JP2013256099A - Resin composite molding and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composite molding, the mechanical strength of which can be made higher by using a smaller amount of a filler, and to provide a method for producing the resin composite molding.SOLUTION: A resin composite molding 1 is produced by layering: a plurality of first layers 11, each of which contains a first thermoplastic resin 11a and a filler 15, which comprises a carbon material having a graphene structure, and in each of which the filler 15 is dispersed in the first thermoplastic resin 11a; and a plurality of second layers 12, each of which has a second thermoplastic resin 12a as a main component; wherein the filler 15 comprising the carbon material having the graphene structure is not incorporated in the second layer 12, or X>Y is satisfied when X is the amount of the filler 15 comprising the carbon material contained in the first layer 11, and Y is the amount of the filler 15 comprising the carbon material contained in the second layer 12. The method for producing the resin composite molding 1 is also provided.

Description

  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. .

  Conventionally, various resin composite materials in which various fillers are dispersed in a thermoplastic resin have been proposed. In recent years, a resin composite material in which a filler having a size of several nanometers to several tens of nanometers is dispersed in a thermoplastic resin 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. By dispersing such nano-level fillers in the thermoplastic resin, the mechanical strength of the resulting resin composite material can be increased.

  However, when the nano-level filler as described above is dispersed in the thermoplastic resin, the filler sometimes aggregates in the thermoplastic resin. Therefore, it has been extremely difficult to uniformly disperse the nano-level filler as described above in the thermoplastic resin. Therefore, there is a problem that the mechanical strength of the resin composite material cannot be sufficiently increased.

  As a method for solving such a problem, a method of increasing the dispersibility of the filler by using a dispersant is known. For example, Patent Documents 1 and 2 below disclose resin composite materials containing a resin having an acid group or an acid anhydride group as a dispersant. By molding the resin composite material containing the nano-level filler, the thermoplastic resin, and the dispersant, the mechanical strength of the obtained molded body can be increased. Patent Document 3 discloses that a resin layer in which carbon nanofibers are dispersed is impregnated into a fiber reinforced base material, and by laminating a plurality of layers, the mechanical strength of the obtained structure is increased. It is disclosed.

JP 2008-255230 A JP 2006-124454 A Japanese Patent No. 3735651

  However, in order to further increase the mechanical strength of the molded articles of Patent Documents 1 and 2, it is necessary to add a large amount of filler to the resin composite material. Therefore, there is a problem that it is difficult to increase the mechanical strength of the molded body. Also in Patent Document 3, there is a problem that the manufacturing cost is high because a carbon fiber fabric or a high concentration of carbon nanofibers is used.

  An object of the present invention is to provide a resin composite molded body having a higher mechanical strength with fewer fillers and a method for producing such a resin composite molded body.

  In the resin composite molded body of the present invention, a plurality of first thermoplastic resins including a first thermoplastic resin and a filler made of a carbon material having a graphene structure, the filler being dispersed in the first thermoplastic resin. And a plurality of second layers mainly composed of the second thermoplastic resin are laminated. In the resin composite molded body of the present invention, the second layer does not contain a filler made of a carbon material having a graphene structure, or the amount of filler made of a carbon material contained in the first layer is X, If the amount of filler made of the carbon material contained in the second layer is Y, X> Y.

  In a specific aspect of the resin composite molded body of the present invention, the plurality of first layers and the plurality of second layers are alternately stacked. In that case, the mechanical strength of the resin composite molded body can be further increased.

  In another specific aspect of the resin composite molded body of the present invention, the second layer does not include a filler made of a carbon material having a graphene structure. In that case, the amount of the filler made of a carbon material having a graphene structure used for the resin composite molded body can be efficiently reduced without significantly reducing the mechanical strength of the resin composite molded body.

  In another specific aspect of the resin composite molded body of the present invention, the carbon material having the graphene structure is at least one carbon material selected from the group consisting of graphene, carbon nanotubes, carbon fibers, and exfoliated graphite. . In that case, the carbon material having a graphene structure has a nano size and a large specific surface area. Therefore, the mechanical strength of the resin composite molded body can be further increased.

  In still another specific aspect of the resin composite molded body of the present invention, in the first layer, the filler is contained in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the first thermoplastic resin. ing. In that case, the mechanical strength of the resin composite molded body can be increased more effectively.

  In still another specific aspect of the resin composite molded body of the present invention, the resin composite molded body has a sheet shape. In that case, a resin composite molded body can be easily molded by laminating a plurality of sheet-like first layers and second layers.

  The method for producing a resin composite molded body of the present invention includes a step of preparing a resin composite composition that includes the first thermoplastic resin and the filler, and the filler is dispersed in the first thermoplastic resin. And forming the laminate of the first layer and the second layer by coextrusion molding of the resin composite composition and the second thermoplastic resin, and dividing the laminate And further laminating the divided laminate. Various resin composite molded articles of the present invention can be produced by the above production method.

  In the resin composite molded body of the present invention, the amount of the filler made of the carbon material having a graphene structure dispersed in the first layer is larger than the amount of the filler made of the carbon material having a graphene structure contained in the second layer. In many cases, the mechanical strength of the first layer is increased. In the resin composite molded body of the present invention, since the plurality of first layers and the plurality of second layers are laminated, the mechanical strength of the entire resin composite molded body is increased by the mechanical strength of the first layer. Can be increased. Therefore, according to the resin composite molded body of the present invention, the mechanical strength of the resin composite molded body can be further increased with a smaller filler addition amount. Further, according to the method for producing a resin composite molded body of the present invention, after forming a laminate of the first layer and the second layer by coextrusion molding, the laminate is divided, and the divided laminate Since the multi-layer molding is performed by further laminating the bodies, the resin composite molded body of the present invention in which a plurality of first layers and a plurality of second layers are laminated can be efficiently produced.

It is typical sectional drawing of the resin compound molded object of this invention. It is a schematic diagram for demonstrating each process for obtaining a multilayer molded object in the case of manufacture of the resin compound molded object of this invention. It is a schematic perspective view which shows the shunt adapter used in laminating | stacking a some layer in forming the resin compound molded object which concerns on this invention. 6 is a schematic front view for explaining a shunt adapter used to obtain a multilayer structure in Example 3. FIG.

  Hereinafter, the present invention will be clarified by describing specific embodiments of the present invention with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view of a resin composite molded body of the present invention. In FIG. 1, hatching indicating a cross section is omitted in order to clarify the presence of the filler 15.

  As shown in FIG. 1, in the resin composite molded body 1, a plurality of first layers 11 and a plurality of second layers 12 are laminated. In the present embodiment, a plurality of first layers 11 and a plurality of second layers 12 are alternately stacked. But the lamination | stacking state of the resin compound molded object 1 is not specifically limited, For example, the resin compound molded object 1 is provided with the part by which the some 1st layer 11 or the some 2nd layer 12 was laminated | stacked continuously. It may be.

  Although the shape of the resin composite molded body 1 is not particularly limited, for example, a sheet shape is preferable. In that case, the resin composite molded body 1 can be easily molded by laminating a plurality of thin sheet-like first layers 11 and second layers 12.

  The first layer 11 contains a thermoplastic resin 11a, and a filler 15 is dispersed in the thermoplastic resin 11a. The second layer 12 is made of the thermoplastic resin 12a in the present embodiment, but may be composed mainly of the thermoplastic resin 12a. The main component means that more than half of the weight of the second layer 12 is composed of the weight of the thermoplastic resin 12a contained in the second layer 12. In the resin composite molded body 1 using the thermoplastic resins 11a and 12a, various molded products can be easily obtained by using various molding methods by heating.

  The thermoplastic resins 11a and 12a are not particularly limited, and examples thereof include polyolefin, polyamide, polyester, polystyrene, polyvinyl chloride, and polyvinyl acetate. Preferably, polyolefins such as polypropylene, polyethylene, and ethylene-propylene copolymer are used as the thermoplastic resins 11a and 12a. By using polyolefin, the cost of the resin composite molded body 1 can be reduced, and the resin composite molded body 1 can be manufactured more easily.

  Further, the thermoplastic resins 11a and 12a may be the same resin or different resins. When the thermoplastic resins 11a and 12a are the same resin, the adhesion between the first layer 11 and the second layer 12 can be enhanced. Moreover, when the thermoplastic resins 11a and 12a are different resins, for example, by separating the functions of the first layer 11 including the thermoplastic resin 11a and the second layer 12 including the thermoplastic resin 12a. Functionalities other than mechanical strength can be imparted to the resin composite molded body 1. For example, the resin composite molded body 1 having a high gas barrier property can be obtained by using polyethylene oxide having a high gas barrier property as the thermoplastic resin 12a. Moreover, the resin composite molded object 1 with high impact resistance can be obtained by using ABS with high impact resistance as the thermoplastic resin 12a. Further, a carbon fiber woven fabric may be used for the first layer 11 as the filler 15. By inserting the carbon fiber woven fabric into the thermoplastic resin, the strength can be increased without impairing the toughness of the first layer 11. The first layer 11 may be laminated with a carbon fiber woven fabric. Even in this case, the strength can be increased without impairing the toughness of the first layer 11.

  In the first layer 11, a filler 15 made of a carbon material having a graphene structure is dispersed in the thermoplastic resin 11a. In the present embodiment, the second layer 12 is made of a thermoplastic resin 12a and does not include a filler made of a carbon material having a graphene structure. However, in the resin composite molded body 1 of the present invention, the second layer 12 is made of a filler made of a carbon material having a graphene structure as long as the amount is smaller than the amount of the filler 15 contained in the first layer 11. May be included.

  In the resin composite molded body 1 of the present invention, the amount of the filler 15 contained in the first layer 11 is larger on a weight basis than the amount of the filler made of a carbon material having a graphene structure contained in the second layer 12. That is, in the resin composite molded body 1, fillers made of a carbon material having a graphene structure are unevenly distributed in the plurality of first layers 11. In the plurality of first layers 11, since many fillers 15 are uniformly dispersed in the thermoplastic resin 11 a, the mechanical strength of the plurality of first layers 11 is increased. Thereby, the mechanical strength of the entire resin composite molded body 1 in which the plurality of first layers 11 are laminated can be further increased. That is, according to the present invention, the mechanical strength of the resin composite molded body 1 can be further increased with a small amount of filler.

  The amount of the filler 15 contained in the thermoplastic resin 11a contained in the first layer 11 is preferably in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin 11a. By setting the amount of the filler 15 contained in the thermoplastic resin 11a within the above range, it is possible to obtain the resin composite molded body 1 having an increased mechanical strength such as a tensile elastic modulus. When the amount of the filler 15 contained in the thermoplastic resin 11a is less than 1 part by weight, the mechanical strength of the resin composite molded body 1 may not be sufficiently increased. When the amount of the filler 15 contained in the thermoplastic resin 11a exceeds 50 parts by weight, the rigidity of the resin composite molded body 1 increases, and the resin composite molded body 1 may become brittle.

  The amount of the filler made of the carbon material having a graphene structure contained in the second layer 12 is preferably less than 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin 12a. More preferably, the second layer 12 does not include a filler made of a carbon material having a graphene structure. The smaller the amount of the filler made of the carbon material having a graphene structure contained in the second layer 12, the less the amount of the filler made of the carbon material having a graphene structure without reducing the mechanical strength of the resin composite molded body 1. Can be reduced efficiently.

  As described above, in the present embodiment, the plurality of first layers 11 and the plurality of second layers 12 are alternately stacked. In this case, the plurality of first layers 11 can further increase the mechanical strength of the entire resin composite molded body 1.

  As the carbon material, preferably, at least one selected from the group consisting of graphene, carbon nanotube, graphite, carbon fiber, and exfoliated graphite can be used. More preferably, as the carbon material, a laminate of a plurality of graphene sheets, that is, exfoliated graphite is used. In the present invention, exfoliated graphite is obtained by exfoliating original graphite, and refers to a graphene sheet laminate that is thinner than the original graphite. The number of graphene sheets laminated in exfoliated graphite should be less than that of the original graphite, but is usually about several to 200 layers. A thin graphene sheet is laminated on the exfoliated graphite, and the exfoliated graphite has a shape with a relatively large aspect ratio. Accordingly, in the resin composite molded body of the present invention, when the filler 15 made of exfoliated graphite is uniformly dispersed in the thermoplastic resin 11a included in the first layer 11, the laminated surface of the exfoliated graphite is used. The reinforcing effect against the external force applied in the direction intersecting with can be effectively enhanced.

  The aspect ratio refers to the ratio of the maximum dimension of the exfoliated graphite in the laminated surface direction to the thickness of the exfoliated graphite. If the aspect ratio of the exfoliated graphite is too low, the reinforcing effect against an external force applied in the direction intersecting the laminated surface may not be sufficient. On the other hand, even if the aspect ratio of the exfoliated graphite is too high, the effect may be saturated and a further reinforcing effect may not be expected. Therefore, the preferable lower limit of the aspect ratio is 70, and the preferable upper limit is 500.

  The thickness of the first layer 11 is not particularly limited, but is preferably 1 to 3 times the thickness of the filler 15. In that case, the filler 15 is oriented in a direction parallel to the surface of the first layer 11. Therefore, the tensile elastic modulus of the first layer 11 and the resin composite molded body 1 can be further increased. More preferably, the thickness of the plurality of first layers 11 may be 1 to 2 times the thickness of the filler 15.

  In addition, the thickness of the second layer 12 can be approximately the same as the thickness of the first layer 11.

  In addition, you may determine the total number of layers of the resin composite molded object required in order to make the resin composite molded object 1 into desired thickness from the thickness of the 1st layer 11 and the 2nd layer 12. FIG.

  Next, an embodiment of a method for producing the resin composite molded body 1 of the present invention will be described.

  First, by uniformly dispersing the filler 15 in the thermoplastic resin 11a, a thermoplastic resin composition in which the filler 15 is uniformly dispersed in the thermoplastic resin 11a is obtained. In the dispersion method, for example, the thermoplastic resin 11a and the filler 15 are kneaded under heating using a twin screw kneader or a twin screw extruder such as a plast mill, so that the filler 15 becomes the thermoplastic resin 11a. The thermoplastic resin composition uniformly dispersed therein can be obtained.

  Next, the first layer 11 made of the thermoplastic resin composition and the second layer 12 made of the thermoplastic resin 12a were laminated using the thermoplastic resin composition and the thermoplastic resin 12a. A laminate of two to several layers is obtained. The method for obtaining the laminate is not particularly limited, and examples thereof include a method of laminating a press-formed laminate, a method of laminating stretched sheets, and the like, and preferably a wet lamination method, a dry lamination method, an extrusion Examples thereof include a coating method, a multilayer melt extrusion method, a hot melt lamination method, and a heat lamination method.

  More preferably, as the above production method, a multilayer melt extrusion method in which the production of the resin composite molded body of the present invention is easy can be used. Specifically, by using the two extruders to co-extrusion the thermoplastic resin composition and the thermoplastic resin 12a, the first layer 11 made of the thermoplastic resin composition, A laminate of two to several layers in which the second layer 12 made of the plastic resin 12a is laminated can be obtained. Examples of the multilayer melt extrusion method include a multi-manifold method and a feed block method.

  Next, the laminate is transferred to a multilayer forming block. In the multilayer forming block, the laminated body is divided, and the divided laminated body is further laminated to form a multilayer, whereby the resin composite molded body 1 having 10 or more layers can be obtained.

  An example of a method for obtaining a resin composite molded body composed of a laminate of 10 layers or more will be described with reference to FIG. As shown in FIG. 2, the laminated body 21 formed by laminating the first layer 22 and the second layer 23 is extruded from an extruder. In the extrusion direction, the laminate 21 is divided into a plurality of pieces in the step I. That is, the laminated body 21 is divided along a plurality of surfaces that are parallel to the extrusion direction of the laminated body 21 and are perpendicular to the laminated surface. In this way, divided laminates 21A, 21B, 21C, and 21D are obtained.

  Next, in step II, the laminated bodies 21A to 21D obtained by the division using a diversion adapter or the like are moved so as to be arranged in the lamination direction. Here, the laminated body 21B, the laminated body 21D, the laminated body 21A, and the laminated body 21C are arranged in this order from the top.

  Thereafter, in step III, the stacked body 21B, the stacked body 21D, the stacked body 21A, and the stacked body 21C are expanded in a direction parallel to the stacked surface. Next, in the IV step, the expanded laminates 21A to 21D are superposed and then compressed in a direction perpendicular to the laminate surface. In this way, an eight-layer laminate 24 can be obtained. By repeating these steps I to IV, a multilayer molded article having 10 or more layers can be obtained.

  In addition, the method of dividing | segmenting and laminating | stacking the said laminated body in the said multilayer molding is not specifically limited, It can carry out with a suitable method and apparatus. Hereinafter, the present invention will be clarified by giving specific examples of the present invention. In addition, this invention is not limited to the following Example. The multilayer molded articles of Examples 1 and 2 and Comparative Examples 1 and 2 were produced by the following method. The material of the first layer and the material of the second layer were extruded by two extruders to form the first layer and the second layer. The extruded first layer and second layer were laminated in a feed block with the first layer and the second layer to produce a sheet-like multilayer molded body. Next, in a plurality of multilayer forming blocks, the laminate is divided, and the divided laminate is further laminated to form a multilayer, thereby forming a multilayer having a thickness of 0.3 μm per layer and 900 layers. Got the body.

Example 1
100 parts by weight of polypropylene (manufactured by Nippon Polypro Co., Ltd., trade name: Novatec EA9), exfoliated graphite (manufactured by xScience, trade name “xGnP”, 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) 44 parts by weight were melt-kneaded at 230 ° C. to produce a resin composite composition. Next, using the resin composite composition as the material for the first layer, polypropylene (trade name: Novatec EA9, manufactured by Nippon Polypro Co., Ltd.) as the material for the second layer, and using the shunt adapter shown in FIG. A multilayer molded body was produced.

  In the shunt adapter shown in FIG. 3, the laminates 26A to 26D are laminated according to the steps I to IV shown in FIG. A multilayer molded body was obtained using a plurality of stages of the diversion adapter.

  The obtained multilayer molded body contained 18 parts by weight of graphene with respect to 100 parts by weight of polypropylene. No. 1 dumbbell defined in JIS K7113 was cut out as a test piece from the molded multilayer molded article, and the tensile modulus was measured. The tensile elastic modulus was 2.4 GPa.

(Example 2)
100 parts by weight of high-density polyethylene resin (manufactured by Nippon Polyethylene Co., Ltd., trade name: HF560), exfoliated graphite (manufactured by xGScience, trade name “xGnP”, maximum dimension in the plane direction of the layer surface of the graphene layer = 5 μm, lamination of graphene Number: 180 layers, aspect ratio: 90) 44 parts by weight were melt-kneaded at 230 ° C. to produce a resin composite composition. Next, the resin composite composition is used as the material for the first layer, and a high-density polyethylene resin (trade name: HF560, manufactured by Nippon Polyethylene Co., Ltd.) is used as the material for the second layer. A multilayer molded body was produced. The obtained multilayer molded body contained 18 parts by weight of graphene with respect to 100 parts by weight of the high-density polyethylene resin. No. 1 dumbbell defined in JIS K7113 was cut out as a test piece from the molded multilayer molded article, and the tensile modulus was measured. The tensile modulus was 2.2 GPa.

(Example 3)
A composite resin molded body was prepared in the same manner as in Example 1 except that a multilayer structure was manufactured using the shunt adapter shown in FIG. When the obtained multilayer molded article was measured under the same conditions as in Example 1, the tensile modulus was 2.2 GPa.

  The diversion adapter illustrated in FIG. 4 includes a supply unit 31 and division units 31 </ b> A to 31 </ b> D connected to the supply unit 31. In FIG. 4, in order to show the position of the process performed within a shunt adapter, the position where each process is performed is shown by arrow ag. That is, in the portion from position a to position b, the stacked body in a heated state is expanded in the width direction. At position b, the laminate is thinner and wider than at position a. Next, from the position b to the position d, the stacked body whose width is expanded as described above is further expanded in the width direction. Divided into two at position b and then again into two at position c. Therefore, the laminate is divided into four. By sequentially dividing in this way, the resin flow is evenly distributed. Therefore, unevenness of the resin flow is suppressed.

  From the position d to the position e, each of the divided laminates obtained as described above is twisted 90 degrees with the flow direction of the resin flow as the central axis.

  A plurality of divided laminates are laminated at positions e to g. More specifically, at the position f, two divided laminated bodies are laminated and integrated. Further, at the position g, a laminated body that is laminated and integrated two by two is further laminated. In this way, the stacking process is sequentially performed from the position e to the position g. In this case, the adhesion between the layers can be further increased as compared with the case where all the layers are laminated at once. Furthermore, the quality in the obtained multilayer laminated structure can also be improved. In Example 3, a multilayer molded body was prepared in the same manner as in Example 1 by repeating the laminated structure a plurality of times using the diversion adapter.

Example 4
100 parts by weight of polyamide (trade name “1300S” manufactured by Asahi Kasei) and 44 parts by weight of exfoliated graphite were melt-kneaded at 270 ° C. to produce a resin composite composition. Next, using the resin composite composition as the material for the first layer and the polyamide as the material for the second layer, a multi-layer molded article was produced using the shunt adapter shown in FIG. The obtained multilayer molded body contained 18 parts by weight of graphene with respect to 100 parts by weight of polypropylene. No. 1 dumbbell defined in JIS K7113 was cut out as a test piece from the molded multilayer molded article, and the tensile modulus was measured. The tensile elastic modulus was 4.2 GPa.

(Example 5)
100 parts by weight of ABS (trade name “S210B” manufactured by UMG ABS) and 44 parts by weight of exfoliated graphite were melt-kneaded at 130 ° C. to produce a resin composite composition. Next, using the resin composite composition as the material for the first layer and the polyamide as the material for the second layer, a multi-layer molded article was produced using the shunt adapter shown in FIG. The obtained multilayer molded body contained 18 parts by weight of graphene with respect to 100 parts by weight of ABS. No. 1 dumbbell defined in JIS K7113 was cut out as a test piece from the molded multilayer molded article, and the tensile modulus was measured. The tensile elastic modulus was 3.5 GPa.

(Example 6)
100 parts by weight of the above polypropylene and 44 parts by weight of carbon nanotubes (trade name “CTUBE”, average outer diameter 25 nm, average length 5 μm, manufactured by CNT) are melt-kneaded at 230 ° C. to produce a resin composite composition. did. Next, a multilayer molded article was produced using the resin composite composition as the material for the first layer and the polypropylene as the material for the second layer, and using the shunt adapter shown in FIG. The obtained multilayer molded body contained 18 parts by weight of graphene with respect to 100 parts by weight of polypropylene. The tensile elastic modulus was 1.9 GPa.

(Example 7)
100 parts by weight of the above polypropylene and 44 parts by weight of carbon nanofiber (MD Nanotech, trade name “CNF-T”, average outer diameter 15 nm, average length 5 μm) are melt-kneaded at 230 ° C. to obtain a resin composite. A composition was prepared. Next, a multilayer molded article was produced using the resin composite composition as the material for the first layer and the polypropylene as the material for the second layer, and using the shunt adapter shown in FIG. The obtained multilayer molded body contained 18 parts by weight of graphene with respect to 100 parts by weight of polypropylene. The tensile elastic modulus was 2.0 GPa.

(Example 8)
100 parts by weight of the above polypropylene and 44 parts by weight of carbon fiber (manufactured by West One Corporation, trade name “milled carbon fiber”, average outer diameter 5 μm, average length 100 μm) are melt-kneaded at 230 ° C. to obtain a resin composite A composition was prepared. Next, a multilayer molded article was produced using the resin composite composition as the material for the first layer and the polypropylene as the material for the second layer, and using the shunt adapter shown in FIG. The obtained multilayer molded body contained 18 parts by weight of graphene with respect to 100 parts by weight of polypropylene. The tensile elastic modulus was 1.8 GPa.

(Comparative Example 1)
100 parts by weight of polypropylene (manufactured by Nippon Polypro Co., Ltd., trade name: Novatec EA9), exfoliated graphite (manufactured by xScience, trade name “xGnP”, 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) 20 parts by weight were melt-kneaded at 230 ° C. to produce a resin composite composition. Next, using the resin composite composition as both the first layer material and the second layer material, a sheet-like multilayer molded body was produced by the method described above. No. 1 dumbbell defined in JIS K7113 was cut out as a test piece from the molded multilayer molded article, and the tensile modulus was measured. The tensile elastic modulus was 2.4 GPa.

(Comparative Example 2)
100 parts by weight of high-density polyethylene resin (manufactured by Nippon Polyethylene Co., Ltd., trade name: HF560), exfoliated graphite (manufactured by xGScience, trade name “xGnP”, maximum dimension in the plane direction of the layer surface of the graphene layer = 5 μm, lamination of graphene Number: 180 layers, aspect ratio: 90) 21 parts by weight were melt-kneaded at 230 ° C. to produce a resin composite composition. Next, using the resin composite composition as both the first layer material and the second layer material, a sheet-like multilayer molded body was produced by the method described above. No. 1 dumbbell defined in JIS K7113 was cut out as a test piece from the molded multilayer molded article, and the tensile modulus was measured. The tensile modulus was 2.2 GPa.

(Comparative Example 3)
In Example 4, a resin composite material was obtained in the same manner as in Example 4 except that 21 parts by weight of exfoliated graphite was added and kneaded at 270 degrees. Subsequently, using the composite resin for both the first layer and the second layer, a sheet-like multilayer molded body was produced by the method described above. The tensile elastic modulus was measured under the same measurement conditions as in Example 4. The tensile elastic modulus was 4.2 GPa.

(Comparative Example 4)
In Example 5, a resin composite material was obtained in the same manner as in Example 5 except that 20 parts by weight of exfoliated graphite was added and kneaded at 130 degrees. Subsequently, using the composite resin for both the first layer and the second layer, a sheet-like multilayer molded body was produced by the method described above. The tensile elastic modulus was measured under the same measurement conditions as in Example 5. The tensile elastic modulus was 3.5 GPa.

(Comparative Example 5)
In Example 6, a resin composite material was obtained in the same manner as in Example 6 except that 20 parts by weight of carbon nanotubes were added. Subsequently, using the composite resin for both the first layer and the second layer, a sheet-like multilayer molded body was produced by the method described above. The tensile elastic modulus was measured under the same measurement conditions as in Example 6. The tensile elastic modulus was 1.9 GPa.

(Comparative Example 6)
In Example 7, a resin composite material was obtained in the same manner as in Example 7 except that 21 parts by weight of carbon nanofibers were added. Subsequently, using the composite resin for both the first layer and the second layer, a sheet-like multilayer molded body was produced by the method described above. The tensile elastic modulus was measured under the same measurement conditions as in Example 7. The tensile elastic modulus was 2.0 GPa.

(Comparative Example 7)
In Example 8, a resin composite material was obtained in the same manner as in Example 8 except that 21 parts by weight of carbon fiber was added. Subsequently, using the composite resin for both the first layer and the second layer, a sheet-like multilayer molded body was produced by the method described above. The tensile elastic modulus was measured under the same measurement conditions as in Example 8. The tensile elastic modulus was 1.8 GPa.

  As described above, in Examples 1, 2, 4 to 8 compared to Comparative Examples 1 to 7, the weight parts of exfoliated graphite used was reduced by about 10% despite the same tensile modulus. . This is probably because exfoliated graphite was unevenly distributed in the first layer, and thus the mechanical strength of the first layer was increased. Thereby, it is considered that the tensile elastic modulus of the entire resin composite molded body was increased. The results of Examples and Comparative Examples are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 ... Resin composite molded object 2 ... Manufacturing apparatus 11 ... 1st layer 12 ... 2nd layer 11a, 12a ... Thermoplastic resin 15 ... Filler 21 ... Laminated body 21A, 21B, 21C, 21D ... Laminated body 22 ... 1st Layer 23 ... Second layer 24 ... Laminated body 26A, 26B, 26C, 26D ... Laminated body 31 ... Supply part 31A, 31B, 31C, 31D ... Division part

Claims (7)

A plurality of first layers including a first thermoplastic resin and a filler made of a carbon material having a graphene structure, wherein the filler is dispersed in the first thermoplastic resin;
A resin composite molded body in which a plurality of second layers mainly composed of a second thermoplastic resin are laminated,
The second layer does not contain a filler made of a carbon material having a graphene structure, or the amount of filler made of a carbon material contained in the first layer is X, and the carbon contained in the second layer A resin composite molded body where X> Y, where Y is the amount of filler made of the material.   The resin composite molded body according to claim 1, wherein the plurality of first layers and the plurality of second layers are alternately laminated.   The resin composite molded article according to claim 1 or 2, wherein the second layer does not include a filler made of a carbon material having a graphene structure.   The resin according to any one of claims 1 to 3, wherein the carbon material having the graphene structure is at least one carbon material selected from the group consisting of graphene, carbon nanotubes, carbon fibers, and exfoliated graphite. Composite molded body.   The resin according to any one of claims 1 to 4, wherein in the first layer, the filler is contained in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the first thermoplastic resin. Composite molded body.   The resin composite molded body according to any one of claims 1 to 5, wherein the resin composite molded body has a sheet shape. A method for producing a resin composite molded body according to any one of claims 1 to 6,
Preparing a resin composite composition comprising the first thermoplastic resin and the filler, wherein the filler is dispersed in the first thermoplastic resin;
Forming a laminate of the first layer and the second layer by co-extrusion molding the resin composite composition and the second thermoplastic resin;
Dividing the laminate, and further laminating the divided laminate. A method for producing a resin composite molded article.

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