JPH03186324A - Preparation of porous hollow yarn membrane - Google Patents
Preparation of porous hollow yarn membraneInfo
- Publication number
- JPH03186324A JPH03186324A JP32564089A JP32564089A JPH03186324A JP H03186324 A JPH03186324 A JP H03186324A JP 32564089 A JP32564089 A JP 32564089A JP 32564089 A JP32564089 A JP 32564089A JP H03186324 A JPH03186324 A JP H03186324A
- Authority
- JP
- Japan
- Prior art keywords
- spinning
- membrane
- polymer
- liquid
- poor solvent
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 30
- 238000009987 spinning Methods 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 230000015271 coagulation Effects 0.000 claims abstract description 12
- 238000005345 coagulation Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000012510 hollow fiber Substances 0.000 claims description 15
- 239000011550 stock solution Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 238000000578 dry spinning Methods 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 18
- 239000007788 liquid Substances 0.000 abstract description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001298 alcohols Chemical class 0.000 abstract description 3
- 230000001112 coagulating effect Effects 0.000 abstract description 3
- 229920002492 poly(sulfone) Polymers 0.000 abstract description 3
- 150000002576 ketones Chemical class 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract 1
- -1 etc. Chemical class 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 3
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000001891 gel spinning Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- WYOZQTNUYXDKQU-UHFFFAOYSA-N F.CN(C)C(C)=O Chemical compound F.CN(C)C(C)=O WYOZQTNUYXDKQU-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001756 Polyvinyl chloride acetate Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QSCVRSZHWJOCIJ-UHFFFAOYSA-N acetic acid;n,n-dimethylacetamide Chemical compound CC(O)=O.CN(C)C(C)=O QSCVRSZHWJOCIJ-UHFFFAOYSA-N 0.000 description 1
- XMMFBEWONDCTLD-UHFFFAOYSA-N acetyl(dimethyl)azanium;chloride Chemical compound Cl.CN(C)C(C)=O XMMFBEWONDCTLD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- BHGCNGDTJZDAEX-UHFFFAOYSA-N n,n-dimethylformamide;propan-2-ol Chemical compound CC(C)O.CN(C)C=O BHGCNGDTJZDAEX-UHFFFAOYSA-N 0.000 description 1
- HNPPKZRZKDKXDO-UHFFFAOYSA-N n,n-dimethylformamide;propan-2-one Chemical compound CC(C)=O.CN(C)C=O HNPPKZRZKDKXDO-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (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、多孔質中空糸膜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 a porous hollow fiber membrane.
更に詳しくは、膜の細孔径の制御を可能とする多孔質中
空糸膜の製造方法に関する。More specifically, the present invention relates to a method for producing a porous hollow fiber membrane that allows control of the pore diameter of the membrane.
〔従来の技術〕および〔発明が解決しようとする課題〕
二重環状ノズルから紡糸原液を吐出させた後凝固浴中に
導き、凝固させる乾湿式紡糸法においては、得られる多
孔質中空糸膜の膜性能は、その膜構造によって左右され
る。[Prior art] and [Problem to be solved by the invention]
In the wet-dry spinning method in which a spinning stock solution is discharged from a double annular nozzle and then introduced into a coagulation bath and coagulated, the membrane performance of the resulting porous hollow fiber membrane is influenced by its membrane structure.
この膜構造は１通常紡糸原液を形成する膜形成性重合体
とその可溶性溶媒との混合比、芯液の有無、紡糸ノズル
先端部と凝固浴液面との空間距離などの紡糸条件によっ
て支配されるが、数多くの条件の組合せにより所望の膜
構造の中空糸膜を作り分けるには、手間がかかるなど条
件の設定変更などが容易ではない。This membrane structure is usually controlled by spinning conditions such as the mixing ratio of the membrane-forming polymer that forms the spinning stock solution and its soluble solvent, the presence or absence of a core liquid, and the spatial distance between the tip of the spinning nozzle and the surface of the coagulation bath. However, it is difficult to create hollow fiber membranes with desired membrane structures by combining a large number of conditions, and it is difficult to change the settings of the conditions.
本発明の目的は、容易な紡糸条件の変更により、膜構造
、殊に膜の細孔径の制御を可能とする多孔質中空糸膜の
製造方法を提供することにある。An object of the present invention is to provide a method for producing a porous hollow fiber membrane that allows control of the membrane structure, particularly the pore diameter of the membrane, by easily changing spinning conditions.
かかる本発明の目的は、二重環状ノズルから紡糸原液を
吐出させた後凝固浴中に導き、凝固させる乾湿式紡糸法
において、膜形成性重合体およびその可溶性有機溶媒よ
りなる紡糸原液中に重合体の貧溶媒を添加したものを用
い、多孔質中空糸膜を製造することによって達成される
。The object of the present invention is to use a dry-wet spinning method in which a spinning dope is discharged from a double annular nozzle and then introduced into a coagulation bath to coagulate. This is achieved by manufacturing a porous hollow fiber membrane using a poor solvent for coalescence.
紡糸原液を形成する膜形成性重合体およびその可溶性有
機溶媒とは、例えば次のような組合せで、約１０〜３０
重量２溶液として用いられる。The membrane-forming polymer and its soluble organic solvent forming the spinning dope may be used in the following combinations, for example, in an amount of about 10 to 30
Used as a weight 2 solution.
−一１ｊ量（−一
ポリスルホン ジメチルアセトアミド、ジメチ
ルホルムアミドポリエーテルスルホン ジエチルアセト
アミド、ジエチルホルムアミド、Ｎ−メチルピロリドン
、モルホリン、
トリエチルホスフェート
ポリアクリロニトリル ジメチルアセトアミド、ジメチ
ルホルムアミド芳香族ポリアミド ジエチルアセト
アミド、ジエチルホルムアミドポリ塩化ビニル
ジメチルアセトアミド、ジメチルホルムアミド、ジエチ
ルアセトアミド、ジエチルホルムアミド、Ｎ−メチルピ
ロリドン、アセトン
ポリフッ化ビニリデン ジメチルアセトアミド、ジメチ
ルホルムアミド、トリエチルホスフェート
酢酸セルロース ジメチルアセトアミド、ジメチ
ルホルムアミド、アセトン
本発明方法においては、これらの重合体に対応して用い
られるそれの可溶性有機溶媒の一部、具体的には重合体
の種類にもよるが一般に約２〜５５重量算を重合体の貧
溶媒で置換して用いている。-1j amount (-1 polysulfone dimethylacetamide, dimethylformamide polyethersulfone diethylacetamide, diethylformamide, N-methylpyrrolidone, morpholine, triethylphosphate polyacrylonitrile dimethylacetamide, dimethylformamide aromatic polyamide diethylacetamide, diethylformamide polyvinyl chloride
Dimethylacetamide, dimethylformamide, diethylacetamide, diethylformamide, N-methylpyrrolidone, acetone Polyvinylidene fluoride Dimethylacetamide, dimethylformamide, triethyl phosphate Cellulose acetate Dimethylacetamide, dimethylformamide, acetone The method of the present invention is applicable to these polymers. A part of the organic solvent soluble in the polymer used as a polymer, in general, approximately 2 to 55% by weight, depending on the type of polymer, is replaced with a poor solvent for the polymer.
ただし、用いられる貧溶媒による一部置換が、紡糸原液
中の膜形成性重合体を析出させるようなことがあっては
ならない。However, the partial substitution by the poor solvent used must not precipitate the film-forming polymer in the spinning dope.
かかる貧溶媒としては、凝固浴として一般に用いられる
水または水性液と混和し得る有機溶媒、例えばメタノー
ル、エタノール、ｎ−プロパツール、イソプロパツール
、グリセリンなどの低級アルコール類、アセトン、メチ
ルエチルケトン、テトラヒドロフランなどのケトン類な
どが用いられる。Such poor solvents include organic solvents miscible with water or aqueous liquids commonly used as coagulation baths, such as lower alcohols such as methanol, ethanol, n-propanol, isopropanol, glycerin, acetone, methyl ethyl ketone, and tetrahydrofuran. Ketones and the like are used.
上記組合せからも分かるように、例えばアセトンはポリ
塩化ビニルや酢酸セルロースにとって良溶媒なので、こ
の場合には低級アルコール類などが用いられる。As can be seen from the above combinations, for example, acetone is a good solvent for polyvinyl chloride and cellulose acetate, so lower alcohols are used in this case.
以上の各成分よりなる紡糸原液中には、水溶性無機塩の
微粉末、一般には膜厚以下である約１５０μ−以下、好
ましくは約１００μ園以下の微粉末を、紡糸原液量に対
して約１〜３０重量２、好ましくは約５〜ｌＯ重量算添
加し、多孔質中空糸膜透過速度の向上を図ることができ
る。かかる水溶性無機塩としては、例えば塩化リチウム
、塩化ナトリウム、塩化カリウム、硫酸ナトリウムなど
が用いられる。In the spinning dope consisting of each of the above components, a fine powder of a water-soluble inorganic salt, generally less than the film thickness, about 150 μm or less, preferably about 100 μm or less, is added to the spinning dope, based on the amount of the spinning dope. It is possible to improve the porous hollow fiber membrane permeation rate by adding 1 to 30% by weight, preferably about 5 to 10% by weight. Examples of such water-soluble inorganic salts include lithium chloride, sodium chloride, potassium chloride, and sodium sulfate.
乾湿式紡糸は１通常の方法に従って行われ、その際芯液
、一般には紡糸原液凝固性液体である芯液を使用するこ
ともでき、芯液は環状ノズルの中心部から同時に押し出
される。押し出された紡糸原液は、芯液が用いられた場
合にはそれと共に、ノズル先端部から一定の空間距離を
有する凝固浴、一般には水中に導かれ、そこに浸漬して
ゲル化させる。Wet-dry spinning is carried out according to customary methods, in which case it is also possible to use a core liquid, which is generally a coagulating liquid from the spinning dope, which is simultaneously extruded from the center of an annular nozzle. The extruded spinning stock solution, if a core solution is used, is guided into a coagulation bath, generally water, which has a certain spatial distance from the nozzle tip, and is immersed therein to gel.
〔作用〕および〔発明の効果〕
乾湿式紡糸に際し、紡糸原液中に一部膜形成性重合体の
貧溶媒を添加して用いることにより、紡糸原液と凝固浴
とが接触する際に起こる紡糸原液中の有機溶媒と凝固液
との置換速度をコントロールすることができ、この貧溶
媒添加割合を変えるだけで、他の紡糸条件を変えること
なしに、種々の膜構造、具体的には膜細孔径の中空糸膜
を見掛上同じ紡糸条件で製造することができ、例えば種
々の分画分子量を有するものを容易に得ることができる
。[Action] and [Effects of the Invention] During dry-wet spinning, by adding a portion of a poor solvent for a film-forming polymer to the spinning stock solution, the spinning stock solution that occurs when the spinning stock solution and the coagulation bath come into contact can be improved. The rate of replacement of the organic solvent in the coagulation solution with the coagulating liquid can be controlled, and by simply changing the addition ratio of the poor solvent, various membrane structures, specifically membrane pore diameters, can be created without changing other spinning conditions. Hollow fiber membranes can be produced under apparently the same spinning conditions, and for example, those having various molecular weight cutoffs can be easily obtained.
また、紡糸原液中に添加された貧溶媒は、一般に低沸点
有機溶媒で揮発性が高いことから、ノズル先端部と凝固
浴液面との空間距離の大きさによっても、中空糸膜の外
表面側構造を制御することができる。In addition, since the poor solvent added to the spinning dope is generally a low-boiling organic solvent and highly volatile, the outer surface of the hollow fiber membrane may vary depending on the spatial distance between the nozzle tip and the coagulation bath surface. The side structure can be controlled.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例１
ジメチルホルムアミド−イソプロパノール（重量比９０
： １０）混合溶媒８６重量部、ポリスルホン１３重
量部および界面活性剤ポリビニルピロリジノン（ＭＶ３
６万）１重量部からなる紡糸原液を、芯液としての５０
重量算イソプロパツール水溶液と共に、直径１■および
２■の二重環状構造を有する環状ノズルから、ノズル先
端部から２００１■の空間距離に液面を有する水凝固浴
中に導き、浸漬させて凝固させた。得られた多孔質中空
糸膜は、分画分子量（ポリエチレングリコール使用）が
２００００であった。Example 1 Dimethylformamide-isopropanol (weight ratio 90
: 10) 86 parts by weight of mixed solvent, 13 parts by weight of polysulfone and surfactant polyvinylpyrrolidinone (MV3
60,000) 1 part by weight of the spinning dope, 50,000 parts by weight as the core solution.
A gravimetric aqueous solution of isopropanol is introduced into a water coagulation bath having a liquid level at a spatial distance of 2001 mm from the nozzle tip through an annular nozzle having a double annular structure with diameters of 1 and 2 mm, and is immersed to solidify. I let it happen. The resulting porous hollow fiber membrane had a molecular weight cutoff (using polyethylene glycol) of 20,000.
これに対し、イソプロパツールを用いない場合には、同
じ紡糸条件で分画分子量が６０００の多孔質中空糸膜が
得られた。On the other hand, when isopropanol was not used, a porous hollow fiber membrane with a molecular weight cutoff of 6000 was obtained under the same spinning conditions.
実施例２
ジメチルホルムアミド−アセトン（重量比ｓｏ ： ｓ
ｏ）混合溶媒８０重量部、ポリフッ化ビニリデン２０重
量部および塩化リチウム３重量部からなる紡糸原液を、
ノズル先端部から水凝固浴液面への空間距離を２０〜２
００＋ｕ＋の間で変化させながら、実施例１と同様に乾
湿式紡糸した。得られた多孔質中空糸膜は、上記空間距
離に応じて、５〜ｌＯ万の分画分子量を有していた。Example 2 Dimethylformamide-acetone (weight ratio so:s
o) A spinning stock solution consisting of 80 parts by weight of mixed solvent, 20 parts by weight of polyvinylidene fluoride and 3 parts by weight of lithium chloride,
The spatial distance from the nozzle tip to the water coagulation bath surface is 20 to 2.
Wet-dry spinning was carried out in the same manner as in Example 1 while changing the spinning speed between 00+u+. The obtained porous hollow fiber membrane had a molecular weight cutoff of 50,000 to 10,000, depending on the above-mentioned spatial distance.
これに対し、アセトンを用いない場合には、同じ紡糸条
件でいずれも分画分子量２００００の多孔質中空糸膜が
得られ、この際紡糸原液温度や凝固浴組成などの変更を
行ったが、膜性能に変化はみられなかった。On the other hand, when acetone was not used, porous hollow fiber membranes with a molecular weight cutoff of 20,000 were obtained under the same spinning conditions. No change in performance was observed.
Claims (1)
中に導き、凝固させる乾湿式紡糸法において、膜形成性
重合体およびその可溶性有機溶媒よりなる紡糸原液中に
重合体の貧溶媒を添加したものを用いることを特徴とす
る多孔質中空糸膜の製造方法。 ２、紡糸原液と共に芯液を吐出させる請求項１記載の多
孔質中空糸膜の製造方法。[Scope of Claims] 1. In a wet-dry spinning method in which a spinning stock solution is discharged from a double annular nozzle and then introduced into a coagulation bath and coagulated, a spinning stock solution consisting of a film-forming polymer and its soluble organic solvent is used. 1. A method for producing a porous hollow fiber membrane, characterized by using a polymer containing a poor solvent. 2. The method for producing a porous hollow fiber membrane according to claim 1, wherein the core solution is discharged together with the spinning dope.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32564089A JPH03186324A (en) | 1989-12-15 | 1989-12-15 | Preparation of porous hollow yarn membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32564089A JPH03186324A (en) | 1989-12-15 | 1989-12-15 | Preparation of porous hollow yarn membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03186324A true JPH03186324A (en) | 1991-08-14 |
Family
ID=18179093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32564089A Pending JPH03186324A (en) | 1989-12-15 | 1989-12-15 | Preparation of porous hollow yarn membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03186324A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003031038A1 (en) * | 2001-10-04 | 2003-04-17 | Toray Industries, Inc. | Hollow fiber film and method for production thereof |
| JP2005146230A (en) * | 2003-11-20 | 2005-06-09 | Toray Ind Inc | Membrane stock solution and separation membrane |
| JP2009039716A (en) * | 1998-05-18 | 2009-02-26 | Pall Corp | Highly porous poly(vinylidene difluoride) membrane |
-
1989
- 1989-12-15 JP JP32564089A patent/JPH03186324A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009039716A (en) * | 1998-05-18 | 2009-02-26 | Pall Corp | Highly porous poly(vinylidene difluoride) membrane |
| WO2003031038A1 (en) * | 2001-10-04 | 2003-04-17 | Toray Industries, Inc. | Hollow fiber film and method for production thereof |
| CN100443148C (en) * | 2001-10-04 | 2008-12-17 | 东丽株式会社 | Hollow fiber membrane and its manufacturing method |
| JP2005146230A (en) * | 2003-11-20 | 2005-06-09 | Toray Ind Inc | Membrane stock solution and separation membrane |
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