JPS63224702A - Polypropylene porous membrane and its production - Google Patents
Polypropylene porous membrane and its productionInfo
- Publication number
- JPS63224702A JPS63224702A JP5672887A JP5672887A JPS63224702A JP S63224702 A JPS63224702 A JP S63224702A JP 5672887 A JP5672887 A JP 5672887A JP 5672887 A JP5672887 A JP 5672887A JP S63224702 A JPS63224702 A JP S63224702A
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene
- membrane
- porous membrane
- porous
- producing
- 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 148
- -1 Polypropylene Polymers 0.000 title claims abstract description 122
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 118
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 118
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 238000001816 cooling Methods 0.000 claims abstract description 40
- 239000011148 porous material Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000035699 permeability Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002344 surface layer Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 52
- 239000012766 organic filler Substances 0.000 claims description 33
- 238000007711 solidification Methods 0.000 claims description 30
- 230000008023 solidification Effects 0.000 claims description 30
- 239000003484 crystal nucleating agent Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 150000008282 halocarbons Chemical class 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 37
- 239000000945 filler Substances 0.000 abstract description 9
- 239000012188 paraffin wax Substances 0.000 abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 5
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 239000000306 component Substances 0.000 description 18
- 210000000601 blood cell Anatomy 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 229940057995 liquid paraffin Drugs 0.000 description 12
- 210000004369 blood Anatomy 0.000 description 11
- 239000008280 blood Substances 0.000 description 11
- 238000000605 extraction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 206010018910 Haemolysis Diseases 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000008588 hemolysis Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 241000283690 Bos taurus Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 102000001554 Hemoglobins Human genes 0.000 description 2
- 108010054147 Hemoglobins Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000000110 cooling liquid Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 210000003743 erythrocyte Anatomy 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- AHFMSNDOYCFEPH-UHFFFAOYSA-N 1,2-difluoroethane Chemical compound FCCF AHFMSNDOYCFEPH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 102000004506 Blood Proteins Human genes 0.000 description 1
- 108010017384 Blood Proteins Proteins 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
- 206010018364 Glomerulonephritis Diseases 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241001125929 Trisopterus luscus Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012503 blood component Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 210000004013 groin Anatomy 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000005534 hematocrit Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000009390 immune abnormality Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 206010028417 myasthenia gravis Diseases 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 206010039073 rheumatoid arthritis Diseases 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 201000000596 systemic lupus erythematosus Diseases 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- External Artificial Organs (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、血）１夕を血球成分と血漿成分とに分離する
ための血漿分離、血液中の細菌の除去等に使用される平
膜型のポリプロピレン多孔質膜およびその製造方法に関
Ｊるものである。詳しく述べると本発明は、血漿分離用
として使用した際に血漿分離能力か速く、かつ血球のも
ぐり込みや溶血の虞れの少ない平膜型のポリプロピレン
多孔質膜およびその製造方法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a flat membrane used for plasma separation for separating blood into blood cell components and plasma components, removal of bacteria from blood, etc. The present invention relates to a type of porous polypropylene membrane and a method for manufacturing the same. Specifically, the present invention relates to a flat membrane type porous polypropylene membrane which, when used for plasma separation, has a high plasma separation ability and has little risk of blood cell infiltration or hemolysis, and a method for producing the same.
（従来の技術）
従来、血液を血球成分と血漿成分とに分離するための種
々の透過性膜が使用されている。これらの透過性膜は、
例えば全身性エリテマトーデス、慢性関節リウマチ、糸
球体腎炎、重症筋無力症などの免疫異常による疾患にお
ける異常タンパク、抗原、抗体、免疫複合体などの除去
を目的とする血漿浄化、さらには成分軸面用の血漿製剤
の調製あるいは人工腎臓の前処理等に使用されている。(Prior Art) Conventionally, various permeable membranes have been used to separate blood into blood cell components and plasma components. These permeable membranes are
For example, for plasma purification for the purpose of removing abnormal proteins, antigens, antibodies, immune complexes, etc. in diseases caused by immune abnormalities such as systemic lupus erythematosus, rheumatoid arthritis, glomerulonephritis, and myasthenia gravis, and for component axis. It is used in the preparation of plasma preparations and pretreatment of artificial kidneys.
このような血漿分離用として用いられる透過性膜として
は、セルロースアセテート膜（特開昭５４＝１５．４７
６号）、ポリビニルアルコール膜、ポリエステル膜、ポ
リカーボネート膜、ポリメチルメタクリレート膜、ポリ
エチレン膜（特開昭５７−８４．７０２号）等が使用さ
れてきた。しかしながら、これらの透過性膜は、膜の機
械的強度、空孔率および血漿分離能力が不十分であるの
みならず、血漿分離に使用した場合、目詰まりによる赤
血球の■傷が起こり、また面ｇｌ中の補体成分か活性化
されてしまい９聞１された血’３１か非常に損傷を受（
プるものであった。As a permeable membrane used for such plasma separation, cellulose acetate membrane (Japanese Patent Application Laid-Open No. 1547-15.47)
No. 6), polyvinyl alcohol film, polyester film, polycarbonate film, polymethyl methacrylate film, polyethylene film (Japanese Unexamined Patent Publication No. 57-84.702), etc. have been used. However, these permeable membranes not only have insufficient membrane mechanical strength, porosity, and plasma separation ability, but also cause damage to red blood cells due to clogging when used for plasma separation, and surface damage. The complement component in the GL is activated and the blood '31 that has been removed is extremely damaged (
It was something to do.
また、結晶性ポリオレフィン、ポリアミド等のような溶
媒に対して難溶性で延伸性を有する小合体と、該重合体
に対して部分的に相溶性を有しかつ溶媒に対して易溶性
である化合物との混合物をフィルム、シートまたは中空
体に成形し、該成形体を溶媒で処理し、乾燥後に１軸方
向または２軸方向に５０〜１５０００％延伸してなる透
過性膜が佇案されている（特公昭５７−２０．９７０号
）。しかしながら、このにうな膜は、孔径を大ぎくする
ために延伸されているので、熱収縮が大きく医療用途に
用いた場合、Δ−トクレーブ滅菌ができないものであっ
た。さらに、形成される細孔構造か、延伸により形成さ
れるために、膜厚方向にほぼ平行な直線的なものであり
、かつ両表面および内部の孔構造がほぼ均一なものであ
るため、血漿分Ｈに用いた場合、タンパク質や血球の目
詰まりが起こし易いものとなってしまった。In addition, small polymers such as crystalline polyolefins and polyamides that are poorly soluble in solvents and have stretchability, and compounds that are partially compatible with the polymers and easily soluble in solvents. A permeable membrane is created by molding a mixture of the above into a film, sheet, or hollow body, treating the molded body with a solvent, and stretching it uniaxially or biaxially by 50 to 15,000% after drying. (Special Publication No. 57-20.970). However, since this membrane is stretched to increase the pore size, it has a large thermal shrinkage and cannot be sterilized by Δ-toclave when used for medical purposes. Furthermore, because the pore structure is formed by stretching, it is linear almost parallel to the film thickness direction, and the pore structure on both surfaces and inside is almost uniform, so that plasma When used in minute H, clogging with proteins and blood cells was likely to occur.
さらに血漿分離用の透過性膜に関して補体の活性化等・
シ少なく生体適合性に優れた材質としてポリオレフィン
系高分子か着目され、ポリオレフィン系高分子を用いた
透過性膜の検討が進められている。例えば、パラフィン
１０〜８０１ｆｆｉ％およびポリプロピレン樹脂９０〜
２０重量％の溶融混合物をダイスを通して、フィルム、
シー１〜または中空糸状に押出し、溶融状態のまま５０
℃以下に維持された水中へ導き急冷固化し、次いで得ら
れた成形物からパラフィンを抽出分離する多孔質膜の製
造方法が開示されている（特開昭５５−６０．５３７号
）。しかしながら、この方法によって得られる多孔質膜
は、比熱の大きい水によって急冷されるために表面孔径
・内部孔径共に小さくまた空孔率も低いものとなるため
に、濾過速度が低く速やかな血漿分離には適さないもの
であった。Furthermore, regarding permeable membranes for plasma separation, activation of complement, etc.
Polyolefin-based polymers have attracted attention as materials with low oxidation and excellent biocompatibility, and studies are underway on permeable membranes using polyolefin-based polymers. For example, paraffin 10-801ffi% and polypropylene resin 90-80%
20% by weight of the molten mixture was passed through a die to form a film,
Sheet 1 ~ or extruded into hollow fiber shape, still in molten state 50
A method for producing a porous membrane has been disclosed in which the porous membrane is introduced into water maintained at a temperature below 0.degree. C. and rapidly solidified, and then paraffin is extracted and separated from the resulting molded article (Japanese Patent Application Laid-Open No. 55-60537). However, since the porous membrane obtained by this method is rapidly cooled by water with a high specific heat, both the surface pore size and internal pore size are small and the porosity is low, so the filtration rate is low and it is difficult to quickly separate plasma. was not suitable.
またさらに、前記溶融混合物を冷却固化させる手段とし
て、金属ローラーやパラフィン等の前記有機充填剤との
相溶性の良い冷却固化液を用いる（特願昭６０−２３７
．０６９号）方法が提唱されている。Furthermore, as a means for cooling and solidifying the molten mixture, a cooling solidification liquid having good compatibility with the organic filler such as a metal roller or paraffin is used (Japanese Patent Application No. 60-237
．． No. 069) method has been proposed.
しかしながら、前者の方法で１，１、得られる多孔質膜
の表面孔径か極端に小さくなって血漿の透過速度が遅く
なってしまうものとなっていた。また後者の方法におい
ては、冷却固化液が水と比較して比熱が小さいため、適
切な冷却速度でポリプロピレンの結晶化を促し内部にお
いては血漿分離に用いることが可能な程度に大きな孔径
の細孔を形成するか、その表面部においては、表面のポ
リプロピレンが固化する以前に冷却固化液中に溶は出し
て生じると考えられる非常に大きな網目構造を形成する
ことになる。このような表面層を有する多孔質膜におい
ては、表面層がプレフィルタ−として作用するためタン
パク質、白球の目詰りが少なく、また良好な血漿分離速
度をもって血漿分離を行なえるものであったか、血液と
の接触時に血球のもぐり込みを生じ易く、圧力を加える
と溶血してしまう虞れのあるものであった。However, in the former method, the surface pore diameter of the resulting porous membrane becomes extremely small, resulting in a slow plasma permeation rate. In addition, in the latter method, since the specific heat of the cooled solidified liquid is lower than that of water, the crystallization of polypropylene is promoted at an appropriate cooling rate, and the internal pores are large enough to be used for plasma separation. , or a very large network structure is formed on the surface, which is thought to be caused by the polypropylene on the surface being dissolved into the cooling solidification liquid before solidification. In a porous membrane having such a surface layer, since the surface layer acts as a pre-filter, there is less clogging of proteins and white cells, and plasma separation can be performed with a good plasma separation rate. Blood cells tend to get trapped when they come in contact with the blood cells, and there is a risk of hemolysis when pressure is applied.
（発明が解決しようとする問題点）
従って本発明は、新規なポリプロピレン多孔質膜ａ３よ
びそのＩ！Ａ造方法を提供することを目的とする。本発
明はまた、血液を血球成分と血漿成分とに分離するため
の血漿分離、血液中の細菌の除去等に使用される平膜型
のポリプロピレン多孔質膜およびその製造方法を提供す
ることを目的とする。(Problems to be Solved by the Invention) Therefore, the present invention provides a novel polypropylene porous membrane a3 and its I! The purpose is to provide an A construction method. Another object of the present invention is to provide a flat membrane type polypropylene porous membrane used for plasma separation to separate blood into blood cell components and plasma components, removal of bacteria in blood, etc., and a method for manufacturing the same. shall be.
本発明はさらに、血漿分離用として使用した際に血漿分
離速度か速く、分離された血漿の損傷が少なく、かつま
た血球のもぐり込みや溶面の虞れの少ない平膜型のポリ
プロピレン多孔質膜およびその製造方法を提供すること
を目的とする。The present invention further provides a flat membrane type polypropylene porous membrane that, when used for plasma separation, has a high plasma separation rate, less damage to the separated plasma, and less risk of blood cells penetrating or dissolving the surface. The purpose is to provide a method for producing the same.
（問題点を解決するための手段）
上記開目的は、微細な網目構造を持つ多孔質膜で、該多
孔質膜の一方あるいは両方の表面部には内部と同程度の
網目構造の表面層が形成され、平均孔径が０．１〜５．
０μｍ、バブルポイントが２ 、ＯＫ！Ｊ ｆ ／ ｃ
ｔｉ以下、空孔率が６０〜８５％、透水量か１００ｍ／
ｍｉｎ −ｍｍＨｏ −ｍ以上であり、膜厚が３０〜３
００μｍである実質的にポリプロピレンからなることを
特徴とする平膜型のポリプロピレン多孔質膜により達成
される。(Means for solving the problem) The purpose of the above-mentioned development is to provide a porous membrane with a fine network structure, and one or both surfaces of the porous membrane have a surface layer with the same degree of network structure as the inside. formed with an average pore diameter of 0.1 to 5.
0μm, bubble point 2, OK! J f/c
ti or less, porosity is 60-85%, water permeability is 100m/
min −mmHo −m or more, and the film thickness is 30 to 3
This is achieved by a flat membrane type polypropylene porous membrane characterized by being substantially made of polypropylene and having a diameter of 0.00 μm.
本発明はまた、バブルポイントが１．８Ｎ！９ｆ／ｄ以
下であるポリプロピレン多孔質膜を示すものである。本
発明はさらに透水量が１４０ｍ！！／ｍｉｎ・ｍｍＨｇ
・７１１以」二であるポリプロピレン多孔質膜を示すも
のである。本発明はさらにまた１２０℃で１２０分間の
熱処理による収縮率が６．０％以下であるポリプロピレ
ン多孔質膜を示すものである。The present invention also has a bubble point of 1.8N! This shows a polypropylene porous membrane having a particle diameter of 9 f/d or less. The water permeability of the present invention is furthermore 140m! ! /min・mmHg
・It indicates a polypropylene porous membrane with a rating of 711 or higher. The present invention further provides a polypropylene porous membrane having a shrinkage rate of 6.0% or less when heat treated at 120° C. for 120 minutes.
上記開目的はまた、ポリプロピレン１００重呈部に対し
て、該ポリプロピレン溶融下でポリプロピレンに均一に
分散し得る有機充填剤２００〜６００手量部および結晶
核形成剤０．１〜５．０重量部を加えて溶融混練し、こ
のようにして得られた混合物を溶融状態でダイスより平
膜状に吐出させ、吐出させた溶融膜を前記有機充填剤と
は相溶ぜずかつ比熱容量が０．２〜０．７ｃａｌ ／ｇ
である冷却固化液と接触させて冷却固化し、ついでポリ
プロピレンを溶解せず有機充填剤を溶解する抽出液と接
触させて含有する有機充填剤を抽出除去することを特徴
とする平膜型のポリプロピレン多孔質膜の製造方法によ
り達成される。The above-mentioned objective also includes 200 to 600 parts by weight of an organic filler and 0.1 to 5.0 parts by weight of a crystal nucleating agent, which can be uniformly dispersed in polypropylene while the polypropylene is melted, per 100 parts by weight of polypropylene. The mixture thus obtained is discharged in a molten state from a die in the form of a flat film, and the discharged molten film is incompatible with the organic filler and has a specific heat capacity of 0. 2-0.7cal/g
A flat film type polypropylene characterized in that it is cooled and solidified by being brought into contact with a cooling solidification liquid, and then brought into contact with an extracting liquid that does not dissolve the polypropylene but dissolves the organic filler to extract and remove the organic filler contained therein. This is achieved by a method for producing a porous membrane.
本発明はまた、有機充填剤を抽出除去した後、さらに生
成ポリプロピレン多孔質膜を一定の長さ □に固
定して１１０〜１４０℃の温度で熱処理を行なうもので
あるポリプロピレン多孔質膜の製造方法を示すものであ
る。本発明はさらに溶融膜の冷却固化液との接触は、冷
却固化液中にガイドローラーを設け、このガイトロ・−
ラーの一部を冷却固化液面上に出し、前記混合物をガイ
ドローラー上に吐出させ、ガイドローラーの回転によっ
て冷却固化液中に導くことにより行なわれるものである
ポリプロピレン多孔質膜の製造方法を示すものである。The present invention also provides a method for producing a polypropylene porous membrane, which comprises extracting and removing the organic filler, and then fixing the produced polypropylene porous membrane to a certain length □ and performing heat treatment at a temperature of 110 to 140°C. This shows that. The present invention further provides that the contact between the molten film and the cooled solidified liquid is controlled by providing a guide roller in the cooled solidified liquid.
A method for manufacturing a porous polypropylene membrane is shown in which a part of the mixture is brought out onto the surface of the cooled solidified liquid, the mixture is discharged onto a guide roller, and guided into the cooled solidified liquid by the rotation of the guide roller. It is something.
本発明はさらに冷却固化液がポリエーテル類であるポリ
プロピレン多孔質膜の製造方法を示すものである。本発
明はまた、ポリプロピレンか、ヌル１〜インデツクス５
〜４０のポリプロピレンにヌル１〜インデツクス０．０
５〜５のポリプロピレンをＯ〜５０手量％混練したもの
であるポリプロピレン多孔質膜の製造方法を示すもので
ある。本発明はまた、結晶核形成剤は、０．１〜１．０
１量部添加されているものでおるポリプロピレン多孔質
膜の製造方法を示すものである。本発明はさらに結晶核
形成剤は融点が１５０℃以上でかつゲル化点がポリプロ
ピレンの結晶化開始温度以上の有機耐熱性物質であるポ
リプロピレン多孔質膜の製造方法の製造方法を示すもの
である。本発明はまた、抽出液か、ハロゲン化炭化水素
類もしくはハロゲン化炭化水素類とケトン類との混合物
であるポリプロピレン多孔質膜の製造方法を示すもので
ある。The present invention further provides a method for producing a polypropylene porous membrane in which the cooling solidification liquid is a polyether. The present invention also provides polypropylene, null 1 to index 5.
~40 polypropylene with null 1 ~ index 0.0
This figure shows a method for producing a porous polypropylene membrane obtained by kneading 5 to 5 polypropylene in an amount of 0 to 50% by weight. The present invention also provides that the crystal nucleating agent is 0.1 to 1.0
This figure shows a method for manufacturing a porous polypropylene membrane in which 1 part of polypropylene is added. The present invention further provides a method for producing a polypropylene porous membrane, in which the crystal nucleating agent is an organic heat-resistant substance having a melting point of 150° C. or higher and a gelling point of not lower than the crystallization initiation temperature of polypropylene. The present invention also provides a method for producing a polypropylene porous membrane using an extract or a halogenated hydrocarbon or a mixture of halogenated hydrocarbons and ketones.
（作用）
以下、本発明を実１Ｍ態様に基づきより詳細に説明する
。(Function) Hereinafter, the present invention will be explained in more detail based on an actual 1M embodiment.
本発明によるポリプロピレン多孔質膜は、膜厚が３０〜
３００μ扉、好ましくは６０〜２００μｍの実質的にポ
リプロピレンからなる平膜型の多孔質膜である。このポ
リプロピレン多孔質膜の微細構造は、多孔質膜の製造条
件によって変わるか、概しで後述するように冷却固化液
として、有機充填剤とは相溶せずかつ比熱容量が０．２
〜０．７ｃａｌ／７である溶液を使用することにより、
第３〜４図に示す走査電子顕微鏡写真に見られるような
構造をイ１する。すなわち、本発明のポリプロピレン多
孔質膜は、粒子状ポリプロピレンが連なってできた糸状
体が絡みあってできた微１１１１な網目構造を有してお
り、その一方あるいは両方の表面部には、内部と同程度
の網目構造の表面層が形成されている。このように本発
明のポリプロピレン多孔質膜は、冷却固化液としてパラ
フィン等を用いて得られた多孔質膜（第５〜６図）と膜
内部における孔径と差異がなく、しかも膜表面部におい
ても冷却固化液としてパラフィン等を用いた場合とは異
なり膜内部と同程度の孔径のものとなる。驚くべきこと
に、このような微細構造を有する本発明のポリプロピレ
ン多孔質膜は、冷却固化液としてパラフィン等を用いて
得られた多孔質膜と同様に高い透過速度および分離能を
有し、一方、血液との接触による血球のもぐり込みや溶
血が起こる虞れが極めて少ないことが明らかなものとな
ったものでおる。The polypropylene porous membrane according to the present invention has a thickness of 30~
It is a flat membrane type porous membrane substantially made of polypropylene with a diameter of 300 μm, preferably 60 to 200 μm. The microstructure of this porous polypropylene membrane changes depending on the manufacturing conditions of the porous membrane, or as a general rule, as described later, as a cooling solidification liquid, it is incompatible with organic fillers and has a specific heat capacity of 0.2.
By using a solution that is ~0.7 cal/7,
The structure as seen in the scanning electron micrographs shown in Figures 3 and 4 is shown below. That is, the polypropylene porous membrane of the present invention has a fine 1111 network structure formed by intertwining filaments made of continuous particulate polypropylene, and one or both surfaces of the membrane have internal and external connections. A surface layer with a similar network structure is formed. As described above, the polypropylene porous membrane of the present invention has no difference in pore size inside the membrane from porous membranes obtained using paraffin or the like as a cooling solidification liquid (Figs. 5 and 6), and also in the membrane surface area. Unlike the case where paraffin or the like is used as the cooling solidification liquid, the pore size is the same as that inside the membrane. Surprisingly, the polypropylene porous membrane of the present invention having such a microstructure has high permeation rate and separation ability similar to porous membranes obtained using paraffin or the like as the cooling solidification liquid; It has become clear that there is very little risk of blood cell infiltration or hemolysis due to contact with blood.
本発明のポリプロピレン多孔質膜において、その平均孔
径は０．１〜５．０μｍの範囲にあり、好ましくは０．
２へ・３，０μｍ−ｃ必ることか望まれる。すなわち、
平均孔径が０．１μｍ未渦であると血漿透過速度が低下
しまた目づまりを起こしやずくなり、一方、平均孔径が
５．０μｍを超えるものであると血球成分（赤血球・白
面法・血小板）が血漿成分と共に多孔質膜を透過してし
まう虞れが生じるものであり、上記範囲内であれば白球
成分を透過することなく、血漿成分である総タンパクを
９５％以上透過できる。なお、ここでいう平均孔径は、
水銀ポロシメーターにより実測した膜全体からの平均孔
径であり表面層のみの孔径をいうものではない。さらに
、本発明のポリプロピレン多孔質膜においては、バブル
ポイントが２゜０ Ｋ３ ｆ ／ ｃｒｊ以下であると
され、好ましくは１．８Ｋｇ ｆ ／ ｃｒｔｒ以下で
ある。バブルポイントは膜の最大孔径を規定するもので
あり、２ 、０Ｋｒｔ ｆ ／ｃｉを越えるものである
と膜孔径が小さすぎて速やかな血漿濾過に適さず、血漿
成分の透過性も低下する。In the polypropylene porous membrane of the present invention, the average pore diameter is in the range of 0.1 to 5.0 μm, preferably 0.1 μm to 5.0 μm.
2 to 3.0 μm-c is required. That is,
If the average pore size is 0.1 μm, the plasma permeation rate will decrease and clogging will occur, while if the average pore size exceeds 5.0 μm, blood cell components (red blood cells, white surface method, platelets) will There is a risk that the porous membrane will pass through the porous membrane along with the plasma components, but within the above range, 95% or more of the total protein that is the plasma component can pass through without passing through the white corpuscle components. Note that the average pore diameter here is
This is the average pore diameter of the entire membrane as measured using a mercury porosimeter, and does not refer to the pore diameter of only the surface layer. Furthermore, in the polypropylene porous membrane of the present invention, the bubble point is said to be 2°0 K3 f / crj or less, preferably 1.8 Kg f / crtr or less. The bubble point defines the maximum pore diameter of the membrane, and if it exceeds 2.0 Krt f /ci, the membrane pore diameter will be too small to be suitable for rapid plasma filtration, and the permeability of plasma components will also decrease.
また本発明のポリプロピレン多孔質膜において、空孔率
は６０〜８５％である。すなわち空孔率が６０％未満で
は透過性能の低下が起きたり充分な血漿分出１１速度か
得られす、一方、８５％を越えると使用に絶え得る強度
が得られない虞れかあるためである。また本発明のポリ
プロピレン多孔質膜においては、透水量は１００ｄ／ｍ
ｉｎ −ｍｍＨｇ−ａｔｒ以上であるとされ、好ましく
は１４０ｄ／ｍｉｎ ・ｍｍＨｇ・ｃ／ｊ以上である。Moreover, in the polypropylene porous membrane of the present invention, the porosity is 60 to 85%. In other words, if the porosity is less than 60%, the permeation performance may deteriorate and a sufficient plasma separation rate may not be obtained, whereas if it exceeds 85%, there is a risk that the strength for use may not be obtained. be. Furthermore, in the polypropylene porous membrane of the present invention, the water permeability is 100 d/m
in -mmHg-atr or more, preferably 140 d/min·mmHg·c/j or more.
すなわち透水量が１００ｄ／ｍｉｎ −ｍｍｈｏ−ｃｄ
未満であると充分な血漿分離速度が得られない場合があ
るためで必る。さらに本発明のポリプロピレン多孔質膜
の膜厚は３０〜３００μｍでおり、これは３０μｍ未満
では強度的に問題があり、一方、３００μｍを越えると
モジュールに組込んだ際に大容量のものとなり、実用上
問題のあるためである。That is, the water permeability is 100 d/min -mmho-cd
This is necessary because if it is less than that, a sufficient plasma separation rate may not be obtained. Furthermore, the film thickness of the polypropylene porous membrane of the present invention is 30 to 300 μm, and if it is less than 30 μm, there is a problem in terms of strength, whereas if it exceeds 300 μm, it will have a large capacity when incorporated into a module, and it will not be practical. This is because there is a problem above.
本発明のポリプロピレン多孔質膜は、１２０℃で１２０
分間の熱処理による収縮率が６．０％以下、さらに好ま
しくは３．０％以下であることが望ましい。１２１°Ｃ
で１２０分間の熱処理とは、日本薬局方による高圧蒸気
滅菌を示している。収縮率とは、上記熱処理前と熱処理
後にお（ブる多孔質膜の変化の度合を示すものである。The polypropylene porous membrane of the present invention has a temperature of 120°C at 120°C.
It is desirable that the shrinkage rate after a minute of heat treatment is 6.0% or less, more preferably 3.0% or less. 121°C
120 minutes of heat treatment indicates high-pressure steam sterilization according to the Japanese Pharmacopoeia. The shrinkage rate indicates the degree of change in the porous membrane before and after the heat treatment.
本発明のポリプロピレン多孔質膜は平膜であるので、多
孔質膜の成形軸方向長さおよび成形軸に垂直方向の長さ
の上記熱処理後の変化が６．０％以下であることである
。収縮率が６．０％を越えると熱処理後の透水量、血漿
分離速度が低下し、充分な血液成分の分離ができない虞
れがあるためである。Since the polypropylene porous membrane of the present invention is a flat membrane, the change in the length of the porous membrane in the direction of the forming axis and the length in the direction perpendicular to the forming axis after the heat treatment is 6.0% or less. This is because if the shrinkage rate exceeds 6.0%, the amount of water permeated after heat treatment and the plasma separation rate will decrease, and there is a possibility that sufficient separation of blood components will not be possible.
このような特性を有する本発明のポリプロピレン多孔質
膜は、例えば以下のようにして製造される。The polypropylene porous membrane of the present invention having such characteristics is produced, for example, as follows.
すなわち、第１図に示すようにポリプロピレンと有機充
填剤と結晶核形成剤との配合物１１をホッパー１２から
混練機、例えば二軸型スクリュ一式押出機１３に供給し
て、該配合物を溶融混練し押し出し、−１グイ１／ｌに
送り平膜状に吐出させ、冷却固化液１７を収納した冷ム
１１槽１５内に設けられたガイドローラー１６に冷却固
化液１７の液面よりも上で接触させ、ガイドローラー１
６の回転によって冷ｈＤ固化液１７中に導く。なお本実
施態様においては、溶融膜を冷却固化液と接触させるた
めに）ｊイドローラーを使用したか、溶融膜を直接冷却
固化液中に吐出させることも可能である。That is, as shown in FIG. 1, a blend 11 of polypropylene, an organic filler, and a crystal nucleating agent is fed from a hopper 12 to a kneader, for example, a twin-screw extruder 13, and the blend is melted. The mixture is kneaded and extruded, then fed to -1 Gui 1/l and discharged in the form of a flat film. and guide roller 1.
6 into the cold hD solidification liquid 17. In this embodiment, it is also possible to use a j-id roller (to bring the molten film into contact with the cooling solidification liquid) or to directly discharge the molten film into the cooling solidification liquid.
溶融膜は冷却槽１５を通過する間に完全に冷却固化され
、次いで巻取りローラー１８に巻き取られる。またこの
間にライン１９より供給される冷却固化液１７はライン
２０より排出された後、冷却装置（例えば熱交換器）２
１で所定の温度に冷却されて再循環される。そして巻き
取った膜状物を、更に抽出液の入った抽出槽（図示せず
）へ導き有機充填剤を抽出する。必要によりさらに再抽
出、乾燥、熱処理等の工程を経て巻き取られる。なお得
られる多孔質膜の構造、透過性能の安定化のうえからは
、膜状物を一定の長さに固定して熱処理することが好ま
しい。また有機充填剤の抽出は巻取前に抽出槽を設けて
行ってもよい。The molten film is completely cooled and solidified while passing through the cooling tank 15, and is then wound around the winding roller 18. Also, during this period, the cooled solidified liquid 17 supplied from the line 19 is discharged from the line 20 and then transferred to a cooling device (for example, a heat exchanger) 2.
1, it is cooled to a predetermined temperature and recirculated. Then, the wound-up film-like material is further introduced into an extraction tank (not shown) containing an extraction liquid to extract the organic filler. If necessary, it is further subjected to steps such as re-extraction, drying, and heat treatment before being wound up. Note that from the viewpoint of stabilizing the structure and permeation performance of the porous membrane obtained, it is preferable that the membrane-like material is fixed to a certain length and heat-treated. Further, the organic filler may be extracted by providing an extraction tank before winding.
本発明の製造方法において原料として使用されるポリプ
ロピレンとしては、プロピレンホモポリマーに限らす、
プロピレンを主成分とする他の七ツマ−（例えば、ポリ
エチレン〉とのブロックポリマー等があるか、好ましく
はそのヌル１〜インデツクス（Ｍ、１．）が５〜７０の
ものが好ましく、特にＭ、１．が５〜４０のものが好ま
しい。さらに膜の強度を上げる目的で分子量の大きい、
すなわち、Ｍ、１．の低いポリプロピレンを配合したも
のが好ましく、例えばＭ、１．５〜４ｏのポリプロピレ
ンにＭ、１．０．０５〜５のポリプロピレンを０〜５０
重量％混練したものが好適に使用される。また前記ポリ
プロピレンのうち、プロピレンホモポリマーが特に好ま
しく、中でも結晶性の高いものが最も好ましい。The polypropylene used as a raw material in the production method of the present invention is limited to propylene homopolymer,
There are block polymers with other polymers containing propylene as a main component (e.g., polyethylene), preferably those with null 1 to index (M, 1.) of 5 to 70, especially M, 1 is preferably 5 to 40. Furthermore, in order to increase the strength of the membrane,
That is, M, 1. It is preferable to mix polypropylene with a low molecular weight, for example, polypropylene with a molecular weight of 1.5 to 4 o and polypropylene with a molecular weight of 1.0.05 to 5 o.
A compound kneaded by weight% is preferably used. Among the polypropylenes, propylene homopolymers are particularly preferred, and those with high crystallinity are most preferred.
有機充填剤としては、前記ポリプロピレンの溶融下で該
ポリプロピレンに均一に分散できかつ後述するように抽
出液に対して易溶性のもので必ることが必要である。こ
のような充填剤としては、流動パラフィン（数平均分子
ｆＪａ １００〜２．０００）、α−オレフィンオリゴ
マー［例えばエチレンオリゴマー（数平均分子！１００
〜２，０００）、プロピレンオリゴマー（数平均分子Ｍ
−１００〜２．０００＞、■チレンープロピレンオリゴ
マー（数平均分子！１００〜２，０００＞等］、パラフ
ィンワックス（数平均分子！１００〜２゜５００＞ 、
各種炭化水素等があり、好ましくは流動パラフィンであ
る。The organic filler must be one that can be uniformly dispersed in the polypropylene while it is melted and is easily soluble in the extract as described below. Examples of such fillers include liquid paraffin (number average molecule fJa 100 to 2.000), α-olefin oligomer [e.g. ethylene oligomer (number average molecule fJa 100 to 2.000),
~2,000), propylene oligomer (number average molecule M
-100 to 2,000>, ■Thyrene-propylene oligomer (number average molecule! 100 to 2,000>, etc.), paraffin wax (number average molecule! 100 to 2゜500>,
There are various hydrocarbons, preferably liquid paraffin.
ポリプロピレンと前記有機充填剤との配合割合は、ポリ
プロピレン１００重量部に対して、有機充填剤が２００
〜６００重量部、好ましくは３００〜５００重量部であ
る。すなわちｔ″Ｊｔ！充填剤か２００重量部未満ては
、得られるポリプロピレン多孔質膜の空孔率、透水量か
低すぎて充分な透過性能が得られず、また６００重量部
を越えると、粘度か低ずぎて膜状物の成形加工性か低下
するためである。このような原料配合物は、例えば二軸
押出機等の押出はを用いて所定の組成の混合物を溶融混
練し、押し出した後ペレット化するという前混練方法に
より原料を：Ａ製（設計）する。The blending ratio of polypropylene and the organic filler is 200 parts by weight of the organic filler per 100 parts by weight of polypropylene.
-600 parts by weight, preferably 300-500 parts by weight. In other words, if the t''Jt! filler is less than 200 parts by weight, the porosity and water permeability of the polypropylene porous membrane obtained will be too low to provide sufficient permeation performance, and if it exceeds 600 parts by weight, the viscosity will be too low. This is because the molding processability of the film-like product decreases if the composition is too low.Such raw material mixtures are produced by melt-kneading a mixture of a predetermined composition using an extruder such as a twin-screw extruder, and then extruding the mixture. The raw material is manufactured (designed) by A using a pre-kneading method in which it is pelletized.
本発明において原料中に配合される結晶核形成剤として
は、融点が１５０℃以上、好ましくは２００〜２５０°
Ｃで、かつゲル化点が使用するポリプロピレンの結晶化
聞始謁痕以−にの有機耐熱性物質である。このような結
晶核形成剤を配合する理由は、ポリプロピレン粒子の縮
小化を図り、これによって固相間の間隙、ターなわら形
成される細孔の孔径をコン１−ロールすることにある。In the present invention, the crystal nucleating agent blended into the raw material has a melting point of 150°C or higher, preferably 200 to 250°C.
C, and it is an organic heat-resistant material whose gel point is the same as that of the polypropylene used during crystallization. The reason for blending such a crystal nucleating agent is to reduce the size of the polypropylene particles, thereby controlling the gap between the solid phases and the diameter of the pores formed.
−例を挙げると、例えば１・３，２・４−ジベンジリデ
ンソルビト−ル、１・３，２・４−ビス（ｐ−メチルベ
ンジリデン）ソルビトール、１・３，２・４−ビス（ｐ
−エチルベンジリデン）ソルビト−ル、ビス（４−１−
ブヂルフェニル）リン酸す１〜リウム、安息香酸ナトリ
ウム、アジピン酸、タルク、カオリン等が結晶核形成剤
としてあげられる。これらのうち、１・３，２・４−ジ
ベンジリデンソルビトール、１・３，２・４−ビス（ｐ
−エチルベンジリデン）ソルビ［・−ル、１・３，２・
４−ビス（ｐ−メチルベンジリデン）ソルビトールか白
液中への溶出が少なく好ましい。- Examples include 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-bis(p-methylbenzylidene) sorbitol, 1,3,2,4-bis(p-
-ethylbenzylidene) sorbitol, bis(4-1-
Examples of the crystal nucleating agent include sodium (butylphenyl) phosphate, sodium benzoate, adipic acid, talc, and kaolin. Among these, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-bis(p
-Ethylbenzylidene) sorbyl [-, 1, 3, 2,
4-bis(p-methylbenzylidene) sorbitol is preferred because it is less eluted into white liquor.
ポリプロピレンと前記結晶核形成剤との配合割合は、ポ
リプロピレン１００手量部に対して、結晶核形成剤か０
．１〜５重量部、好ましくは０゜２〜１．０重量部であ
る。The blending ratio of polypropylene and the crystal nucleating agent is 0 parts of the crystal nucleating agent per 100 parts of polypropylene.
．． The amount is 1 to 5 parts by weight, preferably 0.2 to 1.0 parts by weight.
このようにして調ｉ歿された原オ９１配合物をさらに二
軸押出機等の押出はを用いて、例えば１３０〜２５０℃
１好ましくは１４０〜２３０℃の温度で溶融混練し、例
えば王ダイから平膜状に吐出させ、この溶融吐出物を落
下させ、冷却槽内の冷却固化液と接触させる。The thus prepared raw material 91 mixture is further extruded using a twin-screw extruder or the like at, for example, 130 to 250°C.
1. Melt and knead, preferably at a temperature of 140 to 230° C., and discharge it in the form of a flat film from, for example, a king die, and the molten discharged material is dropped and brought into contact with the cooled solidified liquid in a cooling tank.
しかして本発明においては、冷却固化液としては、使用
された有機充填剤とは相溶せす、かつ比熱容量が０．２
〜０．７ｃａｌ ／’Ｊ、より好ましくは０．３〜Ｑ、
６ｃａｌ ／’ｊの液体を用いる。このような冷却固化
液としては例えばポリエチレングリコール等のポリエー
テル類、その他一般に水溶性の溶剤はパラフィン等の有
機充填剤に対して不溶であるものが用いることができる
か、好ましくはポリエチレングリコールであり、特に平
均分子ｆｍ １００〜４００のポリエチレングリコール
、さらに望ましく ＬＪ、平均分子最１８０へ・３３０
のポリエチレングリコールで市る。このように冷却固化
液として、使用された有機充填剤とは相溶せす、かつ比
熱容量が０．２〜０．７ｃａｌ ／（Ｊの液体を用いる
のは以下の理由による。However, in the present invention, the cooling solidification liquid is compatible with the organic filler used and has a specific heat capacity of 0.2.
~0.7 cal/'J, more preferably 0.3~Q,
A liquid of 6 cal/'j is used. As such a cooling solidification liquid, for example, polyethers such as polyethylene glycol, and other generally water-soluble solvents that are insoluble in organic fillers such as paraffin can be used, or preferably polyethylene glycol is used. , especially polyethylene glycol with an average molecular fm of 100 to 400, more preferably LJ, an average molecular maximum of 180 to 330
Made of polyethylene glycol. The reason why a liquid that is compatible with the organic filler used and has a specific heat capacity of 0.2 to 0.7 cal/(J) is used as the cooling solidification liquid is as follows.
すなわち、冷却固化液として前記有機充填剤と同一のも
のあるいはその類似化合物、例えば有機充填剤として流
動パラフィンを用いた際に、該流動パラフィンと数平均
分子量の近似する流動パラフィンを用いると、溶融膜中
の右は充填剤が大きく移行することなく所定の孔密度を
もたせることかできかつ比熱も大きすぎないので適切な
冷却速度でポリプロピレンの結晶化を促し安定した形状
が得られるか、その冷却過程において、表面部のポリプ
ロピレンが固化する以前に冷却固化液中にポリプロピレ
ンが溶は出してしまい、このため表面部には非常に大き
な網目構造が形成されてしまう。さらに冷却固化液とし
て有機充填剤に相溶しない、不活性な液体であっても比
熱容量の大きいもの、例えば比熱容量が約１ 、 Ｑｃ
ａｌ ／ｇと大きな水を用いると、冷却効果か高いため
にポリプロピレンが急冷され、ポリプロピレンと流動パ
ラフィンか十分に相分離せず、表面孔径・内部孔径共に
小さくまた空孔率も低いものとなる。That is, when a liquid paraffin which is the same as the organic filler or a similar compound thereof as the organic filler is used as the cooling solidification liquid, for example, liquid paraffin having a number average molecular weight similar to that of the liquid paraffin is used, the melt film becomes On the right side of the center is the cooling process that allows the filler to have a predetermined pore density without large migration, and the specific heat is not too large, so it is possible to promote crystallization of polypropylene at an appropriate cooling rate and obtain a stable shape. In this case, the polypropylene dissolves into the cooling solidification liquid before the polypropylene on the surface is solidified, and as a result, a very large network structure is formed on the surface. Furthermore, as a cooling solidification liquid, even if it is an inert liquid that is incompatible with the organic filler, it has a large specific heat capacity, for example, a specific heat capacity of about 1, Qc
When water having a large value of al /g is used, the cooling effect is high and the polypropylene is rapidly cooled, and the polypropylene and liquid paraffin do not phase separate sufficiently, resulting in small surface pore diameters, small internal pore diameters, and low porosity.
これに対して、冷却固化液として、前記有機充填剤とは
相溶せず、かつ比熱容量か０．２〜０゜７ｃａｌ ／９
の液体を用いれば、表面部においてポ〜 ２２−
リプロピレンか溶は出してしまうこともまく、ポリプロ
ピレンの冷却速度も適当であり、表面部においても適当
なポリプロピレン組成分率を有したまま結晶化が促准さ
れるので、表面部においても網目構造を大きくしすぎる
こともなく、また同時に内部においても血漿分前に用い
るのに適した十分に大きな孔径を有する網目構造を形成
することができるためである。On the other hand, as a cooling solidified liquid, it is incompatible with the organic filler and has a specific heat capacity of 0.2 to 0.7 cal/9.
If a liquid of is promoted, so that the network structure does not become too large on the surface, and at the same time, a network structure with a sufficiently large pore size suitable for use before plasma separation can be formed inside. It is.
なあ、冷却固化液の温度としては、１０’〜８０′Ｃ１
好ましくは３０’〜６０℃であることが望まれる。ずな
わら１０℃未満では冷却固化速度が速すぎて、形成され
る細孔が非常に小さなものとなってしまい、一方８０℃
を越えると冷却固化が十分に行なわれず、冷却固化液中
で溶融膜が切れてしまう虞れがあるためである。By the way, the temperature of the cooled and solidified liquid is 10' to 80'C1
It is desired that the temperature is preferably 30' to 60°C. Below 10℃, the cooling solidification rate is too fast and the pores formed become very small;
This is because, if the temperature exceeds 100%, cooling and solidification will not be carried out sufficiently, and there is a risk that the molten film will break in the cooling and solidification liquid.
冷却固化槽で完全に冷却固化された膜状物は、抽出液と
接触され、有機充填剤を溶解抽出する。The film-like material completely cooled and solidified in the cooling solidification tank is brought into contact with an extraction liquid to dissolve and extract the organic filler.
前記有機充填剤を溶解抽出する方法としては、抽出槽方
式、ベルミルコンベア上の膜状物に抽出液のシャワーを
降らせるシャワ一方式等かある。Methods for dissolving and extracting the organic filler include an extraction tank method, a one-way shower method in which an extract is showered onto a film-like material on a bell mill conveyor, and the like.
抽出液としては多孔質−膜を構成するボリブ１」ピレン
を溶解せず、かつ有機充填剤を溶解抽出できるものであ
れば何れでもよい。−例を挙げると、例えば、テトラク
１］ロメタン、１，１．２−トリクロロ−Ｌ２，２−１
−リフルオロエタン、トリクロロフルオロメタン、ジク
ロロフルオロメタン、１，１，２．２−テトラクロロ−
１，２−ジフルオロエタン、１〜リクロルエチレン、パ
ークロルエチレン等のハロゲン化炭化水素等があり、有
機充填剤の抽出能力の点および人体に対する安全性の点
から塩化フッ化炭化水素類が好ましい。また結晶核形成
剤としてソルビ１〜−ル類を使用する場合、成形後に多
孔質膜表面からソルヒ１〜−ル類が溶出するのを防ぐた
めに、抽出後にケｊ〜ン類を混合して抽出時に洗い流し
てもよい。Any extracting solution may be used as long as it does not dissolve the pyrene constituting the porous membrane and can dissolve and extract the organic filler. - For example, e.g. tetrac1]lomethane, 1,1,2-trichloro-L2,2-1
-Lifluoroethane, trichlorofluoromethane, dichlorofluoromethane, 1,1,2.2-tetrachloro-
Examples include halogenated hydrocarbons such as 1,2-difluoroethane, 1-lychlorethylene, and perchlorethylene, and chlorinated fluorohydrocarbons are preferred from the viewpoint of extraction ability of organic fillers and safety for the human body. In addition, when using solubiols as a crystal nucleating agent, in order to prevent the solubiols from eluting from the porous membrane surface after molding, it is necessary to mix solubiols after extraction. You can wash it off sometimes.
このようにして得られたポリプロピレン多孔質膜は、さ
らに必要に応じて熱処理にか（プられる。The polypropylene porous membrane thus obtained is further subjected to heat treatment if necessary.
熱処理は、ポリプロピレンの溶融温石より１０〜１５°
Ｃ低い温度、例えば１１０へ・１５０°Ｃ１好ましくは
１３０〜１４０ｍｌ／ｍｉｎ・ｍｍＨｇ・℃の温度で３
０〜１８０秒問、好ましくは６０〜１２０秒間行なわれ
る。上記熱処理を行なう場合は、得られた多孔質膜を予
め一定の長さに固定して行なうことが必要である。Heat treatment is performed at 10 to 15 degrees from the polypropylene molten stone.
C at a lower temperature, e.g. to 110-150 °C1 preferably at a temperature of 130-140 ml/min mmHg °C
It is carried out for 0 to 180 seconds, preferably 60 to 120 seconds. When performing the above heat treatment, it is necessary to fix the obtained porous membrane to a certain length in advance.
本発明のポリプロピレン多孔質膜は、上記のようにして
得られるか、その用途としては血液を血球成分と血漿成
分とに分離するための血漿分離用膜、血液中の細菌を除
去するためのミクロフィルターなどが挙げられ、特にド
ナーフエレーシス等におけるように分離した血漿を使用
する場合の血漿分離用膜として好適に用いられる。The polypropylene porous membrane of the present invention can be obtained as described above, and its applications include plasma separation membranes for separating blood into blood cell components and plasma components, and microorganism membranes for removing bacteria in blood. Examples include filters, and they are particularly suitable for use as membranes for plasma separation when separated plasma is used, such as in donor pheresis.
（実施例） 以下、本発明を実施例に基づきより具体的に説明する。(Example) Hereinafter, the present invention will be explained in more detail based on Examples.
実施例１〜３．比較例１〜３
メルトフローインデックスが３０および０．３のポリプ
ロピレン混合物（混合ｆｆ１ｆｆｉ比１００：４０）１
００重最部当り、第１表に示す割合の流動パラフィン（
数平均分子Ｆｊｉ ３２４ ）おにび結晶核形成剤とし
ての１・３，２・４−ビス（ｐ−エチルベンジリテ′ン
）ソルビｌ〜−ルを二軸型押出機（池貝鉄工株式会社製
、ＰＣＭ−３０−２５＞により溶融混練しペレット化し
た。このペレットを上記押出機を用いて１５０〜２００
℃で溶融しスリット中０．６ｍｍのＴダイより空気中に
押し出し、丁ダイ直下に置かれた冷却液槽のガイドロー
ラーに落下後、このローラーの回転によって冷却固化液
中に導いて冷却固化した後巻き取った。なお冷却固化液
の種類および温度は第１表に示す通りである。巻き取っ
たフィルム状物を一定長（約２００Ｘ２００ｍ）に切断
し、縦横両方向を固定し、１．１．２−トリクロロ−１
，２，２−トリフルオロエタン（液温２５°Ｃ）中に１
０分間計４回浸漬して流動パラフィンの抽出を行い、次
いて１３５°Ｃの空気中で２分間熱処理を行なった。Examples 1-3. Comparative Examples 1 to 3 Polypropylene mixtures with melt flow indexes of 30 and 0.3 (mixture ff1ffi ratio 100:40) 1
Per 00 weight part, liquid paraffin (
Number average molecular Fji 324) 1,3,2,4-bis(p-ethylbenzyrite') sorbyl as a crystal nucleating agent was extracted using a twin-screw extruder (manufactured by Ikegai Iron Works Co., Ltd.). , PCM-30-25> were melt-kneaded and pelletized.The pellets were heated to 150 to 200
It was melted at ℃, extruded into the air through a 0.6 mm T-die in a slit, and fell onto a guide roller in a cooling liquid tank placed directly below the T-die.The rotation of this roller guided it into a cooling liquid, where it was cooled and solidified. I rolled it up afterwards. The type and temperature of the cooling solidification liquid are as shown in Table 1. The wound film-like material was cut into a certain length (approximately 200 x 200 m), fixed both vertically and horizontally, and 1.1.2-trichloro-1
, 1 in 2,2-trifluoroethane (liquid temperature 25°C)
Liquid paraffin was extracted by immersion for 0 minutes four times in total, and then heat treatment was performed in air at 135°C for 2 minutes.
このようにして得られた多孔質膜について膜厚、バブル
ポイント、空孔率、透水量および最高血漿分離速度を測
定した。得られた結果を第１表に示す。The membrane thickness, bubble point, porosity, water permeation rate, and maximum plasma separation rate of the porous membrane thus obtained were measured. The results obtained are shown in Table 1.
また得られた多孔質膜の微細構造を調べるために走査型
電子顕微＆？１（Ｊ「Ｏｌ−製、ＪＳＭ４３／１Ｏ）を
用いて膜の各部位の観察を行なった。すなわち、第３図
は実施例１の多孔質膜の表面（Ｘ１０００）、第４図は
実施例１の多孔質膜の部分断面（Ｘ２５００＞ 、第５
図は比較例１の多孔質膜の表面（Ｘ１０００＞ 、第６
図は比較例１の多孔質膜の部分断面（Ｘ３０００）をそ
れぞれ示す電子顕微鏡写真である。第３図および第４図
より明らかなように本発明に係る実施例１の多孔質膜は
、その表面部においてもその網目構造は膜内部と同程度
のものであり、かつこの表面層は比較的肉厚のない（全
膜厚の０．５％程度）であり、また膜内部においても網
目構造か十分に発達している。We also used scanning electron microscopy to examine the fine structure of the porous membrane obtained. 1 (manufactured by J"Ol-, JSM43/1O). In other words, Fig. 3 shows the surface of the porous film of Example 1 (X1000), and Fig. 4 shows the surface of the porous film of Example 1. Partial cross section of porous membrane No. 1 (X2500>, No. 5
The figure shows the surface of the porous membrane of Comparative Example 1 (X1000>,
The figures are electron micrographs showing a partial cross section (X3000) of the porous membrane of Comparative Example 1. As is clear from FIGS. 3 and 4, the porous membrane of Example 1 according to the present invention has a network structure on the surface that is comparable to that inside the membrane, and this surface layer is It has no target thickness (approximately 0.5% of the total film thickness), and the network structure is sufficiently developed inside the film.
これに対し、冷却固化液として流動パラフィンを用いて
得られた多孔質膜（比較例１）は、第５図および第６図
より明らかなように、膜内部においては実施例１のもの
と同様に網目構造が十分に発達しているか、その表面部
においては網目構造はかなり粗いものであってかつこの
表面層はかなりの肉厚（全膜厚の２４．０％程度）であ
った。このような面から、本発明に係る実施例１の多孔
質膜は、血球のもぐり込みが少ないものであることが裏
付けられる。On the other hand, the porous membrane obtained using liquid paraffin as the cooled and solidified liquid (Comparative Example 1) has the same internal structure as that of Example 1, as is clear from Figures 5 and 6. The network structure was sufficiently developed, but the network structure was quite rough on the surface, and this surface layer was quite thick (approximately 24.0% of the total film thickness). From this point of view, it is confirmed that the porous membrane of Example 1 according to the present invention is one in which the penetration of blood cells is small.
さらに実施例１および比較例１の多孔質膜を実際に積層
型の−Ｅジュールに組込んで牛血の血漿分離を行ない、
血漿分離の性能を比較した。結果を第７〜９図に示す。Furthermore, the porous membranes of Example 1 and Comparative Example 1 were actually incorporated into a laminated -E Joule to perform plasma separation of bovine blood.
The performance of plasma separation was compared. The results are shown in Figures 7-9.
なお、第７図には、血漿分離速度（Ｑ「）に対する絶膜
間圧力（Ｔ、Ｍ、Ｐ、）の関係を、第８図は王、Ｍ、Ｐ
、に対する遊離ヘモグロビン量（Δ１」ｂ）の関係をそ
れぞれ表わす。In addition, Fig. 7 shows the relationship between the membrane pressure (T, M, P,) and the plasma separation rate (Q''), and Fig. 8 shows the relationship between the plasma separation rate (Q'') and the membrane pressure (T, M, P,).
, and the relationship between the amount of free hemoglobin (Δ1''b) and , respectively.
比較例４ 比較のために市販の酢酸セルロース膜（Ｃ△。Comparative example 4 For comparison, a commercially available cellulose acetate membrane (C△.
東洋濾紙製）を用いて膜厚、バブルポイント、空孔率、
透水量および最高血漿分離速度を測定した。(manufactured by Toyo Roshi) to measure film thickness, bubble point, porosity,
Water permeability and maximum plasma separation rate were measured.
得られた結果を第１表に示す。The results obtained are shown in Table 1.
第１
グリコール
実施例２ ４００ ２０
０．３実施例３ ４５６
３５ ０．３比較例１ ４００
流動パラフィン ３８ ０．３フルオロエタン
比較例３ １５０ 流動パラフィン ３０
０．３比較例４ セルロースアセテート膜
表
１４６ １．１ ６６ １６２ ４０１４０ １．１
６５ １５８ −’Ｈ３０，９６８２２９−
１２００，７７１３３０４０
１５００，９７３３０５４０
１２０３，１５５９０４０
１６２３，２７２３２０３５
９＝
第１表に示す結果から明らかなように、本発明のポリプ
ロピレン多孔質膜（実施例１〜３）は、空孔率、透水量
が高く、血漿分離速度も高いものであることがわかる。1st Glycol Example 2 400 20
0.3 Example 3 456
35 0.3 Comparative Example 1 400
Liquid paraffin 38 0.3 Fluoroethane comparative example 3 150 Liquid paraffin 30
0.3 Comparative Example 4 Cellulose acetate membrane Table 146 1.1 66 162 40140 1.1
65 158 -'H30,968229- 1200,77133040 1500,97330540 1203,1559040 1623,27232035 9= As is clear from the results shown in Table 1, the polypropylene porous membrane of the present invention (Examples 1 to 3) It can be seen that the porosity and water permeability are high, and the plasma separation rate is also high.
しかも本発明のポリプロピレン多孔質膜は膜描造上、血
球のもぐり込みが少なく、第７〜８図に示すように溶血
しにくいという利点を有している。Furthermore, the porous polypropylene membrane of the present invention has the advantage that blood cells are less likely to penetrate into the membrane, and hemolysis is less likely to occur, as shown in FIGS. 7 and 8.
これに対し、比較例１〜２のように冷却液に流動パラフ
ィンまた１、１１ハロゲン化炭化水素を用いると、最高
血漿分離速度は、本発明のポリプロピレン多孔質膜と同
程度にとれるか、溶血を起こしやすく膜間圧力を大きく
とれないこととなる。また血漿中の各成分の透過率も第
９ａ−ｃ図に示すように本発明のポリプロピレン多孔質
膜（実施例１）は、表面孔径の大きな比較例１のものに
劣らないものであった。On the other hand, when liquid paraffin or a 1,11 halogenated hydrocarbon is used as the coolant as in Comparative Examples 1 and 2, the maximum plasma separation rate is comparable to that of the polypropylene porous membrane of the present invention, or the hemolysis This tends to occur, making it impossible to maintain a large intermembrane pressure. Furthermore, as shown in Figures 9a-c, the porous polypropylene membrane of the present invention (Example 1) was as good as that of Comparative Example 1, which had a large surface pore size, in terms of the permeability of each component in plasma.
なお本明細書における各用品の定義および測定方法は以
下の通りである。In addition, the definition and measurement method of each article in this specification are as follows.
（１）バブルポイン１〜
ＡＳＴＭ Ｆ３１６修正法に従い、直径４７＃＝ ３
０−
のステンレスホルダを用い、液相としてイソプロピルア
ルコールを用いて、測定した。そして圧力を上げていき
フィルター中央部よりイソプロピルアルコール中を窒素
の一連の気泡か均一に間断なく上昇し始める時の圧力を
バブルポイントとした。(1) Bubble point 1 ~ According to ASTM F316 modified method, diameter 47# = 3
The measurement was carried out using a stainless steel holder of 0- and isopropyl alcohol as the liquid phase. The pressure was then increased, and the pressure at which a series of nitrogen bubbles began to rise uniformly and without interruption from the center of the filter in the isopropyl alcohol was defined as the bubble point.
（２）膜厚 マイクロメーターを用いて実測した。(2) Film thickness Actual measurements were made using a micrometer.
（３）空孔率
多孔質膜をエタノールに浸漬した後、水置換して含水さ
せ含水の重Ｅｉ（Ｗｐ）を測定する。乾燥時の１ｆｉｉ
をＷＷ、ポリマーの缶石をｌ）ｇ／ｄとすると空孔率は
以下の式で算出される。(3) Porosity: After the porous membrane is immersed in ethanol, it is replaced with water to contain water and the weight of water Ei (Wp) is measured. 1fii when dry
If WW is WW and the polymer scale is l) g/d, the porosity is calculated by the following formula.
（４）透水が
膜面積１．４５Ｘ１０−３７Ｆｉの膜に０，１ｇｆ／ｃ
Ａの圧力下で、２５°Ｃの水を透過させ、１００ｄ透過
するのに要する時間を測定した。(4) Water permeability is 0.1gf/c through a membrane with a membrane area of 1.45X10-37Fi
Under pressure A, water at 25°C was permeated and the time required to permeate 100 d was measured.
（５）最高血漿分離速度（Ｑ ｆｍａｘ ）第２図に
示す回路を用いて測定した。測定においてヘマトクリッ
ト４０％ヘパリン加新鮮牛血（５０００ＬＪ 、’Ω）
を用い、膜面積０．４′ｒｄのモジュール３０で血流Ｄ
１００ｄ／ｍ１ｎ１、圧力損失３０ｍｍｈｇで循環し
、ｉ！ヒ液ポンプ流量を１０ｍ／ｍｉｎ、より３０分毎
に１０−＋１５−＋２０→２５−＋３０→４０→／４２
と増加させ３０分以内てＴ、Ｍ、Ｐ。(5) Maximum plasma separation rate (Q fmax ) Measured using the circuit shown in FIG. For measurement, hematocrit was 40% heparinized fresh bovine blood (5000LJ, 'Ω)
using the module 30 with a membrane area of 0.4′rd.
Circulate at 100d/m1n1, pressure loss 30mmhg, i! The liquid pump flow rate is 10 m/min, and every 30 minutes 10-+15-+20→25-+30→40→/42
and increase T, M, P within 30 minutes.
が２０ｍｍＨＯ以上増加する直前の濾過量をＱ ｆｍ
ａＸとする。Q fm is the filtration amount just before the
Let it be aX.
たた′し、Ｔ、 Ｍ、 Ｐ、 ＝Ｐｉｎ＋Ｐｏｕｔ ／
２−Ｐｆｉｌである。第２図に於（プるＧ１、Ｇ２、Ｇ
３は圧力メーターであり、Ｇ１の圧力が１ａｉｎ、Ｇ２
の圧力がＰｆｉｌ 、Ｇ３の圧力がｌ〕Ｏｕｔである。Tatami, T, M, P, =Pin+Pout/
2-Pfil. In Figure 2 (Puru G1, G2, G
3 is a pressure meter, the pressure of G1 is 1ain, the pressure of G2 is
The pressure of G3 is Pfil, and the pressure of G3 is l]Out.
Ｐは、それぞれポンプを示す。P each indicates a pump.
（６）平均孔径 水銀ポロシメーターで実測した。(6) Average pore diameter Measured using a mercury porosimeter.
（発明の効果）
以上述べたように本発明は、微細な網目構造を持つ多孔
質膜で、該多孔質膜の一方あるいは両方の表面部には内
部と同程度の網目構造の表面層か形成され、平均孔径が
０．１〜５．０μ兜、パブルポイントが２ 、０ Ｋ９
ｆ ／ ｃｍ以下、空孔率が６０〜８５％、透水量が１
００ｍ／ｍｉｎ −ｍｍＨｇ −７ｄ以上であり、膜厚
が３０〜３００μｍである実質的にポリプロピレンから
なることを特徴とする平膜型のポリプロピレン多孔質膜
であるから、空孔率、透水量か高く、血漿分離に用いた
場合に、タンパク質、血球等による目詰りが少なく、高
い血漿分離速度が得られ、しかも血球のもぐり込みが少
ないため溶血が生じにくく、このため血液を血球成分と
血漿成分とに分離するための血漿分離用膜として好適に
使用され、特にドナーフエレーシス等のように分離した
面禁を使用する場合の血漿分離用膜として有用である。(Effects of the Invention) As described above, the present invention provides a porous membrane having a fine network structure, in which a surface layer having the same degree of network structure as the inside is formed on one or both surfaces of the porous membrane. Average pore size is 0.1~5.0μ, Pubble point is 2, 0K9
f/cm or less, porosity 60-85%, water permeability 1
00m/min -mmHg -7d or more, and has a film thickness of 30 to 300 μm.Since it is a flat membrane type polypropylene porous membrane that is essentially made of polypropylene, it has a high porosity and water permeability. When used for plasma separation, there is less clogging with proteins, blood cells, etc., and a high plasma separation rate can be obtained.Moreover, there is less infiltration of blood cells, so hemolysis is less likely to occur. It is suitably used as a membrane for plasma separation, and is particularly useful as a membrane for plasma separation when separated membranes are used, such as in donor pheresis.
また本発明のポリプロピレン多孔質膜において、バブル
ポイントが１．８Ｋｇｆ ／ ａｔｒ以下、透水量が１
４０ｍ／ｍｉｎ −ｍｍ１ｌｏ ・ボ以上であり、１２
０℃で１２０分間の熱処理による収縮率か６．０％以下
のものであると、上記のごとき効果はより優れたものと
なる。Furthermore, in the polypropylene porous membrane of the present invention, the bubble point is 1.8 Kgf/atr or less, and the water permeability is 1.
40m/min -mm1lo ・Bo or more, 12
If the shrinkage rate after heat treatment at 0° C. for 120 minutes is 6.0% or less, the above effects will be even better.
さらに、本発明は、ポリプロピレン１００重量部に対し
て、該ポリプロピレン溶融下でポリプロピレンに均一に
分散し得る＠機充填剤２００〜６００重量部および結晶
核形成剤０．１〜５．０重量部を加えて溶融混練し、こ
のようにして得られた混合物を溶融状態でダイスより平
膜状に吐出させ、吐出させた溶融膜を前記有機充填剤と
は相溶せずかつ比熱容量が０．２〜０．７ｃａｌ ／ａ
である冷却固化液と接触させて冷却固化し、ついでポリ
プロピレンを溶解せず有機充填剤を溶解する抽出液と接
触させて含有する６機充填剤を抽出除去することを特徴
とする平膜型のポリプロピレン多孔質膜の製造方法であ
るから、上記のごとき優れた性能を有する多孔質膜を容
易に製造することができる。さらに本発明の製造方法に
おいて、有機充填剤を抽出除去した後、さらに生成ポリ
プロピレン多孔質膜を一定の長さに固定して１１０〜１
４０′Ｃの温度で熱処理を行なうものであると得られる
多孔質膜の性能はより安定したものとなり、また溶融膜
の冷却固化液との接触か、冷却固化液中にガイドローラ
ーを設け、このガイドローラーの一部を冷却固化液面上
に出し、前記混合物をカイドローラー上に吐出させ、ノ
ｊイドローラーの回転によって冷却固化液中に導くこと
により行なわれるものであるとより容易に高品位のポリ
プロピレン多孔質膜を得ることかでき、さらに冷却固化
液かポリエーテル類であり、ポリプロピレンか、メル［
−インデックス５〜４０のポリプロピレンにメルトイン
デックス０．０５〜５のポリプロピレンを０〜５０重量
％混練したものであり、結晶核形成剤か、０．１〜１．
０！尼部添加されてなり、この結晶核形成剤は融点が１
５０°Ｃ以上でかつゲル化点がポリプロピレンの結晶化
開始温度以上の有機耐熱性物質であり、さらに抽出液か
、ハロゲン化炭化水素類もしくはハロゲン化炭化水素類
とケトン類との混合物であると得られるポリプロピレン
多孔質膜の性能はより一層優れたものとなる。Furthermore, the present invention includes, per 100 parts by weight of polypropylene, 200 to 600 parts by weight of a filler and 0.1 to 5.0 parts by weight of a crystal nucleating agent, which can be uniformly dispersed in the polypropylene while the polypropylene is melted. In addition, the mixture thus obtained is discharged in a molten state from a die in the form of a flat film, and the discharged molten film is incompatible with the organic filler and has a specific heat capacity of 0.2. ~0.7cal/a
A flat membrane type, characterized in that it is cooled and solidified by contacting with a cooling solidification liquid, and then brought into contact with an extraction liquid that does not dissolve the polypropylene but dissolves the organic filler to extract and remove the contained six fillers. Since this is a method for producing a porous polypropylene membrane, a porous membrane having the above-mentioned excellent performance can be easily produced. Furthermore, in the production method of the present invention, after the organic filler is extracted and removed, the produced polypropylene porous membrane is further fixed to a certain length,
If the heat treatment is carried out at a temperature of 40'C, the performance of the resulting porous film will be more stable, and the molten film may be brought into contact with the cooling solidification liquid, or a guide roller may be provided in the cooling solidification liquid. High quality can be achieved more easily if a part of the guide roller is brought out above the surface of the cooled solidified liquid, the mixture is discharged onto the guided roller, and guided into the cooled solidified liquid by the rotation of the noded roller. It is possible to obtain a polypropylene porous membrane of 100% by cooling, solidifying liquid or polyethers, polypropylene or mel[
- Polypropylene with a melt index of 0.05 to 5 is kneaded with 0 to 50% by weight of polypropylene with an index of 5 to 40, and contains a crystal nucleating agent or a crystal nucleating agent of 0.1 to 1.
0! This crystal nucleating agent has a melting point of 1.
It is an organic heat-resistant substance with a gelling point of 50°C or higher and a gelation point higher than the crystallization initiation temperature of polypropylene, and is an extract, a halogenated hydrocarbon, or a mixture of halogenated hydrocarbons and ketones. The performance of the polypropylene porous membrane obtained is even more excellent.
第１図は本発明のポリプロピレン多孔質膜の製造方法に
おいて用いられる製造装置の一例を示す概略図、第２図
は最高血景分離速度を測定するための回路図、第３図〜
第４図は本発明のポリプロピレン多孔質膜の一実施例の
膜４．！、７造を示す電子顕微鏡写真、第５〜６図は、
比較例の多孔質膜の膜Ｍ？ｉ造を示す電子顕微鏡写真、
第７図は血漿分離速度（Ｑ’ｆ）に対する総股間圧力（
王、Ｍ、Ｐ、’）の関係を示すグラフ、第８図は総膜問
斤力に対する遊離ヘモグロビン卒（△Ｈｂ）の関係を示
η−グラフであり、また第９８〜Ｃ図は血漿分離速度（
Ｑｆ）に対する血漿の各種成分の透過率を示すものであ
る。なお第７〜９図において○は実施例］のデータを、
またＯは比較例１のデータを示すものである。
１１・・・配合物、 １２・・・ホッパー、１３・・
・二軸型スクリュ一式押出は、１４・・・−１−グイ、
１５・・・冷却槽、１６・・・ガイドローラー、
１７・・・冷却固化液、１Ｂ・・・巻取りローラー。
第７図
Ｑ、 （ｍｌ／ｍｉｎ）
ＴＭＰ （ｍｍＨｇ）
第９ａ図
０１ （ｍｌ／ｍｉｎ）
第９ｂ図
Ｏｆ（ｍｌ／ｍ１ｎ）
Ｑ（（ｍｌ／ｍ１ｎ）FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus used in the method for manufacturing a porous polypropylene membrane of the present invention, FIG. 2 is a circuit diagram for measuring the maximum blood-scene separation speed, and FIGS.
FIG. 4 shows membrane 4 of an embodiment of the polypropylene porous membrane of the present invention. ! , Figures 5 and 6 are electron micrographs showing seven structures.
Membrane M of the porous membrane of the comparative example? Electron micrograph showing i-structure,
Figure 7 shows the total groin pressure (
Figure 8 is an η-graph showing the relationship between free hemoglobin (△Hb) and total membrane concentration, and Figures 98 to C are graphs showing the relationship between plasma separation. speed(
This shows the permeability of various components of plasma to Qf). In addition, in Figs. 7 to 9, ○ indicates the data of Example],
Further, O indicates data of Comparative Example 1. 11... Compound, 12... Hopper, 13...
・For twin screw type extrusion, 14...-1-guy,
15... Cooling tank, 16... Guide roller,
17... Cooling solidification liquid, 1B... Winding roller. Fig. 7 Q, (ml/min) TMP (mmHg) Fig. 9a 01 (ml/min) Fig. 9b Of (ml/m1n) Q ((ml/m1n)
Claims (12)
一方あるいは両方の表面部には内部と同程度の網目構造
の表面層が形成され、平均孔径が０．１〜５．０μｍ、
バブルポイントが２．０Ｋｇｆ／ｃｍ＾２以下、空孔率
が６０〜８５％、透水量が１００ｍｌ／ｍｉｎ・ｍｍＨ
ｇ・ｍ＾２以上であり、膜厚が３０〜３００μｍである
実質的にポリプロピレンからなることを特徴とする平膜
型のポリプロピレン多孔質膜。(1) A porous membrane with a fine network structure, in which one or both surfaces of the porous membrane have a surface layer with the same network structure as the inside, and an average pore size of 0.1 to 5. 0μm,
Bubble point is 2.0Kgf/cm^2 or less, porosity is 60-85%, water permeability is 100ml/min・mmH
g·m^2 or more and a film thickness of 30 to 300 μm, and is substantially made of polypropylene.
ある特許請求の範囲第１項に記載のポリプロピレン多孔
質膜。(2) The polypropylene porous membrane according to claim 1, which has a bubble point of 1.8 Kgf/cm^2 or less.
以上である特許請求の範囲第１項または第２項に記載の
ポリプロピレン多孔質膜。(3) Water permeability is 140ml/min・mmHg・m^2
The polypropylene porous membrane according to claim 1 or 2, which is the above.
．０％以下である特許請求の範囲第１項ないし第３項の
いずれかに記載のポリプロピレン多孔質膜。(4) Shrinkage rate after heat treatment at 120℃ for 120 minutes is 6
．． The polypropylene porous membrane according to any one of claims 1 to 3, wherein the polypropylene porous membrane has a content of 0% or less.
ロピレン溶融下でポリプロピレンに均一に分散し得る有
機充填剤２００〜６００重量部および結晶核形成剤０．
１〜５．０重量部を加えて溶融混練し、このようにして
得られた混合物を溶融状態でダイスより平膜状に吐出さ
せ、吐出させた溶融膜を前記有機充填剤とは相溶せずか
つ比熱容量が０．２〜０．７ｃａｌ／ｇである冷却固化
液と接触させて冷却固化し、ついでポリプロピレンを溶
解せず有機充填剤を溶解する抽出液と接触させて含有す
る有機充填剤を抽出除去することを特徴とする平膜型の
ポリプロピレン多孔質膜の製造方法。(5) For 100 parts by weight of polypropylene, 200 to 600 parts by weight of an organic filler that can be uniformly dispersed in the polypropylene while the polypropylene is melted and 0.0 parts by weight of a crystal nucleating agent.
1 to 5.0 parts by weight are added and melt-kneaded, and the mixture thus obtained is discharged in a molten state from a die in the form of a flat film, and the discharged molten film is not compatible with the organic filler. An organic filler containing an organic filler that is brought into contact with a cooling solidification liquid having a specific heat capacity of 0.2 to 0.7 cal/g and then cooled and solidified, and then brought into contact with an extract that does not dissolve polypropylene but dissolves the organic filler. A method for producing a flat polypropylene porous membrane characterized by extracting and removing.
ロピレン多孔質膜を一定の長さに固定して１１０〜１４
０℃の温度で熱処理を行なうものである特許請求の範囲
第５項に記載のポリプロピレン多孔質膜の製造方法。(6) After extracting and removing the organic filler, the produced polypropylene porous membrane is fixed to a certain length and
The method for producing a porous polypropylene membrane according to claim 5, wherein the heat treatment is performed at a temperature of 0°C.
ガイドローラーを設け、このガイドローラーの一部を冷
却固化液面上に出し、前記混合物をガイドローラー上に
吐出させ、ガイドローラーの回転によって冷却固化液中
に導くことにより行なわれるものである特許請求の範囲
第５項または第６項に記載のポリプロピレン多孔質膜の
製造方法。(7) To bring the molten film into contact with the cooled solidified liquid, a guide roller is provided in the cooled solidified liquid, a part of this guide roller is brought out above the surface of the cooled solidified liquid, and the mixture is discharged onto the guide roller. The method for producing a porous polypropylene membrane according to claim 5 or 6, which is carried out by introducing the porous polypropylene membrane into a cooling solidification liquid by rotating a roller.
囲第５項〜第７項のいずれかに記載のポリプロピレン多
孔質膜の製造方法。(8) The method for producing a porous polypropylene membrane according to any one of claims 5 to 7, wherein the cooling solidification liquid is a polyether.
のポリプロピレンにメルトインデックス０．０５〜５の
ポリプロピレンを０〜５０重量％混練したものである特
許請求の範囲第５項〜第８項のいずれかに記載のポリプ
ロピレン多孔質膜の製造方法。(9) Polypropylene has a melt index of 5 to 40
The method for producing a porous polypropylene membrane according to any one of claims 5 to 8, wherein 0 to 50% by weight of polypropylene having a melt index of 0.05 to 5 is kneaded with polypropylene.
れているものである特許請求の範囲第５項〜第９項のい
ずれかに記載のポリプロピレン多孔質膜の製造方法。(10) The method for producing a polypropylene porous membrane according to any one of claims 5 to 9, wherein the crystal nucleating agent is added in an amount of 0.1 to 1.0 parts by weight.
化点がポリプロピレンの結晶化開始温度以上の有機耐熱
性物質である特許請求の範囲第５項〜第１０項のいずれ
かに記載のポリプロピレン多孔質膜の製造方法。(11) The crystal nucleating agent according to any one of claims 5 to 10, wherein the crystal nucleating agent is an organic heat-resistant substance having a melting point of 150°C or higher and a gelling point higher than the crystallization initiation temperature of polypropylene. Method for producing porous polypropylene membrane.
ゲン化炭化水素類とケトン類との混合物である特許請求
の範囲第５項〜第１１項のいずれかに記載のポリプロピ
レン多孔質膜の製造方法。(12) The method for producing a porous polypropylene membrane according to any one of claims 5 to 11, wherein the method is an extract, a halogenated hydrocarbon, or a mixture of a halogenated hydrocarbon and a ketone. .
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5672887A JPS63224702A (en) | 1987-03-13 | 1987-03-13 | Polypropylene porous membrane and its production |
| EP88901092A EP0341309B1 (en) | 1987-01-20 | 1988-01-20 | Porous polypropylene membrane and process for its production |
| DE3855721T DE3855721T2 (en) | 1987-01-20 | 1988-01-20 | POROUS POLYPROPYLENE MEMBRANE AND METHOD FOR THE PRODUCTION THEREOF |
| KR1019880701129A KR940002379B1 (en) | 1987-01-20 | 1988-01-20 | Porous polypropylene membrane and process for its production |
| US07/392,988 US5139529A (en) | 1987-01-20 | 1988-01-20 | Porous polypropylene membrane and methods for production thereof |
| KR1019940700300A KR940008074B1 (en) | 1987-01-20 | 1988-01-20 | Porous polypropylene membrane |
| PCT/JP1988/000039 WO1988005475A1 (en) | 1987-01-20 | 1988-01-20 | Porous polypropylene membrane and process for its production |
| AU11847/88A AU623848B2 (en) | 1987-01-20 | 1988-01-20 | Porous polypropylene membrane and process for its production |
| CA000560896A CA1310160C (en) | 1987-03-13 | 1988-03-09 | Porous polypropylene hollow fiber membrane, method for production thereof and artificial lung |
| US07/820,481 US5354470A (en) | 1987-01-20 | 1992-01-14 | Porous polypropylene membrane and method for production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5672887A JPS63224702A (en) | 1987-03-13 | 1987-03-13 | Polypropylene porous membrane and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63224702A true JPS63224702A (en) | 1988-09-19 |
| JPH0555174B2 JPH0555174B2 (en) | 1993-08-16 |
Family
ID=13035561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5672887A Granted JPS63224702A (en) | 1987-01-20 | 1987-03-13 | Polypropylene porous membrane and its production |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS63224702A (en) |
| CA (1) | CA1310160C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007061673A (en) * | 2005-08-29 | 2007-03-15 | Toray Ind Inc | Microporous polypropylene sheet for medical separation membrane, and medical separation membrane using the same |
-
1987
- 1987-03-13 JP JP5672887A patent/JPS63224702A/en active Granted
-
1988
- 1988-03-09 CA CA000560896A patent/CA1310160C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007061673A (en) * | 2005-08-29 | 2007-03-15 | Toray Ind Inc | Microporous polypropylene sheet for medical separation membrane, and medical separation membrane using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0555174B2 (en) | 1993-08-16 |
| CA1310160C (en) | 1992-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR940002379B1 (en) | Porous polypropylene membrane and process for its production | |
| JP4656839B2 (en) | Halar film | |
| FR2485943A1 (en) | MEMBRANES FOR MICROFILTRATION, ULTRAFILTRATION OR DIALYSIS, BASED ON METHYL METHACRYLATE COPOLYMERS | |
| US4927576A (en) | Method for the manufacture of flat permeable membrane | |
| US5186835A (en) | Porous hydrophilic polypropylene membrane, method for production thereof, and blood plasma separation apparatus | |
| RU2198725C2 (en) | From-melt formed polysulfone semipermeable membranes and method of preparation thereof | |
| US4964991A (en) | Flat permeable membrane and for manufacture thereof | |
| JPS5891732A (en) | Porous polyvinylidene fluoride resin membrane and preparation thereof | |
| JPH0235918A (en) | Polypropylene porous hollow yarn membrane and its manufacture | |
| JPS63224702A (en) | Polypropylene porous membrane and its production | |
| KR910009814B1 (en) | Hydrophilic polypropylene porous membrane process for its production and apparatus for separating blood plasma | |
| JPS6297603A (en) | Porous membrane of polypropylene and production thereof | |
| JPH0371144B2 (en) | ||
| WO1983001632A1 (en) | Polymethyl methacrylate hollow yarn ultra-filtration membrane and process for its production | |
| JPS5958041A (en) | Preparation of porous polysulfone membrane | |
| JPS61114702A (en) | Flat film type permeable membrane and preparation thereof | |
| JP2501891B2 (en) | Hydrophilic polypropylene porous membrane and plasma separation device | |
| JPS6045358A (en) | Serum separating membrane and its preparation | |
| JPH01228505A (en) | Porous hollow yarn membrane, production thereof and artificial lung utilizing said hollow yarn membrane | |
| JPH0474046B2 (en) | ||
| JPH01168303A (en) | Porous hollow yarn membrane and its preparation and pump-oxygenator | |
| JPH0512969B2 (en) | ||
| JPH0512970B2 (en) | ||
| JPH0521617B2 (en) | ||
| JPS59183761A (en) | Serum separating membrane and production thereof |