JPS63101430A - Production of fluorocarbon resin composite composition - Google Patents
Production of fluorocarbon resin composite compositionInfo
- Publication number
- JPS63101430A JPS63101430A JP24719786A JP24719786A JPS63101430A JP S63101430 A JPS63101430 A JP S63101430A JP 24719786 A JP24719786 A JP 24719786A JP 24719786 A JP24719786 A JP 24719786A JP S63101430 A JPS63101430 A JP S63101430A
- Authority
- JP
- Japan
- Prior art keywords
- dispersion
- composite composition
- resin
- polytetrafluoroethylene resin
- mixture
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000805 composite resin Substances 0.000 title 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 31
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000010556 emulsion polymerization method Methods 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 18
- 239000007787 solid Substances 0.000 abstract description 4
- 238000001226 reprecipitation Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005185 salting out Methods 0.000 abstract description 2
- 150000005826 halohydrocarbons Chemical class 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920001973 fluoroelastomer Polymers 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 229920013648 Perbunan Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229940024463 silicone emollient and protective product Drugs 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、フッ素樹脂複合組成物の製造法に関する。更
に詳しくは、ポリテトラフルオロエチレン樹脂と他の高
分子物質とからなるフッ素樹脂複合組成物の製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a fluororesin composite composition. More specifically, the present invention relates to a method for producing a fluororesin composite composition comprising a polytetrafluoroethylene resin and other polymeric substances.
（従来の技術〕
従来、乳化重合法により製造されたポリテトラフルオロ
エチレン樹脂微粉末を用いて他の物質との複合組成物を
製造する際、その分散性に問題がみられた。例えば、こ
の樹脂微粉末に顔料や染料を混ぜて着色する場合でも、
溶媒などを使用して振どう、撹拌混合しても、そこに形
成された混合物は目で見てすぐに分る程の不均一な分散
状態のものしか得られていない。同様に、他の高分子物
質との混合の場合にも、あまり良い分散は望めないのが
実情である。(Prior Art) Conventionally, when producing a composite composition with other substances using polytetrafluoroethylene resin fine powder produced by an emulsion polymerization method, problems have been observed in its dispersibility. Even when coloring by mixing pigments or dyes with fine resin powder,
Even if the mixture is shaken or stirred using a solvent or the like, the resulting mixture is only in a non-uniform dispersion state that is easily visible to the naked eye. Similarly, when mixed with other polymeric substances, the reality is that very good dispersion cannot be expected.
これは、市販の乳化重合法によるポリテトラフルオロエ
チレン樹脂微粉末（ファインパウダー）が約０・３μの
一次粒子が凝集した平均粒程約５００μの粒子を形成し
ており、この樹脂が濡れ難いこととも合まって、内部に
迄混合成分が浸透しないためと考えられる。This is because commercially available polytetrafluoroethylene resin fine powder (fine powder) produced by the emulsion polymerization method forms particles with an average particle size of approximately 500μ, which is an agglomeration of primary particles of approximately 0.3μ, and this resin is difficult to wet. This is thought to be due to the fact that the mixed components do not penetrate into the interior.
こうした点を改善するためには、このファインパウダー
を平均粒径が数１０μ以下、好ましくは数μ以下となる
ように更に微粒子化させる必要がある。しかしながら、
通常用いられている微粒子化方法、例えばドライまたは
ウェットでの粉砕では粒子同志が融着し、せん断によっ
て結晶質の繊維を生成させるといった欠点を生み出す。In order to improve these points, it is necessary to further refine the fine powder so that the average particle size is several tens of microns or less, preferably several microns or less. however,
Commonly used micronization methods, such as dry or wet grinding, have the disadvantage that particles fuse together and shear produces crystalline fibers.
このようなことは、ファインパウダーをオープンロール
やニーダ−などで混練するときに顕著にみられ、従って
このような方法でも良好な分散物が得られ難い。This phenomenon is most noticeable when fine powders are kneaded using open rolls, kneaders, etc., and it is therefore difficult to obtain a good dispersion even with such methods.
また、他の方法として、予め一次粒子オーダーになって
いるディスパージョンを分散させることも考えられるが
、この方法により単に撹拌しながら混合していっても、
ディスパージョンが融着、凝集を起こして造粒されるた
め、有効な分散混合物を得るには至らない。Another method is to disperse a dispersion that is on the order of primary particles, but even if this method is simply mixed while stirring,
Since the dispersion is fused and aggregated and granulated, it is not possible to obtain an effective dispersion mixture.
そこで、本発明考らは、−次粒子オーダーを形成してい
るポリテトラフルオロエチレン樹脂ディスパージョンを
そのまま用いる上記後者の方法において、混合時にディ
スパージョンが融着、凝集を生ゼしぬないような条件を
求めて種々検討を重ねた結果、他の高分子物質のディス
パージョンまたは溶液とポリテトラフルオロエチレン樹
脂の融着点以下の温度で混合し、フッ素樹脂複合組成物
を形成させることにより、かかる課題が効果的に解決さ
れることを見出した。Therefore, in the latter method described above, in which the polytetrafluoroethylene resin dispersion forming the -order particle order is used as it is, the present invention aims to prevent the dispersion from fusing and aggregating during mixing. As a result of various studies in search of conditions, we found that by mixing a dispersion or solution of another polymer with a polytetrafluoroethylene resin at a temperature below the melting point to form a fluororesin composite composition. We have found that the problem can be effectively solved.
従って、本発明はフッ素樹脂複合組成物の製造法に係り
、フッ素樹脂複合組成物の製造は、ポリテトラフルオロ
エチレン樹脂ディスパージョンおよび他の高分子物質の
ディスパージョンまたは溶液を、ポリテトラプルオロエ
チレン樹脂の融着点以下の温度で混合した後固型物とし
て取得することにより行われる。Therefore, the present invention relates to a method for producing a fluororesin composite composition, and the production of the fluororesin composite composition involves mixing a polytetrafluoroethylene resin dispersion and a dispersion or solution of other polymeric substances with polytetrafluoroethylene This is done by mixing at a temperature below the melting point of the resin and then obtaining a solid product.
ポリテトラフルオロエチレン樹脂ディスパージョンとし
ては、一般に乳化重合法により製造された水性ディスパ
ージョンそれ自体が用いられるが、ポリテトラフルオロ
エチレン樹脂のファインパウダーを塩化メチレン、トリ
クロルトリフルオロエタンなどのハロゲン化炭化水素溶
媒またはそれらとメチルエチルケトンなどの混合溶媒な
どの濡れ易い溶媒中に加え、パウダー中にこれらの溶媒
を浸透させた後、ポリテトラフルオロエチレン樹脂の融
着点以下に冷却しながらそこにフッ素系非イオン界面活
性剤などを加え、ホモジナイザーなどで撹拌して微粒子
化させた混合液としても用いることができる。As a polytetrafluoroethylene resin dispersion, an aqueous dispersion itself produced by an emulsion polymerization method is generally used, but a fine powder of polytetrafluoroethylene resin is mixed with a halogenated hydrocarbon such as methylene chloride or trichlorotrifluoroethane. In addition to a solvent or a mixed solvent thereof such as methyl ethyl ketone or other easily wettable solvent, these solvents are infiltrated into the powder, and then a fluorine-based non-ion is added thereto while cooling to below the melting point of the polytetrafluoroethylene resin. It can also be used as a mixed solution in which a surfactant or the like is added and the mixture is stirred with a homogenizer or the like to form fine particles.
これと混合される他の高分子物質としては、複合組成物
の使用目的に応じて１種々のゴムまたは樹脂が用いられ
る０例えば、耐薬品性、耐熱性、ガスバリヤ−性などが
求められる場合にはフッ素ゴムなどが、また酸素富化膜
などに使用される場合にはシリコーン系高分子などがそ
れぞれ用いられ、これ以外にもＮＢＲ，ブチルゴム、ポ
リイミド便脂などが適宜用いられる。As other polymeric substances to be mixed with this, various rubbers or resins are used depending on the purpose of use of the composite composition.For example, when chemical resistance, heat resistance, gas barrier properties, etc. are required. For example, fluororubber is used, and when used for an oxygen enrichment membrane, a silicone polymer is used, and in addition to these, NBR, butyl rubber, polyimide toilet fat, etc. are used as appropriate.
これら雨音の混合は、ポリテトラプルオロエチレン樹脂
の融着点である約１５℃（結晶化度によっても変化する
）以下、好ましくは約１０℃以下の温度で行われる。こ
れ以上の温度、例えば室温条件下で混合が行われると、
融着、凝集が起り、この複合組成物から成形される成形
品も均質な構造を有するものが得られない。These rain sounds are mixed at a temperature below about 15°C (which varies depending on the degree of crystallinity), which is the melting point of polytetrafluoroethylene resin, preferably at about 10°C or below. If mixing is carried out at higher temperatures, e.g. room temperature conditions,
Fusion and aggregation occur, and molded articles made from this composite composition cannot have a homogeneous structure.
混合物からの固型物の取得は、用いられたディスパージ
ョン、溶液などの性質に応じて、再沈法、塩析法、乾燥
法などにより行われる。A solid substance is obtained from a mixture by a reprecipitation method, a salting-out method, a drying method, etc. depending on the properties of the dispersion, solution, etc. used.
固型物たるフッ素樹脂複合組成物は、一般に体積分率で
ポリテトラフルオロエチレン樹脂が約２０〜８０％、ま
た他の高分子物質が約８０〜２０％を占めるような割合
で用いられ、この他に各種充填剤、着色剤、滑剤などが
適宜添加されて用いられる。The solid fluororesin composite composition is generally used in a volume fraction of about 20 to 80% polytetrafluoroethylene resin and about 80 to 20% of other polymeric substances. In addition, various fillers, colorants, lubricants, etc. may be added as appropriate.
ポリテトラフルオロエチレン樹脂と他の高分子物質とを
液状媒体中で混合するに際し、混合温度をポリテトラフ
ルオロエチレン樹脂の融着点以下に保持することにより
、良好な分散状態のフッ素樹脂複合組成物を得ることが
でき、この複合組成物に圧縮、押呂、延伸、圧延、焼成
などの手段を適宜組合せて適用することにより、均一な
多孔質構造を有する成形品を得ることができる。かかる
成形品は、ポリテトラフルオロエチレン樹脂の特性を有
するばかりではなく、均一な多孔質構造による形状保持
、補強効果などをも有しているため、高機能性の複合材
料を提供することができる。By keeping the mixing temperature below the melting point of the polytetrafluoroethylene resin when mixing the polytetrafluoroethylene resin and other polymeric substances in a liquid medium, a fluororesin composite composition with a good dispersion state can be obtained. A molded article having a uniform porous structure can be obtained by applying appropriate combinations of compression, pressing, stretching, rolling, sintering, etc. to this composite composition. Such molded products not only have the properties of polytetrafluoroethylene resin, but also have shape retention and reinforcing effects due to their uniform porous structure, making it possible to provide highly functional composite materials. .
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例１
ポリテトラフルオロエチレン樹脂（ＰＴＦＥ）ファイン
ハウダー（三井・デュポンフロロケミカル’ＩＩ 品テ
フロン６−Ｊ、平均粒径約５００μ）１３２ｇに、トリ
クロルトリフルオロエタン（同社製品フレオンＴＦ）−
メチルエチルケトン（１：１）混合溶媒４８０ｍΩを加
え、液温が５℃になるように冷却した。これに、フッ素
系非イオン界面活性剤（旭硝子製品サーフロンＳ−３８
１） １．１ｇを加えた後、ホモジナイザー（特殊機化
工業ｆｉＴＫホモミキサー）で撹拌しながら粉砕し、３
００メツシユバス（粒径５０μ）の粒子を形成させた。Example 1 To 132 g of polytetrafluoroethylene resin (PTFE) fine howder (Mitsui DuPont Fluorochemical 'II product Teflon 6-J, average particle size of about 500 μm), trichlorotrifluoroethane (Freon TF, a product of the same company) was added.
A mixed solvent of methyl ethyl ketone (1:1) of 480 mΩ was added, and the mixture was cooled to a temperature of 5°C. In addition, a fluorine-based nonionic surfactant (Asahi Glass Surflon S-38
1) After adding 1.1 g, pulverize while stirring with a homogenizer (Tokushu Kika Kogyo fiTK Homo Mixer), and
Particles of 0.00 mesh bath (particle size 50μ) were formed.
この状態のまま、カーボンブラック６ｇおよびＮＢＲ（
バイエルジャパン製品Ｐｅｒｂｕｎａｎ Ｎ３８０７
ＮＳ）３５ｇを添加したメチルエチルケトン溶液２６０
＋ｎ Ｑを撹拌下に加え、液温を５℃に保った後メタノ
ールを徐々に加えて再沈させ、乾燥して黒色の小塊を得
た。In this state, add 6g of carbon black and NBR (
Bayer Japan product Perbunan N3807
NS) 260 methyl ethyl ketone solution added with 35 g
+n Q was added under stirring, and after keeping the liquid temperature at 5° C., methanol was gradually added to cause reprecipitation, and the mixture was dried to obtain a black lump.
この黒色小塊たるフッ素樹脂複合組成物を、６０ｋｇｆ
／ａ＃で厚さ１ｍｍの板状体にプレスした後、ロールで
厚さ５０μのフィルムに圧延し、その延伸状態を保った
まま１５０℃でプレスした。60 kgf of this fluororesin composite composition in the form of small black lumps
/a# to form a plate with a thickness of 1 mm, and then rolled into a film with a thickness of 50 μm using rolls, and pressed at 150° C. while maintaining the stretched state.
比較例１
実施例１における処理温度の５℃を、室温（２５℃）に
変更した。Comparative Example 1 The treatment temperature of 5°C in Example 1 was changed to room temperature (25°C).
上記実施例１および比較例１について比較すると、黒色
小塊の段階では、比較例１のものでは塊中に白色の粒（
粒径約１００〜５００μ）が存在したが。Comparing Example 1 and Comparative Example 1 above, at the stage of black small lumps, in Comparative Example 1 white particles (
Particle size of approximately 100-500μ) was present.
実施例１のものには光学顕微鏡観察でもそのような粒が
確認されず、また成形試料の段階では、比較例１のもの
には幅約１００μの白い筋が何本も確認されたが、実施
例１のものにはそれが確認できなかった。No such grains were observed in the sample of Example 1 even when observed with an optical microscope, and in the molded sample stage, many white streaks with a width of approximately 100 μm were observed in the sample of Comparative Example 1. This could not be confirmed in Example 1.
実施例２
ＰＴＦＥディスパージョン（三井・デュポンフロロケミ
カル製品テフロン３０−Ｊ）２２０ｇを、予め液温を５
℃にしたフッ素ゴム（デュポン社製品パイトンＧＦ）の
メチル−ｎ−へキシルケトン溶液（ゴム７６．４ｇを溶
媒７６０ｍ Ｑに溶解させた溶液）中に、ゆるやかに撹
拌しながら徐々に加え、その後液温を５℃に保ちながら
エタノールを加えて再沈させ、エタノールで数回洗浄し
た後乾燥した。Example 2 220 g of PTFE dispersion (Mitsui DuPont Fluorochemical product Teflon 30-J) was preliminarily heated to a liquid temperature of 5.
A solution of fluororubber (DuPont product Paiton GF) in methyl-n-hexyl ketone (a solution in which 76.4 g of rubber was dissolved in 760 mQ of solvent) was gradually added with gentle stirring, and then the temperature of the liquid was increased. The mixture was reprecipitated by adding ethanol while keeping it at 5°C, washed several times with ethanol, and then dried.
得られた白色粉体たるフッ素樹脂複合組成物を、６０ｋ
ｇｆ／ ｃｉで円柱状に予備成形し、次いで押出圧力３
．６トン／ｄで厚さ１ｍｍのシートに押出した。これを
、３ 、５ｃｍ／秒の延伸速度で１００％延伸し、延伸
状態を保ったまま１８０℃でプレスして、厚さ０．５ｍ
ｍのシー゛ト状物を得た。The obtained white powder fluororesin composite composition was heated to 60k.
Preform into cylinder shape at gf/ci, then extrusion pressure 3
．． It was extruded into a sheet with a thickness of 1 mm at 6 tons/d. This was stretched 100% at a stretching speed of 3.5 cm/sec, and pressed at 180°C while maintaining the stretched state to a thickness of 0.5 m.
A sheet-like material of m was obtained.
比較例２
実施例２における処理温度の５℃を、室温（２５℃）に
変更した。Comparative Example 2 The treatment temperature of 5°C in Example 2 was changed to room temperature (25°C).
上記実施例２および比較例２について比較すると、混合
、再沈段階では、比較例２のものに混合時にディスパー
ジョンの凝集がみられ、再沈したものは粉体とはならず
塊となる現象がみられ、また成形試料の段階では、アセ
トンでフッ素ゴムを抽出し、抽出残の試料を走査型電子
顕微鏡で観察すると、実施例２のものは連結部と繊維部
とからなるＰＴＦＥ多孔質構造を呈したが、比較例２の
ものからは均質なものが得られなかった。Comparing Example 2 and Comparative Example 2 above, in the mixing and re-sedimentation stages, agglomeration of the dispersion was observed in Comparative Example 2 during mixing, and the re-sedimented material did not become a powder but became a lump. Furthermore, when the fluororubber was extracted with acetone at the molded sample stage and the extracted sample was observed with a scanning electron microscope, it was found that the sample of Example 2 had a PTFE porous structure consisting of connecting parts and fiber parts. However, a homogeneous product could not be obtained from Comparative Example 2.
実施例３
ＰＴＦＥディスパージョン（テフロン３０−Ｊ）１８３
ｇを、予め液温を５℃にしたＮＢＲ系ラテックス（日本
ゼオン製品Ｎ１ｐｏ１１５６１）２６８ｇ中に、ゆるや
かに撹拌しながら徐々に加え、その後液温を５℃に保ち
ながらメタノールを加えて再沈させ、メタノールで数回
洗浄した後乾燥した。Example 3 PTFE dispersion (Teflon 30-J) 183
g was gradually added to 268 g of NBR latex (Nippon Zeon product N1po11561) whose liquid temperature had been set to 5°C in advance with gentle stirring, and then reprecipitated by adding methanol while maintaining the liquid temperature at 5°C. It was washed several times with methanol and then dried.
得られた白色粉体たるフッ素樹脂複合組成物から、実施
例２と同様にして厚さ０．５ｎｕｎのシート状物を成形
し、成形試料についてメチルエチルケトンによるＮＢＲ
ゴム抽出を行ない、走査型電子顕微鏡で観察を行なうと
、連結部と繊維部とからなるＰＴＦＥ多孔質構造を呈し
ていることが確認された。From the obtained fluororesin composite composition as a white powder, a sheet-like product with a thickness of 0.5 nm was molded in the same manner as in Example 2, and the molded sample was subjected to NBR with methyl ethyl ketone.
When the rubber was extracted and observed with a scanning electron microscope, it was confirmed that it had a porous PTFE structure consisting of connecting parts and fiber parts.
実施例４
ＰＴＦＥディスパージョン（テフロン３Ｏ−Ｊ） ２５
７ｇを、予め液温を５℃にしたポリジメチルシロキサン
（東しシリコーン製品Ｓ旧１０）の塩化メチレン溶液（
ポリジメチルシロキサン３０ｇを溶媒１２０ｍΩに溶解
させた溶液）中に、ゆるやかに撹拌しながら徐々に加え
、その後液温を５℃に保ちながらエタノールを加えて再
沈させ、エタノールで数回洗浄した後乾燥した。Example 4 PTFE dispersion (Teflon 3O-J) 25
7g in a methylene chloride solution of polydimethylsiloxane (Toshi Silicone Products S former 10) whose liquid temperature was pre-heated to 5°C (
Add slowly to a solution of 30 g of polydimethylsiloxane dissolved in 120 mΩ of solvent with gentle stirring, then reprecipitate by adding ethanol while keeping the liquid temperature at 5°C, wash with ethanol several times, and then dry. did.
得られた白色粉体たるフッ素樹脂複合組成物を。The resulting white powder is a fluororesin composite composition.
実施例２と同様に予備成形、押出および延伸し。Preforming, extrusion and stretching were carried out in the same manner as in Example 2.
延伸状態を保ったまま３５０℃で１０分間焼成し、厚さ
１ｍｍのシート状物を得た。この成形試料についてメチ
ルエチルケトンによるポリジメチルシロキサン抽出を行
ない、走査型電子顕微ｅｔａｓを行なうと、連結部と繊
維部とからなるＰＴＦＥ多孔質構造を呈していることが
確認された。It was fired at 350° C. for 10 minutes while maintaining the stretched state to obtain a sheet-like product with a thickness of 1 mm. When this molded sample was subjected to polydimethylsiloxane extraction using methyl ethyl ketone and subjected to scanning electron microscopy etas, it was confirmed that it had a PTFE porous structure consisting of connecting parts and fiber parts.
Claims (1)
および他の高分子物質のディスパージョンまたは溶液を
、ポリテトラフルオロエチレン樹脂の融着点以下の温度
で混合した後固型物として取得することを特徴とするフ
ッ素樹脂複合組成物の製造法。 ２、ポリテトラフルオロエチレン樹脂ディスパージョン
として、乳化重合法により製造された水性ディスパージ
ョンが用いられる特許請求の範囲第１項記載のフッ素樹
脂複合組成物の製造法。 ３、ポリテトラフルオロエチレン樹脂ディスパージョン
として、ポリテトラフルオロエチレン樹脂ファインパウ
ダーにそれを濡らし易い溶媒を加え、該樹脂の融着点以
下に冷却しながら、フッ素系非イオン界面活性剤の存在
下で微粒子化させた混合液が用いられる特許請求の範囲
第１項記載のフッ素樹脂複合組成物の製造法。 ４、約１０℃以下の温度で混合が行われる特許請求の範
囲第１項記載のフッ素樹脂複合組成物の製造法。[Claims] 1. A solid product is obtained after mixing a polytetrafluoroethylene resin dispersion and a dispersion or solution of other polymeric substances at a temperature below the melting point of the polytetrafluoroethylene resin. A method for producing a fluororesin composite composition, characterized by: 2. The method for producing a fluororesin composite composition according to claim 1, wherein an aqueous dispersion produced by an emulsion polymerization method is used as the polytetrafluoroethylene resin dispersion. 3. To prepare a polytetrafluoroethylene resin dispersion, add a solvent that easily wets the polytetrafluoroethylene resin fine powder, and add it to the polytetrafluoroethylene resin fine powder in the presence of a fluorine-based nonionic surfactant while cooling it to below the melting point of the resin. The method for producing a fluororesin composite composition according to claim 1, wherein a finely divided mixed solution is used. 4. The method for producing a fluororesin composite composition according to claim 1, wherein the mixing is carried out at a temperature of about 10° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61247197A JPH0653813B2 (en) | 1986-10-17 | 1986-10-17 | Method for producing polytetrafluoroethylene resin composite composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61247197A JPH0653813B2 (en) | 1986-10-17 | 1986-10-17 | Method for producing polytetrafluoroethylene resin composite composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63101430A true JPS63101430A (en) | 1988-05-06 |
| JPH0653813B2 JPH0653813B2 (en) | 1994-07-20 |
Family
ID=17159890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61247197A Expired - Lifetime JPH0653813B2 (en) | 1986-10-17 | 1986-10-17 | Method for producing polytetrafluoroethylene resin composite composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653813B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008311023A (en) * | 2007-06-13 | 2008-12-25 | Mitsubishi Electric Corp | Bypass switch |
| JP2015034194A (en) * | 2013-08-07 | 2015-02-19 | 三菱樹脂株式会社 | Fluorine-based resin porous body, and manufacturing method thereof |
| EP2810958B1 (en) | 2012-02-02 | 2016-11-30 | Asahi Glass Company, Limited | Method for producing polytetrafluoroethylene fine powder |
| JP2018012787A (en) * | 2016-07-21 | 2018-01-25 | 三菱鉛筆株式会社 | Thermosetting resin composition, and insulation material composition prepared therewith |
| WO2019004235A1 (en) * | 2017-06-28 | 2019-01-03 | 大陽日酸株式会社 | Composite resin particle production method, resin molded article, and composite resin particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60258263A (en) * | 1984-05-29 | 1985-12-20 | バイエル・アクチエンゲゼルシヤフト | Polymer powder composition containing tetrafluoroethylene polymer |
-
1986
- 1986-10-17 JP JP61247197A patent/JPH0653813B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60258263A (en) * | 1984-05-29 | 1985-12-20 | バイエル・アクチエンゲゼルシヤフト | Polymer powder composition containing tetrafluoroethylene polymer |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008311023A (en) * | 2007-06-13 | 2008-12-25 | Mitsubishi Electric Corp | Bypass switch |
| EP2810958B1 (en) | 2012-02-02 | 2016-11-30 | Asahi Glass Company, Limited | Method for producing polytetrafluoroethylene fine powder |
| JP2015034194A (en) * | 2013-08-07 | 2015-02-19 | 三菱樹脂株式会社 | Fluorine-based resin porous body, and manufacturing method thereof |
| JP2018012787A (en) * | 2016-07-21 | 2018-01-25 | 三菱鉛筆株式会社 | Thermosetting resin composition, and insulation material composition prepared therewith |
| WO2019004235A1 (en) * | 2017-06-28 | 2019-01-03 | 大陽日酸株式会社 | Composite resin particle production method, resin molded article, and composite resin particles |
| JP2019006963A (en) * | 2017-06-28 | 2019-01-17 | 大陽日酸株式会社 | Manufacturing method of composite resin particle, resin molded body, and composite resin particle |
| CN110753716A (en) * | 2017-06-28 | 2020-02-04 | 大阳日酸株式会社 | Method for producing composite resin particles, resin molded article, and composite resin particles |
| EP3647343A4 (en) * | 2017-06-28 | 2021-03-03 | Taiyo Nippon Sanso Corporation | Composite resin particle production method, resin molded article, and composite resin particles |
| US11149121B2 (en) | 2017-06-28 | 2021-10-19 | Taiyo Nippon Sanso Corporation | Method for producing composite resin particles, resin molded article, and composite resin particles |
| TWI753180B (en) * | 2017-06-28 | 2022-01-21 | 日商大陽日酸股份有限公司 | A method for producing composite resin particle, resin molding, and composite resin particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0653813B2 (en) | 1994-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2814574B2 (en) | Polytetrafluoroethylene porous body and method for producing the same | |
| US20070117930A1 (en) | Fluoropolymer blending process | |
| JPH10505378A (en) | Porous polytetrafluoroethylene mixture | |
| Khan et al. | Rheological and mechanical properties of ABS/PC blends | |
| DE68905525T2 (en) | Process for molding a filler containing polytetrafluoroethylene. | |
| US20140054512A1 (en) | Conductive full vulcanized thermoplastic elastomer and its preparation method | |
| JP2004510880A (en) | Fully vulcanized thermoplastic elastomer, its manufacture and use | |
| Wu et al. | Effect of additives on the morphology evolution of EPDM/PP TPVs during dynamic vulcanization in a twin-screw extruder | |
| Syabani et al. | The effect of PVC’s resin K-value on the mechanical properties of the artificial leather | |
| JPS63101430A (en) | Production of fluorocarbon resin composite composition | |
| US6780363B2 (en) | PTFE-based polymers | |
| JPH10176065A (en) | Production of spherical polymer fine powder | |
| Maldonado et al. | Enhanced thermally conductive TPU/graphene filaments for 3D printing produced by melt compounding | |
| CN111808302A (en) | Method for producing sulfone polymer microparticles for SLS 3D printing | |
| JP2001049068A (en) | Melt-processible polytetrafluoroethylene composition | |
| DE69126681T2 (en) | Process for producing filler-containing polytetrafluoroethylene granule powder and polytetrafluoroethylene granule powder produced thereby | |
| KR102244303B1 (en) | A friction material and a manufacturing method thereof | |
| JP2006070233A (en) | Mixed type of non-melt processable fluororesins | |
| CN110054855A (en) | A kind of polytetrafluoroethylene (PTFE) bubble point film and preparation method thereof | |
| JPH07252365A (en) | Production of fluororesin molding material | |
| US3560425A (en) | Particulate blend of polyacrylonitrile and a latent solvent | |
| JP3263235B2 (en) | Method for producing granulated powder of polytetrafluoroethylene | |
| JPH03170558A (en) | Composite material and its production | |
| CN109294087B (en) | Modified polystyrene material and preparation method thereof | |
| Ramakrishnan et al. | Comparing the morphological evolution of reactive and nonreactive Polystyrene/Polypropylene polymer blends: Processing phase inversion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |