JPH0653813B2 - Method for producing polytetrafluoroethylene resin composite composition - Google Patents
Method for producing polytetrafluoroethylene resin composite compositionInfo
- Publication number
- JPH0653813B2 JPH0653813B2 JP61247197A JP24719786A JPH0653813B2 JP H0653813 B2 JPH0653813 B2 JP H0653813B2 JP 61247197 A JP61247197 A JP 61247197A JP 24719786 A JP24719786 A JP 24719786A JP H0653813 B2 JPH0653813 B2 JP H0653813B2
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- polytetrafluoroethylene resin
- composite composition
- dispersion
- resin composite
- temperature
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ポリテトラフルオロエチレン樹脂複合組成物
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ポリテトラフ
ルオロエチレン樹脂複合組成物の製造法に関する。TECHNICAL FIELD The present invention relates to a method for producing a polytetrafluoroethylene resin composite composition. More specifically, it relates to a method for producing a polytetrafluoroethylene resin composite composition comprising a polytetrafluoroethylene resin and another polymer substance.
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、その分散姓に問題がみられた。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とう、攪拌混合しても、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。Heretofore, when a composite composition with other substances was produced using a polytetrafluoroethylene resin fine powder produced by an emulsion polymerization method, there was a problem in its dispersion. For example, even if you mix pigments and dyes with this resin fine powder,
Even if the mixture is shaken with stirring using a solvent or the like, the mixture formed therein is only in a non-uniform dispersed state that can be seen immediately by the eye. Similarly, in the case of mixing with other polymer substances, it is the actual situation 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径約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 polytetrafluoroethylene resin fine powder (fine powder) obtained by a commercially available emulsion polymerization method forms particles having an average particle size of about 500μ in which primary particles of about 0.3μ are aggregated, and this resin is also difficult to wet. It is considered that this is because the mixed components do not penetrate into the inside.
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
エ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。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
ニーダー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。In order to improve these points, it is necessary to further finen the fine powder so that the average particle diameter is several tens μ or less, preferably several μ or less. However, the commonly used microparticulation methods, such as dry or wet milling, cause the disadvantages that the particles fuse together and form crystalline fibers by shearing. Such a thing is remarkable when kneading fine powder with an open roll, a kneader, etc. Therefore, it is difficult to obtain a good dispersion by such a method.
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攪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。Further, as another method, it is also possible to disperse a dispersion which is in the order of primary particles in advance, but even if the dispersion is simply mixed by stirring by this method, the dispersion is fused and causes aggregation. Since it is granulated, an effective dispersed mixture cannot be obtained.
そこで、本発明者らは、一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、凝集を生ぜしせめないような条件
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、ポリテトラフルオロ
エチレン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, the present inventors use the polytetrafluoroethylene resin dispersion forming the primary particle order as it is, in the latter method, the dispersion is fused at the time of mixing, and conditions under which agglomeration is not caused. As a result of repeated various investigations for obtaining, by mixing at a temperature below the fusion point of the dispersion or solution of the other polymer substance and the polytetrafluoroethylene resin, by forming a polytetrafluoroethylene resin composite composition, It has been found that this problem can be effectively solved.
従って、本発明はポリテトラフルオロエチレン樹脂複合
組成物の製造法に係り、ポリテトラフルオロエチレン樹
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、10℃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 polytetrafluoroethylene resin composite composition, wherein the production of the polytetrafluoroethylene resin composite composition comprises a dispersion or solution of polytetrafluoroethylene resin dispersion and other polymer substances. , And mixed at a temperature of 10 ° C. or lower, and then obtained as 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攪拌して微粒子
化させた混合液としても用いることができる。As the polytetrafluoroethylene resin dispersion, an aqueous dispersion itself produced by an emulsion polymerization method is generally used, but a fine powder of polytetrafluoroethylene resin is used as a halogenated hydrocarbon such as methylene chloride or trichlorotrifluoroethane. Add to a solvent or a solvent with which they are easily mixed such as a mixed solvent such as methyl ethyl ketone, and after impregnating these solvents into the powder, while cooling below the fusion point of the polytetrafluoroethylene resin, there are fluorine-based nonionic It can also be used as a mixed liquid in which a surfactant or the like is added, and the mixture is agitated 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、種々のゴムまたは樹脂が用いられ
る。例えば、耐薬品性、耐熱姓、ガスバリヤー性などが
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
イミド樹脂などが適宜用いられる。As the other polymer substance mixed with this, various rubbers or resins are used depending on the intended use of the composite composition. For example, fluorocarbon rubber is used when chemical resistance, heat resistance, gas barrier property, etc. are required, and silicone polymer is used when used for oxygen-enriched membranes. Also, NBR, butyl rubber, polyimide resin, etc. are appropriately used.
これら両者の混合は、ポリテトラフ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
下の温度である約10℃以下で行われる。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 two are mixed at a temperature of about 10 ° C. or lower which is a temperature of about 15 ° C. (which also changes depending on the crystallinity) which is the fusion point of the polytetrafluoroethylene resin. If mixing is performed at a temperature higher than this, for example, at room temperature, fusion and agglomeration occur, and a molded product molded 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、塩折法、乾燥
法などにより行われる。The solid product is obtained from the mixture by a reprecipitation method, a salt folding method, a drying method or the like depending on the properties of the dispersion, the solution or the like used.
固型物たるポリテトラフルオロエチレン樹脂複合組成物
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 polytetrafluoroethylene resin composite composition is generally used in such a proportion that polytetrafluoroethylene resin accounts for about 20 to 80% by volume and other polymer substances account for about 80 to 20% by volume. In addition to this, various fillers, colorants,
A lubricant or the like is appropriately added for use.
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10℃以下に保
持することにより、良好な分散状態のポリテトラフルオ
ロエチレン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、押出、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。When mixing the polytetrafluoroethylene resin and the other polymer substance in the liquid medium, by maintaining the mixing temperature at 10 ° C. or less, it is possible to obtain a polytetrafluoroethylene resin composite composition in a good dispersed state. It is possible to obtain a molded product having a uniform porous structure by applying a suitable combination of means such as compression, extrusion, stretching, rolling and firing to the composite composition. Since such a molded product has not only the characteristics of polytetrafluoroethylene resin but also the shape retention and the reinforcing effect due to the uniform porous structure, it is possible to provide a highly functional composite material. .
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例1 ポリテトラフルオロエチレン樹脂(PTFE)ファイパウダー
(三井・デュポンフロロケミカル製品テフロン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480ml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-381)1.1gを加えた後、ホモジナイザー(特殊機化
工業製TKホモミキサー(で攪拌しながら粉砕し、300 メ
ッシュバス(粒径50μ)の粒子分散体を形成させた。Example 1 Polytetrafluoroethylene resin (PTFE) powder
(Mitsui DuPont Fluorochemicals Teflon 6-J, average particle size of about 500μ) 132g, trichlorotrifluoroethane
(Manufactured product Freon TF) -Methyl ethyl ketone (1: 1) mixed solvent 480 ml was added, and the liquid temperature was cooled to 5 ° C. After adding 1.1 g of a fluorine-based nonionic surfactant (Asahi Glass Product Surflon S-381) to this, homogenizer (TK Homomixer manufactured by Tokushu Kika Kogyo Co., Ltd., pulverized with stirring, and 300 mesh bath (particle size 50 μm ) Was 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260mlを攪拌下に加え、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, 260 ml of a methyl ethyl ketone solution containing 6 g of carbon black and 35 g of NBR (Perbunan N3807 NS, Bayer Japan) was added with stirring and the liquid temperature was 5 ° C.
After that, methanol was gradually added to reprecipitate and dried to obtain a black lump.
この黒色小塊たるポリテトラフルオロエチレン樹脂複合
組成物を、60kgf/cm2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。This black small lump polytetrafluoroethylene resin composite composition was pressed into a plate-like body having a thickness of 1 mm at 60 kgf / cm 2 , and then rolled into a film having a thickness of 50 μ with a roll, while maintaining its stretched state. Pressed at 150 ° C.
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、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。Comparing Example 1 and Comparative Example 1 described above, in the stage of the black small lumps, the white lumps in the lumps of Comparative Example 1 were white.
(Particle size of about 100 to 500 μ) was present, but such particles were not confirmed by observation with an optical microscope in the case of Example 1, and at the stage of the molded sample, the width of about 100 μ was found in the case of Comparative Example 1. Although many white streaks were confirmed, those of Example 1 could not be confirmed.
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(デュポン社製品バイトンGF)のメチル−n−ヘキ
シルケトン溶液(ゴム76.4gを溶媒760mlに溶解させた溶
液)中に、ゆるやかに攪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 (Teflon 30-J, a product of Mitsui DuPont Fluorochemicals) was used as a methyl-n-hexylketone solution of fluororubber (Viton GF manufactured by DuPont) whose liquid temperature was previously set to 5 ° C. (rubber 76.4 g). (Solution dissolved in 760 ml of solvent) is gradually added while gently stirring, and then ethanol is added to reprecipitate while maintaining the liquid temperature at 5 ° C.
It was washed several times with ethanol and dried.
得られた白色粉体たるポリテトラフルオロエチレン樹脂
複合組成物を、60kgf/cm2で円柱状に予備成形し、次い
で押出圧力3.6トン/cm2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0.5mmのシート状物
を得た。The obtained polytetrafluoroethylene resin composite composition as a white powder was preformed into a cylindrical shape at 60 kgf / cm 2 , and then extruded into a sheet having a thickness of 1 mm at an extrusion pressure of 3.6 ton / cm 2 .
This was 100% stretched at a stretching rate of 3.5 cm / sec and pressed at 180 ° C. while maintaining the stretched state to obtain a sheet-like material having a thickness of 0.5 mm.
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
のからは均質のものが得られなかった。Comparing Example 2 and Comparative Example 2 described above, in the mixing and reprecipitation stage, in Comparative Example 2, dispersion agglomeration was observed during mixing, and the reprecipitated substance did not become a powder but became a lump. At the stage of the molded sample, fluororubber was extracted with acetone, and the sample after the extraction was observed by a scanning electron microscope. As a result, the sample of Example 2 had a PTFE porous structure composed of a connecting part and a fiber part. However, a homogeneous product was not obtained from that of Comparative Example 2.
実施例3 PTFEディスパージョン(テフロン30-J)183gを、予め液温
を5℃にしたNBR系ラテックス(日本ゼオン製品Nipol 15
61)268g中に、ゆるやかに攪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、メタノーで数回洗浄した後乾燥した。Example 3 183 g of PTFE dispersion (Teflon 30-J) was added to NBR latex (Nipol 15 manufactured by Nippon Zeon Co., Ltd.) whose liquid temperature was previously set to 5 ° C.
61) In 268 g, the mixture was gradually added with gentle stirring, and then methanol was added while maintaining the liquid temperature at 5 ° C. for reprecipitation, followed by washing with methanol for several times and then drying.
得られた白色粉体たるポリテトラフルオロエチレン樹脂
複合組成物から、実施例2と同様にして厚さ0.5mm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。A sheet-like material having a thickness of 0.5 mm was molded from the obtained white powder polytetrafluoroethylene resin composite composition in the same manner as in Example 2, and the molded sample was subjected to NBR rubber extraction with methyl ethyl ketone to perform scanning electron scanning. When observed under a microscope, it was confirmed that it had a PTFE porous structure composed of a connecting portion and a fiber portion.
実施例4 PTFEディスパージョン(テフロン30-J)257gを、予め液温
を5℃にしたポリジメチルシロキサン(東レシリコーン
製品SH410)の塩化メチレン溶液(ポリジメチルシロキサ
ン30gを溶媒 120mlに溶解させた溶液)中に、ゆるやかに
攪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、エタノールで数回洗浄
した後乾燥した。Example 4 257 g of PTFE dispersion (Teflon 30-J) was dissolved in polydimethylsiloxane (Toray Silicone product SH410) in methylene chloride solution (solution in which 30 g of polydimethylsiloxane was dissolved in 120 ml of solvent), the liquid temperature of which was previously set to 5 ° C. The mixture was gradually added with gentle stirring, and then methanol was added while maintaining the liquid temperature at 5 ° C. for reprecipitation, followed by washing with ethanol several times and drying.
得られた白色粉体たるポリテトラフルオロエチレン樹脂
複合組成物を、実施例2と同様に予備成形、押出および
延伸し、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、走査型電子顕微鏡観察を行なうと、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。The obtained white powder polytetrafluoroethylene resin composite composition was preformed, extruded and stretched in the same manner as in Example 2, and baked at 350 ° C. for 10 minutes while maintaining the stretched state,
A sheet having a thickness of 1 mm was obtained. When this molded sample was subjected to polydimethylsiloxane extraction with methyl ethyl ketone and observed by a scanning electron microscope, it was confirmed that it had a PTFE porous structure composed of a connecting part and a fiber part.
Claims (3)
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、10℃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ポリテトラフルオロエチレン樹
脂複合組成物の製造法。1. A polytetrafluoroethylene resin characterized by being obtained as a solid after mixing a dispersion or solution of a polytetrafluoroethylene resin dispersion and another polymer substance at a temperature of 10 ° C. or lower. Method for producing composite composition.
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
ポリテトラフルオロエチレン樹脂複合組成物の製造法。2. The method for producing a polytetrafluoroethylene resin composite composition according to claim 1, wherein an aqueous dispersion produced by an emulsion polymerization method is used as the polytetrafluoroethylene resin dispersion.
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、10℃の温
度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項記載のポリテトラフルオロエチレン樹脂複合
組成物の製造法。3. As a polytetrafluoroethylene resin dispersion, a solvent that easily wets it is added to polytetrafluoroethylene resin fine powder, and the mixture is cooled to a temperature of 10 ° C. or lower in the presence of a fluorine-based nonionic surfactant. The method for producing a polytetrafluoroethylene resin composite composition according to claim 1, wherein a mixed solution which is made into fine particles is used.
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 JPS63101430A (en) | 1988-05-06 |
JPH0653813B2 true 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 |
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JP (1) | JPH0653813B2 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4894644B2 (en) * | 2007-06-13 | 2012-03-14 | 三菱電機株式会社 | Bypass switch |
JP5983633B2 (en) | 2012-02-02 | 2016-09-06 | 旭硝子株式会社 | Method for producing polytetrafluoroethylene fine powder |
JP6191323B2 (en) * | 2013-08-07 | 2017-09-06 | 三菱ケミカル株式会社 | Fluororesin porous body and method for producing the same |
JP6835497B2 (en) * | 2016-07-21 | 2021-02-24 | 三菱鉛筆株式会社 | Thermosetting resin composition, insulating material composition using it |
JP6694412B2 (en) * | 2017-06-28 | 2020-05-13 | 大陽日酸株式会社 | Method for producing composite resin particles, resin molded body, and composite resin particles |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3420002A1 (en) * | 1984-05-29 | 1985-12-05 | Bayer Ag, 5090 Leverkusen | POLYMER POWDER COMPOSITIONS CONTAINING TETRAFLUORETHYLENE POLYMER |
-
1986
- 1986-10-17 JP JP61247197A patent/JPH0653813B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
辻薦著「乳化・可溶化の技術」工学図書(昭和56年5月15日)第74頁第8行〜第75頁第2行 |
Also Published As
Publication number | Publication date |
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JPS63101430A (en) | 1988-05-06 |
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