JP2004025067A - Method and device for manufacturing porous hollow fiber membrane - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、多孔質中空糸膜の製造方法とその製造装置に関し、更に詳しくは、高透過係数をもちかつ欠陥点が少なく安定した紡糸が可能な多孔質中空糸膜の製造方法及び製造装置に関する。
【０００２】
【従来の技術とその課題】
各種の膜形成性樹脂溶液を乾湿式紡糸して多孔質中空糸膜を製造する場合、ノズル吐出口から凝固浴表面までを空走させる区間の温度・湿度条件などによって、多孔質中空糸膜の外表面側に形成される多孔質部の孔径が大きく左右される。一般的に非溶媒誘起型相分離法によりスピノーダル分解をさせた製膜法では、空走部における水蒸気の吸収量が多くなるに連れて製造される膜の孔径及び透過係数が大きくなる傾向にある。
特にこのような傾向は、膜形成性樹脂としてポリスルホン系樹脂、ポリフッ化ビニリデン系樹脂、ポリアクリロニトリル系樹脂等を用いた場合に顕著にみられる。
【０００３】
特開昭６３−１３９９３０号公報には、平板上に流延した製膜原液の表面に相対湿度を４０〜５０％に調節した空気に数秒から数十秒接触させたのち凝固浴に浸漬させる方法が開示されている。この方法により膜表層の孔径を制御して透過流量を向上させることが可能となるが、気相部での接触時間が長く紡糸安定性の観点から中空糸膜の製造に適した方法とは言いがたく、接触時間が短い場合には十分な効果が得られないという問題があった。
【０００４】
また、特開平７−１６３８４９号公報及び特開平９−２９０７８号公報等には、空走部の相対湿度を８０〜１００％、温度を４０〜５０℃と高くすることにより、比較的短い距離で十分な吸湿をさせる方法が開示されているが、吐出温度（ノズル表面温度） 条件によってはノズル表面が結露し、紡糸安定性を損なうという問題があった。
【０００５】
これに対し、特開２００２−５８９７１号公報には、乾湿式紡糸法における空走部にノズル吐出口付近の低湿度雰囲気部とそれ以外の高湿度雰囲気部との２領域を設けることにより、ノズル下面への水滴の付着を防止し、安定した紡糸を可能にする方法が開示されている。
【０００６】
しかしながら、上記方法では、凝固浴温度が紡糸雰囲気温度より高く、ノズル付近雰囲気温度が紡糸雰囲気温度以下の場合には、両領域の界面近傍で水蒸気が凝縮して水滴（湯気） を生成することがあった。これが空走中の紡糸原液表面に付着すると、局所的な凝固の斑、水吸収斑となり、膜品質の低下を招くという問題があった。
【０００７】
本発明はこれらの従来の問題を解決し、高い透過性能のみならず、膜品質及び紡糸安定性に優れた多孔質膜の製造方法を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明者らは、上記目的を達成するため多方面からの検討を重ねた結果、乾湿式紡糸における空走部の湿度及び温度を制御することにより高い透過性能を維持したまま、膜品質及び紡糸安定性に優れた多孔質膜の製造方法を得るに至った。
【０００９】
すなわち、本発明方法の基本的構成は、乾湿式紡糸法により中空糸膜を製造するに際し、ノズル吐出口から凝固浴表面に到るまでの空走部雰囲気が、ノズル吐出孔付近の低湿低温雰囲気領域と、凝固液面上の高湿高温雰囲気領域と、両領域の間の低湿高温雰囲気領域を有してなることを特徴とする多孔質中空糸膜の製造方法にある。
【００１０】
また、本発明装置の基本的構成は、乾湿式紡糸法により中空糸膜を製造する装置であって、ノズル吐出口と凝固液面との間の空走部に、膜形成性樹脂溶液の入口と出口とを有する密閉容器が配され、前記密閉容器の内部が上中下の３段の空間領域に区画されてなり、それぞれに調湿・調温された空気の導入口を有してなることを特徴とする多孔質中空糸膜の製造装置にある。
【００１１】
ここで、本発明における重要な要件は、
（１） 高い透過性能を発現するために、空走部において十分に水蒸気を吸収し、表層近傍でのスピノーダル分解を促進することによって孔径と高い空隙率を確保すること、
（２） 紡糸安定性を維持するために、ノズル表面における結露、水滴の付着を防止することにより、糸切れ等の発生を防止すること、
（３） 高い膜品質を得るために、空走部における水蒸気の凝縮、水滴（湯気） の発生を抑えることにより、局所的な凝固の斑、水吸収量の斑を防止すること、
である。
【００１２】
また、十分な水蒸気の吸収は、高い透過性能を確保するのみでなく、分離活性機能を有する緻密層が中空糸膜外表面から膜内部に移動することにより、製膜（後） 工程、及び膜使用時の外的要因に対する品質低下抑制にも効果がある。
【００１３】
なお、本発明にいう高い膜品質とは、空走部における吸湿及び凝固液中での凝固作用による正常な相分離に基づいて得られる孔径分布には明らかに属さない大きな孔（欠陥点） を有する頻度が低い、又は有さないものをいう。
これら総ての要件を満たすことにより本発明の上記目的が達成される。
【００１４】
【発明の実施の形態】
以下、本発明の好適な実施の形態について詳細に説明する。
本発明に使われる膜形成性樹脂は、乾湿式紡糸により多孔質中空糸膜を形成し得るものであれば特に限定されるものではないが、ポリスルホンやポリエーテルスルホンなどのポリスルホン系樹脂、ポリアクリロニトリル、セルロース誘導体、ポリフッ化ビニリデンなどのフッ素系樹脂、ポリアミド、ポリエステル、ポリメタクリレート、ポリアクリレートなどが挙げられる。また、これらの樹脂の共重合体や一部に置換基を導入したものであってもよい。さらに、２種以上の樹脂を混合したものであってもよい。
【００１５】
本発明における膜形成性樹脂に使われる溶媒は、膜形成性樹脂を溶解し得るものであれば特に限定されるものではないが、乾湿式紡糸の空走部において膜形成性樹脂溶液に吸湿させることから、水と均一に混合可能なものが好ましく、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、Ｎ−メチル−２− ピロリドン、Ｎ−メチルモルホリン−Ｎ− オキシドなどが挙げられる。
【００１６】
本発明における膜形成性樹脂溶液は、１０〜３０質量％、好ましくは１５〜２５質量％の膜形成性樹脂を均一に溶解させて得られる。このとき、相分離を制御するための添加剤として、ポリビニルピロリドン、ポリエチレングリコール、ポリビニルアセテート、ポリビニルアルコールなどの親水性高分子や、水、アルコールなどの非溶媒、無機塩などを添加してもよい。添加剤を使用する場合、その濃度は１〜２０質量％が好ましく、５〜１２質量％がより好ましい。
【００１７】
本発明による多孔質中空糸膜は、膜形成性樹脂溶液を二重環状ノズルから押し出し、一定距離を空走させた後、水性凝固浴中に浸漬して凝固させることにより形成させることができる。このとき、必要に応じ二重環状ノズルの芯部から水等の凝固液や、丸打ちの組み紐など多孔質な支持体を同時に押し出してもよく、環状吐出部から繊維等の補強体を同時に吐出してもよい。
【００１８】
本発明においては、膜形成性樹脂溶液をノズルから押し出し、凝固液に達するまでの空走部雰囲気を、ノズル吐出口付近の低湿低温雰囲気領域と、凝固液面上の高湿高温雰囲気領域と、両領域の間の低湿高温雰囲気領域を有しており、
（１）低湿低温雰囲気領域の温度 ≦ 高湿高温雰囲気領域の温度
（２）低湿低温雰囲気領域の温度 ≦ 低湿高温雰囲気領域の温度
（３）低湿低温雰囲気領域の相対湿度≦ 高湿高温雰囲気領域の相対湿度
（４）低湿高温雰囲気領域の相対湿度 ≦ 高湿高温雰囲気領域の相対湿度
の関係を満たすことが必要である。このような条件を満たすことにより、空走部雰囲気中において十分な水の吸収と共に、水蒸気の凝縮やノズル表面への水蒸気の結露を防ぎ、透過性能及び品質に優れた中空糸膜を、安定性良く得ることが可能となる。
【００１９】
本発明における低湿低温雰囲気領域の露点は、ノズル表面温度以下であることが好ましい。低湿低温雰囲気領域の露点がノズル表面温度以上であるとノズル表面が結露し紡糸安定性を損なう。
【００２０】
本発明における高温高湿雰囲気領域の露点は、凝固液の温度以下であることが好ましい。高湿高温雰囲気領域の露点が凝固液の温度より高くなると、高湿高温雰囲気領域が凝固液表面で冷却され、凝固液との界面付近で水蒸気が凝縮し、これが空走する膜形成性樹脂溶液に接触することにより凝固斑が起こり、膜品質を低下させる原因となる。
【００２１】
本発明における低湿高温雰囲気領域の温度は、高湿高温雰囲気領域の露点以上であり、且つ低湿低温雰囲気領域の温度は、低湿高温雰囲気領域の露点以上低湿高温雰囲気領域の温度以下である。低湿高温雰囲気領域の温度が高湿高温雰囲気領域の露点より低くなるか、低湿低温雰囲気領域の温度が低湿高温雰囲気領域の露点以下になると、空走部雰囲気中で水蒸気が凝縮し、これが膜形成性樹脂溶液と接触することにより凝固斑が起こり、品質を低下させる原因となる。
【００２２】
本発明は、前述のごとく低湿高温雰囲気領域を有することにより、膜形成性樹脂溶液の吐出温度（ノズル表面温度）、空走部雰囲気湿度、凝固液温度のそれぞれを幅広く設定することが可能となる。
【００２３】
本発明において、ノズルより吐出された膜形成性樹脂溶液が凝固液に浸漬されるまでの、各空走部領域の絶対湿度と空走時間の積の和が、０．０４ｋｇ／ｍ３ ・ｓ以上であることが好ましい。
【００２４】
すなわち、下式（１） を満たす条件であることが好ましい。
（ＨＬＬ×ｔＬＬ）＋（ＨＬＨ×ｔＬＨ）＋（ＨＨＨ×ｔＨＨ）≧０．０４ｋｇ／ｍ３ ・ｓ…（１）
ここで、
ＨＬＬ：低湿低温雰囲気領域の絶対湿度（ｋｇ／ｍ３）
ＨＬＨ：低湿高温雰囲気領域の絶対湿度（ｋｇ／ｍ３）
ＨＨＨ：高湿高温雰囲気領域の絶対湿度（ｋｇ／ｍ３）
ｔＬＬ：低湿低温雰囲気領域の空走時間（通過時間）（ｓ）
ｔＬＨ：低湿高温雰囲気領域の空走時間（通過時間）（ｓ）
ｔＨＨ：高湿高温雰囲気領域の空走時間（通過時間）（ｓ）
更に好ましくは、式（１） の右辺が０．０８ｋｇ／ｍ３ ・ｓである。
【００２５】
これら空走部雰囲気の絶対湿度と空走時間の積の和が０．０４ｋｇ／ｍ３ ・ｓ未満になると、空走部において十分な吸湿量が得られず、透過性能・膜品質における十分な効果が得られにくい。
【００２６】
本発明における高湿高温雰囲気領域の相対湿度は、６０％以上１００％以下であることが好ましい。更に好ましくは８０％以上１００％以下である。相対湿度が６０％より低くなると、十分な吸湿量を得るためには空走部距離が長くなり、紡糸安定性を低下させる恐れが生じる。
【００２７】
また、空走部距離をより短くするためには、空走部雰囲気の温度を高くし、飽和水蒸気量を高めることが有効である。したがって、高湿高温雰囲気領域の温度は、４０℃以上１００℃以下であることが有効である。更に好ましくは、６０℃以上８０℃以下である。１００℃よりも高くなると、水性凝固液を空走部雰囲気の露点以上に維持することが困難となり好ましくない。
【００２８】
本発明における低湿高温雰囲気領域の温度は、高湿高温雰囲気領域の露点以上であればよいが、あまり高い温度とすると、隣接する低湿低温及び高湿高温雰囲気領域の温度に影響を及ぼす可能性があるので、１００℃以下とすることが好ましく、８０℃以下とすることが更に好ましい。
【００２９】
本発明における低湿高温雰囲気領域の相対湿度は、低く設定するほど、低湿低温雰囲気領域の温度及びノズル表面温度を低くすることができるため、好ましくは６０％以下、更に好ましくは４０％以下であり、２０％以下が最も好ましい。また、ほぼ０％の乾燥空気であっても構わない。
【００３０】
本発明における低湿低温雰囲気領域の相対湿度は、ノズル表面の結露防止という観点からより低い方が好適であり、好ましくは６０％以下、更に好ましくは４０％以下であり、ほぼ０％の乾燥空気であっても構わない。
【００３１】
本発明における空走部雰囲気は、どのような方法・装置を用いてもよいが、例えば、図１に示すように、空走部にノズル１側に吐出された膜形成性樹脂溶液３の入口用の孔と凝固液側に出口用の孔とを設けた以外は密閉した容器２を配し、当該容器２は上・中・下三段の空間領域Ａ〜Ｃに仕切られており、その各段に調湿調温された空気ａ〜ｃを送入することにより達成できる。このとき、上中下に仕切られた各空間領域Ａ〜Ｃ内を、それぞれ上述の低湿低温雰囲気、低湿高温雰囲気、高湿高温雰囲気下に置くことが好ましい。
【００３２】
次に、本発明の繊維強化多孔質膜について好適な実施例を挙げて具体的に説明する。なお、本発明は以下の実施例に限定されるものではないことは勿論である。
【００３３】
（実施例１）
ポリフッ化ビニリデン（カイナー３０１Ｆ；アトケム製） １３．２質量部、ポリフッ化ビニリデン（カイナー９０００ＬＤ；アトケム製） ８．８質量部、ポリビニルピロリドン（Ｋ−９０ ；ＩＳＰ 製１０質量部を、Ｎ，Ｎ−ジメチルアセトアミド７８質量部に６０℃で１２時間加熱攪拌溶解し、均一な溶液を得た。この溶液を、外径１．５ｍｍ、内径０．７ｍｍからなる２０℃に保温された二重環状ノズルの環状部から吐出すると共に、Ｎ，Ｎ−ジメチルアセトアミド３０質量部、グリセリン４０質量部、水３０質量部からなる内部凝固液を同ノズルの芯部から吐出し、相対湿度５％以下、温度２０℃（絶対湿度０．００１ｋｇ／ｍ３ 以下）に保たれた１ｃｍの低湿低温雰囲気領域（露点−４２℃以下） 、次いで相対湿度５％以下、温度７０℃（絶対湿度０．０１１ｋｇ／ｍ３ 以下）に保たれた１ｃｍの低湿高温雰囲気領域（露点８℃以下） 、更に相対湿度１００％、温度６８℃（絶対湿度０．１８２ｋｇ／ｍ３ ）に保たれた３．５ｃｍの高湿高温雰囲気領域（露点６８℃） を経た後、７０℃に保温されたＮ，Ｎ−ジメチルアセトアミド５質量部、水９５質量部からなる凝固液に導き４ｍ／ｍｉｎの速度で枷に巻き取り中空糸膜を得た。
【００３４】
この状態で２４時間の連続紡糸を実施したところ、ノズル下面での水蒸気の凝縮は認められず、安定した連続紡糸が可能であった。
得られた中空糸膜を４０℃、１０００ｍｇ／Ｌの次亜塩素酸ナトリウム水溶液に１２時間浸漬し、次いで６０℃の水に１時間浸漬して洗浄した後、６０℃で３時間乾燥した。
【００３５】
得られた中空糸膜の外径は１．２ｍｍ、内径は０．８ｍｍであり、透過性能を示す純水透過係数は１８０（ｍ３ ／ｍ２ ／ｈｒ／ＭＰａ）であった。また、測定媒体として９９．５％エタノールを用い、ＡＳＴＭ Ｆ３１６−８６の方法に基づいて測定した最大孔径圧力は１３０ｋＰａ（換算孔径約０．５μｍ）、平均孔径圧力は１７０ｋＰａ（換算孔径約０．４μｍ）であった。
【００３６】
この膜の外表面を電子顕微鏡（ＳＥＭ） で観察したところ、約２μｍの網目状の孔が認められ、分離活性層が膜表面より内部に移動していることが確認できた。更に、バブルポイント法（測定媒体：９９．５％エタノール） により、中空糸膜１０ｍ中の品質検査（欠陥点数測定） を実施したところ、１００ｋＰａ以下（換算孔径約０．８μｍ以上） の孔は計測されなかった。
【００３７】
このように、本発明によれば、高い透過性能を発現し、かつ紡糸安定性及び膜品質の優れた多孔質中空糸膜を容易に得ることが可能となった。
【図面の簡単な説明】
【図１】本発明の多孔質中空糸膜製造装置の概略構成例を示す断面図である。
【符号の説明】
１ 紡糸ノズル
２ 密閉容器
３ 膜形成性樹脂溶液
Ａ〜Ｃ 上中下３段の空間領域
ａ〜ｃ 調湿調温された空気[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a porous hollow fiber membrane and an apparatus for manufacturing the same, and more particularly to a method and an apparatus for manufacturing a porous hollow fiber membrane having a high permeability coefficient and capable of stable spinning with few defects. .
[0002]
[Prior art and its problems]
When producing a porous hollow fiber membrane by dry-wet spinning of various film-forming resin solutions, depending on the temperature / humidity conditions of the section that runs idle from the nozzle outlet to the coagulation bath surface, the porous hollow fiber membrane The pore diameter of the porous portion formed on the outer surface side is greatly affected. In general, in a film-forming method in which spinodal decomposition is performed by a non-solvent-induced phase separation method, the pore diameter and permeability coefficient of the produced membrane tend to increase as the amount of water vapor absorbed in the free-running portion increases. .
Such a tendency is particularly noticeable when a polysulfone resin, a polyvinylidene fluoride resin, a polyacrylonitrile resin, or the like is used as the film-forming resin.
[0003]
Japanese Patent Application Laid-Open No. 63-139930 discloses a method in which the surface of a film-forming stock solution cast on a flat plate is contacted with air whose relative humidity is adjusted to 40 to 50% for several seconds to several tens of seconds and then immersed in a coagulation bath. Is disclosed. Although this method can control the pore diameter of the membrane surface layer and improve the permeate flow rate, it is said to be a suitable method for producing a hollow fiber membrane from the viewpoint of spinning stability because of a long contact time in the gas phase. There is a problem that a sufficient effect cannot be obtained when the contact time is short.
[0004]
Further, in Japanese Patent Laid-Open Nos. 7-163849 and 9-29078, etc., by increasing the relative humidity of the idle running portion to 80 to 100% and the temperature to 40 to 50 ° C., the distance is relatively short. Although a method of sufficiently absorbing moisture is disclosed, there is a problem that depending on the discharge temperature (nozzle surface temperature) conditions, the nozzle surface may condense and impair spinning stability.
[0005]
On the other hand, Japanese Patent Application Laid-Open No. 2002-58971 discloses a nozzle by providing two regions of a low-humidity atmosphere part near the nozzle outlet and the other high-humidity atmosphere part in the idle running part in the dry and wet spinning method. A method of preventing water droplets from adhering to the lower surface and enabling stable spinning is disclosed.
[0006]
However, in the above method, when the coagulation bath temperature is higher than the spinning atmosphere temperature and the atmosphere temperature near the nozzle is equal to or lower than the spinning atmosphere temperature, water vapor condenses near the interface between the two regions and water droplets (steam) are generated. there were. If this adheres to the surface of the spinning spinning solution, it becomes a local coagulation spot or water absorption spot, which causes a problem of deterioration in film quality.
[0007]
An object of the present invention is to solve these conventional problems and to provide a method for producing a porous membrane excellent in membrane quality and spinning stability as well as high permeation performance.
[0008]
[Means for Solving the Problems]
As a result of repeated investigations from various aspects in order to achieve the above object, the inventors of the present invention have controlled membrane humidity and temperature by controlling the humidity and temperature of the idle running portion in dry and wet spinning, while maintaining membrane quality and spinning. It came to obtain the manufacturing method of the porous membrane excellent in stability.
[0009]
That is, when the hollow fiber membrane is produced by the dry and wet spinning method, the basic configuration of the method of the present invention is that the idle running portion atmosphere from the nozzle outlet to the coagulation bath surface is a low-humidity and low-temperature atmosphere near the nozzle outlet. A method for producing a porous hollow fiber membrane, comprising: a region, a high-humidity and high-temperature atmosphere region on the coagulation liquid surface, and a low-humidity and high-temperature atmosphere region between both regions.
[0010]
The basic configuration of the device of the present invention is a device for producing a hollow fiber membrane by a dry-wet spinning method, in which an inlet of a film-forming resin solution is introduced into an empty running portion between the nozzle discharge port and the coagulation liquid surface. And an outlet, and the inside of the sealed container is divided into upper, middle, and lower three-stage space areas, each having an air inlet that is conditioned and temperature-controlled. It is in the manufacturing apparatus of the porous hollow fiber membrane characterized by the above-mentioned.
[0011]
Here, the important requirements in the present invention are:
(1) In order to express high permeation performance, sufficiently absorb water vapor in the free-running portion, and ensure the pore size and high porosity by promoting spinodal decomposition near the surface layer;
(2) To prevent spinning breakage by preventing condensation on the nozzle surface and adhesion of water droplets in order to maintain spinning stability.
(3) In order to obtain high film quality, by preventing the condensation of water vapor and water droplets (steam) in the free-running part, local solidification spots and water absorption spots can be prevented.
It is.
[0012]
In addition, sufficient absorption of water vapor not only ensures high permeation performance but also moves a dense layer having a separation activity function from the outer surface of the hollow fiber membrane to the inside of the membrane, thereby forming a membrane (post-) step and membrane It is also effective in suppressing quality degradation due to external factors during use.
[0013]
The high film quality referred to in the present invention refers to large pores (defect points) that do not clearly belong to the pore size distribution obtained based on the normal phase separation due to moisture absorption in the free running portion and coagulation in the coagulation liquid. It means something that has low or no frequency.
The above object of the present invention is achieved by satisfying all these requirements.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described in detail.
The membrane-forming resin used in the present invention is not particularly limited as long as it can form a porous hollow fiber membrane by dry-wet spinning, but polysulfone resins such as polysulfone and polyethersulfone, and polyacrylonitrile. , Fluorocarbon resins such as cellulose derivatives and polyvinylidene fluoride, polyamides, polyesters, polymethacrylates, and polyacrylates. In addition, copolymers of these resins or those having a substituent introduced into a part thereof may be used. Furthermore, what mixed 2 or more types of resin may be used.
[0015]
The solvent used for the film-forming resin in the present invention is not particularly limited as long as it can dissolve the film-forming resin. However, the film-forming resin solution absorbs moisture in the dry running portion of the dry and wet spinning. Therefore, those that can be uniformly mixed with water are preferable, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and N-methylmorpholine-N-oxide. It is done.
[0016]
The film-forming resin solution in the present invention is obtained by uniformly dissolving 10 to 30% by mass, preferably 15 to 25% by mass of a film-forming resin. At this time, as an additive for controlling the phase separation, a hydrophilic polymer such as polyvinyl pyrrolidone, polyethylene glycol, polyvinyl acetate, or polyvinyl alcohol, a non-solvent such as water or alcohol, an inorganic salt, or the like may be added. . When using an additive, the density | concentration is preferable 1-20 mass%, and 5-12 mass% is more preferable.
[0017]
The porous hollow fiber membrane according to the present invention can be formed by extruding a membrane-forming resin solution from a double annular nozzle, allowing it to run idle for a certain distance, and then immersing it in an aqueous coagulation bath to coagulate it. At this time, if necessary, a solid support such as water or a porous support such as a braided braid may be simultaneously extruded from the core of the double annular nozzle, and a reinforcing body such as a fiber is simultaneously discharged from the annular discharge portion. May be.
[0018]
In the present invention, the film forming resin solution is extruded from the nozzle, and the free running portion atmosphere until reaching the coagulating liquid is a low humidity low temperature atmosphere region near the nozzle discharge port, a high humidity high temperature atmosphere region on the coagulating liquid surface, It has a low-humidity high-temperature atmosphere area between both areas,
(1) Temperature in low humidity and low temperature atmosphere region ≦ Temperature in high humidity and high temperature atmosphere region (2) Temperature in low humidity and low temperature atmosphere region ≦ Temperature in low humidity and high temperature atmosphere region (3) Relative humidity in low humidity and low temperature atmosphere region ≦ High humidity and high temperature atmosphere region Relative humidity (4) Relative humidity in low-humidity and high-temperature atmosphere region ≤ Relative humidity in high-humidity and high-temperature atmosphere region must be satisfied. By satisfying these conditions, a hollow fiber membrane with excellent permeation performance and quality can be achieved with sufficient absorption of water in the air running section atmosphere, as well as prevention of water vapor condensation and water vapor condensation on the nozzle surface. It can be obtained well.
[0019]
In the present invention, the dew point in the low humidity and low temperature atmosphere region is preferably not more than the nozzle surface temperature. If the dew point in the low-humidity and low-temperature atmosphere region is equal to or higher than the nozzle surface temperature, the nozzle surface is condensed and the spinning stability is impaired.
[0020]
In the present invention, the dew point of the high temperature and high humidity atmosphere region is preferably not more than the temperature of the coagulation liquid. When the dew point of the high-humidity and high-temperature atmosphere region becomes higher than the temperature of the coagulation liquid, the high-humidity and high-temperature atmosphere area is cooled on the surface of the coagulation liquid, and water vapor is condensed near the interface with the coagulation liquid. Coagulation spots are caused by contact with the film, and the film quality is deteriorated.
[0021]
In the present invention, the temperature of the low-humidity and high-temperature atmosphere region is not less than the dew point of the high-humidity and high-temperature atmosphere region, and the temperature of the low-humidity and low-temperature atmosphere region is not less than the dew point of the low-humidity and high-temperature atmosphere region. When the temperature of the low-humidity and high-temperature atmosphere area becomes lower than the dew point of the high-humidity and high-temperature atmosphere area, or the temperature of the low-humidity and low-temperature atmosphere area falls below the dew point of the low-humidity and high-temperature atmosphere area, water vapor condenses in the free-running atmosphere. Coagulation spots are generated by contact with the conductive resin solution, which causes the quality to deteriorate.
[0022]
Since the present invention has the low-humidity and high-temperature atmosphere region as described above, the discharge temperature (nozzle surface temperature) of the film-forming resin solution, the idling portion atmosphere humidity, and the coagulation liquid temperature can be set widely. .
[0023]
In the present invention, the sum of the product of the absolute humidity and the idle running time of each idle running region until the film-forming resin solution discharged from the nozzle is immersed in the coagulating liquid is 0.04 kg / m 3 · s. The above is preferable.
[0024]
That is, it is preferable that the conditions satisfy the following formula (1).
(HLL × tLL) + (HLH × tLH) + (HHH × tHH) ≧ 0.04 kg / m 3 · s (1)
here,
HLL: Absolute humidity (kg / m 3 ) in the low humidity and low temperature atmosphere region
HLH: Absolute humidity (kg / m 3 ) in low humidity and high temperature atmosphere
HHH: Absolute humidity (kg / m 3 ) in a high humidity and high temperature atmosphere region
tLL: idle running time (passing time) in low humidity and low temperature atmosphere region (s)
tLH: Run time (passing time) in low humidity and high temperature atmosphere region (s)
tHH: idling time (passing time) in high humidity and high temperature atmosphere region (s)
More preferably, the right side of the formula (1) is 0.08 kg / m 3 · s.
[0025]
If the sum of the product of the absolute humidity and the idle running time of these idle running parts is less than 0.04 kg / m 3 · s, a sufficient amount of moisture absorption cannot be obtained in the idle running part, and sufficient permeation performance and membrane quality are obtained. It is difficult to obtain the effect.
[0026]
The relative humidity in the high humidity and high temperature atmosphere region in the present invention is preferably 60% or more and 100% or less. More preferably, it is 80% or more and 100% or less. If the relative humidity is lower than 60%, the free running portion distance becomes long to obtain a sufficient amount of moisture absorption, and the spinning stability may be lowered.
[0027]
Further, in order to shorten the idling portion distance, it is effective to increase the temperature of the idling portion atmosphere and increase the saturated water vapor amount. Therefore, it is effective that the temperature of the high-humidity and high-temperature atmosphere region is 40 ° C. or higher and 100 ° C. or lower. More preferably, it is 60 degreeC or more and 80 degrees C or less. When the temperature is higher than 100 ° C., it is difficult to maintain the aqueous coagulation liquid at or above the dew point of the idling portion atmosphere.
[0028]
The temperature of the low-humidity high-temperature atmosphere region in the present invention may be at least the dew point of the high-humidity high-temperature atmosphere region. However, if the temperature is too high, the temperature of the adjacent low-humidity low-temperature and high-humidity high-temperature atmosphere region may be affected. Therefore, the temperature is preferably 100 ° C. or lower, and more preferably 80 ° C. or lower.
[0029]
The relative humidity of the low-humidity and high-temperature atmosphere region in the present invention is preferably set to 60% or less, more preferably 40% or less, because the temperature of the low-humidity and low-temperature atmosphere region and the nozzle surface temperature can be lowered as the setting is lower. Most preferred is 20% or less. Also, it may be almost 0% dry air.
[0030]
In the present invention, the relative humidity in the low-humidity low-temperature atmosphere region is preferably lower from the viewpoint of preventing condensation on the nozzle surface, preferably 60% or less, more preferably 40% or less, and almost 0% dry air. It does not matter.
[0031]
Any method / apparatus may be used for the idling portion atmosphere in the present invention. For example, as shown in FIG. 1, the inlet of the film-forming
[0032]
Next, the fiber-reinforced porous membrane of the present invention will be specifically described with reference to preferred examples. Needless to say, the present invention is not limited to the following examples.
[0033]
Example 1
Polyvinylidene fluoride (Kayner 301F; manufactured by Atochem) 13.2 parts by mass, Polyvinylidene fluoride (Kayner 9000LD; manufactured by Atochem) 8.8 parts by mass, Polyvinylpyrrolidone (K-90; 10 parts by mass of ISP, N, N- A homogeneous solution was obtained by heating and dissolving in 78 parts by mass of dimethylacetamide at 60 ° C. for 12 hours, and this solution was obtained from a double annular nozzle maintained at 20 ° C. having an outer diameter of 1.5 mm and an inner diameter of 0.7 mm. While discharging from the annular part, an internal coagulating liquid consisting of 30 parts by mass of N, N-dimethylacetamide, 40 parts by mass of glycerin and 30 parts by mass of water is discharged from the core part of the nozzle, and the relative humidity is 5% or less and the temperature is 20 ° C. humidity cold atmosphere region (absolute humidity 0.001 kg / m 3 or less) was hold 1 cm (dew point -42 ° C. or less), then 5% relative humidity or less, the temperature 0 ° C. (absolute humidity 0.011 kg / m 3 or less) 1cm low humidity high temperature atmosphere area (dew point 8 ° C. or less) of which is maintained, further 100% relative humidity, the temperature 68 ° C. (absolute humidity 0.182kg / m 3) After passing through a maintained high-humidity and high-temperature atmosphere (dew point of 68 ° C.) of 3.5 cm, it was led to a coagulating liquid consisting of 5 parts by mass of N, N-dimethylacetamide and 95 parts by mass of water kept at 70 ° C. at 4 m / min. A hollow fiber membrane was obtained by winding it on a kite at a speed of
[0034]
When continuous spinning for 24 hours was carried out in this state, no condensation of water vapor was observed on the lower surface of the nozzle, and stable continuous spinning was possible.
The obtained hollow fiber membrane was immersed in a 1000 mg / L sodium hypochlorite aqueous solution at 40 ° C. for 12 hours, then immersed in water at 60 ° C. for 1 hour for washing, and then dried at 60 ° C. for 3 hours.
[0035]
The hollow fiber membrane thus obtained had an outer diameter of 1.2 mm and an inner diameter of 0.8 mm, and a pure water permeability coefficient indicating permeability was 180 (m 3 / m 2 / hr / MPa). Further, 99.5% ethanol was used as a measurement medium, the maximum pore diameter pressure measured based on the method of ASTM F316-86 was 130 kPa (converted pore diameter of about 0.5 μm), and the average pore diameter pressure was 170 kPa (converted pore diameter of about 0.4 μm). )Met.
[0036]
When the outer surface of the membrane was observed with an electron microscope (SEM), a mesh-like hole of about 2 μm was observed, and it was confirmed that the separation active layer had moved from the membrane surface to the inside. Furthermore, when a quality inspection (measurement of the number of defects) in the hollow fiber membrane 10 m was carried out by the bubble point method (measuring medium: 99.5% ethanol), pores of 100 kPa or less (converted pore diameter of about 0.8 μm or more) were measured. Was not.
[0037]
As described above, according to the present invention, it is possible to easily obtain a porous hollow fiber membrane that exhibits high permeation performance and is excellent in spinning stability and membrane quality.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a schematic configuration example of a porous hollow fiber membrane production apparatus of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1
Claims (8)
空走部雰囲気が、ノズル吐出口付近の低湿低温雰囲気領域と、凝固液面上の高湿高温雰囲気領域と、両領域の間の低湿高温雰囲気領域と、
の３領域を含んでなることを特徴とする多孔質中空糸膜の製造方法。When producing a hollow fiber membrane by dry-wet spinning a film-forming resin solution,
The idling portion atmosphere is a low humidity low temperature atmosphere area near the nozzle outlet, a high humidity high temperature atmosphere area on the solidified liquid surface, and a low humidity high temperature atmosphere area between both areas,
A method for producing a porous hollow fiber membrane comprising the following three regions.
前記低湿低温雰囲気領域の温度が、前記低湿高温雰囲気領域の露点以上低湿高温雰囲気領域温度以下であることを特徴とする請求項１〜３のいずれかに記載の多孔質中空糸膜の製造方法。The temperature of the low-humidity high-temperature atmosphere region is not less than the dew point of the high-humidity high-temperature atmosphere region;
The method for producing a porous hollow fiber membrane according to any one of claims 1 to 3, wherein the temperature of the low-humidity and low-temperature atmosphere region is not less than the dew point of the low-humidity and high-temperature atmosphere region and not more than the low-humidity and high-temperature atmosphere region temperature.
ノズル吐出口と凝固液面との間の空走部に、膜形成性樹脂溶液の入口と出口とを有する密閉容器が配され、
前記密閉容器の内部が上中下の３段の空間領域に区画されてなり、それぞれに調湿・調温された空気の導入口を有してなる
ことを特徴とする多孔質中空糸膜の製造装置。An apparatus for producing a hollow fiber membrane by a dry and wet spinning method,
A closed container having an inlet and an outlet for the film-forming resin solution is disposed in the idle running portion between the nozzle discharge port and the coagulation liquid surface,
A porous hollow fiber membrane characterized in that the inside of the hermetic container is partitioned into upper, middle, and lower three-stage space regions, each having an air inlet for humidity control and temperature control. Manufacturing equipment.
前記上段の空間領域に低湿低温雰囲気に、
前記中段の空間領域が低湿高温雰囲気に、
前記下段の区画空間が高湿高温雰囲気に、
それぞれ調湿・調温された空気が送入されてなることを特徴とする請求項７記載の多孔質中空糸膜の製造装置。Humidity / temperature-controlled air supply passages connected to the upper, middle, and lower three-stage space regions, respectively, from these air supply passages,
Low humidity and low temperature atmosphere in the upper space area,
The middle space area is in a low humidity and high temperature atmosphere.
The lower compartment space has a high humidity and high temperature atmosphere.
8. The apparatus for producing a porous hollow fiber membrane according to claim 7, wherein air conditioned and temperature-controlled is supplied.
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