JP2006144138A - Method for producing fluorine nonwoven fabric and fluorine nonwoven fabric - Google Patents
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本発明は、電界紡糸法により繊維径の小さいフッ素繊維からなるフッ素不織布を製造することができるフッ素不織布の製造方法及びフッ素不織布に関する。 The present invention relates to a method for producing a fluorine nonwoven fabric and a fluorine nonwoven fabric capable of producing a fluorine nonwoven fabric composed of fluorine fibers having a small fiber diameter by electrospinning.
フッ素不織布は、高耐薬品性、高耐熱性、及び、低誘電率性を有することから、半導体用の純水フィルターやバグフィルター；高周波用の多層プリント基板材や多層フレキシブルプリント回路（ＦＰＣ）基材；燃料電池電解質膜基材等に使用されている。 Fluorine nonwoven fabric has high chemical resistance, high heat resistance, and low dielectric constant, so it is a pure water filter and bag filter for semiconductors; high-frequency multilayer printed circuit board materials and multilayer flexible printed circuit (FPC) bases Materials: Used for fuel cell electrolyte membrane substrates.
このようなフッ素不織布に用いられるフッ素繊維は、高い熱溶融温度や高い離型性、大きな比重等の特徴があるために、通常の湿式法や乾式法による不織布化が困難であるが、以下のようなフッ素不織布の製造方法が提案され、一部実施されている。 Fluorine fibers used in such fluorine nonwoven fabrics have characteristics such as a high heat melting temperature, high releasability, and a large specific gravity, so that it is difficult to make a nonwoven fabric by a normal wet method or a dry method. Such a method for producing a fluorine nonwoven fabric has been proposed and partially implemented.
例えば、特許文献１及び特許文献２には、フッ素樹脂を熱溶融させメルトブローン法で直接不織布化する方法が開示され、特許文献３には、フッ素繊維を部分的に熱溶融させて結着する方法が開示され、特許文献４には、フッ素繊維を溶融除去可能な繊維と混合して不織布化した後にフッ素以外の成分を溶解除去する方法が開示され、特許文献５には、フッ素繊維を水溶性樹脂溶液で湿式不織布化し繊維を結着させた後に熱水処理で水溶性樹脂を除去する方法等が開示されている。
For example, Patent Document 1 and
フィルター用途のフッ素不織布では、より細かい異物を除去するために繊維径の小さいフッ素繊維からなるフッ素不織布が求められている。また、ＦＰＣ基板用途でも、多層基板での厚みを低減するために、より薄いフッ素不織布が求められており、また、燃料電池用電解質膜の基材用途でも、内部抵抗低減のために、より薄い基材が求められており、いずれもフッ素繊維の繊維径としてφ１０μｍ以下のフッ素不織布が求められている。 In the fluorine nonwoven fabric for filters, a fluorine nonwoven fabric made of fluorine fibers having a small fiber diameter is required in order to remove finer foreign matters. Further, even for FPC board applications, thinner fluorine nonwoven fabrics are required in order to reduce the thickness of multilayer boards, and even for base materials for fuel cell electrolyte membranes, they are thinner to reduce internal resistance. There is a need for a substrate, and in all cases, a fluorine nonwoven fabric having a fiber diameter of?
しかしながら、フッ素繊維は、フッ素樹脂の溶融粘度が高いために、細い繊維系のものが作りにくく、通常はφ２０μｍ程度の繊維径のフッ素繊維までしかできず、φ１０μｍ以下の繊維径のフッ素樹脂からなる不織布を作製することが困難であった。また、メルトブローン法では、φ１０μｍ以下の繊維径のフッ素不織布を作製することも原理的には可能であるが、熱溶融したフッ素樹脂が腐食性をもつために成形金型やノズル全てを耐腐食性のある合金製にする必要があり、その製造装置が高価でメンテナンス性の悪い装置になるという問題があった。 However, since the fluorine fiber has a high melt viscosity of the fluororesin, it is difficult to make a thin fiber-based one, and usually only a fluorofiber having a fiber diameter of about φ20 μm can be formed, and it consists of a fluororesin having a fiber diameter of φ10 μm or less. It was difficult to produce a nonwoven fabric. In addition, the melt blown method can, in principle, produce a fluorine nonwoven fabric with a fiber diameter of 10 μm or less. However, since the hot-melted fluororesin is corrosive, all molds and nozzles are resistant to corrosion. Therefore, there is a problem that the manufacturing apparatus is expensive and has poor maintainability.
これに対して、電界紡糸法という樹脂溶液からの直接不織布化技術が知られている（例えば、非特許文献１参照）。この方法は、より細繊維の不織布を製造するのに適する方法である。
しかし、フッ素樹脂溶液は極性が低いため、通常の電界紡糸法による不織布化が困難であるという問題があった。
On the other hand, a technique for forming a nonwoven fabric directly from a resin solution called electrospinning is known (for example, see Non-Patent Document 1). This method is suitable for producing a nonwoven fabric having finer fibers.
However, since the fluororesin solution has low polarity, there is a problem that it is difficult to form a nonwoven fabric by a normal electrospinning method.
本発明は、上記現状に鑑み、電界紡糸法により繊維径の小さいフッ素繊維からなるフッ素不織布を製造することができるフッ素不織布の製造方法及びフッ素不織布を提供することを目的とする。 An object of this invention is to provide the manufacturing method of a fluorine nonwoven fabric which can manufacture the fluorine nonwoven fabric which consists of a fluorine fiber with a small fiber diameter by an electrospinning method, and a fluorine nonwoven fabric.
本発明は、電界紡糸法によるフッ素不織布の製造方法であって、非晶質フッ素樹脂溶液に水溶性樹脂水溶液及び／又は電解質溶液を添加し、吐出溶液を調製する工程１と、前記吐出溶液をシリンジに注入する工程２と、前記シリンジの一端に設けられたノズルと前記ノズルに対向する基板との間に電圧を印加し、前記吐出溶液を前記ノズルから前記基板上に吐出させるとともに、前記ノズル及び／又は前記基板を揺動させる工程３とを有するフッ素不織布の製造方法である。
以下に本発明を詳述する。
The present invention is a method for producing a fluorine nonwoven fabric by an electrospinning method, comprising adding a water-soluble resin aqueous solution and / or an electrolyte solution to an amorphous fluororesin solution to prepare a discharge solution; and A step of injecting into a syringe, a voltage is applied between a nozzle provided at one end of the syringe and a substrate facing the nozzle, and the discharge solution is discharged from the nozzle onto the substrate; And / or a step 3 of swinging the substrate.
The present invention is described in detail below.
本発明者らは、鋭意検討の結果、非晶質フッ素樹脂溶液に水溶性樹脂水溶液及び／又は電解質溶液を少量添加することにより、非晶質フッ素樹脂溶液の極性が高まり、電界紡糸法による不織布化を行うことが可能になり、より繊維径の小さいフッ素繊維からなるフッ素不織布を製造することができることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the inventors have added a small amount of a water-soluble resin aqueous solution and / or an electrolyte solution to the amorphous fluororesin solution, so that the polarity of the amorphous fluororesin solution is increased, and the nonwoven fabric obtained by electrospinning is used. As a result, it has been found that a fluorine nonwoven fabric made of fluorine fibers having a smaller fiber diameter can be produced, and the present invention has been completed.
本発明は、電界紡糸法によるフッ素不織布の製造方法である。上記電界紡糸法とは、樹脂溶液又は熱溶融樹脂を高電圧電界の印加された条件で、微小孔径のノズルから吐出させ、基板上に微細径の樹脂繊維の不織布を製造する方法である。
図１に、電界紡糸法の一態様を示す模式図を示した。
図１に示したように、吐出溶液２をシリンジ１に注入し、シリンジ１の一端に設けられたノズル３とノズル３に対向する基板５との間に電圧を印加し、吐出溶液２をノズル３から基板５上のフィルム４に吐出させるとともに、ノズル３及び／又は基板５を揺動させることにより不織布を製造することができる。なお、上記フィルムとしては特に限定されず、一般的なエンプラ樹脂フィルムが挙げられ、例えば、ポリカーボネート、ナイロン、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリエーテルスルフォン、ポリイミド等が挙げられる。
The present invention is a method for producing a fluorine nonwoven fabric by electrospinning. The electrospinning method is a method of manufacturing a nonwoven fabric of fine resin fibers on a substrate by discharging a resin solution or a hot melt resin from a fine pore nozzle under a condition where a high voltage electric field is applied.
FIG. 1 is a schematic diagram showing one embodiment of the electrospinning method.
As shown in FIG. 1, the
本発明のフッ素不織布の製造方法では、まず、非晶質フッ素樹脂溶液に水溶性樹脂水溶液及び／又は電解質溶液を添加し、吐出溶液を調製する工程１を行う。 In the method for producing a fluorine nonwoven fabric of the present invention, first, Step 1 of adding a water-soluble resin aqueous solution and / or an electrolyte solution to an amorphous fluororesin solution to prepare a discharge solution is performed.
上記非晶質フッ素樹脂溶液として特に限定されないが、非晶質フッ素樹脂をパーフルオロ溶剤に溶解させたものであることが好ましい。
上記非晶質フッ素樹脂としては特に限定されず、例えば、パーフルオロタイプのものとしてはＰＴＦＥ（ポリテトラフルオロエチレン）の末端基を置換したものが、部分フッ素タイプのものとしてはＴＦＥ（テトラフルオロエチレン）やＣＴＦＥ（クロロトリフルオロエチレン）等の含フッ素オレフィンを炭化水素オレフィンと共重合させたもの等が挙げられる。これらの非晶質フッ素樹脂のうち市販されているものとしては、例えば、サイトップ（旭硝子社製）等が挙げられる。
上記パーフルオロ溶剤としては特に限定されず、例えば、ＨＦＥ（ハイドロフルオロエーテル）、パーフルオロ第３アミン類、フッ素化アルコール、パーフルオロアルキル、パーフルオロポリエーテル等が挙げられる。これらのパーフルオロ溶剤のうち市販されているものとしては、例えば、ＣＴ−ｓｏｌｖ（旭硝子社製）等が挙げられる。
The amorphous fluororesin solution is not particularly limited, but is preferably a solution obtained by dissolving an amorphous fluororesin in a perfluoro solvent.
The amorphous fluororesin is not particularly limited. For example, a perfluoro type having a terminal group of PTFE (polytetrafluoroethylene) substituted, and a partial fluorine type having a TFE (tetrafluoroethylene) ) And CTFE (chlorotrifluoroethylene) and the like, and those obtained by copolymerization with hydrocarbon olefins. Examples of commercially available amorphous fluororesins include Cytop (Asahi Glass Co., Ltd.).
The perfluoro solvent is not particularly limited, and examples thereof include HFE (hydrofluoroether), perfluoro tertiary amines, fluorinated alcohols, perfluoroalkyl, and perfluoropolyether. Examples of these commercially available perfluoro solvents include CT-solv (manufactured by Asahi Glass Co., Ltd.).
上記非晶質フッ素樹脂溶液における上記非晶質フッ素樹脂の濃度としては特に限定されないが、好ましい下限は３重量％、好ましい上限は３０重量％である。３重量％未満であると、フッ素不織布を製造したときにフッ素不織布の特徴である高耐薬品性、高耐熱性、及び、低誘電率性の効果が得られないことがあり、３０重量％を超えると、水溶性樹脂水溶液及び上記電解質溶液を添加しても吐出溶液の極性が上がらないことがある。より好ましい下限は５重量％、より好ましい上限は１５重量％である。 The concentration of the amorphous fluororesin in the amorphous fluororesin solution is not particularly limited, but a preferred lower limit is 3% by weight and a preferred upper limit is 30% by weight. If it is less than 3% by weight, the effects of high chemical resistance, high heat resistance, and low dielectric constant, which are the characteristics of the fluorine nonwoven fabric, may not be obtained when the fluorine nonwoven fabric is produced. When exceeding, even if the water-soluble resin aqueous solution and the electrolyte solution are added, the polarity of the discharged solution may not be increased. A more preferred lower limit is 5% by weight, and a more preferred upper limit is 15% by weight.
上記水溶性樹脂水溶液及び上記電解質溶液は、上記吐出溶液の極性を高める目的で用いられる。
上記水溶性樹脂水溶液としては特に限定されず、例えば、ポリビニルアルコール、ポリエチレングリコール、ポリビニルピロリドン、酢酸ビニル、ポリ酢酸ビニル、でんぷん、カルボキシメチルセルロース等の水溶液が挙げられる。なかでも、少量の添加で効果的に働き、後処理による除去のしやすさを考慮すると、ポリビニルアルコール水溶液が好適である。
The water-soluble resin aqueous solution and the electrolyte solution are used for the purpose of increasing the polarity of the discharge solution.
The water-soluble resin aqueous solution is not particularly limited, and examples thereof include aqueous solutions of polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, vinyl acetate, polyvinyl acetate, starch, carboxymethyl cellulose, and the like. Of these, an aqueous polyvinyl alcohol solution is preferable in view of working effectively with a small amount of addition and considering ease of removal by post-treatment.
上記水溶性樹脂水溶液の添加量としては特に限定されないが、非晶質フッ素樹脂溶液１００重量部に対して好ましい下限が１重量部、好ましい上限が３０重量部である。１重量部未満であると、吐出溶液全体の粘度や極性が上がらず電界紡糸のときに吐出溶液が繊維状に噴出せず、液滴となって飛散するために不織布化ができなくなることがあり、３０重量部を超えると、吐出溶液の粘度が高くなりすぎ、電界紡糸のときにノズル中で液詰まりを起こすことがある。より好ましい下限は５重量部、より好ましい上限は１５重量部である。 The addition amount of the water-soluble resin aqueous solution is not particularly limited, but a preferable lower limit is 1 part by weight and a preferable upper limit is 30 parts by weight with respect to 100 parts by weight of the amorphous fluororesin solution. If the amount is less than 1 part by weight, the viscosity and polarity of the entire discharge solution will not increase, and the discharge solution may not be ejected into fibers during electrospinning, and may not be formed into a non-woven fabric due to scattering as droplets. If it exceeds 30 parts by weight, the viscosity of the discharged solution becomes too high, and liquid clogging may occur in the nozzle during electrospinning. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 15 parts by weight.
上記電解質溶液としては特に限定されず、例えば、イオン導電性樹脂溶液、４級アンモニウム塩等のイオン導電性低分子物質の溶液、イオン交換樹脂溶液等が挙げられ、なかでも、高粘度のイオン交換樹脂溶液が好適である。具体的には、スルホン化されたパーフルオロフッ素樹脂溶液が好ましい。 The electrolyte solution is not particularly limited, and examples thereof include ion conductive resin solutions, solutions of ion conductive low molecular substances such as quaternary ammonium salts, ion exchange resin solutions, and the like. Resin solutions are preferred. Specifically, a sulfonated perfluoro fluororesin solution is preferable.
上記電解質溶液の添加量としては特に限定されないが、非晶質フッ素樹脂溶液１００重量部に対して好ましい下限が１重量部、好ましい上限が３０重量部である。１重量部未満であると、吐出溶液全体の粘度や極性が上がらず、電界紡糸のときに吐出溶液が繊維状に噴出せず、液滴となって飛散するために不織布化ができなくなることがあり、３０重量部を超えると、吐出溶液の粘度が高くなりすぎ、電界紡糸のときにノズル中での液詰まりの原因になることがある。より好ましい下限は５重量部、より好ましい上限は１５重量部である。 The addition amount of the electrolyte solution is not particularly limited, but a preferable lower limit is 1 part by weight and a preferable upper limit is 30 parts by weight with respect to 100 parts by weight of the amorphous fluororesin solution. If the amount is less than 1 part by weight, the viscosity and polarity of the entire discharged solution will not increase, and the discharged solution will not be ejected into fibers during electrospinning, so that it becomes impossible to form a non-woven fabric due to scattering as droplets. If the amount exceeds 30 parts by weight, the viscosity of the discharged solution becomes too high, which may cause clogging in the nozzle during electrospinning. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 15 parts by weight.
上記吐出溶液の粘度としては、好ましい下限が８０ｍＰａ・ｓ、好ましい上限が１８０ｍＰａ・ｓである。８０ｍＰａ・ｓ未満であると、電界紡糸のときに液だれを起こしたり、吐出溶液が繊維状に噴出せず、液滴となって飛散するために不織布化ができなくなったりすることがあり、１８０ｍＰａ・ｓを超えると、ノズル中で液詰まりを起こすことがある。より好ましい下限は９０ｍＰａ・ｓ、より好ましい上限は１５０ｍＰａ・ｓである。 As for the viscosity of the discharge solution, a preferable lower limit is 80 mPa · s, and a preferable upper limit is 180 mPa · s. If it is less than 80 mPa · s, dripping may occur at the time of electrospinning, or the discharged solution may not be ejected into a fibrous form and may be dispersed as droplets, making it impossible to form a nonwoven fabric.・ If s is exceeded, liquid clogging may occur in the nozzle. A more preferred lower limit is 90 mPa · s, and a more preferred upper limit is 150 mPa · s.
上記吐出溶液の粘度の調整方法としては、上記水溶性樹脂水溶液を用いる場合には、該水溶性樹脂水溶液自体の添加量により調整してもよいし、従来公知の粘度調整剤を添加する方法によってもよい。 As a method for adjusting the viscosity of the discharge solution, in the case of using the water-soluble resin aqueous solution, it may be adjusted by the amount of the water-soluble resin aqueous solution added itself, or by a method of adding a conventionally known viscosity modifier. Also good.
続いて、上記吐出溶液をシリンジに注入する工程２を行う。
上記シリンジとしては特に限定されず、電界紡糸法を行う際に使用する従来公知のものを用いることができる。
上記シリンジの一端には、上記吐出溶液を吐出するためのノズルが設けられている。
上記ノズルの孔径としては特に限定されないが、好ましい下限はφ３０μｍ、好ましい上限はφ５００μｍである。φ３０μｍ未満であると、ノズル中で吐出溶液が液詰まりを起こすことがあり、φ５００μｍを超えると、φ１０μｍ以下の細いフッ素繊維からなるフッ素不織布を製造できないことがある。より好ましい下限はφ５０μｍ、より好ましい上限はφ３００μｍである。
また、このようなノズルは、上記ノズルと基板との間に電圧を印加することを考慮すると、金属製であることが好ましい。
Then, the
It does not specifically limit as said syringe, The conventionally well-known thing used when performing an electrospinning method can be used.
A nozzle for discharging the discharge solution is provided at one end of the syringe.
Although it does not specifically limit as a hole diameter of the said nozzle, A preferable minimum is (phi) 30 micrometers and a preferable upper limit is (phi) 500 micrometers. If the diameter is less than 30 μm, the discharged solution may clog in the nozzle. If the diameter exceeds 500 μm, a fluorine nonwoven fabric composed of fine fluorine fibers having a diameter of 10 μm or less may not be produced. A more preferable lower limit is φ50 μm, and a more preferable upper limit is φ300 μm.
Further, such a nozzle is preferably made of metal in consideration of applying a voltage between the nozzle and the substrate.
続いて、上記シリンジの一端に設けられたノズルと上記ノズルに対向する基板との間に電圧を印加し、上記吐出溶液を上記ノズルから上記基板上に吐出させるとともに、上記ノズル及び／又は上記基板を揺動させる工程３を行う。 Subsequently, a voltage is applied between a nozzle provided at one end of the syringe and a substrate facing the nozzle to discharge the discharge solution from the nozzle onto the substrate, and the nozzle and / or the substrate. Step 3 of swinging is performed.
上記基板としては特に限定されず、従来公知の基板を使用することができ、上記ノズルと上記基板との間に電圧を印加することを考慮すると、金属板や金属箔であることが好ましい。
なお、上記ノズルと上記基板との間での短絡を防ぐ目的で、上記ノズルと上記基板との間の電界中に、樹脂フィルム等の絶縁性基材を配設してもよい。この場合、上記吐出溶液は、絶縁性基材上に吐出されることとなる。
It does not specifically limit as said board | substrate, A conventionally well-known board | substrate can be used and it is preferable that they are a metal plate and metal foil in consideration of applying a voltage between the said nozzle and the said board | substrate.
For the purpose of preventing a short circuit between the nozzle and the substrate, an insulating base material such as a resin film may be disposed in the electric field between the nozzle and the substrate. In this case, the discharge solution is discharged onto the insulating substrate.
上記ノズルと上記基板との間に印加する電界強度の好ましい下限は３ｋＶ／ｃｍ、好ましい上限は１０ｋＶ／ｃｍである。３ｋＶ／ｃｍ未満であると、吐出溶液のノズルから噴射が起こらないことがあり、１０ｋＶ／ｃｍを超えると、ノズルと基板との間での短絡が発生しやすくなる。より好ましい下限は４ｋＶ／ｃｍ、より好ましい上限は６ｋＶ／ｃｍである。 The preferable lower limit of the electric field strength applied between the nozzle and the substrate is 3 kV / cm, and the preferable upper limit is 10 kV / cm. If it is less than 3 kV / cm, ejection from the nozzle of the discharged solution may not occur. If it exceeds 10 kV / cm, a short circuit between the nozzle and the substrate tends to occur. A more preferred lower limit is 4 kV / cm, and a more preferred upper limit is 6 kV / cm.
上記ノズル及び／又は上記基板は、上記ノズルから吐出される上記吐出溶液が、上記基板上で均一な厚さの集合体となるように揺動させることが好ましい。
具体的には、基板面と平行な方向に上記ノズル及び／又は上記基板を前後運動させる方法、基板面と平行な方向に上記ノズル及び／又は上記基板を回転させる方法等が挙げられる。なお、これらの方法は適宜組み合わせてもよい。
It is preferable that the nozzle and / or the substrate is swung so that the discharge solution discharged from the nozzle becomes an aggregate having a uniform thickness on the substrate.
Specific examples include a method of moving the nozzle and / or the substrate back and forth in a direction parallel to the substrate surface, a method of rotating the nozzle and / or the substrate in a direction parallel to the substrate surface, and the like. In addition, you may combine these methods suitably.
上記工程後、必要に応じて上記基板上に形成した集合体に乾燥処理等を行うことでフッ素不織布を製造することができる。 A fluorine nonwoven fabric can be manufactured by performing a drying process etc. to the aggregate | assembly formed on the said board | substrate as needed after the said process.
本発明のフッ素不織布の製造方法によれば、極性の低い非晶質フッ素樹脂溶液に水溶性樹脂水溶液及び／又は電解質溶液を添加することにより調製される吐出溶液の極性を高めることができ、その結果、電界紡糸法により繊維径の小さいフッ素繊維からなるフッ素不織布を製造することができる。 According to the method for producing a fluorine nonwoven fabric of the present invention, the polarity of a discharge solution prepared by adding a water-soluble resin aqueous solution and / or an electrolyte solution to an amorphous fluororesin solution having a low polarity can be increased. As a result, a fluorine nonwoven fabric made of fluorine fibers having a small fiber diameter can be produced by electrospinning.
上記フッ素不織布の製造方法により製造されてなるフッ素不織布もまた、本発明の１つである。 A fluorine nonwoven fabric produced by the above-described method for producing a fluorine nonwoven fabric is also one aspect of the present invention.
本発明のフッ素不織布は、本発明のフッ素不織布の製造方法により製造されたものであるため、構成するフッ素繊維の繊維径がφ１０μｍ以下の細いものとすることができる。従って、本発明のフッ素不織布を純水フィルターやバグフィルター等に用いると、分離フィルターの精密化を図ることができ、高周波用多層プリント基板や多層ＦＰＣ基材に用いると、基材の厚み低減を図ることができ、燃料電池電解質膜基材に用いると、基材の厚み低減による内部抵抗損失の低減を図ることができる。 Since the fluorine nonwoven fabric of the present invention is produced by the method for producing a fluorine nonwoven fabric of the present invention, the fiber diameter of the constituting fluorine fibers can be made as thin as φ10 μm or less. Therefore, when the fluorine nonwoven fabric of the present invention is used for a pure water filter, a bag filter or the like, the separation filter can be refined, and when used for a high frequency multilayer printed circuit board or a multilayer FPC substrate, the thickness of the substrate can be reduced. When used as a fuel cell electrolyte membrane substrate, the internal resistance loss can be reduced by reducing the thickness of the substrate.
本発明によれば、電界紡糸法により繊維径の小さいフッ素繊維からなるフッ素不織布を製造することができるフッ素不織布の製造方法及びフッ素不織布を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a fluorine nonwoven fabric which can manufacture the fluorine nonwoven fabric which consists of a fluorine fiber with a small fiber diameter by an electrospinning method, and a fluorine nonwoven fabric can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみ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. However, the present invention is not limited to these examples.
（実施例１）
サイトップ（旭硝子社製、固形分９％）１０ｇとパーフルオロ溶剤（旭硝子社製、ＣＴ−ｓｏｌｖ）４ｇとを混合撹拌することにより非晶質フッ素樹脂溶液を調製し、非晶質フッ素樹脂溶液にポリビニルアルコール水溶液（固形分３％）１ｇを添加して吐出溶液を作製した。東機産業社製ＴＶ−１０型粘度計を使用して吐出溶液の粘度を測定すると１２０ｍＰａ・ｓであった。
この吐出溶液を専用のシリンジに入れ、先端内孔径２００μｍの金属ノズルから金属基板上のＰＥＴフィルムに定量吐出させ電界紡糸を行った。金属ノズルと金属基板間には、高圧電源でＡＣ４．５ｋＶ／ｃｍの電圧を印加した。
ノズルからＰＥＴフィルム上に微細な液滴を繊維状に噴射しながら、その後基板を規則的に平行移動させることでＰＥＴフィルム上にフッ素繊維の集合体を形成し、その集合体を１００℃３０分乾燥した後、９０℃の熱水に浸漬して、ポリビニルアルコール成分を除去することによりフッ素不織布を製造した。得られたフッ素不織布の繊維径は約φ３μｍであった。
Example 1
An amorphous fluororesin solution was prepared by mixing and stirring 10 g of Cytop (Asahi Glass Co., Ltd., solid content 9%) and 4 g of a perfluoro solvent (Asahi Glass Co., Ltd., CT-solv). 1 g of an aqueous polyvinyl alcohol solution (solid content: 3%) was added to prepare a discharge solution. It was 120 mPa · s when the viscosity of the discharged solution was measured using a TV-10 viscometer manufactured by Toki Sangyo Co., Ltd.
This discharged solution was put into a dedicated syringe and quantitatively discharged from a metal nozzle having a tip inner hole diameter of 200 μm onto a PET film on a metal substrate for electrospinning. A voltage of AC 4.5 kV / cm was applied between the metal nozzle and the metal substrate by a high voltage power source.
While fine droplets are ejected from the nozzle onto the PET film in the form of fibers, the substrate is then regularly translated to form an aggregate of fluorine fibers on the PET film. After drying, it was immersed in hot water at 90 ° C. to remove the polyvinyl alcohol component to produce a fluorine nonwoven fabric. The fiber diameter of the obtained fluorine nonwoven fabric was about φ3 μm.
（実施例２）
サイトップ（旭硝子社製、固形分９％）１０ｇとパーフルオロ溶剤（旭硝子社製、ＣＴ−ｓｏｌｖ）４ｇとを混合撹拌することにより非晶質フッ素樹脂溶液を調製し、非晶質フッ素樹脂溶液にフッ素系イオン交換樹脂溶液（旭硝子社製フレミオンＦＳＳ、固形分１０％）１ｇを添加して吐出溶液を作製した。東機産業社製ＴＶ−１０型粘度計を使用して吐出溶液の粘度を測定すると１０５ｍＰａ・ｓであった。
この吐出溶液を実施例１と同様の方法で電界紡糸、乾燥、熱水処理を行い、ＰＥＴ基板フィルム上にフッ素不織布を作製した。得られたフッ素不織布の繊維径はφ３μｍ程度であった。
(Example 2)
An amorphous fluororesin solution was prepared by mixing and stirring 10 g of Cytop (Asahi Glass Co., Ltd., solid content 9%) and 4 g of a perfluoro solvent (Asahi Glass Co., Ltd., CT-solv). 1 g of a fluorine-based ion exchange resin solution (Flemion FSS manufactured by Asahi Glass Co., Ltd., solid content: 10%) was added to prepare a discharge solution. Using a Toki Sangyo TV-10 viscometer, the viscosity of the discharged solution was measured to be 105 mPa · s.
This discharged solution was subjected to electrospinning, drying, and hot water treatment in the same manner as in Example 1 to produce a fluorine nonwoven fabric on the PET substrate film. The fiber diameter of the obtained fluorine nonwoven fabric was about φ3 μm.
（比較例１）
サイトップ（旭硝子社製、固形分９％）１０ｇとパーフルオロ溶剤（旭硝子社製、ＣＴ−ｓｏｌｖ）４ｇとを混合撹拌することにより吐出溶液を作製した。東機産業社製ＴＶ−１０型粘度計を使用して吐出溶液の粘度を測定すると７０ｍＰａ・ｓであった。
この吐出溶液を実施例１と同様の方法で電界紡糸を行った。専用のシリンジのノズルからＰＥＴフィルム上に微細な液滴が噴出したが、飛散するのみで繊維状にならず不織布化はできなかった。
(Comparative Example 1)
A discharge solution was prepared by mixing and stirring 10 g of Cytop (Asahi Glass Co., Ltd., solid content 9%) and 4 g of a perfluoro solvent (Asahi Glass Co., Ltd., CT-solv). When the viscosity of the discharged solution was measured using a TV-10 viscometer manufactured by Toki Sangyo Co., Ltd., it was 70 mPa · s.
The discharged solution was subjected to electrospinning in the same manner as in Example 1. Fine droplets spouted onto the PET film from the nozzle of a dedicated syringe, but it was not scattered and could not be made into a non-woven fabric simply by scattering.
（比較例２）
サイトップ（旭硝子社製、固形分９％）１０ｇとパーフルオロ溶剤（旭硝子社製、ＣＴ−ｓｏｌｖ）４ｇとを混合撹拌することにより非晶質フッ素樹脂溶液を調製し、非晶質フッ素樹脂溶液にメタノール１ｇを添加して吐出溶液を作製した。東機産業社製ＴＶ−１０型粘度計を使用して吐出溶液の粘度を測定すると５０ｍＰａ・ｓであった。
この吐出溶液を実施例１と同様の方法で電界紡糸を行った。専用のシリンジのノズルからＰＥＴフィルム上に微細な液滴が噴出したが、飛散するのみで繊維状にならず不織布化はできなかった。
(Comparative Example 2)
An amorphous fluororesin solution was prepared by mixing and stirring 10 g of Cytop (Asahi Glass Co., Ltd., solid content 9%) and 4 g of a perfluoro solvent (Asahi Glass Co., Ltd., CT-solv). 1 g of methanol was added to prepare a discharge solution. When the viscosity of the discharged solution was measured using a TV-10 viscometer manufactured by Toki Sangyo Co., Ltd., it was 50 mPa · s.
The discharged solution was subjected to electrospinning in the same manner as in Example 1. Fine droplets spouted onto the PET film from the nozzle of a dedicated syringe, but it was not scattered and could not be made into a non-woven fabric simply by scattering.
（比較例３）
サイトップ（旭硝子社製、固形分９％）１０ｇとパーフルオロ溶剤（旭硝子社製、ＣＴ−ｓｏｌｖ）４ｇとを混合撹拌することにより非晶質フッ素樹脂溶液を調製し、非晶質フッ素樹脂溶液にポリエチレングリコール１ｇを混合して吐出溶液を作製した。東機産業社製ＴＶ−１０型粘度計を使用して吐出溶液の粘度を測定すると１００ｍＰａ・ｓであった。
この吐出溶液を実施例１と同様の方法で電界紡糸を行ったが、吐出溶液の極性が低く、吐出溶液は専用のシリンジのノズル中で液詰まりを起こしノズルからの吐出ができなかった。
(Comparative Example 3)
An amorphous fluororesin solution was prepared by mixing and stirring 10 g of Cytop (Asahi Glass Co., Ltd., solid content 9%) and 4 g of a perfluoro solvent (Asahi Glass Co., Ltd., CT-solv). 1 g of polyethylene glycol was mixed to prepare a discharge solution. When the viscosity of the discharged solution was measured using a TV-10 viscometer manufactured by Toki Sangyo Co., Ltd., it was 100 mPa · s.
This discharge solution was electrospun in the same manner as in Example 1. However, the polarity of the discharge solution was low, and the discharge solution was clogged in the nozzle of a dedicated syringe and could not be discharged from the nozzle.
本発明によれば、電界紡糸法により繊維径の小さいフッ素繊維からなるフッ素不織布を製造することができるフッ素不織布の製造方法及びフッ素不織布を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a fluorine nonwoven fabric which can manufacture the fluorine nonwoven fabric which consists of a fluorine fiber with a small fiber diameter by an electrospinning method, and a fluorine nonwoven fabric can be provided.
１ シリンジ
２ 吐出溶液
３ ノズル
４ フィルム
５ 基板
1
Claims (5)
非晶質フッ素樹脂溶液に水溶性樹脂水溶液及び／又は電解質溶液を添加し、吐出溶液を調製する工程１と、
前記吐出溶液をシリンジに注入する工程２と、
前記シリンジの一端に設けられたノズルと前記ノズルに対向する基板との間に電圧を印加し、前記吐出溶液を前記ノズルから前記基板上に吐出させるとともに、前記ノズル及び／又は前記基板を揺動させる工程３とを有する
ことを特徴とするフッ素不織布の製造方法。 A method for producing a fluorine nonwoven fabric by electrospinning,
Step 1 of adding a water-soluble resin aqueous solution and / or an electrolyte solution to the amorphous fluororesin solution to prepare a discharge solution;
Step 2 of injecting the discharge solution into a syringe;
A voltage is applied between a nozzle provided at one end of the syringe and a substrate opposite to the nozzle to discharge the discharge solution from the nozzle onto the substrate, and the nozzle and / or the substrate are swung. And a step 3 for producing a fluorine nonwoven fabric characterized by comprising:
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