WO2015125916A1 - 炭素材料、樹脂複合材料及びそれらの製造方法 - Google Patents
炭素材料、樹脂複合材料及びそれらの製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/046—Carbon nanorods, nanowires, nanoplatelets or nanofibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/46—Graphite
Definitions
- the present invention relates to a carbon material having a graphene structure, a resin composite material obtained by mixing the carbon material and a thermoplastic resin, and a production method thereof.
- Patent Document 1 discloses a composite material in which fine graphite particles are dispersed in an olefin resin.
- Patent Document 1 it is supposed that physical properties such as electrical conductivity, thermal conductivity, and high elastic modulus can be imparted by adding fine graphite particles to an olefin resin.
- Patent Document 2 discloses a method for producing a resin composite material in which a shearing force is applied to a resin composition containing a resin and a carbon material having a graphene structure under a predetermined condition and then kneaded.
- Patent Document 2 it is said that a resin composite material with increased mechanical strength can be obtained by the above production method.
- Patent Document 1 and Patent Document 2 by adding a carbon material having a graphene structure to the resin, a resin composite material having higher mechanical strength or the like than the original resin can be obtained. Tended to decline. Further, when the obtained resin composite material is molded into a sheet shape or subjected to secondary processing, many voids may be observed. In addition, the void in this specification is a dent with a diameter of 0.1 mm or more.
- An object of the present invention is to provide a carbon material capable of obtaining a resin composite material having few voids and excellent toughness even when combined with a resin, and a method for producing the carbon material.
- Another object of the present invention is to provide a resin composite material having less voids and excellent toughness and a method for producing the resin composite material.
- the carbon material according to the present invention has a graphene structure and the content of volatile components that volatilize at 200 ° C. is less than 1% by weight.
- the carbon material according to the present invention is preferably at least one selected from the group consisting of carbon nanotubes, carbon fibers, graphite, exfoliated graphite and graphene.
- the resin composite material according to the present invention is a resin composite material obtained by mixing the carbon material and a thermoplastic resin.
- the resin composite material according to the present invention preferably contains 5 parts by weight or more of the carbon material with respect to 100 parts by weight of the thermoplastic resin, and the resin composite material is 15 cm ⁇ 15 cm ⁇ 1 mm.
- the thermoplastic resin is a crystalline resin
- the ambient temperature is above the melting point, or when the thermoplastic resin is an amorphous resin, the ambient temperature is at least Tg. After the sheet is left for 1 hour under vacuum, the number of voids generated on the surface is 3 or less.
- the melting point of the crystalline resin refers to a melting peak temperature obtained by DSC (differential scanning calorimetry) measurement based on JIS K7121.
- the Tg of the amorphous resin refers to the midpoint glass transition temperature obtained by DSC measurement based on JIS K7121.
- the resin composite material according to the present invention preferably contains the carbon material in a proportion of 5 parts by weight or more with respect to 100 parts by weight of the thermoplastic resin, and has a fracture strain measured in accordance with JIS K7161. , 50% or more.
- the resin composite material includes a carbon material having a graphene structure and a thermoplastic resin, and the carbon material with respect to 100 parts by weight of the thermoplastic resin.
- the thermoplastic resin is a crystalline resin when the resin composite material is molded into a sheet of 15 cm ⁇ 15 cm ⁇ 1 mm
- the ambient temperature is the melting point.
- the number of voids generated on the surface after the sheet is allowed to stand for 1 hour under vacuum at an atmospheric temperature of Tg or more is 3 or less.
- the carbon material is at least one selected from the group consisting of carbon nanotubes, carbon fibers, graphite, exfoliated graphite, and graphene.
- the resin composite material includes a carbon material having a graphene structure and a thermoplastic resin, and the carbon material with respect to 100 parts by weight of the thermoplastic resin. In a proportion of 5 parts by weight or more, and the breaking strain measured according to JIS K7161 is 50% or more.
- the carbon material having the graphene structure is at least one selected from the group consisting of carbon nanotubes, carbon fibers, graphite, exfoliated graphite, and graphene.
- the resin composite material according to the present invention preferably contains the carbon material in a proportion of 50 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin.
- the thermoplastic resin is a polyolefin.
- the thermoplastic resin is polypropylene.
- the carbon material having a graphene structure is dried until the content of a volatile component that volatilizes at 200 ° C. is less than 1% by weight.
- the carbon material having the graphene structure is at least one selected from the group consisting of carbon nanotubes, carbon fibers, graphite, exfoliated graphite, and graphene.
- the method for producing a resin composite material according to the present invention includes a step of obtaining a carbon material according to the method for producing a carbon material, and a step of obtaining a resin composite material by mixing the carbon material and a thermoplastic resin.
- the carbon material according to the present invention has a graphene structure and the content of volatile components that volatilize at 200 ° C. is less than 1% by weight.
- the carbon material having the graphene structure at least one selected from the group consisting of carbon nanotubes, carbon fibers, graphite, exfoliated graphite, and graphene can be suitably used.
- exfoliated graphite is a laminate of graphene sheets. Exfoliated graphite can be obtained by exfoliating graphite. That is, exfoliated graphite is a laminate of graphene sheets that is thinner than the original graphite.
- the number of graphene sheets laminated in exfoliated graphite is two or more. From the viewpoint of effectively increasing the mechanical strength such as the tensile elastic modulus of the resin, the number of laminated layers is preferably 100 layers or less, and more preferably 30 layers or less. The lower the number of graphene sheets stacked in exfoliated graphite, the more effectively the rigidity such as tensile modulus can be increased.
- Exfoliated graphite has a structure in which thin graphene sheets are laminated. Therefore, the aspect ratio of exfoliated graphite is relatively large.
- the aspect ratio of exfoliated graphite refers to the ratio of the maximum dimension in the laminate surface direction of exfoliated graphite to the thickness of exfoliated graphite.
- the preferable lower limit of the aspect ratio of exfoliated graphite is about 5, and the preferable upper limit is about 100.
- the method for producing exfoliated graphite is not particularly limited, and can be produced by a conventionally known method.
- a chemical treatment method in which ions such as nitrate ions are inserted between graphite layers
- a physical treatment method such as applying ultrasonic waves to graphite
- an electrochemical method in which electrolysis is performed using graphite as a working electrode It is obtained by such a method.
- exfoliated graphite may be commercially available.
- the content of volatile components that volatilize at 200 ° C. in the carbon material is less than 1% by weight.
- moisture content etc. are mentioned.
- the content of the volatile component is a moisture content.
- the moisture content is an index indicating how much weight% moisture is contained in a carbon material at 30 ° C.
- a moisture content can be calculated
- the resin composite material can be usually obtained by mixing the carbon material and the resin at a high temperature, but if the carbon material having a moisture content of 1% by weight or more and the resin are mixed, bubbles are likely to be generated. .
- the bubbles may cause voids, or may be a starting point of breakage when the obtained resin composite material is shaped on a sheet and the sheet is stretched.
- the water content is preferably less than 0.8% by weight, and more preferably less than 0.5% by weight.
- the carbon material according to the present invention can be produced by drying a carbon material having a graphene structure until the moisture content is less than 1% by weight.
- the temperature for the above drying is not particularly limited, but it is desirable to dry at 200 ° C. to 300 ° C. This is because if it is lower than 200 ° C., it may not be sufficiently dried. On the other hand, when the temperature is higher than 300 ° C., the resin grafted on the carbon material may be thermally deteriorated.
- the time for drying is not particularly limited, but is preferably 1 to 2 hours. Note that drying is preferably performed in a nitrogen atmosphere.
- the resin composite material according to the present invention is obtained by mixing the above-described carbon material according to the present invention and a thermoplastic resin. Since the moisture content of the carbon material is less than 1% by weight, even if it is combined with a resin, bubbles are hardly generated. That is, the starting point of breakage when the above-described void or resin composite material is formed into a sheet shape and stretched is unlikely to occur. Here, when there are few starting points of a fracture
- the thermoplastic resin is not particularly limited, and a conventionally known crystalline polymer or amorphous polymer can be used.
- polyolefin can be used.
- the polyolefin is not particularly limited, but polyethylene, polypropylene, ethylene homopolymer, ethylene- ⁇ -olefin copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, Polyethylene resins such as ethylene-vinyl acetate copolymers, propylene homopolymers, polypropylene resins such as propylene- ⁇ -olefin copolymers, butene homopolymers, homopolymers or copolymers of conjugated dienes such as butadiene and isoprene.
- Polypropylene is preferable. More preferably, polypropylene having an MFR (measured under conditions of a temperature of 230 ° C. and a load of 2.16 kgf according to JIS K7210) in the range of 0.5 to 5.0 g / 10 min is used as the polypropylene. In that case, extrusion with high productivity can be performed.
- the resin composite material according to the present invention preferably contains a carbon material having a graphene structure in a proportion of 5 to 50 parts by weight with respect to 100 parts by weight of the resin. More preferably, the carbon material is contained in a proportion of 5 to 20 parts by weight. More preferably, it is contained in a proportion of 5 to 10 parts by weight. This is because if the amount of carbon material is too small, the mechanical strength such as tensile modulus may not be increased effectively, and if the amount is too large, the toughness such as fracture strain may decrease.
- the resin composite material according to the present invention is preferably a resin composite material having 3 or less voids generated on the surface after being molded into a sheet of 15 cm ⁇ 15 cm ⁇ 1 mm and left for 1 hour under vacuum.
- the temperature at the time of leaving for 1 hour under the vacuum when the thermoplastic resin is a crystalline resin, the ambient temperature is equal to or higher than the melting point.
- the thermoplastic resin is an amorphous resin, the ambient temperature is Tg or higher.
- the void is at least a size that can be recognized with the naked eye.
- the resin composite material according to the present invention contains a carbon material having a graphene structure in a proportion of 5 parts by weight or more with respect to 100 parts by weight of the resin, and the number of voids generated on the surface is 3 or less.
- the resin composite material manufactured using the carbon material according to the present invention described above may not be used. That is, you may manufacture by another method. This is because a composite material having excellent toughness can be provided if the number of voids that are the starting points of fracture is small.
- the thermoplastic resin is a crystalline resin
- the ambient temperature is equal to or higher than the melting point
- the thermoplastic resin is an amorphous resin. In some cases, the ambient temperature is Tg or higher.
- at least 1 sort (s) selected from the group which consists of a carbon nanotube, carbon fiber, graphite, exfoliated graphite, and graphene can be used conveniently.
- the resin composite material according to the present invention preferably has a fracture strain measured in accordance with JIS K7161 of 50% or more.
- the breaking strain of 50% or more means that the minimum value of the breaking strain measured according to JIS K7161 is 50% or more.
- the resin composite material according to the present invention contains a carbon material having a graphene structure in a proportion of 5 parts by weight or more with respect to 100 parts by weight of the thermoplastic resin, and measured in accordance with JIS K7161. If the fracture strain is 50% or more, the resin composite material manufactured using the above-described carbon material according to the present invention may not be used. This is because when the breaking strain is 50% or more, the number of voids that are the starting points of the breaking is small. Therefore, it is possible to provide a resin composite material with less voids and excellent toughness.
- the carbon material having the graphene structure at least one selected from the group consisting of carbon nanotubes, carbon fibers, graphite, exfoliated graphite, and graphene can be suitably used.
- additives include, for example, antioxidants such as phenols, phosphoruss, amines, and sulfurs; ultraviolet absorbers such as benzotriazoles and hydroxyphenyltriazines; metal hazard inhibitors; hexabromobiphenyl ether, decabromo Halogenated flame retardants such as diphenyl ether; flame retardants such as ammonium polyphosphate and trimethyl phosphate; various fillers; antistatic agents; stabilizers;
- a carbon material is first obtained by drying a carbon material having a graphene structure until the moisture content is less than 1% by weight.
- a resin composite material is obtained by mixing the obtained carbon material and a thermoplastic resin.
- the method of mixing the carbon material and the thermoplastic resin is not particularly limited, and for example, a method of melt kneading at a high temperature is used.
- the kneading is preferably performed at a temperature that does not cause thermal degradation of the resin.
- the time for kneading is not particularly limited, but is preferably 1 to 5 minutes. If the length is too short, poor dispersion of the carbon material may occur. If the length is too long, the resin may be thermally deteriorated.
- the kneading method is not particularly limited.
- a kneading apparatus such as a twin screw kneader such as a plast mill, a single screw extruder, a twin screw extruder, a Banbury mixer, or a roll is used under heating.
- a kneading method include a kneading method.
- a method of melt kneading using a plast mill is preferable.
- the resin composite material obtained by the present invention can be formed into various shapes by using an appropriate shaping method.
- a shaping method a molding method such as press working, injection molding, or extrusion molding can be suitably used. Further, it may be shaped by a melt coating method. Using the shaping method as described above, a desired shape such as a sheet shape can be obtained.
- Dry exfoliated graphite A was obtained by drying the exfoliated graphite at 200 ° C. for 1 hour in a nitrogen atmosphere.
- dried exfoliated graphite B to D were obtained by drying under the conditions shown in Table 1 below.
- Dry carbon nanotubes G and H were obtained.
- the obtained exfoliated graphite A to D, dry graphite E and F, and carbon nanotubes G and H were thermogravimetrically measured at a heating rate of 10 ° C./min in a temperature range of 30 to 200 ° C. (TGA). Measurement).
- TGA thermogravimetrically measured at a heating rate of 10 ° C./min in a temperature range of 30 to 200 ° C.
- the above graphite was dried under the conditions shown in Table 1 below in a nitrogen atmosphere to obtain dry graphites E and F.
- the obtained graphites E and F were subjected to thermogravimetry (TGA measurement) at a temperature rising rate of 10 ° C./min in the temperature range of 30 to 200 ° C. in an air atmosphere.
- TGA measurement thermogravimetry
- the moisture content was determined by the above formula, where the weight of graphite at 30 ° C. was A weight, and the amount of water volatilized until the temperature was raised to 200 ° C. was B weight.
- Dry carbon nanotubes G and H were obtained by drying the carbon nanotubes under the conditions shown in Table 1 below in a nitrogen atmosphere.
- the obtained carbon nanotubes G and H were subjected to thermogravimetry (TGA measurement) at a temperature rising rate of 10 ° C./min in an air atmosphere at a temperature range of 30 to 200 ° C.
- TGA measurement thermogravimetry
- the water content was determined by the above formula, where the weight of the carbon nanotubes at 30 ° C. was A weight, and the amount of water volatilized until the temperature was raised to 200 ° C. was B weight.
- Example 1 100 parts by weight of polypropylene resin (manufactured by Prime Polypro, trade name: E-150GK, MFR: 0.6 g / 10 min, strain at break: 600% or more) and 10 parts by weight of dried exfoliated graphite A,
- a resin composite material was obtained by melt-kneading for 3 minutes at a temperature of 180 ° C. using a lab plast mill (trade name: R-100, manufactured by Toyo Seiki Co., Ltd.). Subsequently, the obtained resin composite material was formed into a sheet shape by press working to produce a resin composite material sheet having a thickness of 1.0 mm.
- Example 2 A resin composite material sheet having a thickness of 1.0 mm was prepared in the same manner as in Example 1 except that 20 parts by weight of dried exfoliated graphite A was used instead of 10 parts by weight of dried exfoliated graphite A.
- Example 3 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that dry exfoliated graphite B was used instead of dry exfoliated graphite A.
- Example 4 A resin composite material sheet having a thickness of 1.0 mm was prepared in the same manner as in Example 3 except that 50 parts by weight of dried exfoliated graphite B was used instead of 10 parts by weight of dried exfoliated graphite B.
- Example 5 A resin composite material sheet having a thickness of 1.0 mm was prepared in the same manner as in Example 1 except that dry graphite E was used instead of dry exfoliated graphite A.
- Example 6 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 5 except that 20 parts by weight of dry graphite E was used instead of 10 parts by weight of dry graphite E.
- Example 7 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that dry carbon nanotubes G were used instead of dry exfoliated graphite A.
- Example 8 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 7 except that 20 parts by weight of dry carbon nanotubes G was used instead of 10 parts by weight of dry carbon nanotubes G.
- Example 9 Except for using high-density polyethylene resin (trade name: HF560, MFR: 7.0 g / 10 min, breaking strain: 400% or more) instead of polypropylene resin, Examples In the same manner as in Example 1, a resin composite material sheet having a thickness of 1.0 mm was produced.
- high-density polyethylene resin trade name: HF560, MFR: 7.0 g / 10 min, breaking strain: 400% or more
- Example 10 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 10 except that 20 parts by weight of dried exfoliated graphite B was used instead of 10 parts by weight of dried exfoliated graphite A.
- Example 11 Example 1 except that polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, trade name: H-3000, MFR: 30 g / 10 min, strain at break: 100% or more) was used instead of polypropylene resin In the same manner, a resin composite material sheet having a thickness of 1.0 mm was produced.
- polycarbonate resin manufactured by Mitsubishi Engineering Plastics, trade name: H-3000, MFR: 30 g / 10 min, strain at break: 100% or more
- Example 12 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 11 except that 20 parts by weight of dried exfoliated graphite B was used instead of 10 parts by weight of dried exfoliated graphite A.
- Example 1 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that dry exfoliated graphite C was used instead of dry exfoliated graphite A.
- Example 2 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 2 except that dry exfoliated graphite C was used instead of dry exfoliated graphite A.
- Example 3 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that dry exfoliated graphite D was used instead of dry exfoliated graphite A.
- Comparative Example 4 A resin composite material sheet having a thickness of 1.0 mm was prepared in the same manner as in Comparative Example 3 except that 50 parts by weight of dried exfoliated graphite D was used instead of 10 parts by weight of dried exfoliated graphite D.
- Comparative Example 5 A resin composite material sheet having a thickness of 1.0 mm was prepared in the same manner as in Comparative Example 1 except that dry graphite F was used instead of dry exfoliated graphite C.
- Comparative Example 6 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Comparative Example 5 except that 20 parts by weight of dry graphite F was used instead of 10 parts by weight of dry graphite F.
- Comparative Example 7 A resin composite material sheet having a thickness of 1.0 mm was prepared in the same manner as in Comparative Example 1 except that dry carbon nanotube H was used instead of dry exfoliated graphite C.
- Comparative Example 8 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Comparative Example 7, except that 20 parts by weight of dry carbon nanotubes H was used instead of 10 parts by weight of dry carbon nanotubes H.
- Example 9 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 9 except that dry exfoliated graphite C was used instead of dry exfoliated graphite A.
- Comparative Example 10 A resin composite material sheet having a thickness of 1.0 mm was prepared in the same manner as in Comparative Example 9 except that 20 parts by weight of dried exfoliated graphite C was used instead of 10 parts by weight of dried exfoliated graphite C.
- Example 11 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Example 11 except that dry exfoliated graphite C was used instead of dry exfoliated graphite A.
- Comparative Example 12 A resin composite material sheet having a thickness of 1.0 mm was produced in the same manner as in Comparative Example 11 except that 20 parts by weight of dried exfoliated graphite C was used instead of 10 parts by weight of dried exfoliated graphite C.
- Break strain Samples were prepared by punching five No. 1 dumbbells from the resin composite material sheets obtained in Examples 1 to 12 and Comparative Examples 1 to 12. About the obtained sample, the fracture
- rupture distortion in 23 degreeC was measured based on JISK7161 (N 5). The one having the smallest value among the obtained five breaking strains was taken as the breaking strain of the resin composite material sheet.
Abstract
Description
本発明に係る炭素材料は、グラフェン構造を有し、かつ200℃で揮発する揮発成分の含有率が1重量%未満である。上記グラフェン構造を有する炭素材料としては、カーボンナノチューブ、カーボンファイバー、黒鉛、薄片化黒鉛及びグラフェンからなる群から選択された少なくとも1種を好適に用いることができる。
本発明に係る樹脂複合材料は、上述した本発明に係る炭素材料と、熱可塑性樹脂とを混合することにより得られる。上記炭素材料の含水率は、1重量%未満であるため、樹脂と複合化しても、気泡が発生し難い。すなわち、上述したボイドや、樹脂複合材料をシート状に賦型し、延伸させた際の破断の起点が発生し難い。ここで、破断の起点が少ないと、破断歪が低下し難い。従って、靱性に優れた樹脂複合材料を提供することができる。
本発明に係る樹脂複合材料の製造方法においては、まず、グラフェン構造を有する炭素材料を含水率が1重量%未満になるまで乾燥させることにより炭素材料を得る。次に、得られた炭素材料と、熱可塑性樹脂とを混合することにより、樹脂複合材料を得る。
以下、本発明について、具体的な実施例に基づき、さらに説明する。なお、本発明は以下の実施例に限定されるものではない。
薄片化黒鉛としては、xGScience社製、商品名「xGnP-M5」を用いた。使用前にSEMを用いて観察した層面の面方向における平均寸法は、約5.0μmであり、層厚みは約60nmであった。また、グラフェンの積層数は、約180層、BET比表面積は、75m2/gであった。
黒鉛としては、SECカーボン社製、商品名「SNO5」を用いた。使用前にSEMを用いて観察した層面の面方向における平均寸法は、約5.0μmであり、層厚みは約500nmであった。また、グラフェンの積層数は、約1500層であり、BET比表面積は、16m2/gであった。
カーボンナノチューブとしては、CNT社製、商品名「Ctube-100」を用いた。平均直径10~40nm、平均長さ13nm、BET比表面積150m2/gであった。
100重量部のポリプロピレン系樹脂(プライムポリプロ社製、商品名:E-150GK、MFR:0.6g/10分、破断歪:600%以上)と、10重量部の乾燥薄片化黒鉛Aとを、ラボプラストミル(東洋精機社製、商品名:R-100)を用いて、温度180℃で、3分間溶融混練することにより樹脂複合材料を得た。続いて、得られた樹脂複合材料をプレス加工により、シート状に成形して、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥薄片化黒鉛Aの代わりに、20重量部の乾燥薄片化黒鉛Aを用いたこと以外は、実施例1と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
乾燥薄片化黒鉛Aの代わりに乾燥薄片化黒鉛Bを用いたことを除いては、実施例1と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥薄片化黒鉛Bの代わりに、50重量部の乾燥薄片化黒鉛Bを用いたこと以外は、実施例3と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
乾燥薄片化黒鉛Aの代わりに乾燥黒鉛Eを用いたことを除いては、実施例1と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥黒鉛Eの代わりに、20重量部の乾燥黒鉛Eを用いたこと以外は、実施例5と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
乾燥薄片化黒鉛Aの代わりに乾燥カーボンナノチューブGを用いたことを除いては、実施例1と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥カーボンナノチューブGの代わりに、20重量部の乾燥カーボンナノチューブGを用いたこと以外は、実施例7と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
ポリプロピレン系樹脂の代わりに、高密度ポリエチレン系樹脂(日本ポリエチレン社製、商品名:HF560、MFR:7.0g/10分、破断歪:400%以上)を用いたことを除いては、実施例1と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥薄片化黒鉛Aの代わりに、20重量部の乾燥薄片化黒鉛Bを用いた以外は、実施例10と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
ポリプロピレン系樹脂の代わりに、ポリカーボネート系樹脂(三菱エンジニアリングプラスチック社製、商品名:H-3000、MFR:30g/10分、破断歪:100%以上)を用いたことを除いては、実施例1と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥薄片化黒鉛Aの代わりに、20重量部の乾燥薄片化黒鉛Bを用いた以外は、実施例11と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
乾燥薄片化黒鉛Aの代わりに乾燥薄片化黒鉛Cを用いたことを除いては、実施例1と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
乾燥薄片化黒鉛Aの代わりに乾燥薄片化黒鉛Cを用いたことを除いては、実施例2と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
乾燥薄片化黒鉛Aの代わりに乾燥薄片化黒鉛Dを用いたことを除いては、実施例1と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥薄片化黒鉛Dの代わりに、50重量部の乾燥薄片化黒鉛Dを用いたこと以外は、比較例3と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
乾燥薄片化黒鉛Cの代わりに乾燥黒鉛Fを用いたことを除いては、比較例1と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥黒鉛Fの代わりに、20重量部の乾燥黒鉛Fを用いたこと以外は、比較例5と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
乾燥薄片化黒鉛Cの代わりに乾燥カーボンナノチューブHを用いたことを除いては、比較例1と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥カーボンナノチューブHの代わりに、20重量部の乾燥カーボンナノチューブHを用いたこと以外は、比較例7と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
乾燥薄片化黒鉛Aの代わりに乾燥薄片化黒鉛Cを用いたことを除いては、実施例9と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥薄片化黒鉛Cの代わりに、20重量部の乾燥薄片化黒鉛Cを用いた以外は、比較例9と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
乾燥薄片化黒鉛Aの代わりに乾燥薄片化黒鉛Cを用いたことを除いては、実施例11と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
10重量部の乾燥薄片化黒鉛Cの代わりに、20重量部の乾燥薄片化黒鉛Cを用いた以外は、比較例11と同様にして、厚み1.0mmの樹脂複合材料シートを作製した。
ボイド数:実施例1~10及び比較例1~10で得られた樹脂複合材料シートを180℃で、実施例11,12、比較例11、12で得られた樹脂複合シートは250℃で、-0.1MPaにしたオーブンにおいて、1時間放置したときのボイドの数を目視によって確認した。
Claims (14)
- グラフェン構造を有し、かつ200℃で揮発する揮発成分の含有率が1重量%未満である、炭素材料。
- 前記炭素材料が、カーボンナノチューブ、カーボンファイバー、黒鉛、薄片化黒鉛及びグラフェンからなる群から選択された少なくとも1種である、請求項1に記載の炭素材料。
- 請求項1又は2に記載の炭素材料と、熱可塑性樹脂とを混合することにより得られる、樹脂複合材料。
- 前記熱可塑性樹脂100重量部に対して、前記炭素材料を5重量部以上の割合で含有しており、
前記樹脂複合材料を、15cm×15cm×1mmのシートに賦型したときに、前記熱可塑性樹脂が結晶性樹脂の場合には、雰囲気温度が融点以上において、又は前記熱可塑性樹脂が非晶性樹脂の場合には、雰囲気温度がTg以上において、前記シートを、真空下で1時間放置した後に、表面に発生するボイドが3個以下である、請求項3に記載の樹脂複合材料。 - 前記熱可塑性樹脂100重量部に対して、前記炭素材料を5重量部以上の割合で含有しており、
JIS K7161に準拠して測定した破断歪が、50%以上である、請求項3又は4に記載の樹脂複合材料。 - グラフェン構造を有する炭素材料と、熱可塑性樹脂とを含む、樹脂複合材料であって、
前記熱可塑性樹脂100重量部に対して、前記炭素材料を5重量部以上の割合で含有しており、
前記樹脂複合材料を、15cm×15cm×1mmのシートに賦型したときに、前記熱可塑性樹脂が結晶性樹脂の場合には、雰囲気温度が融点以上において、又は前記熱可塑性樹脂が非晶性樹脂の場合には、雰囲気温度がTg以上において、前記シートを、真空下で1時間放置した後に、表面に発生するボイドが3個以下である、樹脂複合材料。 - グラフェン構造を有する炭素材料と、熱可塑性樹脂とを含む、樹脂複合材料であって、
前記熱可塑性樹脂100重量部に対して、前記炭素材料を5重量部以上の割合で含有しており、
JIS K7161に準拠して測定した破断歪が、50%以上である、樹脂複合材料。 - 前記グラフェン構造を有する炭素材料が、カーボンナノチューブ、カーボンファイバー、黒鉛、薄片化黒鉛及びグラフェンからなる群から選択された少なくとも1種である、請求項6又は7に記載の樹脂複合材料。
- 前記熱可塑性樹脂100重量部に対して、前記炭素材料を50重量部以下の割合で含有している、請求項3~8のいずれか1項に樹脂複合材料。
- 前記熱可塑性樹脂が、ポリオレフィンであることを特徴とする、請求項3~9のいずれか1項に記載の樹脂複合材料。
- 前記熱可塑性樹脂が、ポリプロピレンであることを特徴とする、請求項10に記載の樹脂複合材料。
- グラフェン構造を有する炭素材料を、200℃で揮発する揮発成分の含有率が1重量%未満になるまで乾燥させる、炭素材料の製造方法。
- 前記グラフェン構造を有する炭素材料が、カーボンナノチューブ、カーボンファイバー、黒鉛、薄片化黒鉛及びグラフェンからなる群から選択された少なくとも1種である、請求項12に記載の炭素材料の製造方法。
- 請求項12又は13に記載の炭素材料の製造方法により、炭素材料を得る工程と、
前記炭素材料と熱可塑性樹脂とを混合することにより、樹脂複合材料を得る工程とを備える、樹脂複合材料の製造方法。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008239640A (ja) * | 2007-03-23 | 2008-10-09 | Kaneka Corp | 高熱伝導性熱可塑性樹脂組成物及び成形体 |
JP2009160754A (ja) * | 2007-12-28 | 2009-07-23 | Inoac Corp | カーボンナノチューブ担持発泡体及びその製法 |
JP2010045025A (ja) * | 2008-07-18 | 2010-02-25 | Hodogaya Chem Co Ltd | 微細炭素繊維を用いた発熱体及びその製造方法 |
JP2010077300A (ja) * | 2008-09-26 | 2010-04-08 | Fuji Xerox Co Ltd | ポリアミック酸組成物、ポリイミド無端ベルトおよび画像形成装置 |
WO2012124010A1 (ja) * | 2011-03-14 | 2012-09-20 | パナソニック株式会社 | 高分子構造体およびその製造方法 |
WO2013058181A1 (ja) * | 2011-10-18 | 2013-04-25 | 積水化学工業株式会社 | 樹脂複合材料の製造方法及び樹脂複合材料 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB484710A (en) * | 1935-12-19 | 1938-05-09 | Ilija Worobjoff | Improvements in or relating to toy balloons |
JPS5547217A (en) * | 1978-10-02 | 1980-04-03 | Mukaaji Supaankaa | Production of exfoliative graphite |
GB2128629B (en) * | 1982-10-12 | 1985-11-13 | T & N Materials Res Ltd | Lubricant materials |
JPS6030102A (ja) * | 1983-07-28 | 1985-02-15 | 株式会社ミスズ | 抵抗塗料の製造方法 |
US4915925A (en) * | 1985-02-11 | 1990-04-10 | Chung Deborah D L | Exfoliated graphite fibers and associated method |
US4758473A (en) * | 1986-11-20 | 1988-07-19 | Electric Power Research Institute, Inc. | Stable carbon-plastic electrodes and method of preparation thereof |
US8794533B2 (en) * | 2008-08-20 | 2014-08-05 | Omni-Id Cayman Limited | One and two-part printable EM tags |
KR101460876B1 (ko) | 2010-06-07 | 2014-11-13 | 도요타 지도샤(주) | 수지 복합 재료 |
WO2011155486A1 (ja) | 2010-06-07 | 2011-12-15 | 株式会社豊田中央研究所 | 微細化黒鉛粒子、それを含有する黒鉛粒子分散液、および微細化黒鉛粒子の製造方法 |
JP5909053B2 (ja) | 2011-04-28 | 2016-04-26 | 株式会社豊田中央研究所 | 樹脂複合材料 |
RU2011130445A (ru) | 2011-07-22 | 2013-01-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Казанский национальный исследовательский технический университет им. А.Н. Туполева-КАИ | Способ получения полимерного концентрата с нанодобавками |
CN102557031B (zh) | 2011-12-27 | 2013-10-30 | 双流新源圣光科技有限公司 | 一种硅片切割废砂浆中的碳化硅回收利用的方法 |
CN102557011A (zh) * | 2012-03-09 | 2012-07-11 | 桂林理工大学 | 一种利用双氧水进行多壁碳纳米管表面功能化处理的方法 |
JP5564090B2 (ja) | 2012-04-04 | 2014-07-30 | 積水化学工業株式会社 | 樹脂複合材料の製造方法及び樹脂複合材料 |
KR20140147813A (ko) | 2012-04-04 | 2014-12-30 | 세키스이가가쿠 고교가부시키가이샤 | 수지 복합 재료의 제조 방법 및 수지 복합 재료 |
-
2015
- 2015-02-20 KR KR1020167022657A patent/KR20160125378A/ko not_active Application Discontinuation
- 2015-02-20 EP EP15752515.5A patent/EP3147260A4/en not_active Withdrawn
- 2015-02-20 WO PCT/JP2015/054767 patent/WO2015125916A1/ja active Application Filing
- 2015-02-20 CN CN201580009988.0A patent/CN106061895A/zh active Pending
- 2015-02-20 US US15/115,681 patent/US10435533B2/en active Active
- 2015-02-20 JP JP2015511529A patent/JP6445966B2/ja active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008239640A (ja) * | 2007-03-23 | 2008-10-09 | Kaneka Corp | 高熱伝導性熱可塑性樹脂組成物及び成形体 |
JP2009160754A (ja) * | 2007-12-28 | 2009-07-23 | Inoac Corp | カーボンナノチューブ担持発泡体及びその製法 |
JP2010045025A (ja) * | 2008-07-18 | 2010-02-25 | Hodogaya Chem Co Ltd | 微細炭素繊維を用いた発熱体及びその製造方法 |
JP2010077300A (ja) * | 2008-09-26 | 2010-04-08 | Fuji Xerox Co Ltd | ポリアミック酸組成物、ポリイミド無端ベルトおよび画像形成装置 |
WO2012124010A1 (ja) * | 2011-03-14 | 2012-09-20 | パナソニック株式会社 | 高分子構造体およびその製造方法 |
WO2013058181A1 (ja) * | 2011-10-18 | 2013-04-25 | 積水化学工業株式会社 | 樹脂複合材料の製造方法及び樹脂複合材料 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3147260A4 * |
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