【発明の詳細な説明】〔産業上の利用分野〕本発明は、逆浸透、透析、液々分離、ガス分離等に用い
られる高能率な中空繊維状膜の製造法を提供するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a method for producing highly efficient hollow fibrous membranes used in reverse osmosis, dialysis, liquid-liquid separation, gas separation, and the like.
物質を、分離精製する技術は、昔から、数多くの方法が
、開発され、改良が重ねられて来た。BACKGROUND OF THE INVENTION Since ancient times, many methods for separating and purifying substances have been developed and improved.
膜分離技術も、その一つであるが、その改良の経過をみ
ると、優れた膜材料の開発効率を高めるだめの薄膜化技
術の開発、装置としての効率を高めるだめの中空糸膜の
開発等が、大きな技術開発の流れである。Membrane separation technology is one such technology, and if we look at the progress of improvements, we can see the development of thinner membrane technology that increases the efficiency of developing excellent membrane materials, and the development of hollow fiber membranes that increase the efficiency of equipment. These are major trends in technological development.
薄着化技術の一つの方向として、多孔質の基材の上に、
コート法や蒸着法によって、薄膜を形成する方法も、盛
んに行われているが、多孔質基板上にコートするために
、基板の細孔に薄膜材料が侵入して、実質的な薄膜が得
られない。As one direction of thinning technology, on porous substrates,
Methods of forming thin films using coating methods and vapor deposition methods are also widely used, but in order to coat a porous substrate, the thin film material enters the pores of the substrate, making it difficult to form a substantial thin film. I can't.
また、此の現象を邂ける為に、多孔質基板を、予め、溶
解性物質で細孔を埋めておいて、表面に４層を形成した
後に、多孔質基板内の溶解性物質を溶出する方法もある
が、均一な薄層が得られ難く、また、傷つきやすい。In addition, in order to overcome this phenomenon, the pores of the porous substrate are filled in advance with a soluble substance, and after four layers are formed on the surface, the soluble substance within the porous substrate is eluted. Although there are other methods, it is difficult to obtain a uniform thin layer and it is easily damaged.
ピンホーμの発生、膜厚の不均一、耐久性がない、等の
問題から、なかなか実用化が難しい状況にある。It is difficult to put it into practical use due to problems such as the occurrence of pinhole μ, uneven film thickness, and lack of durability.
分離膜を、薄層形成する他の方法として、高分子溶液か
らの成形による非対称膜化法がある。Another method for forming a thin layer of a separation membrane is an asymmetric membrane formation method by molding a polymer solution.
例えば、海水淡水化膜としての逆浸透膜や、限外濾過膜
が製品化されている。デュポン社のバーマセッデ、旭化
成社のポリアクリロニトリル限外濾過１換等である。For example, reverse osmosis membranes as seawater desalination membranes and ultrafiltration membranes have been commercialized. These include DuPont's Vermasede and Asahi Kasei's polyacrylonitrile ultrafiltration.
何れも、高分子溶液から、膜の形成過程において、表面
部分をｍ密に固化させ、内部を凝固条件の選択もしくは
、溶出法によって、多孔化する技術によって形成される
もので中空糸は、単一の材料で構成されている。In both cases, the membrane is formed from a polymer solution by solidifying the surface part densely and making the inside porous by selecting solidification conditions or elution method. It is composed of one material.
従って、このような方法によって得られた膜の構造は、
緻密な表面の薄層の部分から内部の粗な部分に向かって
連続的に変化しており、あまり必要性のない中間構造の
部分を有している。Therefore, the structure of the membrane obtained by this method is
It changes continuously from a thin layer on the surface to a rough layer on the inside, and has an intermediate structure that is not very necessary.
これはｆ過効率上、あまり好ましいものではない。This is not very desirable in terms of f overefficiency.
先に、特開昭６０−１３９８１５号において、我々は、
性能を向上させたコンジュゲート中空繊維を提案した。Previously, in JP-A-60-139815, we
A conjugated hollow fiber with improved performance was proposed.
これは、機能分担を目的とはしているが、薄層化による
効率向上について今一つ十分とは言えない。Although this is aimed at dividing functions, it cannot be said that it is sufficient to improve efficiency through thinner layers.
更に、連続した微細孔径を有する複合中空糸であるため
、逆浸透膜やガス分離膜として用いるには、そのままで
は、性能が不′十分である。Furthermore, since it is a composite hollow fiber having a continuous micropore diameter, its performance is insufficient as it is for use as a reverse osmosis membrane or a gas separation membrane.
我々は、非常に薄い分離膜を有する中空繊維状膜を工業
的に安定に製造する技術を鋭意検討した結果本発明に到
達した。We have arrived at the present invention as a result of extensive research into techniques for industrially and stably manufacturing a hollow fibrous membrane having a very thin separation membrane.
本発明の要旨は延伸により多孔化する未延伸中空糸の表
面に、コート法により薄膜を形成した後、該中空糸を延
伸する事によって、中空糸層を多孔質化する複合中空鍼
維状膜の製造方法にある。The gist of the present invention is to form a thin film by a coating method on the surface of unstretched hollow fibers that become porous through stretching, and then stretch the hollow fibers to make the hollow fiber layer porous. It is in the manufacturing method.
本発明の方法で製造される中空糸膜は、目の粗い透過性
の多孔質構造の膜表面に、４届の好ましくは非多孔質分
離膜層を形成した構成となっている。The hollow fiber membrane produced by the method of the present invention has a structure in which four preferably non-porous separation membrane layers are formed on the surface of the membrane having a coarse permeable porous structure.
本発明における方法の特徴は、多孔質中空繊維の上にコ
ーティングする方法に比べて、（１）：非多孔質表面上
にコートするため、均一コートが容易である。（２）：
コーティング時に孔を詰める事がない。従って孔を予め
詰めておく必要がない。（３）：延伸による多孔化であ
るから、機能薄膜も延伸され、強化される。（４）：延
伸時に機能薄層も延伸されると中空繊維周方向に収縮力
が働く。一方、基材の中空繊維は多孔化し、多孔化しな
い場合に比して、径の縮小が少ない結果、機能薄膜は上
記収縮力により中空繊維表面に密着して機能薄層が安定
になる。The method of the present invention is characterized in that, compared to the method of coating on porous hollow fibers, (1) uniform coating is easy because it is coated on a non-porous surface. (2):
No pores are clogged during coating. Therefore, there is no need to fill the holes in advance. (3): Since porosity is created by stretching, the functional thin film is also stretched and strengthened. (4): When the functional thin layer is also stretched during stretching, a contraction force acts in the circumferential direction of the hollow fibers. On the other hand, the hollow fibers of the base material are made porous, and as a result, the diameter decreases less than when they are not made porous, and the functional thin film adheres closely to the surface of the hollow fibers due to the above-mentioned contractile force, thereby stabilizing the functional thin layer.
さらに、平膜の場合に比べて、延伸時の剥離による形状
破壊がない。これは、中空糸形状における大きな特徴で
ある。Furthermore, compared to the case of a flat film, there is no shape destruction due to peeling during stretching. This is a major feature of the hollow fiber shape.
本発明の中空繊維状膜の製造方法を以下に詳しく述べる
。The method for producing the hollow fibrous membrane of the present invention will be described in detail below.
円筒型の紡糸ノズルから、一般的な方法で中空繊維を溶
融紡糸する。中空繊維製造に用いるポリマーとしては、
延伸によって多孔質化するものを選択する。Hollow fibers are melt-spun using a conventional method from a cylindrical spinning nozzle. Polymers used in hollow fiber manufacturing include:
Select a material that becomes porous when stretched.
例えば、ポリエチレン、ポリプロピレンに代表されるポ
リオレフィン系重合体、ポリカーボネート系ポリマー、
ポリエステル系ポリマー、弗素系樹脂等が有利に用いら
れる。For example, polyolefin polymers such as polyethylene and polypropylene, polycarbonate polymers,
Polyester polymers, fluorine resins, etc. are advantageously used.
溶融紡糸で得られた未延伸糸表面に、分離機能を分担す
る重合体をコートする。The surface of the undrawn yarn obtained by melt spinning is coated with a polymer that performs the separation function.
ここに用いられる重合体は、分離機能を分担する重合体
としては、シリコン系重合体、ウレタン系重合体、セル
ロース系重合体、オレフィン系重合体、スルホン糸重合
体、ＰＶＡ系重合体、エステル系、エーテル糸重合体、
アミド糸重合体、イミド系重合体、そめ他数多くの重合
体が用いられる。The polymers used here include silicone-based polymers, urethane-based polymers, cellulose-based polymers, olefin-based polymers, sulfone thread polymers, PVA-based polymers, and ester-based polymers. , ether thread polymer,
Many polymers such as amide thread polymers, imide polymers, and some are used.
重合体の融点が中空糸のＦＭ点より低い場合は重合体を
溶融コートしてもよく、重合体あるいは重合体のプレポ
リマーの（ｆｊＭをコートしてもよい。この溶液に用い
る溶剤は重合体又はプレポリマーを溶解し、中空糸を溶
解しない溶剤を用いる。このような例として重合体にも
よるがアセトン、クロロホルム、メチレンクロライド、
ジオキサン、ジメチルホルムアミド、ジメチルアセトア
ミド、ジクロルメタン、Ｎ−メチルピロリドン、メチフ
レエチルケトン、メチルイソブチルケトン等を挙げるこ
とができるが、これに限定されるものではない。If the melting point of the polymer is lower than the FM point of the hollow fiber, the polymer may be melt-coated, or a polymer or a prepolymer (fjM) of the polymer may be coated. Alternatively, use a solvent that dissolves the prepolymer but does not dissolve the hollow fibers. Examples of such solvents include acetone, chloroform, methylene chloride,
Examples include, but are not limited to, dioxane, dimethylformamide, dimethylacetamide, dichloromethane, N-methylpyrrolidone, methifrethyl ketone, and methyl isobutyl ketone.
これらの重合体の中には、成型が不可能に近い物も多い
が、本発明は、中空繊維状膜として出来上がった時に、
上記の重合体が分離膜として形作られていれば良いので
ある。Among these polymers, there are many that are almost impossible to mold, but the present invention shows that when completed as a hollow fibrous membrane,
It is sufficient if the above polymer is formed into a separation membrane.
従って、機能膜に使用する重合体としては、膜の破壊が
起こらずに延伸変形性のあるものであれば良い。Therefore, the polymer used for the functional membrane may be any polymer that can be stretched and deformed without causing destruction of the membrane.
従って、延伸が不可能な重合体でも、溶剤、可塑剤、膨
潤剤等を含んだ状態で、延伸変形性があれば良い。Therefore, even if the polymer cannot be stretched, it is sufficient if it has stretching deformability in a state containing a solvent, a plasticizer, a swelling agent, etc.
このことは、本発明の大きな特徴の一つである。This is one of the major features of the present invention.
但し、出来上がった複合中空繊維状膜の分離機能分担部
分、即ち薄層部分を延伸後架橋処理等の強化手段を採る
ことも、任意に行いうる。However, it is also possible to optionally strengthen the separation-functioning portion of the completed composite hollow fibrous membrane, ie, the thin layer portion, by crosslinking or the like after stretching.
薄膜コート用組成物に溶剤とか可塑剤を用いた場合には
、その除去は必要に応じて行われる。When a solvent or a plasticizer is used in the thin film coating composition, their removal is performed as necessary.
この場合、除去が必要な部分は、最外周であるので、除
去は比較的容易に行い得る。In this case, since the portion that needs to be removed is the outermost periphery, removal can be performed relatively easily.
未延伸中空繊維の表面へのコートは、一般に行われてい
る方法が用いられる。溶液を塗布、もしくは溶液に浸漬
する方法、蒸着法等があるが、溶液を用いるのが簡単で
ある。A commonly used method is used to coat the surface of the undrawn hollow fibers. There are methods such as coating or dipping in a solution, vapor deposition, etc., but using a solution is simple.
続いて延伸が行われる。未延伸中空糸を構成するポリマ
ー、或いは、該未延伸中空糸の表面にコートしたポリマ
ーのうちより低い方の融点よシも低い温度で、夕景の延
伸（「冷延伸」と称する）を行って白化させ、続いて前
記冷延伸温度より高くポリマーの融点よりも低い温度で
加熱延伸（「熱延伸」と称する）によって、孔径の拡大
と、孔形状の安定化を計る。Stretching is then performed. Sunset stretching (referred to as "cold stretching") is performed at a temperature lower than the melting point of the polymer constituting the unstretched hollow fibers or the polymer coated on the surface of the unstretched hollow fibers, whichever is lower. Whitening is carried out, followed by heating stretching (referred to as "hot stretching") at a temperature higher than the cold stretching temperature and lower than the melting point of the polymer to enlarge the pore diameter and stabilize the pore shape.
本発明は、薄い分離層を中空糸表面に形成させる新規な
方法であり、この意味からして、基材表面が平滑な状態
で分離層をコートし、次いで、基材を多孔化する。The present invention is a novel method for forming a thin separation layer on the surface of a hollow fiber, and in this sense, the separation layer is coated on a smooth substrate surface, and then the substrate is made porous.
本発明の方法においては基材の中空糸がその表面に微細
孔を有していてもコートするポリマーが侵入ない程度の
微細孔であればよい。従って表層が溶剤等を含んで非常
に変形しやすく、冷延伸によって、フィードロール上等
での側圧等によって破壊される惧れのあるような場合に
は、張力の大きい冷延伸をコーティング前に行っておい
てからコートしてもよい。In the method of the present invention, even if the hollow fibers of the base material have micropores on their surface, the pores may be small enough to prevent the coating polymer from penetrating. Therefore, if the surface layer is very easily deformed due to the presence of solvent, etc., and there is a risk that it will be destroyed by cold stretching due to lateral pressure on feed rolls, etc., cold stretching with high tension should be performed before coating. You can let it stand and then coat it.
中空繊維状膜の形状については、一般的に用いられる範
囲の形状として、内径の範囲として、α１ｍから５ｍ程
度が好ましい。但し、機能膜の膜厚については、薄いほ
ど良く、加工性、特にピンホー〃の発生を考えると、［
１，ｏｌから２．０ミクロン程度が好ましい。Regarding the shape of the hollow fibrous membrane, it is preferable that the inner diameter range is approximately α1 m to 5 m as a generally used shape. However, regarding the thickness of the functional film, the thinner it is, the better; considering the processability, especially the occurrence of pinholes, [
The thickness is preferably about 1.0 to 2.0 microns.
本発明の方法は上記の通りであるので基材の中空糸とコ
ートしたポリマーはむしろ接着していない方が好ましく
、接着していなくても得られる複合中空繊維は前述の収
縮力により機能薄膜は基材の多孔質中空糸表面に密着し
て安定なものとなる。Since the method of the present invention is as described above, it is preferable that the hollow fibers of the base material and the coated polymer are not bonded together, and even if they are not bonded, the composite hollow fibers obtained will not form a functional thin film due to the shrinkage force described above. It becomes stable by adhering closely to the porous hollow fiber surface of the base material.
本発明を実施例を用いて、更に詳しく説明する。The present invention will be explained in more detail using examples.
実施例１円形のスリット状吐出口を有する中空糸製造用ノズｐを
用いて、密度α９６８９７ｃｍ” 、メルトインデック
ス５５のポリエチレンを、吐出温度１６０℃、吐出線速
度５ ｃｍ ／ ｍ１ｎ−、巻取速度２５０７ＦＬ ／
ｍｉｎで紡糸した。Example 1 Polyethylene with a density α of 96897 cm and a melt index of 55 was produced using a hollow fiber manufacturing nozzle P having a circular slit-shaped discharge port at a discharge temperature of 160°C, a discharge linear velocity of 5 cm/m1n-, and a winding speed of 2507FL. /
Spun at min.
得られた未延伸糸は、内径２ｏｏミクロンであり、３０
ミクロンの厚さを有する未延伸中空繊維を得た。The obtained undrawn yarn had an inner diameter of 200 microns and a
Undrawn hollow fibers with a thickness of microns were obtained.
該中空未延伸糸を１１５℃に加熱されたローラー上を定
長下に接触せしめてローラー接触時間１００秒でアニー
ル処理した。The hollow undrawn yarn was annealed by bringing it into contact with a roller heated to 115° C. under a fixed length for a roller contact time of 100 seconds.
次に、密度α９３９７ｃｍ” 、融点１４１℃のトラン
ス１．４ポリブタジ工ン３部をクロロホルム１００部に
溶解して得られた溶液中に該中空糸未延伸糸を１０秒間
浸漬した後、常温常圧の下でクロロホルムを揮散せしめ
た。Next, the undrawn hollow fibers were immersed for 10 seconds in a solution obtained by dissolving 3 parts of trans 1.4 polybutadiene having a density α9397cm" and a melting point of 141°C in 100 parts of chloroform, and then Chloroform was evaporated under
史に該表面コートされた未延伸糸を２８℃に保たれたロ
ーラー間で８０チ冷延伸し、引続き１０５℃に加熱され
た加熱鋼中で総延伸量が４００優になるまで、ローラー
間熱延伸を行い２８％緩和さ？た状態で熱セットを行な
い複合中空膜を得た。The surface-coated undrawn yarn was cold-stretched for 80 inches between rollers kept at 28°C, and then heated between rollers in heated steel heated to 105°C until the total amount of stretching reached 400 mm. 28% relaxation after stretching? Heat setting was performed in this state to obtain a composite hollow membrane.
得られた複合中空糸膜は、内径１９０ミクロンで外トＡ
と内層がそれぞれ１．２０ ミクロンの厚さを有する、
同心円状に配された二層から成っており、電子頭倣鏡で
観察した結果、内層には幅０．５−０．５ミクロン、長
さａ ８−１．１ミクロンのスリット状の孔が形成され
ていたが外層表面には、孔は認められず均質でありピン
ホールも認められなかった。The obtained composite hollow fiber membrane had an inner diameter of 190 microns and an outer diameter of A.
and the inner layer each have a thickness of 1.20 microns,
It consists of two layers arranged in concentric circles, and as a result of observation with an electronic head mirror, the inner layer has slit-like holes with a width of 0.5-0.5 microns and a length a of 8-1.1 microns. However, no pores were observed on the surface of the outer layer, which was homogeneous and no pinholes were observed.
又、酸素透過速度は、ｊ、 ９ Ｘ １０−’ ｃｍ３
／ｃｍ２ｓｅｃ・ｃｍＨｇ、、’ｄ素素踊過速度、ｈ
４ Ｘ ｊ Ｏ−’ ｃｍ”／ｃｍ２ｓｅｃ −ｃｍ
Ｈｇであり、酸素を選択的に透過させ、かつ透過速度が
優れるものであった。Also, the oxygen permeation rate is j, 9 x 10-' cm3
/cm2sec・cmHg,,'d elementary overspeed, h
4 X j O-'cm"/cm2sec -cm
It was Hg, selectively permeated oxygen, and had an excellent permeation rate.
実施例２円形のスリット状吐出口を有する中空糸製造用ノズルを
用いて、舅度α９１３ｇ／ｃＩＮ３、メルトインデック
ス２６のポリプロピレンヲ、吐出温度１９０℃、吐出線
速度５ ｃｍ ／ ｍｉｎ 、巻取速度４００ｍ／ｍｉ
ｎで紡糸した。Example 2 Using a nozzle for manufacturing hollow fibers having a circular slit-shaped discharge port, polypropylene with a diameter α of 913 g/cIN3 and a melt index of 26 was produced at a discharge temperature of 190°C, a discharge linear velocity of 5 cm/min, and a winding speed of 400 m. /mi
Spun at n.
得られた未延伸糸は、内径２８０ミクロンであり、３２
ミクロンの厚さを有する未延伸中空繊維を得た。The obtained undrawn yarn had an inner diameter of 280 microns and a diameter of 32
Undrawn hollow fibers with a thickness of microns were obtained.
該中空未延伸糸を１４０℃に加熱されたローラー上を定
長下に接触せしめてローラー接触時間１００秒でアニー
ル処理した。The hollow undrawn yarn was annealed by bringing it into contact with a roller heated to 140° C. under a fixed length for a roller contact time of 100 seconds.
次に、メルトインデックス６のポリカーボネート５部を
メチレンクロフィト１００部に溶解し得られた溶液をオ
イリングローラ−を用いて、該未延伸中空糸に塗布し、
その後メチレンクロフィトを常温常圧の下で揮散せしめ
た。Next, a solution obtained by dissolving 5 parts of polycarbonate having a melt index of 6 in 100 parts of methylene crophyte is applied to the undrawn hollow fibers using an oiling roller,
Thereafter, methylene crophyte was volatilized at room temperature and pressure.
更に該表面コートされた未延伸糸を６０℃に保たれたロ
ーラー間で２０％冷延伸し、引続き１５５℃に加熱され
た加熱函中で総延伸量が２００チになるまでローラー間
熱延伸を行い、更に、１４０℃に加熱された加熱函中で
２８％緩和させた状態で熱セットを行って、複合中空糸
膜を得た。Furthermore, the surface-coated undrawn yarn was cold-stretched by 20% between rollers kept at 60°C, and then hot-stretched between rollers in a heated box heated to 155°C until the total amount of stretching reached 200 inches. The composite hollow fiber membrane was then heat-set in a heating box heated to 140° C. in a 28% relaxed state.
得られた複合中空糸膜は、内径２６５ミクロンで、２６
．３ミクロンの厚さを有する、同心円状に配された二層
から成っており、電子顕微鏡で観察した結果、内層には
幅α０７−（１０９ミクロン、長す０．２−０．５ミク
ロンのスリット状の孔が形成されていた。又、二酸化炭
素透過速度はａ ＯＸ ｉ Ｏ−’ ｃｍ３／ｃｍ”
ｓｅｃ・ｒｙｎＨｇ ｉｎｎ素踊過速度ｔ ４ｘ ｉ
ｏ−’ ｃｍｊ／ｃｍ２ｓｅｃ・ｃｍＨｇ であり、
二・酸化炭素を選択的に透過略せ、かつ透過速度が優れ
るものであった。The resulting composite hollow fiber membrane had an inner diameter of 265 microns and a
．． It consists of two concentric layers with a thickness of 3 microns, and as a result of observation with an electron microscope, the inner layer has a slit with a width α07-(109 microns and a length of 0.2-0.5 microns). In addition, the carbon dioxide permeation rate was a OX i O-'cm3/cm".
sec・rynHg inn dance overspeed t 4x i
o-' cmj/cm2sec・cmHg,
It was able to selectively permeate carbon dioxide and had an excellent permeation rate.
実施例５円形のスリット状吐出口を有する中空糸製造用ノズルを
用いて、実施例２で使用したポリプロピレンを、吐出温
度２０５℃、吐出線速度４ｃｍ ／ ｍｉｎ、巻取速度
５００ｒｒＬ／ｍｉｎで紡糸した。Example 5 The polypropylene used in Example 2 was spun at a discharge temperature of 205° C., a discharge linear velocity of 4 cm/min, and a winding speed of 500 rrL/min using a hollow fiber manufacturing nozzle having a circular slit-shaped discharge port. .
得られた未延伸糸は、内径２９０ミクロンであり、５６
ミクロンの厚さを有する未延伸中空未番父、ヤｉｍ ５
寸イ与本だ。The resulting undrawn yarn had an inner diameter of 290 microns and a diameter of 56
Unstretched hollow multi-layer with micron thickness, Ya im 5
It's a very good book.
該中空未延伸糸を１３０℃に加熱されたローラー上を定
長下に接触せしめてローラー接触時間１８０秒でアニー
ル処理した。The hollow undrawn yarn was annealed by bringing it into contact with a roller heated to 130° C. under a fixed length for a roller contact time of 180 seconds.
次Ｋ、酢化ｆｆ ５ ｓ ％のセルロースジアセテート
２部、スルホ９７０．１部をアセトン１００部に溶解し
得られた溶液をオイリングローラ−を用いて、該未延伸
中空糸に塗布し、その後、アセトンを常温常圧の下で揮
散せしめた。Next, a solution obtained by dissolving 2 parts of cellulose diacetate with 5 s acetate and 970.1 parts of sulfo in 100 parts of acetone was applied to the undrawn hollow fibers using an oiling roller, and then , acetone was volatilized at room temperature and pressure.
更に、該表面コートされた未延伸糸を６０℃に保たれた
ローラー間で１７％冷延伸し、引続き１３０℃に加熱さ
れた加熱函中で総延伸量が１８０％になるまでローラー
間熱延伸を行い、更に、１５０℃に加熱された加熱函中
で２５％緩和させた状態で熱セットを行い、複合中空糸
膜を得た。Furthermore, the surface-coated undrawn yarn was cold-stretched by 17% between rollers kept at 60°C, and then hot-stretched between rollers in a heated box heated to 130°C until the total amount of stretching reached 180%. This was followed by heat setting in a heating box heated to 150° C. in a 25% relaxed state to obtain a composite hollow fiber membrane.
得られた複合中空糸膜は、内径２７３ミクロンで３１ミ
クロンの厚さを有する同心円上に配された二層から成っ
ており、？と子顕ｆａ鏡で観察しだ結果、内層には幅０
．０７−０．０９ミクロン、長（０，１−０，４ミクロ
ンのスリット状の孔が形成されていた。酸素透過速度は
、１． ＯＸ １０−’ｃｍ” ／ＣＭ” ｓ ｅ ｃ
・ｃｍ Ｈｇ 、窒素透過速度はα５６ ×１０−’
ｃｍ３／ｃｍ２ｓｅｃ−ｃｍＨｇ であり、酸素を選
択的に透過させ、かつ透過速度は極めて高いものであっ
た。The resulting composite hollow fiber membrane consisted of two concentrically arranged layers having an inner diameter of 273 microns and a thickness of 31 microns. As a result of observation with a toko microscope, the inner layer has a width of 0.
．． Slit-like pores with a length of 0.7-0.09 microns and a length of 0.1-0.4 microns were formed.The oxygen permeation rate was 1. OX 10-'cm"/CM" sec
・cm Hg, nitrogen permeation rate is α56 ×10-'
cm3/cm2sec-cmHg, allowing oxygen to permeate selectively, and the permeation rate was extremely high.
実施例４円形のスリット状吐出口を有する中空糸製造用ノズルを
用いて、密度０．９６５、メルトインデックス５．２の
ポリエチレンを、吐出温度１６０℃、吐出口線速度１０
α／ ｍｉｎ 、巻取速度３５０ｍ／ｍｉｎで紡糸した
。Example 4 Polyethylene with a density of 0.965 and a melt index of 5.2 was produced using a hollow fiber manufacturing nozzle having a circular slit-shaped discharge port at a discharge temperature of 160°C and a discharge outlet linear velocity of 10.
The fiber was spun at α/min and a winding speed of 350 m/min.
得られた未延伸糸は、内径２９０ミクロンであり、６３
ミクロンの厚さを有する未延伸中空繊維を得た。The obtained undrawn yarn had an inner diameter of 290 microns and a diameter of 63 μm.
Undrawn hollow fibers with a thickness of microns were obtained.
該中空未延伸糸を１１５℃に加熱されたローラー上を定
長下に接触せしめてローラー接融時間１００秒でア二−
μ処理した。The hollow undrawn yarn was brought into contact with a roller heated to 115° C. under a fixed length, and the yarn was annealed with a roller welding time of 100 seconds.
μ treated.
次ニ、ポリメチルシロキサン２部をジオキサン１００部
に溶解して得られた溶液中に該未延伸中空糸を１０秒間
浸漬後、常温常圧の下でジオキサンを揮散せしめた。Next, the unstretched hollow fibers were immersed for 10 seconds in a solution obtained by dissolving 2 parts of polymethylsiloxane in 100 parts of dioxane, and then the dioxane was volatilized at room temperature and pressure.
更に、該表面コートされた未延伸糸を３０℃に保たれた
ローラー間で５０ｆｉ冷延伸し、引続き１００℃に加熱
された加熱函中で総延伸量が３００チになるまでローラ
ー間熱延伸を行い、史に１１５℃に加熱された加熱函中
で１０チ緩和させた状態で熱セットを行い複合中空糸膜
を得た。Furthermore, the surface-coated undrawn yarn was cold-stretched for 50 fi between rollers kept at 30°C, and then hot-stretched between rollers in a heating box heated to 100°C until the total amount of stretching reached 300 inches. The composite hollow fiber membrane was then heat-set in a heated box heated to 115° C. in a state where the membrane was relaxed by 10 degrees.
得られた複合中空糸膜は、内ｔ１！：２７０ミクロンで
４８ミクロンの厚さを有する同心円上に配された二層か
ら成っており、電子顕微鏡で？ＩＡ察した結果、内側の
層は多孔質化しており、幅α１−α５ミクロン、長すα
５−０．９ミクロンのスリット状孔が形成されていた。The obtained composite hollow fiber membrane has an inner t1! : Consists of two layers arranged in concentric circles with a thickness of 270 microns and 48 microns, under an electron microscope. As a result of IA analysis, the inner layer is porous, with a width of α1-α5 microns and a length of α.
Slit-like pores of 5-0.9 microns were formed.
シリコーンゴムからなる表面層は均質で孔やピンホール
は認められなかった。The surface layer made of silicone rubber was homogeneous and no holes or pinholes were observed.
又、酸素透過速度はｌ ６ Ｘ １０” ｃｍ”／ｅｔ
ａ” ’８１３０・ｃｍＨｇ、 窒素透過速度は１．５
Ｘ １０−’ ｔｍ” ７ｃｍ” ・ｓｅｃ−ｔｍＨ
ｇ と極めて優れたものであった。Also, the oxygen permeation rate is l 6 x 10"cm"/et
a” '8130 cmHg, nitrogen permeation rate is 1.5
X 10-'tm"7cm" ・sec-tmH
g, which was extremely excellent.
実施例５円形のスリット状吐出口を有する中空糸製造用ノズルを
用いて、密度Ｑ、 ９６５ ｇ／ｃｍ” 、メルトイン
デックス５．２のポリエチレンを、吐出温度１６３℃、
吐出線速度１０ ｃｍ ／ ｍｉｎ 、巻取速度３００
ｍ／ｍｉｎで紡糸した。Example 5 Polyethylene with a density Q of 965 g/cm" and a melt index of 5.2 was discharged at a temperature of 163° C. using a hollow fiber manufacturing nozzle having a circular slit-shaped discharge port.
Discharge linear speed 10 cm/min, winding speed 300
Spinning was performed at m/min.
得られた未延伸糸は、内径２５（１：クロンであり、６
１ミクロンの厚さを有する未延伸中空繊維を得た。The obtained undrawn yarn had an inner diameter of 25 (1: Kron, 6
An undrawn hollow fiber having a thickness of 1 micron was obtained.
該中空未延伸糸を１１５℃の加熱炉の中で一時間定長処
理を行った。The hollow undrawn yarn was subjected to a constant length treatment for one hour in a heating furnace at 115°C.
次に、密度１．２４ ｆｉ／ｃｙｎ”のポリスルホン３
部をＫＮ−ジメチルホルムアミド１００部に溶解して得
られた溶液中に該未延伸糸を１０秒間浸漬後、常温減圧
下でＮ、Ｎ−ジメチルホルムアミドを揮散させた。Next, polysulfone 3 with a density of 1.24 fi/cyn''
The undrawn yarn was immersed for 10 seconds in a solution obtained by dissolving 100 parts of KN-dimethylformamide, and then the N,N-dimethylformamide was volatilized at room temperature and under reduced pressure.
更に、該表面コートされた未延伸糸を３０℃の雰囲気で
５０チ冷延伸し、続いて１０５℃に加熱された加熱函中
で、総延伸量が４００チになるまでローラー間熱延伸を
行った。Furthermore, the surface-coated undrawn yarn was cold-stretched to 50 inches in an atmosphere of 30°C, and then hot-stretched between rollers in a heated box heated to 105°C until the total amount of stretching reached 400 inches. Ta.
更に、１１５℃に加熱された加熱函中で、２０％緩和さ
せた状態で熱セットを行って複合中空糸膜を得た。Furthermore, heat setting was performed in a heating box heated to 115° C. in a state of 20% relaxation to obtain a composite hollow fiber membrane.
得られた複合中空糸膜は、内径２００ミクロンで５２ミ
クロンの厚さを有する同心円状に配された二層から成っ
ており、電子顕微鏡で観察した結果内層は多孔質化され
ている事が確認された。The resulting composite hollow fiber membrane consists of two concentrically arranged layers with an inner diameter of 200 microns and a thickness of 52 microns, and observation with an electron microscope confirmed that the inner layer was porous. It was done.
ポリスルホンから成る表面層は均質で多孔質化はされて
いなかった。The surface layer made of polysulfone was homogeneous and not porous.
又、該膜をアルコールで湿潤処理した後、水透過率を測
定した所、ＩＩＬ０２１／１ｒＬ２・ｈｒ−ａｔｍであ
り、食塩排除率は９９チであった。Further, after moistening the membrane with alcohol, the water permeability was measured, and it was found to be IIL021/1rL2.hr-atm, and the salt rejection rate was 99cm.
実施例６円形のスリット状吐出口を有する中空糸Ｓａ用ノノズを
用いて、密度１．７６９／ｃａｒ” 、融点１７６℃の
ポリ弗化ビニリデンを円形の中空糸製造用ノズルを用い
て、２５０℃でｒｇｆＭ１押しだしし、ドラフト比４０
で巻取り、未延伸糸を得た。Example 6 Polyvinylidene fluoride having a density of 1.769/car" and a melting point of 176°C was produced at 250°C using a circular nozzle for manufacturing hollow fibers, using a hollow fiber Sa nozzle having a circular slit-shaped discharge port. Push out rgfM1 and draft ratio 40
The yarn was wound up to obtain an undrawn yarn.
次に、密度１．２９７ｃｍ”のポリカーボネート２部を
ジクロ１７７７７１００部に溶解して得られた溶液中に
、該未延伸糸を５秒間浸漬した後、取りだし、常温下で
ジクロルメタンを揮赦せしめだ。Next, the undrawn yarn was immersed for 5 seconds in a solution obtained by dissolving 2 parts of polycarbonate having a density of 1.297 cm'' in 177777100 parts of dichloromethane, and then taken out and allowed to volatilize dichloromethane at room temperature.
かかる、未延伸糸を、電子顕微鏡で観察した結果、内径
が２４０ミクロン、膜厚が２５ミクロンの内層と２ミク
ロンの外層とから成る二層構造を有していた。When the undrawn yarn was observed under an electron microscope, it was found to have a two-layer structure with an inner diameter of 240 microns and a thickness of an inner layer of 25 microns and an outer layer of 2 microns.
核処理後の未延伸糸を２０℃で３０％、次いで１３０℃
で１００チ延伸し、最後に１５０℃で２０％緩和熱セツ
［した。得られた未延伸糸は、内径が２２０ミクロンで
膜厚が２０ミクロンの内層と１ミクロンの外層から成る
二層構造を有し、電子顕微鏡で観察した結果、内層はα
０１ミクロンから１１ミクロンの大きさの微細孔を有し
、他方、外層にはかかる微細孔は認められなかった。After nuclear treatment, the undrawn yarn was heated to 30% at 20°C, then at 130°C.
The film was stretched for 100 inches, and finally heated at 150° C. for 20% relaxation. The obtained undrawn yarn has an inner diameter of 220 microns and a two-layer structure consisting of an inner layer of 20 microns and an outer layer of 1 micron in thickness, and as a result of observation with an electron microscope, the inner layer has an α
It had micropores with a size of 0.01 to 11 microns, while no such micropores were observed in the outer layer.
此処に得られた中空糸を用いて、６０℃でガス透過試験
を行った結果、Ｃｏ、に対しては、１１．７×１Ｏ−ａ
ｃＷＩ３／ｃＮ１２・５ｅｃ１１譚Ｈｇ１０．に対して
は、１６ Ｘ １０−’ ｃｍ’／ｃｍ” ・ｓｅｃ−
ｍＨ’ｇであった。Using the hollow fiber obtained here, a gas permeation test was conducted at 60°C, and the result was 11.7 x 1 O-a for Co.
cWI3/cN12・5ec11tanHg10. For, 16 X 10-'cm'/cm" ・sec-
It was mH'g.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25432485AJPS62117811A (en) | 1985-11-13 | 1985-11-13 | Production of conjugated hollow fiber membrane |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25432485AJPS62117811A (en) | 1985-11-13 | 1985-11-13 | Production of conjugated hollow fiber membrane |
| Publication Number | Publication Date |
|---|---|
| JPS62117811Atrue JPS62117811A (en) | 1987-05-29 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25432485APendingJPS62117811A (en) | 1985-11-13 | 1985-11-13 | Production of conjugated hollow fiber membrane |
| Country | Link |
|---|---|
| JP (1) | JPS62117811A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63235540A (en)* | 1987-03-20 | 1988-09-30 | 宇部興産株式会社 | Manufacturing method of porous hollow fiber for oxygenator lungs |
| JP2008302359A (en)* | 2000-06-23 | 2008-12-18 | Lg Chemical Co Ltd | Multi-component composite separation membrane and method for producing the same |
| JP2013031834A (en)* | 2011-07-04 | 2013-02-14 | Toyobo Co Ltd | Reverse osmosis membrane for desalinating brine |
| JP2013031836A (en)* | 2011-07-04 | 2013-02-14 | Toyobo Co Ltd | Separation membrane for nanofiltration |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63235540A (en)* | 1987-03-20 | 1988-09-30 | 宇部興産株式会社 | Manufacturing method of porous hollow fiber for oxygenator lungs |
| JP2008302359A (en)* | 2000-06-23 | 2008-12-18 | Lg Chemical Co Ltd | Multi-component composite separation membrane and method for producing the same |
| JP2013031834A (en)* | 2011-07-04 | 2013-02-14 | Toyobo Co Ltd | Reverse osmosis membrane for desalinating brine |
| JP2013031836A (en)* | 2011-07-04 | 2013-02-14 | Toyobo Co Ltd | Separation membrane for nanofiltration |
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