JPS6346097B2 - - Google Patents
Info
- Publication number
- JPS6346097B2 JPS6346097B2 JP1817080A JP1817080A JPS6346097B2 JP S6346097 B2 JPS6346097 B2 JP S6346097B2 JP 1817080 A JP1817080 A JP 1817080A JP 1817080 A JP1817080 A JP 1817080A JP S6346097 B2 JPS6346097 B2 JP S6346097B2
- Authority
- JP
- Japan
- Prior art keywords
- ptfe
- coagulation
- aqueous dispersion
- powder
- carbon fiber
- 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.)
- Expired
Links
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 46
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 46
- 239000000843 powder Substances 0.000 claims description 46
- 239000006185 dispersion Substances 0.000 claims description 36
- 238000005345 coagulation Methods 0.000 claims description 31
- 239000000945 filler Substances 0.000 claims description 29
- 230000015271 coagulation Effects 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 22
- 239000004917 carbon fiber Substances 0.000 claims description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 13
- 239000000701 coagulant Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、カーボン繊維粉末を配合した充填材
入りポリテトラフルオロエチレン・フアインパウ
ダーの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a filled polytetrafluoroethylene fine powder containing carbon fiber powder.
カーボン繊維粉末を充填したポリテトラフルオ
ロエチレン(以下PTFEと略す)成形体は、耐摩
耗特性および圧延特性などに優れ、ガラス繊維粉
末を充填したものに比べ耐薬品性が改良されるた
め特殊な摺動部材などに用いられる。 Polytetrafluoroethylene (hereinafter abbreviated as PTFE) molded bodies filled with carbon fiber powder have excellent abrasion resistance and rolling properties, and have improved chemical resistance compared to those filled with glass fiber powder, so they can be coated with a special adhesive. Used for moving parts, etc.
充填材を配合したPTFEモールデイングパウダ
ーは、すでに広く使用されているが、充填材を配
合したフアインパウダーの実用化は比較的新し
く、この樹脂に対する実用上の要求が多様化する
に従つて、最近増加しつつある。すなわち、この
様な充填材入りPTFEフアインパウダーは、押出
助剤を添加して行ういわゆるペースト押出成形に
よつて薄肉チユーブ、パイプ、シートなどの成形
品として、あるいは電線被覆などに用いることが
できる点で有用である。 PTFE molding powders containing fillers are already widely used, but the practical application of fine powders containing fillers is relatively new, and as the practical requirements for this resin have diversified, It has been increasing recently. In other words, such filler-containing PTFE fine powder can be used as molded products such as thin-walled tubes, pipes, and sheets, or for covering electric wires, etc. by so-called paste extrusion molding performed by adding an extrusion aid. It is useful in this respect.
充填材をPTFEフアインパウダーに配合する方
法としては、乾式法と湿式法とがある。乾式法は
PTFE水性分散体を凝析させ、フアインパウダー
にした後に充填材を加える方法であるが、この方
法を採用すると、フアインパウダー自体が一次粒
子の二次的な凝集体となつているため、充填材と
の均一な混合状態は得られない。その上、混合時
の機械力によつてPTFE粉末が変形するため、内
部構造の均一な成形品は得られない。 There are two methods for blending the filler into the PTFE fine powder: a dry method and a wet method. The dry method is
This method involves adding a filler after coagulating the PTFE aqueous dispersion and turning it into fine powder, but when this method is adopted, the fine powder itself becomes a secondary aggregate of primary particles. Uniform mixing with the filler cannot be achieved. Furthermore, the PTFE powder is deformed by the mechanical force during mixing, making it impossible to obtain a molded product with a uniform internal structure.
従つて、これら欠点のない混合粉末を製造する
ためには混合方法として湿式法を採用することと
なる。湿式混合法は、PTFEの水性分散液に充填
材粉末をそのまま、または同じ水性分散液の形で
添加し、凝析させることによつて充填材入りフア
インパウダーを得る方法である。さらに、一般に
PTFE水性分散液の凝析に際し、水不溶性液体を
共存させれば凝析粒子が適当な大きさの球状ない
しは顆粒状に集塊化されることも知られており、
充填材としてカーボン粉末を用いる場合について
は、湿式混合における凝析の前または後に有機液
体を加える方法が提案されている(特公昭52−
34653号公報参照)。 Therefore, in order to produce a mixed powder free of these drawbacks, a wet method is adopted as the mixing method. The wet mixing method is a method in which filler powder is added to an aqueous PTFE dispersion as it is or in the form of the same aqueous dispersion, and the filler powder is coagulated to obtain a filler-containing fine powder. Furthermore, in general
It is also known that when coagulating a PTFE aqueous dispersion, if a water-insoluble liquid is present, the coagulated particles can be agglomerated into spheres or granules of an appropriate size.
When carbon powder is used as a filler, a method of adding an organic liquid before or after coagulation in wet mixing has been proposed (Japanese Patent Publication No. 1983-
(See Publication No. 34653).
本発明者らは、上記の公知技術に従つてカーボ
ン繊維粉末を充填材として含有するPTFEフアイ
ンパウダーの製造を試みたところ、カーボン充填
材の場合に使用される方法がそのままでは適用で
きないものであることを知つた。すなわち、カー
ボン繊維粉末を用いた場合、カーボン充填材を使
用した場合のように共凝析の前または後にPTFE
水性分散液に水不溶性有機液体を添加するという
方法では、やはりPTFEあるいは充填材の分離、
損失が起り、充填材の混合状態も不均一なものと
なつてしまうことを知つた。 The present inventors attempted to produce a PTFE fine powder containing carbon fiber powder as a filler according to the above-mentioned known technology, but found that the method used for carbon fillers could not be applied as is. I learned something. i.e. when using carbon fiber powder, PTFE before or after co-coagulation as when using carbon filler.
The method of adding a water-insoluble organic liquid to an aqueous dispersion also requires separation of PTFE or filler,
It was found that losses occur and the mixing state of the filler becomes non-uniform.
本発明は、前記欠点のない充填材入りPTFEフ
アインパウダーの製造法であり、その要旨は、
PTFEコロイド状水性分散液とカーボン繊維粉末
とを合して撹拌しながら凝析を行ない、この凝析
の開始から凝析の完了までの間に、沸点が30〜
150℃、20℃における表面張力が35ダイン/cm以
下の水不溶性有機液体を加えることを特徴とする
充填材入りPTFEフアインパウダーの製造法に存
する。 The present invention is a method for producing a filler-containing PTFE fine powder that does not have the above-mentioned drawbacks, and its gist is as follows:
The PTFE colloidal aqueous dispersion and the carbon fiber powder are combined and coagulated while stirring, and from the start of the coagulation to the completion of the coagulation, the boiling point is 30~30.
The present invention relates to a method for producing a PTFE fine powder containing a filler, which comprises adding a water-insoluble organic liquid having a surface tension of 35 dynes/cm or less at 150°C and 20°C.
本発明に使用するPTFEとしては、TFEの単
独重合体、および変性剤として2%以下のオレフ
イン類、たとえばヘキサフルオロプロピレン、ク
ロロトリフルオロエチレン、パーフルオロアルキ
ルビニルエーテルなどを共重合したTFE共重合
体などが挙げられる。 The PTFE used in the present invention includes TFE homopolymers, and TFE copolymers copolymerized with 2% or less of olefins as modifiers, such as hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, etc. can be mentioned.
PTFEコロイド状水性分散液としては、平均粒
径0.1〜0.3μのPTFEコロイド状粒子を5〜35重量
%含む水性分散液の使用が好適である。 As the PTFE colloidal aqueous dispersion, it is preferable to use an aqueous dispersion containing 5 to 35% by weight of PTFE colloidal particles having an average particle size of 0.1 to 0.3 μm.
本発明に使用する充填材であるカーボン繊維粉
末は、カーボン繊維を微粉砕したもので、各粒子
の直径は3〜30μ程度、平均長は10〜1000μ程度
である。カーボン繊維粉末は、通常そのまま
PTFE水性分散液に添加することができるが、粒
径が細かければPTFE水性分散液中へ均一に分散
しにくい場合がある。この様な場合にはカーボン
繊維粉末に水を加えて充分撹拌混合し、均一な水
性分散液にしておくことによりPTFE水性分散液
との均一混合が可能となる。カーボン繊維粉末の
PTFEに対する添加割合は、通常5〜80重量%程
度である。 The carbon fiber powder, which is a filler used in the present invention, is made by finely pulverizing carbon fiber, and each particle has a diameter of about 3 to 30 μm and an average length of about 10 to 1000 μm. Carbon fiber powder is usually left as is.
It can be added to the PTFE aqueous dispersion, but if the particle size is small, it may be difficult to uniformly disperse it in the PTFE aqueous dispersion. In such a case, by adding water to the carbon fiber powder and sufficiently stirring and mixing to form a uniform aqueous dispersion, uniform mixing with the PTFE aqueous dispersion becomes possible. carbon fiber powder
The addition ratio to PTFE is usually about 5 to 80% by weight.
本発明の方法は、通常のPTFE水性分散液の凝
析の場合と同様、撹拌を続けるだけで凝析を起す
ことができる。けれども、凝析に長時間を要する
ことがあり、また撹拌だけによつて凝析を行う場
合、その時期が一定しないことが多いから、その
始点を感知するために注意して監視を続けなけれ
ばならず、操作が繁雑となる。これらの理由から
本発明の方法では一般に凝析剤を使用することが
好ましい。 In the method of the present invention, coagulation can be caused simply by continuing stirring, as in the case of coagulation of a normal aqueous PTFE dispersion. However, coagulation can take a long time, and when coagulation is performed only by stirring, the timing is often inconsistent, so careful monitoring is necessary to detect the starting point. The operation becomes complicated. For these reasons, it is generally preferred to use a coagulant in the method of the invention.
凝析剤としては、PTFE水性分散液の凝析に通
常使用されているものはいずれも使用でき、たと
えば塩化マグネシウム、塩化アルミニウムなどの
水溶性塩、硝酸、塩酸、硫酸などの鉱酸類、アル
コール、アセトンなどの水溶性有機液体類、陽イ
オン界面活性剤類などが挙げられる。 As the coagulant, any commonly used coagulant for coagulating PTFE aqueous dispersions can be used, such as water-soluble salts such as magnesium chloride and aluminum chloride, mineral acids such as nitric acid, hydrochloric acid, and sulfuric acid, alcohols, Examples include water-soluble organic liquids such as acetone, cationic surfactants, and the like.
水不溶性液体としては、沸点30〜150℃、20℃
における表面張力が35ダイン/cm以下のものが好
ましく、その具体例としてはヘキサン、ヘプタ
ン、ガソリン、燈油、トルエンのような炭化水
素、四塩化炭素、トリクロロエチレンのような塩
素化炭化水素、トリクロロトリフルオロエタン、
テトラクロロジフルオロエタン、トリクロロフル
オロメタンのようなフツ素化炭化水素などが挙げ
られる。水不溶性有機液体の添加量は、一般に固
形分100部(重量、以下同様)に対し30〜100部で
あつてよい。 As a water-insoluble liquid, the boiling point is 30-150℃, 20℃
Hydrocarbons such as hexane, heptane, gasoline, kerosene, and toluene, chlorinated hydrocarbons such as carbon tetrachloride, trichloroethylene, and trichlorotrifluoro are preferred. ethane,
Examples include fluorinated hydrocarbons such as tetrachlorodifluoroethane and trichlorofluoromethane. The amount of the water-insoluble organic liquid added may generally be 30 to 100 parts per 100 parts (by weight, hereinafter the same) of the solid content.
次に、本発明方法を実施工程に則し、添付した
第1図を参照して説明する。 Next, the method of the present invention will be explained in accordance with the implementation steps with reference to the attached FIG. 1.
一般に、PTFE水性分散液を撹拌しつつ、これ
に前記カーボン繊維粉末の水性分散液を添加し、
PTFEと充填材が充分均一に混合された後に凝析
剤を加える。もちろん、PTFE水性分散液と充填
材水性分散液の混合順序は前記と逆でもよい。 Generally, the aqueous dispersion of carbon fiber powder is added to the aqueous PTFE dispersion while stirring;
Add coagulant after PTFE and filler are thoroughly and uniformly mixed. Of course, the mixing order of the PTFE aqueous dispersion and the filler aqueous dispersion may be reversed.
第1図は、凝析前後における分散液の撹拌トル
クの時間に対する変化の様子を模式的に表わした
ものである。図の曲線1および2は、トルクの経
時変化の代表例である。図中のQは凝析剤の添加
時点であり、また〔A〕は凝析前ゾーン、〔B〕
は凝析中ゾーンおよび〔C〕は凝析後ゾーンであ
る。各ゾーンにおける固形分の状態は、〔A〕で
はコロイド状粒子、〔B〕ではゼリー状および
〔C〕では疎水状である。この〔C〕における疎
水状とは、液中の分散粒子が水になじまない状態
になつており、撹拌を停止すると直ちに沈殿また
は浮上して水と分離しようとする状態にあること
を意味する。 FIG. 1 schematically shows how the stirring torque of the dispersion changes over time before and after coagulation. Curves 1 and 2 in the figure are representative examples of torque changes over time. Q in the figure is the point of addition of the coagulant, [A] is the pre-coagulation zone, and [B]
is the coagulation zone and [C] is the post-coagulation zone. The state of the solid content in each zone is colloidal particles in [A], jelly-like in [B], and hydrophobic in [C]. The hydrophobic state in [C] means that the dispersed particles in the liquid are not compatible with water, and are in a state where they immediately precipitate or float to separate from the water when stirring is stopped.
PTFE水性分散液の凝析においては、第1図に
示すようにトルクピークは1つ現われる場合と2
つ現われる場合が多いが、いずれの場合も分散液
の状態は撹拌トルクにより上記のように〔A〕,
〔B〕および〔C〕の3つのゾーンに明瞭に区分
することができる。 In the coagulation of an aqueous PTFE dispersion, as shown in Figure 1, there are cases where one torque peak appears and cases where two torque peaks appear.
In many cases, the state of the dispersion liquid changes as described above due to the stirring torque.
It can be clearly divided into three zones: [B] and [C].
すなわち撹拌しつつ凝析剤を添加すると直ちに
凝析が開始し、固形分はゼリー状になり、分散液
の粘度はどんどん上昇し、ついにピークに達する
と疎水化が始まり、粘度は急速に低下する。 In other words, when a coagulant is added while stirring, coagulation begins immediately, the solid content becomes jelly-like, and the viscosity of the dispersion increases rapidly.When it finally reaches a peak, hydrophobicization begins and the viscosity rapidly decreases. .
曲線1の場合、ピークPがこれらの分岐点とな
つている。曲線2の場合、ピークP1は粘度のピ
ークであり、P2は疎水化の始まる点である。そ
して、撹拌トルクが一定化したときが凝析の完了
点Rである。 In the case of curve 1, peak P is the branching point between these two points. For curve 2, peak P 1 is the viscosity peak and P 2 is the point where hydrophobization begins. The point R when the stirring torque becomes constant is the point R when the coagulation is completed.
なお、PTFE水性分散液が充填材を含む場合の
撹拌トルク曲線も第1図の曲線とほぼ同様であ
る。 Note that the stirring torque curve when the PTFE aqueous dispersion contains a filler is also almost the same as the curve in FIG. 1.
本発明製造法においては、凝析に際し第1図の
〔B〕ゾーンにある水性分散液に前記の水不溶性
有機液体を加える必要がある。〔B〕ゾーン内で
も、特に前述の撹拌トルクのピークPまたはP1
付近は液の粘度変化の状態が目視でも明瞭に判別
できるので前記のピークPまたはP1の前後で一
度に注入することが推奨される。 In the production method of the present invention, it is necessary to add the water-insoluble organic liquid to the aqueous dispersion in zone [B] in FIG. 1 during coagulation. [B] Even within the zone, especially the above-mentioned stirring torque peak P or P 1
It is recommended to inject all at once before and after the above-mentioned peak P or P1 , since the state of change in the viscosity of the liquid can be clearly determined visually in the vicinity.
もし、〔A〕ゾーンにおいて水不溶性有機液体
を加えると分散液中のPTFE粒子が先に安定化す
ることにより充填材粒子の粒状化が先行し、結果
として分散液中にPTFE粒子が残留し、PTFE粒
子と充填材の混合が不均一になる。残留した
PTFE粒子は強力な凝析条件(たとえば強い機械
力、加熱、過剰な凝析剤など)によれば凝析させ
ることはできるが、この場合混合の均一性はさら
に損なわれる。 If a water-insoluble organic liquid is added in the [A] zone, the PTFE particles in the dispersion will be stabilized first, leading to granulation of the filler particles, and as a result, the PTFE particles will remain in the dispersion. Non-uniform mixing of PTFE particles and filler. remained
Although PTFE particles can be coagulated by strong coagulation conditions (e.g. strong mechanical force, heat, excess coagulant, etc.), the uniformity of the mixture is further compromised.
また、〔C〕ゾーンにおいて水不溶性有機液体
を加えるとPTFE粒子の粒状化のみが先行し、充
填材であるカーボン繊維粉末は一部が粒状化した
PTFE粒子の外側に付着するだけで大半は遊離し
てしまう。 Furthermore, when a water-insoluble organic liquid was added in the [C] zone, only the PTFE particles were granulated, and some of the carbon fiber powder, which was a filler, was granulated.
Most of it is released by simply adhering to the outside of the PTFE particles.
凝析終了後、得られた充填材入りPTFEフアイ
ンパウダーは水洗、乾燥される。 After coagulation, the obtained filler-containing PTFE fine powder is washed with water and dried.
本発明製造法によつて生成した充填材入り
PTFEフアインパウダーは、通常200〜5000μの粒
径を有しており、分散液からの分離が容易で、流
動性が良く、乾燥後も凝塊を生じないので非常に
取り扱い易い。また、充填材としての固体微粒子
の量が比較的大となつても均一かつ完全な混和が
保証され、操作中における固体微粒子の水媒体中
への脱離は認められない。さらに、この粉末は充
填材であるカーボン繊維粉末が均一に混合されて
おり、高い粉末流動性を有し、ペースト押出成形
およびカレンダリングも容易で、任意の厚みのシ
ート、チユーブ、棒などに成形することが可能で
ある。 Contains filler produced by the production method of the present invention
PTFE fine powder usually has a particle size of 200 to 5000μ, is easy to separate from a dispersion, has good fluidity, and does not form agglomerates even after drying, making it very easy to handle. Further, even if the amount of solid fine particles as a filler is relatively large, uniform and complete mixing is ensured, and no detachment of solid fine particles into the aqueous medium during operation is observed. In addition, this powder is uniformly mixed with carbon fiber powder as a filler, has high powder flowability, and can be easily formed into paste extrusion and calendering to form sheets, tubes, bars, etc. of any thickness. It is possible to do so.
以下、実施例および比較例を挙げて本発明の製
造法を更に具体的に説明する。なお、各例中%と
あるのは特記しない限り重量%を表わす。 Hereinafter, the manufacturing method of the present invention will be explained in more detail with reference to Examples and Comparative Examples. In each example, % represents weight % unless otherwise specified.
比較例 1
ステンレススチール製筒型凝析槽(内径450mm、
内容積100、内壁の相対向する位置に幅15mmの
じやま板を垂直に取付)に水30を入れ、調温用
ジヤケツトにより温度を30±2℃に調節しなが
ら、2枚羽根のイカリ型撹拌翼を持つ撹拌機によ
り200rpmで撹拌しつつ、カーボン繊維(平均直
径12.5μ、平均長130μ)0.9Kgを加えて充分分散さ
せる。ここへ濃度25%のPTFE水性分散液20.4
を投入し、撹拌を続けると、数分後に液の粘度が
上昇し、スラリー状を呈する。さらに撹拌を続け
ると内容物は疎水化して浮上するので撹拌を停止
する。Comparative example 1 Stainless steel cylindrical coagulation tank (inner diameter 450 mm,
Pour 30°C of water into a 100°C (inner volume: 100mm), with 15mm wide bamboo boards mounted vertically on opposite sides of the inner wall, and adjust the temperature to 30±2°C using a temperature control jacket. While stirring at 200 rpm using a stirrer with stirring blades, add 0.9 kg of carbon fiber (average diameter 12.5μ, average length 130μ) and thoroughly disperse. Here PTFE aqueous dispersion with a concentration of 25% 20.4
When added and continued stirring, the viscosity of the liquid increases after a few minutes and becomes slurry-like. If the stirring is continued, the contents become hydrophobic and float, so the stirring is stopped.
浮上した粉末を100メツシユ金網で過して液
から分離し、乾燥する。この際、分離液にはカー
ボン繊維粉末が0.56Kg含まれており、このことは
得られる粉末にはカーボン繊維粉末は約0.34Kgし
か含まれていないことを示す。 The floating powder is separated from the liquid by passing through a 100-mesh wire mesh and dried. At this time, the separated liquid contained 0.56 kg of carbon fiber powder, which means that the obtained powder contained only about 0.34 kg of carbon fiber powder.
実施例 1
比較例1の手順において、液がスラリー状に達
した時(すなわち、第1図のほぼP点において)、
トリクロロトリフルオロエタン1.6を凝析槽へ
投入する以外は同様の手順を繰り返した。この場
合、凝析粒子は液中に沈降して得られるが、これ
を過した時、液へのカーボン繊維粉末の分離
は全く見られなかつた。Example 1 In the procedure of Comparative Example 1, when the liquid reached a slurry state (i.e., approximately at point P in FIG. 1),
The same procedure was repeated except that 1.6 of trichlorotrifluoroethane was added to the coagulation tank. In this case, the coagulated particles were obtained by settling into the liquid, but when this was passed, no separation of the carbon fiber powder into the liquid was observed.
得られた乾燥粉末の平均粒径は1000μ、見掛密
度は600g/であつた。 The average particle size of the obtained dry powder was 1000μ, and the apparent density was 600g/.
次に、得られた粉末84重量部にナフサ16重量部
を混和した押出用混合物を、還元比(Reduction
Ratio)168の下に、ペースト押出しして内径4
mm、外径5mmのチユーブに成形し、押出物を370
℃で10分間焼成した。得られたチユーブの押出方
向の引張試験における破断荷重は11.1Kg、伸びは
160%であつた。 Next, an extrusion mixture prepared by mixing 84 parts by weight of the obtained powder with 16 parts by weight of naphtha was mixed with a reduction ratio (Reduction ratio).
Ratio) Under 168, extrude the paste and inner diameter 4
mm, formed into a tube with an outer diameter of 5 mm, and the extrudate
Baked at ℃ for 10 minutes. The breaking load of the obtained tube in the tensile test in the extrusion direction was 11.1 kg, and the elongation was
It was 160%.
比較例 2
実施例1において、トリクロロトリフルオロエ
タンをPTFE水性分散体の凝析槽への投入直後に
(すなわち、第1図の〔A〕領域において)同槽
へ投入する以外は同様の手順を操り返したとこ
ろ、主としてカーボン繊維粉末が単独で先行的に
凝集することが観察されたため撹拌を停止した。Comparative Example 2 The same procedure as in Example 1 was followed except that trichlorotrifluoroethane was added to the coagulation tank immediately after the PTFE aqueous dispersion was added to the coagulation tank (i.e., in area [A] in Figure 1). When the process was repeated, it was observed that the carbon fiber powder alone precipitated agglomeration, so stirring was stopped.
比較例 3
実施例1において、凝析槽へのトリクロロトリ
フルオロエタンの投入を、撹拌液がスラリー状を
呈した後、撹拌トルクが一定値となつたとき(す
なわち、第1図の〔C〕領域において)行う以外
は同様の手順を繰り返した。Comparative Example 3 In Example 1, trichlorotrifluoroethane was added to the coagulation tank when the stirring torque reached a constant value after the stirring liquid had become slurry-like (i.e., [C] in Fig. 1). The same procedure was repeated except that in the area
凝析終了後の粉末を液から過分離したとこ
ろ、液中へカーボン繊維粉末が0.15Kg分離流出
した。 When the powder after coagulation was over-separated from the liquid, 0.15 kg of carbon fiber powder was separated and flowed out into the liquid.
第1図は、凝析前後における分散液の撹拌トル
クの経時変化を模式的に表わした図である。
1および2……トルクの経時変化を表わす曲
線、〔A〕……凝析前ゾーン、〔B〕……凝析中ゾ
ーン、〔C〕……凝析後ゾーン、Q……凝析剤添
加時点、P……分岐点、P1……粘度のピーク、
P2……疎水化開始点、R……凝析完了点。
FIG. 1 is a diagram schematically showing the change over time in the stirring torque of the dispersion before and after coagulation. 1 and 2...Curve showing the change in torque over time, [A]...Pre-coagulation zone, [B]...During coagulation zone, [C]...Post-coagulation zone, Q...Coagulant addition Time point, P...branch point, P1 ...viscosity peak,
P2 ...Hydrophobization starting point, R...Coagulation completion point.
Claims (1)
トラフルオロエチレン・フアインパウダーを水性
分散液から共凝析により製造するに際し、ポリテ
トラフルオロエチレンコロイド状水性分散液とカ
ーボン繊維粉末とを合して撹拌しながら凝析を行
ない、この凝析の開始から凝析の完了までの間
に、沸点が30〜150℃、20℃における表面張力が
35ダイン/cm以下の水不溶性有機液体を加えるこ
とを特徴とする充填材入りポリテトラフルオロエ
チレン・フアインパウダーの製造法。 2 カーボン繊維粉末を予め水性分散液にしてポ
リテトラフルオロエチレンコロイド状水性分散液
と合するものである特許請求の範囲第1項記載の
製造法。 3 水不溶性有機液体の添加を、凝析開始後ポリ
テトラフルオロエチレン水性分散液の粘度がほぼ
最大に達したときに注入することにより行うもの
である特許請求の範囲第1項または第2項記載の
製造法。[Scope of Claims] 1. When producing polytetrafluoroethylene fine powder containing carbon fiber powder as a filler from an aqueous dispersion by co-coagulation, a polytetrafluoroethylene colloidal aqueous dispersion and carbon fiber powder are co-coagulated. The boiling point is 30 to 150℃, and the surface tension at 20℃ is
A method for producing a filled polytetrafluoroethylene fine powder, characterized by adding a water-insoluble organic liquid of 35 dynes/cm or less. 2. The manufacturing method according to claim 1, wherein the carbon fiber powder is made into an aqueous dispersion in advance and combined with a polytetrafluoroethylene colloidal aqueous dispersion. 3. The water-insoluble organic liquid is added by injecting the polytetrafluoroethylene aqueous dispersion when the viscosity of the aqueous polytetrafluoroethylene dispersion reaches approximately the maximum after the start of coagulation. manufacturing method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1817080A JPS56115325A (en) | 1980-02-15 | 1980-02-15 | Preparation of fine polytetrafluoroethylene powder containing filler |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1817080A JPS56115325A (en) | 1980-02-15 | 1980-02-15 | Preparation of fine polytetrafluoroethylene powder containing filler |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS56115325A JPS56115325A (en) | 1981-09-10 |
JPS6346097B2 true JPS6346097B2 (en) | 1988-09-13 |
Family
ID=11964129
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1817080A Granted JPS56115325A (en) | 1980-02-15 | 1980-02-15 | Preparation of fine polytetrafluoroethylene powder containing filler |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS56115325A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1190352B (en) * | 1985-04-05 | 1988-02-16 | Montefluos Spa | PROCEDURE FOR THE PRODUCTION OF A COMPOSITE MATERIAL BASED ON A POLYMER MATRIX |
US5326381A (en) * | 1993-05-10 | 1994-07-05 | Engelhard Corporation | Use of polytetrafluoroethylene resin particles to reduce the abrasion of abrasive pigments |
GB2319067B (en) † | 1996-11-06 | 2000-06-28 | T & N Technology Ltd | Forming a bearing |
CN101137702B (en) * | 2005-03-07 | 2011-03-09 | 旭硝子株式会社 | Process for producing filler-containing polytetrafluoroethylene granule |
-
1980
- 1980-02-15 JP JP1817080A patent/JPS56115325A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS56115325A (en) | 1981-09-10 |
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