JPH0397993A - Production of fluorinated fiber paper - Google Patents
Production of fluorinated fiber paperInfo
- Publication number
- JPH0397993A JPH0397993A JP17297089A JP17297089A JPH0397993A JP H0397993 A JPH0397993 A JP H0397993A JP 17297089 A JP17297089 A JP 17297089A JP 17297089 A JP17297089 A JP 17297089A JP H0397993 A JPH0397993 A JP H0397993A
- Authority
- JP
- Japan
- Prior art keywords
- paper
- fiber
- fibers
- fluorine
- undrawn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 230000001788 irregular Effects 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 42
- 239000011737 fluorine Substances 0.000 claims description 42
- 229910052731 fluorine Inorganic materials 0.000 claims description 42
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 13
- 229920000297 Rayon Polymers 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000001112 coagulating effect Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 238000009987 spinning Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 101000606535 Homo sapiens Receptor-type tyrosine-protein phosphatase epsilon Proteins 0.000 description 3
- 102100039665 Receptor-type tyrosine-protein phosphatase epsilon Human genes 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920001780 ECTFE Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910001871 ammonium zinc sulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Abstract
Description
【発明の詳細な説明】
く産業上の利用分野〉
本発明はあらゆる産業分野に於で利用し得るフッ素繊維
紙にして、特にフッ素樹脂の有する耐熱性、耐薬品性、
耐候性、不燃性、電気絶縁性、非粘着性の優れた特性を
保有する紙の製造方法に関するもので、特に断熱材料、
濾過材料、スペーサ、絶縁材料、非粘着材料等として広
く産業分野に用いることができるフッ素繊維紙の製造方
法に関するものである．
〈従来の技術〉く発明が解決しようとする課題〉近年、
合威樹脂の目覚ましい発達とともに、これら合戒樹脂を
主威分とした種々の合或繊維紙が開発され、広く産業分
野に利用されている。中でもフッ素樹脂は優れた耐熱性
と耐薬品性とを有するためそのシート化が検討されてき
ており、フィルム、フエルト、クロス等のシート状加工
物が提案されている。しかしながら、これらシート状加
工物においては、フィルムは通気性、通液性に欠け、フ
ェルトは薄葉物となりにくく、クロスは孔径が大きすぎ
る等の欠点を有しているため、用途面で大きな制約があ
った。このような問題を解決するためにフッ素繊維の紙
状物が望まれているが、フッ素繊維の紙状物は、フッ素
樹脂固有の特性、即ち、表面エネルギーが小さく非粘着
性であるため繊維間結合力が不足し、未だ工業的に生産
されていないのが実状である。Detailed Description of the Invention Industrial Fields of Application The present invention is a fluorine fiber paper that can be used in all industrial fields, and in particular has the advantage of heat resistance, chemical resistance,
This paper relates to a method for producing paper that has excellent properties such as weather resistance, nonflammability, electrical insulation, and non-adhesive properties, and is particularly suitable for insulation materials,
This paper relates to a method for producing fluorine fiber paper, which can be used in a wide range of industrial fields as filtration materials, spacers, insulating materials, non-adhesive materials, etc. <Prior art> Problems to be solved by the invention> In recent years,
With the remarkable development of resins, various fiber papers containing these resins as main ingredients have been developed and are widely used in industrial fields. Among them, fluororesins have excellent heat resistance and chemical resistance, and therefore, their production into sheets has been studied, and sheet-like processed products such as films, felts, and cloths have been proposed. However, these sheet-like processed products have drawbacks such as films lacking air permeability and liquid permeability, felts that are difficult to form into thin sheets, and cloths that have too large pores, so there are significant limitations in terms of use. there were. In order to solve these problems, paper-like materials made of fluorine fibers are desired. However, paper-like materials made of fluorine fibers have the unique characteristics of fluororesin, that is, they have low surface energy and are non-adhesive. The reality is that it lacks binding strength and has not yet been produced industrially.
本発明者らはこれらの問題を解決するため、フッ素繊維
紙の製造方法として特開昭６３ − １６５５９８号お
よび特開昭６３ − １６５５９９号を提案した。In order to solve these problems, the present inventors proposed JP-A-63-165598 and JP-A-63-165599 as a method for producing fluorine fiber paper.
しかしこれらの発明は、未だ数多くの課題を残しており
、例えば特開昭６３ − １６５５９８号では自己接着
性物質を溶解除去するために多量の溶媒を必要とし、洗
浄回数も多く工程数も多くなり非能率的であり、又特開
昭６３ − １６５５９９号では自己接着性物質を溶解
除去した後のシートの強度が弱く加工性で問題を有して
いる。However, these inventions still have many problems to solve. For example, in JP-A No. 63-165598, a large amount of solvent is required to dissolve and remove the self-adhesive substance, and the number of washing steps is also large. It is inefficient, and in JP-A No. 63-165599, the strength of the sheet after the self-adhesive substance has been dissolved and removed is weak, causing problems in processability.
〈課題を解決するための手段〉
本発明は上記のような実情に鑑み種々検討の結果、フッ
素繊維の未延伸糸が、通常の延伸糸とは著るし←物理的
性質を異にする点に着目してなされたものであり、その
概要は以下に記すとおりである。<Means for Solving the Problems> In view of the above-mentioned circumstances, the present invention has been made based on various studies, and it has been found that undrawn yarns of fluorine fibers have significantly different physical properties from ordinary drawn yarns. This was done with a focus on the following, and its outline is as follows.
不規則方向に配向した短繊維状のフッ素繊維により構成
され、該繊維の繊維間が熱融着により結合されているフ
ッ素繊維紙において、フ・ノ素繊維の未延伸糸の短繊維
好ましくは機械的破砕処理によりフィブリル化した未延
伸糸の短繊維を配合した原料を湿式抄造法により抄造し
、乾燥して紙状物を得、これを該繊維の融点以上分解点
未満に加熱し、該繊維の絡合点を融着することを特徴と
するフッ素繊維紙の製造方法である。In a fluorine fiber paper composed of short fluorine fibers oriented in irregular directions, the fibers of which are bonded by heat fusion, short fibers of undrawn yarns of the fluorine fibers are preferably machined. A raw material containing short fibers of undrawn yarn that has been fibrillated by mechanical crushing is made into paper using a wet papermaking method, dried to obtain a paper-like product, and heated to a temperature above the melting point of the fibers but below the decomposition point. This is a method for producing fluorine fiber paper characterized by fusing the entangled points of the fluorine fiber paper.
本発明で用いるフッ素繊維は熱可塑性フッ素樹脂から作
威されるもので、その主戒分としてはポリテトラフルオ
ロエチレン（ＰＴＰＥ） ． テトラフルオロエチレン
・バーフルオロアルキルビニルエーテル共重合体（ＰＦ
Ｅ） ，テトラフルオ口エチレン・ヘキサフルオロブロ
ビレン共重合体（ＦＥＰ） ，テトラフルオ口エチレン
・ヘキサフルオ口プロピレン・バーフルオロアルキルビ
ニルエーテル共重合体（ＥＰＥ） ，テトラフルオロエ
チレン・エチレン共重合体（ＥＴＦＥ） ，ポリビニリ
デンフルオライド（ＰＶＤＦ）ポリクロロトリフルオロ
エチレン（ＰＣＴＦＥ） ，ポリビニルフルオライド（
ＰＶＦ） ， クロロトリフルオ口エチレン・エチレン
共重合体（ＥＣＴＦＥ）等があげられるがフッ素樹脂か
ら作られたものであればこれに限定されず、かつ又、こ
れらフッ素樹脂の２種以上を適当に組合わせて使用する
ことも可能である．またこれらフッ素樹脂の単量体をエ
チレン，プロピレン イソブチレン，スチレン，アクリ
ルニトリルなどと共重合させたものであってもよいが、
特にテトラフルオロエチレン戒分を９０モル％より好ま
しくは９５モル％以上を含有する重合体は汎用のポリテ
トラフルオ口エチレン系重合体として挙げられる。The fluorine fiber used in the present invention is made from thermoplastic fluororesin, and its main constituents are polytetrafluoroethylene (PTPE). Tetrafluoroethylene/barfluoroalkyl vinyl ether copolymer (PF
E), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/hexafluoropropylene/perfluoroalkyl vinyl ether copolymer (EPE), tetrafluoroethylene/ethylene copolymer (ETFE), poly vinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), polyvinyl fluoride (
Examples include PVF), chlorotrifluoroethylene-ethylene copolymer (ECTFE), but are not limited to these as long as they are made from fluororesins, and two or more of these fluororesins may be appropriately combined. It is also possible to use them together. Alternatively, these fluororesin monomers may be copolymerized with ethylene, propylene isobutylene, styrene, acrylonitrile, etc.
In particular, polymers containing 90 mol %, preferably 95 mol % or more of tetrafluoroethylene can be mentioned as general-purpose polytetrafluoroethylene polymers.
これらのフッ素繊維は従来の技術によれば紡糸後延伸処
理して製品化されるが、本発明では未延伸糸を用いる点
に特徴がある。According to conventional techniques, these fluorine fibers are produced by spinning and then drawing, but the present invention is characterized in that undrawn yarns are used.
本発明では上記の如きフッ素繊維の未延伸糸の短繊，維
もしくは機械的破砕処理によりフイブリル化したものを
不規則方向に配合して湿式抄造法により紙状物とするも
のであり、そのため単繊維の場合繊維長は２０ｍ１以下
好ましくはＩｏｎ以下の短繊維状とすることが必要で、
かつその織維径は１００μｍφ以下好ましくは３０μｍ
φ以下であることが望ましい。機械的破砕処理によりフ
ィブリル化したものの場合もこれに準じたものが好まし
い。In the present invention, short fibers, fibers, or fibrillated fibers of undrawn fluorine fibers as described above, or those fibrillated by mechanical crushing are blended in an irregular direction to make a paper-like product by a wet papermaking method. In the case of fibers, the fiber length must be short fibers of 20 m or less, preferably Ion or less,
And the woven fiber diameter is 100μmφ or less, preferably 30μm
It is desirable that it is less than or equal to φ. In the case of fibrillation by mechanical crushing treatment, it is also preferable to use something similar to this.
上記に於いて繊維長が２０１ｌよりも長いと地合が悪く
なり、又、繊維径が１００μｍφより太いとシートが粗
いものとなるので好ましい性状の紙を得難い。本発明で
は上記の如き未延伸フッ素繊維の短繊維もしくは機械的
破砕処理によりフィブリル化したものを配合したフッ素
繊維原料を、通常の湿式抄造法により脱水乾燥してシー
ト化するか、未延伸糸の柔軟性と表面性、密着性あるい
は該未延伸糸中に含まれる紡糸用の助剤の接着性の機能
により、ハンドリング可能な強度を持つシートとなり、
従来のフッ素繊維紙の製法で必要とした自己接着性機能
を有する物質を必要としない。In the above, if the fiber length is longer than 201 liters, the texture will be poor, and if the fiber diameter is thicker than 100 μmφ, the sheet will be rough, making it difficult to obtain paper with desirable properties. In the present invention, a fluorine fiber raw material containing short fibers of undrawn fluorine fibers or those fibrillated by mechanical crushing as described above is dehydrated and dried by a normal wet papermaking method to form a sheet, or Due to the flexibility, surface properties, adhesion properties, or the adhesive properties of the spinning aid contained in the undrawn yarn, the sheet becomes strong enough to be handled.
It does not require a substance with self-adhesive function, which is required in the conventional fluorine fiber paper manufacturing method.
本発明では抄紙に関して、湿式抄造法を用いているが、
抄紙機の種類は何等限定されるものではなく、公知の湿
式抄造法が使用できる。湿式抄造法は水を媒体とするも
のでフッ素繊維の分散や混合は最も容易であり、界面活
性剤や粘着剤等の添加剤により繊維の分散性をコントロ
ールすることが可能であり、均一な地合の紙状物を得る
のに有効である。In the present invention, a wet papermaking method is used for papermaking, but
The type of paper machine is not limited in any way, and any known wet paper making method can be used. The wet papermaking method uses water as a medium and is the easiest way to disperse and mix fluorine fibers, and it is possible to control the dispersibility of the fibers with additives such as surfactants and adhesives, making it possible to create a uniform paper. It is effective to obtain a paper-like material with a high temperature.
製紙手段によりシート化した紙状物はフッ素樹脂の融点
以上分解点未満に加熱して、交絡したフッ素繊維同志を
融着することにより強靭なシートを形威するが、更に製
糸用助剤や製紙用助剤などの不純物を除去するために、
加熱処理や薬品処理の工程を経てフッ素繊維紙を製造す
る．上記に於で加熱の条件や装置は使用するフッ素繊維
の本質的な性質やシートの構成条件および目的とする最
終製品の特性により適宜定められる。The paper-like material made into a sheet by paper-making means is heated to a temperature above the melting point of the fluororesin and below the decomposition point, and the entangled fluorine fibers are fused together to form a strong sheet. To remove impurities such as cleaning agents,
Fluorine fiber paper is manufactured through heat treatment and chemical treatment processes. In the above, the heating conditions and equipment are appropriately determined depending on the essential properties of the fluorine fibers used, the structural conditions of the sheet, and the characteristics of the intended final product.
本発明ではシート形成時にフッ素繊維以外の自己接着機
能を有する物質を用いないので、先行技術のようにフッ
素繊維同志を融着後、自己融着機能を有する物質を除去
する工程が省かれることとなり、工程の大巾な短縮化が
可能である．本発明により得られるフッ素繊維紙の構造
は第１図の拡大図のとおり、フッ素繊維ｌは不規則方向
に配向し、かつ該繊維の絡合点２では熱融着している多
孔質の紙層構造を有することが確認された。In the present invention, since a substance with a self-adhesive function other than fluorine fibers is not used when forming the sheet, the step of removing the substance with a self-adhesive function after fusing the fluorine fibers together as in the prior art is omitted. , it is possible to significantly shorten the process. The structure of the fluorine fiber paper obtained by the present invention is as shown in the enlarged view of FIG. It was confirmed that it had a layered structure.
なお、本発明の実施に際しフッ素繊維の未延伸糸を得る
ための代表的手段は、フッ素樹脂を高分子電解質水溶液
またはビスコースからなるマトリソクス物質中に分散し
、これを凝固して凝固繊維状物にするものである。かか
るマトリックス物質としては高分子電解質又はビスコー
スが適用され、このうち高分子電解質としてはポリメク
クリル酸，アルギン酸，蛋白質，核酸およびこれらのア
ルカリ金属塩などの水溶液が用いられる。マトリックス
物質中のフッ素樹脂は均一に分散している程接合が均一
で品質のよい製品が得られる。In carrying out the present invention, a typical means for obtaining an undrawn yarn of fluorine fibers is to disperse a fluororesin in an aqueous polymer electrolyte solution or a matrix substance made of viscose, and to coagulate it to form a coagulated fibrous material. It is meant to be. Polymer electrolytes or viscose are used as such matrix materials, and among these, aqueous solutions of polymethacrylic acid, alginic acid, proteins, nucleic acids, and alkali metal salts thereof are used as the polymer electrolytes. The more uniformly the fluororesin is dispersed in the matrix material, the more uniform the bonding and the better the quality of the product.
次にフッ素繊維の未延伸糸の製造法についてマトリンク
ス物質としてビスコースを用いた例について詳細に示す
。Next, an example in which viscose is used as the matrix material will be described in detail regarding a method for producing undrawn fluorine fiber yarn.
マトリックス物質がビスコースからなる場合は、紡糸原
液、洗浄、アルカリ処理等の各工程で使用される水や薬
剤は全て純度の高い、不純物の少ないものを使用するこ
とが好ましく、例えば水ではイオン交換水や蒸留水が好
ましい。When the matrix material consists of viscose, it is preferable that the water and chemicals used in each process such as spinning dope, washing, and alkali treatment should be of high purity and contain few impurities. Water and distilled water are preferred.
かかる系を採用することによって繊維切れや毛羽立ちを
制御し、結晶のよく戒長したボイドの少ない繊維を提供
することができる。By employing such a system, fiber breakage and fluffing can be controlled, and fibers with well-defined crystals and fewer voids can be provided.
ビスコースとフフソ樹脂ディスバージョンとの混合液を
凝固浴中に吐出し、凝固させた後これを脱酸処理するか
、脱酸処理後更にアルカリ水に浸漬して処理する．
ＰＴＦＥディスバージョンの場合イオン交換水にＰＴＦ
Ｅを好ましくは２０〜７５％特に好ましくは６０％前後
配合分散させる。分散剤としては、非イオン活性剤また
はアニオン活性剤が使用されるが、特に非イオン活性剤
が好ましい。その配合量はＰＴＦＨに対し３〜１０％で
ある。かかる分散剤としては例えばポリオキシアルキレ
ングリコール系非イオン界面活性剤、アルキルアリルポ
リエーテルアルコール等が用いられる。A mixed solution of viscose and fufuso resin dispersion is discharged into a coagulation bath, and after coagulating, it is deoxidized, or after deoxidation, it is further immersed in alkaline water. In the case of PTFE disversion, add PTF to ion exchange water.
Preferably 20 to 75% of E is blended and dispersed, particularly preferably around 60%. As the dispersant, a nonionic active agent or an anionic active agent is used, and a nonionic active agent is particularly preferred. Its blending amount is 3 to 10% based on PTFH. Examples of such dispersants include polyoxyalkylene glycol nonionic surfactants, alkylaryl polyether alcohols, and the like.
ビスコースはセルロース３〜１５％好ましくは２〜１０
％、特に好ましくは６〜９％で、二硫化炭素は２７〜３
２％、特に好ましくは２８〜３０％の範囲で配合したも
のが適用される。フッ素樹脂の重合度は２００〜６００
が好ましく、特に好ましくは３００〜４００である。Viscose is cellulose 3-15%, preferably 2-10%
%, particularly preferably 6 to 9%, and carbon disulfide is 27 to 3
2%, particularly preferably in the range of 28 to 30%. The degree of polymerization of fluororesin is 200 to 600
is preferable, particularly preferably 300 to 400.
かかるＰＴＦＥディスバージョンとビスコースとを混合
して紡糸原液とするが、紡糸原液中の混合ボリマーでは
ＰＴＦＥは７０〜９６％、特に好ましくは８７〜９３％
の範囲に調整される。紡糸原液中の性
セルロースは製糸例の上から５〜２０％、特に好ましく
は１０〜１５％の濃度である。The PTFE dispersion and viscose are mixed to form a spinning dope, and the mixed polymer in the spinning dope contains 70 to 96% PTFE, particularly preferably 87 to 93%.
is adjusted to the range of The concentration of cellulose in the spinning dope is 5 to 20%, particularly preferably 10 to 15%, from the top of the spinning example.
この原液の粘度は２０ ’Ｃで３０〜１９０ｐｏｉｓｅ
特に好ましくは５ ０ 〜１ ４ ０ｐｏｉｓｅに調整
する。また、原液のディスバージョン分散性を安定化す
るために、更に非イオン活性剤やグリセリン、ヘキサメ
タりん酸塩などの分散剤を添加することができる。この
分散剤の添加量はＰＴＦＥに対し３〜１０％である。The viscosity of this stock solution is 30-190 poise at 20'C.
Particularly preferably, it is adjusted to 50 to 140 poise. Furthermore, in order to stabilize the dispersion properties of the stock solution, a nonionic surfactant, a dispersant such as glycerin, hexametaphosphate, etc. can be further added. The amount of this dispersant added is 3 to 10% based on PTFE.
紡糸原液は次に無機鉱酸や無機ｔ酸塩で構戒される凝固
浴水溶液中に紡出される。かかる無機鉱酸としては硫酸
が好ましいが、硝酸、塩酸、りん酸などが適用される。The spinning dope is then spun into an aqueous coagulation bath solution containing an inorganic mineral acid or an inorganic t-acid. As such an inorganic mineral acid, sulfuric acid is preferable, but nitric acid, hydrochloric acid, phosphoric acid, etc. are applicable.
無機鉱酸塩としては、硫酸アンモン、硫酸亜鉛、硫酸ナ
トリウムが選択される。Ammonium sulfate, zinc sulfate, and sodium sulfate are selected as the inorganic mineral salts.
このような凝固浴に前記した紡糸原液を押し出すと、マ
ルチフィラメントとして凝固する。膨出速度は２０〜５
０ｍ／分程度でゆっくり紡糸することが好ましい。また
精練処理で金属塩を十分に脱落させておけば接合性の向
上に有効である。When the above-described spinning stock solution is extruded into such a coagulation bath, it is coagulated as a multifilament. Swelling speed is 20-5
It is preferable to spin slowly at about 0 m/min. Further, if the metal salt is sufficiently removed by the scouring treatment, it is effective in improving the bondability.
なお、本発明ではガラス繊維、セラミソク繊維等の耐熱
性繊維をフッソ繊維と混抄して実施することもできる。In addition, the present invention can also be carried out by mixing heat-resistant fibers such as glass fibers and ceramic fibers with fluorocarbon fibers.
〈実施例〉
本発明を実施例により更に説明する。なお、配合比率は
すべて重量規準で表わす。<Examples> The present invention will be further explained by examples. All compounding ratios are expressed on a weight basis.
実施例ｌ
ビスコースとポリテトラフルオ口エチレン（ＰＴＦＥ）
エマルジョンとの混合液を紡糸原液として、これをノズ
ルを介して凝固浴中に吐出し（エマルジョン紡糸法）、
凝固した繊維を水洗して得られたＰＴＦＥを主或分とす
る未延伸糸を４ｎ長に力７｝し、０．５％濃度で水中に
分散し、ポリアクリルアミド系の合或分敗剤を加えて抄
紙原料とした。この原料から、湿式抄造法を用いて抄紙
してシート化し、乾燥して坪量１８０ｇ／％のＰＴＰＥ
（フッ素樹脂）を主威分とするハンドリング可能な紙
状物を得た。その後この紙状物を遠赤外線ヒータを用い
て３８０℃で１分間加熱し繊維中のＰＴＦＥ粒子を融着
連続化すると共に、抄紙により得られた繊維同志の交絡
部の融着化を行った。その後電気式恒温器を用いて３８
０℃で３時間加熱してシート中のビスコースを熱分解に
より除去し、第ｌ表に示すような坪量２３０ｇｌｒｄの
白色化したＰ丁ＦＢ １００％のフッ素繊維紙を得た。Example l Viscose and polytetrafluoroethylene (PTFE)
The mixed solution with the emulsion is used as a spinning stock solution, and this is discharged into a coagulation bath through a nozzle (emulsion spinning method).
The undrawn yarn mainly made of PTFE obtained by washing the coagulated fibers with water was made into a 4n length, dispersed in water at a concentration of 0.5%, and treated with a polyacrylamide-based coalescent agent. In addition, it was used as a raw material for paper making. From this raw material, paper is made into a sheet using a wet papermaking method, and dried to produce PTPE with a basis weight of 180g/%.
A handleable paper-like material containing (fluororesin) as the main component was obtained. Thereafter, this paper-like material was heated at 380° C. for 1 minute using a far-infrared heater to fuse and continuously fuse the PTFE particles in the fibers, as well as to fuse the intertwined portions of the fibers obtained by paper making. Then, using an electric thermostat,
The viscose in the sheet was removed by thermal decomposition by heating at 0° C. for 3 hours to obtain a whitened 100% P-cho FB fluorine fiber paper with a basis weight of 230 glrd as shown in Table 1.
実施例２
エマルジョン紡糸法によって得たＰＴＦＥを主成分とす
る４ｍｍ長にカソトしたＰＴＦＥ未延伸繊維５０％と延
伸加工し６Ｉ長にカントしたＰＴＦＥ繊維５０％とを配
合し、水中で撹拌混合した原料を用いて、湿式抄造法に
より抄造し、シート化して乾燥し、第１表に示すような
乾紙坪ｉｔ２００ｇ／％のハンドリング可能な紙状物を
得た。その後この紙状物を遠赤外線ヒーターを用いて４
００℃で１分間加熱処理し、更に電気式恒温器を用いて
３８０℃で２時間加熱処理し第１表に示すような坪量２
３５ｇ／ ｎ｛のＰＴＦＥ １００％のフッ素繊維紙を
得た。Example 2 A raw material made by blending 50% undrawn PTFE fibers obtained by an emulsion spinning method and cast to a length of 4 mm, and 50% PTFE fibers drawn and canted to a length of 6I, and stirring and mixing in water. The paper was made into a sheet by a wet papermaking method, and dried to obtain a handleable paper having a dry basis weight of 200 g/% as shown in Table 1. After that, this paper-like material is heated using a far-infrared heater.
Heat treated at 00℃ for 1 minute, and further heated at 380℃ for 2 hours using an electric thermostat to obtain a basis weight of 2 as shown in Table 1.
35 g/n{of PTFE 100% fluorofiber paper was obtained.
実施例３
エマルジョン紡糸法によって得たＰＴＦεを主成分とす
る未延伸糸を６ＩｌＯＩ長にカー／ ｝し、１％濃度で
水中に分散した後、リファイナー処理により該繊維を破
砕しフィブリル化した繊維状物を得た。この原料を更に
希釈して、合威粘剤を加え湿式抄造法を用いてシート化
し乾燥して第１表に示すような坪１１５０ｇ／ｍのＰＴ
ＦＥを主成分とするハンドリング可能な紙状物を得た。Example 3 An undrawn yarn mainly composed of PTFε obtained by an emulsion spinning method was curdred to a length of 6IlOI, dispersed in water at a concentration of 1%, and then crushed by a refiner treatment to form a fibrillated fiber. I got something. This raw material is further diluted, and a adhesive is added to form a sheet using a wet papermaking method, which is then dried to produce a PT with a tsubo of 1150 g/m as shown in Table 1.
A handleable paper-like material containing FE as a main component was obtained.
その後この紙状物を遠赤外線ヒーターを用いて３８０℃
で１分間加熱処理し、更に電気式恒温器を用いて３８０
℃で３時間加熱処理し第１表に示すような坪量］．９０
ｇ／ｎ｛のＰＴＰＥ １００％のフッ素繊維紙を得た．
実施例４
エマルジョン紡糸法によって得たＰＴＦＥを主戒分とす
る未延伸糸を６ｍＩｌ長にカントし、１％濃度で水中に
分敗した後、リファイナー処理により該繊維を破砕しフ
ィブリル化した繊維状物５０％と、延伸加工し６ｍＩＩ
Ｉ長にカントしたＰＴＦＥ繊維５０％とを配合し水中で
撹拌混合した原料を用いて、湿式抄造法により第１表に
示すような乾紙坪量１８０ｇ／ｎ（のハンドリング可能
な紙状物を得た。その後この紙状物を遠赤外線ヒーター
を用いて３８０℃で１分間加熱処理し、更に電気式恒温
器を用いて３８０℃で２時間加熱処理し第１表に示すよ
うな坪ｆｆｉ２ｉ０ ｇ／ｄのＰＴＦＥ １００％のフ
ッ素繊維紙を得た。After that, this paper-like material was heated to 380℃ using a far-infrared heater.
Heat treatment for 1 minute at 380℃ using an electric thermostat.
After heating at ℃ for 3 hours, the basis weight is as shown in Table 1]. 90
A 100% PTPE fluorine fiber paper of g/n{ was obtained. Example 4 An undrawn yarn containing PTFE as the main component obtained by an emulsion spinning method was canted to a length of 6 ml, separated into water at a concentration of 1%, and then crushed by a refiner treatment to form a fibrillated fiber. 6mII after stretching and 50%
Using a raw material mixed with 50% PTFE fibers canted in I length and stirred in water, a handleable paper-like material with a dry paper basis weight of 180 g/n (as shown in Table 1) was produced by a wet papermaking method. Thereafter, this paper-like material was heat-treated at 380°C for 1 minute using a far-infrared heater, and further heat-treated at 380°C for 2 hours using an electric incubator to obtain a tsubo ffi2i0 g as shown in Table 1. /d of 100% PTFE fluorine fiber paper was obtained.
第
ｌ
表
第１表から明らかなとおり本発明による実施例１〜４の
フッ素繊維紙は、いずれもシート状物として所望の引４
張り強度および伸びを有するものであることが確認され
た。Table 1 As is clear from Table 1, the fluorine fiber papers of Examples 1 to 4 according to the present invention all had a desired tensile strength as a sheet material.
It was confirmed that the material had high tensile strength and elongation.
〈発明の効果〉
本発明はフッ素繊維紙を製造するに際し、フッ素繊維の
未延伸糸短繊維を抄紙原料中に配合することにより、抄
造、乾燥後繊維間を加熱融着を可徒ならしめ、これによ
り、別に自己融着機能を有する物質の添加や除去に伴な
う製造工程を不要ならしめ、コストダウンを実現すると
ともに、フッ素繊維自体の有する耐熱性、耐薬品性、不
燃性、電気絶縁性、非粘着性等の優れた機能をそのまま
生かしたフッ素繊維紙を得ることができる。<Effects of the Invention> When producing fluorine fiber paper, the present invention makes it possible to heat-fuse the fibers after papermaking and drying by blending undrawn short fibers of fluorine fibers into papermaking raw materials. This eliminates the need for manufacturing processes that involve the addition and removal of substances that have a self-bonding function, and reduces costs.In addition, the fluorine fiber itself has heat resistance, chemical resistance, nonflammability, and electrical insulation properties. It is possible to obtain fluorine fiber paper that takes advantage of excellent functions such as elasticity and non-adhesiveness.
第１図は本発明のフッ素繊維紙の表面拡大図である。 １・・・フッ素繊維、２・・・融着部 FIG. 1 is an enlarged view of the surface of the fluorine fiber paper of the present invention. 1... Fluorine fiber, 2... Fusion part
Claims (1)
構成され、該繊維の繊維間が熱融着により結合されてい
るフッ素繊維紙において、フッ素繊維の未延伸糸の短繊
維を配合した抄紙原料を湿式抄造法により抄造し、乾燥
して紙状物を得、これを該繊維の融点以上分解点未満に
加熱し、該繊維の絡合点を融着することを特徴とするフ
ッ素繊維紙の製造方法 ２）フッ素繊維の未延伸糸の短繊維として機械的破砕処
理によりフィブリル化したものとした請求項１記載のフ
ッ素繊維紙の製造方法[Claims] 1) Fluorine fiber paper composed of short fluorine fibers oriented in irregular directions, the fibers of which are bonded by heat fusion, in which undrawn yarns of the fluorine fibers are bonded together. A papermaking raw material containing short fibers is made by a wet papermaking method, dried to obtain a paper-like product, and heated to a temperature above the melting point of the fibers and below the decomposition point to fuse the entanglement points of the fibers. Characteristic method for producing fluorine fiber paper 2) The method for producing fluorine fiber paper according to claim 1, wherein short fibers of undrawn fluorine fiber yarn are fibrillated by mechanical crushing treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17297089A JPH0397993A (en) | 1989-07-06 | 1989-07-06 | Production of fluorinated fiber paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17297089A JPH0397993A (en) | 1989-07-06 | 1989-07-06 | Production of fluorinated fiber paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0397993A true JPH0397993A (en) | 1991-04-23 |
Family
ID=15951736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17297089A Pending JPH0397993A (en) | 1989-07-06 | 1989-07-06 | Production of fluorinated fiber paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0397993A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05295691A (en) * | 1992-04-17 | 1993-11-09 | Tomoegawa Paper Co Ltd | Electrically conductive fluorine-based fiber paper and its production |
| US7221571B2 (en) | 2003-08-28 | 2007-05-22 | Fujitsu Limited | Package unit, printed board having the same, and electronic apparatus having the printed board |
| US10998488B2 (en) | 2012-10-31 | 2021-05-04 | Valqua, Ltd. | Piezoelectric stack |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52114710A (en) * | 1976-03-23 | 1977-09-26 | Daikin Ind Ltd | Process for making paper mixed with polytetrafluoroethylene |
| JPS63165598A (en) * | 1986-12-25 | 1988-07-08 | 株式会社 巴川製紙所 | Fluorocarbon fiber paper and its production |
-
1989
- 1989-07-06 JP JP17297089A patent/JPH0397993A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52114710A (en) * | 1976-03-23 | 1977-09-26 | Daikin Ind Ltd | Process for making paper mixed with polytetrafluoroethylene |
| JPS63165598A (en) * | 1986-12-25 | 1988-07-08 | 株式会社 巴川製紙所 | Fluorocarbon fiber paper and its production |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05295691A (en) * | 1992-04-17 | 1993-11-09 | Tomoegawa Paper Co Ltd | Electrically conductive fluorine-based fiber paper and its production |
| US7221571B2 (en) | 2003-08-28 | 2007-05-22 | Fujitsu Limited | Package unit, printed board having the same, and electronic apparatus having the printed board |
| US10998488B2 (en) | 2012-10-31 | 2021-05-04 | Valqua, Ltd. | Piezoelectric stack |
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