JPS6333871B2 - - Google Patents
Info
- Publication number
- JPS6333871B2 JPS6333871B2 JP54004311A JP431179A JPS6333871B2 JP S6333871 B2 JPS6333871 B2 JP S6333871B2 JP 54004311 A JP54004311 A JP 54004311A JP 431179 A JP431179 A JP 431179A JP S6333871 B2 JPS6333871 B2 JP S6333871B2
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- dialysis membrane
- block copolymer
- hollow
- weight
- 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
- 239000012510 hollow fiber Substances 0.000 claims description 72
- 239000012528 membrane Substances 0.000 claims description 54
- 238000000502 dialysis Methods 0.000 claims description 44
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 21
- 239000004417 polycarbonate Substances 0.000 claims description 21
- 229920000515 polycarbonate Polymers 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 21
- 229920001400 block copolymer Polymers 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 230000001112 coagulating effect Effects 0.000 claims description 13
- 230000035699 permeability Effects 0.000 claims description 12
- 230000015271 coagulation Effects 0.000 claims description 11
- 238000005345 coagulation Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 5
- 238000001631 haemodialysis Methods 0.000 claims description 5
- 230000000322 hemodialysis Effects 0.000 claims description 5
- FDJOLVPMNUYSCM-UVKKECPRSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2,7, Chemical compound [Co+3].N#[C-].C1([C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)[N-]\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O FDJOLVPMNUYSCM-UVKKECPRSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 102000008100 Human Serum Albumin Human genes 0.000 claims description 2
- 108091006905 Human Serum Albumin Proteins 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- 229920001281 polyalkylene Polymers 0.000 claims 2
- 239000011796 hollow space material Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 10
- 238000009987 spinning Methods 0.000 description 10
- 239000011550 stock solution Substances 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920001202 Inulin Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 3
- 229940029339 inulin Drugs 0.000 description 3
- 239000002964 rayon Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 102000009027 Albumins Human genes 0.000 description 2
- 108010088751 Albumins Proteins 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940109239 creatinine Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 phosgene Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940045136 urea Drugs 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 238000004804 winding 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/081—Hollow fibre membranes characterised by the fibre diameter
-
- 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
- B01D71/52—Polyethers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
-
- 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
- B01D71/50—Polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- External Artificial Organs (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Description
本発明は、ポリエーテルポリカーボネートブロ
ツク共重合体からなる選択透過性を有する中空繊
維透析膜及びその製造方法に関するものである。
従来、血液透析膜としては、キユプラアンモニ
ウムレーヨンからつくられた平膜及び中空繊維が
最も広く用いられているが、透析膜としては分子
量の比較的大きな物質の透析性能、湿潤状態での
強度などの点で、まだまだ十分に満足のゆく透析
膜とはなりえていなかつた。
ポリエーテルポリカーボネートブロツク共重合
体による平膜は、Trans.Amer.Soc.Artif.Int.
Organs、21巻144頁（1975）、特公昭52−28826、
特開昭52−116692、特開昭52−120597により既知
であり、これらの既知文献には、ポリエーテルポ
リカーボネートブロツク共重合体溶液を平板基体
上に展延して形成した血液透折用の平膜は、中分
子量物質を優先的に除去できる透析膜であること
が紹介されている。
一方平膜は、ロール状に巻いて保存されるため
膜間にブロツキングが生じて人工腎臓の組立のと
きの取扱いに支障を来たすばかりでなく、Kiil型
透析器で使用する場合には透析効率が劣りまた残
血量が大きいため患者の負担を大きくするという
欠点がある。以上の諸点が、ポリエーテルポリカ
ーボネート中空繊維透析膜の開発が望まれている
理由である。
ところで、中空繊維膜においては、透析効率、
プライミング量、血液凝固の防止等を考慮して中
空繊維の内側に血液を流すことが通常行なわれて
いる。
しかるに、ポリエーテルポリカーボネートブロ
ツク重合体の中空繊維透析膜の製造では、血液と
接触する中空繊維の内側に溶媒を蒸発させると云
う方法によつて緻密な層を形成させるのは極めて
困難であり、前記既知平膜の製法を応用して１〜
５分程度空中に押出した中空糸から溶媒蒸発させ
るだけでは中空糸に平膜と同じようなすぐれた透
析性能を与えることはできない。
本発明者らは、ポリエーテルポリカーボネート
ブロツク共重合体の水可溶性溶媒の溶液を中空紡
糸するにあたり、紡出中空繊維の内側を加圧下の
凝固液で凝固させると中空繊維の内表面の溶媒を
乾燥させる工程を経ないでも内表面に薄くて緻密
な層を形成させることができること、及び加圧下
の凝固液の圧力で中空繊維の横断面方向（周方
向）に延伸乃至ドラフトを与えることにより中空
繊維内表面及び外表面の緻密度をコントロールで
きることを見出し、内外両表面に薄い緻密層を有
する比較的分子量の大きな物質の透析性能にすぐ
れ、しかも適度の限外過性能をもつ血液透析に
用いることのできる中空繊維透析膜の発明をなす
に至つた。
本発明は、ポリエーテルポリカーボネートブロ
ツク共重合体からなり、内表面及び外表面に緻密
な層を有する中空繊維透析膜、並びにポリエーテ
ルポリカーボネートブロツク共重合体を溶媒に溶
解した溶液を環状オリフイスから押し出して中空
繊維透析膜を製造するに際し、中空繊維の内部に
凝固液を圧入して、中空繊維を周方向に延伸しな
がら空気中に押し出し、次いで凝固液中で凝固さ
せる中空繊維透析膜の製造方法である。
本発明のポリエーテルポリカーボネートブロツ
ク共重合体中空繊維透析膜は、ポリエーテルポリ
カーボネートブロツク共重合体を溶媒に溶解した
溶液を環状オリフイスから押し出して中空繊維透
析膜を製造するに際し、中空繊維の内部に凝固液
を圧入して、中空繊維を周方向に延伸しながら空
気中に押し出し、次いで凝固液中で凝固させるこ
とによつて製造することができる。
本発明の中空繊維透析膜は、37℃での食塩の拡
散透過係数が700×10-4cm／min以上、ビタミン
B12の拡散透過係数が80×10-4cm／min以上、透
水率が10ml／m2・hr・mmHg以下で、実質的にヒ
ト−アルブミンを通過させないものであり、この
ような性能を内径が100〜500μ、膜厚が10〜40μ
の均一な厚みを有する中空繊維において得ること
ができる。
本発明のポリエーテルポリカーボネートブロツ
ク共重合体中空繊維は、中空繊維の内表面及び外
表面に薄い緻密な層を有し、両表面にはさまれた
中間の層は比較的粗な構造を有しており、それ故
に中分子量物質の透析性能が大きく、しかも適度
な限外過性能を持つものである。
本発明で用いられるポリエーテルポリカーボネ
ートブロツク共重合体は、ポリアルキレングリコ
ール単位とビスフエノールＡ単位とをジオール成
分とし、これにホスゲン等の炭酸誘導体を反応さ
せて得られるものが好適であり、すでに公知のも
のであるが〔Journal of Polymer Science：
Part Ｃ、No.4P707−730（1963）〕ポリアルキレン
グリコール単位を約５〜45％、好ましくは10〜35
重量％を含む共重合体が特に好ましい。５重量％
未満では親水性に劣り、また45重量％を超えると
ゴム弾性がでてくる。
ポリカーボネートブロツク共重合体の溶液を調
製する際の溶媒としては、ポリマーに対する溶解
性が大きく、しかも凝固液、例えば水とよく混合
する有機溶媒、例えば１，４−ジオキサン、１，
３−ジオキサン、１，３−ジオキソラン、テトラ
ヒドロフラン、ブチロラクトンなどが用いられる
が、１，３−ジオキソランが最も好適である。ま
た、外表面の緻密層の形成に支障をきたさない範
囲で膨潤剤、例えば、ジメチルスルホキサイド、
ジメチルアセトアミド、ジメチルホルムアミド等
を加えることにより、得られる膜の性能を調整す
ることが可能である。
次に本発明の中空繊維膜の製造方法について説
明する。
まずポリエーテルポリカーボネートブロツク共
重合体を溶媒中に溶解し紡糸原液を調整する。
ポリマー濃度はポリマーの分子量、目的とする
中空繊維膜の性能等によつて決められるが、通常
５〜35重量％であり、溶液粘度は25℃で2000〜
100000CPが適当である。
この様にして得られた紡糸原液を通常の中空繊
維紡糸用の口金即ち中央部に内部凝固液注入用の
中空管を有する環状オリフイスから空気中に押し
出し、中空繊維を形成させる。中空繊維を形成さ
せるに際し、中空繊維の内部に前述の口金の中央
より水等の凝固液を圧入し、中空繊維の内径を拡
げ、周方向に延伸する。次いで中空繊維を水浴中
に導入し、凝固を完全なものにし、水洗浴中で中
空繊維を巻き取ると共に膜中に残つている溶媒を
洗い流す。
凝固液の例としては、水、エチレングリコー
ル、プロピレングリコールなどがあげられるが、
取扱いやすさ、安全性、経済性などの点から、水
が最も好ましい。凝固液には無機塩類、膨潤剤等
の添加剤を加えることができる。
内部に凝固液を圧入しない場合には、中空繊維
の軸方向にかかわる力により中空繊維の内径は口
金の形状により規定される内径よりも細くなるが
凝固液を圧入した場合には、中空繊維の内径は口
金より規定される内径と同等がそれよりも大きく
なる。
得られる中空繊維透析膜の性能は延伸の度合に
より制御することが可能であり、延伸倍率を大き
くすることにより中空繊維透析膜の透析性能は大
きくなる。延伸倍率は、中空繊維内部への凝固液
の圧入圧、原液の吐出量、巻取速度等によりコン
トロールすることができる。紡糸口金から空気中
に押出された中空繊維が凝固浴中に浸漬するまで
の時間を調節することにより、中空繊維透析膜の
外表面に緻密層を形成させ、膜性能、特に透水性
能をコントロールすることができる。
重合体の溶媒との二成分の溶液を使用する場合
には中空繊維の外表面側の緻密層が極めて短時間
に形成されるので、添加剤を溶液に添加し膜の透
析性能をコントロールすることができる。
本発明の中空繊維では外表面の緻密層は極めて
短い時間空気中を通過させるだけで容易に形成さ
れ、通常空気中の通過に要する時間は10秒以下で
ある。
この外表面の緻密層は透水性能のコントロール
に有効であるだけでなく、中空繊維の取り扱いや
すさを改善するのにも有効である。則ち、外表面
に緻密層のない中空繊維ではお互にくつついてブ
ロツキングがおこりやすくなり、取扱いにくいの
に対し外表面に緻密層があると、ブロツキングが
おこりにくくなる。
得られた中空繊維膜はそのまま湿潤状態で保存
する事が可能であるが、グリセリン水溶液に浸漬
させた後乾燥し、乾燥状態で保存する事も可能で
ある。また、従来他の透析膜で公知の方法である
熱処理、繊維軸方向への延伸処理により、膜性能
をコントロールする方法を、本発明により得られ
る中空繊維透析膜に有効に応用することも可能で
ある。
中空糸の透析性能は37℃のとき食塩の透過係数
が700×10-4cm／min以上、ビタミンB12の拡散係
数が80×10-4／min以上、イヌリンの拡散透過係
数が17×10-4〜25×10-4cm／minと特に中分子量
物質の透析性能にすぐれている。しかも、ヒト−
アルブミンの透過率は０であり、充分に欠陥のな
い透析膜となつている。
更に透水量は10ml／m2、hr、mmHg（37℃）以下
好ましくは２〜７ml／m2、hr、mmHg（37℃）と上
記のような高い透析性能を持つた透析膜としては
充分に低くなつており透析性能と透水性能とのバ
ランスのとれた透析膜であり、血液透析ばかりで
なく、一般透析用中空糸膜として用いることもで
きる。
本発明の中空繊維透析膜の破裂強度は５〜10
Kg／cm2であり、平膜の破裂強度0.4Kg／cm2に比較
して12〜25倍と大幅に向上する。
以下実施例によつて詳細に説明する。
実施例 １
ポリエチレングリコール単位25重量％、ビスフ
エノール−Ａ単位75重量％から成るポリエーテ
ル・ポリカーボネートブロツク共重合体（25℃ク
ロロホルムでの〔η〕＝2.3）65ｇを１，３−ジオ
キソラン435ｇに溶解し、紡糸原液とする。
この紡糸原液を、原液送入口から中空繊維紡糸
用環状オリフイスを有する口金に送入し、内部凝
固液注入用の中空管から、蒸留水を約0.1Kg／cm2
の圧力で圧入しながら紡糸原液を環状オリフイス
から7.5ｍ／分の速度で押し出して中空繊維膜と
する。環状オリフイスの内径と外径はそれぞれ
0.2mm、0.4mmであり、中心部に挿入開口した内径
0.1mmのニードル状の凝固液注入管により内径が
形成されている。
環状オリフイスから押し出された中空繊維膜は
25℃の空気中を約1sec、走行させた後に25℃の水
浴中に浸漬され外側からも凝固と接触させられ
る。凝固させられた中空繊維膜は水洗浴を通り、
次いで巻き取り機では7.5ｍ／分の速度で捲取ら
れる。得られた中空繊維膜は内部凝固水を抜いた
後、蒸留水でよく洗浄され湿潤状態に維持され
る。
この様にして得られた中空繊維透析膜の形状、
尿素、クレアチニン、尿酸、ビタミンB12、イヌ
リン、アルブミンの透析性能及び、限外濾過性能
を、キユプロアンモニウムレーヨン中空繊維と比
較して、表１に示す。
表１に示した結果から、ポリエーテルポリカー
ボネート共重合体からつくられた中空繊維膜が、
キユプロアンモニウムレーヨン中空繊維膜と比較
して、ビタミンB12、イヌリン等の中分子量物質
の透過率が大きく、しかも、限外濾過率は、臨床
上許容されうる程度であることが明らかである。
また、透過型電子顕微鏡で中空繊維断面の構造
を観察したところ、中空繊維の内部及び外部の両
表面ともに緻密な層となつていることが確認され
た。
The present invention relates to a hollow fiber dialysis membrane having permselectivity made of a polyether polycarbonate block copolymer and a method for producing the same. Conventionally, flat membranes and hollow fibers made from cuprammonium rayon have been most widely used as hemodialysis membranes, but dialysis membranes have limited performance in dialysis of substances with relatively large molecular weights, strength in wet conditions, etc. In this respect, the dialysis membrane was still not fully satisfactory. Flat membranes made of polyether polycarbonate block copolymers are manufactured by Trans.Amer.Soc.Artif.Int.
Organs, Vol. 21, p. 144 (1975), Special Publication No. 52-28826,
It is known from JP-A-52-116692 and JP-A-52-120597, and these known documents describe a flat plate for blood dialysis formed by spreading a polyether polycarbonate block copolymer solution on a flat plate substrate. The membrane is introduced as a dialysis membrane that can preferentially remove medium molecular weight substances. On the other hand, since flat membranes are stored in rolls, blocking occurs between the membranes, which not only hinders handling when assembling an artificial kidney, but also reduces dialysis efficiency when used in a Kiil-type dialyzer. It also has the disadvantage of increasing the burden on the patient due to the large amount of residual blood. The above points are the reasons why the development of polyether polycarbonate hollow fiber dialysis membranes is desired. By the way, in hollow fiber membranes, dialysis efficiency,
In consideration of the amount of priming, prevention of blood coagulation, etc., blood is normally allowed to flow inside the hollow fiber. However, in the production of hollow fiber dialysis membranes made of polyether polycarbonate block polymers, it is extremely difficult to form a dense layer on the inside of the hollow fibers that come into contact with blood by evaporating the solvent. Applying the known flat membrane manufacturing method 1~
Simply evaporating the solvent from a hollow fiber extruded into the air for about 5 minutes does not give the hollow fiber the same excellent dialysis performance as a flat membrane. The present inventors discovered that when hollow spinning a solution of a water-soluble solvent of a polyether polycarbonate block copolymer, by coagulating the inside of the spun hollow fibers with a coagulating liquid under pressure, the solvent on the inner surface of the hollow fibers was dried. Hollow fibers can be formed by forming a thin, dense layer on the inner surface without going through the process of drying, and by applying stretching or drafting in the cross-sectional direction (circumferential direction) of the hollow fibers using the pressure of the coagulating liquid under pressure. It was discovered that the density of the inner and outer surfaces can be controlled, and the material has a thin dense layer on both the inner and outer surfaces and has excellent dialysis performance for substances with relatively large molecular weights, as well as a suitable ultrafiltration performance for use in hemodialysis. This led to the invention of a hollow fiber dialysis membrane. The present invention consists of a hollow fiber dialysis membrane made of a polyether polycarbonate block copolymer and having dense layers on the inner and outer surfaces, and a solution of the polyether polycarbonate block copolymer dissolved in a solvent is extruded through an annular orifice. When manufacturing a hollow fiber dialysis membrane, a method for manufacturing a hollow fiber dialysis membrane involves pressurizing a coagulation liquid into the hollow fibers, extruding the hollow fibers into the air while stretching them in the circumferential direction, and then coagulating them in the coagulation liquid. be. The polyether polycarbonate block copolymer hollow fiber dialysis membrane of the present invention coagulates inside the hollow fibers when the hollow fiber dialysis membrane is manufactured by extruding a solution of the polyether polycarbonate block copolymer dissolved in a solvent through an annular orifice. It can be produced by pressurizing a liquid, extruding the hollow fibers into the air while stretching them in the circumferential direction, and then coagulating them in a coagulating liquid. The hollow fiber dialysis membrane of the present invention has a salt diffusion permeability coefficient of 700×10 -4 cm/min or more at 37°C, and a vitamin
B 12 has a diffusion permeability coefficient of 80 x 10 -4 cm/min or more and a water permeability of 10 ml/m 2 · hr · mmHg or less, and does not substantially allow human albumin to pass through. is 100~500μ, film thickness is 10~40μ
can be obtained in hollow fibers with a uniform thickness of . The polyether polycarbonate block copolymer hollow fiber of the present invention has a thin dense layer on the inner and outer surfaces of the hollow fiber, and the intermediate layer sandwiched between both surfaces has a relatively coarse structure. Therefore, it has a high dialysis performance for medium molecular weight substances and also has a moderate ultrafiltration performance. The polyether polycarbonate block copolymer used in the present invention is preferably one obtained by reacting a polyalkylene glycol unit and a bisphenol A unit as a diol component with a carbonic acid derivative such as phosgene, and is already known in the art. [Journal of Polymer Science:
Part C, No. 4P707-730 (1963)] About 5 to 45% polyalkylene glycol units, preferably 10 to 35%
Particularly preferred are copolymers containing % by weight. 5% by weight
If it is less than 45% by weight, the hydrophilicity will be poor, and if it exceeds 45% by weight, rubber elasticity will appear. As a solvent for preparing a solution of a polycarbonate block copolymer, an organic solvent that has high solubility for the polymer and that mixes well with a coagulating liquid, such as water, such as 1,4-dioxane, 1,
3-dioxane, 1,3-dioxolane, tetrahydrofuran, butyrolactone, etc. are used, but 1,3-dioxolane is most preferred. In addition, a swelling agent such as dimethyl sulfoxide,
By adding dimethylacetamide, dimethylformamide, etc., it is possible to adjust the performance of the resulting membrane. Next, a method for manufacturing the hollow fiber membrane of the present invention will be explained. First, a polyether polycarbonate block copolymer is dissolved in a solvent to prepare a spinning stock solution. The polymer concentration is determined depending on the molecular weight of the polymer, the performance of the hollow fiber membrane, etc., but is usually 5 to 35% by weight, and the solution viscosity is 2000 to 2000 at 25℃.
100000CP is appropriate. The spinning dope thus obtained is extruded into the air through a conventional hollow fiber spinning die, ie, an annular orifice having a hollow tube in the center for injecting an internal coagulating liquid, to form hollow fibers. When forming the hollow fibers, a coagulating liquid such as water is forced into the hollow fibers from the center of the above-mentioned die to expand the inner diameter of the hollow fibers and stretch them in the circumferential direction. The hollow fibers are then introduced into a water bath to complete coagulation, and the hollow fibers are wound up in a water wash bath and the solvent remaining in the membrane is washed away. Examples of coagulating liquids include water, ethylene glycol, propylene glycol, etc.
Water is most preferable from the viewpoint of ease of handling, safety, economic efficiency, etc. Additives such as inorganic salts and swelling agents can be added to the coagulation liquid. When the coagulation liquid is not press-fitted inside, the inner diameter of the hollow fiber becomes smaller than the inner diameter defined by the shape of the mouthpiece due to the force related to the axial direction of the hollow fiber. The inner diameter is equal to or larger than the inner diameter defined by the cap. The performance of the hollow fiber dialysis membrane obtained can be controlled by the degree of stretching, and the dialysis performance of the hollow fiber dialysis membrane increases by increasing the stretching ratio. The stretching ratio can be controlled by the injection pressure of the coagulating liquid into the hollow fiber, the discharge amount of the stock solution, the winding speed, etc. By adjusting the time until the hollow fibers extruded into the air from the spinneret are immersed in the coagulation bath, a dense layer is formed on the outer surface of the hollow fiber dialysis membrane, and membrane performance, especially water permeability, is controlled. be able to. When using a two-component solution of a polymer and a solvent, a dense layer on the outer surface of the hollow fibers is formed in a very short time, so it is necessary to add additives to the solution to control the dialysis performance of the membrane. Can be done. In the hollow fibers of the present invention, a dense layer on the outer surface can be easily formed by passing through air for an extremely short period of time, and usually the time required for passing through air is 10 seconds or less. This dense layer on the outer surface is effective not only for controlling water permeability but also for improving the ease of handling the hollow fibers. In other words, hollow fibers without a dense layer on the outer surface are likely to stick together and cause blocking, making them difficult to handle, whereas with a dense layer on the outer surface, blocking is less likely to occur. The obtained hollow fiber membrane can be stored as it is in a wet state, but it can also be stored in a dry state by immersing it in an aqueous glycerin solution and then drying it. Furthermore, methods of controlling membrane performance by heat treatment and stretching in the fiber axis direction, which are conventionally known methods for other dialysis membranes, can be effectively applied to the hollow fiber dialysis membrane obtained by the present invention. be. The dialysis performance of hollow fibers is as follows: At 37°C, the permeation coefficient of common salt is 700×10 -4 cm/min or more, the diffusion coefficient of vitamin B12 is 80×10 -4 /min or more, and the diffusion coefficient of inulin is 17×10 -4 to 25×10 -4 cm/min, which has excellent dialysis performance especially for medium molecular weight substances. Moreover, human-
The albumin permeability was 0, indicating that the dialysis membrane was sufficiently defect-free. Furthermore, the water permeability is 10 ml/m 2 , hr, mmHg (37°C) or less, preferably 2 to 7 ml/m 2 , hr, mmHg (37°C), which is sufficient for a dialysis membrane with the above-mentioned high dialysis performance. This dialysis membrane has a good balance between dialysis performance and water permeability, and can be used not only for hemodialysis but also as a hollow fiber membrane for general dialysis. The bursting strength of the hollow fiber dialysis membrane of the present invention is 5 to 10
Kg/cm 2 , which is significantly improved by 12 to 25 times compared to the flat membrane's burst strength of 0.4 Kg/cm 2 . This will be explained in detail below using examples. Example 1 65 g of a polyether/polycarbonate block copolymer ([η] = 2.3 in chloroform at 25°C) consisting of 25% by weight of polyethylene glycol units and 75% by weight of bisphenol-A units was dissolved in 435 g of 1,3-dioxolane. and use it as a spinning stock solution. This spinning stock solution is sent from the stock solution inlet to a spinneret having an annular orifice for hollow fiber spinning, and about 0.1Kg/cm 2 of distilled water is introduced from the hollow tube for injecting the internal coagulation solution.
The spinning stock solution is extruded from the annular orifice at a speed of 7.5 m/min while being press-fitted at a pressure of 100 to form a hollow fiber membrane. The inner and outer diameters of the annular orifice are
The inner diameter is 0.2mm and 0.4mm, with an insertion opening in the center.
The inner diameter is formed by a 0.1 mm needle-shaped coagulation fluid injection tube. The hollow fiber membrane extruded from the annular orifice is
After running in air at 25°C for about 1 second, it is immersed in a 25°C water bath and brought into contact with the coagulation from the outside. The coagulated hollow fiber membrane passes through a water washing bath,
It is then wound up in a winder at a speed of 7.5 m/min. After removing the internal coagulated water from the obtained hollow fiber membrane, it is thoroughly washed with distilled water and kept in a moist state. The shape of the hollow fiber dialysis membrane obtained in this way,
The dialysis performance and ultrafiltration performance for urea, creatinine, uric acid, vitamin B 12 , inulin, and albumin are shown in Table 1 in comparison with the cuproammonium rayon hollow fiber. From the results shown in Table 1, it is clear that the hollow fiber membrane made from polyether polycarbonate copolymer
It is clear that the permeability of medium molecular weight substances such as vitamin B 12 and inulin is higher than that of the cuproammonium rayon hollow fiber membrane, and the ultrafiltration rate is at a clinically acceptable level. Furthermore, when the structure of the cross section of the hollow fiber was observed using a transmission electron microscope, it was confirmed that both the internal and external surfaces of the hollow fiber had a dense layer.
【表】【table】
【表】
実施例 ２〜４
実施例１で用いたポリエーテルポリカーボネー
トブロツク共重合体65ｇを、１，３−ジオキソラ
ン422ｇとジメチルスルホキシド13ｇとの混合溶
媒中に溶解し、紡糸原液とする。実施例１と同様
にして、内部凝固液の注入圧のみを変化させて中
空繊維を製造し、その性能を測定した結果を表２
に示す。[Table] Examples 2 to 4 65 g of the polyether polycarbonate block copolymer used in Example 1 was dissolved in a mixed solvent of 422 g of 1,3-dioxolane and 13 g of dimethyl sulfoxide to prepare a spinning stock solution. Hollow fibers were manufactured in the same manner as in Example 1 by changing only the injection pressure of the internal coagulation liquid, and the performance was measured.Table 2 shows the results of measuring the performance.
Shown below.
【表】
実施例 ５〜９
実施例１で用いたポリエーテルポリカーボネー
トブロツク共重合体65ｇを、１，３−ジオキソラ
ン422ｇとジメチルスルホキシド13ｇの混合溶媒
中に溶解し、紡糸原液とする。実施例１と同様に
して、空気中を通過させる時間のみを変化させて
中空繊維を製造し、その性能を測定した結果を表
３に示す。[Table] Examples 5 to 9 65 g of the polyether polycarbonate block copolymer used in Example 1 was dissolved in a mixed solvent of 422 g of 1,3-dioxolane and 13 g of dimethyl sulfoxide to prepare a spinning stock solution. Hollow fibers were produced in the same manner as in Example 1 by varying only the time for passing through the air, and the performance was measured. Table 3 shows the results.
Claims (1)
合体からなり、内径が100〜500μ、膜厚が10〜
40μの均一な厚みを有し、内表面及び外表面に実
質的にヒト−アルブミンを通過させない緻密な層
及び両表面にはさまれた中間層に比較的粗な構造
を有する血液透析用の中空繊維透析膜。 ２ ポリエーテルポリカーボネートブロツク共重
合体が約10〜35重量％のポリアルキレンエーテル
カーボネート成分と約90〜65重量％のビスフエノ
ールＡカーボネート成分とからなる特許請求の範
囲第１項記載の中空繊維透析膜。 ３ 37℃での食塩の拡散透過係数が700×10-4
cm／min以上、ビタミンB12の拡散透過係数が80
×10-4cm／min以上、透水率が７ml／m2・hr・mm
Hg以下の特許請求の範囲第１項記載の中空繊維
透析膜。 ４ ポリエーテルポリカーボネートブロツク共重
合体を溶媒に溶解した溶液を環状オリフイスから
押し出して中空繊維透析膜を製造するに際し、中
空繊維の内部に凝固液を圧入して、中空繊維を周
方向に延伸しながら空気中に押し出し、次いで凝
固液中で凝固させることを特徴とする血液透析用
の中空繊維透析膜の製造方法。 ５ ポリエーテルカーボネートブロツク共重合体
が約10〜35重量％のポリアルキレンエーテルカー
ボネート成分と約90〜65重量％のビスフエノール
Ａカーボネート成分とからなる特許請求の範囲第
４項記載の中空繊維透析膜の製造方法。[Scope of Claims] 1. Made of polyether polycarbonate block copolymer, with an inner diameter of 100 to 500 μm and a film thickness of 10 to 500 μm.
A hollow space for hemodialysis having a uniform thickness of 40μ and having a dense layer on the inner and outer surfaces that substantially does not allow human albumin to pass through, and a relatively rough structure in the middle layer sandwiched between both surfaces. Fiber dialysis membrane. 2. The hollow fiber dialysis membrane according to claim 1, wherein the polyether polycarbonate block copolymer comprises about 10 to 35% by weight of a polyalkylene ether carbonate component and about 90 to 65% by weight of a bisphenol A carbonate component. . 3 The diffusion permeability coefficient of salt at 37℃ is 700×10 -4
cm/min or more, the diffusive permeability coefficient of vitamin B 12 is 80
×10 -4 cm/min or more, water permeability 7ml/m 2・hr・mm
The hollow fiber dialysis membrane according to claim 1, in which Hg or less. 4. When manufacturing a hollow fiber dialysis membrane by extruding a solution of a polyether polycarbonate block copolymer dissolved in a solvent through an annular orifice, a coagulating liquid is forced into the inside of the hollow fiber, and the hollow fiber is stretched in the circumferential direction. A method for producing a hollow fiber dialysis membrane for hemodialysis, which comprises extruding it into air and then coagulating it in a coagulation solution. 5. The hollow fiber dialysis membrane according to claim 4, wherein the polyether carbonate block copolymer comprises about 10 to 35% by weight of a polyalkylene ether carbonate component and about 90 to 65% by weight of a bisphenol A carbonate component. manufacturing method.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP431179A JPS5596162A (en) | 1979-01-18 | 1979-01-18 | Polycarbonate hollow fiber dialysis film and its preparation |
| GB7918189A GB2047161B (en) | 1979-01-18 | 1979-05-24 | Hollow fibre form polycarbonate membrane for use in dialysis and process for producing same |
| DE2921138A DE2921138C2 (en) | 1979-01-18 | 1979-05-25 | Hollow fiber-shaped dialysis membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP431179A JPS5596162A (en) | 1979-01-18 | 1979-01-18 | Polycarbonate hollow fiber dialysis film and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5596162A JPS5596162A (en) | 1980-07-22 |
| JPS6333871B2 true JPS6333871B2 (en) | 1988-07-07 |
Family
ID=11580932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP431179A Granted JPS5596162A (en) | 1979-01-18 | 1979-01-18 | Polycarbonate hollow fiber dialysis film and its preparation |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5596162A (en) |
| DE (1) | DE2921138C2 (en) |
| GB (1) | GB2047161B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE423106B (en) * | 1980-07-25 | 1982-04-13 | Gambro Dialysatoren | PLASMAFERES MEMBRANE AND WAY TO MANUFACTURE THIS |
| DE3069709D1 (en) * | 1980-09-01 | 1985-01-10 | Gambro Inc | Dry polycarbonate membrane and process of manufacture |
| EP0046816A1 (en) * | 1980-09-01 | 1982-03-10 | Gambro, Inc. | Polycarbonate hemofiltration membrane and method of hemofiltering using such a membrane |
| SE429441B (en) * | 1982-04-30 | 1983-09-05 | Gambro Dialysatoren | MICROPOROST HALFIBERMENBRAN FOR PLASMAFERES, AS WELL AS MANUFACTURING THE MEMBRANE |
| SE8204103L (en) * | 1982-07-02 | 1984-01-03 | Gambro Lundia Ab | FILTRATION MEMBRANE AND SET TO MAKE THE MEMBRANE |
| SE446505B (en) * | 1982-11-16 | 1986-09-22 | Gambro Dialysatoren | MEMBRANE AND WAY TO MAKE THIS |
| EP0135760A1 (en) * | 1983-08-19 | 1985-04-03 | Bayer Ag | Polyether-polycarbonates for dialysis-membranes |
| SE443584B (en) * | 1985-03-07 | 1986-03-03 | Gambro Dialysatoren | SET TO MAKE A SEMIPERMEABLE HALFIBER |
| KR20110126607A (en) | 2009-02-04 | 2011-11-23 | 도요 보세키 가부시키가이샤 | Hollow-fiber membrane, process for producing same, and blood purification module |
| CN104906972A (en) * | 2015-05-20 | 2015-09-16 | 苏州市贝克生物科技有限公司 | Nano-grade titanium dioxide/polyether hemodialysis membrane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52116692A (en) * | 1976-03-19 | 1977-09-30 | Bard Inc C R | Blood dialyzing polycarbonate membrane |
| JPS52120597A (en) * | 1976-03-31 | 1977-10-11 | Bard Inc C R | Blood dialyzing polycarbonate thin film |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD14882A (en) * | 1957-05-06 | 1900-01-01 | ||
| US3423491A (en) * | 1964-09-02 | 1969-01-21 | Dow Chemical Co | Permselective hollow fibers and method of making |
| JPS5193786A (en) * | 1975-02-15 | 1976-08-17 | Makurokagatano chukuseni | |
| US4061821A (en) * | 1975-12-29 | 1977-12-06 | Asahi Kasei Kogyo Kabushiki Kaisha | Semipermeable composite membranes |
| JPS6029282B2 (en) * | 1976-09-03 | 1985-07-10 | 旭化成株式会社 | Semipermeable membrane and its manufacturing method |
-
1979
- 1979-01-18 JP JP431179A patent/JPS5596162A/en active Granted
- 1979-05-24 GB GB7918189A patent/GB2047161B/en not_active Expired
- 1979-05-25 DE DE2921138A patent/DE2921138C2/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52116692A (en) * | 1976-03-19 | 1977-09-30 | Bard Inc C R | Blood dialyzing polycarbonate membrane |
| JPS52120597A (en) * | 1976-03-31 | 1977-10-11 | Bard Inc C R | Blood dialyzing polycarbonate thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2921138C2 (en) | 1983-10-20 |
| GB2047161B (en) | 1983-01-12 |
| JPS5596162A (en) | 1980-07-22 |
| GB2047161A (en) | 1980-11-26 |
| DE2921138A1 (en) | 1980-07-24 |
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