JP2020172716A - Manufacturing method of fluororesin staple fiber - Google Patents
Manufacturing method of fluororesin staple fiber Download PDFInfo
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- JP2020172716A JP2020172716A JP2019074096A JP2019074096A JP2020172716A JP 2020172716 A JP2020172716 A JP 2020172716A JP 2019074096 A JP2019074096 A JP 2019074096A JP 2019074096 A JP2019074096 A JP 2019074096A JP 2020172716 A JP2020172716 A JP 2020172716A
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- 239000000835 fiber Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000009477 glass transition Effects 0.000 claims abstract description 7
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 238000000527 sonication Methods 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 6
- 239000002121 nanofiber Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004244 micellar electrokinetic capillary chromatography Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- Treatment Of Fiber Materials (AREA)
- Artificial Filaments (AREA)
Abstract
Description
本発明は、フッ素樹脂短繊維の製造方法に関する。 The present invention relates to a method for producing fluororesin short fibers.
ＰＶＤＦなどの繊維はタンパク質の吸着が高いことから、タンパク質などを固定化する材料として利用することができるが、特許文献１で使用する繊維状物質は、不織布のままではなく、何らかの方法で繊維を切断する必要があった。特許文献２には、極細樹脂を超音波処理することで、樹脂が切断され樹脂製極細短繊維が調製できる旨が開示されているが、フッ素樹脂を超音波処理しても、繊維の切断は起こらず、不織布が丸まった固まりが得られるだけで、短く切断されたフッ素樹脂は得られなかった。 Since fibers such as PVDF have high protein adsorption, they can be used as materials for immobilizing proteins and the like. However, the fibrous substance used in Patent Document 1 is not a non-woven fabric, but fibers can be used in some way. I had to disconnect. Patent Document 2 discloses that the resin can be cut to prepare resin-made ultrafine short fibers by ultrasonically treating the ultrafine resin, but even if the fluororesin is ultrasonically treated, the fibers cannot be cut. It did not occur, only a curled mass of the non-woven fabric was obtained, and a short-cut fluororesin could not be obtained.
本発明の課題は、フッ素樹脂短繊維の製造方法を提供する。 An object of the present invention is to provide a method for producing a fluororesin short fiber.
上記課題を解決するために、本発明者は鋭意検討した結果、本発明に到達した。 In order to solve the above problems, the present inventor has arrived at the present invention as a result of diligent studies.
すなわち本発明の一態様は、
静電紡糸法により得られたフッ素樹脂繊維を、ガラス転移温度以下で超音波処理することを特徴とするフッ素樹脂短繊維の製造方法である。
That is, one aspect of the present invention is
This is a method for producing a fluororesin short fiber, which comprises ultrasonically treating a fluororesin fiber obtained by an electrostatic spinning method at a glass transition temperature or lower.
以下に、本発明を詳細に説明する。 The present invention will be described in detail below.
フッ素樹脂繊維としては、ポリテトラフルオロエチレン（ＰＴＦＥ）などの完全フッ素化樹脂、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリフッ化ビニル（ＰＶＦ）などの部分フッ素化樹脂、ペルフルオロアルコキシフッ素樹脂（ＰＦＡ）、四フッ化エチレン・六フッ化プロピレン共重合体（ＦＥＰ）、エチレン・四フッ化エチレン共重合体（ＥＴＦＥ）、エチレン・クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）などのフッ素化樹脂共重合体などが挙げられるが、ポリフッ化ビニリデン（ＰＶＤＦ）が好適である。 Fluororesin fibers include fully fluorinated resins such as polytetrafluoroethylene (PTFE), partially fluorinated resins such as polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF), and perfluoro. Alkane fluoride resin (PFA), ethylene tetrafluoride / propylene hexafluoride copolymer (FEP), ethylene / ethylene tetrafluoride copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), etc. Examples thereof include fluorinated resin copolymers, but polyvinylidene fluoride (PVDF) is preferable.
フッ素樹脂繊維の作製方法は通常報告されている静電紡糸（エレクトロスピニング）法で作製することができ、一例をあげると、フッ素樹脂を有機溶媒で溶解したポリマー溶液を用いて作製する。ポリマー溶液の濃度は２〜３０％が好ましく、５〜１５％がより好ましい。繊維径を細くするために、ＴＢＡＣ（テトラブチルアンモニウムクロライド）などの電荷を有する物質をポリマー溶液に添加してもよい。樹脂を溶解する溶剤は、ポリマーが完全に溶解できれば特に限定されず、例えば、ジメチルホルムアミド、アセトン、ジメチルスルホキシドやそれらの混合溶剤が使用可能である。フッ素樹脂繊維の紡糸方法も不織布状に紡糸する、配向性を持たせて紡糸するなど特に限定されない。 The method for producing the fluororesin fiber can be produced by an electrostatic spinning (electrospinning) method that is usually reported. For example, it is produced by using a polymer solution in which a fluororesin is dissolved in an organic solvent. The concentration of the polymer solution is preferably 2 to 30%, more preferably 5 to 15%. A charged substance such as TBAC (tetrabutylammonium chloride) may be added to the polymer solution in order to reduce the fiber diameter. The solvent for dissolving the resin is not particularly limited as long as the polymer can be completely dissolved, and for example, dimethylformamide, acetone, dimethyl sulfoxide or a mixed solvent thereof can be used. The spinning method of the fluororesin fiber is not particularly limited, such as spinning in the form of a non-woven fabric or spinning with orientation.
上述した方法によって得られたフッ素樹脂繊維は溶剤に溶解させ、繊維のガラス転移温度以下の温度で超音波処理する。溶剤はガラス転移温度で凍結せず、樹脂を溶解し樹脂に損傷をあたえないものであれば特に限定されず、水系の溶剤であればポリエチレングリコールなどを添加して、凝固点をガラス転移温度以下まで下げた溶液であれば使用可能であり、メチルアルコール、エチルアルコール、イソプロピルアルコールなどのアルコール系の溶剤も使用可能であるが、繊維表面への影響を考慮するとイソプロピルアルコールが特に好ましい。 The fluororesin fiber obtained by the above method is dissolved in a solvent and sonicated at a temperature equal to or lower than the glass transition temperature of the fiber. The solvent is not particularly limited as long as it does not freeze at the glass transition temperature and dissolves the resin and does not damage the resin. If it is an aqueous solvent, polyethylene glycol or the like is added to bring the freezing point to below the glass transition temperature. Any lowered solution can be used, and alcohol-based solvents such as methyl alcohol, ethyl alcohol, and isopropyl alcohol can also be used, but isopropyl alcohol is particularly preferable in consideration of the effect on the fiber surface.
ガラス転移温度以下に冷却する方法は特に限定されず、チラーなどの装置で冷却する方法、液体窒素などで冷却する方法、ドライアイスを溶剤中に投入する方法などが挙げられるが、簡便に目的の温度を維持できるためドライアイスを溶剤中に投入する方法が好ましい。 The method of cooling below the glass transition temperature is not particularly limited, and examples thereof include a method of cooling with a device such as a chiller, a method of cooling with liquid nitrogen, a method of putting dry ice into a solvent, and the like. Since the temperature can be maintained, a method of putting dry ice in a solvent is preferable.
超音波処理を長くすれば当然、繊維の切断が進むため短い繊維が多くなってゆくため、超音波処理の時間や超音波の強度によって繊維長を調整することが可能である。つまり、長い繊維が必要な場合は超音波処理の時間を短めに、短い繊維が必要な場合は超音波処理時間を長くとればよい。超音波発生器の強度によって処理時間は大きく異なるが、数分から数時間程度の処理時間が考えられる。 Naturally, if the ultrasonic treatment is lengthened, the number of short fibers increases due to the progress of fiber cutting, so that the fiber length can be adjusted by the time of the ultrasonic treatment and the intensity of the ultrasonic waves. That is, when long fibers are required, the ultrasonic treatment time may be shortened, and when short fibers are required, the ultrasonic treatment time may be long. The processing time varies greatly depending on the strength of the ultrasonic generator, but the processing time can be considered to be several minutes to several hours.
どの程度の長さの繊維が有用かについては目的に応じて変わるが、例えば繊維の均一な分散性を期待する場合は平均繊維長が２０μｍ以下の繊維が好ましく、ろ過してファイバーを分離する事を考えると平均繊維径は２０μｍより長い繊維の方が好ましい。しかし、あまり長いとファイバーが絡み合うため、２０μｍ以上１ｍｍ以下であることが好ましく、３０μｍ以上５００μｍ以下がより好ましく、５０μｍから１００μｍが特に好ましい。 The length of the fiber that is useful depends on the purpose. For example, when the uniform dispersibility of the fiber is expected, the fiber having an average fiber length of 20 μm or less is preferable, and the fiber is separated by filtration. Considering the above, fibers having an average fiber diameter longer than 20 μm are preferable. However, if it is too long, the fibers will be entangled, so it is preferably 20 μm or more and 1 mm or less, more preferably 30 μm or more and 500 μm or less, and particularly preferably 50 μm to 100 μm.
本発明により、フッ素樹脂繊維を簡便に短繊維化することができる。 According to the present invention, the fluororesin fiber can be easily shortened.
以下、実施例及び比較例を用いて本発明をさらに詳細に説明するが、本発明はこれらの例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples.
実施例１ ＰＶＤＦ繊維の作製と冷却下での切断
ＰＶＤＦ（ＳＯＬＥＦ社製）を７ｗｔ％、ＴＢＡＣ（東京化成社製）を０．０４％になるようにＤＭＦ／アセトン（６０／４０）で溶解し、ＮＡＮＯＮ−１（ＭＥＣＣ製）を用い、３，０００ｒｐｍで回転するΦ２００ドラムコレクターを用いて、配向性ナノファイバーをエレクトロスピニング法により作製した（２０ＫＶ、１．０ｍｌ／ｈｒ）。繊維径は１２０ｎｍ±１３ｎｍで厚みは約１０μｍに紡糸した。
得られたナノファイバーシート（２８ｃｍｘ２５ｃｍ）を、３０ｍｌのイソプロピルアルコール中に投入し、ドライアイスを投入したエチルアルコール浴に浸して冷却した。その後、５分間放置し、サンプルが十分に冷却したことを確認した後、ＲＡＮＳＯＮ社製ＳＯＮＩＦＥＲ ４５０を用いて、ＯＵＴ ＰＵＴ６、Ｄｕｔｙ ｃｙｃｌｅ５０％の目盛で１時間超音波処理を行った。ＰＶＤＦの固まりが無くなったことを確認した後に、日新ＥＭ株式会社製のメッシュ（６５１１銅製の２００メッシュ）を用いて、透過型電子顕微鏡（日本電子 ＪＥＭ１４００Ｐｌｕｓ）で繊維の状態を確認した。その結果を図１に示した。ここに示す様に、切断されたＰＶＤＦが確認された。
Example 1 Preparation of PVDF fiber and cutting under cooling PVDF (manufactured by SOLEF) is dissolved in DMF / acetone (60/40) so as to be 7 wt% and TBAC (manufactured by Tokyo Kasei Co., Ltd.) to be 0.04%. , NANON-1 (manufactured by MECC) was used, and oriented nanofibers were prepared by an electrospinning method using a Φ200 drum collector rotating at 3,000 rpm (20 KV, 1.0 ml / hr). The fiber diameter was 120 nm ± 13 nm and the thickness was about 10 μm.
The obtained nanofiber sheet (28 cm x 25 cm) was put into 30 ml of isopropyl alcohol and immersed in an ethyl alcohol bath containing dry ice to cool it. Then, the sample was left to stand for 5 minutes, and after confirming that the sample was sufficiently cooled, ultrasonic treatment was performed for 1 hour on a scale of OUT PUT 6 and Duty cycle 50% using SONIFER 450 manufactured by RANSON. After confirming that the PVDF mass had disappeared, the state of the fibers was confirmed with a transmission electron microscope (JEOL JEM1400Plus) using a mesh manufactured by Nissin EM Co., Ltd. (200 mesh made of 6511 copper). The result is shown in FIG. As shown here, cut PVDF was confirmed.
比較例１ ＰＶＤＦ繊維の作製と切断
実施例１と同じ方法でナノファイバー繊維を調製し、イソプロピルアルコール中で、ＲＡＮＳＯＮ社製ＳＯＮＩＦＥＲ ４５０を用いて、ＯＵＴ ＰＵＴ６、Ｄｕｔｙ ｃｙｃｌｅ５０％の目盛で１時間超音波処理を行った。その結果ナノファイバーは分散せずに図２に示す様な固まりになった。
Comparative Example 1 Preparation and cutting of PVDF fibers Nanofiber fibers were prepared in the same manner as in Example 1, and sonicated in isopropyl alcohol for 1 hour on a scale of OUT PUT6, Duty cycle 50% using SONIFER 450 manufactured by RANSON. Processing was performed. As a result, the nanofibers did not disperse and became a mass as shown in FIG.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55137212A (en) * | 1979-04-11 | 1980-10-25 | Nichibi:Kk | Method of splitting extremely fine polyvinyl alcohol synthetic fiber |
| JPS63210145A (en) * | 1987-02-25 | 1988-08-31 | Nitto Electric Ind Co Ltd | Porous polytetrafluoroethylene material, its production and directional resistor prepared therefrom |
| JPH04194068A (en) * | 1990-11-21 | 1992-07-14 | Nippon Oil Co Ltd | Fibrillated polyolefin material and its production |
| JPH09276707A (en) * | 1996-04-11 | 1997-10-28 | Masahiro Watanabe | Thin film semiconductor photocatalyst element and reaction device using it |
| JP2009114560A (en) * | 2007-11-02 | 2009-05-28 | Nisshinbo Ind Inc | Ultra-fine staple fiber made of resin and method for producing the same |
| JP2017185422A (en) * | 2016-04-01 | 2017-10-12 | Jnc株式会社 | Depth filter |
-
2019
- 2019-04-09 JP JP2019074096A patent/JP7293825B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55137212A (en) * | 1979-04-11 | 1980-10-25 | Nichibi:Kk | Method of splitting extremely fine polyvinyl alcohol synthetic fiber |
| JPS63210145A (en) * | 1987-02-25 | 1988-08-31 | Nitto Electric Ind Co Ltd | Porous polytetrafluoroethylene material, its production and directional resistor prepared therefrom |
| JPH04194068A (en) * | 1990-11-21 | 1992-07-14 | Nippon Oil Co Ltd | Fibrillated polyolefin material and its production |
| JPH09276707A (en) * | 1996-04-11 | 1997-10-28 | Masahiro Watanabe | Thin film semiconductor photocatalyst element and reaction device using it |
| JP2009114560A (en) * | 2007-11-02 | 2009-05-28 | Nisshinbo Ind Inc | Ultra-fine staple fiber made of resin and method for producing the same |
| JP2017185422A (en) * | 2016-04-01 | 2017-10-12 | Jnc株式会社 | Depth filter |
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