JPH0738939B2 - Porous hollow fiber membrane - Google Patents
Porous hollow fiber membraneInfo
- Publication number
- JPH0738939B2 JPH0738939B2 JP62165414A JP16541487A JPH0738939B2 JP H0738939 B2 JPH0738939 B2 JP H0738939B2 JP 62165414 A JP62165414 A JP 62165414A JP 16541487 A JP16541487 A JP 16541487A JP H0738939 B2 JPH0738939 B2 JP H0738939B2
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- acid
- porous
- fiber membrane
- peripheral wall
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、流体、特に水の浄化のための分離膜として好
適な、親水性が飛躍的に向上した中空糸膜に関する。TECHNICAL FIELD The present invention relates to a hollow fiber membrane, which is suitable as a separation membrane for purifying a fluid, especially water, and which has dramatically improved hydrophilicity.
〔従来技術及びその問題点〕 高分子材料製の中空糸膜からなる精密濾過膜、限外濾過
膜は、水又は水溶液の分離精製、処理等の分野や医療分
野で利用されている。[Prior art and its problems] Microfiltration membranes and ultrafiltration membranes made of polymer material hollow fiber membranes are used in fields such as separation and purification of water or aqueous solutions, treatment, and medical fields.
水又は水溶液を精密濾過或いは限外濾過する場合、膜は
親水性を有することが必要である。親水性を有する精密
濾過膜、限外濾過膜を製造する方法としては、親水性高
分子膜素材を溶媒及び膨潤剤、又はそれらと非溶媒との
混合溶媒系に溶解して均一溶液としたものを原液とし、
この原液を膜状にキャストし、揮発性溶媒を一部或いは
完全に蒸発させた後、凝固浴中に浸漬し、溶媒を抽出除
去して多孔質膜とするなどの相転換による方法や、高分
子膜素材に被溶出物質を混合して成膜した後、膜中から
被溶出物質を溶出させて多孔質膜とする抽出による方法
などが知られている。（以下、従来方法１とする） 一方、高密度ポリエチレン、ポリプロピレン、ポリ（4-
メチル−ペンテン‐１）などの熱可塑性樹脂からなる多
孔質膜は、前記の方法の他、中空原糸を紡糸した後、特
定温度範囲及び／又は特定媒体中で延伸して多孔質化す
る方法により製造することができ、力学的特性に優れた
多孔質中空糸膜を得ることが可能となっている。（以
下、従来方法２とする） しかし、親水性を付与するための従来方法１では、前記
の通り極めて複雑な処理工程を必要とし、その結果コス
ト面で難点がある。又、従来方法２に於いては、製造さ
れる多孔質中空糸膜自体は疎水性であって、水又は水溶
液の濾過に使用する際、アルコールなどにより親水化処
理する必要があり、且つ、常に湿潤状態を保持する必要
があり、その維持管理が煩雑となっている。When microfiltration or ultrafiltration of water or an aqueous solution, the membrane must have hydrophilicity. As a method for producing a microfiltration membrane and an ultrafiltration membrane having hydrophilicity, a hydrophilic polymer membrane material is dissolved in a solvent and a swelling agent or a mixed solvent system of them and a non-solvent to form a uniform solution. As the stock solution,
This stock solution is cast in the form of a film, and after partially or completely evaporating the volatile solvent, it is immersed in a coagulation bath and the solvent is extracted and removed to form a porous film. A method is known in which a substance to be eluted is mixed with a molecular film material to form a film, and then the substance to be eluted is eluted from the film to form a porous film. (Hereinafter, referred to as Conventional Method 1) On the other hand, high density polyethylene, polypropylene, poly (4-
The porous membrane made of a thermoplastic resin such as methyl-pentene-1) is not limited to the above-mentioned method, but is also a method in which a hollow raw fiber is spun and then stretched in a specific temperature range and / or a specific medium to be porous. It is possible to obtain a porous hollow fiber membrane having excellent mechanical properties. (Hereinafter, referred to as Conventional Method 2) However, Conventional Method 1 for imparting hydrophilicity requires an extremely complicated treatment step as described above, and as a result, there is a difficulty in cost. Moreover, in the conventional method 2, the porous hollow fiber membrane itself produced is hydrophobic, and when it is used for filtering water or an aqueous solution, it must be hydrophilized with alcohol or the like, and always It is necessary to maintain the wet state, and the maintenance thereof is complicated.
本発明は、上記した従来の多孔質膜の改良を目的とする
もので、優れた親水性を有し、水又は水溶液の濾過に使
用した場合に極めて大きな透水量を示す多孔質中空糸膜
を得るものである。The present invention is intended to improve the above-mentioned conventional porous membrane, and has a porous hollow fiber membrane having excellent hydrophilicity and exhibiting an extremely large water permeability when used for filtering water or an aqueous solution. I will get it.
即ち、本発明によれば、周壁に多数の貫通微細孔を有す
る中空糸基体であって、その周壁部表面及び該貫通微細
孔表面の少なくとも一部が、アルコール類、アセトン、
ベンゼン、トルエン、キシレン及びクロロホルムから選
ばれた一種以上の有機溶媒に、脂肪酸成分としてカプリ
ル酸、カプリン酸、ラウリン酸、パルミチン酸、ステア
リン酸、オレイン酸及びベヘニン酸から選ばれたグリセ
リン高級脂肪酸エステル類を溶解した溶液で浸漬処理し
て被覆されていることを特徴とする多孔質中空糸膜が提
供される。That is, according to the present invention, a hollow fiber substrate having a large number of penetrating micropores in its peripheral wall, wherein the peripheral wall surface and at least a part of the penetrating micropore surface are alcohols, acetone,
Glycerin higher fatty acid esters selected from caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid and behenic acid as fatty acid components in one or more organic solvents selected from benzene, toluene, xylene and chloroform There is provided a porous hollow fiber membrane characterized by being dipped in a solution in which is dissolved and coated.
本発明に於いて用いられる、周壁部に多数の貫通微細孔
を有する中空糸基体を製造する材料の材質については、
特に制限されるものではない。高分子材料を素材とする
ものの例としては、高密度ポリエチレン、低密度ポリエ
チレン、線状低密度ポリエチレン、ポリプロピレン、エ
チレン−酢酸ビニル共重合体、エチレン−エチルアクリ
レート共重合体などのポリオレフィン、フッ素含有高分
子化合物、ポリスルホン、ポリカーボネート、ポリ塩化
ビニル等の多孔質中空糸を挙げることができる。又、無
機材料を素材とするものの例としては、ガラス、セラミ
ックス、炭素などの多孔質中空糸又は多孔質チューブを
挙げることができる。多孔質中空糸基体の外径、周壁部
厚さ、貫通微細孔の孔径も特に制限されるものではない
が、一般には外径は10〜1000ミクロン、周壁部厚さは10
〜200ミクロン、孔径は0.01〜50ミクロン程度の範囲の
ものが好ましい。Regarding the material of the material used in the present invention for producing the hollow fiber substrate having a large number of through fine holes in the peripheral wall,
It is not particularly limited. Examples of materials made of polymeric materials include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, polyolefins such as ethylene-vinyl acetate copolymers and ethylene-ethyl acrylate copolymers, fluorine-containing polymers. Examples thereof include porous hollow fibers such as molecular compounds, polysulfones, polycarbonates and polyvinyl chloride. Further, examples of inorganic materials include porous hollow fibers such as glass, ceramics and carbon, or porous tubes. The outer diameter of the porous hollow fiber substrate, the thickness of the peripheral wall portion, and the diameter of the penetrating micropores are not particularly limited, but generally the outer diameter is 10 to 1000 μm, and the thickness of the peripheral wall portion is 10 to 1000 μm.
.About.200 .mu.m, and the pore size is preferably in the range of 0.01 to 50 .mu.m.
本発明で用いられるグリセリン脂肪酸エステルの脂肪酸
成分としては、カプリル酸、カプリン酸、ラウリン酸、
パルミチン酸、ステアリン酸、オレイン酸、ベヘニン酸
などが挙げられ、又、これらの酸成分とグリセリンとの
反応によって生成されるグリセリン脂肪酸エステルは、
モノグリセライド、ジグリセライド及びトリグリセライ
ドの何れか一つ又はそれらの混合物が使用される。As the fatty acid component of the glycerin fatty acid ester used in the present invention, caprylic acid, capric acid, lauric acid,
Palmitic acid, stearic acid, oleic acid, behenic acid and the like can be mentioned, and the glycerin fatty acid ester produced by the reaction of these acid components and glycerin is
Any one of monoglyceride, diglyceride and triglyceride or a mixture thereof is used.
次に本発明の多孔質中空糸膜の製造方法を説明する。Next, the method for producing the porous hollow fiber membrane of the present invention will be described.
上述したグリセリン脂肪酸エステルを、グリセリン脂肪
酸エステル可溶な溶媒に0.1〜10重量％の濃度となるよ
う溶解する。溶媒としては、メタノール、エタノールな
どのアルコール、アセトン、ベンゼン、トルエン、キシ
レン、クロロホルムなどが好適である。The glycerin fatty acid ester described above is dissolved in a solvent in which the glycerin fatty acid ester is soluble to a concentration of 0.1 to 10% by weight. As the solvent, alcohols such as methanol and ethanol, acetone, benzene, toluene, xylene, chloroform and the like are preferable.
次いで、該グリセリン脂肪酸エステル溶液に多孔質中空
糸基体を浸漬し、多孔質中空糸基体の貫通微細孔内にも
充分該グリセリン脂肪酸エステル溶液を行き渡らせた
後、乾燥して溶媒を除去する。乾燥する手段としては、
溶媒の種類により風乾、減圧乾燥、加熱乾燥などが適宜
用いられる。Then, the porous hollow fiber substrate is dipped in the glycerin fatty acid ester solution to sufficiently spread the glycerin fatty acid ester solution in the through micropores of the porous hollow fiber substrate, and then dried to remove the solvent. As means for drying,
Air drying, reduced pressure drying, heat drying and the like are appropriately used depending on the type of solvent.
このようにして得られた、グリセリン脂肪酸エステルに
よって被覆された多孔質中空糸は、充分な親水性を示
し、且つ、該多孔質中空糸を絶乾状態にまで乾燥した後
でも充分な親水性を維持している。The thus-obtained porous hollow fiber coated with glycerin fatty acid ester shows sufficient hydrophilicity, and exhibits sufficient hydrophilicity even after drying the porous hollow fiber to an absolutely dry state. I am maintaining.
以下に実施例によって本発明を更に詳細に説明する。Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例１ ポリプロピレン（UBE PP J109G、商品名：宇部興産株式
会社製、MFI＝9g/10分）を、直径33mm、内径27mmの気体
供給管を備えた中空糸製造用ノズルを使用し、紡糸温度
200℃、引き取り速度116m/分の条件で紡糸し中空糸を得
た。得られたポリプロピレン中空糸を145℃の加熱空気
槽で６分間加熱処理し、次いで液体窒素（−195℃）中
で、初期長さに対して20％延伸し、延伸状態を保ったま
ま145℃の加熱空気槽内で２分間熱処理を行った。Example 1 Polypropylene (UBE PP J109G, trade name: manufactured by Ube Industries, Ltd., MFI = 9 g / 10 minutes) was used with a hollow fiber manufacturing nozzle equipped with a gas supply pipe having a diameter of 33 mm and an inner diameter of 27 mm and spinning temperature.
A hollow fiber was obtained by spinning at 200 ° C. and a take-up speed of 116 m / min. The obtained polypropylene hollow fiber was heat treated in a heated air bath at 145 ° C for 6 minutes, and then stretched in liquid nitrogen (-195 ° C) by 20% with respect to the initial length, and the stretched state was maintained at 145 ° C. Heat treatment was carried out for 2 minutes in the heated air bath.
このポリプロピレン中空糸を125℃の空気雰囲気で400％
熱延伸し、延伸状態を保ったまま145℃の加熱空気槽内
で15分間熱処理を行い、多孔質ポリプロピレン中空糸を
製造した。This polypropylene hollow fiber is 400% in an air atmosphere at 125 ° C.
It was heat-stretched and heat-treated in a heated air tank at 145 ° C. for 15 minutes while maintaining the stretched state to produce a porous polypropylene hollow fiber.
得られた多孔質ポリプロピレン中空糸の平均透孔径及び
空隙率を水銀圧入法（測定はカルロエルバ（CARLOERB
A）社（イタリア）製のポロシメトロシリーズ（POROSIM
ETRO SERIES）1500を使用して行った〕によって測定し
たところ、平均透孔径は0.30μｍであり、空隙率は76.7
％であった。The average pore diameter and porosity of the obtained porous polypropylene hollow fiber were measured by the mercury intrusion method (measurement was carried out by CARROELB
A) company (Italy) POROSIMETRO series (POROSIM
ETRO SERIES) 1500), the average pore diameter was 0.30 μm, and the porosity was 76.7.
%Met.
上記の多孔質ポリプロピレン中空糸の周壁部を電子顕微
鏡により観察したところ、周壁部に多数の大きな透孔が
均一に形成されており、又透孔径も全体に渡ってほぼ一
定であった。又、この多孔質ポリプロピレン中空糸の外
径は400μｍ、内径は300μｍであり、従って、周壁部厚
さは50μｍであった。When the peripheral wall portion of the above-mentioned porous polypropylene hollow fiber was observed by an electron microscope, a large number of large through holes were formed uniformly in the peripheral wall portion, and the diameter of the through holes was almost constant throughout. The outer diameter of this porous polypropylene hollow fiber was 400 μm, the inner diameter was 300 μm, and therefore the thickness of the peripheral wall was 50 μm.
次に、上記多孔質ポリプロピレン中空糸を、先ずオレイ
ン酸モノグリセライド〔花王(株)社製、エキセルO-95
N〕の2.5重量％アセトン溶液に浸漬した後、アセトンが
なくなるまで風乾した。Next, the porous polypropylene hollow fiber, first oleic acid monoglyceride [Kao Co., Ltd., Exel O-95
It was immersed in a 2.5% by weight acetone solution of N] and then air-dried until the acetone disappeared.
このようにして得られた中空糸膜の周壁部の内外表面及
び周壁部断面を電子顕微鏡で観察したところ、周壁部、
周壁部断面も本質的に原多孔質中空糸と同一の多数の大
きな透孔が保持された形態が観察された。The inner and outer surfaces of the peripheral wall of the hollow fiber membrane thus obtained and the cross section of the peripheral wall were observed with an electron microscope.
It was observed that the cross-section of the peripheral wall portion had essentially the same large number of large pores as the original porous hollow fiber.
得られた中空糸膜をアルコールなどで前処理することな
しに、水の濾過に使用した場合の透水量は82l/min・m2
・atmであった。When the obtained hollow fiber membrane was used for water filtration without pretreatment with alcohol etc., the water permeation rate was 82 l / min ・ m 2
・ It was atm.
比較例１ 実施例１に記載されている多孔質ポリプロピレン中空糸
膜のみをアルコールなどで前処理することなしに使用し
て、水を圧力1.5kg/cm2で濾過することを試みたが透水
量は０であった。又、メチルアルコールで親水化処理し
た後、水を濾過するとその透水量は20l/min・m2・atmで
あった。Comparative Example 1 It was attempted to filter water at a pressure of 1.5 kg / cm 2 using only the porous polypropylene hollow fiber membrane described in Example 1 without pretreatment with alcohol or the like, but the water permeability was Was 0. When water was filtered after hydrophilization with methyl alcohol, the water permeation rate was 20 l / min · m 2 · atm.
実施例２ 実施例１で透水量82l/min・m2・atmを示した多孔質ポリ
プロピレン中空糸膜を24時間減圧乾燥して絶乾状態とし
た後、アルコールなどで前処理することなく用いて水を
濾過した。その透水量は85l/min・m2・atmであって、絶
乾状態としたことにより透水量の低下は全くみられなか
った。Example 2 A porous polypropylene hollow fiber membrane having a water permeation rate of 82 l / min · m 2 · atm in Example 1 was dried under reduced pressure for 24 hours to be completely dried, and then used without pretreatment with alcohol or the like. The water was filtered. The water permeation rate was 85 l / min · m 2 · atm, and no decrease in water permeation was observed due to the absolute dry condition.
以上説明したように、本発明の多孔質中空糸膜は、水又
は水溶液を濾過するに際し、極めて大きな透水量を示
し、更に、上記多孔質ポリプロピレン中空糸膜は絶乾状
態とした後でも充分な親水性を保持されるものである。As described above, the porous hollow fiber membrane of the present invention exhibits an extremely large water permeation rate when filtering water or an aqueous solution, and further, the porous polypropylene hollow fiber membrane is sufficiently dry even after being dried. It retains hydrophilicity.
Claims (1)
体であって、その周壁部表面及び該貫通微細孔内表面の
少なくとも一部が、アルコール類、アセトン、ベンゼ
ン、トルエン、キシレン及びクロロホルムから選ばれた
一種以上の有機溶媒に、脂肪酸成分としてカプリル酸、
カプリン酸、ラウリン酸、パルミチン酸、ステアリン
酸、オレイン酸及びベヘニン酸から選ばれたグリセリン
高級脂肪酸エステル類を溶解した溶液で浸漬処理して被
覆されていることを特徴とする多孔質中空糸膜。1. A hollow fiber substrate having a large number of penetrating micropores on its peripheral wall, wherein at least a part of the peripheral wall surface and the inner surface of the penetrating micropores are alcohols, acetone, benzene, toluene, xylene and chloroform. In one or more organic solvents selected from, caprylic acid as a fatty acid component,
A porous hollow fiber membrane, which is coated by immersion treatment with a solution of glycerin higher fatty acid esters selected from capric acid, lauric acid, palmitic acid, stearic acid, oleic acid and behenic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62165414A JPH0738939B2 (en) | 1987-07-03 | 1987-07-03 | Porous hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62165414A JPH0738939B2 (en) | 1987-07-03 | 1987-07-03 | Porous hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6411605A JPS6411605A (en) | 1989-01-17 |
| JPH0738939B2 true JPH0738939B2 (en) | 1995-05-01 |
Family
ID=15811962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62165414A Expired - Lifetime JPH0738939B2 (en) | 1987-07-03 | 1987-07-03 | Porous hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0738939B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4777666B2 (en) * | 2005-02-01 | 2011-09-21 | 日本碍子株式会社 | Carbon membrane and method for separating water and organic solvent using carbon membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61133105A (en) * | 1984-12-03 | 1986-06-20 | Asahi Medical Kk | Process for improving permeability of porous membrane |
-
1987
- 1987-07-03 JP JP62165414A patent/JPH0738939B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6411605A (en) | 1989-01-17 |
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