WO2014136642A1 - 樹脂複合材料の製造方法及び樹脂複合材料 - Google Patents
樹脂複合材料の製造方法及び樹脂複合材料 Download PDFInfo
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- WO2014136642A1 WO2014136642A1 PCT/JP2014/054814 JP2014054814W WO2014136642A1 WO 2014136642 A1 WO2014136642 A1 WO 2014136642A1 JP 2014054814 W JP2014054814 W JP 2014054814W WO 2014136642 A1 WO2014136642 A1 WO 2014136642A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/10—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a resin composite material in which a carbon material having a graphene structure is dispersed in a synthetic resin and a method for producing the same.
- Patent Document 1 includes a step of preparing a resin composition including a synthetic resin and a carbon material having a graphene structure dispersed in the synthetic resin, and a step of preparing the resin composition at the same time or thereafter.
- a method for producing a resin composite material comprising a step of grafting a synthetic resin onto a carbon material is disclosed. In this production method, grafting is performed by irradiating the resin composition with an electron beam or microwave.
- Patent Document 1 describes that it is desirable to add a reaction aid in order to promote the generation of free radicals by electron beam irradiation.
- a reaction aid Patent Document 1 mentions divinylbenzene, trimethylolpropane trimethacrylate, and the like.
- Patent Document 2 discloses a resin composite material obtained by grafting a synthetic resin onto a carbon material having a graphene structure.
- Patent Document 2 discloses a method of adding a radical initiator to facilitate the generation of radicals during grafting.
- this radical initiator it is shown that azo compounds and the like can be mentioned.
- An object of the present invention is obtained by a method for producing a resin composite material in which a synthetic resin is grafted to a carbon material, and the resin is hardly deteriorated and exhibits high mechanical strength, and the method for producing the resin composite material.
- the object is to provide a resin composite material.
- the resin composite material according to the present invention is a resin composite material including a synthetic resin and a carbon material having a graphene structure, in which a part of the synthetic resin is grafted and dispersed in the synthetic resin. And the MFR measured based on JIS K7210 of the part which is not grafted to the carbon material which has the said graphene structure among the said synthetic resins is 15 g / 10min or less.
- the resin composite material according to the present invention preferably contains 5 parts by weight or more of the carbon material having the graphene structure with respect to 100 parts by weight of the synthetic resin.
- the resin composite material according to the present invention preferably further includes a different type of resin from the synthetic resin.
- the carbon material having the graphene structure is at least one selected from the group consisting of graphite, exfoliated graphite, and graphene.
- the synthetic resin is a thermoplastic resin. More preferably, the thermoplastic resin is a radical decay type resin.
- the method for producing a resin composite material according to the present invention includes a step of preparing a resin composition including a synthetic resin and a carbon material having a graphene structure dispersed in the synthetic resin, and a step of preparing a resin composition.
- the grafting step is performed by mixing the synthetic resin and the carbon material with an initiator whose radical generated when pyrolyzed is a carbon radical, and heating the mixture.
- a step of preparing a resin composition containing a synthetic resin and a carbon material having a graphene structure dispersed in the synthetic resin A step of grafting the synthetic resin onto the carbon material simultaneously with the step of preparing the resin composition or after the step of preparing the resin composition, and the step of grafting includes the synthetic resin and the above
- the carbon material is mixed with a radical initiator and heated, and the dispersion area ratio of the carbon material when the radical initiator is mixed is [Armax] or less represented by the following formula.
- the radical generated when the radical initiator is thermally decomposed is a carbon radical.
- a step of preparing a resin composition that includes a synthetic resin and a carbon material that is dispersed in the synthetic resin and has a graphene structure;
- a step of grafting the synthetic resin onto the carbon material simultaneously with the step of preparing the resin composition or after the step of preparing the resin composition, and the step of grafting includes the synthetic resin and the above This is performed by mixing a carbon material with a radical initiator and a compound having radical trapping properties and heating.
- the radical trapping compound is at least one selected from the group consisting of compounds having the structures of the following formulas (1) to (5).
- the ratio between the weight average molecular weight Mw1 of the synthetic resin and the weight average molecular weight Mw2 of the synthetic resin not grafted to the carbon material in the obtained resin composite material preferably, the ratio between the weight average molecular weight Mw1 of the synthetic resin and the weight average molecular weight Mw2 of the synthetic resin not grafted to the carbon material in the obtained resin composite material.
- the synthetic resin is grafted to the carbon material so that Mw2 / Mw1 is 0.5 or more.
- the method for producing a resin composite material according to the present invention may further include a step of mixing the same type of synthetic resin as the synthetic resin or a different resin after the grafting step.
- the carbon material having the graphene structure is preferably at least one carbon material selected from the group consisting of graphite, exfoliated graphite, and graphene.
- thermoplastic resin is preferably used as the synthetic resin, and a crystalline resin is more preferably used as the thermoplastic resin.
- the resin composite material according to the present invention includes a synthetic resin and a carbon material having a graphene structure dispersed in the synthetic resin.
- a part of the synthetic resin is grafted on the surface of the carbon material having the graphene structure. Therefore, in the resin composite material of the present invention, the adhesion between the synthetic resin and the carbon material is further enhanced. Furthermore, the affinity of the grafted carbon material with the synthetic resin is enhanced. Therefore, in the resin composite material provided with the synthetic resin, the grafted carbon material is uniformly dispersed in the synthetic resin. Therefore, the mechanical strength of the resin composite material can be effectively increased and the linear expansion coefficient can be effectively reduced.
- the MFR measured in accordance with JIS K7210 of the portion of the synthetic resin not grafted to the carbon material having the graphene structure is 15 g / 10 min or less. is there. Therefore, in the resin composite material according to the present invention, since the proportion of the low molecular weight synthetic resin is low, mechanical properties such as elastic modulus and breaking strain are enhanced.
- the MFR is preferably 10 g / 10 min or less, and more preferably 5 g / 10 min or less.
- MFR can be measured by the method described in the item of the evaluation of the Example and comparative example which are mentioned later.
- the synthetic resin contained in the resin composite material of the present invention is not particularly limited, and various known synthetic resins can be used.
- a thermoplastic resin is used as the synthetic resin.
- various molded products can be easily obtained using various molding methods under heating.
- thermoplastic resin examples include polyethylenes such as high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, polyolefins typified by polypropylenes such as homopolypropylene, block polypropylene, and random polypropylene, and cyclics such as norbornene resin.
- Polyvinyl acetates such as polyolefins, polyvinyl acetate and ethylene vinyl acetate, polyvinyl acetate derivatives such as polyvinyl alcohol and polyvinyl butyral, polyesters such as PET, polycarbonate and polylactic acid, polyethylene oxide, polyphenylene ether, Polyether resins such as polyether ether ketone, acrylic resins such as PMMA, sulfone resins such as polysulfone and polyether sulfone, PTFE, PVDF, etc.
- Tsu fluorinated resins polyamide resins such as nylon, polyvinyl chloride, halogenated resins such as vinylidene chloride, polystyrene, polyacrylonitrile or a copolymer resin thereof such and the like.
- synthetic resin only 1 type may be used and 2 or more types may be used together.
- Particularly preferred are polyolefins that are inexpensive and easy to mold under heating.
- thermoplastic resin a crystalline resin may be used, or an amorphous resin may be used.
- a crystalline resin When a crystalline resin is used, the mechanical strength can be further increased.
- the crystalline resin include crystalline polypropylene, crystalline polyethylene, crystalline norbornene, crystalline polyvinyl acetate, crystalline polylactic acid, and semicrystalline PVDF. More preferably, inexpensive crystalline polypropylene is used.
- the fluidity of the amorphous resin can be effectively suppressed by dispersing the carbon material in the amorphous resin.
- the amorphous resin is not particularly limited, and an appropriate amorphous resin can be used.
- Examples of the amorphous resin include atactic polypropylene, amorphous norbornene, amorphous PET, amorphous polycarbonate, polyphenylene ether, polyetheretherketone, atactic PMMA, polysulfone, polyethersulfone, and atactic polystyrene. Etc. More preferably, an inexpensive atactic polypropylene can be used.
- a radical decay type resin can be used as the thermoplastic resin.
- the radical decay type resin refers to a resin in which a main chain cleavage reaction mainly proceeds by generating a radical.
- Specific examples of the radical decay type resin include polypropylene, polyisobutylene, polyvinylene chloride, polytetrafluoroethylene, polymethyl methacrylate, polyvinyl butyral, polyacrylamide, and epoxy resin.
- a resin different from the synthetic resin may be further included.
- the different types of resins may be grafted to the carbon material or may not be grafted.
- thermoplastic resins examples include various thermoplastic resins that can be used as the above-described synthetic resin.
- thermosetting resin examples include an epoxy resin and a polyurethane resin.
- the different types of resins may be crystalline resins or amorphous resins as described above. However, since the crystalline resin is generally superior in mechanical properties such as elastic modulus and molding processability as compared with the amorphous resin, the different types of resins are preferably crystalline resins.
- the blending ratio of the synthetic resin and the different type of resin is not particularly limited, but the blending amount of the different type of resin is preferably 1000 parts by weight or less with respect to 100 parts by weight of the synthetic resin.
- the blending amount of the different types of resins exceeds 1000 parts by weight, the effects of improving the mechanical strength and lowering the linear expansion coefficient due to the carbon material contained in the resin composite material may not be sufficiently exhibited.
- the carbon material having the graphene structure is dispersed in the synthetic resin.
- the mechanical strength of the resin composite material of the present invention can be increased, and the linear expansion coefficient can be decreased.
- the resin composite material of the present invention can be made conductive. Therefore, the resin composite material of the present invention has a possibility that it can be used as a material exhibiting conductivity.
- the synthetic resin is grafted to the carbon material. Therefore, in the resin composite material of the present invention, the adhesion between the synthetic resin and the carbon material is further enhanced. Further, the carbon material grafted with the synthetic resin has enhanced affinity with the synthetic resin. Therefore, in the resin composite material of the present invention, the grafted carbon material is uniformly dispersed in the synthetic resin. Therefore, the mechanical strength can be effectively increased and the linear expansion coefficient can be effectively reduced.
- the carbon material having the graphene structure is not particularly limited, but preferably, at least one selected from the group consisting of graphite, carbon nanotubes, exfoliated graphite and graphene 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.
- the exfoliated graphite has a shape with a relatively large specific surface area. Therefore, in the resin composite material of the present invention, since the exfoliated graphite is dispersed, the mechanical strength against an external force applied in the direction intersecting the graphene sheet lamination surface of the exfoliated graphite can be effectively increased.
- the specific surface area means a BET specific surface area measured by the BET three-point method.
- the preferable lower limit of the BET specific surface area of the exfoliated graphite is 15 m 2 / g, and the preferable upper limit is 2700 m 2 / g. If the specific surface area of the exfoliated graphite is lower than 15 m 2 / g, the mechanical strength against an external force applied in the direction intersecting the laminated surface may not be sufficiently increased. On the other hand, the theoretical BET specific surface area of the single-layer graphene sheet is 2700 m 2 / g, which is a limit value.
- the blending ratio of the carbon material and the synthetic resin is not particularly limited, but the blending amount of the carbon material is preferably 5 parts by weight or more with respect to 100 parts by weight of the synthetic resin. More preferably, the amount is in the range of 10 to 50 parts by weight with respect to 100 parts by weight of the synthetic resin. If the amount of the carbon material is too small, the mechanical strength may not be sufficiently increased and the linear expansion coefficient may not be sufficiently decreased. If the amount of the carbon material is too large, the rigidity of the resin composite material is increased, but the resin composite material becomes brittle and may be easily broken.
- the graft ratio of the carbon material is in the range of 5 wt% to 3300 wt%.
- the graft ratio of the carbon material refers to the weight of the synthetic resin that forms a chemical bond directly by grafting to the carbon material in the resin composite material with respect to the weight of the carbon material contained in the resin composite material. The ratio.
- the graft ratio of the carbon material is in the range of 10 wt% to 2000 wt%, and more preferably in the range of 30 wt% to 1000 wt%.
- the grafting rate of the carbon material contained in the resin composite material can be measured by the following method. For example, ungrafted synthetic resin contained in the resin composite material is dissolved and removed with a solvent to isolate the grafted carbon material. Thereafter, the grafted carbon material is subjected to thermogravimetric measurement (TGA measurement) at a temperature rising rate of 10 ° C./min in a temperature range of 30 to 600 ° C. in an air atmosphere. At this time, the amount of the decomposition product decomposed until the temperature was raised to 500 ° C. was A wt%, and the amount of the undecomposed product that was not decomposed even when the temperature was raised to 500 ° C. The grafting rate of the carbon material can be determined.
- TGA measurement thermogravimetric measurement
- the solvent is not particularly limited as long as it dissolves the ungrafted synthetic resin and hardly dissolves the grafted carbon material, and an appropriate solvent can be used.
- the synthetic resin is an olefin resin, heat xylene at 130 ° C. or the like
- the synthetic resin is an acrylic resin such as PMMA, acetone or dichlorobenzene, or a polyamide resin such as nylon
- Benzyl alcohol or hot nitrobenzene at 200 ° C. such as THF or dichlorobenzene in the case of polystyrene resin, and THF or dichloromethane in the case of polycarbonate resin can be used.
- the resin composite material according to the present invention can be produced.
- a resin composition including a synthetic resin and a carbon material having a graphene structure dispersed in the synthetic resin is prepared.
- the synthetic resin is applied to the carbon material simultaneously with the step of preparing the resin composition including the synthetic resin described above and the carbon material having a graphene structure, or after the step of preparing the resin composition. Graft.
- the step of preparing the resin composition is performed by weighing and blending the synthetic resin and the carbon material by an appropriate method.
- the grafting step can be performed by mixing the synthetic resin and the carbon material with a radical initiator and heating. Therefore, the heating can be performed by heating to a temperature above which the initiator is thermally decomposed. Therefore, what is necessary is just to select heating temperature according to the thermal decomposition temperature of the initiator used.
- the radical initiator is not particularly limited, and various known radical initiators can be used.
- a radical initiator in which the radical generated during thermal decomposition is a carbon radical may be used.
- examples of such an initiator include azobisisobutyronitrile (AIBN), azobis (2-methylpropionitrile), 4,4'-azobis (4-cyanovaleric acid), and the like.
- Initiators in which the radicals generated during thermal decomposition are carbon radicals are mild and not very reactive with hydrogen. Therefore, at the time of grafting, the molecular chain of the synthetic resin as a matrix is hardly broken. Thereby, deterioration of the synthetic resin can be suppressed. In addition, although the reactivity is mild, the synthetic resin can be surely grafted to the carbon material, whereby high mechanical strength and the like can be expressed.
- radical initiator Only one type of radical initiator may be used, or two or more types may be used in combination.
- the mixing ratio of the initiator is not particularly limited, but is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the synthetic resin. When the blending ratio of the initiator is less than 0.1 parts by weight, carbon radicals are not easily generated, and a sufficient grafting reaction may not be caused. More preferably, the mixing ratio of the initiator is 0.5 parts by weight or more with respect to 100 parts by weight of the synthetic resin.
- the mixing ratio of the initiator is desirably 20 parts by weight or less with respect to 100 parts by weight of the synthetic resin.
- the mixing ratio of the initiator exceeds 20 parts by weight, the molecular chain of the synthetic resin may be excessively cleaved. Therefore, the mechanical strength of the obtained resin composite material may be reduced. More preferably, the mixing ratio of the initiator is 10 parts by weight or less with respect to 100 parts by weight of the synthetic resin.
- the grafting step is performed by mixing the synthetic resin and the carbon material with a radical initiator and a compound having radical trapping properties and heating.
- a radical initiator e.g., a compound having radical trapping properties and heating.
- the radical trapping compound is at least one selected from the group consisting of compounds having the structures of the following formulas (1) to (5).
- various known radical initiators can be used as the radical initiator.
- radicals can be captured and stabilized. Therefore, at the time of grafting, the molecular chain of the synthetic resin as a matrix is hardly broken. Thereby, deterioration of the synthetic resin can be suppressed. In addition, the synthetic resin can be surely grafted to the carbon material, whereby high mechanical strength and the like can be expressed.
- the weight average molecular weight of the synthetic resin used in the method for producing the resin composite material is Mw1
- the weight average molecular weight of the synthetic resin not grafted in the resin composite material obtained by grafting is Mw2. It is desirable to perform grafting so that the ratio Mw2 / Mw1 is 0.5 or more. If the ratio Mw2 / Mw1 is 0.5 or more, even if the grafting step is carried out, the shortening of the molecular chain of the synthetic resin in the resin composite material has not progressed so much. Can be more effectively suppressed. More preferably, the ratio Mw2 / Mw1 is 0.7 or more.
- a step of mixing the same type of synthetic resin as the synthetic resin or a different resin may be further provided.
- the resin added after the grafting step may be grafted to the carbon material or may not be grafted.
- the additional resin may be the same resin as the synthetic resin.
- the additional resin may be a resin different from the synthetic resin, and various thermoplastic resins and thermosetting resins can be used.
- the thermoplastic resin include various thermoplastic resins that can be used as the above-described synthetic resin.
- the thermosetting resin include an epoxy resin and a polyurethane resin.
- the additional resin may be a crystalline resin or an amorphous resin as described above. However, since the crystalline resin is generally excellent in mechanical properties such as elastic modulus and molding processability as compared with the amorphous resin, the additional resin is preferably a crystalline resin.
- the blending ratio of the synthetic resin and the additional resin is not particularly limited, but the blending amount of the additional resin is preferably 1000 parts by weight or less with respect to 100 parts by weight of the synthetic resin. If the amount of the additional resin exceeds 1000 parts by weight, the effects of improving the mechanical strength and lowering the linear expansion coefficient due to the carbon material contained in the resin composite material may not be sufficiently exhibited.
- the resin composite material of the present invention may contain various additives as long as the object of the present invention is not impaired.
- additives include phenolic, phosphorous, amine or sulfur antioxidants; metal hazard inhibitors; halogenated flame retardants such as hexabromobiphenyl ether or decabromodiphenyl ether; ammonium polyphosphate or trimethyl. Flame retardants such as phosphates; various fillers; antistatic agents; stabilizers; pigments and the like.
- the resin composite material of the present invention may contain an appropriate reaction aid generally used for promoting radical reaction.
- a reaction aid may be used to promote the grafting reaction of the synthetic resin onto the carbon material in the production of the resin composite material of the present invention.
- the reaction aid include divinylbenzene, trimethylolpropane trimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, trimellitic acid triallyl ester, triallyl isocyanurate, and ethyl vinyl.
- Examples thereof include benzene, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, lauryl methacrylate, stearyl methacrylate, diallyl phthalate, diallyl terephthalate, and diallyl isophthalate.
- a resin composition including a synthetic resin and the carbon material having the graphene structure is prepared.
- the method for preparing the resin composition include a method in which a synthetic resin and a carbon material having a graphene structure are mixed and the carbon material is dispersed in the synthetic resin.
- the said mixing method is not specifically limited, For example, the method of melt-kneading the said synthetic resin and the said carbon material, the method of melt
- the mixing method is a method of melt-kneading the synthetic resin and the carbon material
- the melt-kneading may be performed by an appropriate method such as a plastmill, a single screw extruder, a twin screw extruder, a Banbury mixer, a roll, etc. It can be performed using a kneader.
- the solvent is particularly limited as long as the synthetic resin and the carbon material can be dissolved or dispersed.
- the solvent include dichlorobenzene, N-methyl-2-pyrrolidone, DMF, and higher alcohols.
- the resin composition may further contain an appropriate reaction aid that is generally used to promote the radical reaction described above, if necessary.
- an appropriate reaction aid that is generally used to promote the radical reaction described above, if necessary.
- a grafting reaction can be efficiently caused in the step of grafting the synthetic resin onto the carbon material described later.
- problems associated with the grafting reaction that is, resin degradation due to excessive cleavage of molecular chains can be suppressed.
- reaction aid a polyfunctional compound can be preferably used. Moreover, only 1 type may be used for the said reaction aid, and 2 or more types of reaction aids may be used together.
- the reaction aid is preferably blended in an amount of 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, based on 100 parts by weight of the synthetic resin.
- the reaction aid is preferably blended in an amount of 10 parts by weight or less, more preferably 8 parts by weight or less, with respect to 100 parts by weight of the synthetic resin.
- the resin composition may contain various additives described above. Thereby, various properties can be imparted to the obtained resin composite material.
- Examples of a method for preparing the resin composition containing the reaction aid and / or the additive include a mixing method such as the melt kneading method described above and the method of dissolving or dispersing in a solvent. .
- the reaction aid and / or the additive may be added when the carbon material and the synthetic resin are mixed, or may be added at another time.
- a step of grafting is performed simultaneously with the step of preparing the resin composition or after the step of preparing the resin composition.
- a carbon material having a graphene structure has a property of easily adsorbing free radicals. Therefore, when a radical initiator in which the radical generated by the thermal decomposition is a carbon radical is used, when the carbon radical is generated, a radical is generated in the synthetic resin by the carbon radical, and the radical is adsorbed on the carbon material. Therefore, in the resin composite material, the synthetic resin is grafted on the carbon material surface.
- the initiator is thermally decomposed.
- a radical initiator in which the radical generated by the thermal decomposition is a carbon radical is used, a carbon radical is generated and the grafting proceeds.
- heating method is not particularly limited. It is desirable to mix the resin composition during heating.
- the object of the present invention can be achieved.
- the radical initiator is preferably an initiator in which the radical generated when the radical initiator is thermally decomposed is a carbon radical.
- the dispersion area ratio of the carbon material is [Armax] or less, that is, when the dispersibility of the carbon material is high, mixing the radical initiator increases the probability of contact of the radical initiator with the carbon material. Therefore, it is possible to further suppress the generation of low molecular weight components due to molecular chain breakage and the like. That is, it becomes possible to further suppress resin deterioration.
- the resin composition comprising: a carbon material obtained by grafting the synthetic resin onto the carbon material by the step of grafting the synthetic resin onto the carbon material; and the unreacted synthetic resin that is not grafted onto the carbon material. Can be obtained.
- the resin composition thus obtained can be made into a resin composite material obtained by the production method of the present invention and using the unreacted synthetic resin as a matrix resin.
- the ratio of grafting can be measured by the method described in the evaluation section of Examples and Comparative Examples described later.
- a polypropylene resin when used as the synthetic resin, 130 ° C. hot xylene is used as a solvent for dissolving the ungrafted synthetic resin portion.
- the solvent used for dissolving and removing the ungrafted synthetic resin may be appropriately selected according to the synthetic resin to be used.
- the synthetic resin is a polymethyl methacrylate resin
- dichlorobenzene may be used.
- 200 ° C. hot nitrobenzene may be used.
- dichlorobenzene In the case of a polystyrene resin, dichlorobenzene may be used.
- THF may be used.
- the grafted carbon material is separated from the resin composition containing the carbon material grafted with the synthetic resin.
- a new resin composite material using the new synthetic resin as a matrix resin can be obtained by mixing the separated grafted carbon material and a new synthetic resin.
- the dispersion area ratio of exfoliated graphite at the time of radical initiator mixing was calculated
- the plate-shaped sample was cut in the thickness direction, and observed using a SEM at a magnification of 1000 times.
- the area occupied by exfoliated graphite was measured.
- the area of exfoliated graphite only the area of the portion having a thickness of 1 ⁇ m or more was measured.
- Example 1 the area occupied by exfoliated graphite was divided by the area of the entire field of view of the SEM photograph, and the dispersed area ratio (%) of exfoliated graphite was calculated.
- the dispersion area ratio of exfoliated graphite was 23%.
- the separately calculated [Armax] is 25.
- the dispersion area ratio of exfoliated graphite when the radical initiator is mixed is [Armax] or less.
- Example 2 Except that 2.68 parts by weight of azobisisobutyronitrile (AIBN, manufactured by Wako Pure Chemical Industries, Ltd.) was used as a radical initiator and that the dispersed area ratio of exfoliated graphite when mixed with a radical initiator was 24%
- a polyolefin resin composition was obtained.
- 300 parts by weight of the polypropylene resin was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Example 3 A polyolefin resin composition in the same manner as in Example 1 except that the blending ratio of exfoliated graphite was 20 parts by weight and that the area ratio of exfoliated graphite when the radical initiator was mixed was 11%. It was. 100 parts by weight of the polypropylene resin was added to 120 parts by weight of the polyolefin resin composition, and the mixture was melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Example 4 A polyolefin resin composition was prepared in the same manner as in Example 1, except that the dispersion area ratio of exfoliated graphite at the time of mixing the radical initiator was 21%. To 140 parts by weight of the polyolefin resin composition, 300 parts by weight of the polypropylene resin was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Example 5 A polyolefin resin composition was prepared in the same manner as in Example 1 except that the dispersed area ratio of exfoliated graphite at the time of mixing the radical initiator was 18%. To 140 parts by weight of the polyolefin resin composition, 300 parts by weight of the polypropylene resin was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- a polyolefin resin composition was obtained in the same manner as in Example 1 except that 100 parts by weight were used. To this polyolefin resin composition, 300 parts by weight of the above-mentioned block PP was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- PMMA polymethylmethacrylate
- Mw1 91,000
- MFR 1 0.5 g / 10 min
- a radical decay type resin composition was obtained in the same manner as in Example 1 except that 100 parts by weight were used.
- 300 parts by weight of the above polymethyl methacrylate was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Example 8 Except that the blending ratio of exfoliated graphite was 20 parts by weight and the dispersion area ratio of exfoliated graphite at the time of mixing the radical initiator was 11%, the radical decay type resin composition was the same as in Example 7. I got a thing. 100 parts by weight of the above polymethyl methacrylate resin was added to 120 parts by weight of this radical decay type resin composition, and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Example 9 100 parts by weight of the polypropylene resin and 40 parts by weight of exfoliated graphite used in Example 1 and 0.81 part by weight of butyl 3- (2-furanyl) propenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as a radical stabilizer are extruded.
- the radical initiator 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (day) 0.84 parts by weight of an oil company, trade name “Perhexa 25B”, 1 minute half-life temperature: 180 ° C.) was supplied to obtain a polyolefin resin composition.
- To 140 parts by weight of the polyolefin resin composition 300 parts by weight of the polypropylene resin was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Example 10 4.86 parts by weight of N, N dimethylene p-phenylenebismaleimide (manufactured by Tokyo Chemical Industry Co., Ltd.) is supplied as a radical stabilizer, and 2,5-dimethyl-2,5-bis (t-butylperoxide is used as a radical initiator.
- a polypropylene resin composition was obtained in the same manner as in Example 1 except that 0.40 part by weight of oxy) hexane was supplied and that the dispersed area ratio of exfoliated graphite at the time of mixing the radical initiator was 24%. It was. To 140 parts by weight of this resin composition, 300 parts by weight of the above polypropylene resin was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Example 1 A polyolefin resin composition was obtained in the same manner as in Example 1 except that 0.66 parts by weight of benzoyl peroxide (manufactured by Sigma-Aldrich, 10 hour half-life temperature: 73.6 ° C.) was used as the radical initiator. . To 140 parts by weight of the polyolefin resin composition, 300 parts by weight of the polypropylene resin was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- benzoyl peroxide manufactured by Sigma-Aldrich, 10 hour half-life temperature: 73.6 ° C.
- Example 2 A polyolefin resin composition was obtained in the same manner as in Example 2 except that 3.99 parts by weight of benzoyl peroxide was used as the radical initiator. To 140 parts by weight of the polyolefin resin composition, 300 parts by weight of the polypropylene resin was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Example 3 A polyolefin resin composition was prepared in the same manner as in Example 3 except that 0.66 parts by weight of benzoyl peroxide was used as the radical initiator. 100 parts by weight of the polypropylene resin was added to 120 parts by weight of the polyolefin resin composition, and the mixture was melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Comparative Example 4 A polyolefin resin composition was prepared in the same manner as in Comparative Example 1 except that the dispersion area ratio of exfoliated graphite at the time of mixing the radical initiator was 27%. To 140 parts by weight of the polyolefin resin composition, 300 parts by weight of the polypropylene resin was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Comparative Example 5 A polyolefin resin composition was prepared in the same manner as in Comparative Example 1, except that the dispersion area ratio of exfoliated graphite at the time of mixing the radical initiator was 30%. To 140 parts by weight of the polyolefin resin composition, 300 parts by weight of the polypropylene resin was added and melt-kneaded with an extruder, and a sheet was obtained in the same manner as in Example 1.
- Example 7 A resin composite sheet was obtained in the same manner as in Example 7 except that 0.66 parts by weight of benzoyl peroxide was supplied to the radical initiator.
- Example 8 A resin composite sheet was obtained in the same manner as in Example 8 except that 0.66 parts by weight of benzoyl peroxide was supplied to the radical initiator.
- the synthetic resin used was a polypropylene resin, a high density polyethylene resin, a silane-modified polypropylene resin or an atactic polypropylene resin, 130 ° C. hot xylene was used.
- the grafted exfoliated graphite was isolated by taking out the package from the solvent and vacuum drying.
- thermogravimetric measurement TGA measurement
- TGA measurement thermogravimetric measurement
- MFR is 15 g / 10 min or less, which is smaller than Comparative Examples 1 to 10. That is, it can be seen that in the obtained resin composite material, the molecular chain scission of the synthetic resin has not progressed much.
- the weight average molecular weight ratio Mw2 / Mw1 was as low as less than 0.5 in Comparative Examples 1 to 10. On the other hand, in Examples 1 to 10, it is sufficiently higher than Comparative Examples 1 to 10, and it can be seen that the deterioration of the resin does not progress.
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Abstract
Description
(式中、[Gr]は、上記合成樹脂100重量部に対する上記炭素材料の割合である)
本発明に係る樹脂複合材料は、合成樹脂と、上記合成樹脂中に分散されている、グラフェン構造を有する炭素材料とを含む。上記グラフェン構造を有する炭素材料の表面には、上記合成樹脂の一部がグラフト化している。そのため、本発明の樹脂複合材料では、上記合成樹脂と上記炭素材料との密着性がより一層高められている。さらに、上記グラフト化された炭素材料は、上記合成樹脂との親和性が高められている。そのため、上記合成樹脂を備える上記樹脂複合材料中では、上記合成樹脂中に上記グラフト化された炭素材料が均一に分散されている。従って、上記樹脂複合材料の機械的強度を効果的に高めること及び線膨張率を効果的に低めることができる。
本発明の樹脂複合材料に含まれる上記合成樹脂は特に限定されず、様々な公知の合成樹脂を用いることができる。好ましくは、上記合成樹脂として熱可塑性樹脂が用いられる。熱可塑性樹脂を用いた樹脂複合材料では、加熱下により様々な成形方法を用いて、様々な成形品を容易に得ることができる。
本発明の樹脂複合材料では、上記グラフェン構造を有する炭素材料が、上記合成樹脂に分散されている。それによって、本発明の樹脂複合材料の機械的強度を高めることができ、かつ線膨張係数を低めることができる。さらに、場合によっては、本発明の樹脂複合材料に導電性を発現させることもできる。そのため、本発明の樹脂複合材料は、導電性を発現する材料としても用いることができる可能性を有する。
本発明の樹脂複合材料の製造方法では、本発明に係る上記樹脂複合材料を製造することができる。本発明の樹脂複合材料の製造方法では、まず、合成樹脂と、合成樹脂に分散されているグラフェン構造を有する炭素材料とを含む樹脂組成物を用意する。
本発明では、上記グラフト化させる工程の後に、上記合成樹脂と同種の合成樹脂または異なる樹脂を混合する工程がさらに備えられていてもよい。
本発明の樹脂複合材料においては、本発明の目的を阻害しない範囲で、様々な添加剤を含んでいてもよい。このような添加剤としては、フェノール系、リン系、アミン系もしくはイオウ系等の酸化防止剤;金属害防止剤;ヘキサブロモビフェニルエーテルもしくはデカブロモジフェニルエーテル等のハロゲン化難燃剤;ポリリン酸アンモニウムもしくはトリメチルフォスフェート等の難燃剤;各種充填剤;帯電防止剤;安定剤;顔料等を挙げることができる。
本発明の製造方法では、合成樹脂と、上記グラフェン構造を有する炭素材料とを含む樹脂組成物を用意する。上記樹脂組成物を用意する方法としては、例えば、合成樹脂とグラフェン構造を有する炭素材料とを混合し、上記炭素材料を上記合成樹脂中に分散させる方法が挙げられる。上記混合方法は特に限定されないが、例えば、上記合成樹脂と上記炭素材料とを溶融混練する方法や、上記合成樹脂と上記炭素材料とを溶媒中に溶解または分散させる方法等が挙げられる。
(式中、[Gr]は、上記合成樹脂100重量部に対する上記炭素材料の割合である)
以下、本発明の具体的な実施例及び比較例を挙げることにより、本発明を明らかにする。なお、本発明は以下の実施例に限定されるものではない。
ポリプロピレン系樹脂(hPP、シグマアルドリッチ社製、商品名:ポリプロピレン、重量平均分子量Mw1=25万、23℃における引張弾性率:1.2GPa、MFR:10g/分)100重量部と、薄片化黒鉛(xGScience社製、商品名「xGnP-5」、使用前にSEMを用いて観察した層面の面方向における最大寸法:約5.0μm、層厚み:約60nm、グラフェンの積層数:約180層、BET比表面積:75m2/g)40重量部とを押出機に供給して溶融混練し、薄片化黒鉛の分散面積率が23%であるときに、ラジカル開始剤としてアゾビスイソブチロニトリル(AIBN、和光純薬社製、10時間半減期温度65℃)0.45重量部を押出機に供給して、ポリオレフィン系樹脂組成物とした。
ラジカル開始剤としてアゾビスイソブチロニトリル(AIBN、和光純薬社製)2.68重量部を用いたことと、ラジカル開始剤混合時の薄片化黒鉛の分散面積率が24%であること以外は、実施例1と同様にして、ポリオレフィン系樹脂組成物を得た。このポリオレフィン樹脂組成物140重量部に対し、上記ポリプロピレン樹脂300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
薄片化黒鉛の配合割合を20重量部にしたことと、ラジカル開始剤混合時の薄片化黒鉛の分散面積率が11%であること以外は、実施例1と同様にして、ポリオレフィン系樹脂組成物とした。このポリオレフィン樹脂組成物120重量部に対し、上記ポリプロピレン樹脂100重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ラジカル開始剤混合時の薄片化黒鉛の分散面積率が21%であること以外は、実施例1と同様にして、ポリオレフィン系樹脂組成物とした。このポリオレフィン樹脂組成物140重量部に対し、上記ポリプロピレン樹脂300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ラジカル開始剤混合時の薄片化黒鉛の分散面積率が18%であること以外は、実施例1と同様にして、ポリオレフィン系樹脂組成物とした。このポリオレフィン樹脂組成物140重量部に対し、上記ポリプロピレン樹脂300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ポリプロピレン系樹脂として、ブロックPP(bPP、プライムポリプロ社製、商品名「E-150GK」、重量平均分子量Mw1=55万、23℃における引張弾性率:1.2GPa、MFR:0.6g/10分)100重量部を用いたこと以外は、実施例1と同様にして、ポリオレフィン系樹脂組成物を得た。このポリオレフィン樹脂組成物に、上記ブロックPP、300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ポリプロピレン系樹脂の代わりに、ポリメチルメタクリレート(PMMA、住友化学社製、商品名:「スミペックスEX」、重量平均分子量Mw1=9.1万、23℃における引張弾性率:3.1GPa、MFR:1.5g/10分)100重量部を用いたこと以外は、実施例1と同様にして、ラジカル崩壊型樹脂組成物を得た。このラジカル崩壊型樹脂組成物に、上記ポリメチルメタクリレート300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
薄片化黒鉛の配合割合を20重量部にしたことと、ラジカル開始剤混合時の薄片化黒鉛の分散面積率が11%であること以外は、実施例7と同様にして、ラジカル崩壊型樹脂組成物を得た。このラジカル崩壊型樹脂組成物120重量部に対し、上記ポリメチルメタクリレート樹脂100重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
実施例1で用いたポリプロピレン系樹脂100重量部及び薄片化黒鉛40重量部と、ラジカル安定剤として、ブチル3-(2-フラニル)プロペン酸(東京化成社製)0.81重量部とを押出機に供給して溶融混練し、薄片化黒鉛の分散面積率が23%であるときに、ラジカル開始剤である2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキサン(日油社製、商品名「パーヘキサ25B」、1分間半減期温度:180℃)0.84重量部を供給して、ポリオレフィン系樹脂組成物とした。このポリオレフィン樹脂組成物140重量部に対し、上記ポリプロピレン樹脂300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ラジカル安定剤としてN、Nジメチルレンp-フェニレンビスマレイミド(東京化成社製)4.86重量部を供給し、ラジカル開始剤として、2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキサン0.40重量部を供給したことと、ラジカル開始剤混合時の薄片化黒鉛の分散面積率が24%であること以外は、実施例1と同様にして、ポリプロピレン樹脂組成物を得た。この樹脂組成物140重量部に対して、上記ポリプロピレン樹脂300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ラジカル開始剤として過酸化ベンゾイル(シグマアルドリッチ社製、10時間半減期温度73.6℃)0.66重量部を用いたこと以外は、実施例1と同様にして、ポリオレフィン系樹脂組成物とした。このポリオレフィン樹脂組成物140重量部に対し、上記ポリプロピレン樹脂300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ラジカル開始剤として過酸化ベンゾイル3.99重量部を用いたこと以外は、実施例2と同様にして、ポリオレフィン系樹脂組成物とした。このポリオレフィン樹脂組成物140重量部に対し、上記ポリプロピレン樹脂300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ラジカル開始剤として過酸化ベンゾイル0.66重量部を用いたこと以外は、実施例3と同様にして、ポリオレフィン系樹脂組成物とした。このポリオレフィン樹脂組成物120重量部に対し、上記ポリプロピレン樹脂100重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ラジカル開始剤混合時の薄片化黒鉛の分散面積率が27%であること以外は、比較例1と同様にして、ポリオレフィン系樹脂組成物とした。このポリオレフィン樹脂組成物140重量部に対し、上記ポリプロピレン樹脂300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ラジカル開始剤混合時の薄片化黒鉛の分散面積率が30%であること以外は、比較例1と同様にして、ポリオレフィン系樹脂組成物とした。このポリオレフィン樹脂組成物140重量部に対し、上記ポリプロピレン樹脂300重量部を加え押出機にて溶融混練し、実施例1と同様にしてシートを得た。
ラジカル開始剤として過酸化ベンゾイル0.66重量部を供給したことと、ラジカル開始剤投入時の薄片化黒鉛の分散面積率が23%であること以外は、実施例6と同様にして、樹脂複合シートを得た。
ラジカル開始剤に過酸化ベンゾイル0.66重量部を供給したこと以外は、実施例7と同様にして、樹脂複合シートを得た。
ラジカル開始剤に過酸化ベンゾイル0.66重量部を供給したこと以外は、実施例8と同様にして、樹脂複合シートを得た。
ラジカル安定剤を供給しなかったこと以外は、実施例9と同様にして、樹脂複合シートを得た。
ラジカル安定剤を供給しなかったこと以外は、実施例10と同様にして、樹脂複合シートを得た。
実施例及び比較例で得た各シートについて、グラフト化率、重量平均分子量、重量平均分子量比(Mw2/Mw1)、引張弾性率及びMFRを以下の要領で評価した。
実施例及び比較例により得られた樹脂複合材料シートを小さく裁断し、樹脂複合材料片とした。次に、上記樹脂複合材料片を濾紙で包んだ。上記濾紙から上記樹脂複合材料片が漏れ出ないように上記濾紙の端を折り込み、さらにその周囲を金属クリップで封止した。このようにして得られた包装体を、過剰量の溶媒に60時間浸した。それによって、樹脂複合材料シートに含まれるグラフト化していない合成樹脂を溶解除去した。
上記グラフト率を測定するにあたり、溶媒により溶解除去された薄片化黒鉛にグラフト化されていない合成樹脂を真空乾燥により、抽出した。その後、抽出した樹脂のMFRをJIS K7210によって測定した。
Claims (16)
- 合成樹脂と、前記合成樹脂の一部がグラフトされており、かつ前記合成樹脂中に分散されている、グラフェン構造を有する炭素材料とを含む、樹脂複合材料であって、
前記合成樹脂のうち、前記グラフェン構造を有する炭素材料にグラフトされていない部分のJIS K7210に準拠して測定されたMFRが15g/10分以下である、樹脂複合材料。 - 前記合成樹脂100重量部に対して、前記グラフェン構造を有する炭素材料を、5重量部以上含む、請求項1に記載の樹脂複合材料。
- 前記合成樹脂と異なる種類の樹脂をさらに含む、請求項1又は2に記載の樹脂複合材料。
- 前記グラフェン構造を有する炭素材料が、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1~3のいずれか1項に記載の樹脂複合材料。
- 前記合成樹脂が熱可塑性樹脂である、請求項1~4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、ラジカル崩壊型樹脂である、請求項5に記載の樹脂複合材料。
- 合成樹脂と、前記合成樹脂中に分散されており、グラフェン構造を有する炭素材料とを含む樹脂組成物を用意する工程と、
前記樹脂組成物を用意する工程と同時に、または前記樹脂組成物を用意する工程の後に、前記炭素材料に前記合成樹脂をグラフト化させる工程とを備え、
前記グラフト化させる工程が、前記合成樹脂及び前記炭素材料に、熱分解したときに発生するラジカルが炭素ラジカルである開始剤を混合し、加熱することにより行われる、樹脂複合材料の製造方法。 - 合成樹脂と、前記合成樹脂中に分散されており、グラフェン構造を有する炭素材料とを含む樹脂組成物を用意する工程と、
前記樹脂組成物を用意する工程と同時に、または前記樹脂組成物を用意する工程の後に、前記炭素材料に前記合成樹脂をグラフト化させる工程とを備え、
前記グラフト化させる工程が、前記合成樹脂及び前記炭素材料に、ラジカル開始剤を混合し、加熱することにより行われ、
前記ラジカル開始剤を混合するときの炭素材料の分散面積率が、下記式で表される[Armax]以下である、樹脂複合材料の製造方法。
[Armax]=(5[Gr])/8
(式中、[Gr]は、前記合成樹脂100重量部に対する前記炭素材料の割合である) - 前記ラジカル開始剤を熱分解したときに発生するラジカルが、炭素ラジカルである、請求項8に記載の樹脂複合材料の製造方法。
- 合成樹脂と、前記合成樹脂中に分散されており、グラフェン構造を有する炭素材料とを含む樹脂組成物を用意する工程と、
前記樹脂組成物を用意する工程と同時に、または前記樹脂組成物を用意する工程の後に、前記炭素材料に前記合成樹脂をグラフト化させる工程とを備え、
前記グラフト化させる工程が、前記合成樹脂及び前記炭素材料に、ラジカル開始剤と、ラジカルトラップ性を有する化合物とを混合し、加熱することにより行われる、樹脂複合材料の製造方法。 - 前記合成樹脂の重量平均分子量Mw1と、得られる樹脂複合材料において前記炭素材料にグラフト化されていない合成樹脂の重量平均分子量Mw2との比であるMw2/Mw1が0.5以上となるように、前記合成樹脂を前記炭素材料にグラフト化させる、請求項7~11のいずれか1項に記載の樹脂複合材料の製造方法。
- 前記合成樹脂100重量部に対して、前記グラフェン構造を有する炭素材料を、5重量部以上含む、請求項7~12のいずれか1項に記載の樹脂複合材料の製造方法。
- 前記合成樹脂と異なる種類の樹脂をさらに含む、請求項7~13のいずれか1項に記載の樹脂複合材料の製造方法。
- 前記グラフェン構造を有する炭素材料が、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7~14のいずれか1項に記載の樹脂複合材料の製造方法。
- 前記合成樹脂が熱可塑性樹脂である、請求項7~15のいずれか1項に記載の樹脂複合材料の製造方法。
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