JP2006281202A5 - Method for producing hollow fiber membrane - Google Patents
Method for producing hollow fiber membrane Download PDFInfo
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- JP2006281202A5 JP2006281202A5 JP2006063719A JP2006063719A JP2006281202A5 JP 2006281202 A5 JP2006281202 A5 JP 2006281202A5 JP 2006063719 A JP2006063719 A JP 2006063719A JP 2006063719 A JP2006063719 A JP 2006063719A JP 2006281202 A5 JP2006281202 A5 JP 2006281202A5
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- hollow fiber
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- 239000012510 hollow fiber Substances 0.000 title claims description 25
- 239000012528 membrane Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000005712 crystallization Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 210000004940 Nucleus Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Description
本発明はフッ素系樹脂からなり、優れた耐薬品性と優れた透過性能を備え、かつ、細径で薄膜の中空糸でありながら高い機械的強度を有する中空糸膜の製造方法に関するものである。 The present invention comprises a fluororesin, provided with a good and excellent chemical resistance permeability, and those concerning the manufacturing process of hollow fiber membrane having high mechanical strength yet hollow fiber membrane with a small diameter is there.
上記目的を達成するための本発明は、下記（１）〜（４）の構成によって達成される。
（１）フッ素系樹脂と貧溶媒からなる樹脂溶液を、該樹脂溶液の結晶化温度よりも２０℃以上５０℃以下高い温度で５秒以上１００秒以下保持した後に、中空糸状に成形することを特徴とするフッ素樹脂からなる中空糸膜の製造方法。
（２）得られた中空糸膜が、１００ｋＰａ、２５℃における純水透過性能が０．４ｍ３／ｍ２・ｈｒ以上、破断強度が６ＭＰａ以上、破断伸度が５０％以上、かつ、外径が３００μｍ以上８００μｍ以下であることを特徴とする、（１）に記載の中空糸膜の製造方法。
（３）前記中空糸膜が平均粒径０．５μｍ以上１．５μｍ以下の球状構造からなることを特徴とする（１）または（２）に記載の中空糸膜の製造方法。
（４）前記中空糸膜が平均粒径０．５μｍ以上１．５μｍ以下の球状構造体を有する層と、三次元網目状構造層の両方を有することを特徴とする（１）または（２）に記載の中空糸膜の製造方法。
The present invention for achieving the above object is achieved by the following configurations (1) to (4) .
(1) A resin solution composed of a fluororesin and a poor solvent is held at a temperature 20 ° C. or more and 50 ° C. or less higher than the crystallization temperature of the resin solution for 5 seconds to 100 seconds, and then molded into a hollow fiber shape. A method for producing a hollow fiber membrane comprising a characteristic fluororesin.
(2) The obtained hollow fiber membrane has a pure water permeation performance at 100 kPa and 25 ° C. of 0.4 m 3 / m 2 · hr or more, a breaking strength of 6 MPa or more, a breaking elongation of 50% or more, and an outer diameter you wherein a is 300μm or more 800μm or less, the production method of the hollow fiber membrane according to (1).
(3) The method for producing a hollow fiber membrane according to (1 ) or (2), wherein the hollow fiber membrane has a spherical structure with an average particle size of 0.5 μm or more and 1.5 μm or less .
(4) The hollow fiber membrane has both a layer having a spherical structure having an average particle size of 0.5 μm to 1.5 μm and a three-dimensional network structure layer (1 ) or (2) A method for producing the hollow fiber membrane according to the above .
本発明の中空糸膜の製造方法は、以下に示す通りである。 Production method of the present onset Ming hollow fiber membrane are shown below.
上記フッ素系樹脂とその貧溶媒からなる結晶化温度以上のフッ素系樹脂溶液を、任意の径の二重管状口金から結晶化温度以下の冷却浴に吐出し、固化させる方法において、以下に示す通り、フッ素系樹脂と貧溶媒からなる樹脂溶液を結晶化温度Ｔｃ（℃）より２０℃以上５０℃以下高い温度で５秒以上１００秒以下保持した後に、結晶化温度以下の貧溶媒あるいは良溶媒を含む冷却浴中で固化することにより所望の性能を有する中空糸膜が得られる。 In the method of discharging and solidifying a fluororesin solution having a crystallization temperature or higher composed of the fluororesin and its poor solvent from a double tubular die having an arbitrary diameter to a cooling bath having a crystallization temperature or lower, as shown below. , after holding the resin soluble solution comprising a fluorine-based resins and the poor solvent crystallization temperature Tc (° C.) than 20 ° C. or higher 50 ° C. 100 seconds 5 seconds or less high temperatures, following poor solvent or good crystallization temperature hollow fiber membranes having an O Ri desired performance to solidify in a cooling bath containing a solvent is obtained.
フッ素系樹脂溶液保持温度Ｔｋは、中空糸膜の破断強伸度向上が発現され、かつ曵糸性が著しく奪われない範囲であることが求められ、Ｔｃ＋２０℃以上Ｔｃ＋５０℃以下であることが必要であり、好ましくはＴｃ＋２５℃以上Ｔｃ＋４８℃以下、さらに好ましくはＴｃ＋３０℃以上Ｔｃ＋４６℃以下である。また、フッ素系樹脂溶液の保持時間は、中空糸膜の破断強伸度向上の為に必要な数の一次核が生成され、かつ曵糸性が著しく奪われないことが求められ、５秒以上１００秒以下であることが必要であり、好ましくは１０秒以上８０秒以下、さらに好ましくは１５秒以上６０秒以下である。 Fluorine-based resin solution holding temperature Tk is expressed breaking strength and elongation improve hollow fiber membranes, and it is required spinnability is in the range not deprived significantly, that Tc + 20 ° C. or higher Tc + 50 ° C. is below requires, good Mashiku the Tc + 25 ° C. or higher Tc + 48 ° C. or less, much more preferably Tc + 46 ℃ Tc + 30 ℃ or higher. In addition, the retention time of the fluororesin solution is required to be such that the number of primary nuclei required for improving the breaking strength and elongation of the hollow fiber membrane is generated and the spinnability is not significantly deprived. 100 is required to be more seconds is under good Mashiku 80 seconds or 10 seconds, more preferably not more than 60 seconds 15 seconds.
本発明の中空糸膜の膜性能は、１００ｋＰａ、２５℃における純水透過性能が０．４ｍ３／ｍ２・ｈｒ以上、かつ、破断強度が６ＭＰａ以上、かつ、破断伸度が５０％以上であることが好ましい。なお、水処理用途に好適な高い透過性能と高い破断強伸度を両立させた高性能の中空糸膜とするという観点から、１００ｋＰａ、２５℃における純水透過性能が０．４ｍ３／ｍ２・ｈｒ以上８ｍ３／ｍ２・ｈｒ以下、かつ、破断強度が６ＭＰａ以上４０ＭＰａ以下、かつ、破断伸度が５０％以上３００％以下の範囲とすることがその中でも好ましく、より好ましくは、１００ｋＰａ、２５℃における純水透過性能が０．８ｍ３／ｍ２・ｈｒ以上７ｍ３／ｍ２・ｈｒ以下、かつ、破断強度が１０ＭＰａ以上３０ＭＰａ以下、かつ、破断伸度が８０％以上２８０％以下の範囲とすること、さらに好ましくは、１００ｋＰａ、２５℃における純水透過性能が１．６ｍ３／ｍ２・ｈｒ以上６ｍ３／ｍ２・ｈｒ以下、かつ、破断強度が１２ＭＰａ以上２５ＭＰａ以下、かつ、破断伸度が１２０％以上２５０％以下の範囲とすることである。
The membrane performance of the hollow fiber membrane of the present invention is 100 kPa, pure water permeation performance at 25 ° C. of 0.4 m 3 / m 2 · hr or more, breaking strength of 6 MPa or more, and breaking elongation of 50% or more. Preferably there is. From the viewpoint of achieving a high-performance hollow fiber membrane that has both high permeation performance suitable for water treatment applications and high breaking strength and elongation, the pure water permeation performance at 100 kPa and 25 ° C. is 0.4 m 3 / m 2. · hr over 8m 3 / m 2 · hr or less, and breaking strength 6MPa least 40MPa or less, it is good Mashiku among them the breaking extension in the range of 300% or less than 50%, more preferably, Pure water permeation performance at 100 kPa and 25 ° C. is 0.8 m 3 / m 2 · hr or more and 7 m 3 / m 2 · hr or less, breaking strength is 10 MPa or more and 30 MPa or less, and breaking elongation is 80% or more and 280%. be in the following range, more preferably, 100 kPa, 25 pure water permeability at ℃ is 1.6m 3 / m 2 · hr or more 6m 3 / m 2 · hr or less, and, breaking strength 12 Pa above 25MPa or less, and elongation at break is in the range of 250% or less than 120%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006063719A JP2006281202A (en) | 2005-03-11 | 2006-03-09 | Hollow fiber membrane, dipped type membrane module using it, separating apparatus, and production method of hollow fiber membrane |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005068616 | 2005-03-11 | ||
| JP2006063719A JP2006281202A (en) | 2005-03-11 | 2006-03-09 | Hollow fiber membrane, dipped type membrane module using it, separating apparatus, and production method of hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006281202A JP2006281202A (en) | 2006-10-19 |
| JP2006281202A5 true JP2006281202A5 (en) | 2009-02-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006063719A Pending JP2006281202A (en) | 2005-03-11 | 2006-03-09 | Hollow fiber membrane, dipped type membrane module using it, separating apparatus, and production method of hollow fiber membrane |
Country Status (1)
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| JP (1) | JP2006281202A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2009119373A1 (en) * | 2008-03-25 | 2011-07-21 | 東レ株式会社 | Hollow fiber membrane and method for producing the same |
| EP2727555B1 (en) | 2012-10-31 | 2016-10-05 | W.L. Gore & Associates GmbH | Fluoropolymer articles having a high surface roughness and high coarseness |
| WO2016006611A1 (en) * | 2014-07-07 | 2016-01-14 | 東レ株式会社 | Separation membrane and method for producing same |
| HUE061492T2 (en) * | 2015-12-28 | 2023-07-28 | Toray Industries | Hollow fiber membrane module and method for operating same |
| EP3466527B1 (en) * | 2016-05-31 | 2024-04-03 | Toray Industries, Inc. | Porous hollow-fiber membrane and production process therefor |
| US10974199B2 (en) | 2016-05-31 | 2021-04-13 | Toray Industries, Inc. | Hollow fiber membrane module |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0660246B2 (en) * | 1988-10-07 | 1994-08-10 | 住友電装株式会社 | Resin molding method and molded body |
| JP3328330B2 (en) * | 1992-09-02 | 2002-09-24 | 呉羽化学工業株式会社 | Vinylidene fluoride resin film, its use, and its production method |
| TW581709B (en) * | 1999-10-22 | 2004-04-01 | Asahi Kasei Corp | Heat-resistant microporous film |
| KR100904943B1 (en) * | 2001-10-04 | 2009-06-29 | 도레이 카부시키가이샤 | Hollow fiber film and method for production thereof |
| JP4269576B2 (en) * | 2002-05-07 | 2009-05-27 | 東レ株式会社 | Method for producing microporous membrane |
| AU2003241797B2 (en) * | 2002-06-14 | 2008-10-09 | Toray Industries, Inc. | Porous membrane and method of manufacturing the porous membrane |
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- 2006-03-09 JP JP2006063719A patent/JP2006281202A/en active Pending
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