JP2006116383A - Cartridge filter for precise filtration and manufacturing method therefor - Google Patents
Cartridge filter for precise filtration and manufacturing method therefor Download PDFInfo
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本発明は、ビールやワイン、清酒、ジュース等の飲料食品の除菌、注射液や輸液等の医薬品の除菌、電子工業用洗浄水の除粒子等の高い精度の濾過を行うための精密濾過用カートリッジフィルターに関するものであり、１０μm以下、特に１μｍ以下のサブミクロンオーダーの微粒子や微生物を効率良く濾過するための精密濾過用カートリッジフィルター及びその製造方法に関するものである。 The present invention is a microfiltration for performing high-accuracy filtration such as sterilization of beverage foods such as beer, wine, sake, and juice, sterilization of pharmaceuticals such as injections and infusions, and particles of electronic industrial washing water. The present invention relates to a cartridge filter for microfiltration for efficiently filtering particles and microorganisms of submicron order of 10 μm or less, particularly 1 μm or less, and a method for producing the same.
精密濾過膜の素材としては、一般的にセルロースアセテート、ポリアミド、ポリエーテルスルホン、ポリスルホン等が用いられているが、そのうちポリエーテルスルホン及びポリスルホンは、機械的強度、耐熱性、耐薬品性等に優れ、蒸気滅菌も可能であることから、医療用、食品用の濾過膜の素材として、大変有用である。 Cellulose acetate, polyamide, polyethersulfone, polysulfone, etc. are generally used as the material for microfiltration membranes. Of these, polyethersulfone and polysulfone are excellent in mechanical strength, heat resistance, chemical resistance, etc. Since steam sterilization is also possible, it is very useful as a material for filtration membranes for medical and food use.
また、精密濾過膜としては、その断面構造において、膜の厚み方向の孔径が変化せず、膜の両表面の孔径が同じである等方性膜と、膜の一方の面から他方の面へと孔径が変化し、膜の両表面が異なった孔径を有する異方性膜とに区分することができる。 In addition, the microfiltration membrane has an isotropic membrane in which the pore diameter in the thickness direction of the membrane does not change and the pore diameter on both surfaces of the membrane is the same, and from one surface of the membrane to the other in the cross-sectional structure. And an anisotropic film having different pore diameters on both surfaces of the film.
これらのうち、前記等方性膜は、粒子捕捉性は良好であるが、濾過にあたって膜全体が流体の流れに対して大きな抵抗を示し、小さな流速しか得られないうえ、1次側表面だけで粒子を捕捉するため、濾過寿命が短い。 Of these, the isotropic membrane has good particle trapping properties, but the whole membrane exhibits a large resistance to fluid flow during filtration, and only a small flow rate is obtained. Filter life is short due to trapping particles.
一方、異方性膜は緻密層と呼ばれる孔径の小さい層を膜の片方の表面もしくは内側に有し、反対表面へ向かうに従って孔のサイズが次第に増加する構造を持っていることから、粒子がその大きさによって段階的に捕捉され、膜の厚みを有効に濾材として活用することが出来るので、同じ濾過効率の等方性膜と比較すると大きな流速が得られるうえ、濾過寿命も長い。更に濾過性能をより向上させるために、異方性膜の表裏の孔径比を大きくして、異方性をより高度にした構造とする手段がとられている。このように膜構造の異方性を高度にすることは、濾過寿命を長くできることから、濾過性能を向上させるのに大変有用である。 On the other hand, the anisotropic film has a layer having a small pore diameter called a dense layer on one surface or inside of the film, and has a structure in which the pore size gradually increases toward the opposite surface. Since it is captured stepwise depending on the size and the thickness of the membrane can be effectively used as a filter medium, a large flow rate is obtained and a filtration life is long as compared with an isotropic membrane having the same filtration efficiency. Furthermore, in order to further improve the filtration performance, a means is adopted in which the pore diameter ratio between the front and back surfaces of the anisotropic membrane is increased so that the structure has a higher degree of anisotropy. In this way, increasing the anisotropy of the membrane structure is very useful for improving the filtration performance because the filtration life can be extended.
これらの精密濾過膜は、実用上においては、体積当たりの濾過膜の組み込み面積（有効濾過面積）を大きくすることができるため、膜をひだ折り加工して組み立てたカートリッジフィルターとして使用される場合が多い。 In practical use, these microfiltration membranes can be used as cartridge filters assembled by folding the membrane because it can increase the filtration membrane's built-in area (effective filtration area) per volume. Many.
しかしながら、膜の表裏の孔径比を大きくし、異方性を高度にするほど、濾過性能は向上するが、必然的に膜の強度を律速する緻密層の厚さが薄くなり、膜の強度が弱くなる。その結果、膜をひだ折りしてカートリッジフィルターとした場合、膜の折り目表面に亀裂が発生し易くなり、特に、高度な異方性を有する精密濾過膜の場合、機械的な折り曲げにより亀裂が発生しなくても、カートリッジフィルターの完全性試験や洗浄するための通水、乾燥等により、折り目表面に亀裂が発生し易くなる。 However, as the pore size ratio on the front and back of the membrane increases and the anisotropy increases, the filtration performance improves, but the thickness of the dense layer that inevitably controls the strength of the membrane decreases, and the strength of the membrane decreases. become weak. As a result, when the membrane is folded and used as a cartridge filter, cracks are likely to occur on the surface of the folds of the membrane, and in particular, in the case of microfiltration membranes with a high degree of anisotropy, cracks occur due to mechanical bending. Even if not, cracks are likely to occur on the surface of the crease due to the integrity test of the cartridge filter, water flow for cleaning, drying, and the like.
このような問題により、カートリッジフィルターに採用できる異方性膜の表裏の孔径比は制約され、それとともに得られる濾過性能も限られたものとなっている。 Due to such problems, the pore diameter ratio between the front and back surfaces of the anisotropic membrane that can be employed in the cartridge filter is restricted, and the filtration performance obtained therewith is also limited.
上記問題を解決するため、特許文献１においては、緻密層が膜表面ではなく、膜の内部に存在する構造の濾過膜が、また、特許文献２においては、二枚の異方性精密濾過膜の緻密層同士が向かい合うように積層させた濾過膜が提案されている。 In order to solve the above problem, in Patent Document 1, a dense membrane is not a membrane surface, but a filtration membrane having a structure existing inside the membrane. In Patent Document 2, two anisotropic microfiltration membranes are used. Filtration membranes have been proposed in which the dense layers are laminated so that they face each other.
しかしながら、特許文献１のように膜の内部に緻密層を有する濾過膜であっても、膜の折り目表面における亀裂は、内部の緻密層にまで達することもあり不完全である。 However, even in a filtration membrane having a dense layer inside the membrane as in Patent Document 1, cracks on the fold surface of the membrane may reach the inside dense layer and are incomplete.
また、特許文献２のように二枚の異方性濾過膜を積層した場合、保護膜分のコストが増加し、更に、ひだ折り加工を行いカートリッジ化する場合には、膜の厚さが増すため、カートリッジに入れることができる膜面積が少なくなり、コストが高いにも拘わらず、低流量、短濾過寿命となってしまい、極めて不経済である。 In addition, when two anisotropic filtration membranes are laminated as in Patent Document 2, the cost for the protective membrane increases, and when the cartridge is formed by fold folding, the thickness of the membrane increases. Therefore, the membrane area that can be put in the cartridge is reduced, and the cost is high, but the flow rate is short and the filtration life is short, which is extremely uneconomical.
そこで、本発明は、異方性の精密濾過膜がひだ折り加工されているカートリッジフィルターにおいて、通液、乾燥等の作業に曝されても濾過膜の折り目表面に亀裂が発生せず、濾過性能に優れた精密濾過用カートリッジフィルター及びその製造方法を提供することを目的とする。 Therefore, the present invention is a cartridge filter in which an anisotropic microfiltration membrane is fold-folded, and even when exposed to operations such as liquid passing and drying, no cracks occur on the fold surface of the filtration membrane, and the filtration performance It is an object of the present invention to provide a microfiltration cartridge filter excellent in the above and a method for producing the same.
上記目的を達成するため、本発明は、ポリエーテルスルホンと親水性ポリマーを含有する異方性の精密濾過膜がひだ折り加工されて成型されている精密濾過用カートリッジフィルターにおいて、前記ポリエーテルスルホンの４０％以上が、重量平均分子量５万〜１０万であり、さらに、精密濾過膜がひだ折りされて成型された後に、純水を通水することによる湿潤状態において、１１０℃〜１３５℃の高圧蒸気処理が施されていることを特徴とする。 In order to achieve the above object, the present invention provides a cartridge filter for microfiltration in which an anisotropic microfiltration membrane containing polyethersulfone and a hydrophilic polymer is formed by folding and molding, More than 40% has a weight average molecular weight of 50,000 to 100,000, and after the microfiltration membrane is folded and molded, in a wet state by passing pure water, a high pressure of 110 ° C. to 135 ° C. It is characterized by being steamed.
また、本発明は、ポリエーテルスルホンと親水性ポリマーを含有する異方性の精密濾過膜がひだ折り加工されて成型されている精密濾過用カートリッジフィルターの製造方法において、前記ポリエーテルスルホンの４０％以上が、重量平均分子量５万〜１０万であり、さらに、精密濾過膜をひだ折りして成型した後に、純水を通水することによる湿潤状態において、１１０℃〜１３５℃の高圧蒸気処理を施す工程を含むことを特徴とする精密濾過用カートリッジフィルターの製造方法である。 The present invention also relates to a method for producing a cartridge filter for microfiltration in which an anisotropic microfiltration membrane containing polyethersulfone and a hydrophilic polymer is formed by fold-folding, and is 40% of the polyethersulfone. The above is a weight average molecular weight of 50,000 to 100,000, and further, high-pressure steam treatment at 110 ° C. to 135 ° C. is performed in a wet state by passing pure water after the microfiltration membrane is folded and molded. The manufacturing method of the cartridge filter for microfiltration characterized by including the process to give.
以上のように、本発明に係わる精密濾過用カートリッジフィルター及びその製造方法は、ポリエーテルスルホンの４０％以上を重量平均分子量５万〜１０万とし、さらに前記精密濾過膜をひだ折りして、カートリッジフィルターを成型した後に、純水を通水することによる湿潤状態において、１１０℃〜１３５℃の高圧蒸気処理を施すといった安価で簡便な方法により、通液、乾燥等の作業に曝されても濾過膜の折り目表面に亀裂が発生しない精密濾過用カートリッジフィルター及びその製造法を提供することができる。 As described above, the cartridge filter for microfiltration according to the present invention and the manufacturing method thereof have a weight average molecular weight of 50,000 to 100,000 in the polyethersulfone and further fold the microfiltration membrane into a cartridge. Even if it is exposed to work such as liquid passing and drying by an inexpensive and simple method such as performing high-pressure steam treatment at 110 ° C to 135 ° C in a wet state by passing pure water after molding the filter. It is possible to provide a cartridge filter for microfiltration that does not cause cracks on the fold surface of the membrane and a method for producing the same.
また、本発明に係わるカートリッジフィルターは、十分な強度を有するため、保護膜を必要としないことから経済的であり、十分な濾過面積の濾過膜をカートリッジ内に納めることができる。また更に、濾過性能に優れた高度な異方性膜を用いても亀裂が発生しないことから、優れた濾過流量及び濾過寿命を得ることができる。 Further, the cartridge filter according to the present invention is economical because it has sufficient strength and does not require a protective membrane, and a filtration membrane having a sufficient filtration area can be accommodated in the cartridge. Furthermore, since a crack does not occur even when a highly anisotropic membrane excellent in filtration performance is used, an excellent filtration flow rate and filtration life can be obtained.
高度に異方性の膜は、膜の緻密層の厚さが薄く、等方性の膜や低度に異方性の膜に比べ、強度が弱くなる。時には機械的な折り曲げに対する強度も得られなくなり、ひだ折り加工さえも難しくなる。しかし、原料であるポリエーテルスルホン樹脂中に重量平均分子量５万〜１０万のポリエーテルスルホン樹脂を４０％以上含有させることにより、強度を向上させることができ、５０％以上含有させることがより好ましい。 A highly anisotropic film has a thin dense layer and is weaker than an isotropic film or a less anisotropic film. Sometimes mechanical strength cannot be obtained, and even fold folding is difficult. However, the strength can be improved by adding 40% or more of the polyethersulfone resin having a weight average molecular weight of 50,000 to 100,000 in the raw material polyethersulfone resin, and more preferably 50% or more. .
膜構造の異方性の度合いは、膜の厚み、バブルポイント及び平均水流速の値より判断できる。平均水流速は、単位時間当たりに膜の単位面積を通過する水の容積である。膜厚とバブルポイントが同じである場合、膜の厚み方向の孔径変化が大きい高度な異方性膜の場合、低度の異方性膜に比べ平均水流速が大きいが、逆に膜の強度は低下する。 The degree of anisotropy of the membrane structure can be determined from the values of membrane thickness, bubble point, and average water flow rate. The average water flow rate is the volume of water that passes through the unit area of the membrane per unit time. When the film thickness is the same as the bubble point, the average water flow rate is higher in the case of highly anisotropic membranes with large changes in the pore size in the thickness direction of the membrane, compared to low-grade anisotropic membranes. Will decline.
本発明の精密濾過用カートリッジフィルターには、膜の厚みが８０〜１４０μｍであり、平均孔径１０μm以下の精密濾過膜に有用であり、特に、イソプロピルアルコールによるバブルポイントが０．０９〜０．１２ＭＰａで且つ平均水流速が６２〜１２５ｍｌ／ｍｉｎ／ｃｍ２ａｔ５２±１ｃｍＨｇ、もしくはイソプロピルアルコールによるバブルポイントが０．１８〜０．２２ＭＰａで、且つ平均水流速が３０〜４５ｍｌ／ｍｉｎ／ｃｍ２ａｔ５２±１ｃｍＨｇの膜に有用である。 The cartridge filter for microfiltration of the present invention has a membrane thickness of 80 to 140 μm and is useful for microfiltration membranes having an average pore diameter of 10 μm or less. Particularly, the bubble point due to isopropyl alcohol is 0.09 to 0.12 MPa. And the average water flow rate is 62-125 ml / min / cm 2 at52 ± 1 cmHg, or the bubble point by isopropyl alcohol is 0.18-0.22 MPa, and the average water flow rate is 30-45 ml / min / cm 2 at52 ± 1 cmHg. Useful for membranes.
前記精密濾過膜をカートリッジフィルターに加工後、純水で湿潤状態として、高圧蒸気処理を行うが、カートリッジを湿潤させるために使用する水は、純水を用いることが好ましく、更に湿潤水には、超純水を使用することがより好ましい。純度の低い水や乾燥した状態で高圧蒸気処理を行っても所望の効果を得ることは出来ない。 After the microfiltration membrane is processed into a cartridge filter, it is wetted with pure water and subjected to high-pressure steam treatment. The water used to wet the cartridge is preferably pure water. It is more preferable to use ultrapure water. Even if the high-pressure steam treatment is performed in low-purity water or in a dry state, a desired effect cannot be obtained.
また、高圧蒸気処理する際の温度と時間は、１１０℃〜１３５℃にて１０〜６０分処理することが好ましく、特に温度は、１２１〜１２６℃であることが好ましく、時間は１５〜４０分処理することが好ましい。それら以下の場合、亀裂発生を十分に防止することができず、逆にそれら以上の場合、膜強度が低下する場合もある。本発明において、高圧蒸気処理は、１００℃以上の水の飽和蒸気圧下における水蒸気を用いて加熱処理することをいい、例えばオートクレーブによって高圧蒸気処理が施される。 Further, the temperature and time for the high-pressure steam treatment are preferably 10 to 60 minutes at 110 ° C. to 135 ° C., particularly preferably the temperature is 121 to 126 ° C., and the time is 15 to 40 minutes. It is preferable to process. If it is less than these, the occurrence of cracks cannot be sufficiently prevented. Conversely, if it is more than that, the film strength may decrease. In the present invention, high-pressure steam treatment refers to heat treatment using water vapor at a saturated vapor pressure of water of 100 ° C. or higher. For example, high-pressure steam treatment is performed by an autoclave.
親水性ポリマーとしては、１０万〜１６万の重量平均分子量を１０％〜６０％含むヒドロキシプロピルセルロースか、重量平均分子量４万〜６万のポリビニルピロリドン、若しくはこれらを併用することが好ましい。また、親水性ポリマーは、膜の重量に対して０．５〜６．０重量％含有されていることが好ましく、１．０〜３．０重量％含有させることが特に好ましい。０．５重量％以下であると親水性が不十分となり、６．０重量％以上となると平均水流速の低下を引き起こす。 As the hydrophilic polymer, it is preferable to use hydroxypropyl cellulose having a weight average molecular weight of 100,000 to 160,000 to 10% to 60%, polyvinyl pyrrolidone having a weight average molecular weight of 40,000 to 60,000, or a combination thereof. The hydrophilic polymer is preferably contained in an amount of 0.5 to 6.0% by weight, particularly preferably 1.0 to 3.0% by weight, based on the weight of the membrane. If it is 0.5% by weight or less, the hydrophilicity is insufficient, and if it is 6.0% by weight or more, the average water flow rate is lowered.
以下、本発明の内容を具体的に実施例によって説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the content of the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
重量平均分子量が約４万のポリエーテルスルホン樹脂（住友化学工業製４８００P）６．２５部、重量平均分子量が約７万のポリエーテルスルホン樹脂（住友化学工業製７６００Ｐ）６．２５部、Ｎ−メチル−２−ピロリドン４７．５部、ポリビニルピロリドン（Ｋ−３０）１５部、エチレングリコール１５部、アセトン１０部を均一に溶解することによって、製膜溶液を得た。この製膜溶液を支持体であるフィルム上に流延し、温度を２５℃、湿度を６０％に調節した風を風速０．３ｍ／ｓｅｃで約２６秒間当てた後、水からなる凝固浴中に浸漬させ精密濾過膜を得た。得られた精密濾過膜を水で洗浄した後、親水化を行う為、ヒドロキシプロピルセルロース（日本曹達製ＨＰＣ・ＭグレードとＨＰＣ・ＳＬグレードの各５０％の混合）０．５重量％アルコール溶液中に浸漬した後、熱ドライヤーにて乾燥して試験膜１を得た。得られた膜の構造は高度な異方性であり、物性値は０．４５μmに相当する値を示した。膜性能等の詳細は表１に示す。 6.25 parts of a polyethersulfone resin having a weight average molecular weight of about 40,000 (Sumitomo Chemical 4800P), 6.25 parts of a polyethersulfone resin having a weight average molecular weight of about 70,000 (7600P made by Sumitomo Chemical), N- A film-forming solution was obtained by uniformly dissolving 47.5 parts of methyl-2-pyrrolidone, 15 parts of polyvinylpyrrolidone (K-30), 15 parts of ethylene glycol, and 10 parts of acetone. This film-forming solution is cast on a film as a support, and a wind adjusted to a temperature of 25 ° C. and a humidity of 60% is applied for about 26 seconds at a wind speed of 0.3 m / sec. To obtain a microfiltration membrane. The resulting microfiltration membrane is washed with water and then hydrophilized, so that hydroxypropylcellulose (50% each of HPC / M grade and HPC / SL grade manufactured by Nippon Soda) is in a 0.5% by weight alcohol solution. Then, the film was dried with a heat dryer to obtain a test film 1. The structure of the obtained film was highly anisotropic, and the physical properties showed a value corresponding to 0.45 μm. Details of membrane performance and the like are shown in Table 1.
次に試験膜１をひだ折り加工して、濾過面積０．３７ｍ２のカートリッジフィルターを組み立てた。このカートリッジフィルターに超純水を２Ｌ通水し湿潤状態として、１２１℃で３０分間オートクレーブ処理を行った後、カートリッジフィルターに超純水を２００Ｌ通水し、温度６０℃の空気中にて乾燥することによって、実施例１に係る精密濾過用カートリッジフィルターを得た。 Next, the test membrane 1 was folded and a cartridge filter having a filtration area of 0.37 m 2 was assembled. After passing 2 L of ultrapure water through this cartridge filter and making it wet, autoclaving was performed at 121 ° C. for 30 minutes, and then 200 L of ultrapure water was passed through the cartridge filter and dried in air at a temperature of 60 ° C. Thus, a microfiltration cartridge filter according to Example 1 was obtained.
この実施例１に係る精密濾過用カートリッジフィルターを分解し、試験膜１を取り出し、目視にて膜表面における亀裂発生を確認したところ、亀裂発生は見られなかった。また、この実施例１に係る精密濾過用カートリッジフィルターは、０．３７ｍ２という少ない濾過面積にも係らず、異方性のポリスルホン微孔性濾過膜が組み込まれている市販品のカートリッジフィルター（ポール社製、ＡＸＶＲ４５０、濾過面積０．５７ｍ２）と濾過効率は同等であるが、１．２倍の濾過寿命を示した。この結果は、高度な異方性を有する精密濾過膜の亀裂発生防止を達成したことにより、カートリッジフィルターの濾過面積が少なくても、濾過寿命の長い安価なカートリッジフィルターが得られたことを表している。 The microfiltration cartridge filter according to Example 1 was disassembled, the test film 1 was taken out, and when cracks were visually confirmed on the film surface, no cracks were observed. In addition, the cartridge filter for microfiltration according to Example 1 is a commercially available cartridge filter (Pole) in which an anisotropic polysulfone microporous filtration membrane is incorporated regardless of a filtration area as small as 0.37 m 2. AXVR450, filtration area of 0.57 m 2 ) and filtration efficiency were equivalent, but the filter life was 1.2 times longer. This result shows that by achieving the prevention of cracks in microfiltration membranes with high anisotropy, an inexpensive cartridge filter with a long filtration life can be obtained even if the filtration area of the cartridge filter is small. Yes.
次に、重量平均分子量が約４万のポリエーテルスルホン樹脂（住友化学工業製４８００Ｐ）５部、重量平均分子量が約５万のポリエーテルスルホン樹脂（ＢＡＳＦ製Ｅ６０２０Ｐ）１０部、ジメチルアセトアミド４６部、ポリビニルピロリドン（Ｋ−３０）１７部、グリセリン１２部、アセトン１０部を均一に溶解することによって、製膜溶液を得た。この製膜溶液を支持体であるフィルム上に流延し、温度を２５℃、湿度を６０％に調節した風を風速０．３ｍ／ｓｅｃで約７秒間当て、水からなる凝固浴中に浸漬させ精密濾過膜を得た。得られた精密濾過膜を水で洗浄した後、親水化する為、ヒドロキシプロピルセルロース（日本曹達製ＨＰＣ・ＭグレードとＨＰＣ・ＳＬグレードの各５０％の混合）０．５重量％アルコール溶液中に浸漬した後、熱ドライヤーにて乾燥して試験膜２を得た。得られた膜の構造は高度な異方性であり、物性値は０．２μｍに相当する値を示した。膜性能等の詳細は表１に示す。 Next, 5 parts of a polyethersulfone resin (Sumitomo Chemical 4800P) having a weight average molecular weight of about 40,000, 10 parts of a polyethersulfone resin (BASF E6020P) having a weight average molecular weight of about 50,000, 46 parts of dimethylacetamide, A film-forming solution was obtained by uniformly dissolving 17 parts of polyvinylpyrrolidone (K-30), 12 parts of glycerin and 10 parts of acetone. This film-forming solution is cast on a film as a support, and a wind adjusted to a temperature of 25 ° C. and a humidity of 60% is applied for about 7 seconds at a wind speed of 0.3 m / sec, and immersed in a water coagulation bath. To obtain a microfiltration membrane. The obtained microfiltration membrane was washed with water and then hydrophilized. Hydroxypropyl cellulose (50% each of HPC / M grade and HPC / SL grade manufactured by Nippon Soda) in 0.5% by weight alcohol solution After soaking, the test membrane 2 was obtained by drying with a heat dryer. The structure of the obtained film was highly anisotropic, and the physical property value was equivalent to 0.2 μm. Details of membrane performance and the like are shown in Table 1.
試験膜２をひだ折り加工して濾過面積０．４１ｍ２カートリッジフィルターとして組み立てた。カートリッジフィルターに超純水を２Ｌ通水し湿潤状態として、１２６℃で１５分間オートクレーブ処理を行った後、カートリッジフィルターに超純水を２００Ｌ通水し、温度６０℃の空気中にて乾燥することによって、実施例２に係る精密濾過用カートリッジフィルターを得た。 The test membrane 2 pleated to assembly as filtration area 0.41 m 2 cartridge filter. 2L of ultrapure water is passed through the cartridge filter to make it wet, and after autoclaving at 126 ° C for 15 minutes, 200L of ultrapure water is passed through the cartridge filter and dried in air at a temperature of 60 ° C. Thus, a cartridge filter for microfiltration according to Example 2 was obtained.
この実施例２に係る精密濾過用カートリッジフィルターを分解し、試験膜２を取り出し、目視にて膜表面における亀裂発生を確認したところ、亀裂発生は無かった。また、この実施例２に係る精密濾過用カートリッジフィルターは、０．４１ｍ２という少ない濾過面積にも係らず、異方性のポリスルホン微孔性濾過膜が組み込まれている市販品のポール製カートリッジフィルターＡＸＶＲ２００（濾過面積０．５７ｍ２）と濾過効率は同等であるが、１．４倍の濾過寿命を示した。 The microfiltration cartridge filter according to Example 2 was disassembled, the test film 2 was taken out, and when cracks were visually observed on the film surface, there were no cracks. The cartridge filter for microfiltration according to Example 2 is a commercially available Pall cartridge filter in which an anisotropic polysulfone microporous filtration membrane is incorporated, regardless of a filtration area as small as 0.41 m 2. Although the filtration efficiency was the same as that of AXVR200 (filtration area 0.57 m 2 ), the filtration life was 1.4 times longer.
上記試験膜１を実施例１と同様にひだ折り加工してカートリッジフィルターとして組み立て、オートクレーブ処理せずに超純水を２００Ｌ通水し、６０℃の空気中にて乾燥することによって、比較例１に係る精密濾過用カートリッジフィルターを得た。この比較例１に係る精密濾過用カートリッジフィルターを分解し、試験膜１を取り出し、目視にて膜表面における亀裂発生を確認したところ、プリーツ折り目で数多くの亀裂が生じ実用に耐えうるものではなかった。 The test membrane 1 was folded and assembled as a cartridge filter in the same manner as in Example 1, 200 L of ultrapure water was passed through without autoclaving, and the sample was dried in air at 60 ° C. A cartridge filter for microfiltration according to was obtained. The cartridge filter for microfiltration according to Comparative Example 1 was disassembled, the test film 1 was taken out, and when cracks were visually confirmed on the film surface, many cracks were generated at the pleat folds, and this was not practical. .
上記試験膜１を実施例１と同様にひだ折り加工してカートリッジフィルターとして組み立て、超純水を通水せずに、乾燥状態で１２１℃、３０分間のオートクレーブ処理を行った後、カートリッジフィルターに超純水を２００Ｌ通水し、温度６０℃の空気中にて乾燥することによって、比較例２に係る精密濾過用カートリッジフィルターを得た。この比較例２に係る精密濾過用カートリッジフィルターを分解し、試験膜１を取り出し、目視にて膜表面における亀裂発生を確認したところ、プリーツ折り目で数多くの亀裂が生じ実用に耐えうるものではなかった。 The test membrane 1 was folded and assembled as a cartridge filter in the same manner as in Example 1, and after autoclaving at 121 ° C. for 30 minutes in a dry state without passing ultrapure water, By passing 200 L of ultrapure water and drying in air at a temperature of 60 ° C., a cartridge filter for microfiltration according to Comparative Example 2 was obtained. The microfiltration cartridge filter according to Comparative Example 2 was disassembled, the test membrane 1 was taken out, and the occurrence of cracks on the membrane surface was confirmed by visual observation. As a result, many cracks were generated at the pleat folds, and this was not practical. .
上記試験膜１を実施例１と同様にひだ折り加工してカートリッジフィルターとして組み立て、８５℃の温純水を２００Ｌ通水し、６０℃の空気中で乾燥することによって、比較例３に係る精密濾過用カートリッジフィルターを得た。この比較例３に係る精密濾過用カートリッジフィルターを分解し、試験膜１を取り出し、目視にて膜表面における亀裂発生を確認したところ、プリーツ折り目で数多くの亀裂が生じ実用に耐えうるものではなかった。 The test membrane 1 is folded and assembled as a cartridge filter in the same manner as in Example 1, and 200 L of warm pure water at 85 ° C. is passed through and dried in the air at 60 ° C., for microfiltration according to Comparative Example 3. A cartridge filter was obtained. The cartridge filter for microfiltration according to Comparative Example 3 was disassembled, the test film 1 was taken out, and when cracks were visually confirmed on the film surface, many cracks were generated at the pleat folds, and this was not practical. .
重量平均分子量が約４万のポリエーテルスルホン樹脂（住友化学工業製４８００Ｐ）１３部、Ｎ−メチル−２−ピロリドン４６部、ポリビニルピロリドン（Ｋ−３０）１５部、エチレングリコール１６部、アセトン１０部を均一に溶解し、製膜溶液を得た。これを実施例１と同様の方法で製膜、親水化し試験膜３を得た。得られた膜の構造は高度な異方性であり、物性値は０．４５μｍに相当する値を示した。膜性能等の詳細は表１に示す。 13 parts polyethersulfone resin (Sumitomo Chemical 4800P) having a weight average molecular weight of about 40,000, 46 parts N-methyl-2-pyrrolidone, 15 parts polyvinylpyrrolidone (K-30), 16 parts ethylene glycol, 10 parts acetone Was uniformly dissolved to obtain a film forming solution. This was made into a film and made hydrophilic by the same method as in Example 1 to obtain a test film 3. The structure of the obtained film was highly anisotropic, and the physical properties showed a value corresponding to 0.45 μm. Details of membrane performance and the like are shown in Table 1.
次いで、試験膜３を実施例１と同様にカートリッジフィルターとして組み立て、オートクレーブ処理を行った後、超純水を２００Ｌ通水し、温度６０℃の空気中にて乾燥することによって、比較例４に係る精密濾過用カートリッジフィルターを得た。この比較例４に係る精密濾過用カートリッジフィルターを分解し、試験膜３を取り出し、目視にて膜表面における亀裂発生を確認したところ、プリーツ折り目に亀裂が生じていた。 Next, the test membrane 3 was assembled as a cartridge filter in the same manner as in Example 1, and after autoclaving, 200 L of ultrapure water was passed through and dried in air at a temperature of 60 ° C. Such a cartridge filter for microfiltration was obtained. The microfiltration cartridge filter according to Comparative Example 4 was disassembled, the test membrane 3 was taken out, and when cracks were visually observed on the membrane surface, cracks were found in the pleat folds.
重量平均分子量が約４万のポリエーテルスルホン樹脂（住友化学工業製４８００Ｐ）１３部、Ｎ−メチル−２−ピロリドン５７部、エチレングリコール３０部を均一に溶解し、製膜溶液を得た。これを、支持体であるフィルム上に流延し、温度を２５℃、湿度を６０％に調節した風を風速０．３ｍ／ｓｅｃで約５秒間当てた後、水からなる凝固浴中に浸漬させ精密濾過膜を得た。得られた精密濾過膜を実施例１と同様に洗浄、親水化を行い試験膜４を得た。得られた膜の構造は低度な異方性であり、物性値は０．４５μｍに相当する値を示した。膜性能等の詳細は表１に示す。 13 parts of a polyethersulfone resin (4800P manufactured by Sumitomo Chemical Co., Ltd.) having a weight average molecular weight of about 40,000, 57 parts of N-methyl-2-pyrrolidone, and 30 parts of ethylene glycol were uniformly dissolved to obtain a film forming solution. This is cast on a film as a support, and a wind whose temperature is adjusted to 25 ° C. and humidity is adjusted to 60% is applied for about 5 seconds at a wind speed of 0.3 m / sec, and then immersed in a coagulation bath made of water. To obtain a microfiltration membrane. The obtained microfiltration membrane was washed and hydrophilized in the same manner as in Example 1 to obtain a test membrane 4. The structure of the obtained film had a low degree of anisotropy, and the physical properties showed a value corresponding to 0.45 μm. Details of membrane performance and the like are shown in Table 1.
次いで試験膜４をひだ折り加工してカートリッジフィルターとして組み立てた。このカートリッジフィルターをオートクレーブ処理せずに超純水を２００Ｌ通水し、６０℃の空気中にて乾燥することによって、比較例５に係る精密濾過用カートリッジフィルターを得た。この比較例５に係る精密濾過用カートリッジフィルターを分解し、試験膜４を取り出し、目視にて膜表面における亀裂発生を確認したところ、異方性の度合いが低度の膜であったため、プリーツ折り目に亀裂は生じていなかった。しかし、試験膜４を用いて作製したカートリッジフィルター（濾過面積０．３７ｍ２）は、試験膜１から作製したカートリッジフィルター（濾過面積０．３７ｍ２）と濾過効率は同等であるものの、濾過寿命は約０．５５倍であった。
Next, the test membrane 4 was folded and assembled as a cartridge filter. The cartridge filter was passed through 200 L of ultrapure water without being autoclaved, and dried in air at 60 ° C. to obtain a microfiltration cartridge filter according to Comparative Example 5. The cartridge filter for microfiltration according to Comparative Example 5 was disassembled, the test film 4 was taken out, and when cracks were visually confirmed on the film surface, it was a film with a low degree of anisotropy. There were no cracks. However, although the cartridge filter (filtration area 0.37 m 2 ) produced using the test membrane 4 has the same filtration efficiency as the cartridge filter (filtration area 0.37 m 2 ) produced from the test membrane 1, the filtration life is It was about 0.55 times.
Claims (6)
前記ポリエーテルスルホンの４０％以上が、重量平均分子量５万〜１０万であり、
さらに、精密濾過膜がひだ折りされて成型された後に、純水を通水することによる湿潤状態において、１１０℃〜１３５℃の高圧蒸気処理が施されていることを特徴とする精密濾過用カートリッジフィルター。 In a cartridge filter for microfiltration, in which an anisotropic microfiltration membrane containing polyethersulfone and a hydrophilic polymer is formed by fold processing,
40% or more of the polyethersulfone has a weight average molecular weight of 50,000 to 100,000,
Further, the microfiltration cartridge is subjected to high-pressure steam treatment at 110 ° C. to 135 ° C. in a wet state by passing pure water after the microfiltration membrane is folded and molded. filter.
イソプロピルアルコールによるバブルポイントが０．０９〜０．１２ＭＰａであり、
さらに平均水流速が６２〜１２５ｍｌ／ｍｉｎ／ｃｍ２ａｔ５２±１ｃｍＨｇであることを特徴とする請求項１又は２記載の精密濾過用カートリッジフィルター。
The film thickness of the microfiltration membrane is 80 to 140 μm,
The bubble point by isopropyl alcohol is 0.09 to 0.12 MPa,
The cartridge filter for microfiltration according to claim 1 or 2, wherein the average water flow rate is 62 to 125 ml / min / cm 2 at52 ± 1 cmHg.
イソプロピルアルコールによるバブルポイントが０．１８〜０．２２ＭＰａであり、
さらに平均水流速が３０〜４５ｍｌ／ｍｉｎ／ｃｍ２ａｔ５２±１ｃｍＨｇであることを特徴とする請求項１又は２記載の精密濾過用カートリッジフィルター。 The film thickness of the microfiltration membrane is 80 to 140 μm,
The bubble point by isopropyl alcohol is 0.18 to 0.22 MPa,
The cartridge filter for microfiltration according to claim 1 or 2, wherein the average water flow rate is 30 to 45 ml / min / cm 2 at52 ± 1 cmHg.
前記ポリエーテルスルホンの４０％以上が、重量平均分子量５万〜１０万であり、
精密濾過膜をひだ折りして成型した後に、純水を通水することによる湿潤状態において、１１０℃〜１３５℃の高圧蒸気処理を施す工程を含むことを特徴とする精密濾過用カートリッジフィルターの製造方法。 In the manufacturing method of a cartridge filter for microfiltration, in which an anisotropic microfiltration membrane containing polyethersulfone and a hydrophilic polymer is formed by fold processing,
40% or more of the polyethersulfone has a weight average molecular weight of 50,000 to 100,000,
Manufacture of a cartridge filter for microfiltration characterized by including a step of performing high-pressure steam treatment at 110 ° C. to 135 ° C. in a wet state by passing pure water after forming a microfiltration membrane with folds Method.
6. The method for producing a microfiltration cartridge filter according to claim 5, wherein the high-pressure steam treatment is performed for 10 to 60 minutes.
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| KR20190087449A (en) * | 2016-12-09 | 2019-07-24 | 프레제니우스 메디칼 케어 도이칠란드 게엠베하 | Hollow fiber membranes with improved resolution and methods of making hollow fiber membranes with improved resolution |
| WO2019240254A1 (en) * | 2018-06-15 | 2019-12-19 | 富士フイルム株式会社 | Hydrophilic porous membrane, and method for producing hydrophilic porous membrane |
| WO2020175416A1 (en) | 2019-02-26 | 2020-09-03 | 富士フイルム株式会社 | Hydrophilic porous membrane and method for producing hydrophilic porous membrane |
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| JP2003144128A (en) * | 2001-11-06 | 2003-05-20 | Toyo Roshi Kaisha Ltd | Laminated filter for filtering beer |
| JP2003251152A (en) * | 2002-03-01 | 2003-09-09 | Toyo Roshi Kaisha Ltd | Precision porous poly(ether sulfone) filter membrane |
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2004
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| JPH01184001A (en) * | 1988-01-20 | 1989-07-21 | Teijin Ltd | Porous membrane of polysulfone |
| JPH02139022A (en) * | 1988-11-18 | 1990-05-29 | Nitto Denko Corp | Treatment process for aromatic polysulfone porous membrane |
| JPH02191533A (en) * | 1989-01-18 | 1990-07-27 | Kitazawa Valve:Kk | Wet-sterilized precision filter element and its preserving method |
| JP2001515396A (en) * | 1995-06-07 | 2001-09-18 | メムテック アメリカ コーポレイション | Microfiltration membrane with high porosity and mixed isotropic and anisotropic structure |
| JP2003144128A (en) * | 2001-11-06 | 2003-05-20 | Toyo Roshi Kaisha Ltd | Laminated filter for filtering beer |
| JP2003251152A (en) * | 2002-03-01 | 2003-09-09 | Toyo Roshi Kaisha Ltd | Precision porous poly(ether sulfone) filter membrane |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190087449A (en) * | 2016-12-09 | 2019-07-24 | 프레제니우스 메디칼 케어 도이칠란드 게엠베하 | Hollow fiber membranes with improved resolution and methods of making hollow fiber membranes with improved resolution |
| US11478759B2 (en) | 2016-12-09 | 2022-10-25 | Fresenius Medical Care Deutschland Gmbh | Hollow fibre membrane with improved separating efficiency, and production of a hollow fibre membrane with improved separating efficiency |
| KR102477959B1 (en) * | 2016-12-09 | 2022-12-15 | 프레제니우스 메디칼 케어 도이칠란드 게엠베하 | Hollow fiber membranes with improved resolving power and methods for producing hollow fiber membranes with improved resolving power |
| WO2019240254A1 (en) * | 2018-06-15 | 2019-12-19 | 富士フイルム株式会社 | Hydrophilic porous membrane, and method for producing hydrophilic porous membrane |
| JPWO2019240254A1 (en) * | 2018-06-15 | 2021-07-08 | 富士フイルム株式会社 | Hydrophilic Porous Membrane and Method for Producing Hydrophilic Porous Membrane |
| JP7124074B2 (en) | 2018-06-15 | 2022-08-23 | 富士フイルム株式会社 | Hydrophilic porous membrane and method for producing hydrophilic porous membrane |
| WO2020175416A1 (en) | 2019-02-26 | 2020-09-03 | 富士フイルム株式会社 | Hydrophilic porous membrane and method for producing hydrophilic porous membrane |
| US12005401B2 (en) | 2019-02-26 | 2024-06-11 | Fujifilm Corporation | Hydrophilic porous membrane and method for producing hydrophilic porous membrane |
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