Patent Publication Number: US-2015073082-A1

Title: Resin composite material

Description:
TECHNICAL FIELD 
     The present invention relates to a resin composite material comprising a thermoplastic resin and a filler. 
     BACKGROUND ART 
     Conventionally, there has been known a resin composite material prepared by blending a filler with a thermoplastic resin. A thermoplastic resin can be blended with various fillers to thereby impart various physical properties to a resin composite material, for example, to increase the coefficient of linear expansion of the resin composite material. 
     As a resin composite material containing a filler, for example, a resin composite material using graphite as a filler is known. 
     For example, Patent Literature 1 discloses a resin composite material prepared by blending graphite powder with a thermoplastic resin. Patent Literature 1 proposes obtaining a resin composite material having a high modulus of elasticity by blending graphite powder with a resin. 
     CITATION LIST 
     Patent Literature 
     
         
         Patent Literature 1: Japanese Patent Laid-Open No. 6-32939 
       
    
     SUMMARY OF INVENTION 
     Technical Problem 
     However, in a resin composite material as disclosed in Patent Literature 1, the modulus of elasticity of the resin composite material may not sufficiently be increased only by blending a small amount of graphite powder with a thermoplastic resin. 
     A main object of the present invention is to provide a resin composite material having a high modulus of elasticity. 
     Solution to Problem 
     The resin composite material according to the present invention comprises a thermoplastic resin, exfoliated graphite, and an inorganic filler different from the exfoliated graphite. 
     In a specific aspect of the resin composite material according to the present invention, the number of stacked graphene sheets constituting the exfoliated graphite is 1000 or less. 
     In another specific aspect of the resin composite material according to the present invention, the number of stacked graphene sheets constituting the exfoliated graphite is 150 or less. 
     In another specific aspect of the resin composite material according to the present invention, the aspect ratio of exfoliated graphite is 20 or more. 
     In still another specific aspect of the resin composite material according to the present invention, the exfoliated graphite is contained in an amount of 0.1 part by mass to 40 parts by mass based on 100 parts by mass of the thermoplastic resin. 
     In still another specific aspect of the resin composite material according to the present invention, the thermoplastic resin is polyolefin. 
     In still another specific aspect of the resin composite material according to the present invention, the inorganic filler is at least one selected from the group consisting of silica, mica, talc, clay, bentonite, montmorillonite, kaolinite, Wollastonite, calcium carbonate, titanium oxide, alumina, barium sulfate, potassium titanate, and glass fiber. Preferably, talc is used. 
     In still another specific aspect of the resin composite material according to the present invention, the inorganic filler is contained in an amount of 50 parts by mass or more based on 100 parts by mass of the thermoplastic resin. 
     Advantageous Effects of Invention 
     The present invention can provide a resin composite material having a high modulus of elasticity. 
    
    
     
       BRIEF DESCRIPTION OF DRAWING 
         FIG. 1  is a schematic front sectional view of a cup manufactured in Examples and Comparative Examples. 
     
    
    
     DESCRIPTION OF EMBODIMENTS 
     Hereinafter, the details of the present invention will be described. The resin composite material according to the present invention comprises a thermoplastic resin, exfoliated graphite, and an inorganic filler different from the exfoliated graphite. 
     The thermoplastic resin is not particularly limited, but a known thermoplastic resin can be used as the thermoplastic resin. Specific examples of the thermoplastic resin include polyolefin, polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, polyester, polyamide, polyurethane, polyethersulfone, polyetherketone, polyimide, polydimethylsiloxane, polycarbonate, and a copolymer of at least two thereof. The thermoplastic resin may be contained in a resin composite material singly or in combination of two or more. 
     The thermoplastic resin is preferably polyolefin. Polyolefin is inexpensive and easily molded under heating. Therefore, the use of polyolefin as a thermoplastic resin can reduce the manufacturing cost of a resin composite material and allows a resin composite material to be easily molded. 
     Examples of polyolefin include polyethylene; polypropylene; polyethylene resins such as an ethylene homopolymer, an ethylene-α-olefin copolymer, an ethylene-(meth)acrylic acid copolymer, an ethylene-(meth)acrylate copolymer, and an ethylene-vinylacetate copolymer; polypropylene resins such as a propylene homopolymer, a propylene-α-olefin copolymer, a propylene-ethylene random copolymer, and a propylene-ethylene block copolymer; a butene homopolymer; and homopolymers or copolymers of conjugated dienes such as butadiene and isoprene. Polypropylene resins are particularly preferred as the thermoplastic resin. 
     In the present invention, exfoliated graphite is a stack of graphene sheets each constituted by one layer of graphene. Exfoliated graphite is obtained by exfoliation of graphite. That is, exfoliated graphite is a stack of graphene sheets which is thinner than original graphite. The number of stacked graphene sheets in exfoliated graphite is two or more. The number of stacked graphene sheets is preferably 1000 or less, and more preferably 150 or less from the viewpoint of effectively increasing the mechanical strength such as tensile modulus of elasticity of a resin composite material. 
     The average particle size of exfoliated graphite is preferably about 0.1 to 50 μm. Note that the average particle size of exfoliated graphite is a value measured with a particle size distribution measuring device. 
     Exfoliated graphite has a shape having a high aspect ratio. Therefore, when exfoliated graphite is uniformly dispersed in the resin composite material according to the present invention, its reinforcing effect against an external force exerted in a direction intersecting a stacked plane of exfoliated graphite can be effectively enhanced. However, if the aspect ratio of exfoliated graphite is too low, its reinforcing effect against an external force exerted in a direction intersecting the stacked plane may be not sufficient. If the aspect ratio of exfoliated graphite is too high, the effect may be saturated, and a further improved reinforcing effect may not be expected. From the viewpoint as described above, the aspect ratio of exfoliated graphite is preferably 20 or more, and more preferably 50 or more. The aspect ratio of exfoliated graphite is preferably 5000 or less. Note that in the present invention, the aspect ratio refers to the ratio of the maximum size in the direction of the stacked plane of exfoliated graphite to the thickness of exfoliated graphite. 
     A commercial product of exfoliated graphite is available, and exfoliated graphite can also be manufactured by a conventionally known process. For example, exfoliated graphite is obtained by processes, e.g., a chemical treatment process in which ions such as nitrate ions are inserted between the layers of graphite and then heat-treated, a physical treatment process such as applying an ultrasonic wave to graphite, and an electrochemical process of performing electrolysis using graphite as a working electrode. 
     Exfoliated graphite may be surface-modified. Examples of the surface modification include grafting of a resin to the surface of exfoliated graphite and introducing a hydrophilic functional group or a hydrophobic functional group into the surface of exfoliated graphite. The compatibility of exfoliated graphite with a thermoplastic resin can be improved by the surface modification of exfoliated graphite. When the compatibility of exfoliated graphite with the thermoplastic resin is increased, the mechanical strength such as the modulus of elasticity of a resin composite material can be increased. 
     In the resin composite material, the exfoliated graphite is contained in an amount of preferably 0.1 part by mass or more, and more preferably 1 part by mass or more based on 100 parts by mass of the thermoplastic resin from the viewpoint of effectively increasing the mechanical strength such as the modulus of elasticity of the resin composite material. In the resin composite material, the exfoliated graphite is contained in an amount of preferably 50 parts by mass or less, and more preferably 40 parts by mass or less based on 100 parts by mass of the thermoplastic resin from the viewpoint of suppressing the resin composite material from becoming brittle and being easily ruptured. 
     The inorganic filler different from the exfoliated graphite is not particularly limited, and a known inorganic filler can be used. Specific examples of the inorganic filler include silica, mica, talc, clay, bentonite, montmorillonite, kaolinite, Wollastonite, calcium carbonate, titanium oxide, alumina, barium sulfate, potassium titanate, and glass fiber. Preferably, talc is used. In this case, the mechanical strength can be further increased, and the coefficient of linear expansion can be further reduced. The inorganic filler may be contained in a resin composite material singly or in combination of two or more. 
     The average particle size of the inorganic filler is preferably about 0.1 to 100 μm, and more preferably about 1 to 50 μm from the viewpoint of effectively increasing the mechanical strength of a resin composite material. Note that the average particle size of the inorganic filler is a value measured with a particle size distribution measuring device. 
     In the resin composite material, the inorganic filler is contained in an amount of preferably 50 parts by mass or more, and more preferably 55 parts by mass or more based on 100 parts by mass of the thermoplastic resin from the viewpoint of effectively increasing the mechanical strength such as the modulus of elasticity of the resin composite material. In the resin composite material, the inorganic filler is contained in an amount of preferably 200 parts by mass or less, and more preferably 150 parts by mass or less based on 100 parts by mass of the thermoplastic resin from the viewpoint of suppressing the resin composite material from becoming brittle and being easily ruptured. 
     In the resin composite material, the exfoliated graphite and the inorganic filler are contained in a mass ratio (exfoliated graphite:inorganic filler) preferably ranging from about 1:2 to about 1:30, and more preferably ranging from about 1:3 to about 1:20. When the exfoliated graphite and the inorganic filler are contained in such a mass ratio, the modulus of elasticity of the resin composite material can be effectively increased. 
     The resin composite material may further contain an additive. Examples of the additive include antioxidants such as a phenol-based, phosphorus-based, amine-based, and sulfur-based antioxidants; ultraviolet absorbers such as a benzotriazole-based and hydroxyphenyl triazine-based ultraviolet absorbers; metal harm inhibitors; halogenated flame retardants such as hexabromobiphenyl ether and decabromodiphenyl ether; flame retardants such as ammonium polyphosphate and trimethyl phosphate; various fillers; antistatic agents; stabilizers; and pigments. 
     As described above, an attempt has been made to obtain a resin composite material having a high modulus of elasticity by mixing graphite powder or the like with a thermoplastic resin. However, it has been difficult to sufficiently increase the modulus of elasticity of a resin composite material only by blending a small amount of graphite powder with a thermoplastic resin. 
     The resin composite material according to the present invention further contains an inorganic filler different from exfoliated graphite in a thermoplastic resin in addition to the exfoliated graphite. The resin composite material according to the present invention has a high modulus of elasticity by further containing an inorganic filler different from exfoliated graphite in addition to the exfoliated graphite. Moreover, the resin composite material according to the present invention has a low coefficient of linear expansion, and is excellent also in fabricability. 
     The tensile modulus of elasticity of the resin composite material according to the present invention is preferably 5.0 GPa or more. When the tensile modulus of elasticity of the resin composite material is 5.0 GPa or more, the resin composite material can be suitably used for the applications such as vehicle parts and structural materials which require high tensile modulus of elasticity. The coefficient of linear expansion of the resin composite material according to the present invention is preferably 7.5×10 −5 /K or less. When the coefficient of linear expansion of a resin composite material is 7.5×10 −5 /K or less, the resin composite material can be suitably used for the applications such as vehicle parts and structural materials in which a low coefficient of linear expansion is required. Note that the modulus of elasticity and coefficient of linear expansion of a resin composite material each are values measured by the methods described in Examples. 
     The resin composite material according to the present invention can be manufactured, for example, as follows. 
     First, the thermoplastic resin, the exfoliated graphite, and the inorganic filler are provided. Next, the thermoplastic resin, the exfoliated graphite, and the inorganic filler are mixed. The mixing method is not particularly limited as long as it is a method by which a thermoplastic resin, exfoliated graphite, and an inorganic filler can be mixed. The mixing is preferably carried out at a temperature where a thermoplastic resin melts. 
     Examples of the mixing method include a method of kneading with heating using a kneading apparatus such as a twin-screw kneading machine such as a plastomill, a single-screw extruder, a twin-screw extruder, a Banbury mixer, and a roll. The method of melt-kneading using a plastomill is preferred among them. 
     Moreover, a resin composite material can also be molded into a desired shape such as a sheet form to obtain a resin molded product such as a resin composition sheet by subjecting the resin composite material to press-processing, injection molding, extrusion molding, or the like. 
     Hereinafter, the present invention will be further described in detail based on specific Examples. The present invention is not limited to the following Examples at all and can be implemented by appropriately changing it without departing from the scope of the invention. 
     Example 1 
     One hundred parts by mass of polypropylene (trade name “J-721GR”, tensile modulus of elasticity: 1.2 GPa, coefficient of linear expansion: 11×10 −5 /K, manufactured by Prime Polymer Co., Ltd.), 10 parts by mass of exfoliated graphite (graphene, trade name “xGnP-M5”, number of stacked graphene sheets: 90, aspect ratio: 168, manufactured by XG Sciences, Inc.), and 100 parts by mass of talc (trade name “L-1”, particle size: 5 μm, manufactured by Nippon Talc Co., Ltd.) were melt-kneaded with a Labo Plastomill (trade name “R-100”, manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 180° C. to obtain a resin composition. The resulting resin composition was molded into a sheet form by press-processing to obtain a resin composition sheet having a thickness of 0.5 mm. 
     Example 2 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that 0.1 part by mass of exfoliated graphite was used. 
     Example 3 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that 40 parts by mass of exfoliated graphite was used. 
     Example 4 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that polyethylene (trade name “1300)”, flexural modulus: 1.3 GPa, coefficient of linear expansion: 11×10 −5 /K, manufactured by Prime Polymer Co., Ltd.) was used instead of polypropylene. 
     Example 5 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that bentonite (trade name “S-BEN N400”, manufactured by HOJUN Co., Ltd.) was used instead of talc. 
     Example 6 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that calcium carbonate (trade name “BF300”, particle size: 8.0 μm, manufactured by Shiraishi Calcium Kaisha, Ltd.) was used instead of talc. 
     Example 7 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that 50 parts by mass of talc was used. 
     Example 8 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that exfoliated graphite having a different number of stacked graphene sheets from that of the exfoliated graphite used in Example 1 (graphene, trade name “xGnP-H5”, number of stacked graphene sheets: 120, aspect ratio: 126, manufactured by XG Sciences, Inc.) was used. 
     Example 9 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that polycarbonate (trade name: “H-4000”, tensile modulus of elasticity: 2.4 GPa, coefficient of linear expansion: 6.5×10 −5 /K, manufactured by Mitsubishi Engineering-Plastics, Corporation) was used instead of polypropylene. 
     Example 10 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that polyester (trade name: “5010R3-2”, tensile modulus of elasticity: 2.4 GPa, coefficient of linear expansion: 10×10 −5 /K, manufactured by Mitsubishi Engineering-Plastics, Corporation) was used instead of polypropylene. 
     Example 11 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that polyamide (trade name “1300S”, flexural modulus: 2.7 GPa, coefficient of linear expansion: 8×10 −5 /K, manufactured by Asahi Kasei Corporation) was used instead of polypropylene. 
     Example 12 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that polystyrene (trade name: “CR-3500”, flexural modulus: 3.3 GPa, manufactured by DIC Corporation) was used instead of polypropylene. 
     Example 13 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that polymethylmethacrylate (trade name: “VH000”, tensile modulus of elasticity: 3.3 GPa, coefficient of linear expansion: 6×10 −5 /K, manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of polypropylene. 
     Comparative Example 1 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that talc was not used. 
     Comparative Example 2 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that exfoliated graphite was not used. 
     Comparative Example 3 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that natural graphite (trade name: “SNO”, number of stacked graphene sheets: 1500, manufactured by SEC Carbon, Ltd.) was used instead of exfoliated graphite. 
     Comparative Example 4 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Comparative Example 3 except that talc was not used. 
     Comparative Example 5 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 2 except that talc was not used. 
     Comparative Example 6 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 3 except that talc was not used. 
     Comparative Example 7 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Comparative Example 6 except that 50 parts by mass of exfoliated graphite was used. 
     Comparative Example 8 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 4 except that talc was not used. 
     Comparative Example 9 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 4 except that exfoliated graphite was not used. 
     Comparative Example 10 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 5 except that exfoliated graphite was not used. 
     Comparative Example 11 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 6 except that exfoliated graphite was not used. 
     Comparative Example 12 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 7 except that exfoliated graphite was not used. 
     Comparative Example 13 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that exfoliated graphite was not used, and 25 parts by mass of talc was used. 
     Comparative Example 14 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 8 except that talc was not used. 
     Comparative Example 15 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 9 except that talc was not used. 
     Comparative Example 16 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 9 except that exfoliated graphite was not used. 
     Comparative Example 17 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 10 except that talc was not used. 
     Comparative Example 18 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 10 except that exfoliated graphite was not used. 
     Comparative Example 19 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 11 except that talc was not used. 
     Comparative Example 20 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 11 except that exfoliated graphite was not used. 
     Comparative Example 21 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 12 except that talc was not used. 
     Comparative Example 22 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 12 except that exfoliated graphite was not used. 
     Comparative Example 23 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 13 except that talc was not used. 
     Comparative Example 24 
     A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 13 except that exfoliated graphite was not used. 
     The resin composite material sheets of Examples 1 to 13 and Comparative Examples 1 to 24 obtained as described above were evaluated for tensile modulus of elasticity, a coefficient of linear expansion, and fabricability by the following procedures. 
     (1) Evaluation of Tensile Modulus of Elasticity 
     Flat rectangular test pieces each having a length of 75 mm and a width of 6.0 mm were cut from the resin composite material sheets obtained in Examples 1 to 13 and Comparative Examples 1 to 24. Each test piece was measured for the tensile modulus of elasticity at 23° C. according to JIS K7161. The tensile modulus of elasticity (GPa), and the relative rate (%) of increase in the tensile modulus of elasticity based on the tensile modulus of elasticity of a thermoplastic resin (100%) are shown in Tables 1 to 3. 
     (2) Evaluation of Coefficient of Linear Expansion 
     The average coefficient of linear expansion at 30 to 100° C. of the resin composite material sheets obtained in Examples 1 to 13 and Comparative Examples 1 to 24 was measured according to JIS K7197. The coefficient of linear expansion (%) and the relative rate (%) of improvement in the coefficient of linear expansion based on the coefficient of linear expansion of a thermoplastic resin (100%) are shown in Tables 1 to 3. 
     (3) Evaluation of Fabricability 
     The resin composite material sheets obtained in Examples 1 to 13 and Comparative Examples 1 to 24 each were molded into a cup having a shape as shown in  FIG. 1  using a pair of upper and lower press dies. The resulting cup was evaluated for its appearance by visual observation. At this time, the fabricability was rated as good (G) when the cup had neither wrinkles nor rupture, and the fabricability was rated as poor (P) when the cup had wrinkles and rupture. 
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
             
            
               
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
                 Ex. 5 
                 Ex. 6 
                 Ex. 7 
               
               
                   
               
               
                 Thermoplastic resin 
                 Polypro- 
                 Polypro- 
                 Polypro- 
                 Polyeth- 
                 Polypro- 
                 Polypro- 
                 Polypro- 
               
               
                   
                 pylene 
                 pylene 
                 pylene 
                 ylene 
                 pylene 
                 pylene 
                 pylene 
               
               
                 Carbon material 
                 Exfoliated 
                 Exfoliated 
                 Exfoliated 
                 Exfoliated 
                 Exfoliated 
                 Exfoliated 
                 Exfoliated 
               
               
                 (parts by mass) 
                 graphite 
                 graphite 
                 graphite 
                 graphite 
                 graphite 
                 graphite 
                 graphite 
               
               
                   
                 10 
                 0.1 
                 40 
                 10 
                 10 
                 10 
                 10 
               
               
                 Inorganic filler 
                 Talc 
                 Talc 
                 Talc 
                 Talc 
                 Bentonite 
                 Calcium 
                 Talc 
               
               
                 (parts by mass) 
                 100 
                 100 
                 100 
                 100 
                 100 
                 carbonate 
                 50 
               
               
                   
                   
                   
                   
                   
                   
                 100 
               
               
                 Tensile modulus 
                 7.1 
                 5.0 
                 8.1 
                 7.0 
                 6.5 
                 5.9 
                 4.2 
               
               
                 of elasticity (GPa) 
               
               
                 Rate of increase in tensile 
                 492 
                 317 
                 575 
                 483 
                 442 
                 392 
                 250 
               
               
                 modulus of elasticity (%) 
               
               
                 Coefficient of linear expansion 
                 41 
                 72 
                 37 
                 51 
                 56 
                 64 
                 65 
               
               
                 (×10 −5 /° C.) 
               
               
                 Rate of improvement in coefficient 
                 63 
                 35 
                 66 
                 54 
                 49 
                 42 
                 41 
               
               
                 of linear expansion (%) 
               
               
                 Evaluation of fabricability 
                 G 
                 G 
                 G 
                 G 
                 G 
                 G 
                 G 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 Ex. 8 
                 Ex. 9 
                 Ex. 10 
                 Ex. 11 
                 Ex. 12 
                 Ex. 13 
               
               
                   
               
               
                 Thermoplastic resin 
                 Polypro- 
                 Polycar- 
                 Polyester 
                 Polyamide 
                 Polysty- 
                 Polymethyl- 
               
               
                   
                 pylene 
                 bonate 
                   
                   
                 rene 
                 methacrylate 
               
               
                 Carbon material 
                 Exfoliated 
                 Exfoliated 
                 Exfoliated 
                 Exfoliated 
                 Exfoliated 
                 Exfoliated 
               
               
                 (parts by mass) 
                 graphite 
                 graphite 
                 graphite 
                 graphite 
                 graphite 
                 graphite 
               
               
                   
                 10 
                 10 
                 10 
                 10 
                 10 
                 10 
               
               
                 Inorganic filler 
                 Talc 
                 Talc 
                 Talc 
                 Talc 
                 Talc 
                 Talc 
               
               
                 (parts by mass) 
                 100 
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                 Tensile modulus 
                 6.8 
                 7.9 
                 7.8 
                 8.3 
                 8 
                 8.1 
               
               
                 of elasticity (GPa) 
               
               
                 Rate of increase in tensile 
                 467 
                 229 
                 225 
                 207 
                 142 
                 145 
               
               
                 modulus of elasticity (%) 
               
               
                 Coefficient of linear expansion 
                 40 
                 38 
                 43 
                 40 
                 40 
                 32 
               
               
                 (×10 −5 /° C.) 
               
               
                 Rate of improvement in coefficient 
                 64 
                 42 
                 57 
                 50 
                 40 
                 47 
               
               
                 of linear expansion (%) 
               
               
                 Evaluation of fabricability 
                 G 
                 G 
                 G 
                 G 
                 G 
                 G 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
             
            
               
                   
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
               
               
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
                 Ex. 5 
                 Ex. 6 
                 Ex. 7 
               
               
                   
               
               
                 Thermoplastic resin 
                 Polypro- 
                 Polypro- 
                 Polypro- 
                 Polypro- 
                 Polypro- 
                 Polypro- 
                 Polypro- 
               
               
                   
                 pylene 
                 pylene 
                 pylene 
                 pylene 
                 pylene 
                 pylene 
                 pylene 
               
               
                 Carbon material 
                 Exfoliated 
                 — 
                 Natural 
                 Natural 
                 Exfoliated 
                 Exfoliated 
                 Exfoliated 
               
               
                 (parts by mass) 
                 graphite 
                   
                 graphite 
                 graphite 
                 graphite 
                 graphite 
                 graphite 
               
               
                   
                 10 
                   
                 10 
                 10 
                 0.1 
                 40 
                 50 
               
               
                 Inorganic filler 
                 — 
                 Talc 
                 Talc 
                 — 
                 — 
                 — 
                 — 
               
               
                 (parts by mass) 
                   
                 100 
                 100 
               
               
                 Tensile modulus 
                 1.8 
                 4.5 
                 4.6 
                 1.4 
                 1.3 
                 3.6 
                 4.1 
               
               
                 of elasticity (GPa) 
               
               
                 Rate of increase in tensile 
                 50 
                 275 
                 283 
                 17 
                 8 
                 200 
                 242 
               
               
                 modulus of elasticity (%) 
               
               
                 Coefficient of linear expansion 
                 86 
                 79 
                 78 
                 102 
                 106 
                 81 
                 79 
               
               
                 (×10 −5 /° C.) 
               
               
                 Rate of improvement in coefficient 
                 22 
                 28 
                 29 
                 7 
                 4 
                 26 
                 28 
               
               
                 of linear expansion (%) 
               
               
                 Evaluation of fabricability 
                 G 
                 G 
                 G 
                 G 
                 G 
                 G 
                 P 
               
               
                   
               
               
                   
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
               
               
                   
                 Ex. 8 
                 Ex. 9 
                 Ex. 10 
                 Ex. 11 
                 Ex. 12 
                 Ex. 13 
                 Ex. 14 
               
               
                   
               
               
                 Thermoplastic resin 
                 Polyeth- 
                 Polyeth- 
                 Polypro- 
                 Polypro- 
                 Polypro- 
                 Polypro- 
                 Polypro- 
               
               
                   
                 ylene 
                 ylene 
                 pylene 
                 pylene 
                 pylene 
                 pylene 
                 pylene 
               
               
                 Carbon material 
                 Exfoliated 
                 — 
                 — 
                 — 
                 — 
                 — 
                 Exfoliated 
               
               
                 (parts by mass) 
                 graphite 
                   
                   
                   
                   
                   
                 graphite 
               
               
                   
                 10 
                   
                   
                   
                   
                   
                 10 
               
               
                 Inorganic filler 
                 — 
                 Talc 
                 Bentonite 
                 Calcium 
                 Talc 
                 Talc 
                 — 
               
               
                 (parts by mass) 
                   
                 100 
                 100 
                 carbonate 
                 50 
                 25 
               
               
                   
                   
                   
                   
                 100 
               
               
                 Tensile modulus 
                 1.7 
                 4.2 
                 4.1 
                 3.6 
                 3.2 
                 2.3 
                 1.7 
               
               
                 of elasticity (GPa) 
               
               
                 Rate of increase in tensile 
                 42 
                 250 
                 242 
                 200 
                 167 
                 92 
                 42 
               
               
                 modulus of elasticity (%) 
               
               
                 Coefficient of linear expansion 
                 88 
                 85 
                 88 
                 95 
                 91 
                 100 
                 84 
               
               
                 (×10 −5 /° C.) 
               
               
                 Rate of improvement in coefficient 
                 20 
                 23 
                 20 
                 14 
                 17 
                 9 
                 24 
               
               
                 of linear expansion (%) 
               
               
                 Evaluation of fabricability 
                 G 
                 G 
                 G 
                 G 
                 G 
                 G 
                 G 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
             
            
               
                   
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
                 Comp. 
               
               
                   
                 Ex. 15 
                 Ex. 16 
                 Ex. 17 
                 Ex. 18 
                 Ex. 19 
                 Ex. 20 
                 Ex. 21 
               
               
                   
               
               
                 Thermoplastic resin 
                 Polycar- 
                 Polycar- 
                 Polyester 
                 Polyester 
                 Polyamide 
                 Polyamide 
                 Polysty- 
               
               
                   
                 bonate 
                 bonate 
                   
                   
                   
                   
                 rene 
               
               
                 Carbon material 
                 Exfoliated 
                 — 
                 Exfoliated 
                 — 
                 Exfoliated 
                 — 
                 Exfoliated 
               
               
                 (parts by mass) 
                 graphite 
                   
                 graphite 
                   
                 graphite 
                   
                 graphite 
               
               
                   
                 10 
                   
                 10 
                   
                 10 
                   
                 10 
               
               
                 Inorganic filler 
                 — 
                 Talc 
                 — 
                 Talc 
                 — 
                 Talc 
                 — 
               
               
                 (parts by mass) 
                   
                 100 
                   
                 100 
                   
                 100 
               
               
                 Tensile modulus 
                 3.4 
                 5.7 
                 3.3 
                 5.9 
                 4.2 
                 6.1 
                 3.8 
               
               
                 of elasticity (GPa) 
               
               
                 Rate of increase in tensile 
                 42 
                 138 
                 38 
                 146 
                 56 
                 126 
                 15 
               
               
                 modulus of elasticity (%) 
               
               
                 Coefficient of linear expansion 
                 57 
                 52 
                 85 
                 70 
                 68 
                 58 
                 61 
               
               
                 (×10 −5 /° C.) 
               
               
                 Rate of improvement in coefficient 
                 12 
                 20 
                 15 
                 30 
                 15 
                 28 
                 9 
               
               
                 of linear expansion (%) 
               
               
                 Evaluation of fabricability 
                 G 
                 G 
                 G 
                 G 
                 G 
                 G 
                 G 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Comp. 
                 Comp. 
                 Comp. 
               
               
                   
                   
                 Ex. 22 
                 Ex. 23 
                 Ex. 24 
               
               
                   
                   
               
               
                   
                 Thermoplastic resin 
                 Polysty- 
                 Polymethyl- 
                 Polymethyl- 
               
               
                   
                   
                 rene 
                 methacrylate 
                 methacrylate 
               
               
                   
                 Carbon material 
                 — 
                 Exfoliated 
                 — 
               
               
                   
                 (parts by mass) 
                   
                 graphite 
               
               
                   
                   
                   
                 10 
               
               
                   
                 Inorganic filler 
                 Talc 
                 — 
                 Talc 
               
               
                   
                 (parts by mass) 
                 100 
                   
                 100 
               
               
                   
                 Tensile modulus 
                 7.0 
                 4.3 
                 6.2 
               
               
                   
                 of elasticity (GPa) 
               
               
                   
                 Rate of increase in tensile 
                 112 
                 30 
                 88 
               
               
                   
                 modulus of elasticity (%) 
               
               
                   
                 Coefficient of linear expansion 
                 49 
                 52 
                 48 
               
               
                   
                 (×10 −5 /° C.) 
               
               
                   
                 Rate of improvement in coefficient 
                 27 
                 22 
                 20 
               
               
                   
                 of linear expansion (%) 
               
               
                   
                 Evaluation of fabricability 
                 G 
                 G 
                 G