JP5792957B2 - Resin composite molded body and method for producing the same - Google Patents
Resin composite molded body and method for producing the same Download PDFInfo
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Description
本発明は、熱可塑性樹脂にフィラーが分散されている樹脂複合成形体及びその製造方法に関し、特に、グラフェン構造を有するフィラーが熱可塑性樹脂中に分散されている樹脂複合成形体及びその製造方法に関する。 The present invention relates to a resin composite molded body in which a filler is dispersed in a thermoplastic resin and a method for producing the same, and more particularly to a resin composite molded body in which a filler having a graphene structure is dispersed in a thermoplastic resin and a method for producing the same. .
従来、熱可塑性樹脂中に、各種フィラーを分散させてなる複合材料が種々提案されている。近年、このようなフィラーとして、数ｎｍから数十ｎｍの寸法のフィラーを分散させてなる複合材料がナノコンポジットとして注目されている。このようなナノレベルのフィラーとして、炭素カーボンファイバー、多層カーボンナノチューブ、カーボンファイバー、薄片化グラフェン、粘土などが知られている。 Conventionally, various composite materials in which various fillers are dispersed in a thermoplastic resin have been proposed. In recent years, as such a filler, a composite material obtained by dispersing a filler having a size of several nanometers to several tens of nanometers has attracted attention as a nanocomposite. As such nano-level fillers, carbon carbon fibers, multi-walled carbon nanotubes, carbon fibers, exfoliated graphene, clay and the like are known.
しかしながら、上記のようなナノレベルのフィラーを分散してなる樹脂成形物を成形して得られた成形品では、必ずしも十分な物性を得ることができないことがあった。 However, a molded product obtained by molding a resin molded product in which nano-level fillers are dispersed as described above may not always have sufficient physical properties.
そこで、下記の特許文献１では、樹脂とナノレベルのフィラーとをスクリューを備えたシリンダーに、加熱部を有する溶融混練部から投入し、スクリューの回転数を６００ｒｐｍ〜３０００ｒｐｍ、剪断速度を９００〜４５００ｓｅｃ−１の条件下で溶融混練した後、成形する方法が開示されている。 Therefore, in Patent Document 1 below, a resin and a nano-level filler are introduced into a cylinder equipped with a screw from a melt-kneading part having a heating part, the rotational speed of the screw is 600 rpm to 3000 rpm, and the shear rate is 900 to 4500 sec. A method of forming after melt-kneading under the condition of -1 is disclosed.
特許文献１では、上記のように、ナノレベルのフィラーと樹脂とを上記特定の条件下で溶融混練した後に成形することにより、得られる成形品の物性を高めることができるとされている。 In patent document 1, as mentioned above, it is said that the physical property of the molded product obtained can be improved by melt-kneading a nano level filler and resin under the said specific conditions, and shape | molding.
他方、用途によっては、樹脂成形品の弾性率を高めることが強く求められている。上記樹脂複合材料からなる複合材料からなる成形品において、弾性率を高めるには、フィラーを成形品中で特定の方向に配向させることが必要である。 On the other hand, depending on the application, it is strongly required to increase the elastic modulus of the resin molded product. In a molded product made of a composite material made of the resin composite material, in order to increase the elastic modulus, it is necessary to orient the filler in a specific direction in the molded product.
しかしながら、特許文献１に記載のような従来の製造方法では、ナノレベルのフィラーを十分に特定の向きに配向させることは困難であった。加えて、フィラーを充填することにより、得られる成形品等の表面が粗くなるという問題もあった。 However, in the conventional manufacturing method as described in Patent Document 1, it has been difficult to sufficiently orient the nano-level filler in a specific direction. In addition, filling the filler has a problem that the surface of the obtained molded product or the like becomes rough.
本発明の目的は、上述した従来技術の欠点を解消し、強度及び表面平滑性に優れた樹脂複合成形体、並びにそのような樹脂複合成形体を得ることを可能とする製造方法を提供することにある。 An object of the present invention is to provide a resin composite molded article excellent in strength and surface smoothness, and a production method that makes it possible to obtain such a resin composite molded article, eliminating the above-mentioned drawbacks of the prior art. It is in.
本発明に係る樹脂複合成形体は、熱可塑性樹脂と、該熱可塑性樹脂中に分散されており、グラフェン構造を有する炭素材料からなるフィラーとを含み、全フィラーの長手方向の平均方向とフィラーの長手方向とのなす角度とその角度を満たすフィラーの割合が図１に示す領域Ａ（前記割合をｙ、前記角度をｘとしたときに、ｙ≧６．６７ｘ）内に位置している、樹脂複合成形体である。 The resin composite molded body according to the present invention includes a thermoplastic resin and a filler made of a carbon material having a graphene structure dispersed in the thermoplastic resin. Resin in which the angle formed with the longitudinal direction and the proportion of the filler satisfying the angle are located in the region A shown in FIG. 1 (where y is the proportion and y ≧ 6.67x where the angle is x) It is a composite molded body.
本発明に係る樹脂複合成形体のある特定の局面では、前記フィラーはグラフェン構造を有する炭素材料、すなわち、グラフェン、カーボンナノチューブ、薄片化グラファイト及びこれらの集合体からなる群から選択された少なくとも１種の炭素材料であり、引っ張り弾性率が２．７ＧＰａ以上、表面の算術平均粗さＲａが０．１μｍ以下である。この場合には、上記特定のフィラーがフィラーの長手方向に対して配向されており、従って、引っ張り弾性率が２．７ＧＰａ以上と非常に高く、かつ算術平均粗さＲａが０．１μｍ以下と、表面平滑性により一層優れた樹脂複合成形体を提供することができる。 In a specific aspect of the resin composite molded body according to the present invention, the filler is a carbon material having a graphene structure, that is, at least one selected from the group consisting of graphene, carbon nanotubes, exfoliated graphite, and aggregates thereof. Carbon material having a tensile modulus of elasticity of 2.7 GPa or more and an arithmetic average roughness Ra of 0.1 μm or less. In this case, the specific filler is oriented with respect to the longitudinal direction of the filler. Therefore, the tensile elastic modulus is very high as 2.7 GPa or more, and the arithmetic average roughness Ra is 0.1 μm or less. It is possible to provide a resin composite molded body that is more excellent in surface smoothness.
本発明に係る樹脂複合成形体では、好ましくは、上記熱可塑性樹脂１００重量部に対し、フィラーは１〜５０重量部の割合で含有されている。フィラーがこの割合で含有されているため、樹脂複合成形体の引っ張り弾性率等の機械的物性を効果的に高めることができる。 In the resin composite molded body according to the present invention, preferably, the filler is contained in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Since the filler is contained at this ratio, mechanical properties such as tensile elastic modulus of the resin composite molded body can be effectively increased.
本発明に係る樹脂複合成形体の形状は特に限定されないが、本発明の他の特定の局面では、樹脂複合成形体はシート状物である。シート状物である場合、本発明にしたがって引っ張り弾性率を効果的に高めることができる。 The shape of the resin composite molded body according to the present invention is not particularly limited, but in another specific aspect of the present invention, the resin composite molded body is a sheet-like product. In the case of a sheet-like material, the tensile elastic modulus can be effectively increased according to the present invention.
本発明に係る樹脂複合成形体の製造方法は、熱可塑性樹脂と、グラフェン構造を有するフィラーとを含む熱可塑性樹脂組成物を剪断速度１．０×１０３ｓｅｃ−１以上の条件で射出成形し、１５０℃／分以上の冷却速度で冷却することを特徴とする。 In the method for producing a resin composite molded body according to the present invention, a thermoplastic resin composition containing a thermoplastic resin and a filler having a graphene structure is injection-molded under a shear rate of 1.0 × 10 3 sec −1 or more. And cooling at a cooling rate of 150 ° C./min or more.
本発明に係る樹脂複合成形体の製造方法のある特定の局面では、前記熱可塑性樹脂がポリオレフィンであり、前記フィラーが、長手方向を有し、長手方向の寸法と、最小外形寸法との比であるアスペクト比が７０以上であるフィラーである。 In a specific aspect of the method for producing a resin composite molded body according to the present invention, the thermoplastic resin is a polyolefin, the filler has a longitudinal direction, and a ratio of a dimension in the longitudinal direction to a minimum external dimension. A filler having an aspect ratio of 70 or more.
本発明に係る樹脂複合成形体の製造方法の他の特定の局面では、前記樹脂複合成形体が、前記熱可塑性樹脂１００重量部に対し、前記フィラーを１〜５０重量部含有している。 In another specific aspect of the method for producing a resin composite molded body according to the present invention, the resin composite molded body contains 1 to 50 parts by weight of the filler with respect to 100 parts by weight of the thermoplastic resin.
本発明に係る樹脂複合成形体では、全フィラーの長手方向の平均方向とフィラーの長手方向のなす角度とその角度を満たすフィラーの割合の関係が図１に示す領域Ａ内に位置しているので、長手方向を有するフィラーの配向性が高度に高められている。そのため、樹脂複合成形体の引っ張り弾性率等の強度を大幅に高めることが可能となる。加えて、上記のようにフィラーの配向性が高められているため、表面平滑性においても優れている。 In the resin composite molded body according to the present invention, the relationship between the average direction in the longitudinal direction of all fillers and the angle formed by the longitudinal direction of the filler and the proportion of the filler that satisfies the angle is located in the region A shown in FIG. The orientation of the filler having the longitudinal direction is highly enhanced. Therefore, it is possible to significantly increase the strength such as the tensile elastic modulus of the resin composite molded body. In addition, since the orientation of the filler is enhanced as described above, the surface smoothness is also excellent.
本発明に係る樹脂複合成形体の製造方法では、上記熱可塑性樹脂組成物を、上記特定の剪断速度範囲の剪断速度で射出成形し、上記特定の範囲の冷却速度で冷却するため、本発明の樹脂複合成形体を確実に得ることができ、それによって外的強度に優れかつ表面平滑性優れた樹脂複合成形体を提供することが可能となる。 In the method for producing a resin composite molded body according to the present invention, the thermoplastic resin composition is injection-molded at a shear rate in the specific shear rate range and cooled at the cooling rate in the specific range. A resin composite molded body can be obtained with certainty, whereby a resin composite molded body having excellent external strength and excellent surface smoothness can be provided.
以下、本発明の詳細を説明する。 Details of the present invention will be described below.
（熱可塑性樹脂）
本発明に係る樹脂複合成形体において用いられる上記熱可塑性樹脂としては、ポリオレフィン、ポリアミド、ポリエステル、ポリスチレンなどを挙げることができる。好ましくは、ポリプロピレン、ポリエチレン、エチレン−プロピレン共重合体などのポリオレフィンが用いられる。ポリオレフィンを用いることにより、樹脂複合成形体のコストを低減でき、かつ樹脂複合成形体の成形を容易に行うことができる。
(Thermoplastic resin)
Examples of the thermoplastic resin used in the resin composite molded body according to the present invention include polyolefin, polyamide, polyester, and polystyrene. Preferably, polyolefin such as polypropylene, polyethylene, and ethylene-propylene copolymer is used. By using polyolefin, the cost of the resin composite molded body can be reduced, and the resin composite molded body can be easily molded.
（フィラー）
本発明において、上記熱可塑性樹脂に分散されるフィラーとしては、グラフェン構造を有する炭素材料が用いられる。このような炭素材料としては、薄片化黒鉛、グラフェン、通常の黒鉛（グラファイト）などを好適に用いることができる。なお、薄片化黒鉛とは、通常の黒鉛すなわち元の黒鉛を剥離処理することにより薄くされた黒鉛である。「グラフェン」は、このような黒鉛や薄片化黒鉛を構成している一層のシート状物を言うものとされており、上記薄片化黒鉛は、数層〜２００層のグラフェンが積層されている構造を有する。
(Filler)
In the present invention, a carbon material having a graphene structure is used as the filler dispersed in the thermoplastic resin. As such a carbon material, exfoliated graphite, graphene, ordinary graphite (graphite), or the like can be suitably used. Note that exfoliated graphite is normal graphite, that is, graphite thinned by exfoliating original graphite. “Graphene” refers to a sheet-like material constituting such graphite or exfoliated graphite, and the exfoliated graphite has a structure in which several to 200 layers of graphene are laminated. Have
上記のような薄片化黒鉛は、黒鉛に層間に硝酸イオンなどのイオンを挿入し、加熱処理する化学的処理方法、超音波の印加などの物理的処理方法、あるいは黒鉛を作用極として電気分解を行う電気化学的方法などにより得ることができる。 The exfoliated graphite as described above is a chemical treatment method in which ions such as nitrate ions are inserted between the layers of graphite and heat treatment, a physical treatment method such as application of ultrasonic waves, or electrolysis using graphite as a working electrode. It can be obtained by the electrochemical method performed.
上記のようなフィラーの形状は特に限定されないが、上記薄片化黒鉛のように、層状構造のものが望ましい。層状構造の場合、樹脂複合成形体としてシート状物を得た場合、表面の平滑性を高めかつ引っ張り弾性率等の機械的強度性を高めることが容易となる。 The shape of the filler as described above is not particularly limited, but a layered structure like the exfoliated graphite is desirable. In the case of a layered structure, when a sheet-like material is obtained as a resin composite molded body, it becomes easy to enhance the surface smoothness and mechanical strength such as tensile elastic modulus.
上記フィラーの含有割合は、好ましくは、上記熱可塑性樹脂１００重量部に対し、１〜５０重量部の範囲である。フィラーの含有割合が少なすぎると、樹脂複合成形体の引っ張り弾性率等の機械的強度を高めることができないおそれがある。１重量部以上フィラーを配合することにより、機械的強度に優れた樹脂複合成形体を得ることができる。また、フィラーの配合割合が多すぎると、複合材料がもろくなることがある。 The content of the filler is preferably in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If the filler content is too small, the mechanical strength such as tensile modulus of the resin composite molded article may not be increased. By compounding 1 part by weight or more of the filler, a resin composite molded body having excellent mechanical strength can be obtained. Moreover, when there are too many mixture ratios of a filler, a composite material may become weak.
（樹脂複合成形体の製造方法）
本発明に係る樹脂複合成形体の製造方法では、上記熱可塑性樹脂と、上記グラフェン構造を有するフィラーとを含む熱可塑性樹脂組成物を、剪断速度１．０×１０３ｓｅｃ−１以上の条件で射出成形し、次に１５０℃／分以上の冷却速度で冷却する。それによって、本発明にしたがって、全フィラーの長手方向の平均方向とフィラーの長手方向のなす角度と、その角度にあるフィラーの割合との関係が図１に示す領域Ａ内に位置している樹脂複合成形体を得ることができる。領域Ａは図１において実線Ｂよりも上方の領域である。射出成形に際しての剪断速度が遅すぎると、フィラーの平均方向と長手方向のなす角度とその角度に含まれるフィラーの割合の関係が領域Ａを外れてしまい、配向性が低下する。冷却速度が遅すぎると、射出成形により配向したフィラーの向きが変化し、やはりフィラーの平均方向と長手方向のなす角度とその角度を満たすフィラーとの割合の関係が領域Ａを外れてしまい、配向がわるくなる。
(Method for producing resin composite molded body)
In the method for producing a resin composite molded body according to the present invention, a thermoplastic resin composition containing the thermoplastic resin and the filler having the graphene structure is subjected to a shear rate of 1.0 × 10 3 sec −1 or more. It is injection molded and then cooled at a cooling rate of 150 ° C./min or more. Accordingly, in accordance with the present invention, the resin in which the relationship between the average direction in the longitudinal direction of all the fillers and the angle between the longitudinal directions of the fillers and the proportion of the fillers at that angle is located in the region A shown in FIG. A composite molded body can be obtained. Region A is a region above solid line B in FIG. If the shear rate at the time of injection molding is too slow, the relationship between the angle formed by the average direction and the longitudinal direction of the filler and the proportion of the filler contained in the angle is out of the region A, and the orientation is deteriorated. If the cooling rate is too slow, the orientation of the filler oriented by injection molding changes, and the relationship between the angle formed by the average direction and the longitudinal direction of the filler and the ratio of the filler satisfying the angle deviates from the region A. I am disappointed.
好ましくは、上記のように、熱可塑性樹脂としてのポリオレフィンと、上記グラフェン構造を有するフィラーとを含む熱可塑性樹脂組成物を用いる。それによって、樹脂複合成形体をより一層容易にかつ確実に得ることができる。従って、引っ張り弾性率が２．７ＧＰａ以上であり、かつ表面の算術平均粗さＲａが０．１μｍ以下である平滑性に優れた樹脂複合成形体を得ることができる。 Preferably, as described above, a thermoplastic resin composition containing a polyolefin as a thermoplastic resin and the filler having the graphene structure is used. Accordingly, the resin composite molded body can be obtained more easily and reliably. Accordingly, it is possible to obtain a resin composite molded body having excellent smoothness with a tensile elastic modulus of 2.7 GPa or more and an arithmetic average roughness Ra of 0.1 μm or less.
なお、上記樹脂複合成形体の成形方法は射出成形に限らず、押し出し成形法であってもよい。 The molding method of the resin composite molded body is not limited to injection molding, and may be an extrusion molding method.
（樹脂複合成形体）
本発明に係る樹脂複合成形体は、上記熱可塑性樹脂と、該熱可塑性樹脂中に分散されており、グラフェン構造を有する炭素材料からなる上記フィラーとを含み、該フィラーの長手方向の平均方向とフィラーの長手方向とのなす角度と、その角度を満たすフィラーの割合との関係が、図１に示す領域Ａ内に位置していることを特徴とする。ここで、上記割合をｙ、上記フィラーの長手方向の平均方向とフィラーの長手方向とのなす角度をｘとすると、図１の実線Ｂは、ｙ＝６．６７ｘで表される。領域Ａは、この実線Ｂよりも図１において上方の領域、すなわち領域Ａは、ｙ≧６．６７ｘで表される領域である。ｙ≧６．６７ｘであれば、フィラーの長手方向の平均方向と、該フィラーの長手方向とがなす角度が小さいフィラーの割合が高く、従って、フィラーが長手方向に高度に配向していることになる。そのため、樹脂複合成形の引っ張り弾性率などの強度を大幅に高めることができる。さらに、フィラーの配向性が高められているため、表面平滑性も高められる。
(Resin composite molding)
The resin composite molded body according to the present invention includes the thermoplastic resin and the filler made of a carbon material having a graphene structure dispersed in the thermoplastic resin, and an average direction in the longitudinal direction of the filler. The relationship between the angle formed by the longitudinal direction of the filler and the ratio of the filler that satisfies the angle is located in the region A shown in FIG. Here, the solid line B in FIG. 1 is represented by y = 6.67x, where y is the ratio and x is the angle formed between the average direction in the longitudinal direction of the filler and the longitudinal direction of the filler. The area A is an area above the solid line B in FIG. 1, that is, the area A is an area represented by y ≧ 6.67x. If y ≧ 6.67x, the proportion of fillers having a small angle formed by the average direction of the filler in the longitudinal direction and the longitudinal direction of the filler is high, and therefore the filler is highly oriented in the longitudinal direction. Become. Therefore, the strength such as the tensile elastic modulus of the resin composite molding can be greatly increased. Furthermore, since the orientation of the filler is enhanced, the surface smoothness is also enhanced.
本発明により提供される樹脂複合成形体の形状は特に限定されず、成形により構成し得る適宜の形状とすることができる。好ましくは、シート状物である樹脂複合成形体が望ましい。その場合には、フィラーの配向性が高められるので、引っ張り弾性率の高い、高強度のシート状樹脂複合成形体を得ることができる。この場合においても、上記長手方向を有するフィラーが全フィラーの長手方向の平均値に沿うように高度に配向されるため、樹脂複合成形体からなるシート状物の表面平滑性も損なわれ難い。 The shape of the resin composite molded body provided by the present invention is not particularly limited, and can be an appropriate shape that can be formed by molding. Preferably, a resin composite molded body that is a sheet-like material is desirable. In that case, since the orientation of the filler is enhanced, a high-strength sheet-like resin composite molded body having a high tensile elastic modulus can be obtained. Also in this case, since the filler having the longitudinal direction is highly oriented so as to be along the average value in the longitudinal direction of all fillers, the surface smoothness of the sheet-like material made of the resin composite molded body is hardly impaired.
なお、本発明の樹脂複合成形体における上記フィラーの長手方向の角度とは、複合成形体を上記フィラーの最も配向している方向、通常成形時の樹脂流動方向と平行な方向に切断し、得られた端面をＳＥＭで観察することによって決定される。 The angle in the longitudinal direction of the filler in the resin composite molded body of the present invention is obtained by cutting the composite molded body in the direction in which the filler is most oriented, the direction parallel to the resin flow direction during normal molding. It is determined by observing the formed end face with SEM.
図２に、上記切断面をＳＥＭにより拡大した画像を示す。また、図３は、上記画像に、フィラーの長手方向を示す直線を表示させた状態を示す図である。すなわち、ＳＥＭで拡大して得られた画像において、フィラーの長手方向を直線で記入し、画像に現れている全フィラーにおいて、フィラーの長手方向を示す直線と画像の水平方向とのなす角度を測定する。そして、全てのフィラーについての角度の平均値を０度とし、そこから各フィラーの長手方向の角度を算出することにより、図１の関係を導くことができる。 FIG. 2 shows an image obtained by enlarging the cut surface with an SEM. Moreover, FIG. 3 is a figure which shows the state which displayed the straight line which shows the longitudinal direction of a filler on the said image. That is, in the image obtained by SEM enlargement, the longitudinal direction of the filler is entered with a straight line, and the angle between the straight line indicating the longitudinal direction of the filler and the horizontal direction of the image is measured for all fillers appearing in the image. To do. And the relationship of FIG. 1 can be derived | led-out by making the average value of the angle about all the fillers into 0 degree | times, and calculating the angle of the longitudinal direction of each filler from there.
また、樹脂複合成形体の表面の算術平均粗さＲａは、ＪＩＳ Ｂ ０６０１に準拠して測定することができる。 Further, the arithmetic average roughness Ra of the surface of the resin composite molded body can be measured in accordance with JIS B 0601.
次に、本発明の具体的な実施例及び比較例を挙げることにより、本発明を明らかにする。 Next, the present invention will be clarified by giving specific examples and comparative examples of the present invention.
（実施例１）
ポリプロピレン（日本ポリプロ社製、商品名：ノバテックＥＡ９）１００重量部と、薄片化黒鉛（グラフェン層の層面の面方向における最大寸法＝５μｍ、グラフェンの積層数：１８０層、アスペクト比：９０）１０重量部とを含む複合樹脂組成物を剪断速度１．３×１０４ｓｅｃ−１及び冷却速度１６０℃／分の条件で射出成形した。成形されたシートから試験片としてＪＩＳ Ｋ ７１１３に規定の１号のダンベルを切り出した。上記シートを上記射出成形における射出方向に沿って切断し、前述した方法にしたがって切断面を観察し、角度と割合の関係を求めた。その結果、図１に実施例１で示す位置（１．２，１０）に位置することがわかった。また、上記のようにして得たダンベルについて、ＪＩＳ Ｋ ７１１３に基づき引っ張り弾性率を測定したところ、３．２ＧＰａであった。また、ＪＩＳ Ｂ ０６０１に準拠して、上記シートの表面の算術平均粗さＲａを求めたところ、０．０８６μｍであった。
Example 1
100 parts by weight of polypropylene (manufactured by Nippon Polypro Co., Ltd., trade name: Novatec EA9) and exfoliated graphite (maximum dimension in the plane direction of the layer surface of the graphene layer = 5 μm, number of graphene layers: 180 layers, aspect ratio: 90) The composite resin composition containing a part was injection molded under the conditions of a shear rate of 1.3 × 10 4 sec −1 and a cooling rate of 160 ° C./min. No. 1 dumbbell defined in JIS K 7113 was cut out from the molded sheet as a test piece. The sheet was cut along the injection direction in the injection molding, and the cut surface was observed according to the method described above to determine the relationship between the angle and the ratio. As a result, it was found that it was located at the position (1.2, 10) shown in FIG. Further, the tensile modulus of the dumbbell obtained as described above was measured based on JIS K 7113 and found to be 3.2 GPa. Moreover, it was 0.086 micrometer when arithmetic mean roughness Ra of the surface of the said sheet | seat was calculated | required based on JISB0601.
（比較例５）
実施例１と同様のポリプロピレン１００重量部と、薄片化黒鉛１０重量部とを含む複合樹脂組成物を剪断速度１．３×１０４ｓｅｃ−１及び冷却速度１１０℃／分の条件で射出成形した。このシートから実施例１と同様にサンプルとしてダンベルを切り出した。
( Comparative Example 5 )
A composite resin composition containing 100 parts by weight of the same polypropylene as in Example 1 and 10 parts by weight of exfoliated graphite was injection molded under the conditions of a shear rate of 1.3 × 10 4 sec −1 and a cooling rate of 110 ° C./min. . A dumbbell was cut out from this sheet as a sample in the same manner as in Example 1.
得られたシートにおいて、フィラーの長手方向の角度と割合の関係及び表面の算術平均粗さＲａを実施例１と同様にして評価した。また、上記ダンベルを用いて引っ張り弾性率を実施例１と同様にして測定した。その結果、角度と割合の関係は図１に比較例５で示す位置（９．４，７０）であった。また、引っ張り弾性率は３．０ＧＰａであり、シート表面の算術平均粗さＲａは０．１２μｍであった。 In the obtained sheet, the relationship between the angle in the longitudinal direction of the filler and the ratio and the arithmetic average roughness Ra of the surface were evaluated in the same manner as in Example 1. Further, the tensile elastic modulus was measured in the same manner as in Example 1 using the dumbbell. As a result, the relationship between the angle and the proportion was located (9.4,70) shown in Comparative Example 5 in FIG. The tensile elastic modulus was 3.0 GPa, and the arithmetic average roughness Ra of the sheet surface was 0.12 μm.
（実施例３）
比較例５と同様のポリプロピレン１００重量部と、薄片化黒鉛１０重量部とを含む複合樹脂組成物を剪断速度９．０×１０３ｓｅｃ−１及び冷却速度１６０℃／分の条件で射出成形した。このシートから比較例５と同様にサンプルとしてダンベルを切り出した。
(Example 3)
A composite resin composition containing 100 parts by weight of the same polypropylene as in Comparative Example 5 and 10 parts by weight of exfoliated graphite was injection molded under the conditions of a shear rate of 9.0 × 10 3 sec −1 and a cooling rate of 160 ° C./min. . A dumbbell was cut out from this sheet as a sample in the same manner as in Comparative Example 5 .
得られたシートにおいて、フィラーの長手方向の角度と割合の関係及び表面の算術平均粗さＲａを比較例５と同様にして評価した。その結果、角度と割合の関係は図１に実施例３で示す位置（５．９，４３）であった。また、引っ張り弾性率は２．９ＧＰａであり、シート表面の算術平均粗さＲａは０．０９２μｍであった。 In the obtained sheet, the relationship between the angle in the longitudinal direction and the ratio of the filler and the arithmetic average roughness Ra of the surface were evaluated in the same manner as in Comparative Example 5 . As a result, the relationship between the angle and the ratio was the position (5.9, 43) shown in FIG. Further, the tensile elastic modulus was 2.9 GPa, and the arithmetic average roughness Ra of the sheet surface was 0.092 μm.
（実施例４）
実施例３と同様のポリプロピレン１００重量部と、薄片化黒鉛１０重量部とを含む複合樹脂組成物を剪断速度１．７×１０４ｓｅｃ−１及び冷却速度１６０℃／分の条件で射出成形した。このシートから実施例３と同様にサンプルとしてダンベルを切り出した。
Example 4
A composite resin composition containing 100 parts by weight of the same polypropylene as in Example 3 and 10 parts by weight of exfoliated graphite was injection molded under the conditions of a shear rate of 1.7 × 10 4 sec −1 and a cooling rate of 160 ° C./min. . A dumbbell was cut out from this sheet as a sample in the same manner as in Example 3.
得られたシートにおいて、フィラーの長手方向の角度と割合の関係及び表面の算術平均粗さＲａを実施例３と同様にして評価した。その結果、角度と割合の関係は図１に実施例４で示す位置（４．７，７２）であった。また、引っ張り弾性率は３．５ＧＰａであり、シート表面の算術平均粗さＲａは０．０９０μｍであった。 In the obtained sheet, the relationship between the angle in the longitudinal direction and the ratio of the filler and the arithmetic average roughness Ra of the surface were evaluated in the same manner as in Example 3. As a result, the relationship between the angle and the ratio was the position (4.7, 72) shown in FIG. The tensile elastic modulus was 3.5 GPa, and the arithmetic average roughness Ra of the sheet surface was 0.090 μm.
（実施例５）
実施例４と同様のポリプロピレン１００重量部と、薄片化黒鉛１０重量部とを含む複合樹脂組成物を剪断速度１．８×１０４ｓｅｃ−１及び冷却速度１６０℃／分の条件で射出成形した。このシートから実施例４と同様にサンプルとしてダンベルを切り出した。
(Example 5)
A composite resin composition containing 100 parts by weight of the same polypropylene as in Example 4 and 10 parts by weight of exfoliated graphite was injection molded under the conditions of a shear rate of 1.8 × 10 4 sec −1 and a cooling rate of 160 ° C./min. . A dumbbell was cut out from this sheet as a sample in the same manner as in Example 4.
得られたシートにおいて、フィラーの長手方向の角度と割合の関係及び表面の算術平均粗さＲａを実施例４と同様にして評価した。その結果、角度と割合の関係は図１に実施例５で示す位置（１１．８，９２）であった。また、引っ張り弾性率は３．６ＧＰａであり、シート表面の算術平均粗さＲａは０．０８８μｍであった。 In the obtained sheet, the relationship between the angle in the longitudinal direction of the filler and the ratio and the arithmetic average roughness Ra of the surface were evaluated in the same manner as in Example 4. As a result, the relationship between the angle and the ratio was the position (11.8, 92) shown in FIG. The tensile elastic modulus was 3.6 GPa, and the arithmetic average roughness Ra of the sheet surface was 0.088 μm.
上記実施例１，３〜５及び比較例５の結果を下記の表１に示す。 The results of Examples 1 and 3 to 5 and Comparative Example 5 are shown in Table 1 below.
表１から明らかなように、冷却速度が１５０℃未満であった比較例５では、弾性率は２．７ＭＰａ以上あったが、表面粗さが０．１２μｍと表面性状が悪かった。 As is clear from Table 1, in Comparative Example 5 in which the cooling rate was less than 150 ° C., the elastic modulus was 2.7 MPa or more, but the surface roughness was poor at 0.12 μm.
また、実施例３では、剪断速度が９．０×１０３ｓｅｃ−１と最も低い値であったため、領域Ａの境界付近の値を取っており、弾性率が最も低くなっている。実施例５では、剪断速度が１．８×１０４ｓｅｃ−１と最も大きいので、領域Ａの中でもより多くのフィラーが限られた角度に入っており、弾性率も３．６ＭＰａと最も大きくなった。 In Example 3, since the shear rate was the lowest value of 9.0 × 10 3 sec −1 , the value in the vicinity of the boundary of the region A was taken and the elastic modulus was the lowest. In Example 5, since the shear rate is the largest at 1.8 × 10 4 sec −1 , more fillers are included in a limited angle in the region A, and the elastic modulus is the largest at 3.6 MPa. It was.
（比較例１）
剪断速度を７．２×１０２ｓｅｃ−１及び冷却速度を１６０℃／分の条件としたことを除いては、実施例１と同様にしてシートを得た。得られたシートにおけるフィラーの長軸の角度と割合の関係は図１に比較例１で示す位置（２．７，１０）であった。シート表面の算術平均粗さＲａは０．０９７μｍであった。また、得られたシートから切り出されたダンベルの引っ張り弾性率は２．４ＧＰａであった。
(Comparative Example 1)
A sheet was obtained in the same manner as in Example 1 except that the shear rate was 7.2 × 10 2 sec −1 and the cooling rate was 160 ° C./min. The relationship between the angle of the major axis of the filler and the ratio in the obtained sheet was the position (2.7, 10) shown in Comparative Example 1 in FIG. The arithmetic average roughness Ra of the sheet surface was 0.097 μm. Moreover, the tensile elastic modulus of the dumbbell cut out from the obtained sheet was 2.4 GPa.
（比較例２）
剪断速度を７．５×１０２ｓｅｃ−１及び冷却速度を１６０℃／分の条件としたことを除いては、実施例１と同様にしてシートを得た。得られたシートにおけるフィラーの長軸の角度と割合の関係は図１に比較例２で示す位置（４．４，２０）であった。シート表面の算術平均粗さＲａは０．０９５μｍであった。また、得られたシートから切り出されたダンベルの引っ張り弾性率は２．６ＧＰａであった。
(Comparative Example 2)
A sheet was obtained in the same manner as in Example 1 except that the shear rate was 7.5 × 10 2 sec −1 and the cooling rate was 160 ° C./min. The relationship between the major axis angle and the ratio of the filler in the obtained sheet was the position (4.4, 20) shown in Comparative Example 2 in FIG. The arithmetic average roughness Ra of the sheet surface was 0.095 μm. Moreover, the tensile elastic modulus of the dumbbell cut out from the obtained sheet was 2.6 GPa.
（比較例３）
剪断速度を７．０×１０２ｓｅｃ−１及び冷却速度を１６０℃／分の条件としたことを除いては、実施例１と同様にしてシートを得た。得られたシートにおけるフィラーの長軸の角度と割合の関係は図１に比較例３で示す位置（１０．７，４０）であった。シート表面の算術平均粗さＲａは０．０８９μｍであった。また、得られたシートから切り出されたダンベルの引っ張り弾性率は２．３ＧＰａであった。
(Comparative Example 3)
A sheet was obtained in the same manner as in Example 1 except that the shear rate was 7.0 × 10 2 sec −1 and the cooling rate was 160 ° C./min. The relationship between the angle of the major axis of the filler and the ratio in the obtained sheet was the position (10.7, 40) shown in Comparative Example 3 in FIG. The arithmetic average roughness Ra of the sheet surface was 0.089 μm. Moreover, the tensile elastic modulus of the dumbbell cut out from the obtained sheet | seat was 2.3 GPa.
（比較例４）
剪断速度を７．５×１０２ｓｅｃ−１及び冷却速度を１１０℃／分の条件としたことを除いては、実施例１と同様にしてシートを得た。得られたシートにおけるフィラーの長軸の角度と割合の関係は図１に比較例４で示す位置（７．７，３３）であった。シート表面の算術平均粗さＲａは０．１５μｍであった。また、得られたシートから切り出されたダンベルの引っ張り弾性率は２．５ＧＰａであった。
(Comparative Example 4)
A sheet was obtained in the same manner as in Example 1 except that the shear rate was 7.5 × 10 2 sec −1 and the cooling rate was 110 ° C./min. The relationship between the angle of the major axis of the filler and the ratio in the obtained sheet was the position (7.7, 33) shown in FIG. The arithmetic average roughness Ra of the sheet surface was 0.15 μm. Moreover, the tensile elastic modulus of the dumbbell cut out from the obtained sheet was 2.5 GPa.
上記比較例１から４の結果を下記の表２に示す。 The results of Comparative Examples 1 to 4 are shown in Table 2 below.
表２から明らかなように、比較例１から３では、成形時のせん断速度が小さいため、フィラーの角度と割合の関係が領域Ａを外れており、得られた樹脂複合成形体としてのシートの引っ張り弾性率も２．７ＧＰａ未満であり低かった。もっとも、冷却速度は１５０度以上であるために、表面平滑性には優れていた。 As apparent from Table 2, in Comparative Examples 1 to 3, since the shear rate at the time of molding is small, the relationship between the angle and the ratio of the filler is out of the region A, and the sheet as the obtained resin composite molded body The tensile modulus was also low, less than 2.7 GPa. However, since the cooling rate was 150 degrees or more, the surface smoothness was excellent.
また、比較例４では、成形時のせん断速度が小さいため、フィラーの角度と割合の関係が領域Ａを外れており、得られた樹脂複合成形体としてのシートの引っ張り弾性率が２．５ＧＰａ未満であり若干低かった。また、冷却速度が１１０度であるために、表面の算術平均粗さＲａも０．１５μｍと表面平滑性は悪かった。 In Comparative Example 4, since the shear rate at the time of molding is low, the relationship between the filler angle and the ratio is out of the region A, and the tensile modulus of the sheet as the obtained resin composite molded body is less than 2.5 GPa. It was a little low. In addition, since the cooling rate was 110 degrees, the arithmetic average roughness Ra of the surface was also 0.15 μm and the surface smoothness was poor.
（実施例６）
ポリエチレン（日本ポリエチレン社製、商品名：ノバテックＨＤ）１００重量部と、薄片化黒鉛（グラフェンの層面の面方向における最大寸法＝５μｍ、グラフェンの積層数＝１８０層、アスペクト比＝９０）１０重量部とを剪断速度１．３×１０４ｓｅｃ−１及び冷却速度１６０℃／分の条件で射出成形し、樹脂複合成形体としてのシートを得た。このシートからＪＩＳ Ｋ ７１１３に準拠してサンプルとしてダンベルを切り出した。
(Example 6)
100 parts by weight of polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec HD) and 10 parts by weight of exfoliated graphite (maximum dimension in plane direction of graphene layer surface = 5 μm, number of graphene layers = 180 layers, aspect ratio = 90) Were injection molded under the conditions of a shear rate of 1.3 × 10 4 sec −1 and a cooling rate of 160 ° C./min to obtain a sheet as a resin composite molded body. A dumbbell was cut out from this sheet as a sample in accordance with JIS K7113.
得られたシートにおいて、フィラーの長手方向の角度と割合の関係及び表面の算術平均粗さＲａを実施例５と同様にして評価した。また、上記ダンベルを用いて引っ張り弾性率を実施例１と同様にして測定した。その結果、角度と割合の関係は図１に実施例６で示す位置（５．２，４８）であった。また、引っ張り弾性率は２．９ＧＰａであり、シート表面の算術平均粗さＲａは０．０８９μｍであった。 In the obtained sheet, the relationship between the angle in the longitudinal direction and the ratio of the filler and the arithmetic average roughness Ra of the surface were evaluated in the same manner as in Example 5. Further, the tensile elastic modulus was measured in the same manner as in Example 1 using the dumbbell. As a result, the relationship between the angle and the ratio was the position (5.2, 48) shown in FIG. Further, the tensile elastic modulus was 2.9 GPa, and the arithmetic average roughness Ra of the sheet surface was 0.089 μm.
（実施例７）
ポリプロピレン（日本ポリプロ社製、商品名：ノバテックＥＡ９）１００重量部と、黒鉛（グラフェンの層面の面方向における最大寸法＝５μｍ、グラフェンの積層数＝１５００層、アスペクト比＝１０）１０重量部とを含む複合樹脂組成物を、比較例５と同じ剪断速度及び冷却速度で射出成形し、樹脂複合成形体としてのシートを得た。このシートからサンプルとして比較例５と同様にダンベルを切り出した。シート及びダンベルについて実施例６と同様にして測定した。その結果、シートにおけるフィラーの長手方向の角度と割合の関係は図１に実施例７で示す位置（７．０，６２）であった。また、引っ張り弾性率は２．８ＧＰａであり、シート表面の算術平均粗さＲａは、０．０９３μｍであった。
(Example 7)
100 parts by weight of polypropylene (manufactured by Nippon Polypro Co., Ltd., trade name: Novatec EA9) and 10 parts by weight of graphite (maximum dimension in the plane direction of the graphene layer surface = 5 μm, number of graphene layers = 1500 layers, aspect ratio = 10) The composite resin composition was injection molded at the same shear rate and cooling rate as in Comparative Example 5 to obtain a sheet as a resin composite molded body. A dumbbell was cut out as a sample from this sheet in the same manner as in Comparative Example 5 . The sheet and dumbbell were measured in the same manner as in Example 6. As a result, the relationship between the angle and the ratio of the filler in the longitudinal direction in the sheet was the position (7.0, 62) shown in Example 7 in FIG. In addition, the tensile elastic modulus was 2.8 GPa, and the arithmetic average roughness Ra of the sheet surface was 0.093 μm.
上記実施例６及び７の結果を下記の表３に示す。 The results of Examples 6 and 7 are shown in Table 3 below.
表３から明らかなように、実施例６及び７では、長手方向の角度と割合の関係が領域Ａに含まれており、配向性に優れていた。また、引っ張り弾性率も十分高く、かつ表面粗さの算術平均粗さＲａも０．０８９μｍ及び０．０９３μｍと低かった。 As apparent from Table 3, in Examples 6 and 7, the relationship between the angle in the longitudinal direction and the ratio was included in the region A, and the orientation was excellent. Further, the tensile elastic modulus was sufficiently high, and the arithmetic average roughness Ra of the surface roughness was also as low as 0.089 μm and 0.093 μm.
Claims (7)
全フィラーの長手方向の平均方向とフィラーの長手方向とのなす角度をｘとし、
全フィラーの長手方向の平均方向に対する長手方向のなす角度が前記ｘより小さいフィラーの全フィラーに対する割合をｙとしたときに、
前記ｘ及び前記ｙが、図１に示す領域Ａ（ｙ≧６．６７ｘ）内に位置しており、表面の算術平均粗さＲａが０．１μｍ以下である、樹脂複合成形体。 A thermoplastic resin and a filler made of exfoliated graphite, dispersed in the thermoplastic resin,
The angle formed by the average direction of the longitudinal direction of all fillers and the longitudinal direction of the filler is x
When the ratio of the filler in the longitudinal direction with respect to the average direction of the longitudinal direction of all fillers to the filler of all fillers smaller than x is y,
The resin composite molded body in which the x and the y are located in the region A (y ≧ 6.67x) shown in FIG. 1 and the arithmetic average roughness Ra of the surface is 0.1 μm or less.
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