の一体性を保持させ、この「弛緩」した状態で加熱 すると、前述の編みほぐしたトウおよび／またはヤーンを実質的に同じ性質をも つバネ状のトウかえられた。However, the coiled tow was removed from the rod before it reached 275°C, and the Insert the spring to maintain the integrity of the spring-like shape, and heat in this "relaxed" state. The aforementioned loosened tows and/or yarns are then combined with substantially the same properties. The spring-like toe was changed.
国際調査報告international search report
Claims (18)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72444085A | 1985-04-18 | 1985-04-18 | |
| US82756786A | 1986-02-10 | 1986-02-10 | |
| US724440 | 1986-02-10 | ||
| PCT/US1986/000802 WO1986006110A1 (en) | 1985-04-18 | 1986-04-17 | Carbonaceous fibers with spring-like reversible deflection and method of manufacture |
| US827567 | 1997-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1295169A Division JPH0327121A (en) | 1985-04-18 | 1989-11-15 | Carbonaceous fiber |
| JP1295171A Division JPH0663138B2 (en) | 1985-04-18 | 1989-11-15 | Wool-like fluff and its manufacturing method |
| JP1295170A Division JPH0663137B2 (en) | 1985-04-18 | 1989-11-15 | Carbon fiber manufacturing method |
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| Publication Number | Publication Date |
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| JPS62500600A true JPS62500600A (en) | 1987-03-12 |
| JPH0670286B2 JPH0670286B2 (en) | 1994-09-07 |
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| JP61502457A Expired - Fee Related JPH0670286B2 (en) | 1985-04-18 | 1986-04-17 | Carbonaceous fiber |
| JP1295170A Expired - Lifetime JPH0663137B2 (en) | 1985-04-18 | 1989-11-15 | Carbon fiber manufacturing method |
| JP1295169A Pending JPH0327121A (en) | 1985-04-18 | 1989-11-15 | Carbonaceous fiber |
| JP1295171A Expired - Lifetime JPH0663138B2 (en) | 1985-04-18 | 1989-11-15 | Wool-like fluff and its manufacturing method |
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| JP1295170A Expired - Lifetime JPH0663137B2 (en) | 1985-04-18 | 1989-11-15 | Carbon fiber manufacturing method |
| JP1295169A Pending JPH0327121A (en) | 1985-04-18 | 1989-11-15 | Carbonaceous fiber |
| JP1295171A Expired - Lifetime JPH0663138B2 (en) | 1985-04-18 | 1989-11-15 | Wool-like fluff and its manufacturing method |
Country Status (8)
| Country | Link |
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| EP (1) | EP0199567B1 (en) |
| JP (4) | JPH0670286B2 (en) |
| KR (1) | KR890000129B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH01239147A (en) * | 1988-03-15 | 1989-09-25 | Chisso Corp | Fiber mat and production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4898783A (en) * | 1986-10-14 | 1990-02-06 | The Dow Chemical Company | Sound and thermal insulation |
| WO1988002695A1 (en) * | 1986-10-14 | 1988-04-21 | The Dow Chemical Company | Sound and thermal insulation |
| JP2648711B2 (en) * | 1986-11-07 | 1997-09-03 | 株式会社 ペトカ | Manufacturing method of pitch-based carbon fiber three-dimensional fabric |
| US4868038A (en) * | 1987-10-23 | 1989-09-19 | The Dow Chemical Company | Carbonaceous fiber reinforced composites |
| US4950540A (en) * | 1987-10-28 | 1990-08-21 | The Dow Chemical Company | Method of improving the flame retarding and fire blocking characteristics of a fiber tow or yarn |
| US4950533A (en) * | 1987-10-28 | 1990-08-21 | The Dow Chemical Company | Flame retarding and fire blocking carbonaceous fiber structures and fabrics |
| US4879168A (en) * | 1987-10-28 | 1989-11-07 | The Dow Chemical Company | Flame retarding and fire blocking fiber blends |
| US4844974A (en) * | 1987-11-18 | 1989-07-04 | The Dow Chemical Company | Antistatic, antislosh, flame arresting structure for use in containers holding flammable fluids |
| US4857394A (en) * | 1988-01-29 | 1989-08-15 | The Dow Chemical Company | Flame retardant foams |
| US4869962A (en) * | 1988-01-29 | 1989-09-26 | The Dow Chemical Company | Asbestos-like structures |
| US4944999A (en) * | 1988-03-04 | 1990-07-31 | The Dow Chemical Company | Carbonaceous fiber or fiber assembly with inorganic coating |
| US5028477A (en) * | 1988-03-04 | 1991-07-02 | The Dow Chemical Company | Carbonaceous fiber or fiber assembly with inorganic coating |
| US4902563A (en) * | 1988-03-04 | 1990-02-20 | The Dow Chemical Company | Carbonaceous fiber or fiber assembly with inorganic coating |
| US4978571A (en) * | 1988-03-04 | 1990-12-18 | The Dow Chemical Company | Carbonaceous fiber or fiber assembly with inorganic coating |
| US4956235A (en) * | 1988-03-04 | 1990-09-11 | The Dow Chemical Company | Carbonaceous fiber or fiber assembly with inorganic coating |
| US5034267A (en) * | 1988-03-04 | 1991-07-23 | The Dow Chemical Company | Carbonaceous fiber or fiber assembly with inorganic coating |
| BR8905710A (en) * | 1988-03-04 | 1990-11-20 | Dow Chemical Co | STRUCTURES OF DENSITY CARBONACE FIBERS |
| US4897303A (en) * | 1988-03-07 | 1990-01-30 | The Dow Chemical Company | Buoyant coated fibers |
| JP2838140B2 (en) * | 1988-03-17 | 1998-12-16 | 株式会社ペトカ | Twisted carbon fiber and method for producing the same |
| US4923747A (en) * | 1988-08-18 | 1990-05-08 | The Dow Chemical Company | Ceramic thermal barriers |
| US5024877A (en) * | 1989-04-14 | 1991-06-18 | The Dow Chemical Company | Fire resistant materials |
| JP3737849B2 (en) * | 1996-03-31 | 2006-01-25 | 大阪瓦斯株式会社 | Method for producing carbon fiber three-dimensional structure |
| JP4226642B2 (en) | 2005-09-02 | 2009-02-18 | 富士通株式会社 | RF tag and method of manufacturing RF tag |
| GB2477531B (en) * | 2010-02-05 | 2015-02-18 | Univ Leeds | Carbon fibre yarn and method for the production thereof |
| DE102013206984A1 (en) * | 2013-04-18 | 2014-10-23 | Bayerische Motoren Werke Aktiengesellschaft | Process for producing carbon fibers |
| KR101504726B1 (en) * | 2013-11-15 | 2015-03-30 | 한국건설기술연구원 | Fire resisting structure of high strength for preventing explosive fracture with carbon fiber mesh and fire-resist mortar covering, and constructing method for the same |
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|---|---|---|---|---|
| GB1190269A (en) * | 1966-07-08 | 1970-04-29 | Nat Res Dev | The Manufacture of Cloth from Polymeric Fibre Material |
| US4014725A (en) * | 1975-03-27 | 1977-03-29 | Union Carbide Corporation | Method of making carbon cloth from pitch based fiber |
| GB1587515A (en) * | 1976-11-03 | 1981-04-08 | Courtaulds Ltd | Composite structure |
| JPS5398423A (en) * | 1977-02-04 | 1978-08-28 | Toshiba Corp | Method of shaping carbon fibers |
| US4193252A (en) * | 1978-06-28 | 1980-03-18 | Hitco | Knit-deknit method of handling yarn to produce carbon or graphite yarn |
| JPS5742925A (en) * | 1980-08-22 | 1982-03-10 | Toho Rayon Co Ltd | Production of high-performance carbon fiber strand |
| US4351816A (en) * | 1980-12-17 | 1982-09-28 | Union Carbide Corporation | Method for producing a mesophase pitch derived carbon yarn and fiber |
| JPS57175664A (en) * | 1981-04-20 | 1982-10-28 | Murata Mach Ltd | Accomodation of pitch fiber bundle |
| JPS57188464A (en) * | 1981-05-11 | 1982-11-19 | Mitsubishi Pencil Co | Carbon spring and manufacture |
-
1986
- 1986-04-17 CA CA000506941A patent/CA1284858C/en not_active Expired - Fee Related
- 1986-04-17 BR BR8606634A patent/BR8606634A/en active Search and Examination
- 1986-04-17 KR KR1019860700908A patent/KR890000129B1/en not_active IP Right Cessation
- 1986-04-17 WO PCT/US1986/000802 patent/WO1986006110A1/en unknown
- 1986-04-17 JP JP61502457A patent/JPH0670286B2/en not_active Expired - Fee Related
- 1986-04-18 AU AU56359/86A patent/AU590879B2/en not_active Ceased
- 1986-04-18 EP EP86302959A patent/EP0199567B1/en not_active Expired - Lifetime
- 1986-04-18 DE DE8686302959T patent/DE3686504T2/en not_active Expired - Fee Related
-
1989
- 1989-11-15 JP JP1295170A patent/JPH0663137B2/en not_active Expired - Lifetime
- 1989-11-15 JP JP1295169A patent/JPH0327121A/en active Pending
- 1989-11-15 JP JP1295171A patent/JPH0663138B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01239147A (en) * | 1988-03-15 | 1989-09-25 | Chisso Corp | Fiber mat and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0327122A (en) | 1991-02-05 |
| EP0199567A3 (en) | 1988-01-13 |
| AU5635986A (en) | 1986-10-23 |
| JPH0327121A (en) | 1991-02-05 |
| DE3686504T2 (en) | 1993-01-21 |
| JPH0663137B2 (en) | 1994-08-17 |
| AU590879B2 (en) | 1989-11-23 |
| WO1986006110A1 (en) | 1986-10-23 |
| DE3686504D1 (en) | 1992-10-01 |
| EP0199567A2 (en) | 1986-10-29 |
| KR890000129B1 (en) | 1989-03-08 |
| EP0199567B1 (en) | 1992-08-26 |
| JPH0663138B2 (en) | 1994-08-17 |
| JPH0327123A (en) | 1991-02-05 |
| KR880700109A (en) | 1988-02-15 |
| BR8606634A (en) | 1987-08-04 |
| JPH0670286B2 (en) | 1994-09-07 |
| CA1284858C (en) | 1991-06-18 |
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| LAPS | Cancellation because of no payment of annual fees |