JPH06121920A - Hollow fiber membrane - Google Patents
Hollow fiber membraneInfo
- Publication number
- JPH06121920A JPH06121920A JP4073308A JP7330892A JPH06121920A JP H06121920 A JPH06121920 A JP H06121920A JP 4073308 A JP4073308 A JP 4073308A JP 7330892 A JP7330892 A JP 7330892A JP H06121920 A JPH06121920 A JP H06121920A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- hollow fiber
- oxygen
- sec
- stp
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は特定の酸素／窒素の分離
係数を有する中空繊維膜に関するものであり、ボイラー
供給水脱酸素装置等用の気液接触装置、培養槽等に用い
られるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hollow fiber membrane having a specific oxygen / nitrogen separation coefficient, and is used for a gas-liquid contactor such as a boiler feed water deoxygenator, a culture tank and the like. is there.
【０００２】[0002]
【従来の技術】気液接触用隔膜として用いられる中空繊
維膜としては、多孔質層と非多孔質層とからなり、酸素
／窒素の分離係数が１.２以上のものが知られている
（特開昭５９−１９６７０６号）。2. Description of the Related Art As a hollow fiber membrane used as a gas-liquid contacting membrane, one having a porous layer and a non-porous layer and having an oxygen / nitrogen separation coefficient of 1.2 or more is known ( JP-A-59-196706).
【０００３】かかる中空繊維膜は、各種用途に用いられ
るが、よりガス交換速度が高い中空繊維膜が要望されて
いる。Although such hollow fiber membranes are used for various purposes, there is a demand for hollow fiber membranes having a higher gas exchange rate.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、気液接触装
置に用いた場合、ガス交換速度がより向上した中空繊維
膜を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a hollow fiber membrane having a higher gas exchange rate when used in a gas-liquid contactor.
【０００５】[0005]
【課題を解決するための手段】本発明は２５℃における
酸素透過速度Ｑ(Ｏ2)が１×１０-6［cm3（ＳＴＰ）／cm
2・sec・cmＨg]以上であり、酸素／窒素の分離係数が
０.９４〜１.１５であり、かつ実質的にエタノールを透
過せず、空孔率が７〜５０％であり、主としてポリオレ
フィン系重合体からなり、内径が１０〜５００μｍでか
つ厚さが５〜１００μｍであることを特徴とする中空繊
維膜、又、該膜が圧力差０.５kgf／cm2でのエタノール
透過量が３００cm3／(min・m2)以下または／および空孔
率が７〜５０％であるものに関する。The present invention has an oxygen permeation rate Q (O 2 ) of 1 × 10 −6 [cm 3 (STP) / cm at 25 ° C.
2 · sec · cmHg] or more, the separation coefficient of oxygen / nitrogen is 0.94 to 1.15, it is substantially impermeable to ethanol, and the porosity is 7 to 50%. A hollow fiber membrane composed of a polymer, having an inner diameter of 10 to 500 μm and a thickness of 5 to 100 μm, and having a pressure difference of 0.5 kgf / cm 2 and an ethanol permeation amount of 300 cm. 3 / (min · m 2 ) or less and / or a porosity of 7 to 50%.
【０００６】本発明の中空繊維膜は、膜内部に微細な細
孔（空隙）を有するものの、膜の表裏は実質上細孔によ
って連通していない、所謂非連通孔タイプの多孔質膜で
ある。膜内部に細孔が多く存在するほど酸素や二酸化炭
素等のガス透過速度が高くなり、気体−液体間のガス交
換速度が増す。しかしながら、空孔率を高くし過ぎると
細孔は互いに連結し、膜の表裏を連通する細孔（連通
孔）が発生する。そのため本発明の膜は、その空孔率
（体積空孔率）が７〜５０％のものが好ましく、膜の製
造方法によって多少異なるが、１０〜３５％のものがよ
り好ましい。本発明での膜は、上記の様に実質上連通孔
を有しない多孔質膜、換言すると、部分的な連通孔およ
び独立気泡の一方または両方を複雑に保有する多孔質膜
であるが、さらにその構造について詳しく論じると、膜
の一方の側（中空繊維膜の外表面もしくは内表面）には
細孔が開孔しているが他の側に細孔が開孔していない場
合、膜の内部には細孔が存在するものの膜の内外両表面
には細孔が開孔していない場合、膜の内外両表面共に細
孔が開孔しているものの該細孔が膜内部で途切れてい
て、表裏を連通していない場合等があり、実際にはこれ
らの構造が混在する事が多い。膜表面における細孔の開
口状態は、走査型電子顕微鏡（ＳＥＭ）による表面から
の観察で視認できる。本発明の膜は上記のいずれの構造
であっても良いが、膜の少なくとも一方の側に細孔が開
孔していない層を持つものが好ましい。細孔の大きさに
特に制限は無いが、酸素透過速度や膜強度等の点から、
直径０.００５〜１０μｍが好ましく、０.０３〜１μｍ
がさらに好ましい。The hollow fiber membrane of the present invention is a so-called non-communicating pore type porous membrane having fine pores (voids) inside the membrane, but the front and back of the membrane are not substantially connected by pores. . The more pores are present inside the membrane, the higher the gas permeation rate of oxygen, carbon dioxide, etc., and the faster the gas-liquid gas exchange rate. However, if the porosity is too high, the pores are connected to each other, and pores (communication holes) that connect the front and back of the membrane are generated. Therefore, the membrane of the present invention preferably has a porosity (volume porosity) of 7 to 50%, and more preferably 10 to 35%, although it varies somewhat depending on the method of producing the membrane. The membrane in the present invention is a porous membrane having substantially no communication holes as described above, in other words, a porous membrane having one or both of the communication holes and the closed cells in a complicated manner. If we discuss the structure in detail, if there are pores on one side of the membrane (outer or inner surface of the hollow fiber membrane) but not on the other side, the membrane will be When there are pores in the interior but no pores are formed on both the inner and outer surfaces of the membrane, the pores are open on both the inner and outer surfaces of the membrane, but the pores are interrupted inside the membrane. Therefore, there are cases where the front and back are not connected, and in reality, these structures are often mixed. The opening state of the pores on the film surface can be visually confirmed by observation from the surface with a scanning electron microscope (SEM). The membrane of the present invention may have any of the above structures, but it is preferable that the membrane has a layer in which pores are not opened on at least one side of the membrane. The size of the pores is not particularly limited, but in terms of oxygen permeation rate and membrane strength,
The diameter is preferably 0.005 to 10 μm, and 0.03 to 1 μm
Is more preferable.
【０００７】本発明の膜は酸素透過速度Ｑ（Ｏ2）が１
×１０-6［cm3（ＳＴＰ）／cm2・sec・cmＨg］以上、好
ましくは７×１０-6［cm3（ＳＴＰ）／ cm2・sec・cmＨ
ｇ］以上、より好ましくは５×１０-5〜１×１０-3［cm
3(ＳＴＰ)／(cm2・sec・cmＨg)］のものである。（酸素
透過速度はＡＳＴＭ Ｄ１４３４に準拠して測定され
る）酸素透過速度がこの値より低い場合は、気体−液体
間、例えば血液とのガス交換速度が遅くなる。本発明の
膜の場合、二酸化炭素の透過速度は酸素の透過速度ほぼ
同程度若しくは高くなるため、酸素透過速度が上記値で
あれば、例えば血液からの二酸化炭素除去量は十分であ
る。酸素透過速度は高い方が好ましいのは勿論である。
酸素透過速度を高めるには酸素透過係数の大きな素材を
選定すること、空孔率を高めること、気体が膜素材の重
合体中を溶解・拡散機構で透過すべき実質膜厚を薄くす
ること、といった方法をとる事ができる。しかし、その
達し得る酸素透過速度には自ずと限界はあろうが、高い
こと自体による不都合はないので、その意味から酸素透
過速度に上限を定めることを要しない。The membrane of the present invention has an oxygen permeation rate Q (O 2 ) of 1
× 10 −6 [cm 3 (STP) / cm 2 · sec · cmHg] or more, preferably 7 × 10 −6 [cm 3 (STP) / cm 2 · sec · cmH]
g] or more, more preferably 5 × 10 −5 to 1 × 10 −3 [cm
3 (STP) / (cm 2 · sec · cmHg)]. If the oxygen permeation rate is lower than this value (the oxygen permeation rate is measured according to ASTM D1434), the gas exchange rate between gas and liquid, for example with blood, will be slow. In the case of the membrane of the present invention, the permeation rate of carbon dioxide is almost the same as or higher than the permeation rate of oxygen. Therefore, if the permeation rate of oxygen is the above value, for example, the amount of carbon dioxide removed from blood is sufficient. Of course, it is preferable that the oxygen transmission rate is high.
To increase the oxygen permeation rate, select a material with a large oxygen permeation coefficient, increase the porosity, and reduce the substantial film thickness that gas must permeate through the polymer of the membrane material by the dissolution / diffusion mechanism, You can take such a method. However, although there is a limit to the oxygen transmission rate that can be reached, there is no inconvenience due to the high value, and therefore it is not necessary to set an upper limit on the oxygen transmission rate.
【０００８】膜の表裏を連通した細孔、所謂連通孔が存
在すると、酸素透過速度は高くなるものの、液体の漏出
が生じる場合があり好ましくない。連通孔の有無と存在
量は、エタノールの透過量で判定できる。エタノール
は、膜に連通孔が存在すれば、その内部に浸入して液状
のまま膜を透過する。例えば、多孔膜型人工肺に用いら
れる連通孔タイプのポリプロピレン膜の場合、膜の一方
の側より０.５kgf／cm2の加圧下に７０％エタノールを
圧入すると、１０００〜４００００ml／(min・m2)の速
度でエタノールが透過してくるが、本発明の膜ではエタ
ノール透過量は著しく少なく、実質的に不透過である。
ここでいう「実質的に不透過」とは、同じ測定条件下で
エタノール透過量が３０ml／(min・m2)以下であること
を意味する。エタノール透過量は、好ましくは１０ml／
(min・m2)以下、さらに好ましくは２ml／(min・m2)以下
である。The presence of so-called communicating pores in the front and back of the membrane is not preferable because the oxygen permeation rate increases but liquid leakage may occur. The presence or absence and the amount of the communication holes can be determined by the amount of permeation of ethanol. If the membrane has a communication hole, ethanol penetrates into the inside of the membrane and permeates the membrane in a liquid state. For example, in the case of a polypropylene membrane of a continuous pore type used for a porous membrane oxygenator, if 70% ethanol is pressed under 0.5 kgf / cm 2 of pressure from one side of the membrane, 1000 to 40,000 ml / (min · m) Although ethanol permeates at the rate of 2 ), the membrane of the present invention has a remarkably small amount of ethanol permeation and is substantially impermeable.
The term “substantially impermeable” as used herein means that the amount of ethanol permeation is 30 ml / (min · m 2 ) or less under the same measurement conditions. Ethanol permeation rate is preferably 10 ml /
(min · m 2 ) or less, more preferably 2 ml / (min · m 2 ) or less.
【０００９】本発明の膜における連通していない部分、
即ちこのエタノールを「実質的に不透過」とするエタノ
ール遮断層が本発明の膜のどの位置に存在するかを特定
することは、本発明において必須ではなく、膜の表面の
片側または両側に存在しても良いことは勿論、膜の内部
に、単層、複層を問わず、複雑な形状で実質的に存在す
るのであっても良い。 特に中空繊維膜の内表面もしく
は外表面にエタノール遮断層を形成する事が好ましい。
さらに、遮断層の厚みを薄くする目的から、遮断層は１
層である事が好ましい。この様な遮断層(非多孔層)が膜
表面に形成されているかどうかは、走査型電子顕微鏡
(ＳＥＭ)で確認する事ができる。The non-communicating portion of the membrane of the present invention,
That is, it is not essential in the present invention to specify at which position of the membrane of the present invention the ethanol blocking layer that renders this ethanol "substantially impermeable" is not present in the present invention and is present on one side or both sides of the surface of the membrane. Of course, it may be a single layer or a multi-layer inside the film, and the film may substantially exist in a complicated shape. In particular, it is preferable to form an ethanol blocking layer on the inner or outer surface of the hollow fiber membrane.
Further, in order to reduce the thickness of the barrier layer, the barrier layer is 1
It is preferably a layer. Whether or not such a blocking layer (non-porous layer) is formed on the surface of the film is determined by a scanning electron microscope.
You can check with (SEM).
【００１０】エタノール遮断層の膜全体に於る平均的な
全実質厚みは気体透過速度の実測値から計算により推定
する事ができる。即ち、膜を透過する気体は、膜中の遮
断層を溶解・拡散流れで透過する部分と膜の表裏を連結
する連通孔をクヌーセン流れで透過する部分の和である
として(並列構造)解いた式(１)を用い、酸素透過速度お
よび窒素透過速度の実測値から計算される。The average total substantial thickness of the entire ethanol barrier layer can be estimated by calculation from the measured value of the gas permeation rate. That is, the gas that permeates the membrane is the sum of the part that permeates the barrier layer in the membrane by the dissolution / diffusion flow and the part that permeates the communication hole that connects the front and back of the membrane by the Knudsen flow (parallel structure). It is calculated from the measured values of the oxygen permeation rate and the nitrogen permeation rate using the equation (1).
【００１１】[0011]
【数３】 但し[Equation 3] However
【００１２】[0012]
【数４】 Ｐ(Ｏ2) ［＊１］：素材ポリマーの酸素透過係数 Ｐ(Ｎ2) ［＊１］：素材ポリマーの窒素透過係数 Ｑ(Ｏ2) ［＊２］：膜の酸素透過速度(実測値) Ｑ(Ｎ2) ［＊２］：膜の窒素透過速度(実測値) Ｌ［μm］ ：遮断層の平均厚み (注)［＊１］：cm3(ＳＴＰ)・cm／(cm2・sec・cmＨg) ［＊２］：cm3(ＳＴＰ)／(cm2・sec・cmＨg) 本発明に於ける、(１)式で計算される中空繊維膜の遮断
層厚みは１０μm以下、好ましくは２μm以下、さらに好
ましくは０.７μm以下である。しかしながら製造技術
上、遮断層厚みを０.０１μm以下にする事は極めて困難
である。[Equation 4] P (O 2 ) [* 1]: Oxygen permeability coefficient of the material polymer P (N 2 ) [* 1]: Nitrogen permeability coefficient of the material polymer Q (O 2 ) [* 2]: Oxygen permeability rate of the membrane (measured value) ) Q (N 2 ) [* 2]: Nitrogen permeation rate of the membrane (measured value) L [μm]: Average thickness of the barrier layer (Note) [* 1]: cm 3 (STP) · cm / (cm 2 · sec · cmHg) [* 2]: cm 3 (STP) / (cm 2 · sec · cmHg) In the present invention, the thickness of the blocking layer of the hollow fiber membrane calculated by the formula (1) is 10 μm or less, preferably It is 2 μm or less, and more preferably 0.7 μm or less. However, in terms of manufacturing technology, it is extremely difficult to reduce the thickness of the barrier layer to 0.01 μm or less.
【００１３】上記(１)式で計算される遮断層の厚みはα
＜１の場合には誤差が大きくなる。この様な場合には、
酸素／窒素の測定の代わりに二酸化炭素／窒素の測定か
ら求めることができる。The thickness of the barrier layer calculated by the above equation (1) is α
When <1, the error becomes large. In this case,
Instead of the oxygen / nitrogen measurement, it can be determined from the carbon dioxide / nitrogen measurement.
【００１４】又、本発明に用いられる膜としては、上述
のα(酸素／窒素の分離係数)が０.９４〜１.１５、好ま
しくは０.９５〜１.０９のものである。The membrane used in the present invention has the above-mentioned α (oxygen / nitrogen separation coefficient) of 0.94 to 1.15, preferably 0.95 to 1.09.
【００１５】而して、中空繊維膜は、２５℃における酸
素透過速度Ｑ(Ｏ2)が１×１０-6以上、酸素／窒素の分
離係数αが０.９４〜１.１５、酸素透過速度と窒素透過
速度から計算される遮断層(非多孔層)の厚みが２μm以
下であり、かつ圧力差０.５kgf／cm2でのエタノール透
過量が３００cm3／(min・m2)以下、空孔率が７〜５０％
であり、内径が１０〜５００μmで、且つ厚さが５〜１
００μmであるものが好適である。かかる膜は、特開昭
５９−１９６７０６号に開示されている、多孔質層と非
多孔質層とからなり、酸素／窒素の分離係数αが１.２
以上の中空繊維膜に比べて、一般の膜型気液接触装置、
例えばボイラー供給水の脱酸素、培養槽等に於いて、ガ
ス交換速度が高く、装置がコンパクトにできるメリツト
を有する。即ち、特開昭５９−１９６７０６号の膜でも
気液接触装置に用いて有効であるが、より優れた性能を
指向して止まない市場要求からすれば、上記の好適な中
空繊維膜が要望に応じ得るものである。Thus, the hollow fiber membrane has an oxygen permeation rate Q (O 2 ) at 25 ° C. of 1 × 10 −6 or more, an oxygen / nitrogen separation coefficient α of 0.94 to 1.15, and an oxygen permeation rate. The thickness of the barrier layer (non-porous layer) calculated from the above and the nitrogen permeation rate is 2 μm or less, and the amount of ethanol permeation at a pressure difference of 0.5 kgf / cm 2 is 300 cm 3 / (min · m 2 ) or less, Porosity 7 to 50%
With an inner diameter of 10 to 500 μm and a thickness of 5 to 1
A thickness of 00 μm is suitable. Such a membrane comprises a porous layer and a non-porous layer disclosed in JP-A-59-196706 and has an oxygen / nitrogen separation coefficient α of 1.2.
Compared to the above hollow fiber membranes, general membrane gas-liquid contactor,
For example, in the deoxidation of boiler feed water, a culture tank, etc., the gas exchange rate is high and the device can be made compact. That is, although the membrane of JP-A-59-196706 is also effective for use in a gas-liquid contactor, the above-mentioned suitable hollow fiber membranes are demanded from the market demands for better performance. You can accept.
【００１６】尚、上記中空繊維膜は、前述する如く、一
般の膜型気液接触装置、即ち膜を介して液体と気体を接
触せしめ、液体中への気体の溶解若しくは液体中に含溶
存する気体の放出若しくはこれらの溶解と放出とを同時
に行わしめることを目的としたもの、例えばボイラー供
給水の脱酸素装置、培養槽、生物廃水処理における酸素
供給装置等に利用できる。一般の気液接触装置において
は、特に素材がポリ-４-メチルペンテン-１の場合、親
水化されるような事態は生じない。この為、一般の気液
接触装置用ガス交換膜として用い得る膜のエタノール透
過量は３００cm3／(min・m2)以下である。As mentioned above, the hollow fiber membrane is brought into contact with a liquid and a gas through a general membrane-type gas-liquid contact device, that is, a membrane, and the gas is dissolved in the liquid or is dissolved in the liquid. It can be used for the purpose of releasing gas or simultaneously dissolving and releasing these, for example, a deoxygenation device for boiler feed water, a culture tank, an oxygen supply device for biological wastewater treatment, and the like. In a general gas-liquid contactor, especially when the material is poly-4-methylpentene-1, there is no occurrence of hydrophilicity. Therefore, the amount of ethanol permeation of a membrane that can be used as a gas exchange membrane for a general gas-liquid contactor is 300 cm 3 / (min · m 2 ) or less.
【００１７】本発明の膜を構成する重合体はポリオレフ
ィンが好適である。ポリオレフィン系重合体は、素材と
しての酸素および二酸化炭素の透過係数が大きいこと、
非連通孔形多孔質膜に成形し易いこと、残留溶剤の恐れ
の無い溶融法で膜を成形できること、機械的強度が強く
て膜厚を小さく出来るため装置がコンパクトになるこ
と、有害な不純物を含有しにくいこと、吸水性が無く取
扱いが容易なこと、耐薬品性があり滅菌が容易なこと、
安価であること、といった特長を有している。本発明に
用いるポリオレフィン系重合体としては、例えばポリ−
４−メチルペンテン−１、ポリプロピレン、ポリエチレ
ン、ポリブテン−１およびこれらの共重合体等を例示す
ることができるが、これらの中でポリ−４−メチルペン
テン−１が気体透過係数が大きいことにより酸素透過速
度Ｑ(Ｏ2)を高くして遮断層厚みＬを薄くする事がで
き、かつ膜表面に遮断層を形成し易いので特に好まし
い。また、ポリ−４−メチルペンテン−１は、その表面
エネルギーが前記例示の各ポリオレフィン系重合体の中
で最も小さいため、膜表面に凝縮した水蒸気が膜を濡ら
して広がり、ガス交換面積を低下させる現象が起こりに
くいなどから、本発明において好適な素材である。The polymer forming the membrane of the present invention is preferably polyolefin. The polyolefin-based polymer has a large permeability coefficient of oxygen and carbon dioxide as materials,
It is easy to form a non-communicatable porous membrane, can be formed by a melting method without the risk of residual solvent, has a strong mechanical strength and can reduce the film thickness, thus making the device compact, and removing harmful impurities. Difficult to contain, easy to handle with no water absorption, chemical resistant and easy to sterilize,
It has the features of being inexpensive. Examples of the polyolefin-based polymer used in the present invention include poly-
Examples thereof include 4-methylpentene-1, polypropylene, polyethylene, polybutene-1, and copolymers thereof. Among these, poly-4-methylpentene-1 has a large gas permeability coefficient, and thus oxygen It is particularly preferable because the barrier layer thickness L can be reduced by increasing the permeation rate Q (O 2 ) and the barrier layer can be easily formed on the film surface. Further, since the surface energy of poly-4-methylpentene-1 is the smallest among the polyolefin polymers exemplified above, the water vapor condensed on the surface of the membrane wets and spreads the membrane, reducing the gas exchange area. It is a suitable material in the present invention because it hardly causes a phenomenon.
【００１８】本発明で用いられる主としてポリオレフィ
ン系重合体から成る素材は、ポリオレフィンの１種以上
を主要成分とするものであればよく、他の物質を含有す
ることも可能である。例えば、架橋剤や抗菌剤等を含有
しても良いし、他のポリマーとブレンドする事もでき
る。また、プラズマ処理等の表面処理や放射線架橋等の
処理を行なう事も可能である。The material mainly composed of a polyolefin polymer used in the present invention may be one having at least one kind of polyolefin as a main component, and may contain other substances. For example, it may contain a crosslinking agent, an antibacterial agent, or the like, or may be blended with another polymer. It is also possible to perform surface treatment such as plasma treatment or treatment such as radiation crosslinking.
【００１９】本発明に用いる膜の形状は、中空繊維状も
しくは管状であり、内径は１０〜５００μｍ、好ましく
は１００〜３００μｍ、膜厚は５〜１００μｍ、好まし
くは１０〜４０μｍである。本発明の膜はシリコン均質
膜に比べて、内径に対する膜厚が小さい。又、本発明の
膜は、中空繊維を簾状のシートとして用いるのが好まし
い。かかる簾状シートは中空繊維に対して垂直方向に縦
糸又は粘着テープで中空繊維を編組するか、接着剤が付
着した糸で中空接着剤を接着する等によつて得たものが
使用できる。勿論、該簾状シートは上記のもののみに限
定されるものではない。The shape of the membrane used in the present invention is hollow fiber or tubular, the inner diameter is 10 to 500 μm, preferably 100 to 300 μm, and the film thickness is 5 to 100 μm, preferably 10 to 40 μm. The film of the present invention has a smaller film thickness with respect to the inner diameter than the silicon homogeneous film. Further, in the membrane of the present invention, it is preferable to use hollow fibers as a blind-shaped sheet. As such a cord-like sheet, one obtained by braiding the hollow fiber in the direction perpendicular to the hollow fiber with a warp or an adhesive tape, or by adhering the hollow adhesive with a thread having an adhesive attached thereto can be used. Of course, the blind-shaped sheet is not limited to the above.
【００２０】本発明に用いる膜は、その製法については
特に限定はないが、一般には溶融法、乾式法および乾湿
式法が適しており（中でも溶融法が膜の性能および生産
性の両面に於て特に好適であり）、例えば、特開昭５９
−１９６７０６、特開昭５９−２２９３２０、特開昭６
１−１０１２０６、特開昭６１−１０１２２７に開示さ
れている方法で製造する事ができる。The production method of the membrane used in the present invention is not particularly limited, but in general, a melting method, a dry method and a dry-wet method are suitable (among others, the melting method is effective in terms of both performance and productivity of the membrane). Are particularly preferable), for example, JP-A-59
196706, JP-A-59-229320, JP-A-6-
It can be produced by the method disclosed in JP-A-1-101206 or JP-A-61-101227.
【００２１】特に、次の様な条件で製造するのが好まし
い。即ち、溶融温度を(Ｔｍ＋１５)〜(Ｔｍ＋６５)℃
(但し、Ｔｍはポリマーの結晶融点)、非晶延伸のＤＲを
１.０〜１.１熱処理の温度を(Ｔｍ−３５)〜(Ｔｍ−１
０)℃、熱処理時間を２〜３０秒、ＤＲを１.０〜１.
２、冷延伸ＤＲを１.１〜１.６、熱延伸ＤＲを１.３〜
２.０の範囲で製造する。又、到達結晶化度２０％以上
のポリオレフィン重合体を中空繊維状に溶融押出成形
し、これを必要に応じ配向延伸と熱処理を行ない、冷延
伸と熱固定を行なう事により中空繊維膜の少なくとも一
方の側に平滑な遮断層を有する多孔質膜を製造する事が
できる。この方法で製造した膜は、その生成機構に由来
して膜中の細孔が膜表面に対して垂直方向に長い構造を
持つためか、比較的低い空孔率で十分に高い酸素透過速
度と実質的にアルコール不透過性を示し、しかも高い機
械的強度を持ち膜厚を小さくできる事、溶剤等を一切使
用しないので有害物の溶出が無い事、生産性が高く複合
膜に比べてはるかに低コストの膜を製造できる事、とい
った特徴を持つ。In particular, it is preferable to manufacture under the following conditions. That is, the melting temperature is (Tm + 15) to (Tm + 65) ° C.
(However, Tm is a crystalline melting point of the polymer), DR of the amorphous stretching is 1.0 to 1.1, and the temperature of the heat treatment is (Tm-35) to (Tm-1).
0) ° C., heat treatment time 2 to 30 seconds, DR 1.0 to 1.
2. Cold stretching DR 1.1-1.6, hot stretching DR 1.3-
Manufactured in the range of 2.0. At least one of the hollow fiber membranes is obtained by melt-extruding a polyolefin polymer having an ultimate crystallinity of 20% or more into a hollow fiber shape, and subjecting this to oriented stretching and heat treatment, and cold stretching and heat setting. It is possible to produce a porous membrane having a smooth barrier layer on the side of the. The membrane produced by this method may have a sufficiently high oxygen permeation rate with a relatively low porosity, probably because the pores in the membrane have a structure that is long in the direction perpendicular to the membrane surface due to its generation mechanism. It is substantially impermeable to alcohol, has high mechanical strength and can reduce the film thickness, does not elute harmful substances because it does not use solvents at all, has high productivity, and is far superior to the composite film. It has the feature of being able to manufacture low-cost membranes.
【００２２】[0022]
【実施例】以下実施例等によって本発明をさらに具体的
に説明する。EXAMPLES The present invention will be described in more detail with reference to the following examples.
【００２３】（実施例１）メルトインデックス（ＡＳＴ
Ｍ Ｄ１２３８による）２６のポリ−４−メチルペンテ
ン−１を、直径６mmの円環型中空繊維用ノズルを用い
て、紡糸温度２９０℃、引取速度３００ｍ／分、ドラフ
ト３８０で溶融紡糸し、中空繊維を得た。この時ノズル
口下３〜３５cmの範囲を温度２５℃、風速１.５ｍ／秒
の風で冷却した。得られた中空繊維を温度３５℃、延伸
倍率（ＤＲ）１.０５で、ローラー系を用いて連続的に
非晶延伸し、次いで２２０℃、ＤＲ １.１で熱風循環
型恒温槽中に導入して５秒間滞留させる事により熱処理
を行ない、引続き３５℃、ＤＲ１.２の冷延伸、１５０
℃、ＤＲ１.４の熱延伸、および２００℃、ＤＲ０.９３
の熱固定を行なって、外径２４６μｍ、膜厚２５μｍの
中空繊維膜を得た。この膜の内外表面を１２,０００倍
のＳＥＭで観察したところ、中空糸内表面には孔径約
０.１μmの細孔が１cm2当り約５０×１０9個開口してい
るのが観測されるのに対し、外表面にはその１／５０程
度の開口しか存在しなかつた。この膜の気体透過性はＱ
(Ｏ2)＝２.０×１０-4cm3（ＳＴＰ）／(cm2・sec・cmＨ
ｇ)、α＝１.０９、であり、第(１)式およびポリ４-メ
チルペンテン-１の特性値Ｐ(Ｏ2)＝２.０×１０-9cm
3（ＳＴＰ）／(cm2・sec・cmＨｇ)、α1＝４.１、を用
いて計算した遮断層厚みは０.５３μmであつた。Example 1 Melt Index (AST
M.D. 1238) 26 poly-4-methylpentene-1 was melt-spun at a spinning temperature of 290 ° C., a take-up speed of 300 m / min and a draft of 380 using a circular ring-shaped hollow fiber nozzle having a diameter of 6 mm to give a hollow fiber. Got At this time, the range of 3 to 35 cm below the nozzle mouth was cooled with a wind at a temperature of 25 ° C. and a wind speed of 1.5 m / sec. The obtained hollow fiber was continuously amorphously drawn using a roller system at a temperature of 35 ° C. and a draw ratio (DR) of 1.05, and then introduced into a hot air circulation type thermostat at 220 ° C. and DR 1.1. Then, heat treatment is carried out by allowing it to stay for 5 seconds, followed by cold stretching at 35 ° C and DR 1.2, 150
C, DR 1.4 hot stretch, and 200 C, DR 0.93
Was heat-fixed to obtain a hollow fiber membrane having an outer diameter of 246 μm and a film thickness of 25 μm. When the inner and outer surfaces of this membrane were observed with a SEM of 12,000 times, it was observed that about 50 × 10 9 pores having a pore diameter of about 0.1 μm were opened per cm 2 on the inner surface of the hollow fiber. On the other hand, only about 1/50 of the openings were present on the outer surface. The gas permeability of this membrane is Q
(O 2 ) = 2.0 × 10 -4 cm 3 (STP) / (cm 2 · sec · cmH
g), α = 1.09, and the characteristic value P (O 2 ) of the formula (1) and poly-4-methylpentene-1 = 2.0 × 10 −9 cm.
The barrier layer thickness calculated using 3 (STP) / (cm 2 · sec · cmHg), α 1 = 4.1 was 0.53 μm.
【００２４】この中空繊維膜０.５ｇを長さ約１０mmに
切って比重びんに詰め、真空ポンプで１×１０-2torr以
下に脱気したのち水銀を充填し、重量を計ったところ２
５℃における中空繊維膜の体積は０.８００cm3であっ
た。ポリ−４−メチルペンテン−１の真比重０.８２を
用いて計算すると、この中空繊維膜の空孔率は２３.８
％であつた。0.5 g of this hollow fiber membrane was cut into a length of about 10 mm, packed in a specific gravity bottle, degassed to 1 × 10 -2 torr or less by a vacuum pump, filled with mercury, and then weighed.
The volume of the hollow fiber membrane at 5 ° C. was 0.800 cm 3 . Calculated using the true specific gravity of poly-4-methylpentene-1 of 0.82, the porosity of this hollow fiber membrane is 23.8.
It was in%.
【００２５】上記中空糸膜２０本(実効長１０cm)を図３
に示した装置に組込み、液体が中空糸膜の外表面に接す
る系での酸素の溶解速度を測定した。図３において、液
体(水)を満すケース(８)は、バルブ(１６)(１７)が付さ
れた液体導入口(１２)および液体排出口(１３)が設けら
れており、磁気撹拌機(９)上に配置されている。(１０)
は撹拌子であり、(１１)は酸素センサーである。繊維束
状の中空糸膜(１８)は両端付近で樹脂封止部(２０)によ
り束ねられており、主体部分が液体中に浸漬され、ゴム
栓(１９)を介してケース(８)外にその開口端が出てお
り、気体導入口(１４)および気体排気口(１５)に接続さ
れている。The above 20 hollow fiber membranes (effective length 10 cm) are shown in FIG.
It was incorporated into the device shown in 1 above and the dissolution rate of oxygen was measured in the system in which the liquid was in contact with the outer surface of the hollow fiber membrane. In FIG. 3, a case (8) filled with a liquid (water) is provided with a liquid inlet (12) provided with valves (16) and (17) and a liquid outlet (13), and a magnetic stirrer. (9) Located above. (10)
Is an agitator, and (11) is an oxygen sensor. The fiber bundle-shaped hollow fiber membrane (18) is bundled by the resin sealing parts (20) near both ends, and the main body part is immersed in the liquid, and is put out of the case (8) through the rubber stopper (19). Its open end is exposed and connected to the gas inlet (14) and the gas outlet (15).
【００２６】測定に当つては、中空糸膜の中空部に酸素
を通じ、水中の酸素濃度を酸素センサー(１１)により測
定した。測定及び解析はＹＡＳＵＤＡ等；Ｊ.Ａppl.Ｐo
lym.Ｓci.，１６、５９５(１９７２)に記載されている
方法によつた。測定は２５℃恒温室内で行ない溶存酸素
濃度計として電気化学計器(株)社製ＤＯＣ−１０型を用
いた。また膜面積の計算に当つては、中空糸外表面積を
膜面積とした。 測定で得た気液系での酸素透過速度Ｑ
1(Ｏ2)は１.２９×１０-5cm3（ＳＴＰ）／(cm2・sec・c
mＨｇ)であつた。In the measurement, oxygen was passed through the hollow portion of the hollow fiber membrane and the oxygen concentration in water was measured by an oxygen sensor (11). Measurement and analysis is YASUDA, etc .; J. Appl. Po
lym. Sci., 16 , 595 (1972). The measurement was carried out in a constant temperature chamber at 25 ° C. and a DOC-10 model manufactured by Electrochemical Instruments Co., Ltd. was used as a dissolved oxygen concentration meter. Further, in calculating the membrane area, the outer surface area of the hollow fiber was defined as the membrane area. Oxygen transmission rate Q in gas-liquid system obtained by measurement
1 (O 2 ) is 1.29 × 10 -5 cm 3 (STP) / (cm 2 · sec · c
mHg).
【００２７】（実施例２）紡糸ドラフトが３９０、熱処
理条件が２２０℃、ＤＲ１.０５、熱延伸ＤＲが１.４、
熱固定のＤＲが０.９３であること以外には実施例１と
同条件で製造した中空繊維膜は、外径２４５μm、膜厚
２４μmであつた。ＳＥＭにより観察すると、中空糸内
表面には孔径約０.１μmの細孔が１cm2当り約５０×１
０9個開口しているのが観測されるのに対し、外表面に
はその１／５０程度の開口しか存在しなかつた。この膜
の気体透過性はＱ(Ｏ2)＝８.７×１０-4cm3（ＳＴＰ）
／(cm2・sec・cmＨｇ)、α＝０.９６０、であり、第
(１)式およびポリ-４メチルペンテン-１の特性値Ｐ
(Ｏ2)＝２.０×１０-9cm3（ＳＴＰ）・cm／(cm2・sec・
cmＨｇ)、α1＝４.１、を用いて計算した遮断層厚みは
０.６８μmであつた。実施例１と同様にして測定したこ
の中空糸の空孔率は２４.３％であつた。Example 2 A spinning draft of 390, a heat treatment condition of 220 ° C., a DR of 1.05, and a hot drawing DR of 1.4,
The hollow fiber membrane produced under the same conditions as in Example 1 except that the DR for heat setting was 0.93 had an outer diameter of 245 μm and a thickness of 24 μm. Observed by SEM, the inner surface of the hollow fibers had pores with a pore size of about 0.1 μm, about 50 × 1 per cm 2.
Although it was observed that there were 09 openings, only about 1/50 of the openings were present on the outer surface. The gas permeability of this membrane is Q (O 2 ) = 8.7 × 10 −4 cm 3 (STP)
/ (Cm 2 · sec · cmHg), α = 0.960,
Formula (1) and characteristic value P of poly-4-methylpentene-1
(O 2 ) = 2.0 × 10 -9 cm 3 (STP) ・ cm / (cm 2・ sec ・
cmHg), α 1 = 4.1, the barrier layer thickness calculated was 0.68 μm. The porosity of this hollow fiber measured in the same manner as in Example 1 was 24.3%.
【００２８】上記中空糸膜を用いて実施例１と同様にし
て測定を行なつたところ気液系での酸素透過速度Ｑ1(Ｏ
2)は９.０５×１０-6cm3（ＳＴＰ）／(cm2・sec・cmＨ
ｇ)であつた。Using the above hollow fiber membrane, the measurement was carried out in the same manner as in Example 1. As a result, the oxygen permeation rate Q 1 (O
2 ) is 9.05 × 10 -6 cm 3 (STP) / (cm 2 · sec · cmH
g).
【００２９】（比較例１）紡糸ドラフトが２７０、熱処
理条件が２００℃、ＤＲ１.３、熱延伸ＤＲが１.２、熱
固定のＤＲが０.９であること以外には実施例１と同条
件で製造した中空繊維膜は、外径２７２μm、膜厚２７
μmであつた。ＳＥＭによると、図１に見られる様に、
内表面は平滑で、細孔がほとんど認められず、又、図２
に見られるように外表面には０.２μｍ程度の微細孔が
多数認められた。実施例１と同様にして測定したこの中
空糸の空孔率は１８.０％であつた。(Comparative Example 1) The same as Example 1 except that the spinning draft was 270, the heat treatment conditions were 200 ° C., DR 1.3, the hot drawing DR was 1.2, and the heat setting DR was 0.9. The hollow fiber membrane manufactured under the conditions has an outer diameter of 272 μm and a thickness of 27
It was μm. According to SEM, as seen in Figure 1,
The inner surface was smooth, few pores were observed, and Fig. 2
As can be seen from the above, many fine pores of about 0.2 μm were recognized on the outer surface. The porosity of this hollow fiber measured in the same manner as in Example 1 was 18.0%.
【００３０】またこの中空膜をガラス管に封入し、ＡＳ
ＴＭ Ｄ１４３４圧力法に準拠して２５℃にて気体透過
速度を測定したところの、Ｑ（Ｏ2）＝４.５×１０-5cm
3（ＳＴＰ）／（cm2・sec・cmＨg）、Ｑ（ＣＯ2）＝３.
４×１０-5（cm3（ＳＴＰ）／（cm2・sec・cmＨg）、α
（Ｏ2／Ｎ2）＝１.２、Ｌ（遮断層）＝１.３μｍであつ
た。The hollow membrane was sealed in a glass tube and
When the gas permeation rate was measured at 25 ° C. according to the TM D1434 pressure method, Q (O 2 ) = 4.5 × 10 −5 cm
3 (STP) / (cm 2 · sec · cmHg), Q (CO 2 ) = 3.
4 × 10 -5 (cm 3 (STP) / (cm 2 · sec · cmHg), α
(O 2 / N 2 ) = 1.2 and L (blocking layer) = 1.3 μm.
【００３１】上記膜を用いて実施例１と同様にして測定
を行なったところ、この膜の気液系での酸素透過速度Ｑ
1（Ｏ2）は６.６×１０-6cm3（ＳＴＰ）／（cm2・sec・
cmＨg）であつた。When the measurement was performed using the above membrane in the same manner as in Example 1, the oxygen permeation rate Q of this membrane in the gas-liquid system was measured.
1 (O 2 ) is 6.6 × 10 -6 cm 3 (STP) / (cm 2 · sec ·
cmHg).
【００３２】（比較例２）紡糸温度が３００℃である事
および非晶延伸の延伸倍率が１.２である事以外は比較
例１と全く同様にして中空繊維膜を製造した。この中空
繊維膜には、ＳＥＭ観察によれば、内表面、外表面共に
ＳＥＭの解像力（約３０Å）以上の孔径の細孔は全く認
められなかつた。また、この膜の外径は２５０μｍ、膜
厚は２５μｍ、空孔率は１１％、酸素透過速度Ｑ
（Ｏ2）は８×１０-6cm3（ＳＴＰ）／（cm2・sec・cmＨ
g）、αは４.１、Ｌは２.５μｍ、Ｑ（ＣＯ2）は３.９
×１０-5cm3（ＳＴＰ）／cm2・sec・cmＨg）であつた。(Comparative Example 2) A hollow fiber membrane was produced in exactly the same manner as Comparative Example 1 except that the spinning temperature was 300 ° C and the draw ratio of the amorphous stretching was 1.2. According to SEM observation, no pores having a pore size equal to or larger than the resolution of SEM (about 30 Å) were observed in this hollow fiber membrane by SEM observation. The outer diameter of this film is 250 μm, the film thickness is 25 μm, the porosity is 11%, and the oxygen permeation rate Q is
(O 2 ) is 8 × 10 -6 cm 3 (STP) / (cm 2 · sec · cmH
g), α is 4.1, L is 2.5 μm, and Q (CO 2 ) is 3.9.
× 10 −5 cm 3 (STP) / cm 2 · sec · cmHg).
【００３３】上記膜を用いて実施例１と同様にして測定
を行なったところ、この膜の気液系での酸素透過速度Ｑ
1（Ｏ2）は４.６×１０-6cm3（ＳＴＰ）／（cm2・sec・
cmＨg）であつた。When the measurement was performed in the same manner as in Example 1 using the above membrane, the oxygen permeation rate Q of this membrane in the gas-liquid system was measured.
1 (O 2 ) is 4.6 × 10 -6 cm 3 (STP) / (cm 2 · sec ・
cmHg).
【００３４】（実施例３）メルトインデックス（ＡＳＴ
Ｍ Ｄ１２３８による）３．５のポリプロピレンを、直
径６mmの円環型中空繊維用ノズルを用いて、紡糸温度２
５０℃、引取速度３００ｍ／分、ドラフト２７０で溶融
紡糸し、外径３４５μｍ、膜厚３４μｍの中空繊維を得
た。この時ノズル口下３〜３５cmの範囲を温度８℃、風
速１.５ｍ／秒の風で冷却した。得られた中空繊維を温
度３５℃、延伸倍率（ＤＲ）１.２で、ローラー系を用
いて連続的に非晶延伸し、次いで１４０℃、ＤＲ１.３
で熱風循環型恒温槽中に導入して５秒間滞留させる事に
より熱処理を行ない、引続き１０℃、ＤＲ１.２の冷延
伸、１４０℃、ＤＲ１.２の熱延伸、および１４０℃、
ＤＲ０.９の熱固定を行なって、外径２５７μｍ、内径
２０５μｍ、膜厚２６μｍの中空繊維膜を得た。この膜
の内外表面を１２,０００倍のＳＥＭで観察したとこ
ろ、内表面には微細孔がほとんど認められず、外表面に
は０.１μｍ程度の微細孔が多数存在した。この膜の空
孔率は３１％、酸素透過速度Ｑ(Ｏ2)は３.４×１０-4cm
3（ＳＴＰ)／(cm2・sec・cmＨｇ)、αは０.９４、Ｌは
１.６μm、Ｑ(ＣＯ2)は２.９２×１０-4cm3（ＳＴＰ）
／(cm2・sec・cmＨｇ)であった。尚、Ｌの計算はＱ
(Ｏ2)を用いた場合は誤差が大きいため、Ｑ(ＣＯ2)に基
づいた。(Example 3) Melt index (AST
Polypropylene of 3.5) (according to MD 1238) is spun at a spinning temperature of 2 by using a ring type hollow fiber nozzle having a diameter of 6 mm.
Melt spinning was performed at 50 ° C., a take-up speed of 300 m / min, and a draft 270 to obtain a hollow fiber having an outer diameter of 345 μm and a film thickness of 34 μm. At this time, a range of 3 to 35 cm below the nozzle mouth was cooled with a wind at a temperature of 8 ° C and a wind speed of 1.5 m / sec. The resulting hollow fiber was continuously amorphously drawn using a roller system at a temperature of 35 ° C. and a draw ratio (DR) of 1.2, and then at 140 ° C. and DR 1.3.
Then, heat treatment is performed by introducing it into a hot-air circulation type constant temperature bath and allowing it to stay for 5 seconds, followed by 10 ° C., cold stretching at DR 1.2, 140 ° C., hot stretching at DR 1.2, and 140 ° C.
DR0.9 was heat-set to obtain a hollow fiber membrane having an outer diameter of 257 μm, an inner diameter of 205 μm and a film thickness of 26 μm. When the inner and outer surfaces of this film were observed with a SEM of 12,000 times, almost no micropores were observed on the inner surface, and many micropores of about 0.1 μm were present on the outer surface. This membrane has a porosity of 31% and an oxygen permeation rate Q (O 2 ) of 3.4 × 10 −4 cm.
3 (STP) / (cm 2 · sec · cmHg), α is 0.94, L is 1.6 μm, and Q (CO 2 ) is 2.92 × 10 −4 cm 3 (STP)
It was / (cm 2 · sec · cmHg). The calculation of L is Q
Since the error is large when (O 2 ) is used, it is based on Q (CO 2 ).
【００３５】（実施例４）メルトインデックス１.８、
密度０.９６のポリエチレンを、直径１０mmの円環型中
空繊維用ノズルを用いて、紡糸温度２３０℃、ドラフト
７００、冷却風温１２℃、冷却風速１.５ｍ／ｓで溶融
紡糸した。得られた中空繊維を、ローラー系にて連続的
に、２０℃、ＤＲ１.２で非晶延伸し、８０℃、ＤＲ１.
２、滞留時間５秒で熱処理し、２０℃、ＤＲ１.３で冷
延伸し、６０℃、ＤＲ１.２で熱延伸し、８０℃、ＤＲ
１.０で熱固定して、内径２００μｍ、膜厚２４μｍの
中空繊維膜を得た。ＳＥＭ観察によれば、この膜は、内
外両表面共に細孔は認められず、膜断面の内外表面間は
孔径約１μｍの細孔から成る多孔質層であった。またこ
の膜の空孔率は２５％、酸素透過速度Ｑ(Ｏ2)は１.５×
１０-4cm3(ＳＴＰ)／(cm2・sec・cmＨｇ)、αは０.９
５、Ｌは０.６μm、Ｑ(ＣＯ2)は１.３３×１０-4cm
3（ＳＴＰ）／(cm2・sec・cmＨg)であった。尚、Ｌは実
施例３と同様にして算出した。Example 4 Melt index 1.8,
Polyethylene having a density of 0.96 was melt-spun at a spinning temperature of 230 ° C., a draft 700, a cooling air temperature of 12 ° C., and a cooling air speed of 1.5 m / s using a circular ring type hollow fiber nozzle having a diameter of 10 mm. The obtained hollow fiber was continuously drawn amorphously at 20 ° C. and DR1.2 by a roller system, and then at 80 ° C. and DR1.2.
2. Heat treatment with residence time of 5 seconds, cold drawing at 20 ℃, DR1.3, hot drawing at 60 ℃, DR1.2, 80 ℃, DR
It was heat-fixed at 1.0 to obtain a hollow fiber membrane having an inner diameter of 200 μm and a film thickness of 24 μm. According to SEM observation, no pores were observed on both the inner and outer surfaces of this membrane, and the membrane was a porous layer composed of pores having a pore diameter of about 1 μm between the inner and outer surfaces. The porosity of this membrane is 25%, and the oxygen permeation rate Q (O 2 ) is 1.5 ×.
10 -4 cm 3 (STP) / (cm 2 · sec · cmHg), α is 0.9
5, L is 0.6 μm, Q (CO 2 ) is 1.33 × 10 −4 cm
It was 3 (STP) / (cm 2 · sec · cmHg). Incidentally, L was calculated in the same manner as in Example 3.
【００３６】（実施例５）紡糸ドラフトが３５０、熱処
理条件が２２０℃、ＤＲ１.１、熱延伸ＤＲが１.４であ
ること以外には実施例１と同条件で製造した中空繊維膜
は、外径２５５μm、膜厚２６μmであつた。ＳＥＭによ
り観察すると、中空糸内表面には孔径約０.１μmの細孔
が１cm2当り約５０×１０9個開口しているのが観測され
るのに対し、外表面にはその１／５０程度の開口しか存
在しなかつた。この膜の気体透過性はＱ(Ｏ2)＝３×１
０-4cm3（ＳＴＰ）／(cm2・sec・cmＨg)、α＝１.０
２、Ｑ(ＣＯ2)＝３.４×１０-4cm3（ＳＴＰ）／(cm2・s
ec・cmＨg)であり、第(１)式およびポリ４メチルペンテ
ン-１の特性値Ｐ(Ｏ2)＝２.０×１０-9cm3（ＳＴＰ）／
(cm2・sec・cmＨg)、α1＝４.１、を用いて計算した遮
断層厚みＬは０.６μmであつた。製造例１と同様にして
測定したこの中空糸の空孔率は２３.５％であつた。(Example 5) A hollow fiber membrane produced under the same conditions as in Example 1 except that the spinning draft was 350, the heat treatment conditions were 220 ° C, the DR1.1 and the hot drawing DR were 1.4, The outer diameter was 255 μm and the film thickness was 26 μm. When observed by SEM, it was observed that about 50 × 10 9 pores having a pore size of about 0.1 μm were opened per cm 2 on the inner surface of the hollow fiber, whereas 1/50 of the pores were opened on the outer surface. There was only a small opening. The gas permeability of this membrane is Q (O 2 ) = 3 × 1
0 -4 cm 3 (STP) / (cm 2 · sec · cmHg), α = 1.0
2, Q (CO 2 ) = 3.4 × 10 -4 cm 3 (STP) / (cm 2 · s
ec · cmHg), and the characteristic value P (O 2 ) of the formula (1) and poly (4-methylpentene-1) = 2.0 × 10 −9 cm 3 (STP) /
The barrier layer thickness L calculated using (cm 2 · sec · cmHg) and α 1 = 4.1 was 0.6 μm. The porosity of this hollow fiber measured in the same manner as in Production Example 1 was 23.5%.
【００３７】（実施例６）熱処理の時間が１０秒、冷延
伸倍率が１.３、熱延伸倍率が１.８であること以外は実
施例５と同様の方法で製造した中空繊維膜の特性はＱ
(Ｏ2)＝３.０×１０-4cm3（ＳＴＰ）／(cm2・sec・cmＨ
g)、α＝０.９８、Ｌ＝１.１μm、Ｑ(ＣＯ2)＝３.０×
１０-4cm3（ＳＴＰ）／(cm2・sec・cmＨg)、空孔率＝２
７％であつた。(Example 6) Characteristics of a hollow fiber membrane produced in the same manner as in Example 5 except that the heat treatment time was 10 seconds, the cold draw ratio was 1.3, and the hot draw ratio was 1.8. Is Q
(O 2 ) = 3.0 × 10 -4 cm 3 (STP) / (cm 2 · sec · cmH
g), α = 0.98, L = 1.1 μm, Q (CO 2 ) = 3.0 ×
10 -4 cm 3 (STP) / (cm 2 · sec · cmHg), porosity = 2
It was 7%.
【００３８】[0038]
【発明の効果】本発明の中空繊維膜は、従来の中空繊維
膜に比べてガス交換速度が向上したものであり、気液接
触装置等のガス交換膜として有用なものである。INDUSTRIAL APPLICABILITY The hollow fiber membrane of the present invention has an improved gas exchange rate as compared with conventional hollow fiber membranes, and is useful as a gas exchange membrane for gas-liquid contactors and the like.
【図１】比較例１の中空繊維の内表面を走査型電子顕微
鏡写真である。FIG. 1 is a scanning electron micrograph of the inner surface of a hollow fiber of Comparative Example 1.
【図２】比較例１の中空繊維の外表面を走査型電子顕微
鏡写真である。2 is a scanning electron micrograph of the outer surface of the hollow fiber of Comparative Example 1. FIG.
【図３】実施例１〜２及び比較例１で用いられる気液接
触装置の概略図である。FIG. 3 is a schematic diagram of a gas-liquid contact device used in Examples 1 and 2 and Comparative Example 1.
１ ケース ２ 磁気撹拌機 ３ 撹拌子 ４ 酸素センサー ５ 液体導入口 ６ 液体排出口 ７ 気体導入口 ８ 気体排出口 ９ バルブ １０ 中空糸膜 １１ ゴム栓、 １２ 樹脂封止部 1 Case 2 Magnetic Stirrer 3 Stirrer 4 Oxygen Sensor 5 Liquid Inlet 6 Liquid Outlet 7 Gas Inlet 8 Gas Outlet 9 Valve 10 Hollow Fiber Membrane 11 Rubber Plug, 12 Resin Sealing Part
Claims (3)
１×１０-6［cm3（ＳＴＰ）／cm2・sec・cmHg]以上であ
り、酸素／窒素の分離係数が０.９４〜１.１５であり、
かつ実質的にエタノールを透過せず、空孔率が７〜５０
％であり、主としてポリオレフィン系重合体からなり、
内径が１０〜５００μｍでかつ厚さが５〜１００μｍで
あることを特徴とする中空繊維膜。1. The oxygen permeation rate Q (O 2 ) at 25 ° C. is 1 × 10 −6 [cm 3 (STP) / cm 2 · sec · cmHg] or more, and the oxygen / nitrogen separation coefficient is 0.94. ~ 1.15,
And it is substantially impermeable to ethanol and has a porosity of 7 to 50.
%, Mainly composed of a polyolefin-based polymer,
A hollow fiber membrane having an inner diameter of 10 to 500 μm and a thickness of 5 to 100 μm.
過量が３００cm3／(min・m2)以下であることを特徴とす
る請求項1記載の中空繊維膜。2. The hollow fiber membrane according to claim 1, which has an ethanol permeation amount of 300 cm 3 / (min · m 2 ) or less at a pressure difference of 0.5 kgf / cm 2 .
みが２μｍ以下である請求項１記載の中空繊維膜。記 【数１】 但し 【数２】 Ｐ(Ｏ2) ［＊１］：素材ポリマーの酸素透過係数 Ｐ(Ｎ2) ［＊１］：素材ポリマーの窒素透過係数 Ｑ(Ｏ2) ［＊２］：膜の酸素透過速度(実測値) Ｑ(Ｎ2) ［＊２］：膜の窒素透過速度(実測値) Ｌ［μm］ ：非多孔層(遮断層)の平均厚み (注)［＊１］：cm3(ＳＴＰ)・cm／(cm2・sec・cmＨg) ［＊２］：cm3(ＳＴＰ)／(cm2・sec・cmＨg)3. The hollow fiber membrane according to claim 1, wherein the thickness of the non-porous layer calculated by the following formula (1) is 2 μm or less. Note [Equation 1] However, [Equation 2] P (O 2 ) [* 1]: Oxygen permeability coefficient of the material polymer P (N 2 ) [* 1]: Nitrogen permeability coefficient of the material polymer Q (O 2 ) [* 2]: Oxygen permeability rate of the membrane (measured value) ) Q (N 2 ) [* 2]: Nitrogen permeation rate of membrane (measured value) L [μm]: Average thickness of non-porous layer (blocking layer) (Note) [* 1]: cm 3 (STP) ・ cm / (Cm 2 · sec · cmHg) [* 2]: cm 3 (STP) / (cm 2 · sec · cmHg)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4073308A JPH07121340B2 (en) | 1987-07-11 | 1992-02-25 | Hollow fiber membrane |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17206787 | 1987-07-11 | ||
| JP62-172067 | 1987-07-11 | ||
| JP4073308A JPH07121340B2 (en) | 1987-07-11 | 1992-02-25 | Hollow fiber membrane |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63170783A Division JP2700170B2 (en) | 1987-07-11 | 1988-07-11 | Membrane oxygenator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06121920A true JPH06121920A (en) | 1994-05-06 |
| JPH07121340B2 JPH07121340B2 (en) | 1995-12-25 |
Family
ID=26414460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4073308A Expired - Fee Related JPH07121340B2 (en) | 1987-07-11 | 1992-02-25 | Hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07121340B2 (en) |
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| JP2009298907A (en) * | 2008-06-12 | 2009-12-24 | Shin Etsu Polymer Co Ltd | Selectively permeable material for house and house air conditioning system |
| JP2011036743A (en) * | 2009-08-06 | 2011-02-24 | Nomura Unison Co Ltd | Hollow fiber membrane for degassing |
| US9005343B2 (en) | 2010-05-05 | 2015-04-14 | New Health Sciences, Inc. | Integrated leukocyte, oxygen and/or CO2 depletion, and plasma separation filter device |
| US9067004B2 (en) | 2011-03-28 | 2015-06-30 | New Health Sciences, Inc. | Method and system for removing oxygen and carbon dioxide during red cell blood processing using an inert carrier gas and manifold assembly |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62106770A (en) * | 1985-07-16 | 1987-05-18 | テルモ株式会社 | Hollow yarn membrane for artificial lang, its production andartificial lang using said hollow yarn membrane |
-
1992
- 1992-02-25 JP JP4073308A patent/JPH07121340B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62106770A (en) * | 1985-07-16 | 1987-05-18 | テルモ株式会社 | Hollow yarn membrane for artificial lang, its production andartificial lang using said hollow yarn membrane |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH07121340B2 (en) | 1995-12-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |