JP6038370B1 - Support for semipermeable membrane for membrane separation activated sludge treatment, filtration membrane and module - Google Patents
Support for semipermeable membrane for membrane separation activated sludge treatment, filtration membrane and module Download PDFInfo
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 239000003242 anti bacterial agent Substances 0.000 description 1
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- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
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- 239000000356 contaminant Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Multicomponent Fibers (AREA)
- Paper (AREA)
Abstract
【課題】本発明の課題は、強度が高く、フレーム材との接着強度及び半透膜用支持体の塗布面と非塗布面との接着強度に優れ、半透膜との接着性にも優れる膜分離活性汚泥処理用半透膜用支持体を実現し、衝撃に強く、フレーム材との接着性が良好であり、半透膜用支持体の融着部分と半透膜との接着性も良好な膜分離活性汚泥処理用濾過膜と該濾過膜を用いてなるモジュールを提供することである。【解決手段】延伸ポリエステル繊維とバインダー繊維とを主成分としてなる不織布からなる膜分離活性汚泥処理用半透膜用支持体において、該不織布は、バインダー繊維として未延伸ポリエステル繊維と、共重合ポリエステルを鞘部とする芯鞘型ポリエステル複合繊維とを含有し、バインダー繊維として未延伸ポリエステル繊維と芯鞘型ポリエステル複合繊維とを含有する第一表面層と、バインダー繊維として未延伸ポリエステル繊維のみを含有する第二表面層とを有する多層不織布であることを特徴とする膜分離活性汚泥処理用半透膜用支持体。【選択図】なしThe subject of the present invention is high strength, excellent adhesion strength with a frame material, excellent adhesion strength between a coated surface and a non-coated surface of a semipermeable membrane support, and excellent adhesion with a semipermeable membrane. Realizes a semipermeable membrane support for membrane-separated activated sludge treatment, is strong against impact, has good adhesion to the frame material, and also has good adhesion between the fusion part of the semipermeable membrane support and the semipermeable membrane A good membrane separation activated sludge treatment membrane and a module using the membrane are provided. A support for a semipermeable membrane for membrane separation activated sludge treatment comprising a nonwoven fabric mainly composed of a stretched polyester fiber and a binder fiber, wherein the nonwoven fabric comprises unstretched polyester fiber and copolymer polyester as binder fibers. 1st surface layer which contains the core-sheath-type polyester composite fiber used as a sheath part, and contains an unstretched polyester fiber and a core-sheath-type polyester composite fiber as a binder fiber, and contains only an unstretched polyester fiber as a binder fiber A support for a semipermeable membrane for membrane separation activated sludge treatment, which is a multilayer nonwoven fabric having a second surface layer. [Selection figure] None
Description
本発明は、膜分離活性汚泥処理用半透膜用支持体、濾過膜及びモジュールに関する。 The present invention relates to a support for a semipermeable membrane for membrane separation activated sludge treatment, a filtration membrane, and a module.
海水の淡水化、浄水器、食品の濃縮、廃水処理、血液濾過に代表される医療用、半導体洗浄用の超純水製造等の分野で、半透膜が広く用いられている。半透膜の分離機能層としては、セルロース系樹脂、ポリスルホン系樹脂、ポリアクリロニトリル系樹脂、フッ素系樹脂、ポリエステル系樹脂等の多孔質性樹脂で構成されている。しかし、これら多孔質性樹脂単体では機械的強度に劣るため、不織布や織布などの繊維基材からなる半透膜用支持体の片面に半透膜が設けられた複合体の形態である濾過膜が使用されている。半透膜用支持体において、半透膜が設けられる面を「塗布面」と称する。 Semipermeable membranes are widely used in the fields of desalination of seawater, water purifiers, food concentration, wastewater treatment, ultrapure water production for medical use and semiconductor cleaning, such as blood filtration. The separation functional layer of the semipermeable membrane is composed of a porous resin such as a cellulose resin, a polysulfone resin, a polyacrylonitrile resin, a fluorine resin, or a polyester resin. However, since these porous resins alone are inferior in mechanical strength, filtration is a composite form in which a semipermeable membrane is provided on one side of a support for a semipermeable membrane made of a fibrous base material such as a nonwoven fabric or a woven fabric. A membrane is used. In the semipermeable membrane support, a surface on which the semipermeable membrane is provided is referred to as an “application surface”.
これら半透膜や濾過膜の使用形態の一つに、膜分離活性汚泥処理法（Ｍｅｍｂｒａｎｅ Ｂｉｏｒｅａｃｔｏｒ、ＭＢＲ）が挙げられる。膜分離活性汚泥処理法は、有機性汚水の処理に際し、処理水質が安定していることや、維持管理が容易なことから、広く普及している。膜分離活性汚泥処理法では、汚水中の夾雑物を除去した後、生物処理槽（曝気槽）で活性汚泥により汚水中の有機物質を分解除去し、生物処理槽に浸漬設置した浸漬型膜分離装置で混合液を固液分離し、透過した濾過液を処理水として放流する。こうした膜分離装置中の膜分離部は、使用中に砂のような無機物や汚泥、その他の固形物が激しく衝突したり、活性汚泥への酸素の供給や目詰まり防止のために行うエアレーション操作による気泡が膜面に激しく衝突したりするので、そのような衝撃にも十分に耐える強度を備えていることが要求される。 One of the usage forms of these semipermeable membranes and filtration membranes is a membrane separation activated sludge treatment method (Membrane Bioreactor, MBR). The membrane-separated activated sludge treatment method is widely used since the quality of treated water is stable and maintenance is easy when treating organic sewage. In the membrane separation activated sludge treatment method, after removing contaminants in the sewage, the organic matter in the sewage is decomposed and removed by activated sludge in the biological treatment tank (aeration tank) and immersed in the biological treatment tank. The mixed solution is subjected to solid-liquid separation with an apparatus, and the permeated filtrate is discharged as treated water. The membrane separation part in such a membrane separator is aerated by an aeration operation to prevent minerals such as sand, sludge, and other solids from colliding violently during use, or to supply oxygen to activated sludge and clogging. Since the bubbles violently collide with the film surface, it is required to have strength enough to withstand such an impact.
加えて、濾過膜はモジュール化されて使用される。シート状の濾過膜における代表的なモジュールは、平膜型モジュールとスパイラル型モジュールである。管状の濾過膜における代表的なモジュールは、管型／チューブラー型モジュールである（例えば、非特許文献１参照）。平膜型モジュールでは、ポリプロピレンやアクリロニトリル（Ａｃｒｙｌｏｎｉｔｒｉｌｅ）・ブタジエン（Ｂｕｔａｄｉｅｎｅ）・スチレン（Ｓｔｙｒｅｎｅ）共重合合成樹脂（ＡＢＳ樹脂）等の樹脂からなるフレーム材に、濾過膜を接着・固定して用いられる。フレーム材への接着・固定には加熱融着処理、超音波融着処理等が行われるのが一般的である。特に、近年、装置の簡便さから、超音波融着処理で加工するケースが増えてきている。しかしながら、従来の半透膜用支持体は、フレーム材への接着を考慮しておらず、接着性に劣り、フレーム材と半透膜用支持体が簡単に剥がれるといった問題や、使用中に半透膜がフレーム材から脱落するといった問題が生じている。 In addition, the filtration membrane is used in a modular form. Typical modules in the sheet-like filtration membrane are a flat membrane type module and a spiral type module. A typical module in a tubular filtration membrane is a tubular / tubular module (see, for example, Non-Patent Document 1). In the flat membrane module, a filtration membrane is used by adhering and fixing to a frame material made of a resin such as polypropylene, acrylonitrile, butadiene, styrene, or a synthetic resin (ABS resin). For adhesion and fixation to the frame material, heat fusion treatment, ultrasonic fusion treatment, or the like is generally performed. In particular, in recent years, the number of cases of processing by ultrasonic fusion processing has increased due to the simplicity of the apparatus. However, the conventional semipermeable membrane support does not consider adhesion to the frame material, has poor adhesion, and the frame material and the semipermeable membrane support are easily peeled off. There is a problem that the permeable membrane falls off the frame material.
一般的な半透膜用支持体として、ポリエチレン、ポリプロピレン等のオレフィン繊維を含有する半透膜用支持体が挙げられる。例えば、ポリプロピレンを芯材、ポリエチレンを鞘材とした複合繊維を熱処理した半透膜用支持体（例えば、特許文献１参照）や、ポリプロピレン単繊維から形成された不織布層を表面に有する半透膜用支持体（例えば、特許文献２参照）等が提案されている。オレフィン繊維を含有する半透膜用支持体上に半透膜を設けた濾過膜をフレーム材に超音波融着処理によって接着すると、接着はするものの、半透膜用支持体とフレーム材との接着性は充分でなかった。 Examples of a general support for semipermeable membrane include a support for semipermeable membrane containing olefin fibers such as polyethylene and polypropylene. For example, a semipermeable membrane support (for example, see Patent Document 1) obtained by heat-treating a composite fiber using polypropylene as a core material and polyethylene as a sheath material, or a semipermeable membrane having a nonwoven fabric layer formed from a single polypropylene fiber on the surface Supports (for example, see Patent Document 2) and the like have been proposed. When a filtration membrane provided with a semipermeable membrane on a semipermeable membrane support containing olefin fibers is bonded to the frame material by ultrasonic fusion treatment, it adheres, but the semipermeable membrane support and the frame material Adhesiveness was not sufficient.
また、管型／チューブラー型モジュールでは、管状基体やマンドレルを使用して、側縁部を相互に一部重ね合わせて、テープ状半透膜用支持体を螺旋状に巻き、重ね合わせた部分を加熱融着処理、超音波融着処理等によって融着して、管状半透膜用支持体を製造し、この管状半透膜用支持体の外部又は内部に半透膜が設けられた濾過膜を、複数本束ねてモジュール化している。テープ状半透膜用支持体を螺旋状に巻くため、重ね合わせた部分では、半透膜用支持体の塗布面と、塗布面の反対面である非塗布面とが融着されている。オレフィン繊維を含有する半透膜用支持体は融着しやすいため、半透膜用支持体の塗布面と非塗布面との接着強度に優れ、管状半透膜用支持体を製造しやすい。しかし、半透膜用支持体が重ね合って融着された部分が皮膜化するため、皮膜化された部分への半透膜の食い込みにくくなり、半透膜と半透膜用支持体との接着性が不十分となって、半透膜が剥離する場合があった。 In the tubular / tubular module, a tubular base or mandrel is used, the side edges are partially overlapped with each other, and the tape-shaped semipermeable membrane support is spirally wound and overlapped. Are fused by heat fusion treatment, ultrasonic fusion treatment, etc. to produce a tubular semipermeable membrane support, and the filtration is provided with a semipermeable membrane outside or inside the tubular semipermeable membrane support. A plurality of membranes are bundled to form a module. In order to wind the tape-shaped semipermeable membrane support spirally, the application surface of the semipermeable membrane support and the non-application surface opposite to the application surface are fused in the overlapped portion. Since the semipermeable membrane support containing olefin fibers is easily fused, it has excellent adhesive strength between the coated surface and the non-coated surface of the semipermeable membrane support, and it is easy to produce a tubular semipermeable membrane support. However, since the part where the semipermeable membrane support is superposed and fused is formed into a film, it is difficult for the semipermeable film to bite into the coated part, and the semipermeable membrane and the semipermeable membrane support In some cases, the semipermeable membrane peeled off due to insufficient adhesion.
別の一般的な半透膜用支持体として、延伸ポリエステル繊維とバインダーポリエステル繊維を含有する半透膜用支持体が挙げられる。例えば、延伸ポリエステル繊維と芯鞘型ポリエステル複合繊維を含有する半透膜用支持体（例えば、特許文献３参照）、延伸ポリエステル繊維とポリオレフィン繊維と鞘部の融点が１２０℃以上１５０℃以下である芯鞘型ポリエステル複合繊維とを含有する半透膜用支持体（例えば、特許文献４参照）、延伸ポリエステル繊維と未延伸ポリエステル繊維と鞘部の融点が１２５℃以上１６０℃以下である芯鞘型ポリエステル複合繊維とを含有する半透膜用支持体（例えば、特許文献５参照）等が提案されている。 Another common semipermeable membrane support is a semipermeable membrane support containing stretched polyester fibers and binder polyester fibers. For example, the support for a semipermeable membrane containing a stretched polyester fiber and a core-sheath type polyester composite fiber (see, for example, Patent Document 3), the melting point of the stretched polyester fiber, the polyolefin fiber, and the sheath is 120 ° C. or more and 150 ° C. or less. A semi-permeable membrane support containing a core / sheath polyester composite fiber (see, for example, Patent Document 4), a core / sheath type having a melting point of 125 ° C. or higher and 160 ° C. or lower between a stretched polyester fiber, an unstretched polyester fiber, and a sheath portion. A semipermeable membrane support (for example, see Patent Document 5) containing a polyester composite fiber has been proposed.
特許文献３で提案されている半透膜用支持体は、延伸ポリエステル繊維と芯鞘型ポリエステル複合繊維を含有することによって、強度と地合が良くなるという効果を達成しているが、フレーム材との接着強度や管状半透膜用支持体における半透膜と半透膜用支持体との接着性については、何ら検討されていなかった。 The support for a semipermeable membrane proposed in Patent Document 3 achieves the effect that the strength and formation are improved by containing the stretched polyester fiber and the core-sheath type polyester composite fiber. The adhesive strength between the semipermeable membrane and the semipermeable membrane support in the tubular semipermeable membrane support has not been studied at all.
特許文献４では、２００℃における加熱融着処理によって半透膜用支持体をフレーム材に接着させる評価を行っている。そして、半透膜用支持体がポリオレフィン繊維を含有することによって、フレーム材との接着強度を高めている。しかしながら、上述したように、オレフィン繊維を含有する半透膜用支持体とフレーム材とを超音波融着処理によって接着すると、接着はするものの、半透膜用支持体とフレーム材との接着性は充分でなかった。 In patent document 4, evaluation which adhere | attaches the support body for semipermeable membranes to a frame material by the heat-fusion process in 200 degreeC is performed. And since the support body for semipermeable membranes contains polyolefin fiber, the adhesive strength with a frame material is raised. However, as described above, when the support for the semipermeable membrane containing the olefin fiber and the frame material are bonded by the ultrasonic fusion treatment, the adhesion is made between the support for the semipermeable membrane and the frame material. Was not enough.
特許文献５の半透膜用支持体では、鞘部の融点が１２５℃以上１６０℃以下である芯鞘型ポリエステル複合繊維を含有することによって、十分な強度を保ちつつ、不織布の通気度を特定範囲にすることが可能となり、製膜時における幅の収縮及び皺の発生が抑制できるという効果を達成している。また、未延伸ポリエステル繊維を併用することによって、強度を向上させるという効果を達成している。しかし、本発明の発明者が検討したところ、延伸ポリエステル繊維と未延伸ポリエステル繊維と鞘部の融点が１２５℃以上１６０℃以下である芯鞘型ポリエステル複合繊維とを含有する半透膜用支持体において、フレーム材との接着性が不十分になる場合があった。 In the semipermeable membrane support of Patent Document 5, the air permeability of the nonwoven fabric is specified while maintaining sufficient strength by containing a core-sheath type polyester composite fiber whose melting point of the sheath is 125 ° C. or higher and 160 ° C. or lower. It becomes possible to make it into a range, and the effect of suppressing the shrinkage of width and the generation of wrinkles during film formation is achieved. Moreover, the effect of improving an intensity | strength is achieved by using an unstretched polyester fiber together. However, when the inventors of the present invention have studied, a support for a semipermeable membrane comprising a stretched polyester fiber, an unstretched polyester fiber, and a core-sheath type polyester composite fiber having a sheath having a melting point of 125 ° C. or higher and 160 ° C. or lower. However, the adhesiveness with the frame material may be insufficient.
本発明の課題は、強度が高く、フレーム材との接着強度及び半透膜用支持体の塗布面と非塗布面との接着強度に優れ、半透膜との接着性にも優れる膜分離活性汚泥処理用半透膜用支持体を実現し、衝撃に強く、フレーム材との接着性が良好であり、半透膜用支持体の融着部分と半透膜との接着性も良好な膜分離活性汚泥処理用濾過膜と該濾過膜を用いてなるモジュールを提供することである。 The object of the present invention is a membrane separation activity that has high strength, excellent adhesion strength to the frame material, excellent adhesion strength between the coated surface and non-coated surface of the support for semipermeable membrane, and excellent adhesion to the semipermeable membrane Realizes a support for semipermeable membrane for sludge treatment, is strong against impact, has good adhesion to the frame material, and has good adhesion between the fused part of the support for semipermeable membrane and the semipermeable membrane A separation membrane for treating activated sludge and a module using the filtration membrane are provided.
上記課題を解決するために鋭意検討した結果、下記発明を見出した。 As a result of intensive studies to solve the above problems, the following invention has been found.
（１）膜分離活性汚泥処理用半透膜用支持体において、該半透膜用支持体は、延伸ポリエステル繊維と、バインダー繊維として未延伸ポリエステル繊維と、共重合ポリエステルを鞘部とする芯鞘型ポリエステル複合繊維とを含有し、バインダー繊維として未延伸ポリエステル繊維と芯鞘型ポリエステル複合繊維とを含有する第一表面層と、バインダー繊維として未延伸ポリエステル繊維のみを含有する第二表面層とを有する多層不織布であり、該芯鞘型ポリエステル複合繊維の鞘部が、ガラス転移点４０〜８０℃の共重合ポリエステルであることを特徴とする膜分離活性汚泥処理用半透膜用支持体。 (1) A semi-permeable membrane support for membrane separation activated sludge treatment, wherein the semi-permeable membrane support comprises a stretched polyester fiber, an unstretched polyester fiber as a binder fiber, and a core sheath having a copolymer polyester as a sheath. A first surface layer containing unstretched polyester fibers and core-sheath polyester composite fibers as binder fibers, and a second surface layer containing only unstretched polyester fibers as binder fibers. multilayer nonwoven der is, the sheath portion of the core-sheath type polyester composite fiber, membrane separation activated sludge process for semipermeable membrane supporting body, wherein the copolymerized polyester der Rukoto glass transition point 40 to 80 ° C. with .
（２）第一表面層において、第一表面層に含まれる繊維全体に対し、バインダー繊維の含有量が２０〜６０質量％であり、芯鞘型ポリエステル複合繊維の含有量が５〜４０質量％である上記（１）に記載の膜分離活性汚泥処理用半透膜用支持体。 ( 2 ) In 1st surface layer, content of binder fiber is 20-60 mass% with respect to the whole fiber contained in 1st surface layer, and content of core-sheath-type polyester composite fiber is 5-40 mass%. The support for a semipermeable membrane for membrane separation activated sludge treatment according to the above (1 ) .
（３）第二表面層において、第二表面層に含まれる繊維全体に対し、バインダー繊維の含有量が２０〜６０質量％である上記（１）又は（２）に記載の膜分離活性汚泥処理用半透膜用支持体。 ( 3 ) In the second surface layer, the membrane separation activated sludge treatment according to the above (1) or (2) , wherein the content of the binder fiber is 20 to 60% by mass with respect to the entire fibers contained in the second surface layer. Semipermeable membrane support.
（４）上記（１）〜（３）のいずれかに記載の膜分離活性汚泥処理用半透膜用支持体に半透膜が設けられてなる膜分離活性汚泥処理用濾過膜。 ( 4 ) A filtration membrane for membrane separation activated sludge treatment comprising a semipermeable membrane provided on the support for membrane separation activated sludge treatment according to any one of (1) to ( 3 ) above.
（５）上記（４）記載の膜分離活性汚泥処理用濾過膜を用いてなるモジュール。 (5) A module using the membrane separation activated sludge treatment membrane described in (4) above.
（６）モジュールが、平膜型モジュール、管型モジュール及びチューブラー型モジュールの群から選ばれる少なくとも一種である上記（５）記載のモジュール。 ( 6 ) The module according to ( 5 ), wherein the module is at least one selected from the group consisting of a flat membrane module, a tube module, and a tubular module.
本発明の膜分離活性汚泥処理用半透膜用支持体は、強度が高く、フレーム材との接着強度及び半透膜用支持体の塗布面と非塗布面との接着強度（すなわち、第一表面層と第二表面層との接着強度）に優れ、半透膜との接着強度にも優れるため、本発明の膜分離活性汚泥処理用半透膜用支持体を用いることにより、衝撃に強く、半透膜を保持するフレーム材との接着性が良好であり、半透膜用支持体の融着部分と半透膜との接着性も良好な膜分離活性汚泥処理用濾過膜と該濾過膜を用いてなるモジュールを提供することが可能となる。 The support for a semipermeable membrane for membrane separation activated sludge treatment of the present invention has high strength, adhesion strength with the frame material, and adhesion strength between the coated surface and the non-coated surface of the semipermeable membrane support (that is, the first Excellent adhesion strength between the surface layer and the second surface layer), and excellent adhesion strength with the semipermeable membrane. By using the support for semipermeable membrane for membrane separation activated sludge treatment of the present invention, it is strong against impact. A membrane separation activated sludge treatment filtration membrane having good adhesion to the frame material holding the semipermeable membrane and good adhesion between the fused portion of the semipermeable membrane support and the semipermeable membrane, and the filtration It is possible to provide a module using a membrane.
本発明において、濾過膜とは、膜分離活性汚泥処理用半透膜用支持体の片面である塗布面に、分離機能層の原料となる塗布液が塗布され、水処理用の半透膜が形成され、半透膜用支持体の片面に半透膜が設けられた複合体の形態を有する。分離機能層の原料としては、例えば、塩化ビニル樹脂（ＰＶＣ）系、ポリスルホン（ＰＳ）系、ポリビニリデンフルオライド（ＰＶＤＦ）系、ポリエチレン（ＰＥ）系、酢酸セルロース（ＣＡ）系、ポリアクリロニトリル（ＰＡＮ）系、ポリビニルアルコール（ＰＶＡ）系、ポリイミド（ＰＩ）系等の種々の高分子材料が用いられる。特に、膜分離活性汚泥処理用半透膜では、ＰＶＣ系が利用されるようになってきている。半透膜用支持体上に、原料となる高分子材料を溶かした溶液である塗布液を塗布し、ゲル化させて微多孔膜を形成させる。以下では、このように半透膜用支持体上に分離機能層を塗布形成する処理は「製膜」と称される。 In the present invention, the filtration membrane means that a coating liquid that is a raw material of the separation functional layer is applied to one side of the support for a semipermeable membrane for membrane separation activated sludge treatment, and the semipermeable membrane for water treatment is applied. The composite is formed and has a semipermeable membrane provided on one side of the semipermeable membrane support. Examples of the material for the separation functional layer include vinyl chloride resin (PVC), polysulfone (PS), polyvinylidene fluoride (PVDF), polyethylene (PE), cellulose acetate (CA), and polyacrylonitrile (PAN). ) Type, polyvinyl alcohol (PVA) type, polyimide (PI) type and the like. In particular, PVC systems have been used for semipermeable membranes for membrane separation activated sludge treatment. On the semipermeable membrane support, a coating solution, which is a solution in which a polymer material as a raw material is dissolved, is applied and gelled to form a microporous membrane. Hereinafter, the process of coating and forming the separation functional layer on the semipermeable membrane support is referred to as “film formation”.
濾過膜はモジュール化されて使用される。シート状の濾過膜における代表的なモジュールは、平膜型モジュールとスパイラル型モジュールである。管状の濾過膜における代表的なモジュールは、管型／チューブラー型モジュールである。 The filtration membrane is used in a modular form. Typical modules in the sheet-like filtration membrane are a flat membrane type module and a spiral type module. A typical module in a tubular filtration membrane is a tubular / tubular module.
平膜型モジュールでは、半透膜用支持体における塗布面の反対面である非塗布面をフレーム材接着面として、ポリプロピレンやアクリロニトリル（Ａｃｒｙｌｏｎｉｔｒｉｌｅ）・ブタジエン（Ｂｕｔａｄｉｅｎｅ）・スチレン（Ｓｔｙｒｅｎｅ）共重合合成樹脂（ＡＢＳ樹脂）等の樹脂からなるフレーム材に、濾過膜を接着・固定して用いられる。フレーム材への接着・固定には加熱融着処理、超音波融着処理等が行われるのが一般的である。 In the flat membrane module, polypropylene, acrylonitrile, butadiene, styrene copolymer synthetic resin is used with the non-coated surface, which is the opposite surface of the coated surface of the semipermeable membrane support, as the frame material bonding surface. A filter membrane is bonded and fixed to a frame material made of a resin such as (ABS resin). For adhesion and fixation to the frame material, heat fusion treatment, ultrasonic fusion treatment, or the like is generally performed.
管型／チューブラー型モジュールでは、管状基体やマンドレルを使用して、半透膜用支持体の側縁部を相互に一部重ね合わせて、テープ状半透膜用支持体を螺旋状に巻き、重ね合わせた部分を加熱融着処理、超音波融着処理等によって融着して、管状半透膜用支持体を製造し、この管状半透膜用支持体の外部又は内部に半透膜が設けられた濾過膜を、複数本束ねてモジュール化している。 In the tubular / tubular module, a tubular substrate or mandrel is used, and the side edges of the semipermeable membrane support are partially overlapped with each other, and the tape-shaped semipermeable membrane support is wound spirally. The overlapped portion is fused by heat fusion treatment, ultrasonic fusion treatment or the like to produce a tubular semipermeable membrane support, and the semipermeable membrane is provided outside or inside the tubular semipermeable membrane support. A plurality of filtration membranes provided with the above are bundled into a module.
本発明の膜分離活性汚泥処理用半透膜用支持体は、延伸ポリエステル繊維と、バインダー繊維として未延伸ポリエステル繊維と、共重合ポリエステルを鞘部とする芯鞘型ポリエステル複合繊維とを含有し、バインダー繊維として未延伸ポリエステル繊維と芯鞘型ポリエステル複合繊維とを含有する第一表面層と、バインダー繊維として未延伸ポリエステル繊維のみを含有する第二表面層とを有する多層不織布であることを特徴とする。 The support for a semipermeable membrane for membrane separation activated sludge treatment of the present invention contains a stretched polyester fiber, an unstretched polyester fiber as a binder fiber, and a core-sheath type polyester composite fiber having a copolymer polyester as a sheath, It is a multilayer nonwoven fabric having a first surface layer containing unstretched polyester fibers and core-sheath polyester composite fibers as binder fibers, and a second surface layer containing only unstretched polyester fibers as binder fibers. To do.
本発明の膜分離活性汚泥処理用半透膜用支持体は、塗布面とする第二表面層にバインダー繊維として未延伸ポリエステル繊維のみを含有し、非塗布面とする第一表面層にバインダー繊維として未延伸ポリエステル繊維と芯鞘型ポリエステル複合繊維を含有することにより、半透膜用支持体とフレーム材との接着強度及び第一表面層と第二表面層との接着強度に優れ、半透膜用支持体と半透膜との接着強度にも優れるという効果が得られる。平膜型モジュールの場合、第二表面層が塗布面となり、第一表面層がフレーム材接着面となる。管状／チューブラー型モジュールにおける管状半透膜用支持体において、管状半透膜用支持体の外部に半透膜が設けられる場合には、第二表面層が外になるようにテープ状半透膜用支持体を螺旋状に巻き、逆に、管状半透膜用支持体の内部に半透膜が設けられる場合には、第二表面層が内になるようにテープ状半透膜用支持体を螺旋状に巻く。本発明の膜分離活性汚泥処理用半透膜用支持体は、第一表面層と第二表面層とからなる二層不織布であっても良いし、第一表面層と第二表面層との間に、別の層を有する三層以上の多層不織布であっても良い。 The support for a semipermeable membrane for membrane separation activated sludge treatment of the present invention contains only unstretched polyester fibers as binder fibers in the second surface layer as the coating surface, and binder fibers in the first surface layer as the non-coating surface. As an unstretched polyester fiber and a core-sheath type polyester composite fiber, the adhesive strength between the support for a semipermeable membrane and the frame material and the adhesive strength between the first surface layer and the second surface layer is excellent. The effect that it is excellent also in the adhesive strength of the support body for membranes and a semipermeable membrane is acquired. In the case of a flat membrane module, the second surface layer is the application surface, and the first surface layer is the frame material bonding surface. In the tubular semipermeable membrane support in the tubular / tubular module, when the semipermeable membrane is provided outside the tubular semipermeable membrane support, the tape-shaped semipermeable membrane is disposed so that the second surface layer is outside. When the membrane support is spirally wound and, conversely, when a semipermeable membrane is provided inside the tubular semipermeable membrane support, the tape-shaped semipermeable membrane support is placed so that the second surface layer is inside. Wrap the body in a spiral. The support for a semipermeable membrane for membrane separation activated sludge treatment of the present invention may be a two-layer nonwoven fabric composed of a first surface layer and a second surface layer, or a first surface layer and a second surface layer. It may be a multilayer nonwoven fabric of three or more layers having another layer therebetween.
本発明において、バインダー繊維として用いられる未延伸ポリエステル繊維としては、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート及びそれを主体とした共重合体などのポリエステルを紡糸速度８００〜１，２００ｍ／分で紡糸した未延伸繊維が挙げられる。これらの未延伸ポリエステル繊維が熱カレンダー処理によって熱圧融着されることにより、強度の高い半透膜用支持体を得ることができる。 In the present invention, as the unstretched polyester fiber used as the binder fiber, a polyester such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and a copolymer mainly composed thereof is spun. Examples thereof include undrawn fibers spun at a speed of 800 to 1,200 m / min. These unstretched polyester fibers are heat-pressure fused by thermal calendering, whereby a high strength semipermeable membrane support can be obtained.
本発明において、バインダー繊維として用いられる芯鞘型ポリエステル複合繊維の鞘部は共重合ポリエステルであり、ガラス転移点が４０〜８０℃の共重合ポリエステルであることが好ましい。共重合ポリエステルとしては、テレフタル酸成分とエチレングリコール成分を含有し、且つ、イソフタル酸成分、アジピン酸成分、セバシン酸成分、ナフタレンジカルボン酸成分、ジエチルグリコール成分、１，４−ブタンジオール成分及び脂肪族ラクトン成分の群から選ばれる少なくとも一成分を含有する共重合ポリエステルが挙げられる。この共重合ポリエステルは非晶質でも良いし、結晶性でも良い。 In the present invention, the sheath portion of the core-sheath polyester composite fiber used as the binder fiber is a copolymer polyester, and is preferably a copolymer polyester having a glass transition point of 40 to 80 ° C. Copolyester includes a terephthalic acid component and an ethylene glycol component, and an isophthalic acid component, adipic acid component, sebacic acid component, naphthalenedicarboxylic acid component, diethyl glycol component, 1,4-butanediol component and aliphatic Examples thereof include a copolyester containing at least one component selected from the group of lactone components. This copolyester may be amorphous or crystalline.
一般的に、バインダー繊維が軟化又は溶融するまで温度を上げる工程を、半透膜用支持体の製造方法に組み入れることで、バインダー繊維が半透膜用支持体の機械的強度を向上させる。そのため、芯鞘型ポリエステル複合繊維の鞘部の融点に関しては、例えば、特許文献４（特開２０１２−１０１２１３号公報）及び特許文献５（特開２０１３−２２０３８２号公報）においても検討されている。本発明者が、半透膜用支持体とフレーム材との接着強度及び第一表面層と第二表面層との接着強度を高めることを目的として検討したところ、ガラス転移点が４０〜８０℃の共重合ポリエステルを鞘部とする場合、加熱融着処理や超音波融着処理した際の、半透膜用支持体とフレーム材との密着性や半透膜用支持体の第一表面層と第二表面層との密着性に優れ、半透膜用支持体とフレーム材との接着強度及び半透膜用支持体の第一表面層と第二表面層との接着強度が高くなること、及び、加熱融着処理だけでなく、超音波融着処理においても効果があることを見出した。 In general, the binder fiber improves the mechanical strength of the semipermeable membrane support by incorporating the process of raising the temperature until the binder fiber is softened or melted into the method for producing the semipermeable membrane support. Therefore, regarding melting | fusing point of the sheath part of a core sheath type polyester composite fiber, patent document 4 (Unexamined-Japanese-Patent No. 2012-101213) and patent document 5 (Unexamined-Japanese-Patent No. 2013-220382) are also examined, for example. The present inventor studied for the purpose of increasing the adhesive strength between the support for a semipermeable membrane and the frame material and the adhesive strength between the first surface layer and the second surface layer, and the glass transition point was 40 to 80 ° C. When the copolyester is used as the sheath, the adhesion between the semipermeable membrane support and the frame material and the first surface layer of the semipermeable membrane support when heat fusion treatment or ultrasonic fusion treatment is performed. Excellent adhesion between the second surface layer and the adhesive strength between the semipermeable membrane support and the frame material and the adhesive strength between the first surface layer and the second surface layer of the semipermeable membrane support. And it discovered that it was effective not only in heat fusion processing but also in ultrasonic fusion processing.
芯鞘型ポリエステル複合繊維の鞘部における共重合ポリエステルのガラス転移点が４０℃以上である場合、鞘部の機械的強度が高くなるため、該ガラス転移点が４０℃未満の場合と比較して、半透膜用支持体とフレーム材との接着強度や第一表面層と第二表面層との接着強度が高くなる。一方、ガラス転移点が８０℃以下である場合、加熱融着処理や超音波融着処理した際の、半透膜用支持体とフレーム材との密着性や第一表面層と第二表面層との密着性が向上し、該ガラス転移点が８０℃を超える場合と比較して、半透膜用支持体とフレーム材との接着強度や第一表面層と第二表面層との接着強度が向上する。 When the glass transition point of the copolyester in the sheath part of the core-sheath polyester composite fiber is 40 ° C. or higher, the mechanical strength of the sheath part is increased, so that the glass transition point is lower than 40 ° C. The adhesive strength between the semipermeable membrane support and the frame material and the adhesive strength between the first surface layer and the second surface layer are increased. On the other hand, when the glass transition point is 80 ° C. or lower, the adhesion between the support for the semipermeable membrane and the frame material or the first surface layer and the second surface layer when the heat fusion treatment or the ultrasonic fusion treatment is performed. As compared with the case where the glass transition point exceeds 80 ° C., the adhesive strength between the semipermeable membrane support and the frame material and the adhesive strength between the first surface layer and the second surface layer Will improve.
本発明において、芯鞘型ポリエステル複合繊維の芯部は、主たる繰り返し単位がアルキレンテレフタレートであるポリエステルであり、耐熱性の高いポリエチレンテレフタレートであることが好ましい。 In the present invention, the core of the core-sheath type polyester composite fiber is a polyester whose main repeating unit is alkylene terephthalate, and is preferably polyethylene terephthalate having high heat resistance.
本発明において、芯鞘型ポリエステル複合繊維の断面形状は特に限定しないが、円形が好ましい。また、芯部と鞘部の比率は、体積比で芯／鞘＝３０／７０〜７０／３０の範囲が好ましく、４０／６０〜６０／４０がより好ましい。 In the present invention, the cross-sectional shape of the core-sheath polyester composite fiber is not particularly limited, but is preferably circular. Further, the ratio of the core part to the sheath part is preferably in the range of core / sheath = 30/70 to 70/30, more preferably 40/60 to 60/40, in terms of volume ratio.
第一表面層において、第一表面層に含まれる繊維全体に対し、バインダー繊維の含有量は２０〜６０質量％であることが好ましく、２５〜５０質量％であることがより好ましい。バインダー繊維の含有量が２０質量％未満では、第一表面層の繊維間の接着が不十分となりやすく、半透膜用支持体とフレーム材との接着強度が低下する場合や、第一表面層と第二表面層との接着強度が低下する場合がある。一方、バインダー繊維の含有量が６０質量％を超えると、熱カレンダー処理における加熱された金属ロールへの貼り付きによって、第一表面層の表面が皮膜化しやすく、加熱融着処理や超音波融着処理などで溶融したフレーム材が半透膜用支持体に食い込みにくくなることによって、半透膜用支持体とフレーム材の接着強度が低下する場合がある。また、管状半透膜用支持体において、第一表面層と第二表面層との融着部分が皮膜化しやすく、半透膜が融着部分に食い込みにくくなることによって、半透膜用支持体と半透膜との接着強度が低下する場合がある。 In the first surface layer, the content of the binder fiber is preferably 20 to 60% by mass, and more preferably 25 to 50% by mass with respect to the entire fibers contained in the first surface layer. When the content of the binder fiber is less than 20% by mass, the adhesion between the fibers of the first surface layer tends to be insufficient, and the adhesive strength between the semipermeable membrane support and the frame material is reduced, or the first surface layer And the adhesive strength between the second surface layer may decrease. On the other hand, if the binder fiber content exceeds 60% by mass, the surface of the first surface layer tends to be formed into a film by sticking to the heated metal roll in the thermal calendering process, so that the heat fusion treatment or ultrasonic fusion is performed. When the frame material melted by the treatment or the like becomes difficult to bite into the semipermeable membrane support, the adhesive strength between the semipermeable membrane support and the frame material may be lowered. Further, in the tubular semipermeable membrane support, the fusion part between the first surface layer and the second surface layer is easily formed into a film, and the semipermeable membrane is less likely to bite into the fusion part. And the adhesive strength between the semipermeable membrane and the semipermeable membrane may be reduced.
非塗布面である第一表面層においては、芯鞘型ポリエステル複合繊維を含有することにより、平膜型モジュール製造時における加熱融着処理や超音波融着処理の際に、フレーム材と半透膜用支持体との密着性が向上し、フレーム材との接着強度が高い半透膜用支持体を得ることができる。また、管型／チューブラー型モジュールにおける管状半透膜用支持体を製造時には、第一表面層と第二表面層との密着性が向上し、第一表面層と第二表面層との接着強度が高い半透膜用支持体を得ることができる。 The first surface layer, which is a non-coated surface, contains a core-sheath type polyester composite fiber, so that the frame material and the semi-transparent layer can be used in the heat-sealing process and the ultrasonic fusing process during the production of the flat membrane module. Adhesion with the membrane support is improved, and a semipermeable membrane support with high adhesion strength to the frame material can be obtained. Also, when manufacturing a tubular semipermeable membrane support in a tubular / tubular module, the adhesion between the first surface layer and the second surface layer is improved, and the adhesion between the first surface layer and the second surface layer is improved. A semipermeable membrane support having high strength can be obtained.
第一表面層の芯鞘型ポリエステル複合繊維の含有量は、第一表面層に含まれる繊維全体に対し、５〜４０質量％であり、７〜３５質量％がより好ましく、１０〜３０質量％であることが更に好ましい。芯鞘型ポリエステル複合繊維の含有量が５質量％未満では、半透膜用支持体とフレーム材との密着性や第一表面層と第二表面層との密着性が不十分となる場合があり、半透膜用支持体とフレーム材との接着強度や第一表面層と第二表面層との接着強度が低下する場合がある。一方、芯鞘型ポリエステル複合繊維の含有量が４０質量％を超えると、相対的に未延伸ポリエステル繊維の含有量が減るため、熱カレンダー処理における加熱された金属ロールへの貼り付きによって、第一表面層の表面に存在する繊維が毛羽立ちやすくなり、半透膜用支持体とフレーム材との接着強度が低下する場合がある。 The content of the core-sheath type polyester composite fiber of the first surface layer is 5 to 40% by mass, more preferably 7 to 35% by mass, and more preferably 10 to 30% by mass with respect to the entire fibers contained in the first surface layer. More preferably. When the content of the core-sheath type polyester composite fiber is less than 5% by mass, the adhesion between the semipermeable membrane support and the frame material and the adhesion between the first surface layer and the second surface layer may be insufficient. In some cases, the adhesive strength between the semipermeable membrane support and the frame material and the adhesive strength between the first surface layer and the second surface layer may be reduced. On the other hand, when the content of the core-sheath polyester composite fiber exceeds 40% by mass, the content of the unstretched polyester fiber is relatively reduced. The fibers present on the surface layer are likely to fluff, and the adhesive strength between the semipermeable membrane support and the frame material may be reduced.
第二表面層において、第二表面層に含まれる繊維全体に対し、バインダー繊維として含まれる未延伸ポリエステル繊維の含有量は２０〜６０質量％であることが好ましく、２５〜５０質量％であることがより好ましい。バインダー繊維の含有量が２０質量％未満では、繊維間の接着が不十分となりやすく、第二表面層の表面の繊維が毛羽立ちやすくなり、半透膜の塗布性が損なわれる場合がある。一方、バインダー繊維の含有量が６０質量％を超えると、第二表面層の表面及び第一表面層と第二表面層との融着部分において皮膜化しやすくなり、塗布液の浸透性が低下して、半透膜用支持体と半透膜の接着強度が低下する場合がある。 In the second surface layer, the content of unstretched polyester fibers contained as binder fibers is preferably 20 to 60% by mass, and preferably 25 to 50% by mass with respect to the entire fibers contained in the second surface layer. Is more preferable. If the content of the binder fiber is less than 20% by mass, the adhesion between the fibers tends to be insufficient, the fibers on the surface of the second surface layer tend to fluff, and the coating property of the semipermeable membrane may be impaired. On the other hand, when the content of the binder fiber exceeds 60% by mass, the surface of the second surface layer and the fused portion between the first surface layer and the second surface layer are easily formed into a film, and the permeability of the coating liquid is reduced. Thus, the adhesive strength between the semipermeable membrane support and the semipermeable membrane may be reduced.
本発明において、バインダー繊維の繊維径は２〜２５μｍが好ましく、５〜２０μｍがより好ましく、１０〜２０μｍが更に好ましい。繊維径が２μｍ未満のバインダー繊維を使用した場合には、半透膜用支持体の強度が不十分となる場合がある。一方、繊維径が２５μｍを超えるバインダー繊維を使用した場合には、抄紙の際の繊維分散が悪くなり、半透膜用支持体の地合が不均一となりやすく、半透膜の製膜性を損なう場合がある。 In the present invention, the fiber diameter of the binder fiber is preferably 2 to 25 μm, more preferably 5 to 20 μm, and still more preferably 10 to 20 μm. When binder fibers having a fiber diameter of less than 2 μm are used, the strength of the semipermeable membrane support may be insufficient. On the other hand, when a binder fiber having a fiber diameter of more than 25 μm is used, fiber dispersion at the time of papermaking deteriorates, the formation of the support for the semipermeable membrane tends to be uneven, and the film forming property of the semipermeable membrane is improved. It may be damaged.
本発明において、バインダー繊維の繊維長は、好ましくは１〜１２ｍｍであり、より好ましくは３〜１０ｍｍであり、更に好ましくは４〜６ｍｍである。繊維長が１ｍｍ未満の場合には、半透膜用支持体の強度が低下する場合があり、１２ｍｍを超える場合には、繊維分散性が低下しやすく、半透膜用支持体の地合が不均一となりやすく、半透膜の製膜性を損なう場合がある。 In the present invention, the fiber length of the binder fiber is preferably 1 to 12 mm, more preferably 3 to 10 mm, and still more preferably 4 to 6 mm. When the fiber length is less than 1 mm, the strength of the semipermeable membrane support may decrease. When the fiber length exceeds 12 mm, the fiber dispersibility tends to decrease, and the formation of the semipermeable membrane support may be reduced. It tends to be non-uniform and may impair the film-forming properties of the semipermeable membrane.
本発明の膜分離活性汚泥処理用半透膜用支持体においては、主体繊維として延伸ポリエステル繊維を含有する。本発明においては、バインダー繊維が軟化又は溶融するまで温度を上げる工程を、半透膜用支持体の製造方法に組み入れることで、バインダー繊維が半透膜用支持体の機械的強度を向上させる。この温度を上げる工程において、延伸ポリエステル繊維は軟化又は溶融しにくく、断面形状が変化することはあるものの、繊維としての形状が損なわれることがなく、主体繊維として、半透膜用支持体の骨格を形成する。該延伸ポリエステル繊維としては、主たる繰り返し単位がアルキレンテレフタレートであるポリエステルが挙げられるが、耐熱性の高いポリエチレンテレフタレートであることが好ましい。また、繊維の断面形状は円形が好ましい。ただし、Ｔ型、Ｙ型、三角等の異形断面を有する繊維も、裏抜け防止や、塗布面平滑性のために、他の特性を阻害しない範囲内で含有することができる。 The support for a semipermeable membrane for membrane separation activated sludge treatment of the present invention contains a stretched polyester fiber as a main fiber. In the present invention, the binder fiber improves the mechanical strength of the semipermeable membrane support by incorporating the process of raising the temperature until the binder fiber is softened or melted into the method for producing the semipermeable membrane support. In the step of raising the temperature, the stretched polyester fiber is difficult to soften or melt, and the cross-sectional shape may change, but the shape as a fiber is not impaired, and the skeleton of the support for a semipermeable membrane is used as a main fiber. Form. Examples of the stretched polyester fiber include polyesters whose main repeating unit is alkylene terephthalate, but polyethylene terephthalate having high heat resistance is preferable. The cross-sectional shape of the fiber is preferably circular. However, fibers having irregular cross-sections such as T-type, Y-type, and triangle can also be contained within a range that does not hinder other characteristics for preventing back-through and smoothing the coated surface.
延伸ポリエステル繊維の繊維径は、２〜３５μｍが好ましく、５〜３０μｍがより好ましく、７〜２７μｍが更に好ましい。延伸ポリエステル繊維の繊維径が２μｍ未満の場合には、半透膜用支持体の強度が不十分となる場合がある。一方、延伸ポリエステル繊維の繊維径が３５μｍを超える場合には、抄紙の際の繊維分散が悪くなり、半透膜用支持体の地合が不均一となりやすく、半透膜の製膜性を損なう場合がある。 The fiber diameter of the stretched polyester fiber is preferably 2 to 35 μm, more preferably 5 to 30 μm, and still more preferably 7 to 27 μm. When the fiber diameter of the stretched polyester fiber is less than 2 μm, the strength of the semipermeable membrane support may be insufficient. On the other hand, when the fiber diameter of the stretched polyester fiber exceeds 35 μm, the fiber dispersion at the time of papermaking deteriorates, the formation of the support for the semipermeable membrane tends to be uneven, and the film forming property of the semipermeable membrane is impaired. There is a case.
延伸ポリエステル繊維の繊維長は、特に限定しないが、好ましくは１〜１５ｍｍであり、より好ましくは３〜１２ｍｍであり、更に好ましくは３〜１０ｍｍである。繊維長が１ｍｍ未満の場合には、半透膜用支持体の強度が低下する場合があり、１５ｍｍを超える場合には、繊維分散性が低下しやすく、半透膜用支持体の地合が不均一となりやすく、半透膜の製膜性を損なう場合がある。 The fiber length of the stretched polyester fiber is not particularly limited, but is preferably 1 to 15 mm, more preferably 3 to 12 mm, and still more preferably 3 to 10 mm. When the fiber length is less than 1 mm, the strength of the semipermeable membrane support may decrease. When the fiber length exceeds 15 mm, the fiber dispersibility tends to decrease, and the formation of the semipermeable membrane support may be reduced. It tends to be non-uniform and may impair the film-forming properties of the semipermeable membrane.
本発明の膜分離活性汚泥処理用半透膜用支持体においては、必要に応じて、前記した延伸ポリエステル繊維及びバインダー繊維以外の繊維を加えても良い。具体的には、合成繊維としては、ポリオレフィン系、ポリアミド系、ポリアクリル系、ビニロン系、ビニリデン、ポリ塩化ビニル、ベンゾエート、ポリクラール、フェノール系などの繊維が挙げられる。天然繊維としては、皮膜の少ない麻パルプ、コットンリンター、リント；再生繊維としては、リヨセル繊維、レーヨン、キュプラ；半合成繊維としては、アセテート、トリアセテート、プロミックス；無機繊維としては、アルミナ繊維、アルミナ・シリカ繊維、ロックウール、ガラス繊維、マイクロガラス繊維、ジルコニア繊維、チタン酸カリウム繊維、アルミナウィスカ、ホウ酸アルミウィスカなどの繊維が挙げられる。上記の繊維の他に、植物繊維として、針葉樹パルプ、広葉樹パルプなどの木材パルプや藁パルプ、竹パルプ、ケナフパルプなどの木本類、草本類を使用することもできる。また、上記の繊維は、通液性、通気性を阻害しない範囲であれば、フィブリル化されていてもなんら差し支えない。さらに、古紙、損紙などから得られるパルプ繊維等も使用することができる。また、断面形状が円型の繊維だけでなく、Ｔ型、Ｙ型、三角等の異形断面を有する繊維も含有できる。 In the support for a semipermeable membrane for membrane separation activated sludge treatment of the present invention, fibers other than the above-described stretched polyester fiber and binder fiber may be added as necessary. Specifically, examples of synthetic fibers include polyolefin fibers, polyamide fibers, polyacrylic resins, vinylon resins, vinylidene, polyvinyl chloride, benzoate, polyclar, and phenol fibers. Natural fiber includes hemp pulp, cotton linter, lint; regenerated fiber is lyocell fiber, rayon, cupra; semi-synthetic fiber is acetate, triacetate, promix; inorganic fiber is alumina fiber, alumina -Fibers such as silica fiber, rock wool, glass fiber, micro glass fiber, zirconia fiber, potassium titanate fiber, alumina whisker, and aluminum borate whisker. In addition to the above-mentioned fibers, wood fibers such as conifer pulp and hardwood pulp, woods such as bamboo pulp, bamboo pulp, kenaf pulp, and herbs can be used as plant fibers. Moreover, as long as the said fiber is a range which does not inhibit liquid permeability and air permeability, it may be fibrillated at all. Furthermore, pulp fibers obtained from waste paper, waste paper, and the like can also be used. Further, not only fibers having a circular cross-sectional shape but also fibers having an irregular cross section such as T-type, Y-type, and triangle can be contained.
本発明における芯鞘型ポリエステル複合繊維の鞘部のガラス転移点は、示差走査熱量計（パーキンエルマー社製、装置名：ＤＳＣ８５００）を用いて、昇温速度１０℃／分で測定した。ガラス転移点は、各ベースラインの延長した直線から縦軸方向に等距離にある直線と、ガラス転移の段階状変化部分の曲線とが交わる点の温度とした。 The glass transition point of the sheath part of the core-sheath type polyester composite fiber in the present invention was measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (manufactured by Perkin Elmer, apparatus name: DSC8500). The glass transition point was defined as the temperature at which the straight line equidistant in the vertical axis direction from the extended straight line of each baseline intersects with the curve of the stepwise change portion of the glass transition.
本発明の膜分離活性汚泥処理用半透膜用支持体の坪量は、３０〜２５０ｇ／ｍ２が好ましく、４０〜２３０ｇ／ｍ２がより好ましく、５０〜２２０ｇ／ｍ２が更に好ましい。３０ｇ／ｍ２未満の場合には、半透膜用支持体の強度が不十分となる場合がある。また、２５０ｇ／ｍ２を超えた場合には、通液抵抗が高くなる場合や、半透膜用支持体の厚みが増して、規定量の半透膜を収納するには、モジュールやユニットを大型化する必要が発生する。 The basis weight of the membrane separation activated sludge process for semipermeable membrane support of the present invention is preferably from 30 to 250 g / m 2, more preferably 40~230g / m 2, 50~220g / m 2 is more preferable. If it is less than 30 g / m 2 , the strength of the semipermeable membrane support may be insufficient. In addition, if it exceeds 250 g / m 2 , the module or unit may be used in order to increase the flow resistance or to increase the thickness of the semipermeable membrane support so as to accommodate a prescribed amount of semipermeable membrane. It is necessary to increase the size.
本発明の膜分離活性汚泥処理用半透膜用支持体の厚みは、６０〜３００μｍであることが好ましく、８０〜２５０μｍであることがより好ましく、１００〜２２０μｍであることが更に好ましい。厚みが３００μｍを超えると、ユニットに組み込める濾過膜の面積が小さくなってしまい、結果として、濾過膜のライフが短くなってしまうことがある。一方、厚みが６０μｍ未満の場合には、十分な強度が得られない場合がある。 The thickness of the support for a semipermeable membrane for membrane separation activated sludge treatment of the present invention is preferably 60 to 300 μm, more preferably 80 to 250 μm, and still more preferably 100 to 220 μm. When the thickness exceeds 300 μm, the area of the filtration membrane that can be incorporated into the unit is reduced, and as a result, the life of the filtration membrane may be shortened. On the other hand, when the thickness is less than 60 μm, sufficient strength may not be obtained.
本発明の膜分離活性汚泥処理用半透膜用支持体の密度は、０．３０〜１．００ｇ／ｃｍ３であることが好ましく、０．３５〜０．９８ｇ／ｃｍ３がより好ましく、０．４０〜０．９５／ｃｍ３が更に好ましい。密度が０．３０ｇ／ｃｍ３未満の場合には、半透膜を半透膜用支持体上に設ける際に、塗布液の半透膜用支持体への染み込みが大きくなってしまい、分離機能の均一性を損なう場合がある。一方、密度が１．００ｇ／ｃｍ３よりも大きい場合には、加熱融着処理や超音波融着処理などで、溶融したフレーム材が半透膜用支持体に食い込みにくくなる場合や第一表面層と第二表面層との密着性が低下する場合があり、半透膜用支持体とフレーム材との接着強度や第一表面層と第二表面層との接着強度が弱くなる場合がある。また、塗布液の浸透性が低下し、半透膜用支持体と半透膜の接着強度が弱くなる場合がある。 Density of the membrane separation activated sludge treatment for semipermeable membrane support of the present invention is preferably 0.30~1.00g / cm 3, more preferably 0.35~0.98g / cm 3, 0 More preferably, it is 40 to 0.95 / cm 3 . When the density is less than 0.30 g / cm 3 , when the semipermeable membrane is provided on the semipermeable membrane support, the penetration of the coating liquid into the semipermeable membrane support becomes large, and the separation function There is a case where the uniformity of the is impaired. On the other hand, when the density is larger than 1.00 g / cm 3 , the case where the melted frame material is difficult to bite into the semipermeable membrane support by heat fusion treatment or ultrasonic fusion treatment or the first surface The adhesion between the layer and the second surface layer may be reduced, and the adhesive strength between the semipermeable membrane support and the frame material and the adhesive strength between the first surface layer and the second surface layer may be weakened. . In addition, the permeability of the coating solution may decrease, and the adhesive strength between the semipermeable membrane support and the semipermeable membrane may be weakened.
本発明の膜分離活性汚泥処理用半透膜用支持体に係わる不織布は、乾式法、又は湿式抄造法により製造することができる。湿式抄造法により形成された湿式不織布であることが好ましい。 The nonwoven fabric related to the support for a semipermeable membrane for membrane separation activated sludge treatment of the present invention can be produced by a dry method or a wet papermaking method. A wet nonwoven fabric formed by a wet papermaking method is preferred.
湿式抄造法では、まず、延伸ポリエステル繊維（主体繊維）、バインダー繊維を均一に水中に分散させ、その後、スクリーン（異物、塊等除去）等の工程を通り、最終の繊維濃度を０．０１〜０．５０質量％に調整されたスラリーが抄紙機で抄き上げられ、湿紙が得られる。繊維の分散性を均一にするために、工程中で分散剤、消泡剤、親水剤、帯電防止剤、高分子粘剤、離型剤、抗菌剤、殺菌剤等の薬品を添加する場合もある。 In the wet papermaking method, first, stretched polyester fibers (main fibers) and binder fibers are uniformly dispersed in water, and then passed through processes such as screen (removal of foreign matters, lumps, etc.), and the final fiber concentration is 0.01 to The slurry adjusted to 0.50% by mass is made by a paper machine to obtain a wet paper. In order to make the dispersibility of the fibers uniform, chemicals such as dispersants, antifoaming agents, hydrophilic agents, antistatic agents, polymer thickeners, mold release agents, antibacterial agents, bactericides, etc. may be added during the process. is there.
抄紙機としては、例えば、長網、円網、傾斜ワイヤー等の抄紙網が単独で設置されている抄紙機、又はこれらの抄紙網の同種又は異種の２種以上がオンラインで設置されているコンビネーション抄紙機などにより製造することができる。本発明の膜分離活性汚泥処理用半透膜用支持体は多層不織布であるが、その製造方法としては、各々の抄紙網で抄き上げた湿紙を積層する抄き合わせ法や、先に形成した一層上に繊維を分散したスラリーを流延して、他の層を形成して積層していく流延法等が挙げられる。流延法において、先に形成した一層は湿紙状態であっても良いし、乾燥状態であっても良い。また、２枚以上の乾燥状態の層を熱融着させて、多層不織布とすることもできる。 As the paper machine, for example, a paper machine in which a paper net such as a long net, a circular net, or an inclined wire is installed alone, or a combination in which two or more of the same or different types of these paper nets are installed online. It can be manufactured by a paper machine. The support for a semipermeable membrane for membrane separation activated sludge treatment of the present invention is a multilayer nonwoven fabric, and as a manufacturing method thereof, for example, a combination method of laminating wet papers made by each papermaking net, Examples thereof include a casting method in which a slurry in which fibers are dispersed is cast on the formed layer, and another layer is formed and laminated. In the casting method, the previously formed layer may be in a wet paper state or in a dry state. In addition, two or more dry layers can be heat-sealed to form a multilayer nonwoven fabric.
抄紙網で製造された湿紙を、ヤンキードライヤー、エアードライヤー、シリンダードライヤー、サクションドラム式ドライヤー、赤外方式ドライヤー等で乾燥することにより、シート（原紙）を得る。湿紙の乾燥の際に、ヤンキードライヤー等の熱ロールに密着させて熱圧乾燥させることによって、密着させた面の平滑性が向上する。熱圧乾燥とは、タッチロール等で熱ロールに湿紙を押しつけて乾燥させることをいう。熱ロールの表面温度は、１００〜１８０℃が好ましく、１００〜１６０℃がより好ましく、１１０〜１６０℃が更に好ましい。圧力は、好ましくは５〜１００ｋＮ／ｍ、より好ましくは１０〜８０ｋＮ／ｍである。 Sheets (base paper) are obtained by drying wet paper produced by a papermaking net with a Yankee dryer, air dryer, cylinder dryer, suction drum dryer, infrared dryer, or the like. When the wet paper is dried, it is brought into close contact with a hot roll such as a Yankee dryer and dried by heat and pressure to improve the smoothness of the contacted surface. Hot-pressure drying means that the wet paper is pressed against the heat roll with a touch roll or the like and dried. The surface temperature of the hot roll is preferably 100 to 180 ° C, more preferably 100 to 160 ° C, and still more preferably 110 to 160 ° C. The pressure is preferably 5 to 100 kN / m, more preferably 10 to 80 kN / m.
本発明において、不織布（原紙）には、熱カレンダー処理が更に施されていることが好ましい。熱カレンダー処理においては、金属ロール−金属ロール、金属ロール−弾性ロール、金属ロール−コットンロール、金属ロール−シリコンロールなどのロール構成のカレンダーユニットを単独、又は組み合わせて用いることができる。カレンダーユニットの少なくとも一方の金属ロールが加熱される。本発明においては、不織布に十分な熱量を付与させることができて、強度の高い半透膜用支持体を得ることができるため、金属ロール−弾性ロールのカレンダーユニットを用いることが好ましい。 In the present invention, the nonwoven fabric (base paper) is preferably further subjected to a thermal calendar treatment. In the thermal calendering process, calender units having a roll configuration such as metal roll-metal roll, metal roll-elastic roll, metal roll-cotton roll, metal roll-silicon roll can be used alone or in combination. At least one metal roll of the calendar unit is heated. In the present invention, since a sufficient amount of heat can be imparted to the nonwoven fabric and a high strength semipermeable membrane support can be obtained, it is preferable to use a metal roll-elastic roll calender unit.
熱カレンダー処理時の金属ロール温度は、未延伸ポリエステル繊維の融点又は軟化温度に対して−４０〜−１０℃であることが好ましく、−３０〜−２０℃であることがより好ましい。金属ロールの温度が未延伸ポリエステル繊維の融点又は軟化温度に対して−４０℃より低い場合では、未延伸ポリエステルの熱圧融着が不十分となりやすく、半透膜用支持体の強度が低下する場合がある。一方、金属ロールの温度が未延伸ポリエステル繊維の融点又は軟化温度に対して−１０℃より高い場合には、半透膜用支持体が金属ロールに貼り付きやすくなり、半透膜用支持体の表面が不均一となる場合がある。 The metal roll temperature during the heat calendering is preferably −40 to −10 ° C., more preferably −30 to −20 ° C. with respect to the melting point or softening temperature of the unstretched polyester fiber. When the temperature of the metal roll is lower than −40 ° C. with respect to the melting point or softening temperature of the unstretched polyester fiber, the heat-pressure fusion of the unstretched polyester tends to be insufficient, and the strength of the semipermeable membrane support decreases. There is a case. On the other hand, when the temperature of the metal roll is higher than −10 ° C. with respect to the melting point or softening temperature of the unstretched polyester fiber, the semipermeable membrane support easily adheres to the metal roll, and the semipermeable membrane support The surface may be uneven.
熱カレンダー処理時のニップのニップ圧力（線圧）は、好ましくは１９〜１８０ｋＮ／ｍであり、より好ましくは３９〜１５０ｋＮ／ｍである。加工速度は、好ましくは５〜１５０ｍ／ｍｉｎであり、より好ましくは１０〜８０ｍ／ｍｉｎである。 The nip pressure (linear pressure) of the nip during the heat calendar process is preferably 19 to 180 kN / m, more preferably 39 to 150 kN / m. The processing speed is preferably 5 to 150 m / min, and more preferably 10 to 80 m / min.
以下、実施例を挙げて本発明を具体的に説明するが、本発明は本実施例に限定されるものではない。なお、実施例中における部や百分率は断りのない限り、すべて質量によるものである。実施例１５及び１６は参考例である。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples. In the examples, all parts and percentages are by mass unless otherwise specified. Examples 15 and 16 are reference examples.
＜延伸ＰＥＴ繊維１＞
ポリエチレンテレフタレートからなる、繊維径７μｍ、繊維長３ｍｍの延伸ポリエステル繊維を延伸ＰＥＴ繊維１とした。
<Stretched PET fiber 1>
A stretched polyester fiber made of polyethylene terephthalate and having a fiber diameter of 7 μm and a fiber length of 3 mm was designated as a stretched PET fiber 1.
＜延伸ＰＥＴ繊維２＞
ポリエチレンテレフタレートからなる、繊維径１３μｍ、繊維長５ｍｍの延伸ポリエステル繊維を延伸ＰＥＴ繊維２とした。
<Stretched PET fiber 2>
A stretched polyester fiber made of polyethylene terephthalate and having a fiber diameter of 13 μm and a fiber length of 5 mm was designated as stretched PET fiber 2.
＜延伸ＰＥＴ繊維３＞
ポリエチレンテレフタレートからなる、繊維径１８μｍ、繊維長１０ｍｍの延伸ポリエステル繊維を延伸ＰＥＴ繊維３とした。
<Stretched PET fiber 3>
A stretched polyester fiber made of polyethylene terephthalate and having a fiber diameter of 18 μm and a fiber length of 10 mm was designated as stretched PET fiber 3.
＜延伸ＰＥＴ繊維４＞
ポリエチレンテレフタレートからなる、繊維径２５μｍ、繊維長１０ｍｍの延伸ポリエステル繊維を延伸ＰＥＴ繊維４とした。
<Stretched PET fiber 4>
A stretched polyester fiber made of polyethylene terephthalate and having a fiber diameter of 25 μm and a fiber length of 10 mm was designated as a stretched PET fiber 4.
＜延伸ＰＥＴ繊維５＞
ポリエチレンテレフタレートからなる、繊維径３０μｍ、繊維長１０ｍｍの延伸ポリエステル繊維を延伸ＰＥＴ繊維５とした。
<Stretched PET fiber 5>
A drawn polyester fiber 5 made of polyethylene terephthalate and having a fiber diameter of 30 μm and a fiber length of 10 mm was used as a drawn PET fiber 5.
＜未延伸ＰＥＴ繊維１＞
ポリエチレンテレフタレートとイソフタル酸からなる、繊維径１１μｍ、繊維長５ｍｍの未延伸ポリエステル繊維（融点：２３０℃）を未延伸ＰＥＴ繊維１とした。
<Unstretched PET fiber 1>
Unstretched polyester fiber (melting point: 230 ° C.) made of polyethylene terephthalate and isophthalic acid and having a fiber diameter of 11 μm and a fiber length of 5 mm was designated as unstretched PET fiber 1.
＜未延伸ＰＥＴ繊維２＞
ポリエチレンテレフタレートからなる、繊維径１１μｍ、繊維長５ｍｍの未延伸ポリエステル繊維（融点：２６０℃）を未延伸ＰＥＴ繊維２とした。
<Unstretched PET fiber 2>
Unstretched polyester fiber (melting point: 260 ° C.) made of polyethylene terephthalate and having a fiber diameter of 11 μm and a fiber length of 5 mm was used as unstretched PET fiber 2.
＜芯鞘ＰＥＴ繊維１＞
芯部がポリエチレンテレフタレート（融点：２６０℃）、鞘部がポリエチレンテレフタレートとイソフタル酸からなる非晶性の共重合ポリエステル（ガラス転移点：７２℃）であり、繊維径１５μｍ、繊維長５ｍｍ、芯部／鞘部の体積比が５０／５０の芯鞘型ポリエステル複合繊維を、芯鞘ＰＥＴ繊維１とした。
<Core sheath PET fiber 1>
The core is polyethylene terephthalate (melting point: 260 ° C.), the sheath is amorphous copolymer polyester (glass transition point: 72 ° C.) made of polyethylene terephthalate and isophthalic acid, fiber diameter 15 μm, fiber length 5 mm, core A core-sheath polyester composite fiber having a volume ratio of / sheath part of 50/50 was designated as core-sheath PET fiber 1.
＜芯鞘ＰＥＴ繊維２＞
芯部がポリエチレンテレフタレート、鞘部がポリエチレンテレフタレートと１，４−ブタンジオールとε−カプロラクトンからなる結晶性の共重合ポリエステル（ガラス転移点：４５℃、融点：１７５℃）であり、繊維径１５μｍ、繊維長５ｍｍ、芯部／鞘部の体積比が５０／５０の芯鞘型ポリエステル複合繊維を、芯鞘ＰＥＴ繊維２とした。
<Core sheath PET fiber 2>
The core is a polyethylene terephthalate, the sheath is a crystalline copolyester composed of polyethylene terephthalate, 1,4-butanediol and ε-caprolactone (glass transition point: 45 ° C., melting point: 175 ° C.), fiber diameter 15 μm, A core-sheath type polyester composite fiber having a fiber length of 5 mm and a core / sheath volume ratio of 50/50 was designated as core-sheath PET fiber 2.
＜芯鞘ＰＥＴ繊維３＞
芯部がポリエチレンテレフタレート、鞘部がポリエチレンテレフタレートと１，４−ブタンジオールからなる結晶性の共重合ポリエステル（ガラス転移点：８６℃、融点：２３２℃）であり、繊維径１５μｍ、繊維長５ｍｍ、芯部／鞘部の体積比が５０／５０の芯鞘型ポリエステル複合繊維を、芯鞘ＰＥＴ繊維３とした。
<Core sheath PET fiber 3>
The core is polyethylene terephthalate, the sheath is a crystalline copolymerized polyester composed of polyethylene terephthalate and 1,4-butanediol (glass transition point: 86 ° C., melting point: 232 ° C.), fiber diameter 15 μm, fiber length 5 mm, The core-sheath polyester composite fiber having a core / sheath volume ratio of 50/50 was designated as core-sheath PET fiber 3.
＜芯鞘ＰＥＴ繊維４＞
芯部がポリエチレンテレフタレート、鞘部がポリエチレンテレフタレートと１，４−ブタンジオールとε−カプロラクトンからなる結晶性の共重合ポリエステル（ガラス転移点：３２℃、融点：１５４℃）であり、繊維径１５μｍ、繊維長５ｍｍ、芯部／鞘部の体積比が５０／５０の芯鞘型ポリエステル複合繊維を、芯鞘ＰＥＴ繊維４とした。
<Core sheath PET fiber 4>
The core is polyethylene terephthalate, the sheath is a crystalline copolyester composed of polyethylene terephthalate, 1,4-butanediol and ε-caprolactone (glass transition point: 32 ° C., melting point: 154 ° C.), fiber diameter 15 μm, A core-sheath polyester composite fiber having a fiber length of 5 mm and a core / sheath volume ratio of 50/50 was designated as core-sheath PET fiber 4.
実施例１〜１６、比較例１〜３の膜分離活性汚泥処理用半透膜用支持体を、以下の条件で製造した。 The support bodies for semipermeable membranes for membrane separation activated sludge treatment of Examples 1 to 16 and Comparative Examples 1 to 3 were produced under the following conditions.
（原紙の製造）
２ｍ３の分散タンクに水を投入後、表１に示す原料配合比率（％）で配合し、分散濃度０．２質量％で５分間分散して、傾斜／円網複合式抄紙機を用い、傾斜ワイヤー上で第二表面層の湿紙を形成し、円網ワイヤー上で第一表面層の湿紙を形成して、両湿紙を乾燥させる前に積層させた後に、表面温度１３０℃のヤンキードライヤーにて熱圧乾燥し、表１に示す坪量を目標にして、幅１０００ｍｍの湿式不織布（原紙１〜１９）を得た。
(Manufacture of base paper)
After charging water into a 2 m 3 dispersion tank, blended at the raw material blending ratio (%) shown in Table 1, dispersed at a dispersion concentration of 0.2% by weight for 5 minutes, and using a slanted / circular mesh paper machine, After forming the wet paper of the second surface layer on the inclined wire and forming the wet paper of the first surface layer on the circular mesh wire and laminating both wet papers, the surface temperature of 130 ° C. The wet nonwoven fabric (base papers 1 to 19) having a width of 1000 mm was obtained with a target of the basis weight shown in Table 1 by hot-pressure drying with a Yankee dryer.
（熱カレンダー処理）
得られた原紙１〜１９に対して、金属ロール−弾性ロールのカレンダーユニットにて、表２に記載する条件で熱カレンダー処理を行い、実施例１〜１６及び比較例１〜３の膜分離活性汚泥処理用半透膜用支持体を得た。１回目の処理で金属ロールに当たった面が、２回目の処理で弾性ロールに当たるように処理した。
(Thermal calendar processing)
The obtained base papers 1 to 19 were subjected to thermal calendering treatment under the conditions described in Table 2 in a metal roll-elastic roll calender unit, and membrane separation activities of Examples 1 to 16 and Comparative Examples 1 to 3 were performed. A support for a semipermeable membrane for sludge treatment was obtained. It processed so that the surface which contacted the metal roll by the 1st process might hit an elastic roll by the 2nd process.
実施例１〜１６及び比較例１〜３で得られた膜分離活性汚泥処理用半透膜用支持体に対して、以下の測定及び評価を行い、結果を表３及び４に示した。 The following measurements and evaluations were performed on the membrane-permeable activated sludge treatment semipermeable membrane supports obtained in Examples 1 to 16 and Comparative Examples 1 to 3, and the results are shown in Tables 3 and 4.
（膜分離活性汚泥処理用半透膜用支持体の坪量）
ＪＩＳ Ｐ８１２４に準拠して、坪量を測定した。
(Basis weight of support for semipermeable membrane for membrane separation activated sludge treatment)
The basis weight was measured according to JIS P8124.
（膜分離活性汚泥処理用半透膜用支持体の厚みと密度）
半透膜用支持体の厚みは、ＪＩＳ Ｐ８１１８に準拠して測定した。
(Thickness and density of the semipermeable membrane support for membrane separation activated sludge treatment)
The thickness of the semipermeable membrane support was measured in accordance with JIS P8118.
（半透膜用支持体とフレーム材との接着強度）
幅３０ｍｍ、長さ５０ｍｍに切り揃えた各半透膜用支持体を、同じサイズのＡＢＳ樹脂板上に置き、超音波式接着機（ＳＥＮＺＨＥＮ ＫＥＩＪＩＧＳＴＡＲ ＴＥＣＨＮＯＬＯＧＹ ＬＴＤ社製、製品名：ＭＳＫ−８００）のヘッド（品番：Ｎ１、４ｍｍ×４ｍｍ）を半透膜用支持体に当て、出力４０％、元空気圧０．１５ＭＰａ、接着時間１．０秒で、ＡＢＳ樹脂板と半透膜用支持体を、超音波融着点において図１のように接着させた。さらに、図１の点線で示した折り返し部分で半透膜用支持体を折り返し、図２に示したように、半透膜用支持体とＡＢＳ樹脂板を卓上型材料試験機（装置名：ＳＴＡ−１１５０、株式会社オリエンテック製）のチャックに、チャック間隔１５ｍｍで固定し、１００ｍｍ／ｍｉｎの一定速度で、半透膜用支持体とＡＢＳ樹脂板が剥離するまで、上チャックを引き上げて行った時の最大荷重を測定した。この最大荷重によって、「半透膜用支持体とフレーム材との接着強度」を評価した。
(Adhesive strength between semipermeable membrane support and frame material)
The support for each semipermeable membrane cut to a width of 30 mm and a length of 50 mm is placed on an ABS resin plate of the same size, and an ultrasonic bonding machine (manufactured by SENZHEN KEIJIGSTAR TECHNOLOGY LTD, product name: MSK-800) The head (part number: N1, 4 mm × 4 mm) is applied to the semipermeable membrane support, the output is 40%, the original air pressure is 0.15 MPa, the adhesion time is 1.0 second, and the ABS resin plate and the semipermeable membrane support are Bonding was performed as shown in FIG. 1 at the ultrasonic fusion point. Further, the semipermeable membrane support is folded at the folded portion indicated by the dotted line in FIG. 1, and as shown in FIG. 2, the semipermeable membrane support and the ABS resin plate are connected to a tabletop material testing machine (device name: STA). -1150, manufactured by Orientec Co., Ltd.), the upper chuck was pulled up at a constant speed of 100 mm / min until the semipermeable membrane support and the ABS resin plate were peeled off. The maximum load at the time was measured. Based on this maximum load, the “adhesive strength between the semipermeable membrane support and the frame material” was evaluated.
（第一表面層と第二表面層との接着強度）
幅３０ｍｍ、長さ５０ｍｍに切り揃えた２枚の半透膜用支持体を準備し、１枚の半透膜用支持体の先端部１０ｍｍと、もう１枚の半透膜用支持体の末端部１０ｍｍとを、第一表面層と第二表面層とが接するように重ね合わせ、超音波式接着機（ＳＥＮＺＨＥＮ ＫＥＩＪＩＧＳＴＡＲ ＴＥＣＨＮＯＬＯＧＹ ＬＴＤ社製、製品名：ＭＳＫ−８００、ヘッド品番：Ｎ１（４ｍｍ×４ｍｍ））を用いて、出力５％、元空気圧０．１０ＭＰａ、接着時間１．０秒で、２枚の半透膜用支持体の第一表面層と第二表面層とを、超音波融着点において図３のように接着させた。さらに、図４に示したように、２枚の半透膜用支持体を卓上型材料試験機（装置名：ＳＴＡ−１１５０、株式会社オリエンテック製）のチャックに、チャック間隔１５ｍｍで固定し、１００ｍｍ／ｍｉｎの一定速度で、２枚の半透膜用支持体が剥離するまで、上チャックを引き上げて行った時の最大荷重を測定した。この最大荷重によって、「第一表面層と第二表面層との接着強度」を評価した。
(Adhesive strength between the first surface layer and the second surface layer)
Two semipermeable membrane supports having a width of 30 mm and a length of 50 mm are prepared, the tip of one semipermeable membrane support is 10 mm, and the other end of the semipermeable membrane support is The 10 mm portion is superposed so that the first surface layer and the second surface layer are in contact with each other, and an ultrasonic bonding machine (manufactured by SENZHEN KEIJIGSTAR TECHNOLOGY LTD, product name: MSK-800, head product number: N1 (4 mm × 4 mm )), The first surface layer and the second surface layer of the two semipermeable membrane supports were ultrasonically fused with an output of 5%, an original air pressure of 0.10 MPa, and an adhesion time of 1.0 second. The dots were bonded as shown in FIG. Further, as shown in FIG. 4, two semipermeable membrane supports are fixed to a chuck of a tabletop material testing machine (device name: STA-1150, manufactured by Orientec Co., Ltd.) with a chuck interval of 15 mm. The maximum load when the upper chuck was pulled up was measured at a constant speed of 100 mm / min until the two semipermeable membrane supports were peeled off. Based on this maximum load, “adhesive strength between the first surface layer and the second surface layer” was evaluated.
（半透膜用支持体の半透膜接着性評価）
一定のクリアランスを有する定速塗工装置（商品名：ＴＱＣ全自動フィルムアプリケーター、コーテック社）を用いて、半透膜用支持体の第二表面層面にマジックインキ（登録商標）で着色したポリフッ化ビニリデン（ＰＶＤＦ）のＮ−メチルピロリドン溶液（濃度：１２％）を塗布し、水洗、乾燥を行い、半透膜用支持体の第二表面層上にＰＶＤＦ膜を形成させ、半透膜を作製した。
(Semipermeable membrane adhesion evaluation of semipermeable membrane support)
Using a constant speed coating device (trade name: TQC fully automatic film applicator, Cortec Co., Ltd.) having a certain clearance, the polyfluoride in which the second surface layer surface of the semipermeable membrane support is colored with magic ink (registered trademark) An N-methylpyrrolidone solution (concentration: 12%) of vinylidene (PVDF) is applied, washed with water and dried to form a PVDF membrane on the second surface layer of the support for semipermeable membrane, thereby producing a semipermeable membrane. did.
半透膜作製１日後、幅２４ｍｍ（塗布方向に対してクロス方向）×長さ５０ｍｍ（塗布方向）に断裁して試料とする。断裁した半透膜用支持体の第一表面層に幅２４ｍｍ、長さ３０ｍｍに切ったセロハン粘着テープ（ニチバン社製、商品名：エルパック（登録商標）ＬＰ２４）を長さ１０ｍｍ部分のみ貼り付け、残りの幅２４ｍｍ、長さ２０ｍｍ部分は粘着部分として残す。次に、半透膜面の幅２４ｍｍ×長さ１０ｍｍ部分に、粘着メモ（ライオン事務器社製、商品名：スティックオンノートＳＮ−２３）の粘着部分を貼り付ける。セロハン粘着テープの粘着部分（２４ｍｍ×２０ｍｍ）と粘着メモの非粘着部分を持ち、半透膜と半透膜用支持体とが剥離する方向に手で引っ張って、力をかけた時の状態によって、半透膜接着性を判断した。試料を５枚準備して、５回のテストを行った。 One day after preparation of the semipermeable membrane, the sample is cut into a width of 24 mm (cross direction with respect to the application direction) × length of 50 mm (application direction). A cellophane adhesive tape (product name: Elpac (registered trademark) LP24, manufactured by Nichiban Co., Ltd.) cut to a width of 24 mm and a length of 30 mm is pasted on the first surface layer of the cut semipermeable membrane support only in a 10 mm length portion. The remaining width of 24 mm and length of 20 mm is left as an adhesive part. Next, the adhesive part of the adhesive memo (product name: stick-on-note SN-23, manufactured by Lion Corporation) is pasted on the 24 mm wide × 10 mm long part of the semipermeable membrane surface. It has an adhesive part (24mm x 20mm) of cellophane adhesive tape and a non-adhesive part of an adhesive memo, and it is pulled by hand in the direction where the semipermeable membrane and the semipermeable membrane support peel, and depending on the state when the force is applied The semipermeable membrane adhesion was judged. Five samples were prepared and tested five times.
セロハン粘着テープを半透膜面及び第一表面層に貼って、両方のセロハン粘着テープを引っ張った場合、ほとんどの場合において、半透膜と半透膜用支持体との間で剥離が起こり、半透膜接着性を評価することが困難であった。セロハン粘着テープと比較して粘着性が低い粘着メモを使用して、どこが剥離したかを確認することによって、半透膜と半透膜用支持体の接着性を判断できる。以下の判断基準にて「半透膜用支持体と半透膜との接着性」を評価した。 When cellophane adhesive tape is applied to the semipermeable membrane surface and the first surface layer and both cellophane adhesive tapes are pulled, in most cases, peeling occurs between the semipermeable membrane and the semipermeable membrane support, It was difficult to evaluate semipermeable membrane adhesion. The adhesiveness between the semipermeable membrane and the semipermeable membrane support can be determined by using an adhesive memo having a lower adhesiveness than the cellophane adhesive tape and confirming where the peeling has occurred. The “adhesiveness between the semipermeable membrane support and the semipermeable membrane” was evaluated according to the following criteria.
判断基準
Ａ：５回全てのテストで、半透膜と粘着メモ間で剥離が起こった。非常に良好なレベル。
Ｂ：３〜４回のテストで、半透膜と粘着メモ間で剥離が起こった。良好なレベル。
Ｃ：１〜２回のテストで、半透膜と粘着メモ間で剥離が起こった。実用上、下限レベル。
Ｄ：５回全てのテストで、半透膜と半透膜用支持体間で剥離が起こった。使用不可レベル。
Judgment criteria A: Peeling occurred between the semipermeable membrane and the adhesive memo in all five tests. Very good level.
B: Peeling occurred between the semipermeable membrane and the adhesive memo in 3 to 4 tests. Good level.
C: Peeling occurred between the semipermeable membrane and the adhesive memo in one or two tests. Practically lower limit level.
D: Peeling occurred between the semipermeable membrane and the semipermeable membrane support in all five tests. Unusable level.
（第一表面層と第二表面層の融着部分と半透膜との接着性評価）
幅１３０ｍｍ、長さ１８０ｍｍに切り揃えた２枚の半透膜用支持体を、第一表面層と第二表面層とが接するように重ね合わせ、超音波式接着機（ＳＥＮＺＨＥＮ ＫＥＩＪＩＧＳＴＡＲ ＴＥＣＨＮＯＬＯＧＹ ＬＴＤ社製、製品名：ＭＳＫ−８００、ヘッド品番：Ｎ１（４ｍｍ×４ｍｍ））を用いて、出力５％、元空気圧０．１ＭＰａ、接着時間１．０秒で、２枚の半透膜用支持体の第一表面層と第二表面層とを、超音波融着点において図５のように接着させた。なお、超音波融着点の幅は１２ｍｍ、長さは５０ｍｍとした。
(Adhesion evaluation between the fused portion of the first surface layer and the second surface layer and the semipermeable membrane)
Two semipermeable membrane supports, trimmed to a width of 130 mm and a length of 180 mm, are superposed so that the first surface layer and the second surface layer are in contact with each other, and an ultrasonic bonding machine (manufactured by SENZHEN KEIJIGSTAR TECHNOLOGY LTD) , Product name: MSK-800, head product number: N1 (4 mm × 4 mm)), output of 5%, original air pressure of 0.1 MPa, adhesion time of 1.0 second. The first surface layer and the second surface layer were bonded as shown in FIG. 5 at the ultrasonic fusion point. The width of the ultrasonic fusion point was 12 mm and the length was 50 mm.
次いで、一定のクリアランスを有する定速塗工装置（商品名：ＴＱＣ全自動フィルムアプリケーター、コーテック社）を用いて、マジックインキ（登録商標）で着色したＰＶＤＦのＮ−メチルピロリドン溶液（濃度：１２％）を塗布し、水洗、乾燥を行い、超音波融着点を含む半透膜用支持体の第二表面層上にＰＶＤＦ膜を形成させ、半透膜を作製した。 Next, an N-methylpyrrolidone solution of PVDF (concentration: 12%) colored with magic ink (registered trademark) using a constant speed coating apparatus (trade name: TQC fully automatic film applicator, Cortec Co., Ltd.) having a certain clearance. ), Washed with water, and dried to form a PVDF film on the second surface layer of the semipermeable membrane support including the ultrasonic fusion point, thereby producing a semipermeable membrane.
作製１日後、超音波融着点（融着部分、幅１２ｍｍ、長さ５０ｍｍ）を切り出して試料とする。試料の第一表面層に幅１２ｍｍ、長さ３０ｍｍに切ったセロハン粘着テープ（ニチバン社製、商品名：エルパック（登録商標）ＬＰ１２）を長さ１０ｍｍ部分のみ貼り付け、残りの幅１２ｍｍ、長さ２０ｍｍ部分は粘着部分として残す。次に、半透膜面の幅１２ｍｍ×長さ１０ｍｍ部分に、粘着メモ（ライオン事務器社製、商品名：スティックオンノートＳＮ−２３）の粘着部分を貼り付ける。セロハン粘着テープの粘着部分（１２ｍｍ×２０ｍｍ）と粘着メモの非粘着部分を持ち、半透膜と半透膜用支持体とが剥離する方向に手で引っ張って、力をかけた時の状態によって、半透膜接着性を判断した。試料を５枚準備して、５回のテストを行った。以下の判断基準にて「融着部分と半透膜との接着性」を評価した。 One day after the production, an ultrasonic fusion point (fused part, width 12 mm, length 50 mm) is cut out and used as a sample. A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., trade name: Elpac (registered trademark) LP12) cut to a width of 12 mm and a length of 30 mm is pasted on the first surface layer of the sample only for the 10 mm length, and the remaining width is 12 mm. The 20 mm portion is left as an adhesive portion. Next, an adhesive part of an adhesive memo (manufactured by Lion Corporation, product name: Stick-on-note SN-23) is affixed to a 12 mm wide × 10 mm long part of the semipermeable membrane surface. It has an adhesive part (12mm x 20mm) of cellophane adhesive tape and a non-adhesive part of an adhesive memo, and is pulled by hand in the direction in which the semipermeable membrane and the semipermeable membrane support peel off, depending on the state when the force is applied The semipermeable membrane adhesion was judged. Five samples were prepared and tested five times. The “adhesiveness between the fused portion and the semipermeable membrane” was evaluated according to the following criteria.
判断基準
Ａ：５回全てのテストで、半透膜と粘着メモ間で剥離が起こった。非常に良好なレベル。
Ｂ：３〜４回のテストで、半透膜と粘着メモ間で剥離が起こった。良好なレベル。
Ｃ：１〜２回のテストで、半透膜と粘着メモ間で剥離が起こった。実用上、下限レベル。
Ｄ：５回全てのテストで、半透膜と半透膜用支持体間で剥離が起こった。使用不可レベル。
Judgment criteria A: Peeling occurred between the semipermeable membrane and the adhesive memo in all five tests. Very good level.
B: Peeling occurred between the semipermeable membrane and the adhesive memo in 3 to 4 tests. Good level.
C: Peeling occurred between the semipermeable membrane and the adhesive memo in one or two tests. Practically lower limit level.
D: Peeling occurred between the semipermeable membrane and the semipermeable membrane support in all five tests. Unusable level.
（半透膜用支持体の半透膜塗布性評価）
（半透膜用支持体の半透膜接着性評価）で作製した半透膜について、半透膜の幅１０ｃｍ、長さ１０ｃｍの正方形内に存在する、半透膜用支持体表面の毛羽立ちによって半透膜が損傷した部分（損傷部）の個数を倍率１０倍のルーペにより観測し、以下の評価基準にて「半透膜用支持体の半透膜塗布性」を評価した。
(Semipermeable membrane applicability evaluation of semipermeable membrane support)
(Semipermeable membrane adhesion evaluation of semipermeable membrane support) About the semipermeable membrane produced by fuzzing on the surface of the semipermeable membrane support surface existing in a 10 cm wide and 10 cm long square of the semipermeable membrane The number of damaged portions (damaged portions) of the semipermeable membrane was observed with a magnifying glass having a magnification of 10 times, and “semipermeable membrane coatability of the semipermeable membrane support” was evaluated according to the following evaluation criteria.
評価基準
Ａ：損傷部の個数が３個以下であり、良好なレベル
Ｂ：損傷部の個数が５個以下であり、実用可能なレベル
Ｃ：損傷部の個数が５個より多く、実用不可レベル。
Evaluation criteria A: The number of damaged parts is 3 or less, good level B: The number of damaged parts is 5 or less, and the practical level C: The number of damaged parts is more than 5 and the level is not practical .
表４に示すとおり、実施例１〜１６の膜分離活性汚泥処理用半透膜用支持体は、延伸ポリエステル繊維と、バインダー繊維として未延伸ポリエステル繊維と、共重合ポリエステルを鞘部とする芯鞘型ポリエステル複合繊維とを含有し、バインダー繊維として未延伸ポリエステル繊維と芯鞘型ポリエステル複合繊維とを含有する第一表面層と、バインダー繊維として未延伸ポリエステル繊維のみを含有する第二表面層とを有する多層不織布であることから、フレーム材との接着性が高く、半透膜の塗布性が良好であった。 As shown in Table 4, the support for a semipermeable membrane for membrane separation activated sludge treatment of Examples 1 to 16 is a core-sheath having a stretched polyester fiber, an unstretched polyester fiber as a binder fiber, and a copolymer polyester as a sheath. A first surface layer containing unstretched polyester fibers and core-sheath polyester composite fibers as binder fibers, and a second surface layer containing only unstretched polyester fibers as binder fibers. Since it was a multilayer nonwoven fabric, it had high adhesion to the frame material and good semipermeable membrane applicability.
実施例１と９との比較から、第一表面層において、第一表面層に含まれる繊維全体に対し、バインダー繊維の含有量が６０質量％以下である実施例１の半透膜用支持体は、バインダー繊維の含有量が６０質量％を超える実施例９の半透膜用支持体よりも、フレーム材との接着性に優れ、半透膜との接着性も良好であった。また、実施例２と１０の比較から、第一表面層において、第一表面層に含まれる繊維全体に対し、バインダー繊維の含有量が２０質量％以上である実施例２の半透膜用支持体は、バインダー繊維の含有量が２０質量％未満である実施例１０の半透膜用支持体よりも、半透膜用支持体とフレーム材との接着性に優れ、第一表面層と第二表面層との接着性も良好であった。 From the comparison between Examples 1 and 9, in the first surface layer, the support for a semipermeable membrane of Example 1 in which the binder fiber content is 60% by mass or less with respect to the entire fibers contained in the first surface layer. Had better adhesion to the frame material and better adhesion to the semipermeable membrane than the semipermeable membrane support of Example 9 in which the binder fiber content exceeded 60% by mass. In addition, from the comparison between Examples 2 and 10, in the first surface layer, the semipermeable membrane support of Example 2 in which the content of the binder fiber is 20% by mass or more with respect to the entire fibers contained in the first surface layer. The body has better adhesion between the semipermeable membrane support and the frame material than the semipermeable membrane support of Example 10 in which the binder fiber content is less than 20% by mass. Adhesion with the two surface layers was also good.
実施例３及び４と実施例１１及び１２との比較から、第一表面層において、第一表面層に含まれる繊維全体に対し、バインダー繊維の含有量が２０〜６０質量％であり、芯鞘型ポリエステル複合繊維の含有量が５〜４０質量％の範囲にある実施例３及び４の半透膜用支持体は、バインダー繊維の含有量が２０〜６０質量％であっても、芯鞘型ポリエステル繊維の含有量が４０質量を超える実施例１１の半透膜用支持体よりも、フレーム材との接着性が良好であった。また、バインダー繊維の含有量が２０〜６０質量％であっても、芯鞘型ポリエステル複合繊維の含有量が５質量％未満の実施例１２の半透膜用支持体よりも、フレーム材との接着性に優れ、第一表面層と第二表面層との接着性も良好であった。 From the comparison between Examples 3 and 4 and Examples 11 and 12, in the first surface layer, the content of the binder fiber is 20 to 60% by mass with respect to the entire fibers contained in the first surface layer, and the core sheath The support for a semipermeable membrane of Examples 3 and 4 in which the content of the type polyester composite fiber is in the range of 5 to 40% by mass is the core-sheath type, even if the content of the binder fiber is 20 to 60% by mass. The adhesiveness with the frame material was better than the support for the semipermeable membrane of Example 11 in which the content of the polyester fiber exceeded 40 mass. Moreover, even if content of binder fiber is 20-60 mass%, content with a core material is less than the support for semipermeable membranes of Example 12 whose content of polyester composite fiber is less than 5 mass%. The adhesion was excellent, and the adhesion between the first surface layer and the second surface layer was also good.
実施例５と１３との比較から、第二表面層において、第二表面層に含まれる繊維全体に対し、バインダー繊維の含有量が６０質量％以下である実施例５の半透膜用支持体は、バインダー繊維の含有量が６０質量％を超える実施例１３の半透膜用支持体よりも、半透膜との接着性が良好であった。また、実施例６と１４の比較から、第二表面層において、第二表面層に含まれる繊維全体に対し、バインダー繊維の含有量が２０質量％以上である実施例６の半透膜用支持体は、バインダー繊維の含有量が２０質量％未満である実施例１４の半透膜用支持体よりも、半透膜の塗布性が優れていた。 From the comparison between Examples 5 and 13, in the second surface layer, the support for a semipermeable membrane of Example 5 in which the content of the binder fiber is 60% by mass or less with respect to the entire fibers contained in the second surface layer. Had better adhesion to the semipermeable membrane than the support for the semipermeable membrane of Example 13 in which the binder fiber content exceeded 60 mass%. Further, from the comparison between Examples 6 and 14, in the second surface layer, the semipermeable membrane support of Example 6 in which the content of the binder fiber is 20% by mass or more with respect to the entire fibers contained in the second surface layer. The body was superior in the coating property of the semipermeable membrane than the support for the semipermeable membrane of Example 14 in which the binder fiber content was less than 20% by mass.
実施例７と１５との比較から、第一表面層にガラス転移点が８０℃以下の共重合ポリエステルを鞘部とする芯鞘型ポリエステル複合繊維を含有した実施例７は、ガラス転移点が８０℃を超える共重合ポリエステルを鞘部とする芯鞘型ポリエステル複合繊維を含有した実施例１５の半透膜用支持体よりも、フレーム材との接着性に優れ、第一表面層と第二表面層との接着性も良好であった。また、実施例８と１６との比較から、第一表面層にガラス転移点が４０℃以上の共重合ポリエステルを鞘部とする芯鞘型ポリエステル複合繊維を含有した実施例８は、ガラス転移点が４０℃未満の共重合ポリエステルを鞘部とする芯鞘型ポリエステル複合繊維を含有した実施例１６の半透膜用支持体よりも、フレーム材との接着性に優れ、第一表面層と第二表面層との接着性も良好であった。 From a comparison between Examples 7 and 15, Example 7 containing a core-sheath type polyester composite fiber having a sheath of a copolyester having a glass transition point of 80 ° C. or lower in the first surface layer has a glass transition point of 80. The first surface layer and the second surface have better adhesion to the frame material than the support for the semipermeable membrane of Example 15 containing the core-sheath type polyester composite fiber having a copolyester having a temperature exceeding 0 ° C. as the sheath. The adhesion with the layer was also good. Moreover, from the comparison with Examples 8 and 16, Example 8 containing a core-sheath type polyester composite fiber having a sheath portion of a copolyester having a glass transition point of 40 ° C. or higher in the first surface layer has a glass transition point. Is superior to the support for a semipermeable membrane of Example 16 containing a core-sheath polyester composite fiber having a copolyester having a temperature of less than 40 ° C. as the sheath, and the first surface layer and the second layer Adhesion with the two surface layers was also good.
実施例１〜１６に対して、第一表面層に芯鞘型ポリエステル複合繊維を含有しない比較例１と２の半透膜用支持体は、フレーム材との接着性及び第一表面層と第二表面層との接着性が非常に劣る結果となった。 Compared with Examples 1 to 16, the support for a semipermeable membrane of Comparative Examples 1 and 2 in which the core-sheath polyester composite fiber is not contained in the first surface layer has the adhesiveness to the frame material and the first surface layer and the first surface layer. The adhesion with the two surface layers was very poor.
実施例１〜１６に対して、第一表面層と第二表面層の両層に、芯鞘型ポリエステル繊維を含有した比較例３の半透膜用支持体は、熱カレンダー処理時に加熱した金属ロールに半透膜用支持体が貼り付き、シートが切れるトラブルが発生した。また、半透膜用支持体の収縮が大きく、皺が多く発生し、フィルム状であったため、半透膜塗布時に塗布液が支持体に入り込み難くなり、半透膜用支持体と半透膜の接着性が非常に悪く、使用不可レベルであった。 Compared to Examples 1 to 16, the support for the semipermeable membrane of Comparative Example 3 containing the core-sheath type polyester fiber in both the first surface layer and the second surface layer was a metal heated during the heat calendar process. There was a problem that the support for semipermeable membrane adhered to the roll and the sheet was cut. In addition, since the support for the semipermeable membrane is greatly contracted, a lot of wrinkles are generated, and the film is in the form of a film, it is difficult for the coating liquid to enter the support during the semipermeable membrane application, and the semipermeable membrane support and the semipermeable membrane The adhesiveness was very poor, and was unusable.
実施例１７〜２５、比較例４〜６の膜分離活性汚泥処理用半透膜用支持体を、以下の条件で製造した。 The support bodies for semipermeable membranes for membrane separation activated sludge treatment of Examples 17 to 25 and Comparative Examples 4 to 6 were produced under the following conditions.
（原紙の製造）
表５に示す原料配合比率（％）で、原紙１〜１９と同様の方法を用い、表５に示す坪量を目標にして、幅１０００ｍｍの湿式不織布（原紙２０〜３１）を得た。
(Manufacture of base paper)
Using the same raw material blending ratio (%) as shown in Table 5, the same method as that for base papers 1 to 19 was used, and the basis weight shown in Table 5 was targeted, and wet nonwoven fabrics (base papers 20 to 31) having a width of 1000 mm were obtained.
（熱カレンダー処理）
得られた原紙２０〜３１に対して、金属ロール−弾性ロールのカレンダーユニットにて、表６に記載する条件で熱カレンダー処理を行い、実施例１７〜２５及び比較例４〜６の膜分離活性汚泥処理用半透膜用支持体を得た。１回目の処理で金属ロールに当たった面が、２回目の処理で弾性ロールに当たるように処理した。
(Thermal calendar processing)
The obtained base papers 20 to 31 were subjected to thermal calender treatment under the conditions described in Table 6 in a metal roll-elastic roll calender unit, and membrane separation activities of Examples 17 to 25 and Comparative Examples 4 to 6 were performed. A support for a semipermeable membrane for sludge treatment was obtained. It processed so that the surface which contacted the metal roll by the 1st process might hit an elastic roll by the 2nd process.
実施例１７〜２５及び比較例４〜６で得られた膜分離活性汚泥処理用半透膜用支持体に対して、以下の測定及び評価を行い、結果を表７及び８に示した。 The following measurements and evaluations were performed on the membrane-permeable activated sludge treatment semipermeable membrane supports obtained in Examples 17 to 25 and Comparative Examples 4 to 6, and the results are shown in Tables 7 and 8.
（膜分離活性汚泥処理用半透膜用支持体の坪量）
実施例１〜１６及び比較例１〜３と同様の方法にて、坪量を測定した。
(Basis weight of support for semipermeable membrane for membrane separation activated sludge treatment)
The basis weight was measured in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 3.
（膜分離活性汚泥処理用半透膜用支持体の厚みと密度）
実施例１〜１６及び比較例１〜３と同様の方法にて、厚みを測定した。
(Thickness and density of the semipermeable membrane support for membrane separation activated sludge treatment)
The thickness was measured by the same method as in Examples 1 to 16 and Comparative Examples 1 to 3.
（半透膜用支持体とフレーム材との接着強度）
実施例１〜１６及び比較例１〜３と同様の方法にて、「半透膜用支持体とフレーム材との接着強度」を評価した。
(Adhesive strength between semipermeable membrane support and frame material)
“Adhesive strength between the semipermeable membrane support and the frame material” was evaluated in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 3.
（第一表面層と第二表面層との接着強度）
実施例１〜１６及び比較例１〜３と同様の方法にて、「第一表面層と第二表面層との接着強度」を評価した。
(Adhesive strength between the first surface layer and the second surface layer)
“Adhesive strength between the first surface layer and the second surface layer” was evaluated in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 3.
（半透膜用支持体の半透膜接着性評価）
実施例１〜１６及び比較例１〜３と同様の方法でテストを行い、同様の判断基準にて「半透膜用支持体と半透膜との接着性」を評価した。
(Semipermeable membrane adhesion evaluation of semipermeable membrane support)
Tests were performed in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 3, and “adhesiveness between the semipermeable membrane support and the semipermeable membrane” was evaluated according to the same criteria.
（第一表面層と第二表面層の融着部分と半透膜との接着性評価）
実施例１〜１６及び比較例１〜３と同様の方法でテストを行い、同様の判断基準にて「融着部分と半透膜との接着性」を評価した。
(Adhesion evaluation between the fused portion of the first surface layer and the second surface layer and the semipermeable membrane)
Tests were performed in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 3, and “adhesiveness between the fused portion and the semipermeable membrane” was evaluated according to the same criteria.
（半透膜用支持体の半透膜塗布性評価）
実施例１〜１６及び比較例１〜３と同様の方法でテストを行い、同様の評価基準にて「半透膜用支持体の半透膜塗布性」を評価した。
(Semipermeable membrane applicability evaluation of semipermeable membrane support)
Tests were performed in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 3, and “semi-permeable membrane coating property of semi-permeable membrane support” was evaluated according to the same evaluation criteria.
表８に示すとおり、実施例１７〜２５の膜分離活性汚泥処理用半透膜用支持体は、延伸ポリエステル繊維と、バインダー繊維として未延伸ポリエステル繊維と、共重合ポリエステルを鞘部とする芯鞘型ポリエステル複合繊維とを含有し、バインダー繊維として未延伸ポリエステル繊維と芯鞘型ポリエステル複合繊維とを含有する第一表面層と、バインダー繊維として未延伸ポリエステル繊維のみを含有する第二表面層とを有する多層不織布であることから、フレーム材との接着性が高く、半透膜の塗布性が良好であった。 As shown in Table 8, the support for a semipermeable membrane for membrane separation activated sludge treatment of Examples 17 to 25 is a core sheath having a stretched polyester fiber, an unstretched polyester fiber as a binder fiber, and a copolymer polyester as a sheath. A first surface layer containing unstretched polyester fibers and core-sheath polyester composite fibers as binder fibers, and a second surface layer containing only unstretched polyester fibers as binder fibers. Since it was a multilayer nonwoven fabric, it had high adhesion to the frame material and good semipermeable membrane applicability.
実施例１９と２３との比較から、第一表面層において、第一表面層に含まれる繊維全体に対し、バインダー繊維の含有量が２０質量％以上である実施例１９の半透膜用支持体は、バインダー繊維の含有量が２０質量％未満である実施例２３の半透膜用支持体よりも、半透膜用支持体とフレーム材との接着性に優れ、第一表面層と第二表面層との接着性も良好であった。 From the comparison between Examples 19 and 23, in the first surface layer, the support for a semipermeable membrane of Example 19 in which the binder fiber content is 20% by mass or more with respect to the entire fibers contained in the first surface layer. Has better adhesion between the semipermeable membrane support and the frame material than the semipermeable membrane support of Example 23 in which the binder fiber content is less than 20% by mass. Adhesion with the surface layer was also good.
実施例１９と２４との比較から、第二表面層において、第二表面層に含まれる繊維全体に対し、バインダー繊維の含有量が２０質量％以上である実施例１９の半透膜用支持体は、バインダー繊維の含有量が２０質量％未満である実施例２４の半透膜用支持体よりも、半透膜の塗布性が優れていた。 From the comparison between Examples 19 and 24, in the second surface layer, the support for a semipermeable membrane of Example 19 in which the content of the binder fiber is 20% by mass or more with respect to the entire fibers contained in the second surface layer. The coating property of the semipermeable membrane was superior to the support for the semipermeable membrane of Example 24 in which the binder fiber content was less than 20% by mass.
実施例２０及び２５との比較から、第一表面層において、第一表面層に含まれる繊維全体に対し、バインダー繊維の含有量が２０〜６０質量％であり、芯鞘型ポリエステル複合繊維の含有量が５〜４０質量％の範囲にある実施例２０の半透膜用支持体は、バインダー繊維の含有量が２０〜６０質量％であっても、芯鞘型ポリエステル複合繊維の含有量が５質量％未満の実施例２５の半透膜用支持体よりも、フレーム材との接着性に優れ、第一表面層と第二表面層との接着性も良好であった。 From the comparison with Examples 20 and 25, in the first surface layer, the content of the binder fiber is 20 to 60% by mass with respect to the entire fibers contained in the first surface layer, and the core-sheath polyester composite fiber is contained. The support for the semipermeable membrane of Example 20 in which the amount is in the range of 5 to 40% by mass has a core-sheath polyester composite fiber content of 5 even if the binder fiber content is 20 to 60% by mass. The adhesion to the frame material was superior to that of the support for the semipermeable membrane of Example 25 of less than% by mass, and the adhesion between the first surface layer and the second surface layer was also good.
実施例１７〜２５に対して、第一表面層に芯鞘型ポリエステル複合繊維を含有しない比較例４と５の半透膜用支持体は、フレーム材との接着性及び第一表面層と第二表面層との接着性が非常に劣る結果となった。 Compared to Examples 17 to 25, the support for a semipermeable membrane of Comparative Examples 4 and 5 in which the core-sheath polyester composite fiber is not contained in the first surface layer has the adhesiveness to the frame material and the first surface layer and the first surface layer. The adhesion with the two surface layers was very poor.
実施例１７〜２５に対して、第一表面層と第二表面層の両層に、芯鞘型ポリエステル繊維を含有した比較例６の半透膜用支持体は、熱カレンダー処理時に加熱した金属ロールに半透膜用支持体が貼り付き、シートが切れるトラブルが発生した。また、半透膜用支持体の収縮が大きく、皺が多く発生し、フィルム状であったため、半透膜塗布時に塗布液が支持体に入り込み難くなり、半透膜用支持体と半透膜の接着性が非常に悪く、使用不可レベルであった。 For Examples 17 to 25, the semipermeable membrane support of Comparative Example 6 containing a core-sheath polyester fiber in both the first surface layer and the second surface layer was a metal heated during the thermal calendar process. There was a problem that the support for semipermeable membrane adhered to the roll and the sheet was cut. In addition, since the support for the semipermeable membrane is greatly contracted, a lot of wrinkles are generated, and the film is in the form of a film, it is difficult for the coating liquid to enter the support during the semipermeable membrane application, and the semipermeable membrane support and the semipermeable membrane The adhesiveness was very poor, and was unusable.
本発明の膜分離活性汚泥処理用半透膜用支持体は、膜分離活性汚泥処理法による汚水処理の分野で利用することができる。 The support for a semipermeable membrane for membrane separation activated sludge treatment of the present invention can be used in the field of sewage treatment by a membrane separation activated sludge treatment method.
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