WO2010008014A1 - カーボンナノ前駆体、その製造方法、カーボンナノ複合体およびその製造方法 - Google Patents
カーボンナノ前駆体、その製造方法、カーボンナノ複合体およびその製造方法 Download PDFInfo
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- WO2010008014A1 WO2010008014A1 PCT/JP2009/062790 JP2009062790W WO2010008014A1 WO 2010008014 A1 WO2010008014 A1 WO 2010008014A1 JP 2009062790 W JP2009062790 W JP 2009062790W WO 2010008014 A1 WO2010008014 A1 WO 2010008014A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
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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
- C09C1/48—Carbon black
Definitions
- the present invention relates to a carbon nanoprecursor, a production method thereof, a carbon nanocomposite, and a production method thereof.
- Nanocarbon materials such as carbon nanotubes are known as highly functional materials of nanometer size. Nanocarbon materials represented by carbon nanotubes are added to various materials that are required to have high functions.
- Patent Document 1 discloses a conductive precursor composition including an organic polymer precursor, a single-walled nanotube composition, and an optional nano-sized conductive filler.
- Patent Document 2 as a method for producing a nanocarbon-blended rubber composition, a reinforcing agent and / or a filler compounding agent is kneaded and blended with rubber, and then nanocarbon is kneaded and blended.
- Patent Document 3 a technique related to a carbon nanotube composite material composed of carbon nanotubes and other carbon materials and a method for producing the same are disclosed in Japanese Patent Application Laid-Open No. 2006-45034 (Patent Document 3).
- Patent Document 3 in order to generate a carbon nanotube composite material by disaggregating and dispersing the carbon nanotubes that have been agglomerated into a lump, the carbon nanotube and the carbon material having a lower combustion temperature than the carbon nanotubes and having an adsorptive property Are mixed and dispersed in a solvent to form a mixture, and the mixture is dried to obtain a desired mixture.
- Patent Document 4 a technique related to the fine carbon dispersion is disclosed in WO 2005/110594 (Patent Document 4).
- the carbon nanotubes are dispersed in a mixture of carbon nanotubes and activated carbon, but the activated carbon particles are larger than the carbon nanotubes, and the degree of dispersion of the carbon nanotubes in the mixture is also low. It was sufficient, and in the obtained mixture, the physical properties were still not satisfactory.
- An object of the present invention is to provide a carbon nano-precursor that has good handleability and can impart high conductivity and high strength to a substrate.
- Another object of the present invention is to provide a carbon nanocomposite having high conductivity and high strength.
- Still another object of the present invention is to provide a method for producing a carbon nanoprecursor that can easily produce a carbon nanoprecursor capable of imparting high conductivity and high strength to a substrate. is there.
- Still another object of the present invention is to provide a method for producing a carbon nanocomposite that can easily produce a carbon nanocomposite having high conductivity and high strength.
- the carbon nano-precursor according to the present invention includes a monodispersed carbon nanotube and a carbon black in a primary particle state attached to the surface of the carbon nanotube.
- a carbon nanoprecursor has a relatively large shape and good handleability because carbon black in a primary particle state adheres to the surface of a monodispersed carbon nanotube.
- the monodispersed state means that the carbon nanotubes exist in a single state, and includes a state where the carbon nanotubes are dispersed in a network.
- the primary particle state refers to a state of primary particles further dispersed from the level of secondary aggregates of about several micrometers in carbon black.
- attachment refers to a state in which the entire surface of the carbon nanotube is covered, a state in which a part of the surface of the carbon nanotube is exposed, or the carbon nanotube and carbon black are entangled. Such a state is also included.
- the carbon black in the primary particle state adheres to the surface of the carbon nanotube using a surfactant having hydrophilicity and hydrophobicity.
- the carbon nanoprecursor according to the present invention is obtained by adding carbon nanotubes to a solution containing a hydrophilic and hydrophobic surfactant in advance to form a monodispersed state, and then adding carbon black aggregates to the solution.
- the primary particle state carbon black is produced, and the primary particle state carbon black is adhered to the surface of the carbon nanotube.
- the solution containing the above-described hydrophilic and hydrophobic surfactants is described in detail in Patent Document 4.
- the surfactant solution component is removed from the carbon nanoprecursor.
- the removal is performed by, for example, heating, lyophilization, filtration, or the like.
- the carbon nanotube includes a multi-wall carbon nanotube.
- a carbon nanocomposite in another aspect of the present invention, includes a base material and a carbon nanoprecursor contained in a network form in the base material.
- the carbon nano-precursor includes a monodispersed carbon nanotube and a carbon black in a primary particle state attached to the surface of the carbon nanotube. Since such a carbon nanocomposite includes a carbon nanoprecursor composed of monodispersed carbon nanotubes and primary particle carbon black adhering to the surface in a network, it has high conductivity and high strength. .
- the base material includes rubber.
- a method for producing a carbon nanoprecursor includes a step of preparing a solution containing a surfactant having hydrophilicity and hydrophobicity, adding carbon nanotubes to the solution, and adding the carbon nanotubes to the solution. In a monodispersed state, and in a solution in which carbon nanotubes are monodispersed, agglomerated carbon black is added to form a primary particle state, and the carbon black in the primary particle state is attached to the surface of the carbon nanotube. Including. According to such a method for producing a carbon nanoprecursor, since it can be produced in a solution state, it can be produced easily.
- the method further includes a step of removing the solution component after carbon black in a primary particle state is attached to the surface of the carbon nanotube.
- a method for producing a carbon nanocomposite includes the steps of preparing a solution containing a hydrophilic and hydrophobic surfactant, adding carbon nanotubes to the solution, and adding the carbon nanotubes to the solution.
- agglomerated carbon black is added to form a primary particle state, and the carbon black in the primary particle state is attached to the surface of the carbon nanotube.
- removing a solution component to obtain a carbon nanoprecursor after attaching carbon black in a primary particle state to the surface of the carbon nanotube, removing a solution component to obtain a carbon nanoprecursor, and mixing the obtained carbon nanoprecursor and a substrate including.
- the carbon black in the primary particle state adheres to the surface of the monodispersed carbon nanotubes, so that the shape thereof is relatively large and the handleability is good. Moreover, when mixed with the base material by the carbon black in the primary particle state attached to the surface of the monodispersed carbon nanotubes, high conductivity and high strength can be imparted to the base material.
- Such a carbon nanocomposite includes a carbon nanoprecursor composed of monodispersed carbon nanotubes and primary particle carbon black adhering to the surface in a network form, so that it has high conductivity and high strength.
- the carbon nanoprecursor produced in a solution state is used, so that it can be produced easily.
- FIG. 3 is an external view of a test piece having a composition shown in Example 2.
- FIG. 14 is an external view of a test piece having a composition shown in Comparative Example 4.
- FIG. It is a figure which shows the measuring point in the test piece at the time of measuring volume resistivity.
- FIG. 1 is a flowchart showing typical steps of a method for producing a carbon nanoprecursor according to an embodiment of the present invention.
- a solution containing a hydrophilic and hydrophobic surfactant that is, a solution containing a zwitterionic surfactant is prepared (FIG. 1 (A)).
- carbon nanotubes are added to the solution, the carbon nanotubes are dispersed in the solution, and the carbon nanotubes are made into a monodispersed state (FIG. 1B).
- aggregated carbon black is added to the solution in which the carbon nanotubes are in a monodispersed state to form primary particles, which are then attached to the surface of the carbon nanotubes in the primary particle state (FIG. 1C). In this case, carbon black in a primary particle state is attached so as to cover the entire surface of the carbon nanotube.
- the solution component is removed (FIG. 1D).
- the solution component is removed (FIG. 1D).
- the solution does not have to be removed. That is, the step of removing the solution component may be omitted.
- CNT carbon nanotubes
- a zwitterionic surfactant is added in a mass concentration range of 0.01 to 0.4%
- CNT dispersion is performed.
- the carbon nanotubes are made into a monodispersed state by controlling vibration, pH, electrolyte concentration, and the like.
- 70 g of carbon black is added to 60 ml of this 3% by mass CNT dispersion, and a nanocarbon precursor is produced through a process of moving, washing and drying the carbon black in the primary particle state.
- the solution containing the zwitterionic surfactant described above is specifically, for example, “3- (N, N-dimethylmyristylamino) -propanesulfonate” (zwitterionic surfactant, manufactured by Fluka) 2.0 g, polyoxy It is obtained by mixing 2.0 g of ethylene distyrenated phenyl ether (manufactured by Kao), 1.0 g of alkyl (14-18) dimethylbetaine (manufactured by Kao), and 400 ml of deionized water.
- the production of the CNT dispersion liquid is performed, for example, as follows. 20.2 to 20.5 g of carbon nanotubes (diameter 20 nm, length 2 to 10 ⁇ m) are added to the solution containing the zwitterionic surfactant obtained by the above method, and the whole solution is made up to 500 ml with deionized water.
- ASA Rika Institute” ONE rotating base
- Nanocyl-7000 manufactured by Nanoseal specifically, Nanocyl-7000 manufactured by Nanoseal, Baytubes manufactured by Bayer MaterialScience, etc. are used.
- FIG. 2 and 3 are electron micrographs showing a part of the carbon nanoprecursor according to one embodiment of the present invention.
- 2 is a photograph magnified 5000 times
- FIG. 3 is a photograph magnified 10,000 times.
- FIG. 4 is a schematic view schematically showing a carbon nanoprecursor according to an embodiment of the present invention based on the electron micrograph shown in FIG.
- the carbon nano-precursor 11 includes a monodispersed carbon nanotube 12 and a carbon black 13 in a primary particle state attached to the surface of the carbon nanotube 12.
- the carbon nanotube 12 is a multi-wall carbon nanotube.
- carbon nanotubes having a diameter of several nanometers or tens of nanometers can be used.
- carbon black exists as a secondary aggregate
- it does not take the form of a photograph as shown in FIGS.
- Subsequent aggregates of carbon black and monodispersed carbon nanotubes should be seen.
- carbon nanotubes and carbon blacks of the form shown in FIGS. 2 and 3 were seen.
- the carbon nanotubes and carbon black in such a form are considered to be in a state where the surface of the monodispersed carbon nanotubes are attached so as to be covered with the carbon black in the primary particle state.
- the carbon black in the primary particle state is in a state of adhering so as to cover multiple layers.
- FIG. 5 is a photograph magnified 5000 times
- FIG. 6 and FIG. 7 are photographs magnified 10000 times
- FIG. 8 is a photograph magnified 30000 times.
- 6 corresponds to a photograph in which a part of the region of the photograph shown in FIG. 5 is enlarged
- FIG. 8 corresponds to a photograph in which a part of the region of the photograph shown in FIG. 7 is enlarged.
- 5 to 8 the scale, that is, the length reference is shown.
- FIG. 9 is a photograph magnified 10,000 times, and shows the reference of the length outside the frame of the electron micrograph.
- FIG. 5 to FIG. 8 it can be understood that the carbon black in the primary particle state adheres in layers on the surface of the carbon nanotubes, although there are some voids.
- FIG. 9 when FIG. 5 to FIG. 8 are compared with FIG. 9, in FIG. 9, several carbon nanotubes are dispersed around a large lump of activated carbon. Regarding the size of the activated carbon, its diameter is large and is about several micrometers. That is, several carbon nanotubes are dispersed in a state of adhering to activated carbon particles having a size of about several micrometers so that the surface thereof is exposed.
- carbon black adheres in a primary particle state, a particle state smaller than at least 1 micrometer, around each carbon nanotube in a monodispersed state, It is what has become.
- the carbon black in the primary particle state here is at most about 100 nm to about 20 nm to 40 nm.
- the carbon nano-precursor 11 is in a state in which the carbon black in the primary particle state is attached to the surface of the mono-dispersed carbon nanotube as described above, the shape thereof is larger than that of the mono-dispersed carbon nanotube alone. . This is supported by the experiment shown below.
- FIG. 10, FIG. 11 and FIG. 12 are photographs showing the state of filtration of the solution containing the carbon nanoprecursor described above.
- FIG. 10 shows a case where 10 g of carbon black (hereinafter abbreviated as “CB”) (FEF (Fast Extraction Furnace)) is added to 30 ml of a carbon nanotube (hereinafter abbreviated as “CNT”) dispersion.
- CB carbon black
- CNT carbon nanotube
- FIG. 12 shows a case where 10 g of CB (HAF) is added to 60 ml of the CNT dispersion liquid.
- the dispersion means a solution containing a surfactant having hydrophilicity and hydrophobicity.
- filtrates obtained by filtering the carbon nanoprecursor solution are collected. All the colors of the filtrate are colorless and transparent. This is because the carbon nanoprecursor having the above-described configuration, that is, the carbon nanoprecursor containing monodispersed CNT and the primary particle CB adhering to the surface of the CNT is larger than the CNT alone. It is believed that it is filtered and indicates that CNT and CB are not present in the filtrate.
- the material of the filter paper is pulp, the thickness is 0.15 mm, the bulk density is 0.03 g / cm 3 , and the air resistance (Gurley type, four-layered) is 1.4 seconds.
- FIG. 13 shows a case where 10 g of talc (Talc) is added to 30 ml of the CNT dispersion.
- the filtrate in the beaker is black. This is considered to indicate that the monodispersed CNT alone is not filtered and exists in the filtrate.
- FIG. 14 shows a state in which water is added to CNT powder before filtration
- FIG. 15 shows the filtrate after filtration
- FIG. 16 shows the filter paper after filtration.
- the CNT floats on the water, and the CNT does not disperse in the liquid but remains agglomerated. That is, CNT does not exist in a monodispersed state in the liquid.
- the filtrate is colorless and transparent, and CNTs are present on the filter paper. This is considered to be due to the fact that the water component not dispersed with CNT simply passed through the filter paper.
- kneading is very difficult even when kneading into a rubber component.
- FIG. 17, FIG. 18 and FIG. 19 show cases where water is added to CB alone and filtered.
- FIG. 17 shows the state before filtration of water added to CB alone
- FIG. 18 shows the filtrate after filtration
- FIG. 19 shows the filter paper after filtration.
- the filtrate is colorless and transparent, and CB is present on the filter paper. This is because the particle size of CB as the secondary aggregate is large and the CB of the secondary aggregate is filtered. .
- FIG. 20 shows the state before filtration of the CNT dispersion
- FIG. 21 shows the filtrate after filtration
- FIG. 22 shows the filter paper after filtration.
- the CNT dispersion is a solution obtained by adding CNT alone to a solution containing a zwitterionic surfactant.
- CNT is in a monodispersed state in the CNT dispersion.
- the filtrate is black and CNTs are present on the filter paper. This is considered that the CNT present in the liquid in a monodispersed state passes through the filter paper without being filtered and exists in the filtrate. Moreover, it is thought that a part of CNT is filtered and exists on the filter paper.
- the carbon nanocomposite containing the carbon nanoprecursor described above will be described.
- rubber is used as the base material of the carbon nanocomposite.
- a method for producing a carbon nanocomposite according to the present invention will be described.
- a carbon nanoprecursor is produced by the above-described steps.
- the produced carbon nanoprecursor and rubber are mixed to produce a carbon nanocomposite.
- the rubber component and the carbon nano-precursor are kneaded with a hot roll or the like.
- the obtained carbon nanoprecursor has a solution component removed, the material is easily wound around a roll and can be easily kneaded.
- a rubber composition that is a carbon nanocomposite is obtained through a series of processes such as vulcanization. Make it.
- the carbon nanocomposite produced in this way includes rubber and a carbon nanoprecursor contained in a network in the rubber.
- a carbon nanocomposite has high conductivity and high strength because the carbon nanoprecursor described above is contained in the rubber in a network form.
- Comparative Example 1 is based on EPDM (Ethylene Propylene Diene Monomer) as a base material, with respect to 200 parts by weight of EPDM, 80 parts by weight of CB (HAF), 1 part by weight of stearic acid, and 5 parts by weight of zinc oxide. Etc. are added.
- This compounding is a general rubber composition based on EPDM.
- CB 73.4 weight part and CNT 6.6 weight part are mix
- Table 2 is a table showing the characteristics of Comparative Example 1 and Example 1 described above. Referring to Table 2, with respect to tensile strength, Comparative Example 1 is 20.2 MPa, and Example 1 is 21.3 MPa, which is 5% higher than Comparative Example 1. Also, the elongation of Comparative Example 1 is 570%, while that of Example 1 is 640%, which is about 10% higher. The hardness, while Comparative Example 1 is 54H A, Example 1 is 56H A, are somewhat higher. As described above, Example 1 is higher in strength than Comparative Example 1 in mechanical properties such as tensile strength, elongation, and hardness. Also, regarding the electrical characteristics, Comparative Example 1 is 1 ⁇ 10 6 ⁇ ⁇ cm or more, while Example 1 is in the order of 1 ⁇ 10 2 . That is, Example 1 has high conductivity.
- Example 1 and Comparative Example 3 to which powdered CNT was added were compared.
- Example 1 and Comparative Example 3 differ only in the method of adding CNT to be added.
- Example 1 is an addition method using a CNT dispersion.
- Comparative Example 3 although the total blending amount of CNT is the same as that in Example 1, CNT was kneaded with EPDM in the form of agglomerated powder to some extent with other additives only by mechanical dispersion. It is.
- Table 3 is a table showing formulation examples of Comparative Example 3 and Example 1, and corresponds to Table 1.
- Table 4 shows the characteristics of Comparative Example 3 and Example 1, and corresponds to Table 2. Referring to Tables 3 and 4, with respect to tensile strength, Comparative Example 3 is 18.1 MPa, Example 1 is 21.3 MPa, and Comparative Example 1 is 17.7%. It is high. Also, the elongation of Comparative Example 3 is 600%, while that of Example 1 is 640%, which is about 7% higher. The hardness, while Comparative Example 3 is 55H A, Example 1 is 56H A, are somewhat higher. As described above, Example 1 has improved mechanical properties such as tensile strength, elongation, and hardness as compared with Comparative Example 3, and has high strength in comparison with Comparative Example 3. Also, regarding the electrical characteristics, Comparative Example 1 is 1 ⁇ 10 3 ⁇ ⁇ cm or more, while Example 1 is in the order of 1 ⁇ 10 2 . That is, Example 1 has high conductivity in comparison with Comparative Example 3.
- Table 5 is a table showing formulation examples of Comparative Example 2 and Example 2, and corresponds to Table 1.
- SBR Styrene Butadiene Rubber
- Table 6 is a table showing the characteristics of Comparative Example 2 and Example 2, and corresponds to Table 2.
- Example 2 has higher tensile strength and elongation than Comparative Example 2. Although the hardness is the same, it can be said that the mechanical properties are improved and the strength is high. Also, the electrical characteristics are the same as the relationship between Comparative Example 1 and Example 1, and Example 2 has high conductivity.
- Example 2 and Comparative Example 4 with powdered CNT added were compared.
- Example 2 and Comparative Example 4 differ only in the method of adding CNT to be added.
- Example 2 is an addition method using a CNT dispersion.
- Comparative Example 4 although the total blending amount of CNT is the same as that of Example 2, CNT was kneaded with other additives into SBR in a state of being agglomerated to some extent only by mechanical dispersion. It is.
- Table 7 is a table showing formulation examples of Comparative Example 4 and Example 2, and corresponds to Table 1.
- FIG. 23 is an external view of a test piece having the composition shown in Example 2 described above.
- 24 is an external view of a test piece having the composition shown in Comparative Example 4.
- FIG. Each test piece has a length of 12 cm in the vertical direction and a length of 12 cm in the horizontal direction. Referring to FIG. 23 and FIG. 24, the test piece shown in FIG. On the other hand, in the test piece shown in FIG. 24, CNT aggregates were observed in 46 places surrounded by white circles in FIG.
- FIG. 25 is a diagram illustrating measurement points on a test piece when measuring volume resistivity. Referring to FIG. 25, 24 locations indicated by the test piece numbers in FIG. 25 were measured. The measurement was performed using a low resistivity meter. In addition, the test piece produced the rectangular thin plate-shaped thing and evaluated this. The evaluation results are shown in Tables 8 to 11. Tables 8 and 9 are test pieces manufactured using only CB as a comparative example. Table 8 shows the case where the front side surface of the test piece was measured, and Table 9 shows the case where the back side surface of the test piece was measured. Tables 10 and 11 are test pieces prepared using the carbon nanoprecursors described above as examples.
- Table 10 shows the case where the front side surface of the test piece is measured
- Table 11 shows the case where the back side surface of the test piece is measured.
- ⁇ indicates that measurement is not possible, and the unit of numerical values is ⁇ ⁇ cm.
- impossible to measure means that the volume resistance value is 1 ⁇ 10 6 ⁇ ⁇ cm or more.
- the test piece of the comparative example is not measurable at most measurement points.
- the test piece of the example can be measured at almost all measurement points, and the resistance value is 1 ⁇ 10 1 to 1 ⁇ 10 2 , 1 ⁇ 10 3 ⁇ ⁇ cm level. Therefore, the test piece according to the example has high conductivity.
- Table 12 is a table showing formulation examples of Comparative Example 5 and Example 3, and corresponds to Table 1.
- SBR is used as the base material, and the blending ratio of carbon is changed.
- Table 13 shows the characteristics of Comparative Example 5 and Example 3, and corresponds to Table 2.
- Comparative Example 5 is 3.1 MPa, and Example 3 is 3.6 MPa, which is 16% higher than Comparative Example 5. ing. Also, the elongation of Comparative Example 5 is 530%, while that of Example 3 is 540%, which is about 1.9% higher. Regarding the hardness, Comparative Example 5 is 31 HA , while Example 3 is 35 HA, which is 13% higher. As described above, Example 1 is higher in strength than Comparative Example 1 in mechanical properties such as tensile strength, elongation, and hardness. On the other hand, the electrical characteristics are 1 ⁇ 10 6 ⁇ ⁇ cm or more in both Comparative Example 5 and Example 3, and there is no change.
- Table 14 is a table showing formulation examples of Example 4 and Example 5, and corresponds to Table 1. Again, SBR is used as the substrate.
- Table 15 is a table showing the characteristics of Example 4 and Example 5, and corresponds to Table 2.
- Example 4 With reference to Table 14 and Table 15, about the tensile strength, Example 4 is 19.1 MPa and Example 5 is 18 MPa. Regarding the elongation, Example 4 is 390%, and Example 5 is 370%. Regarding hardness, Example 4 is 71H A and Example 5 is 73H A.
- Comparative Example 1 described above that is, the blend without adding CNTs, the mechanical properties are inferior in tensile strength and elongation, but the hardness is improved.
- the electrical characteristics of both Example 4 and Example 5 are greatly improved and are on the order of 1 ⁇ 10 0 ⁇ ⁇ cm. That is, when a significant improvement in volume conductivity is required, it is preferable to use the formulation as in Example 4 and Example 5.
- Table 16 shows the characteristics of Example 6 and Example 7.
- Example 6 1.5 parts of wax was further added from the formulation in Example 4 and kneaded again. 1.5 parts of wax was further added from the formulation in Example 5 and kneaded again.
- Example 6 With reference to Table 16, about tensile strength, Example 6 is 21.7 MPa and Example 7 is 21.8 MPa. Regarding the elongation, Example 6 is 480%, and Example 7 is 480%. Regarding hardness, Example 6 is 69H A and Example 7 is 70H A. Here, the tensile strength is greatly improved as compared with Comparative Example 1. Therefore, when a tensile strength characteristic is required, such a blending example is preferable.
- Example 6 an ozone deterioration test was performed.
- the test piece was exposed in an extended state by 20% in an environment having a temperature of 40 ° C. and an ozone concentration of 50 pphm (parts per hundred million), and the degree of deterioration was evaluated.
- pphm parts per hundred million
- such a carbon nanocomposite includes a carbon nanoprecursor composed of monodispersed carbon nanotubes and primary particle carbon black adhering to the surface in the form of a network. Has strength.
- rubber is used as the base material.
- the present invention is not limited to this, and plastic may be used as the base material, and ceramics may be used as the base material.
- multi-wall carbon nanotubes are used as carbon nanotubes.
- the present invention is not limited to this, and single-wall carbon nanotubes or both may be used. Good.
- the carbon nanoprecursor according to one embodiment of the present invention is manufactured using a solution containing a zwitterionic surfactant.
- the carbon nano-precursor having the above-described configuration may be manufactured.
- Such carbon nano-precursors are effectively used when high conductivity and high strength are required when mixed with a substrate.
- Such carbon nanocomposites are effectively used when high conductivity and high strength are required.
- Such a method for producing a carbon nanoprecursor is effectively used when it is required to easily produce a carbon nanoprecursor that imparts high conductivity and high strength when mixed with a substrate. .
- Such a method for producing a carbon nanocomposite is effectively used when it is required to easily produce a carbon nanocomposite having high conductivity and high strength.
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Abstract
Description
Claims (10)
- 単分散状態のカーボンナノチューブと、
前記カーボンナノチューブの表面に付着する一次粒子状態のカーボンブラックとを含む、カーボンナノ前駆体。 - 前記一次粒子状態のカーボンブラックは、親水性および疎水性を有する界面活性剤を用いて、前記カーボンナノチューブの表面に付着する、請求項1に記載のカーボンナノ前駆体。
- 親水性および疎水性を有する界面活性剤を含む溶液中に前記カーボンナノチューブを予め添加して単分散状態とした後、カーボンブラックの凝集体を前記溶液中に添加して一次粒子状態のカーボンブラックとし、前記一次粒子状態のカーボンブラックを前記カーボンナノチューブの表面に付着させることにより製造される、請求項1に記載のカーボンナノ前駆体。
- 前記カーボンナノ前駆体のうち、前記界面活性剤の溶液成分は、除去されている、請求項2に記載のカーボンナノ前駆体。
- 前記カーボンナノチューブは、マルチウォールカーボンナノチューブを含む、請求項1に記載のカーボンナノ前駆体。
- 基材と、前記基材中にネットワーク状に含まれるカーボンナノ前駆体とを備えるカーボンナノ複合体であって、
前記カーボンナノ前駆体は、単分散状態のカーボンナノチューブと、前記カーボンナノチューブの表面に付着する一次粒子状態のカーボンブラックとを含む、カーボンナノ複合体。 - 前記基材は、ゴムを含む、請求項6に記載のカーボンナノ複合体。
- 親水性および疎水性を有する界面活性剤を含む溶液を準備する工程と、
前記溶液中にカーボンナノチューブを添加し、前記カーボンナノチューブを前記溶液中で単分散状態とする工程と、
前記カーボンナノチューブを単分散状態とした前記溶液中に凝集体のカーボンブラックを添加して一次粒子状態とし、前記カーボンナノチューブの表面に前記一次粒子状態のカーボンブラックを付着させる工程とを含む、カーボンナノ前駆体の製造方法。 - 前記カーボンナノチューブの表面に前記一次粒子状態のカーボンブラックを被覆させた後に、前記溶液成分を除去する工程をさらに含む、請求項8に記載のカーボンナノ前駆体の製造方法。
- 親水性および疎水性を有する界面活性剤を含む溶液を準備する工程と、
前記溶液中にカーボンナノチューブを添加し、前記カーボンナノチューブを前記溶液中で単分散状態とする工程と、
前記カーボンナノチューブを単分散状態とした前記溶液中に凝集体のカーボンブラックを添加して一次粒子状態とし、前記カーボンナノチューブの表面に前記一次粒子状態のカーボンブラックを付着させる工程と、
前記カーボンナノチューブの表面に前記一次粒子状態のカーボンブラックを付着させた後に、前記溶液成分を除去してカーボンナノ前駆体を得る工程と、
得られた前記カーボンナノ前駆体と基材とを混合する工程とを含む、カーボンナノ複合体の製造方法。
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WO2019058911A1 (ja) * | 2017-09-22 | 2019-03-28 | 日本ゼオン株式会社 | ゴム組成物 |
JP2019052275A (ja) * | 2017-09-19 | 2019-04-04 | 三菱ケミカル株式会社 | カーボンナノチューブ/カーボンブラック/ゴム複合体及びその製造方法 |
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