JPH03258330A - Porous hollow fiber membrane - Google Patents
Porous hollow fiber membraneInfo
- Publication number
- JPH03258330A JPH03258330A JP5934690A JP5934690A JPH03258330A JP H03258330 A JPH03258330 A JP H03258330A JP 5934690 A JP5934690 A JP 5934690A JP 5934690 A JP5934690 A JP 5934690A JP H03258330 A JPH03258330 A JP H03258330A
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- membrane
- fiber membrane
- dense layer
- porous
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 92
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011148 porous material Substances 0.000 claims abstract description 36
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 22
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 11
- 238000009751 slip forming Methods 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 abstract description 17
- 230000035699 permeability Effects 0.000 abstract description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 abstract description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 abstract description 5
- 230000004907 flux Effects 0.000 abstract description 3
- 239000004695 Polyether sulfone Substances 0.000 abstract description 2
- 229920006393 polyether sulfone Polymers 0.000 abstract description 2
- 238000009987 spinning Methods 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 9
- 239000011550 stock solution Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 238000005191 phase separation Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000011085 pressure filtration Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- AHJKRLASYNVKDZ-UHFFFAOYSA-N DDD Chemical compound C=1C=C(Cl)C=CC=1C(C(Cl)Cl)C1=CC=C(Cl)C=C1 AHJKRLASYNVKDZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- -1 Liα and ZnO2 Chemical class 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 206010033546 Pallor Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000002166 wet spinning Methods 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は多孔性中空糸膜、特に高い透水性と優れた分画
性を有し、かつ親水性に優れた多孔性中空糸膜に関する
ものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a porous hollow fiber membrane, particularly a porous hollow fiber membrane having high water permeability, excellent fractionation properties, and excellent hydrophilicity. It is.
（従来の技術）
近年、分離操作において選択的な透過性を有する膜を用
いる技術の進展はめざオしく、各種の分野において実用
化されている。特に中空糸形状の膜は、占有体積当りの
膜面積が多くとれるためｔζ戸適量が多く工業的に有利
である。中空糸膜の素材としては、セルロース系、ポリ
アミド系、ポリアクリルニトリル系、ポリビニルアルコ
ール系。(Prior Art) In recent years, the technology of using selectively permeable membranes in separation operations has made remarkable progress and has been put into practical use in various fields. In particular, hollow fiber-shaped membranes are industrially advantageous because they have a large membrane area per occupied volume and can be used in large quantities. Materials for hollow fiber membranes include cellulose, polyamide, polyacrylonitrile, and polyvinyl alcohol.
ポリスルホン系等の樹脂か使用されている。中でもポリ
スルホン系樹脂は、耐熱性、耐酸性、耐アルカリ性、耐
酸化剤性等の物理的及び化学的性質に優れ、また製膜が
容易な点から、各種用途において使用されている。Resins such as polysulfone are used. Among them, polysulfone resins are used in various applications because they have excellent physical and chemical properties such as heat resistance, acid resistance, alkali resistance, and oxidizing agent resistance, and are easy to form into films.
しかし、ポリスルホン系樹脂のような疎水性高分子から
なる中空糸膜の欠点として、中空糸膜を乾燥させると透
過速度が著しく減少することが挙げられる。この欠点を
解決する方法として、例えば特開昭５８−１０４９４０
号公報や特開昭６１−９３８０１号公報に膜中に親水性
のポリビニルピロリドンを含有させた親水化ポリスルホ
ン膜が記載されてい、る。また、特開昭６１−２３８３
０６号公報及び時開６１−２３８８３４号公報にはポリ
スルホン樹脂、ポリビニルピロリドン、膨潤剤、溶媒よ
り構成される紡糸原液を使用して、膜の両堀面に平均孔
径が５００Ａ以上の細孔ｔＶする透水性の高い親水化ポ
リスルホン膜か記載されている。However, a drawback of hollow fiber membranes made of hydrophobic polymers such as polysulfone resins is that the permeation rate decreases significantly when the hollow fiber membranes are dried. As a method to solve this drawback, for example, Japanese Patent Application Laid-Open No. 58-104940
Hydrophilized polysulfone membranes containing hydrophilic polyvinylpyrrolidone in the membrane are described in Japanese Patent Application Laid-Open No. 61-93801. Also, JP-A-61-2383
No. 06 and Jikai No. 61-238834 use a spinning dope consisting of polysulfone resin, polyvinylpyrrolidone, a swelling agent, and a solvent to form pores tV with an average pore diameter of 500 A or more on both moat surfaces of the membrane. A hydrophilic polysulfone membrane with high water permeability has been described.
（発明が解決しようとする課題）
しかしながら前者の親水化ポリスルホン膜は孔径０．０
０１〜０．Ｏ５ｌ１ｍの微小な細孔を有するスキン層を
有する非対称膜であるため透水性が極めて低いという問
題があった０
また後者の親水化ポリスルホン膜は膜表面の微細孔が平
均５００λ以上であるため、透水性は高いが、分画性が
大きいため濾過によるＦＬＵＸの低下が大きいという問
題があった。(Problem to be solved by the invention) However, the former hydrophilized polysulfone membrane has a pore size of 0.0
01~0. Since it is an asymmetric membrane with a skin layer having micropores of O5l1m, it has a problem of extremely low water permeability.In addition, the latter hydrophilized polysulfone membrane has micropores on the membrane surface with an average size of 500λ or more, so it has low water permeability. However, there was a problem in that the FLUX decreased significantly due to filtration due to the high fractionability.
したがって、本発明の目的は高い透水性と優れた分画性
を有し、使用時におけるＦＬＵＸ低下が小さい親水性の
中空糸膜を提供することにある０（課題を解決するため
の手段）
本発明は、疎水性高分子に対して０．５〜１０チの親水
性高分子を含有した多孔性中空糸膜であって、該多孔性
中空糸膜は内表面に不定形の微細孔を開孔率１０〜５０
％の割合で有する、厚さ０．５〜５ｐの緻密層と、該緻
密ｊ−に一体に連続して形成された網状組織とからなる
多孔構造であり、かつ外表面は該網状組織の一部が開孔
してできた最大孔径０．５〜５−の孔を有し、２５℃に
おける純水透過速度が８００ ｔ／♂・ｈｒ−ｋｐ／−
以上であることを特徴とする多孔性中空糸膜である。Therefore, an object of the present invention is to provide a hydrophilic hollow fiber membrane that has high water permeability and excellent fractionation properties and exhibits a small decrease in FLUX during use. The present invention is a porous hollow fiber membrane containing 0.5 to 10 of a hydrophilic polymer to a hydrophobic polymer, the porous hollow fiber membrane having irregularly shaped micropores on its inner surface. Porosity 10-50
It has a porous structure consisting of a dense layer with a thickness of 0.5 to 5p and a network structure integrally and continuously formed in the dense layer, and the outer surface is one part of the network structure. It has pores with a maximum pore diameter of 0.5 to 5-5, and the pure water permeation rate at 25°C is 800 t/♂・hr-kp/-.
This is a porous hollow fiber membrane characterized by the above.
中空糸膜の内表面に形成場れる微細孔の形状は特に制限
はなく、例えば単独微細孔、孔が連続につながった多孔
性微細孔、スリット状微細孔、網状微細孔等が挙げられ
る。か〃・る微細孔の平均孔径は０．２ｔｘｎ以下が望
ましく、これ以上の孔径では膜の表面強度が小ζ〈なり
好ましくない。ここでいう平均孔径とは、表面の電子顕
微鏡写真より存在する全ての不足形微細孔の最大内接円
の直径を測定して総和したものを細孔の総数で割った値
である。この不定形微細孔の開孔至ＦｉｌＯ〜５０チの
割合で存在し、厚さ０．５〜５Ｉｉｎの緻密ＩＭを形成
している。本発明でいう開孔率とは、内表面に開孔して
いる微細孔の全孔面積の外表面積に対する割合を百分率
で示したものである。開孔率が１０チ未満であると透水
性が低くなり、５０ｍを越えると表面強度が小さくなり
膜の取り扱いが悪くなるため好ましくない。開孔率が１
０〜３０チであると膜の透過性能と機械的強度のバラン
スの点で好ましい。また、この微細孔の分布密度はでき
るだけ均一であることが好ましいが、不均一であっても
よい。The shape of the micropores formed on the inner surface of the hollow fiber membrane is not particularly limited, and examples thereof include individual micropores, porous micropores in which pores are continuously connected, slit-like micropores, network micropores, and the like. The average pore diameter of such micropores is preferably 0.2txn or less; a pore diameter larger than this is not preferred because the surface strength of the membrane becomes small. The average pore diameter here is the value obtained by dividing the sum of the diameters of the maximum inscribed circles of all missing micropores measured from an electron micrograph of the surface by the total number of pores. These irregularly shaped micropores are present at a ratio of 50 to 50 mm, forming a dense IM with a thickness of 0.5 to 5 inches. In the present invention, the porosity refers to the ratio of the total pore area of micropores formed on the inner surface to the outer surface area, expressed as a percentage. If the porosity is less than 10 m, the water permeability will be low, and if it exceeds 50 m, the surface strength will decrease and the membrane will be difficult to handle, which is not preferable. Open area ratio is 1
A range of 0 to 30 is preferable in terms of the balance between membrane permeability and mechanical strength. Further, although it is preferable that the distribution density of the micropores be as uniform as possible, it may be non-uniform.
また、本発明の中空糸膜は内表面に形成された緻密層に
一体に連続して網状組織の多孔構造が形成され、かつ外
表面は該網状組織の一部が開孔してできた最大孔径０．
１〜５Ｐｉの孔を有している。In addition, the hollow fiber membrane of the present invention has a porous network structure formed integrally and continuously in the dense layer formed on the inner surface, and the outer surface has the largest pore structure formed by opening a part of the network structure. Pore diameter 0.
It has pores of 1 to 5 Pi.
かかる膜内部に形成された網状組織は、平均１〜５虜の
多数の連続孔を有し、かつ１０−以上の巨大空洞は存在
しない。このため、長期間の使用時における圧密化性が
優れ、さらには強度も優れている。外表面の孔の形状や
開孔率は特に制限はないが、開孔率は内表面と同程度の
１０〜５０係が望ましい。最大孔径に５Ｉｘｎ以上にな
ると耐圧性の点で問題になるばかりではなく、外圧で濾
過した場合に膜内部に残留物が堆積し易くなって透過速
度の低下が早く、まｔ薬洗や逆洗による膜の再生が十分
性われないという傾向があり好ましくない。The network formed inside such a membrane has a large number of continuous pores, on average 1 to 5 holes, and there are no large cavities of 10 or more. Therefore, it has excellent compactability during long-term use and also has excellent strength. There are no particular restrictions on the shape or porosity of the pores on the outer surface, but it is desirable that the porosity is about the same as that on the inner surface, 10-50. If the maximum pore diameter exceeds 5Ixn, not only will pressure resistance become a problem, but when filtration is performed under external pressure, residue will easily accumulate inside the membrane, resulting in a rapid decrease in permeation rate, and chemical washing and backwashing will be difficult. This is undesirable because it tends to result in insufficient regeneration of the membrane.
逆に最大孔径が０．１１ｉｎより小さくなると透水性が
小さくなる。Conversely, if the maximum pore diameter is smaller than 0.11 inch, the water permeability will be reduced.
本発明の中空糸１［１１［は緻密層と網状組織からなる
多孔構造で構成されている。そして緻密層の厚みが０．
５〜５Ａｆｒｉと薄いため、例えば、１３５Ａの粒子を
９０チ以上阻止するにもかかわらず２５℃の純水透過速
度が８００４／ｒａ’−ｈｒ−に？／−以上と高い透水
性を示す。また実際に水を濾過した場合、外圧濾過では
、外表面でサブミクロンオーダー以上の粒子を補捉し膜
内部、または内表面の緻密層で溶解ポリマー等のサブミ
クロン以下の物質を補捉する。すなわち外表面及び膜内
部がブレフィルター的な役割を果たすため、透過速度の
低下が少なく高い透過速度を維持することができる。逆
に内圧濾過では、内表面に緻密層を有しているためクロ
スフロ一方式の濾過に有効であり、膜を透過し念物質は
膜内部で留まりにくいため汚染されにくい０
甘だ本発明の中空糸膜は、緻密層と多孔構造が一体化し
ており、コーディング法などで得られる複合膜のように
緻密層のピンホールや緻密層と支持層との剥離の問題ｉ
ｌ″ｉ、まったくない。The hollow fiber 1[11[ of the present invention] has a porous structure consisting of a dense layer and a network structure. And the thickness of the dense layer is 0.
Because it is as thin as 5~5Afri, for example, the pure water permeation rate at 25°C is 8004/ra'-hr- even though it blocks more than 90 particles of 135A? /- or more, showing high water permeability. Furthermore, when water is actually filtered, in external pressure filtration, particles of submicron order or larger are captured on the outer surface, and submicron or smaller substances such as dissolved polymers are captured inside the membrane or in a dense layer on the inner surface. That is, since the outer surface and the inside of the membrane play the role of a blur filter, a high permeation rate can be maintained with little decrease in permeation rate. On the other hand, internal pressure filtration has a dense layer on the inner surface, so it is effective for cross-flow one-way filtration, and the substances that pass through the membrane are difficult to remain inside the membrane, so they are less likely to be contaminated. Thread membranes have a dense layer and a porous structure integrated, and unlike composite membranes obtained by coating methods, there are problems with pinholes in the dense layer and peeling between the dense layer and the support layer.
l″i, not at all.
さらに、本発明の中空糸膜は膜中に疎水性高分子に対し
て０５〜１０チの親水性高分子を台上′″！る。そのた
め、親水性に優れ、タンパク等の吸着が少なく、沖過に
よる透過性能の低下が小さい。Furthermore, the hollow fiber membrane of the present invention has a hydrophilic polymer of 0.5 to 10 times more than a hydrophobic polymer in the membrane. Therefore, it has excellent hydrophilicity and adsorption of proteins, etc. is small. There is little decrease in permeation performance due to offshore passage.
また、乾燥によって実質的な透水性の低下や中空糸膜の
寸法変化がなく、完全なドライ膜を作製することができ
る。これは、中空糸膜の扱い、モジュール化、モジュー
・ルの輸送等多数の面で有利であり５作業性や生産性を
向上させることができる。In addition, a completely dry membrane can be produced without any substantial decrease in water permeability or dimensional change of the hollow fiber membrane due to drying. This is advantageous in many aspects such as handling of hollow fiber membranes, modularization, and transportation of modules, and can improve workability and productivity.
次に、本発明の多孔性中壁糸膜の製造方法について説明
する○
本発明の中空糸膜を製造するための紡糸原液は、疎水性
高分子、親水性高分子、微孔形成剤及びこれらを溶解す
る極性溶媒から構成される。Next, the method for producing the porous mid-wall fiber membrane of the present invention will be explained.○ The spinning stock solution for producing the hollow fiber membrane of the present invention includes a hydrophobic polymer, a hydrophilic polymer, a pore-forming agent, and It consists of a polar solvent that dissolves
疎水性高分子は、例えば、ポリスルボン、ポリｊ−チッ
トスルホン、ポリフッ化ビニリチン、ボｌ；エチレン、
塩化ビニル等が挙げられる。甲でもポリスルホンやポリ
エーテルスルポンに耐熱性、耐薬品性、耐酸化剤性、強
度に優れ、、 １．、、かも分子間凝集力が強いため
に製膜が容易であり好適である０、親水性高分子は、例
えばポリビニＡ・ビ「コリトン、平％ａ分子１２Ｏ１０
００以−トのポリ］ヂレング１１コ・−ノｔハホリヒニ
ルアルコーＡ、＝、Ｘ→−１／ン伊ビニルアルコ一ル共
重合体等やこれらの変性ポリマーが挙げられるがこれら
に限定さねるものてケユない。〃だし、疎水性高分子・
と溶媒中での相溶性が優れているものが望筺しく、また
ポリビニルヒロリドン′等の水溶性高分子の場合は架橋
等で容易に不溶化できるものが望ましい。親水性高分子
の添加量は高分子量であるほど少なくですむ。％に水溶
性高分子の場合は膜中に残存Ｉ７やすく、水洗、熱水処
理中や膜を使用時に溶出も少なくなるため好１ｍ。Hydrophobic polymers include, for example, polysulfone, polyj-titsulfone, polyvinyritine fluoride, vol; ethylene,
Examples include vinyl chloride. The former also has excellent heat resistance, chemical resistance, oxidizing agent resistance, and strength compared to polysulfone and polyether sulfone. 1. Hydrophilic polymers are suitable because they have a strong intermolecular cohesive force and are therefore easy to form into films.
Examples include, but are not limited to, poly]dilene 11 co--not haholyl alcohol copolymers of 00 or more and vinyl alcohol copolymers and modified polymers thereof. I don't care. 〃Dashi, hydrophobic polymer・
It is desirable that the polymer has excellent compatibility with the polymer in the solvent, and in the case of water-soluble polymers such as polyvinylhydrolidone', it is desirable that the polymer can be easily made insolubilized by crosslinking or the like. The higher the molecular weight, the smaller the amount of hydrophilic polymer added. In the case of water-soluble polymers, I7 is more likely to remain in the membrane, and there is less elution during water washing, hot water treatment, or when the membrane is used, so 1 m is preferable.
い。これら親水性高分子はＳ製造プロセス、各用途にお
ける適合性等を考慮にいれて選択フることができる。stomach. These hydrophilic polymers can be selected taking into account the S manufacturing process, suitability for each application, and the like.
本発明の中空糸膜はミクロ相分離によって微孔六＼
・形成されるが、微孔形成剤はそのミクロ相分離を起こ
〔２やすくする目的で添加する。従来エリ、微孔形成剤
と１７でメタノール、エタノール等のアルコール類、エ
チレングリコール、フロピレンゲリコール、平均分子ｆ
ｉ４００〜２０，０００の低分子量のポリエチレングリ
コール等のグリコール類、Ｌｉα、ＺｎＯ２等の無機塩
類、水等多数用いられており、本発明においても上記微
孔形成剤が使用できる。微孔形成剤の添加ｉは紡糸原液
が均一透明を保つ範囲内に抑える必要があるが、微孔形
成剤が孔の核となると推定されるために添加ｉｔはでき
るだけ多い方が望ましい。分子＠４００〜２０，０００
の低分子量のポリエチレングリコールは紡糸原液への添
加量を多くすることができるため好適である。また、こ
の低分子量のポリエチレングリコールは微細孔形成に優
れ、かつ紡糸原液の増粘効果を有しているため紡糸の安
定性を向上させる利点がある。In the hollow fiber membrane of the present invention, micropores are formed by microphase separation, and the micropore-forming agent is added for the purpose of facilitating the microphase separation. Conventional Eri, pore-forming agent and 17 alcohols such as methanol and ethanol, ethylene glycol, phlopylene gelicol, average molecular f
Many glycols such as polyethylene glycol with a low molecular weight of i400 to 20,000, inorganic salts such as Liα and ZnO2, and water are used, and the above-mentioned pore-forming agents can also be used in the present invention. The addition i of the pore-forming agent must be kept within a range that allows the spinning dope to remain uniform and transparent, but since the pore-forming agent is presumed to form the core of the pores, it is desirable to add it as much as possible. Molecules @400~20,000
Low molecular weight polyethylene glycol is suitable because it can be added in a large amount to the spinning dope. In addition, this low molecular weight polyethylene glycol is excellent in forming micropores and has the effect of thickening the spinning dope, so it has the advantage of improving the stability of spinning.
極性溶媒は、疎水性高分子、親水性高分子および微孔形
成剤を溶解するものであれば肴に制限はなく１．例えば
、Ｎ、Ｎ−ジメチルホルムアミド、ジメチルアセトアミ
ド、Ｎ−メチルピロリドン、ジメチルスルホキシド等が
挙げられる。There are no restrictions on polar solvents as long as they can dissolve hydrophobic polymers, hydrophilic polymers, and pore-forming agents.1. Examples include N,N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and the like.
こｔ′Ｌら４棟類の組成はそれぞれ任意の割合で選択す
ることができるが、本発明の中空糸膜を製造するために
は、紡糸原液をある一足の温度以下で相分離を起こす（
低温相分離型）、あるいはある一定温度以上で相分離を
起こ−ｔ（高温相分離型）ように調製−することが好ブ
しい。The compositions of these four groups can be selected in any proportion, but in order to produce the hollow fiber membrane of the present invention, the spinning stock solution is subjected to phase separation at a temperature below a certain temperature (
It is preferable to prepare the phase separation type (low-temperature phase separation type) or to cause phase separation at a certain temperature or higher (high-temperature phase separation type).
本発明の中空糸膜は、上記の紡糸原液を使用し公知の乾
湿式法によって製造される。紡糸原液と共にノズル中心
部より吐出される内部凝固液は、例えば、水、水と極性
溶媒の混合液、アルコール類、グリコール類等の単独、
あるいはそれらの２攬類以上の混合物を使用する。この
内部凝固液の組成を変えることにより内表面の微細孔の
形状、平均孔径、開孔率および緻密層の厚み等の内表面
近傍の構造が制御できる。The hollow fiber membrane of the present invention is manufactured by a known dry-wet method using the above-mentioned spinning dope. The internal coagulating liquid discharged from the center of the nozzle together with the spinning dope may be, for example, water, a mixture of water and a polar solvent, alcohols, glycols, etc. alone,
Or use a mixture of two or more of them. By changing the composition of this internal coagulation liquid, the structure near the inner surface, such as the shape of the micropores on the inner surface, the average pore diameter, the porosity, and the thickness of the dense layer, can be controlled.
ノズルより吐出させた紡糸原液は、気中（ドライゾーン
）を走行させたのちに、水を主成分とした外部凝固液中
に浸漬される。本発明ではこのドライゾーンの長さ、ド
ライゾーン中の雰囲気湿度や温度を変化させることによ
り、ドライゾーン中に存在する微・の水分量を調節して
、中空糸膜の外表面の孔形成のための制御を行う。この
ドライゾーンの長さは紡糸安定性と膜性能のバランスの
点で０．１〜２００ｃＭ−通常１〜５０５１が適当であ
る。また、ドライゾーンの雰囲気は湿度が高いほど大き
な孔が形成されやすく、開孔！も多くなる。The spinning stock solution discharged from the nozzle travels in the air (dry zone), and then is immersed in an external coagulation liquid mainly composed of water. In the present invention, by changing the length of this dry zone and the atmospheric humidity and temperature in the dry zone, the amount of moisture present in the dry zone is adjusted, thereby reducing the formation of pores on the outer surface of the hollow fiber membrane. Perform control for The length of this dry zone is suitably 0.1 to 200 cM, usually 1 to 5,051 cM, from the viewpoint of the balance between spinning stability and membrane performance. Also, the higher the humidity in the dry zone atmosphere, the more large pores are likely to form, leading to open pores! There will also be more.
凝固液で裏腹した中空糸膜は、次いで、溶媒やさせるた
めに、水を主成分とした浴中で湿熱処理される。親水性
高分子とｊ−て水溶性高分子を用いた場合は、膜中に過
剰に残存する親水性高分子の抽出も水洗や湿熱処理で同
時に行うことができる。The hollow fiber membrane coated with the coagulating liquid is then subjected to a moist heat treatment in a water-based bath to remove the solvent. When a water-soluble polymer is used as the hydrophilic polymer, the excess hydrophilic polymer remaining in the membrane can be extracted at the same time by water washing or moist heat treatment.
ただし、この抽出効果は親水性高分子の種類や分子量に
よって異なるために、場合によっては別の抽出操作を行
い、最終的に膜に残存させる親水性高分子量を調節する
ことが好ましい。抽出後に膜中に残存する親水性高分子
・使用中に溶出することはほとんどないが医療用途等用
途によっては、親水性高分子を物理的またに化学的に不
溶化きせて親水性高分子の溶出を完全に防止することが
望ましい。この親水性高分子の定量は、重量法や元素分
析等の適当な手段で容易に行うことができる。However, since this extraction effect differs depending on the type and molecular weight of the hydrophilic polymer, it is preferable to perform another extraction operation in some cases to adjust the weight of the hydrophilic polymer ultimately remaining in the membrane. Hydrophilic polymers that remain in the membrane after extraction - They rarely elute during use, but depending on the application, such as medical applications, the hydrophilic polymers may be physically or chemically insolubilized to elute the hydrophilic polymers. It is desirable to completely prevent this. Quantification of this hydrophilic polymer can be easily carried out by appropriate means such as gravimetric method or elemental analysis.
上記の方法で得られた中空糸膜は、疎水性高分子に対し
て０５〜１０係の親水性高分子を含有する。親水性高分
子の含有量が１０チを越えると、疎水性高分子の持つ特
性を親水性高分子が阻害してしまう可能性があり、また
０、５チ未満では親水効果を得ることができない。親水
性高分子の含有量は、膜に親水性を与えることができる
最少の量が望ましい。また、中空糸膜中の親水性高分子
の分散状態は特に制限がないが、膜に親水性を与えるた
めにはできるだけ均一に分散させることが望ましい。The hollow fiber membrane obtained by the above method contains a hydrophilic polymer having a ratio of 05 to 10 relative to a hydrophobic polymer. If the content of the hydrophilic polymer exceeds 10%, the hydrophilic polymer may inhibit the properties of the hydrophobic polymer, and if the content is less than 0.5%, no hydrophilic effect can be obtained. . The content of the hydrophilic polymer is preferably the minimum amount that can impart hydrophilicity to the membrane. Further, although there is no particular restriction on the dispersion state of the hydrophilic polymer in the hollow fiber membrane, it is desirable to disperse it as uniformly as possible in order to impart hydrophilicity to the membrane.
（実施例）
以下実施例により本発明を更に具体的に説明する。なお
、純水透過速度および分画性の測定は以下の方法で行っ
た。(Example) The present invention will be explained in more detail with reference to Examples below. Note that the pure water permeation rate and fractionability were measured by the following method.
（１）純水透過速度
２５本の中空糸で有効長２０αの外圧濾過型のラボモジ
ュールを作製し、２５℃の純水を濾過圧１ ｋｆ／−で
膜外部より透過させ、一定時間中に中空部よりでてくる
純水の量を測定した。(1) Pure water permeation rate An external pressure filtration type lab module with an effective length of 20α was made using 25 hollow fibers, and pure water at 25°C was permeated from the outside of the membrane at a filtration pressure of 1 kf/- for a certain period of time. The amount of pure water coming out of the hollow part was measured.
（１１）分画性
測定液として１３５λのコロイダルシリカ（触媒化成工
業 ５Ｉ−３０）の１チ分散液を調製し、濾過圧Ｏ１５
ｋｆ／ｉ、循環線速０．３ ｒｒＶｓｅｃで外圧濾過を
行い、採取した透過液と測定液の蒸発残査の重量を測定
し除去率を算出した。(11) As a fractionation measurement liquid, a 1-ti dispersion of 135λ colloidal silica (catalyst chemical industry 5I-30) was prepared, and the filtration pressure was O15.
External pressure filtration was performed at kf/i and circulation linear velocity of 0.3 rrVsec, and the weight of the collected permeate and the evaporation residue of the measurement solution was measured to calculate the removal rate.
実施例１
ポリスルホン樹脂（アモコ製ＵＤＥＬ Ｐ−１７００）
１９重量部、平均分子量１２０万のポリビニルピロリド
ン（ＧＡＦ製 Ｋ−９０）１．９重量部、平均分子量６
００のポリエチレングリコール（三洋化成製 ＰＥＧφ
６００）３０．４重量部、ジメチルホルムアミド４８，
７重量部を１２０℃で６時間加熱溶解した。この紡糸原
液は７５℃以上と２９℃以下で相分離をおこす原液であ
った。この紡糸原液を４５℃に保ち、２重環状ノズルよ
り内部凝固液として同じ温度に保ったジメチルホルムア
ミド／水： ８０／２０を同時に吐出させ、長さｌＯｃ
！１Ｋ、雰囲気温度４５℃、芥囲気相対湿度８５％のド
ライゾーン全通した後に、４５℃の水に浸して外径０．
６閣、内径０．４■の中空糸膜を得た。この中空糸膜を
９０℃の水で２時間湿熱処理を行ない洗浄したのちに、
６０℃で８時間乾燥させた。得られた中空糸膜の純水透
過速度は、３５００ ｔ／ｄ−ｈｒ −ｋｅ／ｃｄ、１
３５λのコロイダルシリカの除去率Ｆｉ４０チであった
。走査型電子顕微鏡写真から求めた内表面の平均孔径は
６００＾、開孔率は２５優、緻密層の厚さは１．５即り
外表面の最大孔径は１，５岬、膜内部は平均孔１岬の網
状多孔構造でめった。また、元素分析で膜中のポリとニ
ルピロリドン量を測定したところ、ポリスルホンに対し
て４チであった。Example 1 Polysulfone resin (UDEL P-1700 manufactured by Amoco)
19 parts by weight, polyvinylpyrrolidone with an average molecular weight of 1.2 million (GAF K-90) 1.9 parts by weight, average molecular weight 6
00 polyethylene glycol (manufactured by Sanyo Chemical PEGφ
600) 30.4 parts by weight, dimethylformamide 48,
7 parts by weight were heated and dissolved at 120°C for 6 hours. This spinning stock solution caused phase separation at temperatures above 75°C and below 29°C. This spinning stock solution was kept at 45°C, and dimethylformamide/water: 80/20 kept at the same temperature was simultaneously discharged as an internal coagulation liquid from a double annular nozzle to a length of lOc.
! After passing through a dry zone at 1K, an ambient temperature of 45°C, and a relative humidity of 85%, it was immersed in water at 45°C to reduce the outer diameter to 0.
A hollow fiber membrane with a diameter of 6 mm and an inner diameter of 0.4 mm was obtained. After washing this hollow fiber membrane with water at 90°C for 2 hours through moist heat treatment,
It was dried at 60°C for 8 hours. The pure water permeation rate of the obtained hollow fiber membrane was 3500 t/d-hr-ke/cd, 1
The removal rate Fi of 35λ colloidal silica was 40chi. The average pore diameter on the inner surface determined from scanning electron micrographs is 600^, the porosity is 25, the thickness of the dense layer is 1.5, the maximum pore diameter on the outer surface is 1.5, and the inside of the membrane is average. This occurred due to the network-like porous structure of Cape 1. Further, when the amount of poly and nylpyrrolidone in the film was measured by elemental analysis, it was found to be 4% relative to polysulfone.
この中空糸膜に通水したのちに再乾燥して透水性５図に
示す。第１図は中空糸膜の外表面、第２図は内表面、第
３図は外表面側の断面、第４図は１１Ｊぼ中央部の断面
及び第５図に内表面側の断面を示している。After passing water through this hollow fiber membrane, it was re-dried and the water permeability is shown in Figure 5. Figure 1 shows the outer surface of the hollow fiber membrane, Figure 2 shows the inner surface, Figure 3 shows the cross section of the outer surface, Figure 4 shows the cross section of the central part of the hollow fiber membrane, and Figure 5 shows the cross section of the inner surface. ing.
実施例２〜８
紡糸条件を変えて実施例１と同様に１．で中空糸膜を製
造した。表−１に示すように限外濾過１ノベルから精密
濾過レベルまでの広い範囲の性能を持つ中空糸膜が得ら
れ几。Examples 2 to 8 1. Same as Example 1 with different spinning conditions. A hollow fiber membrane was manufactured. As shown in Table 1, hollow fiber membranes with a wide range of performance from the ultrafiltration level to the precision filtration level were obtained.
以下、蒼白
実施例９
ポリスルホンｔｓ３１１１１部、ポリビニルビ０９１７
２重量部、無水塩化リチウム１重重部、ジメチルホルム
アミド７９重重部を６０℃で８時間加熱溶解し紡糸原液
とした。この原液は４５℃で相分離する高温分離型の原
液であった。この原液を用いて実施例１と同一条件で中
空糸膜を製造した。Below, pallor Example 9 Polysulfone TS31111 parts, Polyvinyl vinyl 0917
2 parts by weight, 1 part by weight of anhydrous lithium chloride, and 79 parts by weight of dimethylformamide were dissolved by heating at 60° C. for 8 hours to obtain a spinning stock solution. This stock solution was a high temperature separation type stock solution that undergoes phase separation at 45°C. A hollow fiber membrane was produced using this stock solution under the same conditions as in Example 1.
得られた中空糸膜の純水透過速度は、ｔ、８００ｔ／ｎ
ｉ’ −ｈｒ −’ｑ／ｄ、１３５Ｘのコロイダルシリ
カの除去率は９６４であった。走査型電子顕微鏡写真か
ら求めた内表館の平均孔径は２００λ、開孔率は１５チ
、緻密層の厚さｔ／′１３Ａｆｎ、外表面の最大孔径は
１．５ＩＩｌ′ｎ１膜の内部は平均孔径ｌｌ１ｎの網状
多孔構造であった。また、元素分析に二る膜中のポリビ
ニルピロリドン量にポリスルホンに対して４５壬であっ
た。The pure water permeation rate of the obtained hollow fiber membrane was t, 800t/n.
The removal rate of colloidal silica of i'-hr-'q/d, 135X was 964. The average pore diameter of the inner surface, determined from scanning electron micrographs, is 200λ, the porosity is 15cm, the thickness of the dense layer is t/'13Afn, and the maximum pore diameter on the outer surface is 1.5IIl'n1. It had a network-like porous structure with a pore diameter of 11n. In addition, the amount of polyvinylpyrrolidone in the membrane based on elemental analysis was 45 mm compared to polysulfone.
比較例１
ドライブーンｆＯの（湿式紡糸）とした以外は実施例１
と同一条件で中空糸膜を製造した。得られた中空糸膜の
純水透過速度はｓ ４００ Ｚ／ａ！−ｈｒ・ｋｆ１
５１と低いものであった。また走査型電子顕微鏡写真よ
り、外表面・孔径０．１μｍ以上の孔に存在しておらず
、また内表面と外表面に緻密層が認められた。Comparative Example 1 Example 1 except that dry yarn fO (wet spinning) was used.
Hollow fiber membranes were manufactured under the same conditions. The pure water permeation rate of the obtained hollow fiber membrane was s 400 Z/a! -hr・kf1
It was as low as 51. In addition, scanning electron micrographs showed that it was not present on the outer surface or in pores with a pore diameter of 0.1 μm or more, and dense layers were observed on the inner and outer surfaces.
実施例１０
実施例１および比較例１の中空糸膜を使用して、有効膜
面積１ｒｒ！の外圧濾過型モジュールを作製した。この
モジュールを用いて水道水をｒ過圧Ｑ、 ５呻／ｄで外
圧全濾過を行った０透過速度が半減したときの濾過量を
測定したところ、比較例１の中空糸膜を収容したモジュ
ールが２５ｆｔＩｌ″Ｔ：あったのに対して実施例１の
中空糸膜を収容したモジュールは６０ｒｒｌであった０
（発明の効果）
本発明の多孔性中空糸膜は、特定の構造を有しているた
めに透水性、分画性、目詰まり、耐汚染性等に優れ、し
かも親水性であるため、長期間の使用に適しており、経
済的である。そのため、中工業用途や血液、腹水濾
過等のメディカル用途等幅広い分野で使用することがで
きる。Example 10 Using the hollow fiber membranes of Example 1 and Comparative Example 1, the effective membrane area was 1rr! An external pressure filtration type module was fabricated. Using this module, tap water was subjected to external pressure total filtration at r overpressure Q and 5 m/d, and the filtration amount when the zero permeation rate was halved was measured. was 25ftIl''T: whereas the module containing the hollow fiber membrane of Example 1 had a capacity of 60rrl. It has excellent water permeability, fractionation, clogging and stain resistance, etc., and is hydrophilic, making it suitable for long-term use and economical. It can be used in a wide range of fields including medical applications such as filtration.
第１図〜第５図に実施例１において得られたポリスルホ
ン中空糸膜の走査型電子顕微鏡写真であり、第１図は中
空糸膜の外表面の構造（倍率５．０００）、第２図は中
空糸膜の内表面の構造（倍率５，０００）、第３図は中
空糸膜の外表面側の断面構造（倍率５．０００）、第４
図は中空糸膜の内部（はぼ中央部）の構造（倍率５．０
００）および第５図は中空糸膜の内表面側の断面構造（
倍率５，０００）を示す。Figures 1 to 5 are scanning electron micrographs of the polysulfone hollow fiber membrane obtained in Example 1. Figure 1 is the structure of the outer surface of the hollow fiber membrane (magnification: 5.000), and Figure 2 is a scanning electron micrograph of the polysulfone hollow fiber membrane obtained in Example 1. Figure 3 shows the structure of the inner surface of the hollow fiber membrane (magnification 5,000), Figure 3 shows the cross-sectional structure of the outer surface of the hollow fiber membrane (magnification 5,000), Figure 4
The figure shows the structure of the inside (center part) of the hollow fiber membrane (magnification: 5.0
00) and Figure 5 show the cross-sectional structure of the inner surface side of the hollow fiber membrane (
Magnification: 5,000).
Claims (1)
分子を含有した多孔性中空糸膜であつて、該多孔性中空
糸膜は内表面に不定形の微細孔を開孔率１０〜５０％の
割合で有する、厚さ０．５〜５μｍの緻密層と、該緻密
層に一体に連続して形成された網状組織とからなる多孔
構造であり、かつ外表面は該網状組織の一部が開孔して
できた最大孔径０．５〜５μｍの孔を有し、２５℃にお
ける純水透過速度が８００ｌ／ｍ＾２・ｈｒ・ｋｇ／ｃ
ｍ＾２以上であることを特徴とする多孔性中空糸膜。(1) A porous hollow fiber membrane containing 0.5 to 10% of a hydrophilic polymer to a hydrophobic polymer, the porous hollow fiber membrane having irregularly shaped micropores on its inner surface. It has a porous structure consisting of a dense layer having a porosity of 10 to 50% and a thickness of 0.5 to 5 μm, and a network structure integrally and continuously formed in the dense layer, and the outer surface is It has pores with a maximum pore diameter of 0.5 to 5 μm created by opening a part of the network, and the pure water permeation rate at 25°C is 800 l/m^2・hr・kg/c.
A porous hollow fiber membrane characterized by having a porous hollow fiber membrane of m^2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2059346A JP2899347B2 (en) | 1990-03-09 | 1990-03-09 | Porous hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2059346A JP2899347B2 (en) | 1990-03-09 | 1990-03-09 | Porous hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03258330A true JPH03258330A (en) | 1991-11-18 |
| JP2899347B2 JP2899347B2 (en) | 1999-06-02 |
Family
ID=13110643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2059346A Expired - Lifetime JP2899347B2 (en) | 1990-03-09 | 1990-03-09 | Porous hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2899347B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997034687A1 (en) * | 1996-03-21 | 1997-09-25 | Kaneka Corporation | Hollow yarn membrane used for blood purification and blood purifier |
| KR100426328B1 (en) * | 2001-04-24 | 2004-04-08 | 학교법인 한양학원 | Method for manufacturing microporous chlorinated poly(vinyl chloride) membrane using poly(vinyl pyrrolidone) and microporous chlorinated poly(vinyl chloride) membrane manufactured thereby |
| WO2010035754A1 (en) * | 2008-09-26 | 2010-04-01 | 旭化成ケミカルズ株式会社 | Porous membrane, process for producing porous membrane, process for producing clarified liquid, and porous-membrane module |
| JP2011050914A (en) * | 2009-09-04 | 2011-03-17 | Toray Ind Inc | Method of manufacturing separation membrane |
| JP2014073487A (en) * | 2012-09-11 | 2014-04-24 | Toray Ind Inc | Porous membrane, water purifier incorporating porous membrane and method for producing porous membrane |
| WO2014156644A1 (en) * | 2013-03-28 | 2014-10-02 | 東レ株式会社 | Porous membrane and water purifier |
| CN104208766A (en) * | 2014-08-26 | 2014-12-17 | 东华大学 | High-stain-resistance polyether sulfone blood purifier and manufacturing method thereof |
| JP2016083647A (en) * | 2014-10-29 | 2016-05-19 | 株式会社クラレ | Hollow fiber membrane module |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2006214581B2 (en) | 2005-02-14 | 2012-03-01 | Johnson & Johnson Vision Care, Inc. | A comfortable ophthalmic device and methods of its production |
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1990
- 1990-03-09 JP JP2059346A patent/JP2899347B2/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6042783A (en) * | 1996-03-21 | 2000-03-28 | Kaneka Corporation | Hollow yarn membrane used for blood purification and blood purifier |
| WO1997034687A1 (en) * | 1996-03-21 | 1997-09-25 | Kaneka Corporation | Hollow yarn membrane used for blood purification and blood purifier |
| KR100426328B1 (en) * | 2001-04-24 | 2004-04-08 | 학교법인 한양학원 | Method for manufacturing microporous chlorinated poly(vinyl chloride) membrane using poly(vinyl pyrrolidone) and microporous chlorinated poly(vinyl chloride) membrane manufactured thereby |
| US9126148B2 (en) | 2008-09-26 | 2015-09-08 | Asahi Kasei Chemicals Corporation | Porous membrane, process for producing porous membrane, process for producing clarified liquid, and porous-membrane module |
| WO2010035754A1 (en) * | 2008-09-26 | 2010-04-01 | 旭化成ケミカルズ株式会社 | Porous membrane, process for producing porous membrane, process for producing clarified liquid, and porous-membrane module |
| JP5431347B2 (en) * | 2008-09-26 | 2014-03-05 | 旭化成ケミカルズ株式会社 | Porous membrane, method for producing porous membrane, method for producing clarified liquid, and porous membrane module |
| US9174172B2 (en) | 2008-09-26 | 2015-11-03 | Asahi Kasei Chemicals Corporation | Porous membrane, process for producing porous membrane, process for producing clarified liquid, and porous-membrane module |
| US8883066B2 (en) | 2008-09-26 | 2014-11-11 | Asahi Kasei Chemicals Corporation | Porous membrane, process for producing porous membrane, process for producing clarified liquid, and porous-membrane module |
| JP2011050914A (en) * | 2009-09-04 | 2011-03-17 | Toray Ind Inc | Method of manufacturing separation membrane |
| JP2014073487A (en) * | 2012-09-11 | 2014-04-24 | Toray Ind Inc | Porous membrane, water purifier incorporating porous membrane and method for producing porous membrane |
| WO2014156644A1 (en) * | 2013-03-28 | 2014-10-02 | 東レ株式会社 | Porous membrane and water purifier |
| JPWO2014156644A1 (en) * | 2013-03-28 | 2017-02-16 | 東レ株式会社 | Porous membrane and water purifier |
| JP2019048297A (en) * | 2013-03-28 | 2019-03-28 | 東レ株式会社 | Porous membrane |
| CN104208766A (en) * | 2014-08-26 | 2014-12-17 | 东华大学 | High-stain-resistance polyether sulfone blood purifier and manufacturing method thereof |
| JP2016083647A (en) * | 2014-10-29 | 2016-05-19 | 株式会社クラレ | Hollow fiber membrane module |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2899347B2 (en) | 1999-06-02 |
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