JP2015151543A - Powder for paste extrusion molding and method for producing the same - Google Patents
Powder for paste extrusion molding and method for producing the same Download PDFInfo
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本発明は、ポリテトラフルオロエチレン（以下、「ＰＴＦＥ」という。）のペースト押出成形用粉末及びその製造方法に関し、特にフィラー混合ＰＴＦＥファインパウダーとその製造方法に関する。 The present invention relates to a paste extrusion molding powder of polytetrafluoroethylene (hereinafter referred to as “PTFE”) and a method for producing the same, and more particularly to a filler mixed PTFE fine powder and a method for producing the same.
ＰＴＦＥ単体の成形品物性は、優れた耐熱性、電気絶縁性、低摩擦係数、耐化学薬品性などに優れた樹脂である。しかし、用途により導電性付与や摩擦時の耐摩耗性向上等が求められる。そのためにカーボン、グラファイト、ガラス繊維粉末などを混合して機能を付与することが行われている。 The physical properties of the molded product of PTFE alone is a resin excellent in excellent heat resistance, electrical insulation, low friction coefficient, chemical resistance and the like. However, it is required to impart conductivity or improve wear resistance during friction depending on the application. For this purpose, carbon, graphite, glass fiber powder and the like are mixed to give a function.
一方、販売されているペースト押出成形用粉末としてのＰＴＦＥファインパウダーは、ＰＴＦＥ乳化重合粒子を凝集したものであって、ＰＴＦＥ乳化重合粒子の水性分散体から撹拌の手段で凝析によって得られた平均粒径３００μｍ〜１０００μｍの粉末である。 On the other hand, the PTFE fine powder as a paste extrusion powder on the market is an aggregate of PTFE emulsion polymer particles, and is an average obtained by coagulation from an aqueous dispersion of PTFE emulsion polymer particles by means of stirring. It is a powder having a particle size of 300 μm to 1000 μm.
このようにＰＴＦＥ乳化重合粒子をＰＴＦＥファインパウダーに加工する理由は、製造業者側としてはＰＴＦＥファインパウダーに加工した方が、乾燥、計量、梱包、移送などにおける取り扱い上の困難性が解消し、また、この材料を使用して成形加工する加工者側としては、ＰＴＦＥファインパウダーでなければペースト押出成形における計量、助剤混合、金型充填などの工業生産上の取り扱いができないからである。 The reason why PTFE emulsion polymerized particles are processed into PTFE fine powder in this way is that, as a manufacturer, processing into PTFE fine powder eliminates difficulties in handling in drying, weighing, packaging, transport, etc. This is because, on the side of a processor who performs molding processing using this material, it is impossible to handle industrial production such as measurement, paste mixing, and mold filling in paste extrusion molding unless it is PTFE fine powder.
加工業者が市販のＰＴＦＥファインパウダーにフィラー粉末を単に混合しても機能性を発現する成形品を得ることは殆ど困難である。困難な理由はフィラー粉末の平均サイズが０．０１〜２０μｍであるのに対して、ＰＴＦＥファインパウダーの平均サイズが約５００μｍであり、一方、求められるフィラー粉末の配合量は多くても５０％以下であるため、その配合範囲でペースト押出成形を行うと、フィラー粉末が少ない場合はフィラー粉末の分布が斑な成形品となり、フィラー粉末が多い場合は連続した押出成形品が得られないからである。つまり、極端にサイズの異なる粉末同士を単に混合しても均一な分散は得られないということである。 Even if a processor simply mixes filler powder with commercially available PTFE fine powder, it is almost difficult to obtain a molded product exhibiting functionality. The difficult reason is that the average size of the filler powder is 0.01 to 20 μm, whereas the average size of the PTFE fine powder is about 500 μm, while the required blending amount of the filler powder is at most 50% or less. Therefore, when paste extrusion molding is performed within the blending range, the filler powder distribution is uneven when the filler powder is small, and a continuous extrusion molded product cannot be obtained when the filler powder is large. . That is, even if powders having extremely different sizes are simply mixed, a uniform dispersion cannot be obtained.
そのために、ＰＴＦＥの乳化重合を行う製造業者は、下記特許文献１に示されるように、ＰＴＦＥに水性分散体の安定化剤を加える前に１種以上の粉末を混合することが可能であり、このような手法を使用すれば、目的とする混合ＰＴＦＥファインパウダーを得ることができる。 Therefore, a manufacturer performing emulsion polymerization of PTFE can mix one or more powders before adding a stabilizer of an aqueous dispersion to PTFE, as shown in Patent Document 1 below. If such a method is used, the target mixed PTFE fine powder can be obtained.
このような特許文献１に示される手法を使えるのは、ＰＴＦＥの乳化重合を行う製造業者に限定され、ＰＴＦＥファインパウダーを使用して成形品を成形する加工業者が、市販のＰＴＦＥファインパウダーから容易に目的とする混合ＰＴＦＥファインパウダーを得ることができなかった。 The method disclosed in Patent Document 1 can be used only by a manufacturer that performs emulsion polymerization of PTFE, and a processor that forms a molded product using PTFE fine powder can be easily manufactured from commercially available PTFE fine powder. Thus, the intended mixed PTFE fine powder could not be obtained.
また、ＰＴＦＥ乳化重合品の水性分散体が市販されているが、これらの水性分散体にはＰＴＦＥ乳化重合粒子の密度が２．２ｇ／ｃｍ３もあり、水中での自然沈降を防ぐために、多量の複雑な界面活性剤が分散安定剤として添加されている。上記の水性分散体を用いて１種以上の混合物を得るにはこれらに含まれる多量の複雑な界面活性剤を除去しなければならないという致命的な問題があった。 Also, aqueous dispersions of PTFE emulsion polymerization products are commercially available. These aqueous dispersions have a density of PTFE emulsion polymerization particles of 2.2 g / cm 3, and in order to prevent natural sedimentation in water, These complex surfactants are added as dispersion stabilizers. In order to obtain one or more mixtures using the above-mentioned aqueous dispersion, there has been a fatal problem that a large amount of complicated surfactants contained therein must be removed.
したがって、加工業者が入手できる組成物は製造業者の組成物に限られるという課題があった。 Therefore, the composition which a processor can obtain has the subject that it is restricted to a manufacturer's composition.
本発明者は、加工業者が市場で入手できるＰＴＦＥファインパウダーからフィラー粉末を混合した均一な混合粉末の提供及び当該混合粉末を容易に製造できる製造方法を見出したのである。 The present inventor has found a uniform mixed powder obtained by mixing filler powder from PTFE fine powder available on the market by a processor and a manufacturing method capable of easily manufacturing the mixed powder.
本願の請求項１に係るペースト押出成形用粉末は、ＰＴＦＥ乳化重合粒子の水性分散体から凝析によって得られた乳化重合粒子が凝集したＰＴＦＥ凝集粉末とフィラー粉末との凝集体を、１０℃未満で解砕及び混合したのち、この混合粉体を造粒してなることを特徴とするものである。 The powder for paste extrusion molding according to claim 1 of the present application is an aggregate of PTFE aggregated powder obtained by agglomerating emulsion polymer particles obtained by coagulation from an aqueous dispersion of PTFE emulsion polymerized particles and a filler powder at less than 10 ° C. After pulverizing and mixing, the mixed powder is granulated.
また、本願の請求項２に係るペースト押出成形用粉末は、上記請求項１において、ＰＴＦＥ凝集粉末の解砕サイズは２０μｍ以下であることを特徴とするものである。 Moreover, the paste extrusion molding powder according to claim 2 of the present application is characterized in that, in the above-mentioned claim 1, the pulverized size of the PTFE aggregated powder is 20 μm or less.
さらに、本願の請求項３に係るペースト押出成形用粉末は、上記請求項１において、ＰＴＦＥ凝集粉末の解砕サイズが１０μｍ以下であることを特徴とするものである。 Furthermore, the powder for paste extrusion molding according to claim 3 of the present application is characterized in that, in the above claim 1, the pulverized size of the PTFE aggregated powder is 10 μm or less.
さらにまた、本願の請求項４に係るペースト押出成形用粉末の製造方法は、ＰＴＦＥ乳化重合粒子の水性分散体から凝析によって得られた乳化重合粒子が凝集したＰＴＦＥ凝集粉末とフィラー粉末とドライアイスとを同時に解砕兼混合機に投入し、１０℃未満で解砕・混合したのち、この混合粉体を造粒することを特徴とするものである。 Furthermore, the paste extrusion molding powder manufacturing method according to claim 4 of the present application includes PTFE aggregated powder, filler powder, and dry ice in which emulsion polymerized particles obtained by coagulation from an aqueous dispersion of PTFE emulsion polymerized particles are aggregated. Are put into a pulverizing and mixing machine at the same time, pulverized and mixed at less than 10 ° C., and then the mixed powder is granulated.
本発明に係るペースト押出成形用粉末である混合ＰＴＦＥファインパウダーの製造方法は、主成分としてのＰＴＦＥ凝集粉末であるＰＴＦＥファインパウダーにフィラー粉末であるフィラーパウダーを添加して、１０℃以下の温度下に冷却したＰＴＦＥファインパウダーの凝集粒子を少なくともフィラーパウダーのサイズに近似したサイズに解砕して混合することを同時的に行い、フィラーパウダーをＰＴＦＥファインパウダー中に均一分散させ、さらにこの混合パウダーに湿潤する溶剤を添加して撹拌造粒することによりＰＴＦＥファインパウダーとフィラーパウダーとを均一に分散したペースト押出用粉体を得ることを特徴とするものである。 The method for producing a mixed PTFE fine powder, which is a paste extrusion powder according to the present invention, adds a filler powder, which is a filler powder, to a PTFE fine powder, which is a PTFE agglomerated powder as a main component, at a temperature of 10 ° C. or lower. The agglomerated particles of PTFE fine powder cooled to the size of the filler powder are simultaneously crushed and mixed to at least the size of the filler powder, and the filler powder is uniformly dispersed in the PTFE fine powder. By adding a wetting solvent and stirring and granulating, a powder for paste extrusion in which PTFE fine powder and filler powder are uniformly dispersed is obtained.
本発明の本質は、０．２〜０．４μｍサイズの重合粒子が５００μｍサイズに凝集させたＰＴＦＥファインパウダーを少なくともフィラーパウダーのサイズに近似のサイズまで微細に解砕させることにある。 The essence of the present invention is to finely pulverize the PTFE fine powder in which polymer particles having a size of 0.2 to 0.4 μm are aggregated to a size of 500 μm to at least a size approximate to the size of the filler powder.
この工程において重要なことは１０℃以下の温度下において行うことであり、ＰＴＦＥファインパウダーがフィビリル化ＰＴＦＥとも称されるようにパウダーにシェアを与えるとＰＴＦＥ粒子から容易に発生する微細なフィビリルを発生させないようにすることである。 What is important in this process is that it is performed at a temperature of 10 ° C. or less. When the PTFE fine powder is also referred to as fibrillated PTFE, fine fibrils that are easily generated from the PTFE particles are generated when the powder is given a share. It is not to let you.
また、従来の乳化重合後のＰＴＦＥの水性分散体とフィラーの混合は特定の条件が必要であった。親水性のフィラーが使用できないことである、その理由はＰＴＦＥ水性分散体のＰＴＦＥ粒子が界面活性剤によって包まれているが、凝析という手段、撹拌およびカチオン物質たとえば水素イオンを持つ塩酸や硝酸などの添加と撹拌によりＰＴＦＥ粒子の表面の界面活性剤を切り離すとＰＴＦＥ粒子は疎水化して凝集体の二次粒子を形成するが親水性フィラーはいつまでも水中に残るために共凝集体はできなかった。親水性フィラー、例えばガラス繊維粉末、は表面に疎水性処理を施さねばならなかった。また、ポリイミド粒子、コークス粉粒子は親水性と疎水性の中間状態にあるために、表面疎水化処理を行ったものを使用するか、またはＰＴＦＥの水性分散粒子がゾル化した瞬間に非水溶性溶剤を投入して両者を造粒する複雑な手段が必要であった。また疎水性フィラー、例えばカーボンブラックは予め分散剤を用いて水性分散体にしておく処置が必要であった。 In addition, mixing of the aqueous PTFE dispersion and filler after conventional emulsion polymerization requires specific conditions. The reason is that a hydrophilic filler cannot be used. The reason is that PTFE particles of the PTFE aqueous dispersion are encapsulated by a surfactant, but a means of coagulation, stirring and a cationic substance such as hydrochloric acid or nitric acid having hydrogen ions, etc. When the surfactant on the surface of the PTFE particles was separated by adding and stirring, the PTFE particles became hydrophobic and formed secondary particles of aggregates, but the hydrophilic filler remained in the water forever, so a co-aggregate could not be formed. Hydrophilic fillers, such as glass fiber powder, had to be subjected to a hydrophobic treatment on the surface. In addition, since polyimide particles and coke powder particles are in an intermediate state between hydrophilicity and hydrophobicity, use those that have been subjected to surface hydrophobization treatment or water-insoluble at the moment when the aqueous dispersion particles of PTFE are solated. A complicated means of adding a solvent and granulating both was necessary. Further, a hydrophobic filler such as carbon black needs to be treated in advance with an aqueous dispersion using a dispersant.
このような性質が所以で石油系溶剤をＰＴＦＥ乳化重合粒子の潤滑剤としてＰＴＦＥ乳化重合粒子をほぼ細密充填状態に成形するペースト押出成形という他の高分子有機化合物の成形方法には採用されない成形方法が採られている。 Because of these properties, a molding method that is not adopted in other polymer organic compound molding methods, such as paste extrusion molding, in which a PTFE emulsion polymerized particle is molded into a nearly finely packed state using a petroleum solvent as a lubricant for PTFE emulsion polymerized particles. Has been adopted.
ペースト押出は、ＰＴＦＥ乳化重合粒子の流動によって押出物が形成されるが、微細なフィビリルが発生したＰＴＦＥ粒子は押出時の流動がスムースに行われず、ＰＴＦＥの細密充填を抑制し、ときには乱流状態になり、さらには連続物にならない等の結果を招くのである。 In paste extrusion, extrudates are formed by the flow of PTFE emulsion polymer particles, but the PTFE particles with fine fibrils are not smoothly flowed during extrusion, suppressing the fine filling of PTFE, sometimes in a turbulent state In addition, the result of not becoming a continuous material is caused.
５００μｍサイズに凝集しているＰＴＦＥファインパウダーを微細粒子の状態に戻すことは容易ではないが、本発明者は、このＰＴＦＥファインパウダーが、１９℃〜２１℃にあるＰＴＦＥの転移点以下ではＰＴＦＥ粒子表面からフィビリルが発生しにくいことを活用して、フィラー粉末と共に前記の転移点以下の温度状態で微細に解砕することと解砕後に湿潤溶剤で再造粒することによって従来からのペースト押出成形に展開できることを見出し、混合ＰＴＦＥファインパウダーとそれを製造する方法を開発した。 Although it is not easy to return the PTFE fine powder agglomerated to a size of 500 μm to a fine particle state, the present inventor believes that the PTFE fine powder is below the transition point of PTFE at 19 ° C. to 21 ° C. Utilizing the fact that fibrils are unlikely to be generated from the surface, conventional paste extrusion molding by finely crushing with filler powder at a temperature below the above transition point and re-granulating with a wet solvent after crushing And developed a mixed PTFE fine powder and a method for producing the same.
本発明の効果はフィラーの種類・組成が自由に採用できることにある。 The effect of the present invention is that the type and composition of the filler can be freely adopted.
本発明はＰＴＦＥファインパウダーと混合されるフィラーの種類・組成は特に限定がないことで優れるとともに、表面処理など事前の処理の必要がないために経済的メリットが存在するのである。フィラーの種類としては同類の分子量・変性の状態が異なるファインパウダーおよびモールディングパウダー粒子も含まれる。 The present invention is excellent in that the type and composition of the filler mixed with the PTFE fine powder are not particularly limited, and there is an economic merit because there is no need for prior treatment such as surface treatment. The types of fillers include fine powders and molding powder particles having the same molecular weight and modified state.
「ＰＴＦＥファインパウダーの解砕」
市販のＰＴＦＥ乳化重合粒子が凝集して約５００μｍになっている粒子を微細に解砕するうえにおいて重要なことはＰＴＦＥ乳化重合粒子から小繊維であるフィビリルを発現させないことである。
“Disintegration of PTFE fine powder”
What is important in finely pulverizing particles in which commercially available PTFE emulsion-polymerized particles are aggregated to about 500 μm is to prevent the fibrils that are fibrils from appearing from the PTFE emulsion-polymerized particles.
このためにＰＴＦＥの結晶転移点の１９〜２１℃（室温転移点と呼ばれる）以下で解砕しなければならないことである。解砕のためにカッターミキサーやヘンシェルミキサーを使用すると翼の回転による流動抵抗によってパウダーの温度は必ず上昇する。したがって、回転が停止するまでパウダーの温度は室温転移点に達してはならないこと、及びそのために回転開始温度は室温転移点より遥かに低くなければならない。また、ミキサー槽内には滞留部分あり、局部的に温度が上昇することにも注意しなければならない。 For this purpose, it must be crushed below the crystal transition point of PTFE at 19-21 ° C. (called the room temperature transition point). When a cutter mixer or Henschel mixer is used for crushing, the temperature of the powder always rises due to the flow resistance caused by the rotation of the blades. Therefore, the temperature of the powder must not reach the room temperature transition point until rotation stops, and for that reason the rotation start temperature must be much lower than the room temperature transition point. It should also be noted that there is a stagnant part in the mixer tank and the temperature rises locally.
また、ここで重要なことは、解砕混合粉体を混合機の外部ジャケットから冷却して行う方法は、内部パウダーの流動抵抗や解砕抵抗による昇温速度に冷却速度が追い付かず、ＰＴＦＥ乳化重合粒子が局部的あるいは全的に室温転移点を上回り、ＰＴＦＥ乳化重合粒子が小繊維を発現する確率が高い。このＰＴＦＥ乳化重合粒子が小繊維を発現する現象を確実に抑制する必要がある。 What is important here is that the method of cooling the pulverized mixed powder from the outer jacket of the mixer does not keep up with the temperature rise rate due to the flow resistance or pulverization resistance of the internal powder, and PTFE emulsification. There is a high probability that the polymer particles locally or entirely exceed the room temperature transition point, and the PTFE emulsion polymer particles exhibit fibrils. It is necessary to surely suppress the phenomenon that the PTFE emulsion polymerized particles develop fibrils.
本発明者はこれを確実に行うために、混合される粉体を熱伝導壁なしに、内部から直接冷却する手段として、粉体と共にドライアイス（固体の炭酸ガス）を同時的に投入して解砕と混合を行うことでＰＴＦＥ乳化重合粒子が小繊維を発現する現象を確実に抑制する手段を見出したのである。 In order to ensure this, the present inventor simultaneously put dry ice (solid carbon dioxide gas) together with the powder as a means for directly cooling the powder to be mixed without heat conduction walls from the inside. The present inventors have found a means for reliably suppressing the phenomenon that PTFE emulsion-polymerized particles develop fibrils by crushing and mixing.
なお、カッターミキサーやヘンシェルミキサーの蓋に、ドライアイスが気化して発生する炭酸ガスを放出するベントフィルターを設置することが必要である。 In addition, it is necessary to install the vent filter which discharge | releases the carbon dioxide gas which vaporizes when dry ice vaporizes in the lid | cover of a cutter mixer or a Henschel mixer.
ＰＴＦＥファインパウダーの解砕サイズの程度は、混合するフィラーパウダーのサイズと同等レベルが望ましいが、フィラーパウダーがＰＴＦＥ乳化重合粒子より小さい場合は１０μｍ以下でよい、またフィラーパウダーが１０μｍより大きい場合は２０μｍ以下でよい。 The degree of pulverization size of the PTFE fine powder is desirably the same level as the size of the filler powder to be mixed. However, when the filler powder is smaller than the PTFE emulsion polymerized particles, it may be 10 μm or less, and when the filler powder is larger than 10 μm, 20 μm. The following is acceptable.
「解砕混合した微粉末の造粒」
解砕混合した微細な粉末は、その状態では工業的な製品を加工する工程で用いることが出来ないので約５００μｍ以上の粒径に仕上げなければならない。
"Granulation of finely ground powder"
The fine powder that has been pulverized and mixed cannot be used in the process of processing an industrial product in that state, so it must be finished to a particle size of about 500 μm or more.
その理由はＰＴＦＥ乳化重合粒子をＰＴＦＥファインパウダーに加工するのと同じように、製造業者側としては、ＰＴＦＥファインパウダーに加工した方が、乾燥、計量、梱包、移送などにおける取り扱い上の困難性が解消し、この材料を使用して成形加工する加工者側としては、ＰＴＦＥファインパウダーに加工しなければペースト押出成形における計量、助剤混合、金型充填などの工業生産上の取り扱いができないからである。 The reason for this is that, like the processing of PTFE emulsion polymerized particles into PTFE fine powder, it is difficult for the manufacturer to handle PTFE fine powder in drying, weighing, packing, transporting, etc. The processing side that uses this material to solve the problem, because it can not be handled in industrial production, such as weighing in paste extrusion molding, mixing of auxiliaries, filling molds, etc., unless it is processed into PTFE fine powder. is there.
造粒の方法は微細粉の２０〜３０％重量の溶剤で湿潤させ、その状態で泡立て器（ホイッパー）で撹拌することで微粉末を丸めて造粒することができる。各種の造粒機が販売されているが、あまりせん断力が作用しないものが好ましい。また、造粒工程での温度も室温転移点以下で行うのが最も好ましい。造粒サイズは平均粒径で３００μｍ〜２０００μｍにするのが好ましい。湿潤溶剤の種類は１５０℃以下程度で全量が気化乾燥できることとＰＴＦＥとフィラーを同時に湿潤できるものであればよい、この点で水分が４０％未満のイソプロピルアルコールが使用することができる。湿潤溶剤は気化乾燥されてペースト押出用粉末となる。 In the granulation method, the fine powder can be rounded and granulated by wetting with a solvent of 20 to 30% by weight of the fine powder and stirring with a whisk in that state. Various types of granulators are on the market, but those that do not have much shearing force are preferred. Moreover, it is most preferable to perform the temperature in the granulation step at or below the room temperature transition point. The granulation size is preferably 300 μm to 2000 μm in terms of average particle size. Any type of wet solvent may be used as long as it can vaporize and dry at about 150 ° C. or less, and can wet PTFE and the filler simultaneously. In this respect, isopropyl alcohol having a water content of less than 40% can be used. The wet solvent is vaporized and dried to form a paste extruding powder.
グラファイト混合粉と成形品の作製
１．混合粉の作製
「予備混合」
主成分としてのＰＴＦＥファインパウダーグレードＦ−１０６（ダイキン工業株式会社製、平均粒径が約５００μｍ、嵩比重が４５０ｇ／リットル）８４０ｇと、黒鉛粉末グレード青Ｐ（日本黒鉛工業株式会社製、平均粒径１０μｍ）３６０ｇと、ハンマーで１〜３ｃｍサイズに砕いたドライアイス６００ｇを、ポリエチレン袋内で手持ちで軽く混ぜた。
Production of graphite mixed powder and molded product 1. Preparation of mixed powder "Preliminary mixing"
PTFE fine powder grade F-106 (Daikin Kogyo Co., Ltd., average particle size of about 500 μm, bulk specific gravity 450 g / liter) 840 g and graphite powder grade Blue P (Nippon Graphite Industries Co., Ltd., average particle) 360 g (diameter 10 μm) and 600 g of dry ice crushed to a size of 1 to 3 cm with a hammer were gently mixed by hand in a polyethylene bag.
「混合機への投入」
次にこのポリエチレン袋の内容物をカッターミキサー（ＤＩＴＯ ＳＡＭＡ製 Ｆｏｏｄ Ｐｒｏｃｅｓｓｏｒ Ｃｕｔｔｅｒ Ｍｉｘｅｒ ３．５ＬＴ−２Ｓｐｅｅｄ）の容器内に移した。
“Introducing into the blender”
Next, the contents of the polyethylene bag were transferred into a container of a cutter mixer (Food Processor Cutter Mixer 3.5LT-2Speed manufactured by DITO SAMA).
「低速撹拌混合」
混合機への投入後カッターの回転を低速撹拌の１５００ｒｐｍで３０秒間撹拌を行った。回転停止後の粉体温度をアルコール温度計で測定した。温度は−１５℃であった。
"Low speed mixing"
After feeding into the mixer, the cutter was stirred for 30 seconds at 1500 rpm with low speed stirring. The powder temperature after the rotation was stopped was measured with an alcohol thermometer. The temperature was -15 ° C.
「高速撹拌混合一回目」
次にカッターの回転を高速撹拌の３０００ｒｐｍで３０秒間撹拌を行った。回転停止後の粉体温度は−５℃であった。
"High-speed stirring mixing first"
Next, the rotation of the cutter was performed at 3000 rpm, which is high-speed stirring, for 30 seconds. The powder temperature after the rotation stopped was -5 ° C.
「二回目の高速撹拌混合」
混ざり具合を均一にするために、二回目の高速撹拌を３０秒間行った。回転停止後の粉体温度は２℃であった。
"Second high-speed stirring and mixing"
In order to make the mixing condition uniform, the second high-speed stirring was performed for 30 seconds. The powder temperature after the rotation stopped was 2 ° C.
「三回目の高速撹拌混合」
混ざり具合をさらに均一にするために、砕いたドライアイス２５０ｇを追加して、低速撹拌で５秒程の回転後に、続いて三回目の高速撹拌を３０秒間行った。回転停止後の粉体温度は−５℃であった。
"The third high-speed stirring and mixing"
In order to make the mixing even more uniform, 250 g of crushed dry ice was added, and after about 5 seconds of rotation with low speed stirring, the third high speed stirring was performed for 30 seconds. The powder temperature after the rotation stopped was -5 ° C.
得られた混合粉の性状は流動性に欠けた無定形状粉であった。嵩比重は約３８０ｇ／リットルであった。 The property of the obtained mixed powder was an amorphous powder lacking fluidity. The bulk specific gravity was about 380 g / liter.
混合粉末をレーザ回析／散乱式粒子径分布測定装置で測定した結果、９０％以上がグラファイト公称径の２０μｍ以下であった。 As a result of measuring the mixed powder with a laser diffraction / scattering particle size distribution measuring apparatus, 90% or more was 20 μm or less of the nominal graphite diameter.
２．混合粉の造粒
ミキサー内の混合粉１．２ｋｇを５リットルの丸底の容器に移し、７０％イソプロピルアルコール（ＩＰＡ）水を３００ｃｃ添加して電動の泡立て器（ホイッパー）で撹拌して大凡１〜２ｍｍの大きさに造粒した段階で撹拌を停止した。
2. Granulation of the mixed powder Transfer 1.2kg of the mixed powder in the mixer to a 5 liter round bottom container, add 300cc of 70% isopropyl alcohol (IPA) water, and stir it with an electric whisk (whipper). Stirring was stopped at the stage of granulation to a size of ˜2 mm.
続いて、ＩＰＡ水で湿った造粒粉を１２０℃の乾燥器に入れ水分がなくなるまで乾燥した。 Subsequently, the granulated powder moistened with IPA water was placed in a dryer at 120 ° C. and dried until there was no moisture.
造粒品の粒径は約０．５〜２ｍｍであった、嵩比重は約５５０ｇ／リットルであった。 The granulated product had a particle size of about 0.5 to 2 mm and a bulk specific gravity of about 550 g / liter.
３．ＲＲ１００−２．５φストランド成形性評価
２５０ｃｃの広口ポリエチレン瓶に造粒粉１００ｇを入れ、そこに石油溶剤アイソパーＨ（エクソン社製）２３ｇを加えて４０℃の保温箱に１５時間放置した。
3. Evaluation of RR100-2.5φ strand moldability 100 g of granulated powder was put in a 250 cc wide-mouth polyethylene bottle, 23 g of petroleum solvent Isopar H (manufactured by Exxon) was added thereto, and the mixture was left in a heat-retaining box at 40 ° C. for 15 hours.
続いて助剤混合した混合粉をＲＲ１００ストランド成形テスト金型（内径２５ｍｍφのシリンダー部と先端ダイオリフィス２．５ｍｍφ）内に充填してラム速度２０ｍｍ／分で内填物を押出、いわゆるペースト押出方法でストランドの押出成形をおこなった。図１に示すように、ストランドはスムースに押出することができた。図２はスムースに押し出されたストランドを示し、図３は押出乱流によりスムースに押し出されなかったストランドを示す。 Subsequently, the mixed powder mixed with the auxiliary agent is filled into an RR100 strand molding test mold (cylinder portion with an inner diameter of 25 mmφ and a tip die orifice of 2.5 mmφ), and the inner material is extruded at a ram speed of 20 mm / min. The strand was extruded. As shown in FIG. 1, the strand could be smoothly extruded. FIG. 2 shows strands that are smoothly extruded, and FIG. 3 shows strands that are not smoothly extruded due to extrusion turbulence.
４．１５０幅シート押出成形性評価
２リットルの広口ポリエチ瓶に造粒粉５００ｇを入れ、そこに石油溶剤アイソパーＨ（エクソン社製）２３ｇを加えて４０℃の保温箱に１５時間放置した。
4. Evaluation of 150-width sheet extrusion moldability 500 g of granulated powder was put into a 2 liter wide-mouthed polyethylene bottle, 23 g of petroleum solvent Isopar H (manufactured by Exxon) was added thereto, and the mixture was left in a heat-retaining box at 40 ° C. for 15 hours.
続いて助剤混合した混合粉を、断面が１辺５０ｍｍの正方形のシリンダー部と先端のダイ出口が１５０ｍｍ幅に広がり、厚みが２ｍｍに絞られる構造の金型内に充填してラム速度２５ｍｍ／分で内填物を押出し、いわゆるペースト押出を行い、幅１５０ｍｍ、厚み２ｍｍのシートをスムースに成形することができた。 Subsequently, the mixed powder mixed with the auxiliary agent is filled into a mold having a structure in which a square cylinder portion having a cross section of 50 mm on one side and a die outlet at the front end is widened to 150 mm and the thickness is reduced to 2 mm, and the ram speed is 25 mm / The inner material was extruded in minutes, and so-called paste extrusion was performed, and a sheet having a width of 150 mm and a thickness of 2 mm could be smoothly formed.
さらに、圧延ロールで１５０μｍのシートに圧延し、３７０℃の電気炉で焼結した。 Further, it was rolled into a 150 μm sheet with a rolling roll and sintered in an electric furnace at 370 ° C.
焼結シートをテスターで抵抗を測定したところ２〜５Ωと導電性を示した。 When the resistance of the sintered sheet was measured with a tester, it showed conductivity of 2 to 5Ω.
（弁柄）顔料混合粉と成形品の作製
１．混合粉の作製
「予備混合」
主成分としてのＰＴＦＥファインパウダーグレードＦ−１０６（ダイキン工業株式会社製、平均粒径が約５００μｍ、嵩比重が４５０ｇ／リットル）１０００ｇと、弁柄グレードＮＳＲ−５００（森下弁柄工業株式会社製、）４ｇと、ハンマーで１〜３ｃｍサイズに砕いたドライアイス４００ｇをポリエチレン袋内で手持ちで軽く混ぜた。
(Valve) Preparation of pigment mixed powder and molded product Preparation of mixed powder "Preliminary mixing"
PTFE fine powder grade F-106 (Daikin Kogyo Co., Ltd., average particle size of about 500 μm, bulk specific gravity 450 g / liter) 1000 g as a main component, and petal grade NSR-500 (Morishita Valve Co., Ltd., ) 4 g and 400 g of dry ice crushed to a size of 1 to 3 cm with a hammer were gently mixed by hand in a polyethylene bag.
「混合機への投入」
次にこのポリエチレン袋の内容物をカッターミキサー（ＤＩＴＯ ＳＡＭＡ製 Ｆｏｏｄ Ｐｒｏｃｅｓｓｏｒ Ｃｕｔｔｅｒ Ｍｉｘｅｒ ３．５ＬＴ−２Ｓｐｅｅｄ）の容器内に移した。
“Introducing into the blender”
Next, the contents of the polyethylene bag were transferred into a container of a cutter mixer (Food Processor Cutter Mixer 3.5LT-2Speed manufactured by DITO SAMA).
「低速撹拌混合」
混合機への投入後、カッターの回転を低速撹拌の１５００ｒｐｍで３０秒間撹拌を行った。回転停止後の粉体温度をアルコール温度計で測定した。温度は−５℃であった。
"Low speed mixing"
After feeding into the mixer, the cutter was stirred for 30 seconds at 1500 rpm with low speed stirring. The powder temperature after the rotation was stopped was measured with an alcohol thermometer. The temperature was -5 ° C.
「高速撹拌混合一回目」
予備混合の終了温度がやや高いので、ドライアイス３００ｇを追加してから低速撹拌で５秒間撹拌の回転後、カッターの回転を高速撹拌の３０００ｒｐｍで３０秒間撹拌を行った。回転停止後の粉体温度は−１５℃であった。
"High-speed stirring mixing first"
Since the end temperature of the preliminary mixing was slightly high, 300 g of dry ice was added, and after stirring for 5 seconds with low speed stirring, the rotation of the cutter was stirred for 30 seconds at 3000 rpm with high speed stirring. The powder temperature after the rotation stopped was -15 ° C.
「二回目の高速撹拌混合」
混ざり具合を均一にするために、二回目の高速撹拌を３０秒間行った。回転停止後の粉体温度は−５℃であった。
"Second high-speed stirring and mixing"
In order to make the mixing condition uniform, the second high-speed stirring was performed for 30 seconds. The powder temperature after the rotation stopped was -5 ° C.
「三回目の高速撹拌混合」
混ざり具合をさらに均一にするために三回目の高速撹拌を３０秒間行った。回転停止後の粉体温度は５℃であった。
"The third high-speed stirring and mixing"
In order to make the mixing condition even more uniform, the third high-speed stirring was performed for 30 seconds. The powder temperature after stopping the rotation was 5 ° C.
得られた混合粉の性状は流動性に欠けた無定形状粉であった。嵩密度は約３５０ｇ／リットルであった。 The property of the obtained mixed powder was an amorphous powder lacking fluidity. The bulk density was about 350 g / liter.
混合粉末１００ｇをＪＩＳ標準篩５８０メッシュ（目開き２２μｍ）上に置き、ＩＰＡのシャワ−で粉末を繰り返し濾過した。濾過物のＩＰＡを乾燥除去した濾過固形分は９９ｇであった。 100 g of the mixed powder was placed on a JIS standard sieve 580 mesh (aperture 22 μm), and the powder was repeatedly filtered with an IPA shower. The filtered solid content obtained by drying and removing IPA of the filtrate was 99 g.
２．混合粉の造粒
ミキサー内の混合粉１ｋｇを５リットルの丸底の容器に移し、７０％イソプロピルアルコール（ＩＰＡ）水を２５０ＣＣ添加して電動の泡立て器（ホイッパー）で撹拌して大凡１〜２ｍｍの大きさに造粒した段階で撹拌を停止した。
2. Granulation of the mixed powder Transfer 1kg of the mixed powder in the mixer to a 5 liter round bottom container, add 250CC of 70% isopropyl alcohol (IPA) water, and stir it with an electric frother (whipper). Stirring was stopped at the stage of granulation to the size of.
続いて、ＩＰＡ水で湿った造粒粉を１２０℃の乾燥器に入れ水分がなくなるまで乾燥した。 Subsequently, the granulated powder moistened with IPA water was placed in a dryer at 120 ° C. and dried until there was no moisture.
造粒品の粒径は約０．５〜２ｍｍであった、嵩比重は約５５０ｇ／リットルであった。 The granulated product had a particle size of about 0.5 to 2 mm and a bulk specific gravity of about 550 g / liter.
３．ＲＲ１００−２．５φストランド成形性評価
２５０ｃｃの広口ポリエチレン瓶に造粒粉１００ｇを入れ、そこに石油溶剤アイソパーＨ（エクソン社製）２３ｇを加えて４０℃の保温箱に１５時間放置した。
3. Evaluation of RR100-2.5φ strand moldability 100 g of granulated powder was put in a 250 cc wide-mouth polyethylene bottle, 23 g of petroleum solvent Isopar H (manufactured by Exxon) was added thereto, and the mixture was left in a heat-retaining box at 40 ° C. for 15 hours.
続いて助剤混合した混合粉を内径２５ｍｍφのシリンダー部と先端ダイオリフィス２．５ｍｍφの金型内に充填してラム速度２０ｍｍ／分で内填物を押出し、いわゆるペースト押出により、ストランドの押出成形をおこなった。ストランドは実施例１と同様にスムースに押出することができた。 Subsequently, the mixed powder mixed with the auxiliary agent is filled into a cylinder portion having an inner diameter of 25 mmφ and a die having a tip die orifice of 2.5 mmφ, and the inner material is extruded at a ram speed of 20 mm / min. I did it. The strand could be smoothly extruded as in Example 1.
４．１５０幅シート押出成形評価と薄膜圧延による顔料着色のバラツキの検査
２リットルの広口ポリエチ瓶に造粒粉５００ｇを入れ、そこに石油溶剤アイソパーＨ（エクソン社製）１１５ｇを加えて４０℃の保温箱に１５時間放置した。
4. Evaluation of 150-width sheet extrusion molding and variation in pigmentation by thin film rolling Put 500 g of granulated powder into a 2 liter wide-mouthed polyethylene bottle, add 115 g of petroleum solvent Isopar H (manufactured by Exxon) to 40 ° C. It was left in a heat insulation box for 15 hours.
続いて助剤混合した混合粉を、断面が１辺５０ｍｍの正方形のシリンダー部と先端のダイ出口が１５０ｍｍ幅に広がり、厚みが２ｍｍに絞られる構造の金型内に充填してラム速度２５ｍｍ／分で内填物を押出し、いわゆるペースト押出を行い、幅１５０ｍｍ、厚み２ｍｍのシートをスムースに成形することができた。 Subsequently, the mixed powder mixed with the auxiliary agent is filled into a mold having a structure in which a square cylinder portion having a cross section of 50 mm on one side and a die outlet at the front end is widened to 150 mm and the thickness is reduced to 2 mm, and the ram speed is 25 mm / The inner material was extruded in minutes, and so-called paste extrusion was performed, and a sheet having a width of 150 mm and a thickness of 2 mm could be smoothly formed.
さらに、圧延ロールで１００μｍのフィルムに圧延した。助剤を乾燥したシートは肉眼で見て色ムラのバラツキがない均一な着色フィルムであった。 Further, the film was rolled into a 100 μm film with a rolling roll. The sheet dried from the auxiliary agent was a uniform colored film with no unevenness in color when viewed with the naked eye.
熱伝導性に優れた炭化ケイ素との混合粉と成形品の作製
１．混合粉の作製
混合粉は主成分としてのＰＴＦＥファインパウダーグレードＦ−１０６（ダイキン工業株式会社製、平均粒径が約５００μｍ、嵩比重が４５０ｇ／リットル）７２０ｇと、炭化ケイ素ＧＣ２００００（ライオン株式会社製平均粒径０．５μｍのＳｉＣ）４８０ｇの重量比と、ハンマーで１〜３ｃｍサイズに砕いたドライアイス４００ｇをポリエチレン袋内で手持ちで軽く混ぜた。その後の撹拌混合工程は実施例２と同様に行った。
Preparation of powder mixture and molded product of silicon carbide with excellent thermal conductivity Preparation of mixed powder The mixed powder is PTFE fine powder grade F-106 (manufactured by Daikin Industries, Ltd., average particle size is about 500 μm, bulk specific gravity is 450 g / liter) as a main component, and silicon carbide GC20000 (manufactured by Lion Corporation). A weight ratio of 480 g of SiC having an average particle diameter of 0.5 μm and 400 g of dry ice crushed to a size of 1 to 3 cm with a hammer were gently mixed by hand in a polyethylene bag. The subsequent stirring and mixing step was performed in the same manner as in Example 2.
撹拌終了後の温度は殆ど同じであった。 The temperature after completion of stirring was almost the same.
混合粉末をレーザ回析／散乱式粒子径分布測定装置で測定した結果、最小粒子径０．３３９μｍ以上、最大粒子径１２μｍ以下で平均粒径が３．１μｍであった。図４に測定結果を示す。 As a result of measuring the mixed powder with a laser diffraction / scattering particle size distribution measuring apparatus, the minimum particle size was 0.339 μm or more, the maximum particle size was 12 μm or less, and the average particle size was 3.1 μm. FIG. 4 shows the measurement results.
２．混合粉の造粒
ミキサー内の混合粉１Ｋｇをボール（５リットルの丸底の容器）に移し、イソプロピルアルコール（ＩＰＡ）を２５０ＣＣ添加して電動の泡立て器（ホイッパー）で撹拌して大凡１〜２ｍｍの大きさに造粒した段階で撹拌を停止した。
2. Granulation of the mixed powder Transfer 1kg of the mixed powder in the mixer to a bowl (5 liter round bottom container), add 250 CC of isopropyl alcohol (IPA), and stir it with an electric whisk (whipper). Stirring was stopped at the stage of granulation to the size of.
続いて、ＩＰＡで湿った造粒粉を１２０℃の乾燥器で乾燥した。 Subsequently, the granulated powder moistened with IPA was dried with a drier at 120 ° C.
造粒品の粒径は約０．５〜３ｍｍであった。嵩比重は約５５０ｇ／リットルであった。 The particle size of the granulated product was about 0.5-3 mm. The bulk specific gravity was about 550 g / liter.
３．造粒粉によるシートのペースト押出成形と圧延フィルムの作製
２リットルの広口ポリエチ瓶に造粒粉５００ｇを入れ、そこに石油溶剤アイソパーＨ（エクソン社製）１２５ｇを加えて４０℃の保温箱に１５時間放置した。
3. Sheet extrusion with granulated powder and production of rolled film Put 500 g of granulated powder into a 2 liter wide-mouthed polyethylene bottle, add 125 g of petroleum solvent Isopar H (manufactured by Exxon), and add 15 Left for hours.
続いて助剤混合した混合粉を、断面が１辺５０ｍｍの正方形のシリンダー部と先端のダイ出口が１５０ｍｍ幅に広がり、厚みが２ｍｍに絞られる構造の金型内に充填してラム速度２５ｍｍ／分で内填物を押出し、いわゆるペースト押出を行い幅１５０ｍｍ、厚み２ｍｍのシートをスムースに成形することができた。 Subsequently, the mixed powder mixed with the auxiliary agent is filled into a mold having a structure in which a square cylinder portion having a cross section of 50 mm on one side and a die outlet at the front end is widened to 150 mm and the thickness is reduced to 2 mm, and the ram speed is 25 mm / The insert was extruded in minutes, and so-called paste extrusion was carried out to smoothly form a sheet having a width of 150 mm and a thickness of 2 mm.
さらに、圧延ロールで１００μｍのフィルムに圧延した。 Further, the film was rolled into a 100 μm film with a rolling roll.
続いてＰＴＦＥの融点を超える３７０℃の電気炉で焼結して熱伝導性フィルムを作製した。 Subsequently, it was sintered in an electric furnace at 370 ° C. exceeding the melting point of PTFE to produce a heat conductive film.
３リットルの広口ポリエチレン瓶に実施例１と同じ割合でＰＴＦＥファインパウダーグレードＦ−１０６（ダイキン工業株式会社製、平均粒径が約５００μｍ、嵩比重が４５０ｇ／リットル）８４０ｇを入れ、続いて黒鉛粉末グレード青Ｐ（日本黒鉛工業株式会社製、平均粒径１０μｍ）３６０ｇを加え、蓋をして５分間程ハンドシェークで両粉末を混合した。 840 g of PTFE fine powder grade F-106 (manufactured by Daikin Industries, Ltd., average particle diameter of about 500 μm, bulk specific gravity of 450 g / liter) is put in a 3 liter wide-mouth polyethylene bottle at the same ratio as in Example 1, followed by graphite powder 360 g of grade blue P (manufactured by Nippon Graphite Industry Co., Ltd., average particle size 10 μm) was added, and the powder was mixed by handshaking for about 5 minutes.
混合後にアイソパーＨを２７６ｇ注入して、また５分間程ハンドシェークで混合した後、 実施例１と同様にＲＲ１００−２．５ｍｍφのストランド成形と１５０ｍｍ幅シート押出成形を行ったがいずれも連続した成形物を得ることができなかった。 After mixing, 276 g of Isopar H was injected and mixed by handshaking for about 5 minutes, and then RR100-2.5 mmφ strand molding and 150 mm width sheet extrusion molding were carried out in the same manner as in Example 1, but both were continuous moldings. Could not get.
実施例１と同様の品種と組成のＰＴＦＥファインパウダーとグラファイト粉末とをポリエチレン袋内で手持ちで軽く混ぜた。 PTFE fine powder and graphite powder having the same varieties and compositions as in Example 1 were lightly mixed by hand in a polyethylene bag.
この最初の温度は２３℃であった。 This initial temperature was 23 ° C.
ドライアイスを用いず実施例１の手順で混合粉の作製をした。 The mixed powder was prepared according to the procedure of Example 1 without using dry ice.
「混合機への投入」
次にこのポリエチレン袋の内容物をカッターミキサー（ＤＩＴＯ ＳＡＭＡ製 Ｆｏｏｄ Ｐｒｏｃｅｓｓｏｒ Ｃｕｔｔｅｒ Ｍｉｘｅｒ ３．５ＬＴ−２Ｓｐｅｅｄ）の容器内に移した。
“Introducing into the blender”
Next, the contents of the polyethylene bag were transferred into a container of a cutter mixer (Food Processor Cutter Mixer 3.5LT-2Speed manufactured by DITO SAMA).
「低速撹拌混合」
混合機への投入後、カッターの回転を低速撹拌の１５００ｒｐｍで３０秒間撹拌を行った。回転停止後の粉体温度をアルコール温度計で測定した。温度は２７℃であった。
"Low speed mixing"
After feeding into the mixer, the cutter was stirred for 30 seconds at 1500 rpm with low speed stirring. The powder temperature after the rotation was stopped was measured with an alcohol thermometer. The temperature was 27 ° C.
「高速撹拌混合一回目」
次にカッターの回転を高速撹拌の３０００ｒｐｍで３０秒間撹拌を行った。回転停止後の粉体温度は５５℃であった。
"High-speed stirring mixing first"
Next, the rotation of the cutter was performed at 3000 rpm, which is high-speed stirring, for 30 seconds. The powder temperature after stopping the rotation was 55 ° C.
「二回目の高速撹拌混合」
混ざり具合を均一にするために、二回目の高速撹拌を３０秒間行った。回転停止後の粉体温度は８０℃であった。
"Second high-speed stirring and mixing"
In order to make the mixing condition uniform, the second high-speed stirring was performed for 30 seconds. The powder temperature after stopping the rotation was 80 ° C.
「三回目の高速撹拌混合」
混ざり具合をさらに均一にするために、三回目の高速撹拌を３０秒間行った。回転停止後の粉体温度は１００℃であった。
"The third high-speed stirring and mixing"
In order to make the mixing even more uniform, the third high-speed stirring was performed for 30 seconds. The powder temperature after the rotation stopped was 100 ° C.
得られた混合粉の性状は流動性が全くなく、粉末とは呼べない粘りのある様相であった。 The properties of the obtained mixed powder had no fluidity and had a sticky appearance that could not be called a powder.
２５０ｃｃの広口瓶内では塊化して助剤が混ぜられないものであった。 In the 250 cc wide-mouthed bottle, it was agglomerated and the auxiliary could not be mixed.
３リットルの広口ポリエチレン瓶に実施例２と同じ割合でＰＴＦＥファインパウダーＦ−１０６を１０００ｇ入れ、続いて弁柄グレードＮＳＲ−５００を４ｇ入れ、蓋をして５分間程ハンドシェークで両物を混合した。 Place 1000 g of PTFE fine powder F-106 in the same proportion as in Example 2 in a 3 liter wide-mouth polyethylene bottle, then add 4 g of petal grade NSR-500, cover and mix both items by handshaking for about 5 minutes. .
混合後にアイソパーＨを２３０ｇ注入して、また５分間程ハンドシェークで混合した後、実施例２と同様に１５０ｍｍ幅のシート押出成形を行って連続した成形物を得ることができた。さらに圧延ロールで１００μｍのフィルムにしたが、肉眼で着色部と非着色部が濃淡として明白に存在した。 After mixing, 230 g of Isopar H was injected, and after mixing by handshaking for about 5 minutes, a 150 mm width sheet extrusion was performed in the same manner as in Example 2 to obtain a continuous molded product. Furthermore, although it was set as the film of 100 micrometers with the rolling roll, the colored part and the non-colored part existed clearly as light and dark with the naked eye.
均一な混合は得られなかった。 Uniform mixing was not obtained.
３リットルの広口ポリエチレン瓶に実施例３と同じ割合でＰＴＦＥファインパウダーグレードＦ−１０６ ７２０ｇと炭化ケイ素４８０ｇを入れて比較例１と同様に混合した。 720 g of PTFE fine powder grade F-106 and 480 g of silicon carbide were put in a 3 liter wide-mouth polyethylene bottle at the same ratio as in Example 3, and mixed in the same manner as in Comparative Example 1.
また、混合後にアイソパーＨ ３００ｇ注入して、また５分間程ハンドシェークで混合した後、比較例２と同様に１５０ｍｍ幅シート押出成形を行ったが連続した成形物を得ることができなかった。 After mixing, 300 g of Isopar H was injected, and after mixing by handshaking for about 5 minutes, 150 mm width sheet extrusion was performed as in Comparative Example 2, but a continuous molded product could not be obtained.
Claims (4)
ことを特徴とするペースト押出成形用粉末の製造方法。 The polytetrafluoroethylene agglomerated powder obtained by agglomeration from the aqueous dispersion of polytetrafluoroethylene emulsion polymerized particles, agglomerated polytetrafluoroethylene agglomerated powder, filler powder and dry ice are simultaneously put into a crushing and mixing machine, and 10 ° C. A method for producing a powder for paste extrusion molding, characterized by granulating the mixed powder after pulverizing and mixing in less.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2020019894A (en) * | 2018-08-01 | 2020-02-06 | 大陽日酸株式会社 | Method for producing composite resin particles and composite resin particles |
| WO2020114419A1 (en) | 2018-12-04 | 2020-06-11 | 大金氟化工（中国）有限公司 | Preparation method for polytetrafluoroethylene composition, polytetrafluoroethylene composition, forming product, conductive pipe, heat conduction film, and substrate ccl |
| KR20210099067A (en) | 2018-12-04 | 2021-08-11 | 다이킨 플루오로케미컬즈 (차이나) 컴퍼니, 리미티드 | Method for producing polytetrafluoroethylene composition, polytetrafluoroethylene composition, molded article, conductive tube, thermally conductive film and substrate for CCL |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237254A (en) * | 1997-02-26 | 1998-09-08 | Polyplastics Co | Method for mixing thermoplastic resin with fluoro resin and method for producing fluoro-resin-containing thermoplastic resin composition |
| JP2007191563A (en) * | 2006-01-18 | 2007-08-02 | Yamakatsu Labo:Kk | Method for producing mixed polytetrafluoroethylene fine powder and mixed polytetrafluoroethylene fine powder obtained by the method for production |
-
2014
- 2014-02-19 JP JP2014029894A patent/JP2015151543A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237254A (en) * | 1997-02-26 | 1998-09-08 | Polyplastics Co | Method for mixing thermoplastic resin with fluoro resin and method for producing fluoro-resin-containing thermoplastic resin composition |
| JP2007191563A (en) * | 2006-01-18 | 2007-08-02 | Yamakatsu Labo:Kk | Method for producing mixed polytetrafluoroethylene fine powder and mixed polytetrafluoroethylene fine powder obtained by the method for production |
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