JPH0364514A - Production of acrylic precursor yarn for carbon fiber - Google Patents
Production of acrylic precursor yarn for carbon fiberInfo
- Publication number
- JPH0364514A JPH0364514A JP20107889A JP20107889A JPH0364514A JP H0364514 A JPH0364514 A JP H0364514A JP 20107889 A JP20107889 A JP 20107889A JP 20107889 A JP20107889 A JP 20107889A JP H0364514 A JPH0364514 A JP H0364514A
- Authority
- JP
- Japan
- Prior art keywords
- yarn
- baths
- stretching
- bath
- fibers
- 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 description 26
- 239000004917 carbon fiber Substances 0.000 title claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000002243 precursor Substances 0.000 title claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title description 12
- 238000009987 spinning Methods 0.000 claims abstract description 14
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 9
- -1 polysiloxane Polymers 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 39
- 239000000314 lubricant Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 22
- 230000004927 fusion Effects 0.000 abstract description 16
- 239000013557 residual solvent Substances 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical group OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical group N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Landscapes
- Inorganic Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、炭素繊維用アクリル系前駆体糸条の製造法、
特に品質および物性の優れた炭素繊維を製造するのに好
適である、炭素繊維用アクリル系前駆体糸条の製造法に
関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention provides a method for producing an acrylic precursor yarn for carbon fibers,
The present invention particularly relates to a method for producing an acrylic precursor yarn for carbon fibers, which is suitable for producing carbon fibers with excellent quality and physical properties.
（従来の技術）
炭素繊維はその前廂体であるアクリル系、レーヨン系、
ピンチ系、あるいはポリビニルアルコール系繊維を紡糸
する製糸工程、２００〜４００’Ｃの空気雰囲気中で加
熱焼成して、酸化繊維に転換する耐炭化工程、窒素、ヘ
リウム、アルゴン等の不活性雰囲気中でさらに３００〜
２５００℃に加熱して炭化あるいは黒鉛化する炭化工程
や黒鉛化工程を経ることで得られ（耐炎化工程、炭化工
程、黒鉛化工程をあわせて焼成工程と呼ぶ）、複合材料
用強化繊維や電気特性を生かした用途などに幅広く利用
されている。(Conventional technology) Carbon fiber is made of its predecessors such as acrylic, rayon,
A spinning process for spinning pinch-type or polyvinyl alcohol-based fibers, a carbonization process for converting into oxidized fibers by heating and firing in an air atmosphere at 200 to 400'C, and an inert atmosphere such as nitrogen, helium, or argon. Another 300~
It is obtained through a carbonization or graphitization process in which carbonization or graphitization is performed by heating to 2,500°C (flame resistance process, carbonization process, and graphitization process are collectively called the firing process), and it is used as reinforcing fibers for composite materials and electricity. It is used in a wide range of applications that take advantage of its characteristics.
上記製造工程のうち、耐炎化工程はアクリル繊維内にナ
フチリジン環等の環化構造を形成し、該繊維の耐熱性を
向上せしめて炭素繊維の品質やその生産性を左右する重
要な工程である。この耐炎化工程は発熱反応であるため
高温処理を行うと急激に反応が進行し、局部的に蓄熱が
起こり単繊維間の融着が発生したり繊維が分解・切断し
たりすることもあり、炭素繊維の品質・生産性を著しく
低下させてしまう。単繊維間の融着は、耐炎化工程に先
立つ製糸工程においても、その延伸工程・乾燥緻密化工
程ですでに確認でき、製糸工程からの融着をいかに減少
させるかが炭素繊維製造上の品質面・操業面の大きなポ
イントである。Among the above manufacturing processes, the flame-retardant process is an important process that forms cyclized structures such as naphthyridine rings within the acrylic fibers, improves the heat resistance of the fibers, and influences the quality and productivity of carbon fibers. . This flame-retardant process is an exothermic reaction, so if high temperature treatment is performed, the reaction will progress rapidly, causing local heat accumulation, which may cause fusion between single fibers or fibers to decompose or break. This will significantly reduce the quality and productivity of carbon fiber. Fusion between single fibers can already be confirmed in the drawing process and drying and densification process, even in the spinning process that precedes the flame-retardant process, and the quality of carbon fiber manufacturing is determined by how to reduce the fusion from the spinning process. This is a major point from an operational and operational perspective.
このような製糸工程・耐炎化工程での１１４糸間の融着
防止には製糸工程でのシリコーン油剤の使用が特に有効
である。例えば特聞昭６０−１８５８７９号公報には、
アミノ変化光を右したオルガノポリシロキサン油剤が開
示されている。また、特公昭５１−↓２７３９号公報に
は、ポリジメチルシロキサン化合物などをアクリル繊維
に付与したのち、焼成して高性能炭素繊維とすることが
開示されている。また油剤のほかにも製糸工程の最後に
、疑似融着した糸条を空気によって開繊し、単糸間融着
を防ぐ方法が特公昭６０−５９３２３号公報に開示され
ている。The use of silicone oil in the yarn spinning process is particularly effective in preventing fusion between the 114 yarns in the yarn spinning process and flameproofing process. For example, in Special Publication No. 60-185879,
Organopolysiloxane oils with amino-converted light are disclosed. Furthermore, Japanese Patent Publication No. 51-2739 discloses that a polydimethylsiloxane compound or the like is added to acrylic fibers and then fired to produce high-performance carbon fibers. In addition to the oil agent, Japanese Patent Publication No. 60-59323 discloses a method in which the pseudo-fused yarns are opened with air at the end of the spinning process to prevent fusion between single yarns.
しかしながら単糸間融着は製糸工程中の延伸過程ですで
に発現しており、上記方法を単独にあるいは種々組み合
わせたとしても単糸間融着を１−分に防止することはで
きず、根本的解決に至ることはできない。However, fusion between single yarns has already occurred during the drawing process during the spinning process, and even if the above methods are used alone or in various combinations, it is not possible to prevent fusion between single yarns within 1 minute. It is not possible to reach a solution.
（発明が解決しようとする課題）
本発明の課題は、製糸から焼成にいたる炭素繊維製造過
程において発生する単繊維同志の融着を防止せしめ、高
品質で同時に物性の優れた炭素繊維を得ることのできる
、炭素繊維用アクリル系前駆体糸条の製造方法を提供す
ることにある。(Problems to be Solved by the Invention) An object of the present invention is to prevent the fusion of single fibers that occurs in the carbon fiber manufacturing process from spinning to firing, and to obtain carbon fibers of high quality and excellent physical properties. An object of the present invention is to provide a method for producing an acrylic precursor yarn for carbon fibers.
（課題を解決するための手段）
本発明の上記課題は、アクリロニトリル９０重量％以上
からなるアクリル系重合体溶液を紡糸後、湿潤糸条を延
伸する方法において、少なくとも２つ以上の分離した延
伸浴槽間にフリーローラーを配し、該延伸浴槽中３０〜
９８°Ｃの水中で多槽延伸することを特徴とする、炭素
繊維用アクリル系前開体系条の製造法によって達成する
ことができる。(Means for Solving the Problem) The above object of the present invention is to provide a method for drawing a wet yarn after spinning an acrylic polymer solution containing 90% by weight or more of acrylonitrile. A free roller is arranged between the stretching baths, and the stretching time is 30~
This can be achieved by a method for producing an acrylic pre-opening system for carbon fiber, which is characterized by multi-tank stretching in water at 98°C.
以下、本発明の詳細と好ましい態様について説３− 明する。The details and preferred embodiments of the present invention will be explained below. I will clarify.
本発明に使用するアクリル系重合体はアクリロニトリル
９０重量％以上からなる重合体である必要がある。従っ
て、１．０重量％以内で他のコモノマーと共重合されて
いてもよい。コモノマーとしてはアクリル酸、メタアク
リル酸、イタコン酸、およびそれらのメチルエステル、
エチルエステル、アルカリ金属塩、アンモニウム塩、あ
るいはアリルスルホン酸、メタリルスルホン酸、スチレ
ンスルホン酸およびそれらのアルカリ金属塩、等をあげ
ることができるが、好ましいのはイタコン酸であり、好
ましい共重合量は０．０１〜５重量％である。The acrylic polymer used in the present invention must be a polymer containing 90% by weight or more of acrylonitrile. Therefore, it may be copolymerized with other comonomers within 1.0% by weight. Comonomers include acrylic acid, methacrylic acid, itaconic acid, and their methyl esters,
Examples include ethyl ester, alkali metal salts, ammonium salts, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, and their alkali metal salts, but itaconic acid is preferred, and the preferred amount of copolymerization is is 0.01 to 5% by weight.
アクリル系重合体は公知の乳化重合、塊状重合、溶液重
合等の重合法を用いて重合され、さらにこれらの重合体
からアクリル系繊維を製造するに際してはジメチルアセ
トアミド、ジメチルスルホキシド、ジメチルホルムアミ
ド、硝酸、ロダンソーダ水溶液等のポリマー溶液を紡糸
原液として、通常の湿式紡糸法、乾湿式紡糸法によって
紡糸し、繊維化することができる。特に乾湿式紡糸法に
よる場合には、単繊維間の融着がより一層生じやすいの
で、本発明の効果がより顕著にあられれる。Acrylic polymers are polymerized using known polymerization methods such as emulsion polymerization, bulk polymerization, and solution polymerization, and when producing acrylic fibers from these polymers, dimethylacetamide, dimethylsulfoxide, dimethylformamide, nitric acid, Using a polymer solution such as a Rodan soda aqueous solution as a spinning dope, it can be spun into fibers by a normal wet spinning method or wet/dry spinning method. In particular, when wet-dry spinning is used, the effects of the present invention are more pronounced because fusion between single fibers is more likely to occur.
本発明で最も特徴的なことの一つは、少なくとも２つ以
上の分離した延伸浴槽間にフリーローラーを配し、該延
伸浴槽中３０〜９８°Ｃの水中で多槽延伸することであ
る。浴延伸は通常個々の延伸浴槽の人出に即動ローラー
を設置し、延伸浴借内で配向、ローラ一部で緩和を行い
、これを何段か重ねてなされる。浴延伸の入／出ローラ
ーは延伸倍率を規制するために即動ローラーであるのが
杼道であるが、ローラーが強制的に即動されるため走行
糸条にかかる圧着力が大きく、単繊維同志の融着や接着
が増大する。糸条切れをなくし安定して延伸するために
、延伸浴数を増やし多段延伸する方法が採用されている
が、浴延伸段数を多くすればするほどその浴槽人出にお
いて糸条と接触するローラー数が増え、そのたびに糸条
はローラー上に強く圧着され、前記融着は激増する。One of the most characteristic features of the present invention is that free rollers are disposed between at least two or more separate stretching baths, and multi-tank stretching is carried out in water at 30 to 98°C in the stretching baths. Bath-stretching is usually carried out by installing quick-acting rollers in individual stretching baths, orienting in the stretching bath, and relaxing with a portion of the rollers, which are stacked in several stages. The input/exit rollers for bath drawing are instant-moving rollers in order to regulate the stretching ratio, but since the rollers are forced to move immediately, the pressure applied to the traveling yarn is large, and the single fiber Fusion and adhesion of comrades increases. In order to eliminate yarn breakage and achieve stable stretching, a method of increasing the number of drawing baths and performing multi-stage drawing has been adopted. increases, and each time the yarn is strongly pressed onto the roller, the fusion increases dramatically.
本発明においては延伸浴槽間にフリーローラーを配し、
延伸浴槽を出た糸条はフリーローラーのみに接触し次に
続く延伸浴槽へと導かれる。従来の和動ローラ一方式の
延伸法では、各浴槽での糸条とローラーとの滑りをなく
すために接触角を大きくとってローラー本数を増やして
いたが、本発明においては浴槽間に土木のフリーローラ
ーがあれば良く、このため糸条に接触するローラー数は
極端に減少させることができる。またフリーローラーで
あるために糸条への圧着力が減少し浴延伸工程での単繊
維同士の融着を防止することができる。通常延伸浴中に
もローラーを設けるが、本発明においては延伸工程の入
／出ローラーさえ開動であれば途中過程（浴中、浴外）
のローラーもフリーローラーである方が好ましい。これ
らフリーローラーは糸条によって回転されるため、浴中
フリーローラー、浴外フリーローラーともその回転トル
クはできるだけ小さい方が好ましい。In the present invention, a free roller is arranged between the stretching baths,
The yarn leaving the drawing bath contacts only the free rollers and is guided to the next drawing bath. In the conventional drawing method using one type of Wado roller, the number of rollers was increased by increasing the contact angle in order to eliminate slippage between the yarn and the roller in each bathtub, but in the present invention, a civil engineering All that is required is a free roller, and therefore the number of rollers that come into contact with the yarn can be drastically reduced. Furthermore, since it is a free roller, the pressing force against the yarn is reduced, and it is possible to prevent single fibers from fusing together in the bath drawing process. Normally, rollers are provided in the stretching bath, but in the present invention, if even the rollers entering and exiting the stretching process are open, it is possible during the process (in the bath, outside the bath).
It is preferable that the roller is also a free roller. Since these free rollers are rotated by the yarn, it is preferable that the rotational torque of both the in-bath free roller and the out-of-bath free roller is as small as possible.
本発明においては延伸時の温度条件を選ぶことも重要で
ある。浴延伸工程は糸条の脱溶媒工程も兼ねているため
、脱溶媒が不十分なうちに高温で延伸を行うと、残存溶
媒で糸条が溶けて単繊維間の融着が進み好ましくない。In the present invention, it is also important to select the temperature conditions during stretching. Since the bath drawing step also serves as a step for removing the solvent from the yarn, if drawing is carried out at a high temperature before the solvent has been removed sufficiently, the remaining solvent will melt the yarn and promote fusion between single fibers, which is undesirable.
このため延伸初刊の脱溶媒が不十分なうちは延伸温度を
極力下げるのが好ましく、糸条中の残存溶媒が１％以」
二の時は温度３０〜５０℃、１％未満の時は４０〜９８
°Ｃで延伸するのが好ましい。また延伸倍率条件を高く
とりすぎると、単糸切れが増え、生産性を著しく低下さ
せるおそれがある。従って延伸倍率（ト−タル浴延伸倍
率）は２．０〜Ｇ、 ０倍であるのが好ましい。For this reason, it is preferable to lower the drawing temperature as much as possible while the solvent removal in the first drawing is insufficient, so that the residual solvent in the yarn is 1% or more.
When the temperature is 2, the temperature is 30-50℃, and when it is less than 1%, it is 40-98℃.
Preference is given to stretching at °C. Furthermore, if the stretching ratio is set too high, single yarn breakage may increase, which may significantly reduce productivity. Therefore, the stretching ratio (total bath stretching ratio) is preferably 2.0 to G, 0 times.
本発明の浴延伸方法は従来の多段浴延伸方法に比べて恥
動部分が少なくてすみ、設備費も減少させることができ
る。The bath stretching method of the present invention requires fewer moving parts than the conventional multi-stage bath stretching method, and can also reduce equipment costs.
本発明においては、上記延伸に続いて少なくともｌ成分
がアミノ変性ポリシロキサンからなる原糸油剤を糸条に
付与することが望ましい。すなわち製糸工程においては
延伸工程に続く乾燥工程でも単糸間の融着が発生するた
め、乾燥緻密化前に油剤を付与して１１′Ｌ繊維表面に
皮膜を形成させる必要がある。アクリル系前駆体糸条は
焼成工程にお−
いて過酷な熱処理を受けるため、該表面皮膜を耐熱性に
優れたものにする必要があり、このため糸条に付与する
油剤としては少なくともｌ成分はアミノ変性シリコーン
であることが望ましい。本発明に使用されるアミノ変性
シリコーンの例としては次に示す構造式のものがある。In the present invention, it is desirable that, following the above-mentioned stretching, a raw yarn oil agent in which at least the l component is an amino-modified polysiloxane is applied to the yarn. That is, in the spinning process, fusion between single yarns occurs even in the drying process following the drawing process, so it is necessary to apply an oil agent to form a film on the surface of the 11'L fibers before drying and densification. Since the acrylic precursor yarn undergoes severe heat treatment during the firing process, it is necessary to make the surface film excellent in heat resistance. Preferably, it is an amino-modified silicone. Examples of amino-modified silicones used in the present invention include those with the following structural formula.
ここでＲ１，Ｒｅはアルキル基、水酸基、アルコキシル
基、アリール基、およびアルキル基、エポキシ基、チオ
アルコール基などを含む一価の有機基から選択される基
、Ｒ２）Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７はメチル基、ま
たはフェニル基に代表される置換または非置換の一価の
炭化水素基、Ｘｌ、Ｉ２はアミノ基、エポキシ基、アル
コキシル基、ポリオ８
キシアルキレン基、水酸基、チオアルコール基、カルボ
キシル基、ハロゲン基などの変性基を含む一価の有機基
から選択されたものである。また、ｍ、 ＩＩ、ＰはＯ
または１以上の整数であって、ｍ＋ｌｌ＋ｐが１０〜２
０００であり、分子中に少なくとも１つはアミノ基を有
しているものである。Here, R1, Re is a group selected from an alkyl group, a hydroxyl group, an alkoxyl group, an aryl group, and a monovalent organic group including an alkyl group, an epoxy group, a thioalcohol group, etc.; R2) R3, R4, R5, R6 , R7 is a methyl group or a substituted or unsubstituted monovalent hydrocarbon group represented by a phenyl group, Xl, I2 are an amino group, an epoxy group, an alkoxyl group, a polyoxyalkylene group, a hydroxyl group, a thioalcohol group, It is selected from monovalent organic groups containing modified groups such as carboxyl groups and halogen groups. Also, m, II, and P are O
or an integer greater than or equal to 1, where m+ll+p is 10 to 2
000, and at least one amino group is present in the molecule.
特にアミノ変性ポリシロキサンの構造が上記式のＲ１−
Ｒ８がメチル基であり、ｎ ＝ Ｏで、Ｉ２が（ＣＨ２
）３ＮＨ（ＣＩ−（２）２ＮＩ−Ｉ２であるものに適用
すると、焼成工程における単繊椎間融着防止効果が著し
く、炭素繊維物性の面から好ましい。In particular, the structure of the amino-modified polysiloxane is R1-
R8 is a methyl group, n = O, and I2 is (CH2
)3NH(CI-(2)2NI-I2), the effect of preventing single fiber intervertebral fusion in the firing process is remarkable and is preferable from the viewpoint of carbon fiber physical properties.
またアミノ変性ポリシロキサンを含んでいれば必要に応
じてジメチルポリシロキサン、ジフェニルポリシロキサ
ン、メチルフェニルポリシロキサン、ポリエーテル変性
、エポキシ変性、メルカプト変性、アルコール変性、カ
ルボキシル変性、フッ素変性などの各オルガノポリシロ
キサンなどを併用することができる。In addition, if amino-modified polysiloxane is included, various organopolymer such as dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, polyether-modified, epoxy-modified, mercapto-modified, alcohol-modified, carboxyl-modified, fluorine-modified etc. Siloxane etc. can be used together.
これらの油剤は非イオン界面活性剤、カチオン界面活性
剤などとともに乳化され、また静電気防止剤などの他の
威勢を含んでいてもよい。シリコーン油剤を水に乳化し
て使用する場合はその乳化安定性から、使用に当たって
は３０℃以下、好ましくは２０’Ｃ以下に保った油剤溶
液とするのが好ましい。These oils are emulsified with nonionic surfactants, cationic surfactants, etc., and may also contain other agents such as antistatic agents. When a silicone oil is emulsified in water and used, it is preferable to maintain the oil solution at a temperature of 30° C. or below, preferably 20'C or below, in view of its emulsion stability.
油剤の付与方法としては特に限定されるものではなく、
デイツプ式、ガイド相油式、噴霧式、バイブロ給油式、
キスリングロール式などの公知の付与方法が採用される
が、単繊維間の融着防止のために乾燥緻密化前に付与す
る必要がある。抽剤の付与量としては、通常糸に対して
０．１〜３％の範囲から選ばれる。The method of applying the oil agent is not particularly limited;
Dip type, guide phase oil type, spray type, vibro oil type,
A known application method such as the Kissling roll method is employed, but it must be applied before drying and densification to prevent fusion between single fibers. The amount of extraction agent applied is usually selected from the range of 0.1 to 3% based on the yarn.
（実施例） 以下実施例により本発明をさらに具体的に説明する。(Example) The present invention will be explained in more detail with reference to Examples below.
本例中、炭素繊維の性能（強度）はＪＩＳＲ−７６０１
に準じて測定したエポキシ樹脂含浸ストランドの物性で
あり、測定回数ｎ＝１０の平均から求めた値である。In this example, the performance (strength) of carbon fiber is JISR-7601
These are the physical properties of an epoxy resin-impregnated strand measured according to the method, and are values determined from the average of n=10 measurements.
また、浴延伸糸の融着判定は、油剤付与前の膨潤糸を約
５ ｒｎ ｍに切断しノイゲンＳＳの０． １重量％水
溶液に分散させ、スタラーで６Ｏｒｐｍ／土分間攪拌後
黒色ろ紙でろ過し、融着繊維本数を数えて融着状態を次
のように級判定した。In addition, to determine the adhesion of the bath-drawn yarn, the swollen yarn before applying the oil agent was cut into approximately 5 rn m, and the 0. It was dispersed in a 1% by weight aqueous solution, stirred with a stirrer at 6 rpm, filtered through black filter paper, counted the number of fused fibers, and graded the fused state as follows.
１級＝融着本数１本以下
２級＝融着本数２〜３本
３級＝融着本数４〜５本
４級＝融着本数６〜７本
５級＝融着本数８本以上
実施例
アクリロニトリル９９．３％、イタコン酸０゜７％から
なるアクリル系共重合体の２０％ジメチルスルホキシド
溶液（４５℃における溶液粘度が６００ポイズの重合体
）を乾湿式紡糸し、溶液とともに下方に引き取り、３５
°Ｃの水中で脱溶媒を行い、膨潤繊維糸条を形成した。1st grade = 1 or less fused strands 2nd grade = 2 to 3 fused strands 3rd grade = 4 to 5 fused strands 4th grade = 6 to 7 fused strands 5th grade = 8 or more fused strands A 20% dimethyl sulfoxide solution of an acrylic copolymer consisting of 99.3% acrylonitrile and 0.7% itaconic acid (a polymer with a solution viscosity of 600 poise at 45°C) is wet-dry spun, and the solution is drawn downward together with the solution. 35
The solvent was removed in water at °C to form a swollen fiber thread.
ついで、５４ｖからなり第１槽の入ローラーおよび第５
槽の出ローラー以外はフリーローラーから構成される浴
延伸工程で、７０°Ｃの熱水中２．５倍延伸を行った。Next, the input roller of the first tank and the fifth
The film was stretched 2.5 times in hot water at 70°C in a bath stretching process in which all rollers other than the exit roller were free rollers.
この延伸糸条をアミノ変性シリコーン（アミン基１１−
の含有量はＮｌ２として１．０％のもの）をノニルフェ
ノールＥＯ付加物を用いて乳化した油剤またはネオペン
チルアルコール系油剤の浴液中に、含浸走行させ、油分
として０．７％付与し、次に乾燥緻密化後連続して加圧
スチーム延伸を行い（全倍率１２倍）巻取って、単繊維
デニール１． Ｏｄ、フィラメント数１２０００のアク
リロニトリル系炭素繊維前恥体系条を得た。This drawn thread is impregnated in a bath solution of an oil agent or a neopentyl alcohol oil agent in which amino-modified silicone (the content of amine group 11- is 1.0% as Nl2) is emulsified using a nonylphenol EO adduct. It was run, 0.7% oil was applied, and then after drying and densification, it was continuously stretched with pressurized steam (total magnification: 12 times) and wound up to obtain a single fiber with a denier of 1. An acrylonitrile-based carbon fiber anterior pubic stratum with Od and 12,000 filaments was obtained.
得られた糸条を２００〜２８０’Ｃの空気中で耐炎化処
理し、のち最高温度１３００’Ｃの炭化炉に導入し、窒
素雰囲気中で炭化し炭素繊維を得た。The obtained yarn was flame-resistant treated in air at 200 to 280'C, then introduced into a carbonization furnace with a maximum temperature of 1300'C, and carbonized in a nitrogen atmosphere to obtain carbon fibers.
得られた炭素繊維（ＣＦ、と略記する）のストランド強
度を第工表に示す。The strand strength of the obtained carbon fiber (abbreviated as CF) is shown in Table 1.
なお比較のため、５槽からなる浴延伸槽の各摺入／出ロ
ーラーが強制邪動ローラーで各浴槽の延伸倍率が１．２
倍で延伸したもの（Ｎｏ、３／Ｎｏ、４、浴延伸温度７
０℃、トータル浴延伸倍率２．５倍）、について得られ
た炭素繊維物性を第１表にあわせて示した。For comparison, each sliding in/out roller of the bath stretching tank consisting of 5 tanks was a forced perturbation roller, and the stretching ratio of each bath was 1.2.
Stretched at double (No, 3/No, 4, bath stretching temperature 7
The physical properties of the carbon fibers obtained at 0° C. and a total bath stretching ratio of 2.5 times are also shown in Table 1.
第工表より本発明の延伸方法によって単繊維間１２−
融着を減少させて炭素繊維の強度を向上させることがで
き、アミノ変性シリコーン油剤の付与により炭素繊維強
度向上効果はさらに高まることが明らかである。It is clear from Table 1 that the stretching method of the present invention can reduce the 12-fusion between single fibers and improve the strength of carbon fibers, and that the effect of improving carbon fiber strength is further enhanced by adding amino-modified silicone oil. It is.
このように本発明によれば、その物性を著しく向上させ
ることのできる、炭素繊維の製造が可能である。As described above, according to the present invention, it is possible to produce carbon fibers whose physical properties can be significantly improved.
（以下余白）
第１表
延伸方法 Ａ：フリーローラ一方弐
Ｂ：郭動ローラ一方式
（発明の効果）
本発明の炭素繊維用アクリル系前駆体糸条の製造法によ
れば、単繊椎間融着のない糸条を焼成工程に供給でき、
安定して高品質・高性能の炭素繊維を製造することが可
能になる。(Margin below) Table 1 Stretching method A: One free roller, two B: One disintegrating roller (effects of the invention) According to the method for producing an acrylic precursor yarn for carbon fibers of the present invention, a single fiber intervertebral Unfused yarn can be supplied to the firing process,
It becomes possible to stably produce high-quality, high-performance carbon fiber.
Claims (2)
ル系重合体溶液を紡糸後、湿潤糸条を延伸する方法にお
いて、少なくとも２つ以上の分離した延伸浴槽間にフリ
ーローラーを配し、該延伸浴槽中３０〜９８℃の水中で
多槽延伸することを特徴とする、炭素繊維用アクリル系
前駆体糸条の製造法。(1) In a method of drawing a wet yarn after spinning an acrylic polymer solution containing 90% by weight or more of acrylonitrile, a free roller is arranged between at least two or more separate drawing baths, A method for producing an acrylic precursor yarn for carbon fibers, the method comprising multi-tank drawing in water at ~98°C.
少なくとも１成分はアミノ変性ポリシロキサンからなる
原糸油剤を付与することを特徴とする、炭素繊維用アク
リル系前駆体糸条の製造法。(2) In claim 1, the acrylic precursor yarn for carbon fibers is characterized in that a yarn lubricant, at least one component of which is an amino-modified polysiloxane, is applied to the stretched yarn. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1201078A JPH0627367B2 (en) | 1989-08-01 | 1989-08-01 | Method for producing acrylic precursor yarn for carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1201078A JPH0627367B2 (en) | 1989-08-01 | 1989-08-01 | Method for producing acrylic precursor yarn for carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0364514A true JPH0364514A (en) | 1991-03-19 |
| JPH0627367B2 JPH0627367B2 (en) | 1994-04-13 |
Family
ID=16435028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1201078A Expired - Fee Related JPH0627367B2 (en) | 1989-08-01 | 1989-08-01 | Method for producing acrylic precursor yarn for carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0627367B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05171522A (en) * | 1991-12-26 | 1993-07-09 | Toray Ind Inc | Production of precursor fiber for carbon fiber |
| WO1997045576A1 (en) * | 1996-05-24 | 1997-12-04 | Toray Industries, Inc. | Carbon fiber, acrylic fiber, and method of manufacturing them |
| KR101470250B1 (en) * | 2013-12-17 | 2014-12-08 | 주식회사 효성 | Method of manufacturing precursor for carbon fiber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50154531A (en) * | 1974-05-30 | 1975-12-12 | ||
| JPS60185879A (en) * | 1984-02-29 | 1985-09-21 | 竹本油脂株式会社 | Oil agent for producing carbon fiber |
| JPS62275718A (en) * | 1986-05-26 | 1987-11-30 | Nippon Denso Co Ltd | Resin molding tool |
-
1989
- 1989-08-01 JP JP1201078A patent/JPH0627367B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50154531A (en) * | 1974-05-30 | 1975-12-12 | ||
| JPS60185879A (en) * | 1984-02-29 | 1985-09-21 | 竹本油脂株式会社 | Oil agent for producing carbon fiber |
| JPS62275718A (en) * | 1986-05-26 | 1987-11-30 | Nippon Denso Co Ltd | Resin molding tool |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05171522A (en) * | 1991-12-26 | 1993-07-09 | Toray Ind Inc | Production of precursor fiber for carbon fiber |
| WO1997045576A1 (en) * | 1996-05-24 | 1997-12-04 | Toray Industries, Inc. | Carbon fiber, acrylic fiber, and method of manufacturing them |
| KR101470250B1 (en) * | 2013-12-17 | 2014-12-08 | 주식회사 효성 | Method of manufacturing precursor for carbon fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0627367B2 (en) | 1994-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4378343A (en) | Process for producing carbon fiber tows | |
| KR870000533B1 (en) | Carbon fiber's making method | |
| JP2006299439A (en) | Carbon fiber, method for producing the same, acrylonitrile precursor fiber and method for producing the same | |
| JP2001172880A (en) | Silicone oil agent for carbon fiber and method for producing carbon fiber | |
| US4659623A (en) | Acrylic fibers for producing preoxidized fibers | |
| JPH0364514A (en) | Production of acrylic precursor yarn for carbon fiber | |
| JPH0340152B2 (en) | ||
| JP4862226B2 (en) | Precursor fiber for carbon fiber and method for producing carbon fiber | |
| JP2596092B2 (en) | Manufacturing method of raw yarn for carbon fiber | |
| JP2004169198A (en) | Precursor fiber strand for carbon fiber and method for producing the same | |
| JPH08246284A (en) | Drawing apparatus by steam and drawing method by steam | |
| JPH0291225A (en) | Production of raw material yarn for carbon yarn | |
| JPH0433891B2 (en) | ||
| JP2875667B2 (en) | Method of stretching acrylic yarn for carbon fiber precursor in bath | |
| JPS6183374A (en) | Acrylic precursor fiber bundle | |
| JP6729665B2 (en) | Acrylonitrile precursor fiber bundle for carbon fiber and method for producing the same | |
| JP4048230B2 (en) | Precursor fiber for carbon fiber and method for producing the same | |
| JP2555826B2 (en) | Acrylic yarn manufacturing method for carbon fiber precursor | |
| JP7408406B2 (en) | Method for manufacturing flame-resistant fiber bundle, method for manufacturing carbon fiber bundle, and connection device | |
| JP2589192B2 (en) | Wet spinning and storage of acrylic fibers | |
| JP2002371438A (en) | Graphitized fiber and composite material | |
| JPS6059116A (en) | Acrylic fiber as precursor for carbon fiber | |
| JPS63135510A (en) | Production of precursor yarn for producing carbon yarn | |
| JPS62133123A (en) | Production of carbon fiber and graphite fiber | |
| JP2015161056A (en) | Acrylonitrile precursor fiber bundle for carbon fiber and production method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080413 Year of fee payment: 14 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090413 Year of fee payment: 15 |
|
| LAPS | Cancellation because of no payment of annual fees |