JPH03249215A - Production of hollow acrylic fiber - Google Patents
Production of hollow acrylic fiberInfo
- Publication number
- JPH03249215A JPH03249215A JP4875990A JP4875990A JPH03249215A JP H03249215 A JPH03249215 A JP H03249215A JP 4875990 A JP4875990 A JP 4875990A JP 4875990 A JP4875990 A JP 4875990A JP H03249215 A JPH03249215 A JP H03249215A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- core
- sheath
- hollow
- fiber
- 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.)
- Pending
Links
- 229920002972 Acrylic fiber Polymers 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 3
- 239000004917 carbon fiber Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
- Multicomponent Fibers (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は中空アクリル系繊維の製造方法、特に細繊度で
中空部が実質的に連続した中空アクリル系繊維の製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing hollow acrylic fibers, and particularly to a method for manufacturing hollow acrylic fibers having a fineness and having substantially continuous hollow portions.
［従来の技術］
近年中空アクリル系繊維の用途展開が進み、見掛比重が
低く嵩高で保温性、吸水性に優れているという特長を生
かした用途、および分離膜として血液透析、血漿分離、
ガス分離などの各種分離用途に展開が進められている。[Conventional technology] In recent years, the use of hollow acrylic fibers has expanded, and applications that take advantage of their characteristics of low apparent specific gravity, bulk, and excellent heat retention and water absorption properties, as well as separation membranes for hemodialysis, plasma separation,
It is being developed for various separation applications such as gas separation.
しかし、従来の中空アクリル系繊維は、孔径２〜３■の
中心部にガスを吹き込むタイプのモノホール口金を用い
たものであり、単繊維デニールか１０デニール以上、外
径が数１００μｍ以上と非常に太いものしか得られてい
なかった（たとえば特開昭６１−２８０１４号公報、特
開昭６１−２９６１１５号公報など）。そのために、嵩
高性、吸水性等が不十分てあったり、分離装置内での中
空繊維の充填率を上げられないといった問題があった。However, conventional hollow acrylic fibers use a monohole ferrule that blows gas into the center of the pores, which have a diameter of 2 to 3 cm, and are very large, with a single fiber denier or more than 10 deniers and an outer diameter of several hundred micrometers or more. Only thick ones have been obtained (for example, JP-A-61-28014, JP-A-61-296115, etc.). For this reason, there have been problems such as insufficient bulkiness, water absorption, etc., and the inability to increase the filling rate of hollow fibers within the separation device.
さらに細繊度の中空アクリル系繊維の製造方法として、
芯鞘口金を用いて共重合体濃度の異なるポリマーを入れ
中空化する技術（特公昭６０−１８３３２号公報）か提
案されているが、同一のポリマーで単に芯部ポリマーの
濃度を下げているだけなので完全な中空化ができず芯部
が微小空孔群よりなる多孔質な構造しか得られず、嵩高
性が不十分である２分離膜繊維としての活用ができない
、あるいは繊度が３デニ一ル以上と太いものしか得られ
ないという問題があった。Furthermore, as a method for producing fine-grained hollow acrylic fibers,
A technique has been proposed (Japanese Patent Publication No. 18332/1983) in which polymers with different copolymer concentrations are placed in a core-sheath cap to create a hollow core, but this method simply lowers the concentration of the core polymer using the same polymer. Therefore, it cannot be completely hollowed out and only a porous structure consisting of a group of micropores is obtained in the core, and the bulkiness is insufficient. 2. It cannot be used as a separation membrane fiber, or the fineness is 3 denier. There was a problem that only thicker pieces could be obtained.
そこで本発明者らは細繊度でかつ中空部が実質的に連続
した中空アクリル系繊維の製造方法を鋭意検討して本発
明に至った。Therefore, the present inventors conducted extensive research into a method for producing hollow acrylic fibers having a fineness and a substantially continuous hollow portion, and arrived at the present invention.
［発明が解決しようとする課題］
本発明の課題は、上記従来技術では達成し得なかった細
繊度でかつ中空部の連続した中空アクリル系繊維の製造
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 provide a method for producing hollow acrylic fibers with fine fineness and continuous hollow portions, which could not be achieved with the above-mentioned conventional techniques.
［課題を解決するための手段］
本発明の上記課題は、芯鞘口金を用いて、鞘部ポリマー
に対して極限粘度が１．５倍以上で、ポリマー濃度が０
．５倍未満のアクリル系ポリマーを芯部に入れることを
特徴とする中空アクリル系繊維の製造方法によって解決
することができる。[Means for Solving the Problems] The above-mentioned problems of the present invention are to provide a core-sheath base with an intrinsic viscosity of at least 1.5 times that of the sheath polymer and a polymer concentration of 0.
．． This problem can be solved by a method for manufacturing hollow acrylic fibers, which is characterized by incorporating less than 5 times as much acrylic polymer into the core.
すなわち、アクリル系繊維の紡糸方法には、湿式紡糸法
および乾湿式紡糸法を採用できるが、細繊度が得られや
すい乾湿式紡糸法がより好ましい。That is, although a wet spinning method and a wet-dry spinning method can be adopted as a spinning method for the acrylic fiber, the wet-dry spinning method is more preferable because it can easily obtain fineness.
いずれの場合にも芯鞘口金を用いて、鞘部ポリマーに対
して極限粘度が１．５倍以上、好ましくは２．０倍以上
で、ポリマー濃度が０，５倍未満。In either case, using a core-sheath ferrule, the intrinsic viscosity is 1.5 times or more, preferably 2.0 times or more, and the polymer concentration is less than 0.5 times that of the sheath polymer.
好ましくは０．３倍未満、さらに好ましくは０゜１５倍
未満のアクリル系ポリマーを芯部に入れることが必須で
ある。It is essential that the core contains preferably less than 0.3 times the amount of acrylic polymer, more preferably less than 0.15 times.
すなわち、濃度の比か０． ５倍以上では芯部か微小な
空孔よりなる多孔質な構造しか得られず、完全な中空が
得られないので好ましくない。芯部ポリマーの濃度が低
いほど中空部かより連続した完全なものとなり好ましい
が、濃度が下がることによって芯部ポリマーの粘度が低
くなりすぎると、口金近傍で糸切れか多発して安定して
紡糸することができない。濃度の比を０．５未満に下げ
ても安定して紡糸するためには、極限粘度の比で１゜５
倍以上であることが必須である。That is, the ratio of concentrations is 0. If it is 5 times or more, only a porous structure consisting of minute pores in the core will be obtained, and complete hollowness will not be obtained, which is not preferable. The lower the concentration of the core polymer, the more continuous and complete the hollow part becomes, which is preferable. However, if the viscosity of the core polymer becomes too low due to a decrease in concentration, the yarn may break frequently near the spinneret, resulting in unstable spinning. Can not do it. In order to perform stable spinning even if the concentration ratio is lowered to less than 0.5, the intrinsic viscosity ratio must be 1°5.
It is essential that it is at least twice as large.
芯および鞘部ポリマーとして用いるアクリル系ポリマー
としては、アクリロニトリル１００％のホモポリマーあ
るいは少なくとも６０モル％以上のアクリロニトリルと
４０モル％以下の共重合可能なビニル系モノマ、たとえ
ばアクリル酸、メタクリル酸、イタコン酸およびそれら
のアルカリ金属塩、アンモニウム塩および低級アルキル
エステル類、アクリルアミドおよびその誘導体、アリル
スルホン酸、メタリルスルホン酸およびそれらの塩類ま
たはアルキルエステル類などとの共重合体を挙げること
ができる。芯および鞘ポリマーの共重合組成は同一のも
のでもよいが、鞘ポリマーの共重合成分を芯ポリマーよ
り多くすることが中空形成にとってより好ましい方向で
ある。The acrylic polymer used as the core and sheath polymer is a homopolymer of 100% acrylonitrile or a vinyl monomer copolymerizable with at least 60 mol% or more of acrylonitrile and 40 mol% or less, such as acrylic acid, methacrylic acid, itaconic acid. and copolymers thereof with alkali metal salts, ammonium salts and lower alkyl esters, acrylamide and its derivatives, allylsulfonic acid, methallylsulfonic acid and their salts or alkyl esters. Although the copolymerization composition of the core and sheath polymers may be the same, it is more preferable for hollow formation to have a copolymerization component of the sheath polymer greater than that of the core polymer.
鞘部ポリマーとしては極限粘度が好ましくは１．０〜３
．０．より好ましくは１．５〜２．５で、濃度が好まし
くは１０〜４０％、より好ましくは１５〜３０％である
。The intrinsic viscosity of the sheath polymer is preferably 1.0 to 3.
．． 0. The concentration is more preferably 1.5 to 2.5, preferably 10 to 40%, and more preferably 15 to 30%.
これら芯および鞘の吐出量を調節することにより、自由
に中空率を調節することができる。口金としては、公知
の芯鞘口金を用いることができるが、偏心タイプでは中
空部の位置が偏るので、同心タイプの口金が好ましい。By adjusting the discharge amount of these cores and sheaths, the hollowness ratio can be freely adjusted. As the cap, a well-known core/sheath cap can be used, but since an eccentric type has a hollow portion unevenly positioned, a concentric cap is preferable.
口金孔数については１００〜１００００程度が選定され
るが、生産性および口金コスト等から適宜最適化するこ
とが好ましい。The number of die holes is selected to be approximately 100 to 10,000, but it is preferable to appropriately optimize the number from the viewpoint of productivity, die cost, etc.
延伸倍率については、２〜１５倍程度から選定されるが
、あまり倍率を高く設定すると中空がつぶれる場合があ
るので２〜１０倍程度が好ましい。The stretching magnification is selected from about 2 to 15 times, but is preferably about 2 to 10 times, since if the magnification is set too high, the hollow space may collapse.
延伸方式としては、浴延伸、乾熱延伸あるいは湿熱延伸
などを組み合わせることができるが、中空がつぶれにく
い浴延伸あるいは湿熱延伸の組み合わせが好ましい。As for the stretching method, a combination of bath stretching, dry heat stretching, or wet heat stretching can be used, but a combination of bath stretching or wet heat stretching is preferred since the hollows are less likely to collapse.
乾燥緻密化工程においても、急速に乾燥を行なうと中空
がつぶれる場合があるので、１００〜１３０℃程度の低
温で徐々に行なうことが好ましい。Also in the drying and densification step, it is preferable to carry out gradually at a low temperature of about 100 to 130° C., since rapid drying may cause hollow spaces to collapse.
最終糸の単繊維繊度としては、１．５デニール以下、好
ましくは１．０デニール以下にすることがしなやかさ、
嵩高性、吸水性および分離装置への充填率を向上させる
上で重要である。The single fiber fineness of the final yarn should be 1.5 denier or less, preferably 1.0 denier or less for flexibility,
It is important for improving bulk, water absorption, and filling rate of separation equipment.
なお、本発明における極限粘度（［η］）は１ｏｕｒｎ
ａｌ ｏｆ Ｐｏｌｙｍｕ ５ｃｉｅｎｃｅ（＾−１）
、第６巻、ｐ１４７〜１５７ （１９６８年）に記載さ
れている測定法に従って、ジメチルホルムアミドを溶剤
として温度２５℃で測定した値である。In addition, the intrinsic viscosity ([η]) in the present invention is 1hour
al of Polymu 5science (^-1)
, Vol. 6, pp. 147-157 (1968), measured at a temperature of 25° C. using dimethylformamide as a solvent.
［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] Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
アクリロニトリル（ＡＮ）９８．．０モル％とメタクリ
ル酸２． ０モル％からなる極限粘度が１゜５の共重合
体を用いて、濃度か２２重量％のジメチルスルホキシド
（ＤＭＳＯ）溶液（ポリマーＡ）を作製するとともに、
ＡＮ１００モル％からなる極限粘度３．５の重合体を用
いて、濃度が３重量％のＤＭＳＯ溶液（ポリマーＢ）を
作製した。ポリマーＡおよびポリマーＢをそれぞれ鞘お
よび芯用ポリマーとして、いずれも温度３５℃に調整し
、孔径０．１２ｍｍφ、ホール数５００の同心タイプの
芯鞘口金を通して一旦空気中に吐出して約３ｍｍの空間
を走らせた後、温度０９Ｃ９濃度３０％のＤＭＳＯ水溶
液中で凝固させた。引取速度は４０ｍ／分であった。吐
出量の比は芯部１に対して鞘部は２であった。凝固糸条
を水洗後、３段の温水延伸浴で２．５倍に延伸しシリコ
ーン系油剤を付与した後、１１０℃に加熱されたローラ
ー表面に接触させて乾燥緻密化し、さらに３． ５ｋｇ
／ｃｄの加圧スチーム中で３倍に延伸して単糸繊度１．
３ｄ。Example 1 Acrylonitrile (AN) 98. ．． 0 mol% and methacrylic acid2. A dimethyl sulfoxide (DMSO) solution (polymer A) with a concentration of 22% by weight was prepared using a copolymer containing 0% by mole and having an intrinsic viscosity of 1°5.
A DMSO solution (polymer B) having a concentration of 3% by weight was prepared using a polymer having an intrinsic viscosity of 3.5 and consisting of 100% by mole of AN. Polymer A and Polymer B were used as polymers for the sheath and core respectively, and both were adjusted to a temperature of 35°C and discharged into the air through a concentric core-sheath nozzle with a hole diameter of 0.12 mmφ and 500 holes to create a space of about 3 mm. After running the sample, it was coagulated in a DMSO aqueous solution having a temperature of 09C9 and a concentration of 30%. The withdrawal speed was 40 m/min. The discharge amount ratio was 1 for the core and 2 for the sheath. After washing the coagulated yarn with water, it was stretched 2.5 times in a three-stage hot water stretching bath, and a silicone oil was applied thereto, and then it was brought into contact with a roller surface heated to 110°C to be dried and densified. 5kg
/cd in pressurized steam to a single yarn fineness of 1.
3d.
トータルデニール６５０Ｄの繊維束を得た。得られたア
クリル繊維は芯部に繊維軸方向に連続した中空部を有し
、同心円状の中空アクリル系繊維であった。A fiber bundle with a total denier of 650D was obtained. The obtained acrylic fiber had a hollow part continuous in the fiber axis direction in the core, and was a concentric hollow acrylic fiber.
この中空繊維を用いることにより、従来の外径３００μ
ｍの中空アクリル系繊維に比較して充填率を１０倍以上
に上げることができた。By using this hollow fiber, the outer diameter of the conventional one is 300 μm.
Compared to hollow acrylic fibers, the filling rate could be increased by more than 10 times.
また、得られた繊維束を２４０〜２７０℃の空気中で加
熱して耐炎化繊維に転換し、ついて最高温度１４００℃
の窒素雰囲気中で焼成することにより、安定して中空炭
素繊維を製造することができた。In addition, the obtained fiber bundles were heated in air at 240 to 270°C to convert them into flame-resistant fibers, and the maximum temperature was 1400°C.
By firing in a nitrogen atmosphere, hollow carbon fibers could be stably produced.
比較例１
実施例１において芯にもポリマーＡを入れた以外は、実
施例１と同様に製糸してアクリル繊維を作った。得られ
たアクリル繊維は中空を有さす、中実繊維しか得られな
かった。Comparative Example 1 An acrylic fiber was produced by spinning in the same manner as in Example 1, except that Polymer A was also added to the core. The obtained acrylic fibers were only hollow, solid fibers.
比較例２
実施例１において空気を芯に吹き込んだ以外は、実施例
１と同様に製糸したが、口金比でドリップが発生して安
定して紡糸することができなかった。Comparative Example 2 Silk spinning was carried out in the same manner as in Example 1 except that air was blown into the core in Example 1, but the spinneret ratio caused drips and stable spinning could not be achieved.
実施例２〜４．比較例３〜４
実施例１において芯ポリマーの極限粘度および濃度を表
１のように変える以外は実施例１と同様に製糸してアク
リル系繊維を得た。製糸の安定性および得られた繊維の
中空状態を表１に示す。Examples 2-4. Comparative Examples 3 to 4 Acrylic fibers were obtained by spinning in the same manner as in Example 1 except that the intrinsic viscosity and concentration of the core polymer were changed as shown in Table 1. Table 1 shows the stability of yarn spinning and the hollow state of the obtained fibers.
（以下、余白）
［発明の効果］
本発明の製造方法により、従来の技術では困難な細繊度
な中空アクリル系繊維が得られ、従来の外径数１００μ
ｍの中空アクリル系繊維に対して数１０μｍと細く設定
しても製造が可能となったために、しなやかさが増すと
ともに嵩高性、吸水性および分離装置への充填率を向上
させることが可能となった。さらに細くなったことによ
って安定して焼成することが可能となり、炭素繊維用プ
リカーサ−としての活用も可能となるなど各種用途への
展開を大幅に拡大することが可能となった。(Hereinafter, blank space) [Effects of the invention] The production method of the present invention makes it possible to obtain hollow acrylic fibers with a fineness that is difficult to obtain using conventional techniques, and it is possible to obtain hollow acrylic fibers with a fineness that is difficult to obtain using conventional techniques.
Since it is now possible to manufacture fibers as thin as several tens of micrometers compared to the hollow acrylic fibers of m, it is possible to increase flexibility, as well as improve bulk, water absorption, and the filling rate of separation equipment. Ta. By becoming thinner, it is now possible to stably fire the material, and it has become possible to use it as a precursor for carbon fibers, greatly expanding its use in a variety of applications.
Claims (1)
１．５倍以上で、ポリマー濃度が０．５倍未満のアクリ
ル系ポリマーを芯部に入れることを特徴とする中空アク
リル系繊維の製造方法。A hollow acrylic fiber characterized in that an acrylic polymer having an intrinsic viscosity of 1.5 times or more and a polymer concentration of less than 0.5 times that of the sheath polymer is put into the core using a core-sheath ferrule. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4875990A JPH03249215A (en) | 1990-02-27 | 1990-02-27 | Production of hollow acrylic fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4875990A JPH03249215A (en) | 1990-02-27 | 1990-02-27 | Production of hollow acrylic fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03249215A true JPH03249215A (en) | 1991-11-07 |
Family
ID=12812210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4875990A Pending JPH03249215A (en) | 1990-02-27 | 1990-02-27 | Production of hollow acrylic fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03249215A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002253939A (en) * | 2001-03-05 | 2002-09-10 | Mitsubishi Rayon Co Ltd | Method for manufacturing hollow fiber membrane |
-
1990
- 1990-02-27 JP JP4875990A patent/JPH03249215A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002253939A (en) * | 2001-03-05 | 2002-09-10 | Mitsubishi Rayon Co Ltd | Method for manufacturing hollow fiber membrane |
| JP4522600B2 (en) * | 2001-03-05 | 2010-08-11 | 三菱レイヨン株式会社 | Method for producing hollow fiber membrane |
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