JPS627287B2 - - Google Patents
Info
- Publication number
- JPS627287B2 JPS627287B2 JP55152558A JP15255880A JPS627287B2 JP S627287 B2 JPS627287 B2 JP S627287B2 JP 55152558 A JP55152558 A JP 55152558A JP 15255880 A JP15255880 A JP 15255880A JP S627287 B2 JPS627287 B2 JP S627287B2
- Authority
- JP
- Japan
- Prior art keywords
- chitin
- yarn
- fibers
- solvent
- dope
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920002101 Chitin Polymers 0.000 claims description 70
- 239000000835 fiber Substances 0.000 claims description 46
- 238000005345 coagulation Methods 0.000 claims description 35
- 230000015271 coagulation Effects 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 17
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical group OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 230000001112 coagulating effect Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002166 wet spinning Methods 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 6
- -1 poly(N-acetyl-D-glucosamine) Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- 241000238424 Crustacea Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009954 braiding Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940035674 anesthetics Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003193 general anesthetic agent Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Artificial Filaments (AREA)
Description
本発明は、キチン繊維の製造法に関するもので
あり、さらに詳しくは高強力でかつ柔軟性があ
り、とくに吸収性外科用縫合糸の調製に適したキ
チン繊維およびその製造法に関するものである。
キチンはポリ(N―アセチル―D―グルコサミ
ン)からなる多糖類であり、甲殻類の外骨格など
天然に広く分布している物質であり、その分子の
くり返し単位ごとに1個のアミノアセチル基を有
するため多くの興味ある独特の性質を有してい
る。その性質の一つとして、人体内で酵素分解を
起して組織内に吸収されることおよび良好な染色
性を有することがあげられ、このためキチンを繊
維化して吸収性外科用縫合糸として利用すること
が提案されている。
吸収性外科用縫合糸は、生体適合性がよいこ
と、生体内で一定期間強度を保持した後に吸収さ
れることおよび滅菌が可能なことは当然の条件と
して、さらに縫いやすさや結びやすさなどの使用
性がよいこと、引張強度や柔軟性などをはじめと
する縫合糸としての適当な物性をもつなどの条件
が必要である。縫合糸は通常、複数本の繊維を撚
つてから編み糸にするかあるいは組みひもにする
ことにより製造されるが、縫合糸が上記のごとき
性能を満足するためには、とくに上記のごとき使
用性の良さと縫合糸としての適当な物性を有する
ためには、少なくともこれを構成する繊維が適当
な強度と太さをもつことが必要である。具体的に
は、繊維は少なくとも2g/dの乾強度と20デニ
ール以下の太さ、望ましくは0.5〜20デニールの
太さをもつことが必要である。
従来、キチン溶液を湿式紡糸として繊維を製造
することは種々提案されているが、上記のごとき
強度と太さの両性能を兼ね備えたものは得られて
いないのが現状である。
たとえば、特開昭51―133367号公報には、キチ
ンをトリクロル酢酸を含有する溶液に溶解してキ
チンドープを調製し、このものを湿式紡糸したの
ち冷延伸して高強力のキチン繊維を得たことが記
載されているが、得られた繊維は太さが非常に太
いものである。すなわち、その実施例2には抗張
力が63Kg/mm2のフイラメントが得られたことが示
されており、この値は密度を1.4として算定すれ
ば5g/dに相当するものであり高強力のキチン
繊維が得られていることが明らかであるが、その
太さは、たとえば実施例3にみられるように直径
が0.25mmのものであり、これは密度を1.4として
算定すれば618デニールに相当し、前記条件を満
足するものではない。
また、特開昭53―127500号公報には、キチンを
ジクロル酢酸などの溶剤に溶解してキチンドープ
を調製し、このものを湿式紡糸したのち延伸して
細デニールのキチン繊維を得たことが記載されて
いるが、得られた繊維は強度の小さいものであ
る。すなわち、その実施例には3.0〜3.5デニール
のキチン繊維が得られたことが示されているので
あるが、その強度は1.2〜1.5g/dであり、前記
条件を満足するものではない。
以上のように、従来、外科用縫合糸の調製に使
用できるほどに十分な強度と十分な柔軟性、すな
わち適当な太さを有するキチン繊維は知られてい
なかつた。
本発明者らは、かかる現状に鑑み、外科用縫合
糸の調製に使用できるほどに十分な強度と十分な
柔軟性、すなわち適当な太さを有する繊維、さら
に具体的には少なくとも2g/dの強度と0.5〜
20デニールの太さをもつキチン繊維を提供するこ
とを目的として鋭意研究を重ねた結果、凝固浴で
形成された糸条をフリーな状態でさらに凝固液で
処理することによつて上記の目的が達成できるこ
とを見い出し、本発明に到達したものである。
すなわち本発明は、キチンと溶剤とからなるキ
チンドープを湿式紡糸してキチン繊維を製造する
に際し、キチンドープをノズルを通し凝固浴中に
押出し、引取ることにより溶剤を含有する糸条を
形成し、形成した糸条を、糸条に実質的に緊張力
が作用しない状態で凝固液にて処理することを特
徴とするキチン繊維の製造法である。
本発明におけるキチンには、キチンそのものの
ほかにキチンの誘導体も含まれる。本発明に用い
るキチンは、たとえば甲殻類、昆虫類などを塩酸
処理ならびにカ性ソーダ処理してタン白およびカ
ルシウム分を分離精製することにより、あるいは
それらをたとえばエーテル化、エステル化などす
ることにより調製することができる。本発明に用
いられるキチンの誘導体としては、たとえばカル
ボキシメチル化チキン、ヒドロキシエチル化キチ
ンなどのエーテル化キチン、アセチル化キチン、
スルホン化キチンなどのエステル化キチンがあげ
られる。エステル化物としては、たとえばギ酸、
酢酸、酪酸、吉草酸、イソ酪酸、イソ吉草酸、安
息香酸、ケイ皮酸、サリチル酸、アントラニル
酸、フタル酸などのカルボン酸類、硫酸、トルエ
ンスルホン酸、スルフアニル酸などのスルホン酸
類、炭酸類あるいはそれらの無水物のエステル化
物があげられる。これらのエステル化物を調製す
るには、たとえばキチンの粉末を上記のごとき酸
またはその水溶液で処理すればよく、必要に応じ
て触媒として、たとえば硫酸、塩酸、トルエンス
ルホン酸などを用いることもできる。エステル化
度は処理液の組成、温度あるいは処理時間で調整
が可能である。たとえばアセチル化の場合は比較
的短時間で処理が可能である。たとえば90%酢酸
でキチンの粉末を常温において10分間浸漬したの
ち十分に水洗し、ついで水酸化アンモニウムなど
で中和して遊離の酢酸を完全に除去し、乾燥する
ことによりアセチル化度約6%のアセチル化キチ
ンを調製することができる。
本発明においてキチンドープの調製に用いる溶
剤としては公知の種々のキチンの溶剤があげられ
るが、トリクロル酢酸が好ましく用いられる。ト
リクロル酢酸は融点が57℃であるのでキチンドー
プを得るためには少なくとも57℃以上に維持する
必要がある。かかる温度ではある程度キチンの分
解が伴うので、溶媒としてトリクロル酢酸ととも
に、好ましくは50℃以下、より好ましくは常温以
下でトリクロル酢酸を溶解しうる有機溶剤を併用
するのが望ましい。トリクロル酢酸を溶解し、常
温で均一なキチンドープを提供しうる溶剤として
は、たとえば塩素化炭化水素があげられる。好ま
しい塩素化炭化水素としては、たとえばクロルメ
タン、ジクロルメタン、クロロホルム、四塩化炭
素、1,2―ジクロルエタン、1,1,1―トリ
クロルエタン、1,1,2―トリクロルエタンな
どがあげられ、これらは単独で使用してもよい
し、2種以上混合して使用することもできる。ト
リクロル酢酸と塩素化炭化水素の混合割合は25〜
75:75〜25(重量比)の範囲が好ましい。トリク
ロル酢酸の割合が高いほどキチンの溶解性はよい
が、キチンの分解に伴う分子量低下をさけるため
には、混合溶剤が常温以下で液状である上記の範
囲が好ましい。本発明においてキチンドープは、
たとえば以下のようにして調製することができ
る。すなわち溶剤としてトリクロル酢酸のみを用
いる場合はトリクロル酢酸を少なくとも57℃以上
に加温しながらキチンの粉末を徐々に加え、撹拌
混合して溶解させればよい。また、溶剤としてト
リクロル酢酸と塩素化炭化水素の混合溶剤を用い
る場合は予め塩素化炭化水素にトリクロル酢酸を
添加混合し、できるだけ低温、好ましくは10℃以
下で液状の混合溶剤を得、しかるのちこの混合溶
剤中にキチンの粉末を徐々に加え、撹拌混合して
溶解させればよい。キチンドープ中のキチンの濃
度は、好ましくは0.5〜20重量%、より好ましく
は0.5〜10重量%、さらに好ましくは1〜10重量
%である。キチンの濃度が高くなりすぎると溶解
がしにくく、またそのようなキチンドープからの
繊維の製造もしにくくなるし、一方、低くなりす
ぎると機械的性質のすぐれた繊維が得にくくなる
ので好ましくない。
本発明においてはキチンドープ中に、たとえば
染料、顔料、安定剤、酸化防止剤、耐熱剤、殺菌
剤、防腐剤、麻酔剤、充填剤などの添加剤を必要
に応じて添加することができる。
本発明の方法によつてキチン繊維を製造するに
は、まず上記のようにして調製したキチンドープ
をノズルを通し凝固浴中に押出し、引取ることに
より溶剤を含有する糸条を形成することが必要で
ある。凝固浴としては、たとえばアセトン、メチ
ルエチルケトン、メチルイソブチルケトン、ジエ
チルケトン、シクロペンタノンなどの有機ケトン
類、エチレンクロリド、四塩化炭素、トリクロル
エチレン、テトラヒドロフランなどの塩素化炭化
水素、シクロヘキサン、ヘキサン、石油エーテル
などの炭化水素、メタノール、エタノール、イソ
プロピルアルコール、n―ブチルアルコールなど
のアルコール類、酢酸エチルなどのエステル類、
ジメチルホルムアミド、N―メチルピロリドンな
どのアミド類などを使用することができるが、と
くに無水アセトン、無水メタノールあるいは無水
エタノールなどが好ましい。凝固浴の温度は10〜
25℃程度が好適である。キチンドープは、必要に
応じて濾過、脱泡されたのちノズルより凝固浴中
に押出され、引取られるが、このためには慣用の
湿式紡糸装置および方法を採用することができ
る。この際、引取られた糸条は溶剤を含有してい
る状態、すなわち不完全凝固の状態であることが
必要である。
本発明においては、上記のようにして形成され
た糸条を、ついで、糸条に実質的に緊張力が作用
しない状態で凝固液で処理することが必要であ
る。引取られた糸条は、上述のごとくいまだ溶剤
を一部含有しているものであるが、このものを実
質的に緊張力が作用しない状態で凝固液で処理す
るには、たとえば紡出後、凝固浴(第1凝固浴)
を経てロールに引取られた糸条を第2凝固浴に導
入して処理する方法を採用することができる。こ
の方法をより具体的に示すために、実施の一形態
を第1図に示す。第1図において、ノズルより第
1凝固浴に押出されたのちローラーにより引取ら
れた糸条1aは、導入ローラー2よりコンベヤー
3上に振落され糸山1bを形成する。コンベヤー
3は第2凝固浴4中にあり、糸条1aの導入速度
より遅い速度で移動しており、糸条は第2凝固浴
4中で凝固が進められたのち糸山1bから再び糸
条1cの状態に戻され、引取りローラー5により
引取られる。また、他の実施の一形態を第2図に
示す。第2図において、ノズルより第1凝固浴に
押出されたのちローラーにより引取られた糸条1
aは導入ローラー2により糸条の詰め込みが可能
な曲面パイプの形状を有する装置、たとえばU字
管6中に落され、積層される。U字管6中には凝
固液が満されており、糸条は積層圧によりU字管
6の他の口に移動しながら凝固が進められたのち
再び糸条1cの状態に戻され、引取りローラー5
により引取られる。本発明においては、第2凝固
浴を複数個設けることも可能であるし、また第2
凝固浴中に導入された糸条をそのまま凝固浴中に
積層したのち引取ることも可能であるし、さらに
は改めて第2凝固浴を設けることなく第1凝固浴
中で処理を行なうなど、糸条に実質的に緊張力が
作用しない状態で処理できるものであればいかな
る方法も採用することができる。かかる処理に用
いられる凝固液としては、前述の凝固浴(紡糸
浴)に用いられたものが使用できる。
本発明において前述の凝固液による処理を行な
うにあたり、糸条の溶剤残存量は処理前で10〜50
重量%(ポリマーに対し)、処理後で10重量%以
下の範囲にあることが好ましい。処理時間は1分
以上、とくに10分以上であることが望ましい。ま
た、一晩以上放置することも好ましい方法であ
る。
上記のようにして得られた繊維は、そのままで
も2g/d以上の乾強度を有しているが、このも
のを延伸することにより、さらに高強度の繊維を
得ることができる。延伸は凝固液による処理に引
続き行なつてもよく、また中和、洗浄後に行なう
こともでき、公知の種々の装置を用いることがで
きるが、たとえば元の長さの約20〜80%延伸する
ことができる。
凝固液による処理がなされた糸条は、必要に応
じ中和、洗浄、乾燥される。中和、洗浄、乾燥に
は公知の種々の装置および方法を按用することが
できる。
以上のように本発明によれば0.5〜20デニール
の単糸デニールを有し、しかも少なくとも2g/
d、好ましくは2.5g/d以上、より好ましくは
3g/d以上、さらに好ましくは3.5g/d以上
の乾強度を有するキチン繊維を得ることが可能で
あり、このものはとくに吸収性外科用縫合糸を調
製するための繊維としては好ましいものである。
本発明の方法により得られるキチン繊維は、た
とえばトータルデニールが30〜200デニールのも
のとして衣料用糸や特殊糸に、さらには編物、織
物としても使用ができる。
以下実施例をあげて本発明をさらに具体的に説
明する。なお、例中の乾強度は25℃、60%R.H.
調湿下にインストロン引張試験器で測定したもの
である。
実施例1、比較例1,2
キチン粉末〔共和油脂(株)製、重合度約100万〕
3重量部を、トリクロル酢酸50重量部および塩化
メチレン50重量部からなる混合溶剤に5℃で溶解
してキチンドープを得た。得られたドープは透明
で粘稠な溶液であつた。このドープを1480メツシ
ユのステンレス製金網を用いて4Kg/cm2の加圧下
に濾過したのち、減圧下に十分脱泡した。脱泡し
たドープをタンクに移したのち2.5Kg/cm2の加圧
下、ギヤーポンプで送液して孔径0.08mm、孔数40
のノズルから吐出量2.3ml/分で14℃に調温され
たアセトン(第1凝固浴)中に紡出して糸条を形
成し、10m/分の速度でローラーに引取つた。引
取つた糸条を引続き第1図に示す装置に導き、15
℃に調温されたメタノール(第2凝固浴)中、
0.5m/分の速度で移動するコンベヤー上で5分
間処理したのち9m/分の速度でワインダーに捲
取つた。捲取つた糸条を濃度0.3g/のカ性ソ
ーダ水溶液に1時間浸漬して中和したのちイオン
交換水で洗浄水のPHが中性になるまで洗浄し、つ
いで遠心脱水機で脱水し、室温で一晩減圧乾燥し
て、キチン繊維を得た(試料A)。得られたキチ
ン繊維のデニール、乾強度および残留伸度を測定
した結果は表1に示すとおりであつた。
比較のため、ベルトコンベヤーを使用せずに、
第2凝固浴中を緊張状態のまま単に通過させた他
は実施例1と同様にしてキチン繊維を得た(試料
B)。また、ベルトコンベヤーを使用せずに、第
2凝固浴中にローラー部が凝固浴中に浸漬されて
いる平行の対ローラーを設け、この対ローラーに
糸条を20回捲きつけて緊張状態で処理した他は実
施例1と同様にしてキチン繊維を得た(試料
C)。得られた試料B,Cについて試料Aと同様
にその性能を測定した。その結果は表1に示すと
おりであつた。
TECHNICAL FIELD The present invention relates to a method for producing chitin fibers, and more particularly to chitin fibers having high strength and flexibility, and particularly suitable for the preparation of absorbable surgical sutures, and a method for producing the same. Chitin is a polysaccharide consisting of poly(N-acetyl-D-glucosamine), a substance widely distributed in nature such as the exoskeleton of crustaceans, and has one aminoacetyl group in each repeating unit of its molecule. It has many interesting and unique properties. One of its properties is that it undergoes enzymatic decomposition within the human body and is absorbed into tissues, and that it has good dyeability.For this reason, chitin is turned into fibers and used as absorbable surgical sutures. It is proposed to do so. Absorbable surgical sutures must have good biocompatibility, be absorbed after retaining their strength within the body for a certain period of time, and be sterilizable, as well as being easy to sew and tie. It must be easy to use and have suitable physical properties as a suture thread, such as tensile strength and flexibility. Sutures are usually manufactured by twisting multiple fibers and then knitting or braiding them, but in order for sutures to satisfy the above performance, they must be particularly usable as described above. In order to have good properties and appropriate physical properties as a suture thread, at least the fibers constituting it need to have appropriate strength and thickness. Specifically, the fibers need to have a dry strength of at least 2 g/d and a thickness of 20 denier or less, preferably 0.5 to 20 denier. In the past, various proposals have been made to produce fibers by wet spinning a chitin solution, but at present no fibers have been obtained that have both the above-mentioned properties of strength and thickness. For example, JP-A-51-133367 discloses that a chitin dope was prepared by dissolving chitin in a solution containing trichloroacetic acid, which was wet-spun and then cold-stretched to obtain highly strong chitin fibers. However, the obtained fibers are very thick. In other words, Example 2 shows that a filament with a tensile strength of 63 kg/mm 2 was obtained, and this value is equivalent to 5 g/d when the density is calculated as 1.4, which is a high-strength chitin. It is clear that fibers have been obtained, but the diameter of the fibers is 0.25 mm as seen in Example 3, which corresponds to 618 denier when calculated with a density of 1.4. , does not satisfy the above conditions. Additionally, JP-A-53-127500 describes that chitin dope was prepared by dissolving chitin in a solvent such as dichloroacetic acid, which was wet-spun and then drawn to obtain fine denier chitin fibers. However, the strength of the obtained fibers is low. That is, although the example shows that chitin fibers of 3.0 to 3.5 deniers were obtained, the strength thereof was 1.2 to 1.5 g/d, which does not satisfy the above conditions. As described above, chitin fibers having sufficient strength and flexibility, that is, appropriate thickness, to be used for preparing surgical suture threads have not been known so far. In view of the current situation, the present inventors have developed a fiber having sufficient strength and sufficient flexibility, that is, an appropriate thickness, to be used in the preparation of surgical sutures, and more specifically, a fiber having a thickness of at least 2 g/d. Strength and 0.5~
As a result of extensive research with the aim of providing chitin fibers with a thickness of 20 denier, the above objective was achieved by further treating the threads formed in a coagulation bath in a free state with a coagulation solution. We have discovered what can be achieved and arrived at the present invention. That is, the present invention, when producing chitin fiber by wet spinning a chitin dope consisting of chitin and a solvent, extrudes the chitin dope through a nozzle into a coagulation bath and takes it out to form a thread containing the solvent. This method of producing chitin fibers is characterized in that the obtained yarn is treated with a coagulating liquid in a state where substantially no tension is applied to the yarn. Chitin in the present invention includes not only chitin itself but also chitin derivatives. Chitin used in the present invention can be prepared by, for example, treating crustaceans, insects, etc. with hydrochloric acid and caustic soda to separate and purify protein and calcium components, or by etherifying, esterifying, etc. can do. Examples of chitin derivatives used in the present invention include etherified chitin such as carboxymethylated chicken, hydroxyethylated chitin, acetylated chitin,
Examples include esterified chitin such as sulfonated chitin. Examples of esterified products include formic acid,
Carboxylic acids such as acetic acid, butyric acid, valeric acid, isobutyric acid, isovaleric acid, benzoic acid, cinnamic acid, salicylic acid, anthranilic acid, phthalic acid, sulfonic acids such as sulfuric acid, toluenesulfonic acid, sulfanilic acid, carbonates, or the like. Examples include esterified products of anhydrides. To prepare these esterified products, for example, chitin powder may be treated with the above-mentioned acids or their aqueous solutions, and if necessary, sulfuric acid, hydrochloric acid, toluenesulfonic acid, etc. can also be used as a catalyst. The degree of esterification can be adjusted by changing the composition, temperature, or treatment time of the treatment solution. For example, acetylation can be carried out in a relatively short time. For example, chitin powder is soaked in 90% acetic acid for 10 minutes at room temperature, thoroughly washed with water, then neutralized with ammonium hydroxide to completely remove free acetic acid, and dried to achieve an acetylation degree of approximately 6%. Acetylated chitin can be prepared. In the present invention, various known chitin solvents can be used as the solvent for preparing the chitin dope, but trichloroacetic acid is preferably used. Since the melting point of trichloroacetic acid is 57°C, it is necessary to maintain the temperature at least above 57°C in order to obtain chitin dope. Since chitin decomposes to some extent at such temperatures, it is desirable to use trichloroacetic acid as a solvent together with an organic solvent that can dissolve trichloroacetic acid, preferably at 50° C. or lower, more preferably at room temperature or lower. Examples of solvents that can dissolve trichloroacetic acid and provide a uniform chitin dope at room temperature include chlorinated hydrocarbons. Preferred chlorinated hydrocarbons include, for example, chloromethane, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, etc., and these may be used alone. They may be used alone, or two or more kinds may be used in combination. The mixing ratio of trichloroacetic acid and chlorinated hydrocarbon is 25~
The range of 75:75 to 25 (weight ratio) is preferable. The higher the proportion of trichloroacetic acid, the better the solubility of chitin, but in order to avoid a decrease in the molecular weight due to the decomposition of chitin, the above range in which the mixed solvent is liquid at room temperature or lower is preferable. In the present invention, the chitin dope is
For example, it can be prepared as follows. That is, when only trichloroacetic acid is used as a solvent, chitin powder may be gradually added while heating the trichloroacetic acid to at least 57°C or higher, and the chitin powder may be stirred and mixed to dissolve it. In addition, when using a mixed solvent of trichloroacetic acid and chlorinated hydrocarbon as a solvent, add and mix trichloroacetic acid to the chlorinated hydrocarbon in advance to obtain a liquid mixed solvent at as low a temperature as possible, preferably below 10°C. Chitin powder may be gradually added to the mixed solvent and dissolved by stirring and mixing. The concentration of chitin in the chitin dope is preferably 0.5-20% by weight, more preferably 0.5-10% by weight, even more preferably 1-10% by weight. If the concentration of chitin becomes too high, it will be difficult to dissolve and produce fibers from such a chitin dope, while if it becomes too low, it will be difficult to obtain fibers with excellent mechanical properties, which is undesirable. In the present invention, additives such as dyes, pigments, stabilizers, antioxidants, heat resistant agents, bactericides, preservatives, anesthetics, and fillers may be added to the chitin dope as necessary. To produce chitin fibers by the method of the present invention, it is first necessary to extrude the chitin dope prepared as described above into a coagulation bath through a nozzle and take it off to form a thread containing a solvent. It is. Examples of coagulation baths include organic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and cyclopentanone, chlorinated hydrocarbons such as ethylene chloride, carbon tetrachloride, trichlorethylene, and tetrahydrofuran, cyclohexane, hexane, and petroleum ether. hydrocarbons such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, esters such as ethyl acetate,
Amides such as dimethylformamide and N-methylpyrrolidone can be used, but anhydrous acetone, anhydrous methanol, or anhydrous ethanol are particularly preferred. The temperature of the coagulation bath is 10~
A temperature of about 25°C is suitable. The chitin dope is filtered and defoamed if necessary, and then extruded from a nozzle into a coagulation bath and taken off. For this purpose, a conventional wet spinning device and method can be employed. At this time, it is necessary that the yarn taken off contains a solvent, that is, is in an incompletely coagulated state. In the present invention, it is necessary to treat the yarn formed as described above with a coagulating liquid in a state where substantially no tension is applied to the yarn. As mentioned above, the taken yarn still contains some solvent, but in order to treat it with a coagulation liquid in a state where no tension is applied, for example, after spinning, Coagulation bath (first coagulation bath)
It is possible to adopt a method in which the yarn taken up by a roll through the steps is introduced into a second coagulation bath and treated. In order to show this method more specifically, one embodiment is shown in FIG. In FIG. 1, a yarn 1a is extruded from a nozzle into a first coagulation bath and then taken up by a roller, and is shaken off from an introduction roller 2 onto a conveyor 3 to form a yarn pile 1b. The conveyor 3 is in the second coagulation bath 4 and is moving at a speed slower than the introduction speed of the yarn 1a, and after the yarn is coagulated in the second coagulation bath 4, it is returned from the yarn pile 1b to the yarn 1c. It is returned to the state shown in FIG. Further, another embodiment is shown in FIG. In Fig. 2, a yarn 1 is extruded from a nozzle into a first coagulation bath and then taken off by a roller.
A is dropped by an introduction roller 2 into a device having the shape of a curved pipe capable of stuffing yarn, such as a U-shaped tube 6, and is laminated. The U-shaped tube 6 is filled with a coagulating liquid, and the yarn is moved to the other opening of the U-shaped tube 6 due to the lamination pressure and coagulated, and then returned to the state of the yarn 1c and pulled. Take-off roller 5
It will be taken over by. In the present invention, it is possible to provide a plurality of second coagulation baths, and it is also possible to provide a plurality of second coagulation baths.
It is possible to stack the yarn introduced into the coagulation bath as it is in the coagulation bath and then take it off, or it is also possible to treat the yarn in the first coagulation bath without providing a second coagulation bath. Any method can be used as long as it can be processed without substantially applying tension to the strip. As the coagulating liquid used in this treatment, those used in the above-mentioned coagulating bath (spinning bath) can be used. In the present invention, when performing the treatment with the above-mentioned coagulation liquid, the residual amount of solvent in the yarn is 10 to 50% before treatment.
% by weight (based on the polymer), preferably in a range of 10% by weight or less after treatment. It is desirable that the treatment time is 1 minute or more, particularly 10 minutes or more. Another preferred method is to leave it for one night or more. The fibers obtained as described above have a dry strength of 2 g/d or more as is, but by stretching them, fibers with even higher strength can be obtained. Stretching may be carried out subsequent to treatment with a coagulating solution, or may be carried out after neutralization and washing, and various known devices may be used; be able to. The yarn treated with the coagulation liquid is neutralized, washed, and dried as necessary. Various known devices and methods can be used for neutralization, washing, and drying. As described above, according to the present invention, the single yarn has a denier of 0.5 to 20 denier, and at least 2 g/
It is possible to obtain chitin fibers having a dry strength of d, preferably 2.5 g/d or more, more preferably 3 g/d or more, even more preferably 3.5 g/d or more, which is particularly useful for absorbable surgical sutures. It is preferred as a fiber for preparing yarn. The chitin fibers obtained by the method of the present invention have a total denier of, for example, 30 to 200 deniers and can be used as clothing yarns or special yarns, as well as knitted fabrics and woven fabrics. The present invention will be explained in more detail below by giving examples. In addition, the dry strength in the example is 25℃, 60%RH
It was measured using an Instron tensile tester under controlled humidity. Example 1, Comparative Examples 1 and 2 Chitin powder [manufactured by Kyowa Yushi Co., Ltd., degree of polymerization approximately 1 million]
A chitin dope was obtained by dissolving 3 parts by weight in a mixed solvent consisting of 50 parts by weight of trichloroacetic acid and 50 parts by weight of methylene chloride at 5°C. The dope obtained was a clear and viscous solution. This dope was filtered under a pressure of 4 kg/cm 2 using a stainless wire mesh of 1480 mesh, and then thoroughly defoamed under reduced pressure. After the defoamed dope was transferred to a tank, it was pumped with a gear pump under a pressure of 2.5 kg/cm 2 to form a hole with a pore diameter of 0.08 mm and 40 holes.
The yarn was spun into acetone (first coagulation bath) whose temperature was controlled at 14° C. at a discharge rate of 2.3 ml/min from a nozzle, and the yarn was drawn onto a roller at a speed of 10 m/min. The collected yarn is then guided to the device shown in Figure 1, and 15
In methanol (second coagulation bath) whose temperature was controlled to ℃,
After processing for 5 minutes on a conveyor moving at a speed of 0.5 m/min, it was wound up into a winder at a speed of 9 m/min. The wound yarn was immersed in a caustic soda aqueous solution with a concentration of 0.3 g for 1 hour to neutralize it, then washed with ion-exchanged water until the pH of the washing water became neutral, and then dehydrated with a centrifugal dehydrator. Chitin fibers were obtained by drying under reduced pressure at room temperature overnight (sample A). The results of measuring the denier, dry strength and residual elongation of the obtained chitin fibers are shown in Table 1. For comparison, without using a belt conveyor,
Chitin fibers were obtained in the same manner as in Example 1, except that the fibers were simply passed through the second coagulation bath under tension (Sample B). In addition, instead of using a belt conveyor, a parallel pair of rollers with the roller part immersed in the coagulation bath is installed in the second coagulation bath, and the yarn is wound around this pair of rollers 20 times to process it in a tensioned state. Chitin fibers were obtained in the same manner as in Example 1 except for the above (Sample C). The performance of the obtained Samples B and C was measured in the same manner as Sample A. The results were as shown in Table 1.
【表】
試料Aを12本とつて組ひもとし、米国薬局方×
×版のコラーゲン縫合糸の規格で3―0の太さの
縫合糸を作成した。得られた縫合糸の引張抗張力
は2.41Kgであり、日本薬局方の抗張力の基準とな
る結節抗張力は1.87Kgであり、規格(結節抗張力
1.25Kg以上)に合格するものであつた。また、こ
のものは柔軟であり、取扱い易く、外科用縫合糸
として十分使用可能であつた。
これに対し、試料Bおよび試料Cを用いて試料
Aの場合と同様に組ひもの作成を試みたが、繊維
の強度が低いために組ひもの作成時に糸条の切断
が激しく、良好な組ひもを得ることができなかつ
た。
実施例 2〜6
実施例1と同一のドープを使用し実施例1と同
様の濾過および脱泡を行なつた。脱泡したドープ
をタンクに移したのち2.5Kg/cm2の加圧下、ギヤ
ーポンプで送液して孔径0.07mm、孔数30のノズル
から吐出量2.5ml/分で16℃に調温されたメタノ
ール(第1凝固浴)中に紡出して糸条を形成し、
15m/minの速度でローラーに引取つた。引取つ
た糸条を引続き0.3g/のカ性ソーダを含んだ
メタノール(第2凝固浴)中に実質的に張力のか
からないフリーの状態で蓄積浸漬した。浸漬した
糸条を1分(実施例2)、10分(実施例3)、1時
間(実施例4)、10時間(実施例5)、24時間(実
施例6)の間隔で浴中から取出し、それぞれ0.5
g/の濃度のカ性ソーダ水溶液で約1時間中和
した後、洗浄水が中性になるまでイオン交換水で
洗浄を繰りかえしついで遠心脱水機で脱水し室温
で一晩減圧乾燥して、4種のキチン繊維を得た。
得られたキチン繊維のデニール、乾強度および残
留伸度を測定した結果は表2に示すとおりであつ
た。なお、実施例2〜6の繊維はいずれもシルク
ライクの繊維であつた。
これらの繊維を用いて、実施例1と同様にして
縫合糸の作成を試みたところ、縫合糸の作成は容
易であり、また得られた縫合糸は十分な引張抗強
力と結節抗張力を有し、かつ柔軟で取扱いやす
く、外科用縫合糸として満足すべきものであつ
た。[Table] Take 12 pieces of sample A and make a braid, USP
A suture with a thickness of 3-0 was created using the × version collagen suture standard. The tensile strength of the obtained suture was 2.41 kg, and the knot tensile strength, which is the standard for tensile strength in the Japanese Pharmacopoeia, was 1.87 kg.
1.25Kg or more). In addition, this material was flexible and easy to handle, and could be fully used as a surgical suture thread. On the other hand, we tried to make a braid using Samples B and C in the same way as Sample A, but due to the low strength of the fibers, the threads were severed during the braiding process, and we were unable to make a good braid. I couldn't get the string. Examples 2 to 6 The same dope as in Example 1 was used, and the same filtration and defoaming as in Example 1 were carried out. After the defoamed dope was transferred to a tank, under a pressure of 2.5 kg/cm 2 , the methanol was pumped using a gear pump and the temperature was controlled at 16°C at a discharge rate of 2.5 ml/min from a nozzle with a hole diameter of 0.07 mm and 30 holes. (first coagulation bath) to form a yarn;
It was taken up by rollers at a speed of 15 m/min. The drawn yarn was subsequently immersed in methanol (second coagulation bath) containing 0.3 g of caustic soda in a substantially free and tension-free state. The soaked yarn was removed from the bath at intervals of 1 minute (Example 2), 10 minutes (Example 3), 1 hour (Example 4), 10 hours (Example 5), and 24 hours (Example 6). Take out, 0.5 each
After neutralizing for about 1 hour with a caustic soda aqueous solution with a concentration of 1.5 g/g, the mixture was washed repeatedly with ion-exchanged water until the washing water became neutral, then dehydrated using a centrifugal dehydrator, and dried under reduced pressure at room temperature overnight. Seed chitin fibers were obtained.
The results of measuring the denier, dry strength and residual elongation of the obtained chitin fibers are shown in Table 2. In addition, all the fibers of Examples 2 to 6 were silk-like fibers. When we attempted to create a suture using these fibers in the same manner as in Example 1, we found that the suture was easy to create, and the resulting suture had sufficient tensile strength and knot strength. It was flexible and easy to handle, and was satisfactory as a surgical suture thread.
【表】
比較例 3
キチン粉末〔共和油脂(株)製、重合度約100万〕
6重量部を、トリクロル酢酸50重量部およびジク
ロルメタン50重量部からなる混合溶剤に0℃で溶
解してキチンドープを得た。得られたドープは透
明で粘稠な溶液であつた。このドープを800メツ
シユステンレス製金網を用いて6Kg/cm2の加圧下
に濾過したのち、減圧下に十分脱泡した。脱泡し
たドープをタンクに移したのち4Kg/cm2の加圧下
ギヤーポンプで送液して孔径0.4mm、孔数2のノ
ズルから吐出量2.5ml/分で14℃に調湿されたア
セトン(第1凝固浴)中に紡出して糸条を形成
し、8m/分の速度でローラーに引取つた。引取
つた糸条を引続き0.3g/のカ性ソーダを含む
メタノール(第2凝固液)中に浸漬し1時間中和
した後、浴中より引出し、イオン交換水で洗浄し
た。ついで遠心脱水機で脱水し室温で一晩減圧乾
燥してキチン繊維を得た。得られた繊維は71d
(単糸デニール35.5d)、乾強度2.9g/d、残留伸
度26%の糸質を示していた。この繊維を12本とつ
て実施例1の場合と同様にして組ひもとし、米国
薬局方××版のコラーゲン縫合糸の規格で3―0
の太さの縫合糸を作成したが、得られたものの風
合いは非常に硬くごわごわしたもので、縫合糸と
して使用し難いものであつた。[Table] Comparative Example 3 Chitin powder [manufactured by Kyowa Yushi Co., Ltd., degree of polymerization approximately 1 million]
A chitin dope was obtained by dissolving 6 parts by weight in a mixed solvent consisting of 50 parts by weight of trichloroacetic acid and 50 parts by weight of dichloromethane at 0°C. The dope obtained was a clear and viscous solution. This dope was filtered under a pressure of 6 kg/cm 2 using an 800 mesh stainless steel wire mesh, and then thoroughly defoamed under reduced pressure. After the defoamed dope was transferred to a tank, it was pumped with a gear pump under a pressure of 4 kg/cm 2 and acetone (humidified at 14°C) was discharged from a nozzle with a hole diameter of 0.4 mm and 2 holes at a discharge rate of 2.5 ml/min. The yarn was spun into a coagulation bath (1 coagulation bath) to form a yarn, which was taken up by rollers at a speed of 8 m/min. The taken yarn was then immersed in methanol (second coagulation liquid) containing 0.3 g of caustic soda and neutralized for 1 hour, then taken out from the bath and washed with ion-exchanged water. The fibers were then dehydrated using a centrifugal dehydrator and dried under reduced pressure at room temperature overnight to obtain chitin fibers. The obtained fiber is 71d
(single yarn denier 35.5 d), dry strength 2.9 g/d, and residual elongation 26%. Twelve of these fibers were braided in the same manner as in Example 1, and were rated at 3-0 according to the US Pharmacopoeia XX edition collagen suture standard.
However, the texture of the obtained material was extremely hard and stiff, making it difficult to use as a suture.
第1図および第2図は、本発明の一実施態様を
示す説明図である。
1a,1b,1c……糸条、2……導入ローラ
ー、3……コンベヤー、4……第2凝固浴、5…
…引取りローラー、6……U字管。
FIG. 1 and FIG. 2 are explanatory diagrams showing one embodiment of the present invention. 1a, 1b, 1c... yarn, 2... introduction roller, 3... conveyor, 4... second coagulation bath, 5...
...Take-up roller, 6...U-shaped tube.
Claims (1)
紡糸してキチン繊維を製造するに際し、キチンド
ープをノズルを通して凝固浴中に押出し、引取る
ことにより溶剤を含有する糸条を形成し、形成し
た糸条を、糸条に実質的に緊張力が作用しない状
態で凝固液にて処理することを特徴とするキチン
繊維の製造法。 2 溶剤がトリクロロ酢酸である特許請求の範囲
第1項記載の製造法。 3 溶剤がトリクロロ酢酸と塩素化炭化水素との
混合物である特許請求の範囲第1項記載の製造
法。 4 形成した糸条を、ベルトコンベアーを用いて
凝固液にて処理する特許請求の範囲第1項記載の
製造法。 5 形成した糸条を、糸条の詰め込みが可能な曲
面パイプの形状を有する装置を用いて凝固液にて
処理する特許請求の範囲第1項記載の製造法。 6 少なくとも1分間凝固液にて処理する特許請
求の範囲第1項記載の製造法。[Scope of Claims] 1. When manufacturing chitin fiber by wet spinning a chitin dope consisting of chitin and a solvent, the chitin dope is extruded through a nozzle into a coagulation bath and taken off to form a thread containing a solvent, A method for producing chitin fibers, which comprises treating the formed threads with a coagulating liquid in a state where no tension is substantially applied to the threads. 2. The manufacturing method according to claim 1, wherein the solvent is trichloroacetic acid. 3. The manufacturing method according to claim 1, wherein the solvent is a mixture of trichloroacetic acid and a chlorinated hydrocarbon. 4. The manufacturing method according to claim 1, wherein the formed thread is treated with a coagulating liquid using a belt conveyor. 5. The manufacturing method according to claim 1, wherein the formed yarn is treated with a coagulating liquid using a device having a curved pipe shape capable of stuffing the yarn. 6. The manufacturing method according to claim 1, which comprises treating with a coagulating solution for at least 1 minute.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP55152558A JPS5777310A (en) | 1980-10-29 | 1980-10-29 | Chitin fiber and its production |
DE8181305055T DE3165263D1 (en) | 1980-10-29 | 1981-10-27 | Chitin fibers, process for the production of the same and surgical sutures formed of such chitin fibers |
EP81305055A EP0051421B1 (en) | 1980-10-29 | 1981-10-27 | Chitin fibers, process for the production of the same and surgical sutures formed of such chitin fibers |
US06/316,384 US4431601A (en) | 1980-10-29 | 1981-10-29 | Process for the production of chitin fibers |
US07/368,952 US4932404A (en) | 1980-10-29 | 1989-06-13 | Chitin fibers and process for the production of the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP55152558A JPS5777310A (en) | 1980-10-29 | 1980-10-29 | Chitin fiber and its production |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61213621A Division JPS6278215A (en) | 1986-09-10 | 1986-09-10 | Chitin fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5777310A JPS5777310A (en) | 1982-05-14 |
JPS627287B2 true JPS627287B2 (en) | 1987-02-17 |
Family
ID=15543093
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP55152558A Granted JPS5777310A (en) | 1980-10-29 | 1980-10-29 | Chitin fiber and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5777310A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6299569U (en) * | 1985-12-10 | 1987-06-25 | ||
JPS6445732U (en) * | 1987-09-15 | 1989-03-20 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58214513A (en) * | 1982-06-04 | 1983-12-13 | Unitika Ltd | Production of chitin yarn |
JPS58214512A (en) * | 1982-06-04 | 1983-12-13 | Unitika Ltd | Production of chitin yarn |
JPS59125908A (en) * | 1982-12-28 | 1984-07-20 | Unitika Ltd | Hollow fiber composed of chitin and its manufacture |
JPS6040224A (en) * | 1983-08-16 | 1985-03-02 | Dainichi Seika Kogyo Kk | Manufacture of formed article of chitosan |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51133367A (en) * | 1975-04-16 | 1976-11-19 | Univ Delaware | Fibers * films or plastics and those orientation of regenerated chitin and its manufacturing |
JPS53126090A (en) * | 1977-04-11 | 1978-11-02 | Mitsubishi Rayon Co Ltd | New fiber and film |
JPS53127500A (en) * | 1977-04-11 | 1978-11-07 | Mitsubishi Rayon Co Ltd | Chitin dope |
-
1980
- 1980-10-29 JP JP55152558A patent/JPS5777310A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51133367A (en) * | 1975-04-16 | 1976-11-19 | Univ Delaware | Fibers * films or plastics and those orientation of regenerated chitin and its manufacturing |
JPS53126090A (en) * | 1977-04-11 | 1978-11-02 | Mitsubishi Rayon Co Ltd | New fiber and film |
JPS53127500A (en) * | 1977-04-11 | 1978-11-07 | Mitsubishi Rayon Co Ltd | Chitin dope |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6299569U (en) * | 1985-12-10 | 1987-06-25 | ||
JPS6445732U (en) * | 1987-09-15 | 1989-03-20 |
Also Published As
Publication number | Publication date |
---|---|
JPS5777310A (en) | 1982-05-14 |
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