JPH09164324A - Hollow-fiber membrane module and its production - Google Patents
Hollow-fiber membrane module and its productionInfo
- Publication number
- JPH09164324A JPH09164324A JP29709695A JP29709695A JPH09164324A JP H09164324 A JPH09164324 A JP H09164324A JP 29709695 A JP29709695 A JP 29709695A JP 29709695 A JP29709695 A JP 29709695A JP H09164324 A JPH09164324 A JP H09164324A
- Authority
- JP
- Japan
- Prior art keywords
- fiber membrane
- hollow fiber
- resin
- hollow
- coating
- 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.)
- Pending
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、精密ろ過、限外ろ
過などに使用される、中空糸膜モジュール及びその製造
方法に関し、より詳しくは、中空糸膜束の固定部材近傍
の中空糸膜が損傷し難い中空糸膜モジュール及び製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hollow fiber membrane module used for microfiltration, ultrafiltration and the like, and a method for producing the same, more specifically, a hollow fiber membrane near a fixing member of a hollow fiber membrane bundle. The present invention relates to a hollow fiber membrane module that is not easily damaged and a manufacturing method.
【０００２】[0002]
【従来の技術】中空糸膜はすでに精密ろ過、限外ろ過な
どの様々な分野で使用されているが、温度変動が大き
い、あるいはエアーバブルで中空糸膜を激しく揺動させ
る等、さらに過酷な条件での使用も望まれている。この
ような過酷な使用条件下ではしばしば中空糸膜束の固定
部近傍で中空糸膜が切断したり、破れるという問題が発
生している。2. Description of the Related Art Hollow fiber membranes have already been used in various fields such as microfiltration and ultrafiltration, but they are more severe, such as large temperature fluctuations or vigorous rocking of the hollow fiber membranes by air bubbles. Use under certain conditions is also desired. Under such severe conditions of use, there is often a problem that the hollow fiber membrane is cut or broken near the fixing portion of the hollow fiber membrane bundle.
【０００３】この点を改善するために、固定部近傍の中
空糸膜束外縁を可撓性帯などで保護する方法（実開昭５
５−９９７０３号公報、特開昭５８−１８３９１６号公
報、特開昭５９−１４７６０３号公報、特開昭６１−１
７８９０２号公報、特開昭６３−１５８１０３号公
報）、固定部材よりも柔らかい熱硬化性樹脂で被覆する
方法（特開昭５９−４４０３号公報、特開平２−１０７
３１８号公報）、あるいは、これらを組み合わせた保護
ネットと固定部材表面に弾性樹脂層を設ける方法（特開
平４−３３４５２９号公報、特開平５−２３５５０号公
報）が知られている。In order to improve this point, a method of protecting the outer edge of the hollow fiber membrane bundle in the vicinity of the fixed portion with a flexible band or the like (Shokai Sho 5
5-99703, JP-A-58-183916, JP-A-59-147603, JP-A-61-1.
78902, JP-A-63-158103), a method of coating with a thermosetting resin softer than the fixing member (JP-A-59-4403, JP-A-2-107).
No. 318), or a method in which an elastic resin layer is provided on the surface of the fixing member and a protective net in which these are combined (JP-A-4-334529 and JP-A-5-23550).
【０００４】しかしながら、特開平４−３３４５２９号
公報で詳しく検討されているように、保護ネット単独の
場合、弾性樹脂層単独の場合、及び、特に比較例３に示
されているように保護ネットを長くした場合、のいずれ
においてもリークが発生することからこれらの方法でも
十分とは言えない。However, as discussed in detail in JP-A-4-334529, a protective net alone, an elastic resin layer alone, and in particular, a protective net as shown in Comparative Example 3 were used. If the length is increased, a leak occurs in any of the above cases, and therefore these methods are not sufficient.
【０００５】中空糸膜が固定部近傍で損傷を受ける原因
は、この近傍の中空糸膜に曲げ応力が集中し、この力に
耐えられないからである。したがって、このような力に
対する中空糸膜自身の強度を向上させなければ根本的な
解決にはならない。しかしながら、従来の方法では必ず
しも固定部近傍に集中する曲げ応力に耐えるほど中空糸
膜自身の強度が向上しているとは言えない。The reason why the hollow fiber membrane is damaged in the vicinity of the fixed portion is that bending stress concentrates on the hollow fiber membrane in the vicinity thereof and the hollow fiber membrane cannot withstand this force. Therefore, it is not a fundamental solution unless the strength of the hollow fiber membrane itself against such a force is improved. However, it cannot be said that the conventional method does not necessarily improve the strength of the hollow fiber membrane itself to withstand the bending stress concentrated near the fixed portion.
【０００６】[0006]
【発明が解決しようとする課題】本発明では、まず未処
理の中空糸膜の固定部近傍で曲げ応力が集中したとき、
どの程度中空糸膜の強度が低下するか調べた。図１は、
その測定方法を示す略図である。図中１、２はそれぞれ
中空糸膜及び固定部材である。矢印Ｆは中空糸膜１の引
張り方向であり、αは固定部材２の面と引張り方向のな
す角度である。使用した中空糸膜は、内、外径が５００
μｍ、８００μｍ、孔径が０．２μｍ、破断引張り強度
が１７０ｇ／本（破断引張り応力５６Ｋｇ／ｃｍ2 ）、
破断時の伸びが６０％であり、ウレタン樹脂Ａからなる
固定部材の破断引張り強度は５００Ｋｇ／ｃｍ2 、破断
時の伸びは２０％である。SUMMARY OF THE INVENTION In the present invention, first, when bending stress is concentrated near the fixing portion of an untreated hollow fiber membrane,
It was investigated to what extent the strength of the hollow fiber membrane was reduced. FIG.
It is a schematic diagram showing the measuring method. In the figure, 1 and 2 are a hollow fiber membrane and a fixing member, respectively. The arrow F is the pulling direction of the hollow fiber membrane 1, and α is the angle between the surface of the fixing member 2 and the pulling direction. The hollow fiber membrane used had an inner and outer diameter of 500.
μm, 800 μm, pore size 0.2 μm, breaking tensile strength 170 g / piece (breaking tensile stress 56 Kg / cm 2 ),
The elongation at break is 60%, the tensile strength at break of the fixing member made of urethane resin A is 500 Kg / cm 2 , and the elongation at break is 20%.
【０００７】図２は、角度αと引張り強度の関係を示す
が、角度によらず中空糸膜１の破断は固定部材２の近傍
の根本１Ａで発生し、かつ角度が小さくなるにしたがっ
て引張り強度は低下した。約６０°までは垂直方向に比
べて低下は少ないが、約３０°では垂直方向に比べて約
１／５まで低下した。このとき、中空糸膜１は、固定部
材２の近傍の根本１Ａで引き裂かれるように切れる様子
が観察された。同様な結果は、破断強度が１１０Ｋｇ／
ｃｍ2 、破断時の伸びが８０％の他のウレタン樹脂Ｂを
固定部材に用いたときにも得られた。FIG. 2 shows the relationship between the angle α and the tensile strength. The breaking of the hollow fiber membrane 1 occurs at the root 1A near the fixing member 2 regardless of the angle, and the tensile strength decreases as the angle decreases. Fell. Up to about 60 °, the decrease was small compared to the vertical direction, but at about 30 ° it decreased to about 1/5 compared to the vertical direction. At this time, it was observed that the hollow fiber membrane 1 was cut so as to be torn at the root 1A near the fixing member 2. Similar results show that the breaking strength is 110 kg /
It was also obtained when another urethane resin B having a cm 2 and an elongation at break of 80% was used for the fixing member.
【０００８】次に、特開昭５９−４４０３号公報に準じ
て、図３のように、あらかじめこのウレタン樹脂Ｂを薄
く被覆して被覆層３を形成した中空糸膜１を使って図１
と同様にして測定を行った。この場合、図１の場合に比
べて改善効果は見られたものの、ウレタン樹脂の中空糸
膜への染み込み程度によって大きく測定値が変動した。
また、予測されるように、被覆する樹脂の強度が中空糸
膜よりも小さい場合には補強効果は期待できない。逆
に、あらかじめ強度の大きいウレタン樹脂Ａを被覆した
中空糸膜を用いた場合には、被覆層３が薄いときには固
定部材２の近傍の根本１Ａで脆く折れ、厚いときには被
覆部分と被覆されていない部分の界面１Ｂで引き裂かれ
た。Next, according to Japanese Patent Laid-Open No. 59-4403, a hollow fiber membrane 1 in which a urethane resin B is thinly coated beforehand to form a coating layer 3 as shown in FIG. 3 is used.
The measurement was performed in the same manner as described above. In this case, although the improvement effect was observed as compared with the case of FIG. 1, the measured values varied greatly depending on the extent of the penetration of the urethane resin into the hollow fiber membrane.
Further, as predicted, when the strength of the resin to be coated is smaller than that of the hollow fiber membrane, the reinforcing effect cannot be expected. On the contrary, when the hollow fiber membrane coated with the urethane resin A having high strength is used in advance, when the coating layer 3 is thin, the root 1A near the fixing member 2 is fragilely broken, and when it is thick, it is not covered with the coating portion. It was torn at part interface 1B.
【０００９】これらの結果から、柔軟な固定部材（ウレ
タン樹脂Ｂ）を使用しても中空糸膜を被覆するのでなけ
れば中空糸膜の強度を向上させる効果は乏しく、また、
熱硬化性樹脂を被覆した場合には、樹脂自身の特性だけ
でなく、中空糸膜への染み込み量にもよる変動が大き
く、その制御は困難であると言える。From these results, even if a flexible fixing member (urethane resin B) is used, the effect of improving the strength of the hollow fiber membrane is poor unless the hollow fiber membrane is coated, and
When the thermosetting resin is coated, it is difficult to control it because the fluctuation largely depends on not only the characteristics of the resin itself but also the amount of the resin soaked into the hollow fiber membrane.
【００１０】熱硬化性樹脂で被覆した場合をさらに詳し
く観察すると、樹脂は、中空糸膜のネットワーク骨格の
表面をその空孔を残しながら被覆しているというよりも
文字通り緻密な樹脂層を形成している。したがって、被
覆部分の中空糸膜の機械的な特性はこの被覆層によって
ほとんど決定される。そのため樹脂自身の特性及び染み
込み量に大きく影響され、制御が困難になっている。When the coating with the thermosetting resin is observed in more detail, the resin literally forms a dense resin layer rather than coating the surface of the network skeleton of the hollow fiber membrane while leaving its pores. ing. Therefore, the mechanical properties of the hollow fiber membrane of the coated portion are mostly determined by this coating layer. Therefore, the characteristics of the resin itself and the permeation amount are greatly affected, and the control becomes difficult.
【００１１】以上の考察によれば、中空糸膜を効果的に
補強する被覆樹脂は、その被覆量が容易に制御でき、中
空糸膜自身の機械的な特性を残しながらそのネットワー
ク骨格の表面を被覆し、かつこの程度の被覆量で補強効
果を発揮するものでなければならない。また、このよう
な特性を熱硬化性樹脂の中から見出すことは困難であ
る。According to the above consideration, the coating amount of the coating resin that effectively reinforces the hollow fiber membrane can be easily controlled, and the surface of the network skeleton can be maintained while the mechanical characteristics of the hollow fiber membrane itself are retained. It must be coated and exert a reinforcing effect with this amount of coating. Further, it is difficult to find such characteristics in thermosetting resins.
【００１２】[0012]
【課題を解決するための手段】かくして本発明は、「中
空糸膜の破断時における引張り応力及び弾性率よりもお
よそ１０倍以上大きな引張り応力及び弾性率を有し、破
断時の伸びが５〜２０％の熱可塑性樹脂で、中空糸膜束
集束固定部近傍の中空糸膜を被覆したことを特徴とする
中空糸膜モジュール」であり、「中空糸膜の破断時にお
ける引張り応力及び弾性率よりもおよそ１０倍以上大き
な引張り応力及び弾性率を有し、破断時の伸びが５〜２
０％の熱可塑性樹脂を、中空糸膜を変性させない溶剤に
２〜１５％溶解した溶液を、中空糸膜束集束固定部近傍
の中空糸膜に塗布若しくは浸漬して含浸させたのち、溶
剤を乾燥することを特徴とする中空糸膜モジュールの製
造方法」である。The present invention thus provides that "a hollow fiber membrane has a tensile stress and elastic modulus about 10 times or more greater than the tensile stress and elastic modulus at break, and an elongation at break of 5 to 5. A hollow fiber membrane module characterized by coating a hollow fiber membrane in the vicinity of a bundle fixing portion of a hollow fiber membrane with 20% of a thermoplastic resin, "from tensile stress and elastic modulus at break of hollow fiber membrane" Also has a tensile stress and elastic modulus that are 10 times or more greater, and the elongation at break is 5 to 2
A solution of 2% to 15% of 0% thermoplastic resin dissolved in a solvent that does not modify the hollow fiber membrane is applied or dipped into the hollow fiber membrane near the bundle fixing part of the hollow fiber membrane to impregnate it with the solvent. The method for producing a hollow fiber membrane module is characterized by drying. "
【００１３】ここで、熱可塑性樹脂で中空糸膜束集束固
定部近傍の中空糸膜を被覆する場合に、熱可塑性樹脂で
中空糸膜の空孔のすべてを埋没させないようにすること
が、中空糸膜の切断を防止する意味での補強効果におい
てより好ましい。Here, when covering the hollow fiber membranes in the vicinity of the hollow fiber membrane bundle converging and fixing portion with a thermoplastic resin, it is necessary not to bury all the pores of the hollow fiber membrane with the thermoplastic resin. It is more preferable in terms of the reinforcing effect in the sense of preventing the cutting of the thread film.
【００１４】ここで、前記中空糸膜がポリスルホン系樹
脂からなり、前記熱可塑性樹脂がポリビニルブチラール
又はポリスチレン系樹脂であることが好適であり、中空
糸膜にこれらの熱可塑性樹脂を被覆する場合には、ポリ
ビニルブチラールをエタノールで溶解した溶液又はポリ
スチレン系樹脂をシクロヘキサンで溶解した溶液を塗布
若しくは浸漬した後、それら溶剤を乾燥するのである。Here, it is preferable that the hollow fiber membrane is made of polysulfone resin and the thermoplastic resin is polyvinyl butyral or polystyrene resin, and when the hollow fiber membrane is coated with these thermoplastic resins. Is to coat or immerse a solution of polyvinyl butyral dissolved in ethanol or a solution of polystyrene resin dissolved in cyclohexane, and then to dry the solvent.
【００１５】本発明によれば、被覆樹脂は中空糸膜より
もはるかに大きい機械的な強度を有するので少量被覆す
るだけで大きな補強効果が得られ、その希薄な溶液を用
いて被覆するので被覆量のバラツキが小さい。この結
果、従来使用された可撓性帯や保護ネットなどの補強体
は必ずしも必要でなくなり、モジュールの製造も簡単に
なる。According to the present invention, since the coating resin has much higher mechanical strength than that of the hollow fiber membrane, a large reinforcing effect can be obtained by coating a small amount thereof, and the coating is performed using a dilute solution thereof. The variation in quantity is small. As a result, conventionally used reinforcements such as flexible bands and protective nets are not always necessary, and the manufacture of the module is simplified.
【００１６】[0016]
【発明の実施の形態】本発明に使用する中空糸膜は、補
強樹脂の溶液が浸透する孔径を有する限外ろ過や精密ろ
過などに利用する中空糸膜である。その素材には特に制
限はないが、例えば、セルロース系、ポリスルホン系、
ふっ素樹脂系、ポリオレフィン系、ポリビニルアルコー
ル系などが使用できる。BEST MODE FOR CARRYING OUT THE INVENTION The hollow fiber membrane used in the present invention is a hollow fiber membrane having a pore size that allows a solution of a reinforcing resin to permeate and used for ultrafiltration or microfiltration. The material is not particularly limited, for example, cellulose-based, polysulfone-based,
Fluorine resin type, polyolefin type, polyvinyl alcohol type, etc. can be used.
【００１７】中空糸膜モジュールの形態としては、中空
糸膜の開口部を一カ所に集束固定したもの、両端で固定
したもの、いずれでもよい。図４に、中空糸膜の開口部
を一カ所に集束固定した構造のカートリッジ型の中空糸
膜モジュール１０を例示している。この中空糸膜モジュ
ール１０を簡単に説明すれば、中央部でループ状に折り
返された中空糸膜１１の束はその一端部で円筒１２の一
端に集束固定部１３にてポッティングされ、中空糸膜１
１の端部はこの集束固定部１３（固定部材２に相当す
る）の端面に開口し、前記円筒１２の端部にはヘッダー
１４が固着されている。そして、円筒１２の孔１５およ
び底の穴１６を通って中空糸膜１１の表面に供給された
被処理液は、中空糸膜１１の外側から内側へろ過し、ろ
過液は集束固定部１３の先端から前記ヘッダー１４の出
口１７に集まり、図示しないハウジングのろ過液出口か
ら取り出される。ここで、前記中空糸膜モジュール１０
は、ヘッダー１４に設けたＯリング１８を介してハウジ
ングのろ過室とろ過液室を区画する仕切機構に装着され
ている。The form of the hollow fiber membrane module may be either one in which the openings of the hollow fiber membrane are converged and fixed in one place, or in which both ends are fixed. FIG. 4 illustrates a cartridge-type hollow fiber membrane module 10 having a structure in which the openings of the hollow fiber membrane are focused and fixed at one place. Briefly explaining this hollow fiber membrane module 10, a bundle of hollow fiber membranes 11 folded back in a loop at the central portion is potted at one end thereof to an end of a cylinder 12 by a focusing and fixing portion 13 to form a hollow fiber membrane. 1
The end of 1 is opened to the end face of the focusing and fixing portion 13 (corresponding to the fixing member 2), and the header 14 is fixed to the end of the cylinder 12. Then, the liquid to be treated supplied to the surface of the hollow fiber membrane 11 through the hole 15 of the cylinder 12 and the hole 16 at the bottom is filtered from the outside to the inside of the hollow fiber membrane 11, and the filtrate is collected from the focusing fixing part 13. Collected from the tip to the outlet 17 of the header 14, and taken out from the filtrate outlet of the housing (not shown). Here, the hollow fiber membrane module 10
Is attached to a partitioning mechanism that divides the filtrate chamber and the filtrate chamber of the housing via an O-ring 18 provided in the header 14.
【００１８】被覆樹脂は、中空糸膜の破断時の引張り応
力及び弾性率よりもおよそ１０倍以上の引張り応力及び
弾性率を持つことが必要である。このような特性を有す
る樹脂で、中空糸膜束集束固定部近傍の中空糸膜を被覆
することによって、中空糸膜の強度を補強することがで
きる。この際、被覆樹脂で中空糸膜の空孔のすべてを埋
没させることなく、中空糸膜のネットワーク骨格を被覆
することによって、中空糸膜の切断を防止する意味での
補強効果がより高くなる。これらの値が小さいときに
は、被覆量を多くしなければならず、前記したように被
覆量の制御が困難になるだけでなく、固定部材の近傍の
根本１Ａで脆く折れたり、界面１Ｂで引き裂ける。The coating resin is required to have a tensile stress and elastic modulus about 10 times or more than the tensile stress and elastic modulus at the time of breaking the hollow fiber membrane. The strength of the hollow fiber membrane can be reinforced by coating the hollow fiber membrane in the vicinity of the bundle fixing portion of the hollow fiber membrane with the resin having such characteristics. At this time, by covering the network skeleton of the hollow fiber membrane without burying all the pores of the hollow fiber membrane with the coating resin, the reinforcing effect in the sense of preventing cutting of the hollow fiber membrane becomes higher. When these values are small, the amount of coating must be increased, which makes it difficult to control the amount of coating as described above, and the base 1A near the fixing member is fragilely broken or is torn at the interface 1B. .
【００１９】被覆樹脂の破断時の伸びは、中空糸膜の素
材にほぼ等しいことが望ましい。中空糸膜のネットワー
ク骨格の表面に薄く被覆したとき、例えば、この値が中
空糸膜の素材よりも著しく小さい場合には被覆層の破断
が中空糸膜よりも先に発生し、逆に著しく大きい場合に
は中空糸膜の破断を抑えることができず、いずれの場合
でも補強効果は乏しい。前記した中空糸膜の素材の破断
時の伸びは５〜２０％程度であり、したがって、被覆樹
脂の破断時の伸びもこの程度であることが望ましい。The elongation at break of the coating resin is preferably substantially equal to the material of the hollow fiber membrane. When the surface of the network skeleton of the hollow fiber membrane is thinly coated, for example, if this value is significantly smaller than the material of the hollow fiber membrane, the coating layer breaks before the hollow fiber membrane, and conversely significantly larger. In that case, the breakage of the hollow fiber membrane cannot be suppressed, and in any case, the reinforcing effect is poor. The elongation at break of the material of the hollow fiber membrane is about 5 to 20%, and therefore the elongation at break of the coating resin is also preferably about this.
【００２０】被覆層の長さは固定部材の根本から２〜５
０ｍｍの範囲で中空糸膜の長さなどを考慮して決定され
るが、５〜３０ｍｍがより好ましい。短すぎると曲げ応
力を緩和する効果が乏しく、長すぎても効果はなく、か
つ中空糸膜の有効膜面積が少なくなる。ここで、固定部
材の中に埋没している中空糸膜の根本近傍では、通常固
定部材が中空糸膜表面の薄い層までしか侵入していない
ので、固定部材が侵入していないところも補強樹脂で被
覆されるために、中空糸膜の被覆が集束固定する前でも
後でもあまり効果は変わらない。The length of the coating layer is 2 to 5 from the root of the fixing member.
The length is determined in consideration of the length of the hollow fiber membrane in the range of 0 mm, but 5 to 30 mm is more preferable. If it is too short, the effect of relaxing the bending stress is poor, and if it is too long, there is no effect, and the effective membrane area of the hollow fiber membrane is reduced. Here, in the vicinity of the root of the hollow fiber membrane embedded in the fixing member, the fixing member usually penetrates only up to the thin layer on the surface of the hollow fiber membrane, so that the reinforcing resin can be used even when the fixing member does not penetrate. Therefore, the effect of the hollow fiber membrane does not change much before or after focusing and fixing.
【００２１】中空糸膜同士が被覆樹脂で接着すると、引
き離すときに中空糸膜が破れることがあるので、被覆量
は、中空糸膜の重量の２〜２０％の範囲に設定すること
が好ましく、５〜１５％がより好ましい。この範囲であ
れば、中空糸膜同士が接着して互いに引き離す時に破れ
ることはない。また、この範囲の被覆量のときには、中
空糸膜の空孔のすべてを被覆樹脂が埋没させることな
く、多数の空孔が残っている様子が顕微鏡で観察され
る。When the hollow fiber membranes are adhered to each other with the coating resin, the hollow fiber membranes may be broken when they are separated. Therefore, the coating amount is preferably set within the range of 2 to 20% by weight of the hollow fiber membranes. 5 to 15% is more preferable. Within this range, the hollow fiber membranes do not break when they are adhered to each other and separated from each other. Further, when the coating amount is within this range, it is observed with a microscope that a large number of pores remain without the coating resin burying all the pores of the hollow fiber membrane.
【００２２】本発明に使用する被覆用の熱可塑性樹脂
は、中空糸膜の構造を変えない溶剤に溶解しなければな
らない。その溶液の濃度は、樹脂の分子量、直接的には
粘度によるが、２〜１５重量％の範囲が好ましく、より
好ましくは５〜１０％である。被覆用の熱可塑性樹脂の
溶液の粘度が大きいと被覆量が多量になり、中空糸膜同
士が接着するので、およそ０．１Ｐａ・ｓ以下、０．０
５Ｐａ・ｓ以下がより好ましい。The coating thermoplastic resin used in the present invention must be dissolved in a solvent that does not change the structure of the hollow fiber membrane. The concentration of the solution depends on the molecular weight of the resin and directly on the viscosity, but is preferably in the range of 2 to 15% by weight, more preferably 5 to 10%. If the viscosity of the thermoplastic resin solution for coating is large, the coating amount will be large and the hollow fiber membranes will adhere to each other.
It is more preferably 5 Pa · s or less.
【００２３】前記例示したセルロース系樹脂、ポリスル
ホン系樹脂及びふっ素系樹脂からなる中空糸膜の場合に
は、被覆用の熱可塑性樹脂の溶剤してメタノール、エタ
ノールなどのアルコール、ｎ−ヘキサン、シクロヘキサ
ンなどの無極性有機溶剤などが使用可能である。多くの
有機溶剤に対して耐溶剤性のあるポリオレフィン系樹
脂、ポリビニルアルコール系樹脂からなる場合には、ア
セトンなどのケトン類、酢酸メチルなどのエステル類も
好適な溶剤である。In the case of the hollow fiber membrane made of the above-mentioned cellulose resin, polysulfone resin and fluorine resin, the solvent of the thermoplastic resin for coating is alcohol such as methanol or ethanol, n-hexane or cyclohexane. The non-polar organic solvent can be used. When a polyolefin resin or polyvinyl alcohol resin having solvent resistance to many organic solvents is used, ketones such as acetone and esters such as methyl acetate are also suitable solvents.
【００２４】これらに溶解し、前記した機械的な特性を
有する熱可塑性樹脂として、ポリビニルブチラール、ポ
リスチレン及びスチレンを主成分とする共重合体、ポリ
塩化ビニル、ポリウレタン、ポリアクリル酸エステルな
どの疎水性樹脂、エチレン−ビニルアルコール共重合
体、セルロース誘導体などの親水性樹脂が挙げられる。
これらの内で、疎水性樹脂は、被覆層が疎水性になり、
この部分ではろ過されず、汚染物の蓄積による固定部近
傍の中空糸膜の劣化が防止できるためにより好ましい。As the thermoplastic resin which is dissolved in these and has the above-mentioned mechanical characteristics, polyvinyl butyral, a copolymer containing polystyrene and styrene as a main component, a hydrophobic resin such as polyvinyl chloride, polyurethane, polyacrylic acid ester, etc. Examples of the hydrophilic resin include resins, ethylene-vinyl alcohol copolymers, and cellulose derivatives.
Among these, the hydrophobic resin makes the coating layer hydrophobic,
This portion is not filtered, and it is more preferable because deterioration of the hollow fiber membrane near the fixed portion due to accumulation of contaminants can be prevented.
【００２５】例えば、ポリスルホン系樹脂からなる中空
糸膜の場合には、被覆用の熱可塑性樹脂としてポリビニ
ルブチラール若しくはポリスチレン系樹脂が、その溶剤
として各々エタノール若しくはシクロヘキサンが好例で
ある。特に、ポリビニルブチラールは、ポリスルホン中
空糸膜の補強効果に優れており、また、安全性の高い溶
剤であるエタノールに溶解するので好ましい。For example, in the case of a hollow fiber membrane made of polysulfone type resin, polyvinyl butyral or polystyrene type resin is preferable as a thermoplastic resin for coating, and ethanol or cyclohexane is preferable as a solvent thereof. In particular, polyvinyl butyral is preferable because it has an excellent reinforcing effect on the polysulfone hollow fiber membrane and is soluble in ethanol, which is a highly safe solvent.
【００２６】中空糸膜に熱可塑性の樹脂の溶液を含浸さ
せる場合、前記したように中空糸膜を集束固定する前で
も後でもよい。また、中空糸膜の先端は開口していても
いなくてもよい。いずれの場合でも、被覆の方法は、被
覆箇所を前記の熱可塑性樹脂の２〜１５重量％、好まし
くは５〜１０％の溶液に５〜１０分間浸すか、被覆箇所
にこの溶液を塗布すればよいが、浸漬する方がすべての
中空糸膜が均等に被覆されるので好ましい。また、集束
固定してから含浸させる方が作業が簡単である。When the hollow fiber membrane is impregnated with the solution of the thermoplastic resin, it may be before or after the hollow fiber membrane is focused and fixed as described above. Further, the tip of the hollow fiber membrane may or may not be open. In any case, the method of coating is to immerse the coated part in a solution of 2 to 15% by weight, preferably 5 to 10%, of the above-mentioned thermoplastic resin for 5 to 10 minutes, or to apply this solution to the coated part. It is preferable, but dipping is preferable because all the hollow fiber membranes are uniformly covered. Further, it is easier to carry out the work by concentrating and fixing and then impregnating.
【００２７】中空糸膜に含浸させた被覆樹脂の溶液の溶
剤を乾燥して除去する際、前記例示した溶剤は揮発性が
高いので、通常加温しないでそのまま１〜３時間放置す
るだけでよいが、さらに、被覆樹脂の熱変形温度以上で
加温することによって補強効果が向上することもある。When the solvent of the coating resin solution with which the hollow fiber membrane is impregnated is dried and removed, the above-exemplified solvents have high volatility, so that they are usually left to stand for 1 to 3 hours without heating. However, the reinforcing effect may be improved by heating the coating resin at a temperature higher than the heat deformation temperature.
【００２８】先端が開口した中空糸膜を被覆樹脂の溶液
に浸すと、当然中空糸膜の内側にもこの溶液が入り込む
が、垂れ落ちない程度に液切りしてから開口端が上方に
なるようにして乾燥すると、粘度が低く、濃度も小さい
ので乾燥後は、樹脂が被覆された中空糸膜の内径は、被
覆前とほとんど変わらない。開口端を下にして乾燥する
と、開口端に薄い樹脂被膜ができることがあるが、その
ときにはこの部分を切り落とせばよい。When a hollow fiber membrane having an open tip is dipped in a solution of a coating resin, the solution naturally enters the inside of the hollow fiber membrane, but the liquid is drained to such an extent that it does not drip and the open end is placed upward. When dried, the viscosity is low and the concentration is low. Therefore, after drying, the inner diameter of the hollow fiber membrane coated with the resin is almost the same as that before coating. If the opening end is dried and dried, a thin resin film may be formed on the opening end. At that time, this portion may be cut off.
【００２９】乾燥後の中空糸膜は、予想したことではな
かったが、互いに接着することなく、それぞれ独立に補
強されている。このようにして被覆された樹脂の量は、
中空糸膜に対し２〜２０％、通常５〜１５％である。Although not expected, the hollow fiber membranes after drying are reinforced independently of each other without adhering to each other. The amount of resin coated in this way is
It is 2 to 20%, usually 5 to 15% with respect to the hollow fiber membrane.
【００３０】以上のようにして、固定部材との角度を小
さくして引っ張ったときにも、中空糸膜自身の引張り強
度の５０％を下回らないだけでなく、固定部材の根本で
切断しないほどの補強効果が発揮される。以下の実施例
で本発明をさらに具体的に説明するが、これらの実施例
は本発明を限定するものではない。As described above, even when the hollow fiber membrane is pulled at a small angle with respect to the fixing member, it does not fall below 50% of the tensile strength of the hollow fiber membrane itself, and is not cut at the root of the fixing member. The reinforcing effect is exhibited. The present invention will be described in more detail by the following examples, but these examples do not limit the present invention.
【００３１】[0031]
（実施例１） 評価試料の作成 長さが約５０ｃｍ、内、外径が５００及び８００μｍ、
孔径が約０．２μｍで、引張り強度が１７０ｇ／本、破
断時の伸びが６０％の親水性ポリスルホン中空糸膜１７
００本を中央でループ状に折り返し、充填率（ただし、
充填率は、中空糸膜の外径が占める面積と集束固定部の
中空糸膜本数との積を、集束固定部の束の外径が占める
面積で割った数である）が約６０％になるように束ね
て、破断強度が約５００Ｋｇ／ｃｍ2 、破断時の伸びが
約２０％のウレタン樹脂で集束固定し、固定部の長さが
約１５ｍｍになるように端部を切断して中空糸膜の端部
を開口した。(Example 1) Preparation of evaluation sample Length is about 50 cm, inner and outer diameters are 500 and 800 μm,
A hydrophilic polysulfone hollow fiber membrane 17 having a pore size of about 0.2 μm, a tensile strength of 170 g / piece, and an elongation at break of 60%.
00 pieces are folded in a loop at the center, and the filling rate (however,
The filling factor is the product of the area occupied by the outer diameter of the hollow fiber membrane and the number of hollow fiber membranes in the focusing and fixing section divided by the area occupied by the outer diameter of the bundle in the focusing and fixing section) to about 60%. Bundled together, and then fixed and bundled with urethane resin having a breaking strength of about 500 kg / cm 2 and an elongation at break of about 20%, and the ends are cut so that the length of the fixing part is about 15 mm The end of the thread membrane was opened.
【００３２】これを集束固定部を下にして、重合度が約
７００のポリビニルブチラールの５重量％エタノール溶
液に５分間浸し、固定部の根本から約２ｃｍまで中空糸
膜に含浸させた。中空糸膜束を引き上げてから、ポリビ
ニルブチラールの溶液を軽く振って液切りしてから開口
部をろ紙に乗せてそのまま３時間放置した。束の外側か
ら中央までの中空糸膜の強度が測定できるように、集束
固定部を中央で半分に分割した。This was immersed in a 5 wt% ethanol solution of polyvinyl butyral having a degree of polymerization of about 700 for 5 minutes with the focusing and fixing part facing downward, and the hollow fiber membrane was impregnated from the root of the fixing part to about 2 cm. After pulling up the hollow fiber membrane bundle, the solution of polyvinyl butyral was shaken lightly to drain the solution, and the opening was put on a filter paper and left as it was for 3 hours. The focusing and fixing part was divided in half at the center so that the strength of the hollow fiber membrane from the outside to the center of the bundle could be measured.
【００３３】補強効果の測定 図１のようにして（ただし、引張り方向の内側に他の中
空糸膜が無いようにした）束の外側から内側までの中空
糸膜の引張り強度を角度αを変えながら測定した。位置
による差はほとんど無く、その結果を、未処理のものと
図２に一緒に示した。この図から補強効果は明らかであ
る。Measurement of Reinforcing Effect As shown in FIG. 1 (however, there was no other hollow fiber membrane inside the drawing direction), the tensile strength of the hollow fiber membrane from the outside to the inside of the bundle was changed by changing the angle α. While measuring. There was little difference by position, and the results are shown together with the untreated one in FIG. The reinforcing effect is clear from this figure.
【００３４】（実施例２）孔径が０．０４μｍである以
外、実施例１とほぼ同じ特性のポリスルホン中空糸膜束
を用いて、実施例１と同様にして補強効果の評価を行っ
たが、実施例１と同様な結果が得られた。Example 2 A reinforcing effect was evaluated in the same manner as in Example 1 using a polysulfone hollow fiber membrane bundle having substantially the same characteristics as in Example 1 except that the pore diameter was 0.04 μm. The same result as in Example 1 was obtained.
【００３５】（実施例３）孔径が０．４５μｍである以
外、実施例１とほぼ同じ特性のポリスルホン中空糸膜束
を用いて、実施例１と同様にして補強効果の評価を行っ
たが、実施例１に比べて少しではあるが、強度がさらに
向上した。Example 3 Using the polysulfone hollow fiber membrane bundle having substantially the same characteristics as in Example 1 except that the pore diameter was 0.45 μm, the reinforcing effect was evaluated in the same manner as in Example 1. Although slightly smaller than Example 1, the strength was further improved.
【００３６】（実施例４）長さが約１６０ｃｍである以
外は実施例１と同様にして中空糸膜モジュールを作成し
た。このモジュールを水平にして水に埋没させ、集束固
定部を固定して垂直方向に１５ｃｍの振幅で７０ｒｐｍ
の振動数で１０００回振動させた。この後でモジュール
を観察したが、切れた中空糸膜はなく、また、中空糸膜
の内側から１００ＫＰａの空気で加圧してももれは無か
った。(Example 4) A hollow fiber membrane module was prepared in the same manner as in Example 1 except that the length was about 160 cm. This module is placed horizontally and submerged in water, the focusing and fixing part is fixed, and the vertical direction is 70 rpm with an amplitude of 15 cm.
Was vibrated 1000 times. After that, the module was observed, but there was no broken hollow fiber membrane, and there was no leakage even when pressurized with 100 KPa of air from the inside of the hollow fiber membrane.
【００３７】（比較例１）被覆処理をしなかった以外、
実施例４と同様な実験を行った結果、数十本の中空糸膜
が集束固定部の根本で切れた。(Comparative Example 1) Except that no coating treatment was carried out,
As a result of conducting the same experiment as in Example 4, several tens of hollow fiber membranes were cut at the root of the focusing and fixing part.
【００３８】（実施例５）実施例４で、水をベンガラの
分散水に代え、モジュールの開口部から吸引ろ過した。
ろ過後モジュールを引き上げて外観を観察したところ、
集束固定部の根本からポリビニルブチラールを被覆した
約２ｃｍの部分までの中空糸膜は白いままで、その他の
部分は赤く着色していた。(Example 5) In Example 4, the water was replaced with the dispersal water of red iron oxide, and suction filtration was performed from the opening of the module.
After filtration, pulling up the module and observing the appearance,
The hollow fiber membrane from the root of the focusing and fixing portion to the polyvinyl butyral-coated portion up to about 2 cm remained white, and the other portions were colored red.
【００３９】[0039]
【発明の効果】以上にしてなる本発明の中空糸膜モジュ
ール及びその製造方法によれば、特定の性質を備えた熱
可塑性樹脂で、中空糸膜集束固定部近傍の中空糸膜を被
覆したことにより、曲げ応力が集中する固定部近傍の中
空糸膜の根本を効果的に補強することができ、中空糸膜
の破断や引き裂きを防止する上で有効である。特に、熱
可塑性樹脂で、中空糸膜の空孔のすべてを埋没させるこ
となく被覆すれば、その効果はより高くなる。また、特
定の性質を備えた熱可塑性樹脂を被覆する方法として
は、該熱可塑性樹脂を中空糸膜を変性させない溶剤に２
〜１５％溶解した溶液を、目的部分に塗布若しくは浸漬
して含浸させたのち、溶剤を乾燥させるだけの簡単な作
業で済むので、工業的にも有効である。According to the hollow fiber membrane module and the method for producing the same of the present invention as described above, the hollow fiber membrane in the vicinity of the hollow fiber membrane focusing and fixing portion is coated with the thermoplastic resin having the specific property. This makes it possible to effectively reinforce the root of the hollow fiber membrane in the vicinity of the fixed portion where bending stress concentrates, and is effective in preventing breakage and tearing of the hollow fiber membrane. In particular, if the thermoplastic resin is coated without burying all the pores of the hollow fiber membrane, the effect is further enhanced. In addition, as a method for coating a thermoplastic resin having a specific property, the thermoplastic resin is used in a solvent that does not modify the hollow fiber membrane.
It is industrially effective because a simple operation of coating or dipping a solution of -15% dissolved in a target portion to impregnate it and then drying the solvent is sufficient.
【図１】中空糸膜の引張り強度を固定部材との角度αを
変えて測定する時の略図である。FIG. 1 is a schematic view when the tensile strength of a hollow fiber membrane is measured by changing the angle α with a fixing member.
【図２】本発明の中空糸膜の引張り強度と未処理の中空
糸膜の引張り強度を比較して示したグラフである。FIG. 2 is a graph showing a comparison between the tensile strength of the hollow fiber membrane of the present invention and the tensile strength of an untreated hollow fiber membrane.
【図３】あらかじめ熱硬化性樹脂で被覆した中空糸膜を
固定部材に埋没させた場合の強度を説明するための略図
である。FIG. 3 is a schematic diagram for explaining the strength when a hollow fiber membrane previously coated with a thermosetting resin is embedded in a fixing member.
【図４】中空糸膜モジュールの一例を示す部分断面図で
ある。FIG. 4 is a partial cross-sectional view showing an example of a hollow fiber membrane module.
１ 中空糸膜 １Ａ 根本 １Ｂ 界面 ２ 固定部材 ３ 被覆層 １０ 中空糸膜モジュール １１ 中空糸膜 １２ 円筒 １３ 集束固定部（固定部材） １４ ヘッダー １５ 孔 １６ 穴 １７ 出口 １８ Ｏリング 1 Hollow Fiber Membrane 1A Root 1B Interface 2 Fixing Member 3 Covering Layer 10 Hollow Fiber Membrane Module 11 Hollow Fiber Membrane 12 Cylinder 13 Focusing Fixing Part (Fixing Member) 14 Header 15 Hole 16 Hole 17 Outlet 18 O Ring
Claims (7)
び弾性率よりもおよそ１０倍以上大きな引張り応力及び
弾性率を有し、破断時の伸びが５〜２０％の熱可塑性樹
脂で、中空糸膜束集束固定部近傍の中空糸膜を被覆した
ことを特徴とする中空糸膜モジュール。1. A hollow fiber, which is a thermoplastic resin having a tensile stress and elastic modulus about 10 times or more greater than the tensile stress and elastic modulus at break of the hollow fiber membrane, and an elongation at break of 5 to 20%. A hollow fiber membrane module characterized by coating a hollow fiber membrane in the vicinity of a membrane bundle focusing and fixing portion.
定部近傍の中空糸膜を、その空孔のすべてを埋没させる
ことなく被覆してなる請求項１記載の中空糸膜モジュー
ル。2. The hollow fiber membrane module according to claim 1, wherein the thermoplastic resin covers the hollow fiber membrane in the vicinity of the bundle fixing portion of the hollow fiber membrane bundle without burying all of its pores.
り、熱可塑性樹脂がポリビニルブチラールである請求項
１又は２記載の中空糸膜モジュール。3. The hollow fiber membrane module according to claim 1, wherein the hollow fiber membrane is made of a polysulfone-based resin and the thermoplastic resin is polyvinyl butyral.
り、熱可塑性樹脂がポリスチレン系樹脂である請求項１
又は２記載の中空糸膜モジュール。4. The hollow fiber membrane is made of polysulfone-based resin, and the thermoplastic resin is polystyrene-based resin.
Alternatively, the hollow fiber membrane module according to item 2.
び弾性率よりもおよそ１０倍以上大きな引張り応力及び
弾性率を有し、破断時の伸びが５〜２０％の熱可塑性樹
脂を、中空糸膜を変性させない溶剤に２〜１５％溶解し
た溶液を、中空糸膜束集束固定部近傍の中空糸膜に塗布
若しくは浸漬して含浸させたのち、溶剤を乾燥すること
を特徴とする中空糸膜モジュールの製造方法。5. A thermoplastic resin having a tensile stress and elastic modulus that is about 10 times or more larger than the tensile stress and elastic modulus at break of the hollow fiber membrane, and an elongation at break of 5 to 20% is used as a hollow fiber. A hollow fiber membrane characterized in that a solution prepared by dissolving 2 to 15% in a solvent that does not denature the membrane is applied to or impregnated into the hollow fiber membrane near the bundle fixing part of the hollow fiber membrane to impregnate it, and then the solvent is dried. Module manufacturing method.
り、熱可塑性樹脂がポリビニルブチラールであり、かつ
その溶剤がエタノールである請求項５記載の中空糸膜モ
ジュールの製造方法。6. The method for producing a hollow fiber membrane module according to claim 5, wherein the hollow fiber membrane is made of polysulfone resin, the thermoplastic resin is polyvinyl butyral, and the solvent thereof is ethanol.
り、熱可塑性樹脂がポリスチレン系樹脂であり、かつそ
の溶剤がシクロヘキサンである請求項５記載の中空糸膜
モジュールの製造方法。7. The method for producing a hollow fiber membrane module according to claim 5, wherein the hollow fiber membrane is made of a polysulfone resin, the thermoplastic resin is a polystyrene resin, and the solvent thereof is cyclohexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29709695A JPH09164324A (en) | 1995-10-13 | 1995-11-15 | Hollow-fiber membrane module and its production |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26572895 | 1995-10-13 | ||
| JP7-265728 | 1995-10-13 | ||
| JP29709695A JPH09164324A (en) | 1995-10-13 | 1995-11-15 | Hollow-fiber membrane module and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09164324A true JPH09164324A (en) | 1997-06-24 |
Family
ID=26547119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29709695A Pending JPH09164324A (en) | 1995-10-13 | 1995-11-15 | Hollow-fiber membrane module and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09164324A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014226618A (en) * | 2013-05-23 | 2014-12-08 | ダイセン・メンブレン・システムズ株式会社 | Hollow fiber membrane module and manufacturing method of the same |
| CN114307655A (en) * | 2021-11-22 | 2022-04-12 | 北京工业大学 | U-shaped hollow fiber pervaporation membrane module and preparation method thereof |
-
1995
- 1995-11-15 JP JP29709695A patent/JPH09164324A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014226618A (en) * | 2013-05-23 | 2014-12-08 | ダイセン・メンブレン・システムズ株式会社 | Hollow fiber membrane module and manufacturing method of the same |
| CN114307655A (en) * | 2021-11-22 | 2022-04-12 | 北京工业大学 | U-shaped hollow fiber pervaporation membrane module and preparation method thereof |
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