JPH073004B2 - Copolyimide hollow fiber and method for producing the same - Google Patents
Copolyimide hollow fiber and method for producing the sameInfo
- Publication number
- JPH073004B2 JPH073004B2 JP61069471A JP6947186A JPH073004B2 JP H073004 B2 JPH073004 B2 JP H073004B2 JP 61069471 A JP61069471 A JP 61069471A JP 6947186 A JP6947186 A JP 6947186A JP H073004 B2 JPH073004 B2 JP H073004B2
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- copolyimide
- average pore
- porous layer
- core
- 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 - Fee Related
Links
- 239000012510 hollow fiber Substances 0.000 title claims description 91
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000003495 polar organic solvent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 238000005345 coagulation Methods 0.000 description 23
- 230000015271 coagulation Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- 239000012528 membrane Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- 238000009987 spinning Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 230000001112 coagulating effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- -1 phenol compound Chemical class 0.000 description 4
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241001648319 Toronia toru Species 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、3,4,3′,4′−ベンゾフエノンテトラカルゴ
ン酸二無水物をトリレンジイソシアネートおよびメチレ
ンビスフエニルイソシアネートの混合物と反応させて得
られた芳香族コポリイミドの中空糸およびその製造方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to 3,4,3 ′, 4′-benzophenone tetracargonic acid dianhydride as a mixture of tolylene diisocyanate and methylene bisphenyl isocyanate. The present invention relates to a hollow fiber of aromatic copolyimide obtained by reaction and a method for producing the hollow fiber.
すなわち、本発明はベンゾフエノンテトラカルボン酸系
の芳香族ポリイミドが特定の極性有機溶媒を主成分とす
る溶媒に溶解しているコポリイミド溶液を中空糸の紡糸
用ドープ液として使用し、そのドープ液の中空糸状体を
形成し、凝固させるコポリイミド中空糸の製造方法に関
するものである。That is, the present invention uses a copolyimide solution in which a benzophenonetetracarboxylic acid-based aromatic polyimide is dissolved in a solvent whose main component is a specific polar organic solvent, as a dope for spinning a hollow fiber, and the dope The present invention relates to a method for producing a copolyimide hollow fiber in which a liquid hollow fiber is formed and solidified.
〔従来の技術〕 ここで、特定の極性有機溶媒とはコポリイミドの溶解性
が良い水溶性の極性有機溶媒のことであり、具体的には
ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メ
チルピロリドン、ジメチルスルホキシド、ジメチルスル
ホン、ヘキサメチルホスホルアミド、テトラメチル尿素
およびピリジンからなる群から選ばれた一種あるいは二
種以上の混合溶媒をさす。[Prior Art] Here, the specific polar organic solvent is a water-soluble polar organic solvent having good solubility of copolyimide, and specifically, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide. , Dimethyl sulfone, hexamethylphosphoramide, tetramethylurea, and a mixed solvent of two or more selected from the group consisting of pyridine.
従来、ポリイミド中空糸の製造方法としては、種々の方
法が提案されており、たとえば、特開昭57-205517号公
報に記載されているように、ベンゾフエノンテトラカル
ボン酸系の芳香族ポリイミドをフエノール系化合物を主
成分とする溶媒に溶解させた溶液をドープ液として使用
して中空糸を製造する方法がある。また、特開昭57-167
414号公報に記載されているように、ビフエニルテトラ
カルボン酸系の芳香族ポリイミドをフエノール系化合物
を主成分とする溶媒に溶解させた溶液をドープ液として
使用して中空糸を製造する方法等が知られているが、こ
の方法によるとフエノール系化合物として、たとえば、
ｐ−クロルフエノールであれば、 （ｉ）高融点（43℃）であるため室温での取扱いが困
難、 （ii）高沸点（219.75℃）であるため中空糸製造の最終
段階で溶媒除去が困難、 （iii）有害、腐食性があるため作業性が悪い、 等の欠点を有しており、有利が方法とは言えない。Conventionally, as a method for producing a polyimide hollow fiber, various methods have been proposed. For example, as described in JP-A-57-205517, a benzophenonetetracarboxylic acid-based aromatic polyimide is used. There is a method of producing a hollow fiber by using a solution prepared by dissolving a phenolic compound as a main component as a dope solution. In addition, JP-A-57-167
As described in Japanese Patent No. 414, a method for producing a hollow fiber by using a solution prepared by dissolving a biphenyltetracarboxylic acid-based aromatic polyimide in a solvent containing a phenol-based compound as a main component as a dope solution, etc. Is known, but according to this method, as a phenol compound, for example,
With p-chlorophenol, (i) high melting point (43 ° C) makes it difficult to handle at room temperature, and (ii) high boiling point (219.75 ° C) makes it difficult to remove the solvent at the final stage of hollow fiber production. (Iii) Poor workability due to harmfulness and corrosiveness, etc., which is not an advantageous method.
本発明者らは耐熱性が高く、耐薬品性、機械的強度に優
れた芳香族ポリイミドの中空糸を有利に製造する方法に
ついて鋭意研究を行つた結果、ベンゾフエノンテトラカ
ルボン酸系の芳香族コポリイミドが特定の極性有機溶媒
に溶解しているコポリイミド溶液をドープ液として使用
して、中空糸を紡糸することによつて、耐熱性が高く、
耐薬品性、機械的強度に優れた芳香族コポリイミド中空
糸を有利に製造できることを見い出し、本発明に到達し
た。The present inventors have conducted extensive studies on a method for advantageously producing a hollow fiber of aromatic polyimide having high heat resistance, chemical resistance, and mechanical strength, and as a result, benzophenone tetracarboxylic acid-based aromatic Using a copolyimide solution in which copolyimide is dissolved in a specific polar organic solvent as a dope solution, by spinning a hollow fiber, high heat resistance,
The present inventors have found that an aromatic copolyimide hollow fiber excellent in chemical resistance and mechanical strength can be advantageously produced, and thus reached the present invention.
すなわち、本発明の要旨は、繰り返し単位の90〜70モル
％が式（Ｉ） で表わされる構造を有し、かつ繰り返し単位の10〜30モ
ル％が式（II） で表わされる構造を有するコポリイミドを主たる構成材
料とする中空糸であつて、該中空糸の外側表面と内側表
面にはさまれた内部に、両表面に連通しかつその平均孔
径が厚み方向において変化した傾斜型多孔質層を有する
コポリイミド中空糸及びその製造方法に存する。That is, the gist of the present invention is that 90 to 70 mol% of the repeating unit is represented by the formula (I). And having a structure represented by the formula (II) A hollow fiber mainly composed of a copolyimide having a structure represented by the following, inside the hollow fiber sandwiched between the outer surface and the inner surface, communicated with both surfaces and its average pore diameter in the thickness direction. The present invention resides in a copolyimide hollow fiber having a graded porous layer and a method for producing the same.
以下に本発明を詳しく説明する。本発明のコポリイミド
中空糸は、繰り返し単位の90〜70モル％が式（Ｉ） で表わされる構造を有し、かつ繰り返し単位の10〜30モ
ル％が式（II） で表わされる構造を有するコポリイミドを主たる構成材
料とする中空糸であつて、該中空糸の外側表面と内側表
面にはさまれた内部に、両表面に連通しかつその平均孔
径が厚み方向において変化した傾斜型多孔質層を有する
コポリイミド中空糸である。The present invention will be described in detail below. In the copolyimide hollow fiber of the present invention, 90 to 70 mol% of repeating units have the formula (I). And having a structure represented by the formula (II) A hollow fiber mainly composed of a copolyimide having a structure represented by the following, inside the hollow fiber sandwiched between the outer surface and the inner surface, communicated with both surfaces and its average pore diameter in the thickness direction. It is a copolyimide hollow fiber having a changed graded porous layer.
本発明においては、繰り返し単位の90〜70モル％が式
（Ｉ） で表わされる構造を有し、かつ繰り返し単位の10〜30モ
ル％が式（II） で表わされる構造を有するコポリイミドを用いることに
より、分離性能、耐熱性、耐薬品性及び機械的強度に優
れた中空糸を再現性よく安定的に製造することができ
る。In the present invention, 90 to 70 mol% of repeating units are represented by the formula (I). And having a structure represented by the formula (II) By using the copolyimide having the structure represented by, it is possible to stably produce a hollow fiber having excellent separation performance, heat resistance, chemical resistance and mechanical strength with good reproducibility.
分離膜の形状としては、シート状、スパイラル状、管
状、中空糸状等種々あるが、本発明のような中空糸状と
することにより単位容積当りの有効膜面積を大きくする
ことができ、また中空糸の外周側から加圧する場合に
は、管壁の厚さが小さい割に高圧に対する機械的強度が
高い等の利点が得られる。The shape of the separation membrane includes various shapes such as a sheet shape, a spiral shape, a tubular shape, and a hollow fiber shape, but the hollow fiber shape as in the present invention can increase the effective membrane area per unit volume, and the hollow fiber When the pressure is applied from the outer peripheral side, the advantages such as high mechanical strength against high pressure despite the small thickness of the tube wall can be obtained.
本発明のような両表面に連通しかつその平均孔径が厚み
方向において変化している傾斜型多孔質構造をとること
により、十分な透過速度及び機掛的強度を得ることがで
きる。比較的孔径の小さい多孔質層のみが存在している
と、多孔質層における透過抵抗が大きくなり、十分な透
過速度を得ることができない。また、比較的孔径の大き
い多孔質層のみが存在していると、多孔質層における透
過抵抗は減少するため好ましいが、多孔質層全体の機械
的強度が低下し、緻密層が存在する場合には緻密層を支
持することが困難となり好ましくない。Sufficient permeation rate and mechanical strength can be obtained by adopting the graded porous structure which is connected to both surfaces and has an average pore diameter varying in the thickness direction as in the present invention. If only the porous layer having a relatively small pore size exists, the permeation resistance in the porous layer becomes large, and a sufficient permeation rate cannot be obtained. Further, the presence of only the porous layer having a relatively large pore size is preferable because the permeation resistance in the porous layer is reduced, but the mechanical strength of the entire porous layer is lowered, and when the dense layer is present, Is not preferable because it becomes difficult to support the dense layer.
多孔質層の平均孔径は、厚み方向の各位置で１μｍ以下
であることが好ましい。これより孔径が大きいと機械的
強度が低下し好ましくない。The average pore diameter of the porous layer is preferably 1 μm or less at each position in the thickness direction. If the pore size is larger than this, the mechanical strength is lowered, which is not preferable.
また本発明の中空糸は、平均孔径が500Å以下であり、
厚みが１μｍ以下である緻密層を両表面のいずれか一方
又は両方に有していてもよい。平均孔径が500Åより大
きいと分離性能が低下し、また厚みがこれより厚いと透
過速度が低くなつて好ましくない。Further, the hollow fiber of the present invention has an average pore diameter of 500 Å or less,
A dense layer having a thickness of 1 μm or less may be provided on either one or both surfaces. If the average pore size is larger than 500Å, the separation performance will be deteriorated, and if the average pore size is larger than this, the permeation rate will be low, such being undesirable.
緻密層を両表面のいずれか一方又は両方に有している場
合には、緻密層に近い方の多孔質層の平均孔径が100〜1
000Å、緻密層から十分はなれた多孔質層の平均孔径が1
000〜5000Åであることが好ましい。これらの範囲より
孔径の小さいものは透過速度が小さくなり、これらの範
囲より孔径の大きいものは緻密層を支持することが困難
となり、機械的強度も小さくなるため、いずれも好まし
くない。また、多孔質層の孔径は緻密層の孔径よりも大
きくなければならない。When having a dense layer on one or both of both surfaces, the average pore diameter of the porous layer closer to the dense layer is 100 to 1
000Å, the average pore size of the porous layer well separated from the dense layer is 1
It is preferably 000 to 5000Å. Those having a pore diameter smaller than these ranges have a low permeation rate, and those having a pore diameter larger than these ranges have difficulty in supporting the dense layer and also have low mechanical strength, and thus are not preferable. The pore size of the porous layer must be larger than that of the dense layer.
次に、上記本発明中空糸の製造方法について説明する。Next, a method for producing the hollow fiber of the present invention will be described.
本発明において使用されるコポリイミドは一般式 の繰り返し単位の存在を特徴とするコポリイミドであ
り、ここで上記繰り返し単位の10〜30モル％はＲが を表わすものであり、上記繰り返し単位の90〜70モル％
はＲ を表わすものである。The copolyimide used in the present invention has the general formula Is a copolyimide characterized by the presence of a repeating unit of Represents 90 to 70 mol% of the above repeating unit
Is R Represents.
このコポリイミドは3,3′,4,4′−ベンゾフエノンテト
ラカルボン酸二無水物を適当なモル比の4,4′−メチレ
ンビスフエニルイソシアネート（4,4′−ジフエニルメ
タンジイソシアネート）およびトリレンジイソシアネー
ト（2,6−異性体、あるいは2,4−異性体、あるいはそれ
らの混合物）とともに極性溶媒の存在下で反応させるこ
とにより容易に得ることができる。This copolyimide comprises 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in an appropriate molar ratio of 4,4'-methylenebisphenyl isocyanate (4,4'-diphenylmethane diisocyanate). And tolylene diisocyanate (2,6-isomer, or 2,4-isomer, or a mixture thereof) can be easily obtained by reacting in the presence of a polar solvent.
この重合に用いられる溶媒は極性有機溶媒であり、ジメ
チルホルムアミド、ジメチルアセトアミド、Ｎ−メチル
ピロリドン、ジメチルスルホキシド、ジメチルスルホ
ン、ヘキサメチルホスホルアミド、テトラメチル尿素、
ピリジンから選ばれた一種または二種以上の混合物であ
る。好ましくはジメチルホルムアミド、ジメチルアセト
アミド、Ｎ−メチルピロリドン、より好ましくはジメチ
ルホルムアミドが好適に用いられる。The solvent used for this polymerization is a polar organic solvent, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dimethylsulfone, hexamethylphosphoramide, tetramethylurea,
One or a mixture of two or more selected from pyridine. Preferably, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and more preferably dimethylformamide are suitably used.
上述の反応に使用する極性有機溶媒の分量はすべての反
応体が最初に溶解するのに少なくとも十分なものである
ことが好ましい。溶媒の使用量はコポリイミドの粘度に
よつて調節されるものであり、重合体固形分（コポリイ
ミド）の重量％はそれほど重要でないが、典型的には約
５重量％から約35重量％までが好ましい。The amount of polar organic solvent used in the above reaction is preferably at least sufficient to initially dissolve all reactants. The amount of solvent used is controlled by the viscosity of the copolyimide, and the weight% of polymer solids (copolyimide) is not critical, but typically from about 5% to about 35% by weight. Is preferred.
コポリイミドの対数粘度は0.1dl/g以上、より好ましく
は0.3〜4dl/g（30℃、Ｎ−メチルピロリドン中0.5％）
の範囲から選ばれる。Copolyimide has an inherent viscosity of 0.1 dl / g or more, more preferably 0.3 to 4 dl / g (30 ° C, 0.5% in N-methylpyrrolidone).
Selected from the range.
上記のドープ液を用いて中空糸を形成する方法として
は、基本的には、中空糸の内側表面を芯液あるいは芯ガ
ス等の流体と接触させ、かつ該中空糸の外側表面を凝固
浴と接触させることによつて行う。本発明による中空糸
はこのような芯液あるいは芯ガスと凝固浴による凝固条
件によつて透過性能がコントロールされ、さらに熱処理
条件によつても透過性能と機械的強度がコントロールさ
れる。As a method for forming a hollow fiber using the above dope solution, basically, the inner surface of the hollow fiber is contacted with a fluid such as core liquid or core gas, and the outer surface of the hollow fiber is used as a coagulation bath. This is done by bringing them into contact. The permeation performance of the hollow fiber according to the present invention is controlled by the coagulation conditions of the core liquid or core gas and the coagulation bath, and the permeation performance and mechanical strength are also controlled by the heat treatment conditions.
また、中空糸用ノズル出口と凝固浴間の距離（エアギヤ
ツプ）の設定の仕方によつても凝固条件をコントロール
することが可能である。Further, the coagulation condition can be controlled also by setting the distance (air gear cup) between the hollow fiber nozzle outlet and the coagulation bath.
芯液あるいは芯ガスと凝固浴による凝固条件のコントロ
ールとは、具体的には凝固速度の制御であり、凝固速度
の速い側の表面ほど緻密層が形成されやすい。The control of the coagulation conditions by the core liquid or the core gas and the coagulation bath is specifically the control of the coagulation rate, and the denser layer is more likely to be formed on the surface with the faster coagulation rate.
本発明では上記のコントロールを行うことにより広範囲
の透過性能を有する中空糸を容易に製造することができ
る。たとえば、中空糸の内側の表面に、透過性能をコン
トロールする緻密層を形成させ、外側の表面に傾斜型多
孔質層を形成させるならば、芯液としては良溶媒である
極性有機溶媒、すなわちジメチルホルムアミド、ジメチ
ルアセトアミド、Ｎ−メチルピロリドン、ジメチルスル
ホキシド、ジメチルスルホン、ヘキサメチルホスホルア
ミド、テトラメチル尿素、ピリジン等が挙げられ、また
貧溶媒である水、プロパノール等の低級アルコール類、
アセトン等のケトン類、エチレングリコール等のエーテ
ル類、トルエン等の芳香族類、あるいはこれらの混合物
等が挙げられる。これらの中で良溶媒と貧溶媒の特定の
混合物が好ましい。なかでもジメチルホルムアミドと水
を特定の割合で混合した混合物が特に好適に用いられ
る。貧溶媒とは溶液中の溶媒と相溶性を有し、かつ溶質
との溶解性の低い溶媒であり、ここではドープ液との相
溶性が良好であつてコポリイミドとの溶解性が低いもの
である。In the present invention, by carrying out the above control, hollow fibers having a wide range of permeation performance can be easily produced. For example, if a dense layer that controls permeation performance is formed on the inner surface of the hollow fiber and a graded porous layer is formed on the outer surface, a polar organic solvent that is a good solvent for the core liquid, that is, dimethyl Formamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dimethylsulfone, hexamethylphosphoramide, tetramethylurea, pyridine and the like, and also poor solvents such as water and lower alcohols such as propanol,
Examples thereof include ketones such as acetone, ethers such as ethylene glycol, aromatics such as toluene, and a mixture thereof. Of these, specific mixtures of good and poor solvents are preferred. Among them, a mixture obtained by mixing dimethylformamide and water in a specific ratio is particularly preferably used. The poor solvent has compatibility with the solvent in the solution, and is a solvent having low solubility with the solute, and here, the solubility with the copolyimide is low and the compatibility with the dope solution is good. is there.
水とジメチルホルムアミドのような良溶媒と貧溶媒の混
合割合は特に制限されるものではなく、混合割合によつ
て異つた透過性能を有する中空糸が得られる。The mixing ratio of water and a good solvent such as dimethylformamide and a poor solvent is not particularly limited, and hollow fibers having different permeation performance can be obtained depending on the mixing ratio.
芯液の代りに芯ガスとして空気、窒素等の不活性気体を
用いてもよい。Instead of the core liquid, an inert gas such as air or nitrogen may be used as the core gas.
凝固浴としては、水、またはこれに少量の、良溶媒であ
る極性有機溶媒を加えたものが用いられる。なかでも水
が好適に用いられる。中空糸用ノズルは凝固浴上に適当
な間隔（エアギヤツプ）をおいて設置されることが好ま
しい。また、中空糸の外側表面に緻密層を形成させる場
合には、芯ガスとして空気等を用い、液体の凝固浴とし
て水あるいは水と良溶媒である極性有機溶媒との混合物
等を用いればよい。As the coagulation bath, water or a mixture of a small amount of a polar organic solvent which is a good solvent is used. Of these, water is preferably used. The hollow fiber nozzles are preferably installed on the coagulation bath at appropriate intervals (air gear cups). When a dense layer is formed on the outer surface of the hollow fiber, air or the like may be used as the core gas, and water or a mixture of water and a polar organic solvent which is a good solvent may be used as the liquid coagulation bath.
この発明の方法において、ポリイミド組成物（ドープ
液）の中空糸状体を形成する中空糸用ノズルとしては、
ポリマー溶液組成物のドープ液から中空糸状体を押出し
て形成することができれば、どのような形式の中空糸用
ノズルであつてもよく、例えば、チユーブ・イン・オリ
フイス型ノズル（tube in orifice type），セグメンテ
イツド・アーク型ノズル（Segmented arc type）などを
挙げることができる。この発明では、チユーブ・イン・
オリフイス型ノズルが、中空糸用ノズルとして好適であ
る。このチユーブ・イン・オリフイス型ノズルとして
は、ノズルヘツドの底面の中央に開口しているオリフイ
ス（内径0.2〜2mm）の中央に、チユーブ（外径0.15〜1.
6mm、内径0.05〜1.4mm）が位置しているものであり、オ
リフイスの開口内周面とチユーブの外周面との間の空隙
部（現状部）からドープ液を背圧で押し出し、同時にチ
ユーブの内孔から気体、または液体（芯液ともいう）を
供給して、中空糸状体を形成するのである。In the method of the present invention, as the hollow fiber nozzle for forming the hollow fiber-shaped body of the polyimide composition (dope liquid),
A hollow fiber nozzle of any type may be used as long as it can be formed by extruding a hollow fiber material from a dope solution of a polymer solution composition, for example, a tube-in-orifice type nozzle (tube in orifice type). , Segmented arc type nozzles and the like. In this invention, the tube in
An orifice type nozzle is suitable as a hollow fiber nozzle. For this tube-in-olifis type nozzle, the tube (outer diameter 0.15 to 1.5 mm) is located at the center of the orifice (inner diameter 0.2 to 2 mm) that opens at the center of the bottom of the nozzle head.
6 mm, inner diameter 0.05 to 1.4 mm) is located, and the dope liquid is pushed out by the back pressure from the gap (current state) between the inner peripheral surface of the opening of the orifice and the outer peripheral surface of the tube. Gas or liquid (also referred to as core liquid) is supplied from the inner hole to form the hollow fiber body.
この発明では、前述の中空糸状体の押し出しの際に、前
記中空糸用ノズルの内部のチユーブから押し出されつつ
ある中空糸状体の内部へ、気体または液体（芯液）を供
給しながら行うのである。In the present invention, when the hollow fiber-shaped body is extruded, the gas or liquid (core liquid) is supplied to the inside of the hollow fiber-shaped body being extruded from the tube inside the hollow fiber nozzle. .
つぎに、中空糸形成時の操作条件について説明する。中
空糸の製造条件、例えば、ドープ液の押出し速度、芯液
あるいは芯ガスの吐出量、ノズル出口と凝固浴間の距離
（エアギヤツプ）、凝固時間、中空糸の引取り速度等
は、中空糸の外径100〜1000μｍ、管壁の厚さ50〜800μ
ｍとなるようにそれぞれの条件を調節することにより決
められるのであつて、目的とする寸法に形成されるなら
ば、特に制限されない。Next, the operating conditions for forming the hollow fiber will be described. The manufacturing conditions of the hollow fiber, such as the extrusion speed of the dope liquid, the discharge amount of the core liquid or the core gas, the distance between the nozzle outlet and the coagulation bath (air gear cup), the coagulation time, the take-up speed of the hollow fiber, etc. Outer diameter 100-1000μm, tube wall thickness 50-800μ
It is determined by adjusting the respective conditions so that it becomes m, and is not particularly limited as long as it is formed to a target dimension.
例えば、中空糸外径670μｍ、内径350μの中空糸を製造
する場合には、ドープ液濃度を５〜35重量％とすると、
ドープ液の押出し速度として0.1〜100g/分、芯液として
水とジメチルホルムアミドを重量比で40〜70/60〜30の
割合で十分混合した液、該芯液の吐出量として0.03〜30
g/分、エアギヤツプとして０〜3m、凝固時間１〜600
秒、引取り速度0.1〜200m/分で製造することができる。For example, in the case of producing a hollow fiber having an outer diameter of 670 μm and an inner diameter of 350 μ, if the dope concentration is 5 to 35% by weight,
Extrusion rate of the dope liquid is 0.1 to 100 g / min, a liquid in which water and dimethylformamide are sufficiently mixed in a weight ratio of 40 to 70/60 to 30 as a core liquid, and the discharge amount of the core liquid is 0.03 to 30.
g / min, 0-3m as air gear cup, coagulation time 1-600
It can be manufactured at a take-up speed of 0.1 to 200 m / min.
中空糸用ノズルから垂直真下に押出されたドープ液およ
び芯液または芯ガスは凝固液中に導かれるが、このとき
ノズル出口と凝固浴の間に間隔があると、この部分でド
ープ液中の溶媒の一部が大気中に蒸発し、一方で、芯液
での凝固速度が速い場合は中空糸内側表面よりゲル化が
進行し、あるいは芯ガスが空気であつて凝固浴中より凝
固速度が遅い場合は中空糸外側表面よりゲル化が進行す
る。The dope liquid and core liquid or core gas extruded vertically downward from the hollow fiber nozzle are introduced into the coagulating liquid. At this time, if there is a gap between the nozzle outlet and the coagulating bath, the dope liquid in the coagulating liquid is When a part of the solvent evaporates into the atmosphere, on the other hand, the coagulation rate in the core liquid is high, gelation progresses from the inner surface of the hollow fiber, or when the core gas is air and the coagulation rate is higher than in the coagulation bath. When it is slow, gelation proceeds from the outer surface of the hollow fiber.
中空糸用ノズルの出口を凝固浴中に浸漬して、直接凝固
浴中に押出してもよい。The outlet of the hollow fiber nozzle may be immersed in the coagulation bath and extruded directly into the coagulation bath.
こうして形成された中空糸状体を十分に乾燥して本発明
の中空糸は製造される。The hollow fiber material thus formed is sufficiently dried to manufacture the hollow fiber of the present invention.
また、本発明の中空糸は、このあと乾燥炉で熱処理を行
うこともできる。熱処理を行うことによつて膜の機械的
強度が耐薬品性、耐溶剤性を増大させることができる。
また熱処理の温度に応じて膜の分離性能を制御すること
が可能であるので、目的とするガス透過速度が得られる
よう熱処理温度、時間等を決めればよい。たとえば、熱
処理の温度としては、100〜350℃、好ましくは250〜350
℃、熱処理の時間としては、１〜60分、好ましくは３〜
30分程度が好適である。Further, the hollow fiber of the present invention can be subsequently heat-treated in a drying furnace. By performing the heat treatment, the mechanical strength of the film can increase chemical resistance and solvent resistance.
Further, since it is possible to control the separation performance of the membrane according to the temperature of the heat treatment, the heat treatment temperature, time, etc. may be determined so that the desired gas permeation rate can be obtained. For example, as the temperature of the heat treatment, 100 ~ 350 ℃, preferably 250 ~ 350
The temperature for heat treatment is 1 to 60 minutes, preferably 3 to
About 30 minutes is suitable.
熱処理の仕方としては徐々に昇温させてもよいし、急激
に昇温させてもよい。As a method of heat treatment, the temperature may be raised gradually or may be raised rapidly.
このようにして本発明の中空糸は製造される。In this way, the hollow fiber of the present invention is manufactured.
なお、上記の中空糸の製造工程において、乾燥、熱処理
以外の部分は室温、大気雰囲気下で行うことができる。
また中空糸は適当な張力下で連続的に製造される。In addition, in the above-mentioned hollow fiber manufacturing process, parts other than drying and heat treatment can be carried out at room temperature in an air atmosphere.
Hollow fibers are continuously manufactured under appropriate tension.
本発明によるコポリイミド中空糸は製造時の諸条件をコ
ントロールすることにより広範囲の性能を付与すること
ができる。The copolyimide hollow fiber according to the present invention can be given a wide range of performance by controlling various conditions during production.
たとえば芯液の組成が極性有機溶媒であるジメチルホル
ムアミド55〜45と水45〜55（重量比）の混合溶液であ
り、熱処理温度が250〜350℃、好ましくは280〜320℃で
ある場合、得られるコポリイミド中空糸は水蒸気透過速
度10-2〜10-4cm3（STP）／cm2・sec・cmHg,メタン透過
速度10-4〜10-7cm3（STP）／cm2・sec・cmHg（いずれも
20〜40℃、１〜5Kg/cm2での測定値）の性能を持ち、メ
タン中の水蒸気の除去に対して効果的に用いることがで
きる。For example, when the composition of the core liquid is a mixed solution of dimethylformamide 55 to 45 which is a polar organic solvent and water 45 to 55 (weight ratio), and the heat treatment temperature is 250 to 350 ° C, preferably 280 to 320 ° C, it is obtained. The copolyimide hollow fiber used has a water vapor transmission rate of 10 -2 to 10 -4 cm 3 (STP) / cm 2 · sec · cmHg, and a methane transmission rate of 10 -4 to 10 −7 cm 3 (STP) / cm 2 · sec ・cmHg (both
It has a performance of 20 to 40 ° C. and a measured value at 1 to 5 kg / cm 2 ) and can be effectively used for removing water vapor in methane.
つぎに本発明の中空糸を製造する装置について説明す
る。本発明の方法は、第１図に示すような紡糸装置によ
つて行うことができる。Next, an apparatus for producing the hollow fiber of the present invention will be described. The method of the present invention can be carried out by a spinning device as shown in FIG.
すなわち、コポリイミド溶液（ドープ液）／を適当な孔
径を有する過フイルター２を通過させながら連続的に
チユーブ・イン・オリフイス型ノズルを有する紡糸用ノ
ズルヘツドに供給し、同時に該ノズルのチユーブに芯液
（あるいは芯ガス）４を供給しつつ、該ノズルのオリフ
イス内周面とチユーブ外周面との間の環状空隙からドー
プ液を中空糸状に押出し、ドープ液の中空糸状体を形成
し、その中空糸状体に引張り力を加えて伸張させながら
凝固浴５の中で凝固させ、次いで、その中空糸状体を適
当な張力下乾燥、熱処理炉６を通過させ、巻取機７によ
り適当な張力、曲率で巻き取る。That is, a copolyimide solution (dope solution) / is continuously supplied to a spinning nozzle head having a tube-in-olift type nozzle while passing through an overfilter 2 having an appropriate pore size, and at the same time, a core liquid is supplied to the tube of the nozzle. While supplying (or core gas) 4, the dope solution is extruded into a hollow fiber form from the annular gap between the orifice inner peripheral surface and the tube outer peripheral surface of the nozzle to form a hollow fiber body of the dope solution. The body is coagulated in a coagulation bath 5 while being stretched by applying a tensile force, and then the hollow fiber body is dried under an appropriate tension and passed through a heat treatment furnace 6 by a winder 7 with an appropriate tension and curvature. Roll up.
本発明の方法で製造されるコポリイミド中空糸は耐熱
性、耐薬品性、機械的強度が優れていると共に芯液の組
成のコントロールや、熱処理条件のコントロールによつ
てガス透過性能の調節が可能であり、ガス分離膜として
きわめて好適である。また、液体分離膜、透析膜、各種
膜材料を支持する多孔質体等としても使用することがで
きる。The copolyimide hollow fiber produced by the method of the present invention has excellent heat resistance, chemical resistance, and mechanical strength, and the gas permeation performance can be adjusted by controlling the composition of the core liquid and the heat treatment conditions. And is very suitable as a gas separation membrane. It can also be used as a liquid separation membrane, a dialysis membrane, a porous body supporting various membrane materials, and the like.
以下に実施例を挙げて本発明をさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
製造参考例−１ 米国特許第3708458号の実施例４に述べられている手順
を使用し3,3′,4,4′−ベンゾフエノンテトラカルボン
酸無水物と80モル％のトリレンジイソシアネート（2,4
−異性体約80モル％と2,6−異性体約20モル％の混合
物）および20モル％の4,4′−ジフエニルメタンジイソ
シアネートを含む混合物より共重合ポリイミドを重合し
た。Preparation Reference Example-1 Using the procedure described in Example 4 of U.S. Pat. No. 3,708,458 3,3 ', 4,4'-benzophenonetetracarboxylic anhydride and 80 mol% tolylene diisocyanate ( 2,4
A copolymerized polyimide was polymerized from a mixture containing about 80 mol% of isomers and about 20 mol% of 2,6-isomers) and 20 mol% of 4,4'-diphenylmethane diisocyanate.
重合溶媒はN,N′−ジメチルホルムアミドを使用し樹脂
物濃度は21重量％であつた。The polymerization solvent was N, N'-dimethylformamide, and the resin concentration was 21% by weight.
このコポリイミドは30℃において固有粘度（ジメチルホ
ルムアミド中0.5％）0.6dl/gを有していた。This copolyimide had an intrinsic viscosity of 0.6 dl / g (0.5% in dimethylformamide) at 30 ° C.
実施例１ 製造参考例１に従つてコポリイミドを製造し、ジメチル
ホルムアミドを添加して固形分濃度を25重量％に調整し
た。Example 1 A copolyimide was produced according to Production Reference Example 1, and dimethylformamide was added to adjust the solid content concentration to 25% by weight.
中空糸製造用ノズルから上記コポリイミド溶液を一定流
量で押出し、同時に芯液として水とジメチルホルムアミ
ドを50/50（重量比）の割合で混合した液を一定流量で
押出し、形成された中空糸状体を約2cmのエアギヤツプ
をとつて水からなる凝固浴中へ導き約10秒間浸漬したの
ち一定速度6m/分で巻き取つた。このあと水中に５分間
浸漬し、一昼夜風乾した。Hollow fiber body formed by extruding the above copolyimide solution at a constant flow rate from a hollow fiber manufacturing nozzle, and at the same time extruding a liquid mixture of water and dimethylformamide at a ratio of 50/50 (weight ratio) as a core fluid at a constant flow rate. Was taken into a coagulation bath of water through an air gear of about 2 cm, immersed for about 10 seconds, and then wound up at a constant speed of 6 m / min. Then, it was immersed in water for 5 minutes and air-dried overnight.
この中空糸の形状及び気体透過速度の測定結果を表１に
示した。The measurement results of the shape and gas permeation rate of this hollow fiber are shown in Table 1.
水蒸気の透過速度は、80℃の飽和水蒸気を含む空気を中
空糸の外側に供給し、中空糸の内側（透過側）を減圧に
して測定した。The water vapor permeation rate was measured by supplying air containing saturated water vapor at 80 ° C. to the outside of the hollow fiber and depressurizing the inside (permeation side) of the hollow fiber.
CH4，N2の透過速度は、20℃、2Kg/cm2Ｇの各純ガスを中
空糸の外側に供給し、中空糸内側を大気に開放して測定
した。The CH 4 and N 2 permeation rates were measured by supplying each pure gas at 20 ° C. and 2 kg / cm 2 G to the outside of the hollow fiber and opening the inside of the hollow fiber to the atmosphere.
実施例２〜３ エアギヤツプを12cmとしたこと以外は実施例１と同様に
して製造した中空糸を、さらに150〜350℃の範囲の各温
度でそれぞれ30分間熱処理を行つた。Examples 2 to 3 Hollow fibers produced in the same manner as in Example 1 except that the air gear cup was 12 cm were further heat-treated for 30 minutes at each temperature in the range of 150 to 350 ° C.
この中空糸の形状及び気体透過速度の測定結果を表１に
示した。The measurement results of the shape and gas permeation rate of this hollow fiber are shown in Table 1.
実施例４〜７ 芯液の組成として水とジメチルホルムアミドの割合を0/
100,25/75,75/25,100/0（重量比）としたこと以外は実
施例１と同様にして中空糸を製造し、さらに300℃で約3
0分間熱処理を行つた。Examples 4 to 7 The ratio of water to dimethylformamide was 0 / as the composition of the core liquid.
A hollow fiber was produced in the same manner as in Example 1 except that 100, 25/75, 75/25, 100/0 (weight ratio) was used, and further, at 300 ° C., about 3
Heat treatment was performed for 0 minutes.
この中空糸の形状及び気体透過速度の測定結果を表１に
示した。The measurement results of the shape and gas permeation rate of this hollow fiber are shown in Table 1.
実施例８ エアギヤツプを12cmとし、芯ガスとして空気を用いたこ
と以外は実施例１と同様にして中空糸を製造し、さらに
200℃で約30分間熱処理を行つた。この中空糸の形状及
び気体透過速度の測定結果を表１に示した。Example 8 A hollow fiber was produced in the same manner as in Example 1 except that the air gap was 12 cm and air was used as the core gas.
Heat treatment was performed at 200 ° C. for about 30 minutes. The measurement results of the shape and gas permeation rate of this hollow fiber are shown in Table 1.
実施例９ 凝固浴としてエアギヤツプ125cmの空気層及び芯液水／
ジメチルホルムアミド＝15/85（重量比）を使用したこ
と以外は実施例１と同様にして中空糸を製造し、さらに
300℃で約30分間熱処理を行つた。この中空糸の形状及
び気体透過速度の測定結果を表１に示した。Example 9 As a coagulating bath, an air layer of 125 cm of air gear and core water /
A hollow fiber was produced in the same manner as in Example 1 except that dimethylformamide = 15/85 (weight ratio) was used.
Heat treatment was performed at 300 ° C. for about 30 minutes. The measurement results of the shape and gas permeation rate of this hollow fiber are shown in Table 1.
〔発明の効果〕 本発明の方法で製造されるコポリイミド中空糸は耐熱
性、耐薬品性、機械的強度が優れていると共に芯液の組
成のコントロールや、熱処理条件のコントロールによつ
てガス透過性能の調節が可能であり、ガス分離膜として
きわめて好適である。また、液体分離膜、透析膜、各種
膜材料を支持する多孔質体等としても使用することがで
きる。 [Effect of the invention] The copolyimide hollow fiber produced by the method of the present invention has excellent heat resistance, chemical resistance, and mechanical strength, and at the same time controls the composition of the core liquid and the heat treatment conditions to allow gas permeation. The performance can be adjusted, and it is extremely suitable as a gas separation membrane. It can also be used as a liquid separation membrane, a dialysis membrane, a porous body supporting various membrane materials, and the like.
第１図は本発明の中空糸を製造する紡糸装置の一例の概
略説明図である。１はドープ液、２は過フイルター、
３は紡糸用ノズル、４は芯液又は芯ガス、５は凝固浴、
６は乾燥・熱処理炉、７は巻取機をそれぞれ示す。FIG. 1 is a schematic explanatory view of an example of a spinning device for producing the hollow fiber of the present invention. 1 is a dope solution, 2 is an overfilter,
3 is a spinning nozzle, 4 is a core liquid or core gas, 5 is a coagulation bath,
Reference numeral 6 represents a drying / heat treatment furnace, and 7 represents a winding machine.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 今奈良 徹 神奈川県横浜市緑区鴨志田町1000番地 三 菱化成工業株式会社総合研究所内 (56)参考文献 特開 昭57−205517（ＪＰ，Ａ) 特開 昭57−167414（ＪＰ，Ａ) 特開 昭60−150806（ＪＰ，Ａ) 特開 昭61−19813（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toru Imanara 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Kogyo Co., Ltd. (56) Reference JP-A-57-205517 (JP, A) JP-A-57-167414 (JP, A) JP-A-60-150806 (JP, A) JP-A-61-19813 (JP, A)
Claims (9)
ル％が式（II） で表わされる構造を有するコポリイミドを主たる構成材
料とする中空糸であって、該中空糸の外側表面と内側表
面にはさまれた内部に、両表面に連通しかつその平均孔
径が厚み方向において変化した傾斜型多孔質層を有する
コポリイミド中空糸。1. 90 to 70 mol% of repeating units are of formula (I) And having a structure represented by the formula (II) A hollow fiber whose main constituent material is copolyimide having a structure represented by the following: inside the hollow fiber sandwiched between the outer surface and the inner surface, and communicating with both surfaces and the average pore diameter in the thickness direction. A copolyimide hollow fiber having an altered graded porous layer.
１μｍ以下であることを特徴とする特許請求の範囲第１
項記載のコポリイミド中空糸。2. The average pore diameter of the porous layer is 1 μm or less at each position in the thickness direction.
The copolyimide hollow fiber according to the item.
が500Å以下であり、厚みが１μｍ以下である緻密層を
有し、内部に多孔質層を有することを特徴とする特許請
求の範囲第１項又は第２項記載のコポリイミド中空糸。3. A dense layer having an average pore size of 500Å or less and a thickness of 1 μm or less on one or both of both surfaces, and a porous layer inside. The copolyimide hollow fiber according to item 1 or 2.
0〜1000Åであり、緻密層から十分はなれた多孔質層の
平均孔径が1000〜5000Åであることを特徴とする特許請
求の範囲第３項記載のコポリイミド中空糸。4. The average pore diameter of the porous layer closer to the dense layer is 10
The copolyimide hollow fiber according to claim 3, characterized in that the average pore diameter of the porous layer sufficiently separated from the dense layer is 1000 to 5000Å.
ル％が式（II） で表わされる構造を有するコポリイミドを、ジメチルホ
ルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリ
ドン、ジメチルスルホキシド、ジメチルスルホン、ヘキ
サメチルホスホルアミド、テトラメチル尿素およびピリ
ジンからなる群から選ばれた一種あるいは二種以上の混
合物から成る極性有機溶媒に溶解させたコポリイミド溶
液をドープ液として使用し、前記ドープ液を中空糸用ノ
ズルから押出し、同時に芯液あるいは芯ガスを該ノズル
の中心部より押出して中空糸状体を形成し、該中空糸状
体を凝固させ、乾燥させることを特徴とするコポリイミ
ド中空糸の製造方法。5. 90 to 70 mol% of the repeating unit has the formula (I) And having a structure represented by the formula (II) A copolyimide having a structure represented by one or more selected from the group consisting of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dimethylsulfone, hexamethylphosphoramide, tetramethylurea and pyridine. A copolyimide solution dissolved in a polar organic solvent consisting of a mixture of the above is used as a dope solution, and the dope solution is extruded from a hollow fiber nozzle, and at the same time, a core liquid or core gas is extruded from the central part of the nozzle to form a hollow fiber body. The method for producing a copolyimide hollow fiber, comprising: forming a hollow fiber-like material, solidifying the hollow fiber-like material, and drying.
に温度100〜350℃の条件下で熱処理することを特徴とす
る特許請求の範囲第５項記載の製造方法。6. The method according to claim 5, wherein the hollow fiber material is coagulated and dried, and then heat-treated at a temperature of 100 to 350 ° C.
なる特許請求の範囲第５項ないし第６項のいずれか１つ
の項記載の製造方法。7. The method according to any one of claims 5 to 6, wherein the core liquid is a mixture of a polar organic solvent and a poor solvent.
第５項ないし第６項のいずれか１つの項記載の製造方
法。8. The method according to any one of claims 5 to 6, wherein the core gas is an inert gas.
で凝固させる特許請求の範囲第５項ないし第６項のいず
れか１つの項記載の製造方法。9. The method according to any one of claims 5 to 6, wherein the hollow fiber material is coagulated in a mixed liquid of a polar organic solvent and water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61069471A JPH073004B2 (en) | 1986-03-27 | 1986-03-27 | Copolyimide hollow fiber and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61069471A JPH073004B2 (en) | 1986-03-27 | 1986-03-27 | Copolyimide hollow fiber and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62231017A JPS62231017A (en) | 1987-10-09 |
| JPH073004B2 true JPH073004B2 (en) | 1995-01-18 |
Family
ID=13403619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61069471A Expired - Fee Related JPH073004B2 (en) | 1986-03-27 | 1986-03-27 | Copolyimide hollow fiber and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH073004B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR8707585A (en) * | 1986-12-15 | 1989-03-14 | Mitsubishi Chem Ind | SEPARATION METHOD FOR A LIQUID MIXTURE |
| US4881954A (en) * | 1987-07-31 | 1989-11-21 | Union Carbide Corporation | Permeable membranes for enhanced gas separation |
| US4988371A (en) * | 1989-09-12 | 1991-01-29 | The Dow Chemical Company | Novel alicyclic polyimide gas separation membranes |
| US5026823A (en) * | 1989-09-12 | 1991-06-25 | The Dow Chemical Company | Novel alicyclic polyimides and a process for making the same |
| JPH0761432B2 (en) * | 1992-01-14 | 1995-07-05 | 工業技術院長 | Method for producing highly functional asymmetric membrane |
| US20120123079A1 (en) * | 2009-07-23 | 2012-05-17 | Evonik Fibres Gmbh | Polyimide membranes made of polymerization solutions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57167414A (en) * | 1981-04-03 | 1982-10-15 | Ube Ind Ltd | Production of polyimide hollow fiber |
| JPS57205517A (en) * | 1981-06-11 | 1982-12-16 | Ube Ind Ltd | Preparation of polyimide hollow fiber |
| JPS60150806A (en) * | 1984-01-20 | 1985-08-08 | Agency Of Ind Science & Technol | Preparation of polyimide hollow yarn membrane |
| JPS6119613A (en) * | 1984-07-07 | 1986-01-28 | Mitsui Petrochem Ind Ltd | Production of partially cyclized polyacetylene |
-
1986
- 1986-03-27 JP JP61069471A patent/JPH073004B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62231017A (en) | 1987-10-09 |
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