JP2006326497A - Semi-permeable membrane for water treatment and its production method - Google Patents
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Abstract
Description
本発明は、水処理用半透膜及びその製造方法に関する。 The present invention relates to a semipermeable membrane for water treatment and a method for producing the same.
従来より、酢酸セルロース半透膜に関する技術が公開されている。酢酸セルロース半透膜は、高い透水性を示し、ファウリングが低いことを特徴とするが、自然界に存在するパルプやコットンを原料としているため、他の合成高分子ポリマーに比べて、耐薬品性や生分解性に劣るという課題があった。 Conventionally, techniques related to a cellulose acetate semipermeable membrane have been disclosed. Cellulose acetate semi-permeable membrane is characterized by high water permeability and low fouling, but it is made from natural pulp and cotton, so it is more resistant to chemicals than other synthetic polymer polymers. There was a problem that it was inferior in biodegradability.
耐薬品性や耐生分解性に優れた合成高分子ポリマーとして、ポリフッ化ビニリデンがある。ポリフッ化ビニリデンは、相転換法による多孔質化が可能である。耐薬品性に優れたポリフッ化ビニリデン半透膜に関しては、いくつかの技術が公開されている（特許文献１〜４）。 Polyvinylidene fluoride is a synthetic polymer having excellent chemical resistance and biodegradability. Polyvinylidene fluoride can be made porous by a phase change method. Regarding the polyvinylidene fluoride semipermeable membrane having excellent chemical resistance, several techniques have been disclosed (Patent Documents 1 to 4).
特許文献１には、中空糸膜の内、外表面に平均０．０５〜５μｍの細孔を有し、該中空糸膜の断面方向においては、実質的に孔径２０μｍ以上のマクロボイドを含まず、かつ２５℃における純水の透過速度が０．００１〜２g／cm2・sec・atmの範囲であるポリフッ化ビニリデン中空糸膜及びその製造方法について明記されている。 Patent Document 1 has average pores of 0.05 to 5 μm on the outer surface of the hollow fiber membrane, and does not substantially contain macrovoids having a pore diameter of 20 μm or more in the cross-sectional direction of the hollow fiber membrane. And a polyvinylidene fluoride hollow fiber membrane having a permeation rate of pure water at 25 ° C. in the range of 0.001 to 2 g / cm 2 · sec · atm and a method for producing the same.
特許文献４には、微多孔を有する透過層を少なくとも３層と、該透過層の間に巨大ボイドを有する支持層が介在された、少なくとも５層構造からなるポリフッ化ビニリデン系樹脂多孔性膜について開示されている。 Patent Document 4 discloses a polyvinylidene fluoride resin porous membrane having at least a five-layer structure in which at least three permeation layers having micropores and a support layer having giant voids are interposed between the permeation layers. It is disclosed.
特許文献２には、ポリフッ化ビニリデンを主体として、親水性ポリビニルピロリドンを１〜２０ｗｔ％含有するブレンドされたポリマーの多孔中空糸膜が開示されている。しかしながら、ポリビニルピロリドンは水溶性ポリマーであるために、製膜直後には膜内にポリビニルピロリドンが保持されていても、膜使用時にポリビニルピロリドンが流出して親水性が徐々に失われるだけでなく、膜構造も変化する恐れがある。 Patent Document 2 discloses a blended polymer porous hollow fiber membrane mainly containing polyvinylidene fluoride and containing 1 to 20 wt% of hydrophilic polyvinylpyrrolidone. However, since polyvinylpyrrolidone is a water-soluble polymer, even if polyvinylpyrrolidone is retained in the membrane immediately after film formation, not only does polyvinylpyrrolidone flow out when the membrane is used, but the hydrophilicity is gradually lost. The film structure may also change.
一方で、ポリビニルピロリドンに不溶性の親水性ポリマー、特に酢酸セルロースをブレンドした半透膜が開示されている（特許文献５、６）。 On the other hand, a semipermeable membrane obtained by blending a polyvinylpyrrolidone insoluble hydrophilic polymer, particularly cellulose acetate, is disclosed (Patent Documents 5 and 6).
特許文献５には、ポリフッ化ビニリデン樹脂と水酸化度が８０％以上かつ１００％未満であるセルロース誘導体とのブレンドポリマーで構成されているポリフッ化ビニリデン樹脂膜について開示されている。しかしながら、製膜後、ポリフッ化ビニリデン樹脂膜に対して水酸化処理を行わなければならず、この処理を施すことにより、膜構造が緻密化し、期待するような高い透水速度や分画が得られない可能性がある。 Patent Document 5 discloses a polyvinylidene fluoride resin film composed of a blend polymer of a polyvinylidene fluoride resin and a cellulose derivative having a degree of hydroxylation of 80% or more and less than 100%. However, after film formation, the polyvinylidene fluoride resin film must be subjected to a hydroxylation treatment. By performing this treatment, the membrane structure is densified, and a high water transmission rate and fraction as expected can be obtained. There is no possibility.
特許文献６には、重量基準で７０％より多いポリフッ化ビニリデンと３０％未満の親水性重合体とを含有する親水性半透膜について開示されているが、この明細書に明記されたポリフッ化ビニリデン多孔膜は、ポリフッ化ビニリデンが元来、疎水性ポリマーであるために極めて親水性が乏しく、ファウリングしやすいため、十分な透水速度が得られない。
本発明は、親水性ポリマーであり、かつ非水溶性ポリマーである酢酸セルロースをポリフッ化ビニリデンとブレンドすることで、酢酸セルロースの特徴とポリフッ化ビニリデンの特徴を生かした、安定に高い透水速度と耐薬品性と耐生分解性を有する半透膜及びその製造方法を提供することを課題とする。 The present invention blends cellulose acetate, which is a hydrophilic polymer and a water-insoluble polymer, with polyvinylidene fluoride so that the characteristics of cellulose acetate and the characteristics of polyvinylidene fluoride can be utilized to achieve a stable and high water transmission rate and resistance. It is an object to provide a semipermeable membrane having chemical properties and biodegradability and a method for producing the same.
本発明者は、酢酸セルロースにポリフッ化ビニリデンをブレンドすることにより上記課題を解決できることを見出した。 The present inventor has found that the above problems can be solved by blending polyvinylidene fluoride with cellulose acetate.
本発明は、課題の解決手段として、酢酸セルロースとポリフッ化ビニリデンを含有し、全ポリマー成分中のポリフッ化ビニリデンの含有割合が５〜６０質量％であることを特徴とする水処理用半透膜を提供する。 The present invention provides a semipermeable membrane for water treatment comprising cellulose acetate and polyvinylidene fluoride as a means for solving the problem, wherein the content of polyvinylidene fluoride in all polymer components is 5 to 60% by mass. I will provide a.
本発明は、他の課題の解決手段として、酢酸セルロースとポリフッ化ビニリデンを含有するポリマー混合物、良溶媒、貧溶媒、並びに無機塩及び親水性ポリマーから選ばれる１つ以上を含む溶液を凝固浴に導いて凝固させ、その後、溶媒を除去することを特徴とする水処理用半透膜の製造方法を提供する。 In another aspect of the present invention, a solution containing at least one selected from a polymer mixture containing cellulose acetate and polyvinylidene fluoride, a good solvent, a poor solvent, and an inorganic salt and a hydrophilic polymer is used as a coagulation bath. Provided is a method for producing a semipermeable membrane for water treatment, characterized by guiding and solidifying, and then removing the solvent.
本発明の水処理用半透膜は、高い透水速度を維持したまま、耐塩素性及び耐生分解性も優れている。 The semipermeable membrane for water treatment of the present invention is excellent in chlorine resistance and biodegradability while maintaining a high water transmission rate.
＜水処理用半透膜＞
水処理用半透膜は、平膜、中空糸膜、チューブラー膜等のいずれの形態であってもよい。
<Semipermeable membrane for water treatment>
The semipermeable membrane for water treatment may be in any form such as a flat membrane, a hollow fiber membrane, and a tubular membrane.
本発明で用いる酢酸セルロースは、酢化度が５５〜６５％が好ましく、５８〜６４％がより好ましく、６０〜６４％が更に好ましい。酢化度が５５％以上であると良好な製膜原液が得られ、６５％以下であると親水性が良くなる。 The cellulose acetate used in the present invention preferably has an acetylation degree of 55 to 65%, more preferably 58 to 64%, and still more preferably 60 to 64%. When the acetylation degree is 55% or more, a good film-forming stock solution is obtained, and when it is 65% or less, the hydrophilicity is improved.
酢酸セルロースの重量平均分子量は、１００〜１，０００が好ましく、２００〜９００がより好ましく、３００〜８００が更に好ましい。重量平均分子量が１００以上であれば、機械的強度が良く、１，０００以下であると多孔化が容易である。 The weight average molecular weight of cellulose acetate is preferably 100 to 1,000, more preferably 200 to 900, and still more preferably 300 to 800. When the weight average molecular weight is 100 or more, the mechanical strength is good, and when the weight average molecular weight is 1,000 or less, porosity is easy.
本発明で用いるポリフッ化ビニリデンは、単独重合体であっても共重合体であってもよいが、フッ化ビニリデン単位が５０％以上であるものが好ましく、７０％以上であるものがより好ましく、８０％以上であるものが更に好ましい。 The polyvinylidene fluoride used in the present invention may be a homopolymer or a copolymer, but preferably has a vinylidene fluoride unit of 50% or more, more preferably 70% or more, What is 80% or more is still more preferable.
共重合体にする場合の他のモノマーとしては、酢酸ビニル系モノマー、アクリル酸系モノマー、メタクリル酸系モノマー、エチレンモノマー、アセチレンモノマー等を挙げることができる。 Examples of other monomers in the case of making a copolymer include vinyl acetate monomers, acrylic acid monomers, methacrylic acid monomers, ethylene monomers, and acetylene monomers.
ポリフッ化ビニリデンの重量平均分子量は、１０万〜１００万が好ましく、２０万〜９０万がより好ましく、３０万〜８０万が更に好ましい。重量平均分子量が１０万以上であれば、機械的強度が良く、１００万以下であると多孔化が容易である。 The weight average molecular weight of polyvinylidene fluoride is preferably 100,000 to 1,000,000, more preferably 200,000 to 900,000, and still more preferably 300,000 to 800,000. If the weight average molecular weight is 100,000 or more, the mechanical strength is good, and if it is 1,000,000 or less, porosity is easy.
本発明で用いるポリマー成分は、酢酸セルロースとポリフッ化ビニリデンの混合物のみからなるものでもよいし、更に他の膜形成成分となるポリマーを含有していてもよい。 The polymer component used in the present invention may be composed only of a mixture of cellulose acetate and polyvinylidene fluoride, or may further contain a polymer that becomes another film forming component.
本発明で用いるポリマー成分中の酢酸セルロースとポリフッ化ビニリデンの含有割合は、酢酸セルロースが４０〜９５質量％、好ましくは４５〜９０質量％、より好ましくは５０〜８０質量％であり、ポリフッ化ビニリデンが５〜６０質量％、好ましくは１０〜５５質量％、より好ましくは２０〜５０質量％である。 The content ratio of cellulose acetate and polyvinylidene fluoride in the polymer component used in the present invention is 40 to 95% by mass of cellulose acetate, preferably 45 to 90% by mass, more preferably 50 to 80% by mass, and polyvinylidene fluoride. Is 5 to 60% by mass, preferably 10 to 55% by mass, and more preferably 20 to 50% by mass.
本発明で用いるポリマー成分を酢酸セルロース、ポリフッ化ビニリデン及び他の膜形成成分となるポリマーの混合物にする場合は、全ポリマー成分中の酢酸セルロース及びポリフッ化ビニリデンの合計含有量は８０質量％以上であることが好ましく、８５質量％以上であることがより好ましく、９０質量％以上であることが更に好ましいが、ポリフッ化ビニリデンは前記した含有割合になるようにする。 When the polymer component used in the present invention is a mixture of cellulose acetate, polyvinylidene fluoride, and other film forming polymer, the total content of cellulose acetate and polyvinylidene fluoride in all polymer components is 80% by mass or more. Preferably, it is 85% by mass or more, more preferably 90% by mass or more, but the polyvinylidene fluoride is made to have the aforementioned content ratio.
＜水処理用半透膜の製造方法＞
本発明の製造方法では、製膜原液として、酢酸セルロース及びポリフッ化ビニリデン、更に必要に応じて他の膜形成成分となるポリマーを含有するポリマー混合物、良溶媒と、必要に応じて貧溶媒からなる溶媒及び必要に応じて無機塩を含む溶液を用いる。
<Method for producing semipermeable membrane for water treatment>
In the production method of the present invention, as a film-forming stock solution, cellulose acetate and polyvinylidene fluoride, and further, if necessary, a polymer mixture containing a polymer that becomes another film-forming component, a good solvent, and if necessary, a poor solvent A solution containing a solvent and, if necessary, an inorganic salt is used.
製膜原液に用いる良溶媒としては、酢酸セルロース及びポリフッ化ビニリデンにとって良溶媒であれば特に限定されないが、ジメチルスルホキシド、ジメチルアセトアミド、ジメチルホルムアミド、N−メチル−２−ピロリドンが好ましく、特にジメチルスルホキシドが好ましい。 The good solvent used for the film-forming stock solution is not particularly limited as long as it is a good solvent for cellulose acetate and polyvinylidene fluoride, but dimethyl sulfoxide, dimethylacetamide, dimethylformamide, and N-methyl-2-pyrrolidone are preferred, and dimethyl sulfoxide is particularly preferred. preferable.
製膜原液に用いる貧溶媒としては、酢酸セルロース及びポリフッ化ビニリデンにとって貧溶媒であれば特に限定されないが、グリセリン、エチレングリコール、トリエチレングリコール、メタノール、エタノール等の水溶性溶媒が好ましく、特にグリセリンが好ましい。 The poor solvent used for the film-forming stock solution is not particularly limited as long as it is a poor solvent for cellulose acetate and polyvinylidene fluoride, but a water-soluble solvent such as glycerin, ethylene glycol, triethylene glycol, methanol, ethanol is preferable, and glycerin is particularly preferable. preferable.
製膜原液には、半透膜の膜孔径を増大させて透水性能を高めるために親水性ポリマー又は水溶性ポリマーを配合することができる。このような親水性ポリマー又は水溶性ポリマーとしては、ポリビニルピロリドン、ポリエチレングリコール、ポリフェニレンオキシド、ポリビニルアルコール、ポリアクリル酸が好ましく、特にポリビニルピロリドンが好ましい。 In the membrane-forming stock solution, a hydrophilic polymer or a water-soluble polymer can be blended in order to increase the membrane pore size of the semipermeable membrane and improve the water permeability. As such a hydrophilic polymer or water-soluble polymer, polyvinyl pyrrolidone, polyethylene glycol, polyphenylene oxide, polyvinyl alcohol, and polyacrylic acid are preferable, and polyvinyl pyrrolidone is particularly preferable.
親水性ポリマー又は水溶性ポリマーの含有量は、製膜原液中１〜１５質量％が好ましく、特に２〜１０質量％が好ましい。親水性ポリマーの製膜原液中に占める割合が、１質量％以上であると膜孔径の増大効果が大きく、１５質量％以下であると膜孔径を適度に維持でき、機械的強度も高くなる。 The content of the hydrophilic polymer or the water-soluble polymer is preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass in the film-forming stock solution. When the proportion of the hydrophilic polymer in the membrane-forming stock solution is 1% by mass or more, the effect of increasing the membrane pore size is large, and when it is 15% by mass or less, the membrane pore size can be appropriately maintained and the mechanical strength is also increased.
また、製膜原液は、無機塩を含有することができる。無機塩としては、例えば、塩化ナトリウム、塩化カルシウム、塩化リチウムを挙げることができる。無機塩を含むことにより、膜の孔径が大きくなり、透水性能が高められるという効果がある。 Moreover, the film-forming stock solution can contain an inorganic salt. Examples of inorganic salts include sodium chloride, calcium chloride, and lithium chloride. By including the inorganic salt, there is an effect that the pore diameter of the membrane is increased and the water permeability is enhanced.
無機塩の含有量は、製膜原液中０．１質量％以上が好ましく、より好ましくは０．５質量％以上である。無機塩の製膜原液中に占める割合が、０．１質量％以上であると膜孔径の増大効果が大きく、０．５質量％以上であると前記効果をより高めることができる。 The content of the inorganic salt is preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the film-forming stock solution. When the proportion of the inorganic salt in the film-forming stock solution is 0.1% by mass or more, the effect of increasing the membrane pore diameter is large, and when it is 0.5% by mass or more, the effect can be further enhanced.
製膜原液中の膜形成成分となるポリマー混合物（上記した半透膜の膜孔径を増大させるための親水性ポリマー又は水溶性ポリマーは含まれない）の割合は、１０〜３０質量％が好ましく、特に１５〜２５質量％が好ましい。１０質量％以上であると機械的強度が良く、３０質量％以下であると製膜が容易である。 The ratio of the polymer mixture (not including the hydrophilic polymer or the water-soluble polymer for increasing the membrane pore diameter of the semipermeable membrane) described above as a film-forming component in the membrane-forming stock solution is preferably 10 to 30% by mass, 15-25 mass% is especially preferable. When it is 10% by mass or more, the mechanical strength is good, and when it is 30% by mass or less, film formation is easy.
製膜原液は、良溶媒、及び必要により貧溶媒からなる溶媒にポリマー混合物を所定濃度になるように溶解させて得ることができる。製膜原液の粘度は、２５℃換算で、５，０００〜１００万mPa・sが好ましく、１万〜５０万mPa・sがより好ましい。 The film-forming stock solution can be obtained by dissolving the polymer mixture in a good solvent and, if necessary, a solvent consisting of a poor solvent so as to have a predetermined concentration. The viscosity of the film-forming stock solution is preferably 5,000 to 1,000,000 mPa · s, more preferably 10,000 to 500,000 mPa · s in terms of 25 ° C.
本発明の製造方法では、製膜原液を凝固浴に導いて凝固させ、製膜する。凝固時における製膜原液の温度は２０〜１５０℃が好ましく、特に４０〜１２０℃が好ましい。製膜原液の温度が２０℃以上であると多孔化が容易で、１５０℃以下であるとポリマー成分の変性の恐れがない。 In the production method of the present invention, the film-forming stock solution is introduced into a coagulation bath to be coagulated to form a film. 20-150 degreeC is preferable and the temperature of the film-forming stock solution at the time of coagulation has especially preferable 40-120 degreeC. When the temperature of the film-forming stock solution is 20 ° C. or higher, porosity is easy, and when it is 150 ° C. or lower, there is no fear of modification of the polymer component.
凝固浴として用いる凝固液としては、水又は上記した良溶媒１０質量％以下の水溶液が好ましく、特に水が好ましい。また、凝固液温度は２０〜８０℃が好ましく、特に３０〜６０℃が好ましい。凝固液温度が２０℃以上であると多孔化が容易で、８０℃以下であると膜形状が損なわれることがない。 As the coagulation liquid used as the coagulation bath, water or an aqueous solution of 10% by mass or less of the good solvent described above is preferable, and water is particularly preferable. Further, the coagulation liquid temperature is preferably 20 to 80 ° C, particularly preferably 30 to 60 ° C. When the coagulation liquid temperature is 20 ° C. or higher, porosity is easy, and when it is 80 ° C. or lower, the film shape is not impaired.
本発明の製造方法では、凝固浴にて製膜後、常温乃至は加温雰囲気にて乾燥し、溶媒を除去する。 In the production method of the present invention, after forming a film in a coagulation bath, the solvent is removed by drying in a normal temperature or a heated atmosphere.
本発明の水処理用半透膜は、一般的な水処理に適用され、例えば、各種施設の排水及び家庭排水の処理、更には河川、湖沼等の浄化処理等に適用することができる。 The semipermeable membrane for water treatment of the present invention is applied to general water treatment, and can be applied to, for example, treatment of wastewater from various facilities and household wastewater, and purification treatment of rivers, lakes, and the like.
以下、実施例により本発明を更に詳しく説明するが、本発明はこれらにより限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited by these.
［純水透水速度測定］
得られた中空糸膜を長さ１ｍに切断し、中空糸の片側を閉じた状態で、もう片側から圧力０．１ＭＰａにて、中空糸内部に純水を透過させ、外表面から得られる透過液量から純水透水速度を算出した。
[Measurement of pure water permeability]
The obtained hollow fiber membrane is cut into a length of 1 m, and with one side of the hollow fiber closed, pure water is allowed to permeate inside the hollow fiber at a pressure of 0.1 MPa from the other side, and the permeation obtained from the outer surface. The pure water permeation rate was calculated from the liquid volume.
［耐塩素性試験］
得られた中空糸膜を有効塩素濃度１，０００mg／Lの次亜塩素酸ナトリウム水溶液中に１０日間浸漬し、引張り強度試験機（EZTest、島津製作所製）により、破断点強度を測定し、浸漬前の強度に対する低下率を算出した。
[Chlorine resistance test]
The obtained hollow fiber membrane was immersed in an aqueous solution of sodium hypochlorite having an effective chlorine concentration of 1,000 mg / L for 10 days, and the strength at break was measured with a tensile strength tester (EZTest, manufactured by Shimadzu Corporation). The rate of decrease relative to the previous strength was calculated.
［耐生分解性試験］
得られた中空糸膜を河川に１００日間浸漬し、引張り強度試験機により、破断点強度を測定し、浸漬前の強度に対する低下率（％）を算出した。
[Biodegradation resistance test]
The obtained hollow fiber membrane was immersed in a river for 100 days, the strength at break was measured with a tensile strength tester, and the rate of decrease (%) with respect to the strength before immersion was calculated.
実施例１
酢酸セルロース（FRK、ダイセル化学工業（株）製、酢化度６０．９、重量平均分子量３００）１４．４質量部、ポリフッ化ビニリデン（ＫＦ＃８５０、呉羽化学工業（株）製、重量平均分子量２．８×１０５）３．６質量部（全ポリマー中の含有割合２０質量％）、ジメチルスルホキシド８１質量部、塩化リチウム１質量部からなる製膜原液を得た。８０℃に保温した製膜原液を二重管ノズルを通過させ、５０℃の水からなる凝固槽で凝固させた。得られた中空糸膜の外径は１．３ｍｍ、内径は０．８ｍｍであった。破断点強度は４１０kg/ｆ、破断点伸度は２２％であった。純水透水速度は５７０ＬＭＨＫであった。また、耐塩素性試験と耐生分解性試験の結果を表１に示す。
Example 1
Cellulose acetate (FRK, manufactured by Daicel Chemical Industries, Ltd., degree of acetylation 60.9, weight average molecular weight 300) 14.4 parts by mass, polyvinylidene fluoride (KF # 850, manufactured by Kureha Chemical Industries, Ltd., weight average molecular weight) 2.8 × 10 5 ) 3.6 parts by mass (content ratio of 20% by mass in all polymers), 81 parts by mass of dimethyl sulfoxide, and 1 part by mass of lithium chloride were obtained. The film-forming stock solution kept at 80 ° C. was passed through a double tube nozzle and coagulated in a coagulation tank composed of water at 50 ° C. The obtained hollow fiber membrane had an outer diameter of 1.3 mm and an inner diameter of 0.8 mm. The strength at break was 410 kg / f, and the elongation at break was 22%. The pure water permeation rate was 570 LMHK. Table 1 shows the results of the chlorine resistance test and the biodegradation resistance test.
実施例２
実施例１で用いた酢酸セルロース１２質量部、実施例１で用いたポリフッ化ビニリデン３質量部（全ポリマー中の含有割合２０質量％）、ジメチルスルホキシド７７質量部、グリセリン８質量部からなる製膜原液を得た。８０℃に保温した製膜原液を二重管ノズルを通過させ、５０℃の水からなる凝固槽で凝固させた。得られた中空糸膜の外径は１．３ｍｍ、内径は０．８ｍｍであった。破断点強度は１９０kg/ｆ、破断点伸度は１５％であった。純水透水速度は６４０ＬＭＨＫであった。また、耐塩素性試験と耐生分解性試験の結果を表１に示す。
Example 2
Film formation consisting of 12 parts by mass of cellulose acetate used in Example 1, 3 parts by mass of polyvinylidene fluoride used in Example 1 (content ratio of 20% by mass in all polymers), 77 parts by mass of dimethyl sulfoxide, and 8 parts by mass of glycerin A stock solution was obtained. The film-forming stock solution kept at 80 ° C. was passed through a double tube nozzle and coagulated in a coagulation tank composed of water at 50 ° C. The obtained hollow fiber membrane had an outer diameter of 1.3 mm and an inner diameter of 0.8 mm. The strength at break was 190 kg / f, and the elongation at break was 15%. The pure water permeation rate was 640 LMHK. Table 1 shows the results of the chlorine resistance test and the biodegradation resistance test.
実施例３
実施例１で用いた酢酸セルロース１０質量部、実施例１で用いたポリフッ化ビニリデン５質量部（全ポリマー中の含有割合３３質量％）、ジメチルスルホキシド８４質量部、塩化リチウム１質量部からなる製膜原液を得た。８０℃に保温した製膜原液を二重管ノズルを通過させ、５０℃の水からなる凝固槽で凝固させた。得られた中空糸膜の外径は１．３ｍｍ、内径は０．８ｍｍであった。破断点強度は１９０kg/ｆ、破断点伸度は１５％であった。純水透水速度は１０４０ＬＭＨＫであった。また、耐塩素性試験と耐生分解性試験の結果を表１に示す。
Example 3
Product made of 10 parts by mass of cellulose acetate used in Example 1, 5 parts by mass of polyvinylidene fluoride used in Example 1 (content ratio of 33% by mass in all polymers), 84 parts by mass of dimethyl sulfoxide, and 1 part by mass of lithium chloride A membrane stock solution was obtained. The film-forming stock solution kept at 80 ° C. was passed through a double tube nozzle and coagulated in a coagulation tank composed of water at 50 ° C. The obtained hollow fiber membrane had an outer diameter of 1.3 mm and an inner diameter of 0.8 mm. The strength at break was 190 kg / f, and the elongation at break was 15%. The pure water permeation rate was 1040 LMHK. Table 1 shows the results of the chlorine resistance test and the biodegradation resistance test.
実施例４
実施例１で用いた酢酸セルロース９．５質量部、実施例１で用いたポリフッ化ビニリデン９．５質量部（全ポリマー中の含有割合５０質量％）、ジメチルスルホキシド８０質量部、塩化リチウム１質量部からなる製膜原液を得た。８０℃に保温した製膜原液を二重管ノズルを通過させ、５０℃の水からなる凝固槽で凝固させた。得られた中空糸膜の外径は１．３ｍｍ、内径は０．８ｍｍであった。破断点強度は６０kg/ｆ、破断点伸度は１０％であった。純水透水速度は１２００ＬＭＨＫであった。また、耐塩素性試験と耐生分解性試験の結果を表１に示す。
Example 4
9.5 parts by mass of cellulose acetate used in Example 1, 9.5 parts by mass of polyvinylidene fluoride used in Example 1 (content of 50% by mass in all polymers), 80 parts by mass of dimethyl sulfoxide, 1 mass of lithium chloride A film-forming stock solution consisting of parts was obtained. The film-forming stock solution kept at 80 ° C. was passed through a double tube nozzle and coagulated in a coagulation tank composed of water at 50 ° C. The obtained hollow fiber membrane had an outer diameter of 1.3 mm and an inner diameter of 0.8 mm. The strength at break was 60 kg / f, and the elongation at break was 10%. The pure water permeation rate was 1200 LMHK. Table 1 shows the results of the chlorine resistance test and the biodegradation resistance test.
実施例５
実施例１で用いた酢酸セルロース９質量部、実施例１で用いたポリフッ化ビニリデン９質量部（全ポリマー中の含有割合５０質量％）、ジメチルスルホキシド７１質量部、グリセリン７質量部、ポリビニルピロリドン（分子量５５，０００）４質量部からなる製膜原液を得た。８０℃に保温した製膜原液を二重管ノズルを通過させ、５０℃の水からなる凝固槽で凝固させた。得られた中空糸膜の外径は１．３ｍｍ、内径は０．８ｍｍであった。破断点強度は８０kg/ｆ、破断点伸度は１２％であった。純水透水速度は１３００ＬＭＨＫであった。また、耐塩素性試験と耐生分解性試験の結果を表１に示す。
Example 5
9 parts by mass of cellulose acetate used in Example 1, 9 parts by mass of polyvinylidene fluoride used in Example 1 (content ratio of 50% by mass in all polymers), 71 parts by mass of dimethyl sulfoxide, 7 parts by mass of glycerin, polyvinylpyrrolidone ( A film-forming stock solution consisting of 4 parts by mass of molecular weight 55,000) was obtained. The film-forming stock solution kept at 80 ° C. was passed through a double tube nozzle and coagulated in a coagulation tank composed of water at 50 ° C. The obtained hollow fiber membrane had an outer diameter of 1.3 mm and an inner diameter of 0.8 mm. The strength at break was 80 kg / f, and the elongation at break was 12%. The pure water permeation rate was 1300 LMHK. Table 1 shows the results of the chlorine resistance test and the biodegradation resistance test.
比較例１
実施例１で用いた酢酸セルロース１質量部、実施例１で用いたポリフッ化ビニリデン１４質量部（全ポリマー中の含有割合９３質量％）、ジメチルスルホキシド７４質量部、グリセリン７質量部、実施例５で用いたポリビニルピロリドン４質量部からなる製膜原液を得た。８０℃に保温した製膜原液を二重管ノズルを通過させ、５０℃の水からなる凝固槽で凝固させた。得られた中空糸膜の外径は１．３ｍｍ、内径は０．８ｍｍであった。破断点強度は２３０kg/ｆ、破断点伸度は６３％であった。純水透水速度は３９９ＬＭＨＫであった。
Comparative Example 1
1 part by mass of cellulose acetate used in Example 1, 14 parts by mass of polyvinylidene fluoride used in Example 1 (content ratio of 93% by mass in all polymers), 74 parts by mass of dimethyl sulfoxide, 7 parts by mass of glycerin, Example 5 A film-forming stock solution comprising 4 parts by mass of polyvinylpyrrolidone used in 1 was obtained. The film-forming stock solution kept at 80 ° C. was passed through a double tube nozzle and coagulated in a coagulation tank composed of water at 50 ° C. The obtained hollow fiber membrane had an outer diameter of 1.3 mm and an inner diameter of 0.8 mm. The strength at break was 230 kg / f, and the elongation at break was 63%. The pure water permeation rate was 399LMHK.
実施例１〜５と比較例１との比較から、実施例の組成は、比較例に対して純水透水速度が高いことが分かる。 From comparison between Examples 1 to 5 and Comparative Example 1, it can be seen that the composition of the Example has a higher pure water permeation rate than the Comparative Example.
Claims (2)
Introducing a polymer mixture containing cellulose acetate and polyvinylidene fluoride, a good solvent, and a solution containing at least one selected from a poor solvent, an inorganic salt and a hydrophilic polymer into a coagulation bath to coagulate, and then removing the solvent; The manufacturing method of the semipermeable membrane for water treatment characterized by these.
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| JP2014001360A (en) * | 2012-05-25 | 2014-01-09 | Olympus Corp | Elastomer composition and molded product |
| CN104548962A (en) * | 2015-01-09 | 2015-04-29 | 王进 | Polyvinylidene fluoride hollow fiber ultra-filtration membrane and preparation method thereof |
| JP2015512784A (en) * | 2012-03-30 | 2015-04-30 | コーロン インダストリーズ インク | Porous membrane and method for producing the same |
| JP2017144358A (en) * | 2016-02-15 | 2017-08-24 | 株式会社ダイセル | Hollow fiber membrane |
| CN108043240A (en) * | 2017-12-29 | 2018-05-18 | 北京清大国华环境股份有限公司 | A kind of resistant to pollution PVDF Modified Membranes of high throughput and preparation method thereof |
| WO2020262490A1 (en) * | 2019-06-27 | 2020-12-30 | 東レ株式会社 | Porous membrane and composite porous membrane |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015512784A (en) * | 2012-03-30 | 2015-04-30 | コーロン インダストリーズ インク | Porous membrane and method for producing the same |
| US9314745B2 (en) | 2012-03-30 | 2016-04-19 | Kolon Industries, Inc. | Porous membrane and method for manufacturing the same |
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| CN108043240A (en) * | 2017-12-29 | 2018-05-18 | 北京清大国华环境股份有限公司 | A kind of resistant to pollution PVDF Modified Membranes of high throughput and preparation method thereof |
| WO2020262490A1 (en) * | 2019-06-27 | 2020-12-30 | 東レ株式会社 | Porous membrane and composite porous membrane |
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