WO2022181193A1 - Matériau composite et corps moulé en caoutchouc vulcanisé - Google Patents

Matériau composite et corps moulé en caoutchouc vulcanisé Download PDF

Info

Publication number
WO2022181193A1
WO2022181193A1 PCT/JP2022/003160 JP2022003160W WO2022181193A1 WO 2022181193 A1 WO2022181193 A1 WO 2022181193A1 JP 2022003160 W JP2022003160 W JP 2022003160W WO 2022181193 A1 WO2022181193 A1 WO 2022181193A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
mass
composite material
removed body
vulcanized rubber
Prior art date
Application number
PCT/JP2022/003160
Other languages
English (en)
Japanese (ja)
Inventor
慶久 武山
奈津子 新藤
Original Assignee
日本ゼオン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to JP2023502205A priority Critical patent/JPWO2022181193A1/ja
Publication of WO2022181193A1 publication Critical patent/WO2022181193A1/fr

Links

Images

Classifications

    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to composite materials and vulcanized rubber moldings, and more particularly to composite materials and vulcanized rubber moldings containing fluorine-containing elastomers and fibrous carbon nanostructures.
  • composite materials made by blending carbon materials with polymers such as resin and rubber have been used as materials with excellent electrical conductivity, thermal conductivity, and mechanical properties.
  • Patent Document 1 a copolymer having a unit based on tetrafluoroethylene and a unit based on perfluoro(alkyl vinyl ether), a cross-linking agent, and a single-walled carbon nanotube are contained, and even if placed under high temperature, Techniques related to fluororubber compositions capable of suppressing deterioration in rubber performance have been proposed.
  • Prior Document 1 the technology of Prior Document 1 is not necessarily sufficient, and there is a demand for a material that exhibits sufficient rubber performance even in an even higher temperature environment, such as exceeding 300°C.
  • an object of the present invention is to provide a composite material and a vulcanized rubber molding that exhibit sufficient rubber performance even at high temperatures exceeding 300°C.
  • the inventors of the present invention have diligently studied to solve the above purpose.
  • the present inventors have also found that a composite material containing a fluorine-containing elastomer and a fibrous carbon nanostructure, wherein the polymer-removed body obtained by removing the polymer component and the polymer carbide of the composite material is a predetermined
  • the inventors have found that a composite material that satisfies these conditions exhibits sufficient rubber performance even at high temperatures, and completed the present invention.
  • an object of the present invention is to advantageously solve the above problems, and the composite material of the present invention is a composite material containing a fluorine-containing elastomer and a fibrous carbon nanostructure, A sheet having a thickness of 500 ⁇ m and a mass of 30 mg containing 4 parts by mass of the fibrous carbon nanostructure relative to 100 parts by mass of the fluorine-containing elastomer is formed from the composite material, and the polymer component and polymer carbide are removed from the sheet. The resulting polymer - removed body was subjected to thermogravimetric analysis under the condition of 700° C. in an air atmosphere to measure the change in the mass of the polymer - removed body over time.
  • the difference (T 90 ⁇ T 10 ) between the required time T 90 until the mass M 1 of the polymer-removed body decreases to 10 and the required time T 10 until the mass M 1 of the polymer-removed body decreases to M 1 ⁇ 0.90 is 100 seconds or less. It is characterized by Mass M 1 of the polymer-removed body obtained by removing the polymer component and the polymer carbide from the sheet having a thickness of 500 ⁇ m and a mass of 30 mg, containing 4 parts by mass of the fibrous carbon nanostructure with respect to 100 parts by mass of the fluorine-containing elastomer. is reduced to M 1 ⁇ 0.10 and the difference (T 90 ⁇ T 10 ) is A composite material with a life time of 100 seconds or less can exhibit sufficient rubber performance even at high temperatures.
  • the composite material of the present invention is a composite material containing a fluorine-containing elastomer and a fibrous carbon nanostructure
  • a polymer-removed body obtained by removing a polymer component and a polymer carbide from a sheet having a thickness of 500 ⁇ m formed using the composite material was subjected to thermogravimetric analysis under an air atmosphere at 700° C. to determine the mass of the polymer-removed body.
  • Time required for the mass M 1 of the polymer-removed body to decrease to M 1 ⁇ 0.90 in the thermogravimetric curve obtained from the values of the mass of the polymer-removed body and the elapsed time when the change over time of the polymer-removed body was measured The weight reduction rate V obtained by the following relational expression using T 10 (seconds) and the required time T 90 (seconds) until the mass M 1 of the polymer-removed body is reduced to M 1 ⁇ 0.10 is 0 .8 or more.
  • Time required for the mass M1 of the polymer - removed body to decrease to M1 ⁇ 0.90 in the thermogravimetric curve obtained from the values of the mass of the polymer-removed body and the elapsed time when measuring the change in mass over time The weight reduction rate V obtained by the above relational expression using T 10 (seconds) and the required time T 90 (seconds) until the mass M 1 of the polymer-removed body is reduced to M 1 ⁇ 0.10 is 0.8.
  • the above composite material can exhibit sufficient rubber performance even at high temperatures.
  • the fibrous carbon nanostructures preferably contain single-walled carbon nanotubes. If the fibrous carbon nanostructure contains single-walled carbon nanotubes, the properties of the composite material can be improved.
  • the G/D ratio of the single-walled carbon nanotubes is 1 or more and 30 or less. If the G/D ratio of the single-walled carbon nanotube is 1 or more and 30 or less, the properties of the composite material can be further improved.
  • the single-walled carbon nanotubes preferably have an average diameter of 1.5 nm or more and 5 nm or less. If the average diameter of the single-walled carbon nanotubes is within the above range, the properties of the composite material can be further improved.
  • the fluorine-containing elastomer is preferably tetrafluoroethylene-perfluoroalkyl vinyl ether rubber (FFKM). If the fluorine-containing elastomer is tetrafluoroethylene-perfluoroalkyl vinyl ether rubber (FFKM), a composite material with excellent heat resistance, chemical resistance and plasma resistance can be obtained.
  • FFKM tetrafluoroethylene-perfluoroalkyl vinyl ether rubber
  • the vulcanized rubber molded article of the present invention is a composite material containing a fluorine-containing elastomer and a fibrous carbon nanostructure.
  • a vulcanized rubber molding obtained by vulcanization which is obtained by removing a polymer component and a polymer carbide from a sheet having a thickness of 500 ⁇ m formed using the vulcanized rubber molding, is placed in an air atmosphere.
  • thermogravimetric curve obtained from the values of the mass and elapsed time of the polymer-removed body, when the change in the mass of the polymer-removed body over time was measured by thermogravimetric analysis under the condition of 700 ° C., the polymer-removed body
  • the difference between the required time T 90 until the mass M 1 of the polymer-removed body decreases to M 1 ⁇ 0.10 and the required time T 10 until the mass M 1 of the polymer-removed body decreases to M 1 ⁇ 0.90 (T 90 ⁇ T 10 ) is 60 seconds or less.
  • the polymer-removed body obtained by removing the polymer component and the polymer carbide from the 500 ⁇ m thick sheet formed using the vulcanized rubber molded body was subjected to thermogravimetric analysis under the condition of 700° C. in an air atmosphere. Until the mass M 1 of the polymer-removed body decreases to M 1 ⁇ 0.10 in the thermogravimetric curve obtained from the values of the mass of the polymer-removed body and the elapsed time when measuring the change in the mass of the polymer-removed body over time.
  • the difference (T 90 ⁇ T 10 ) between the required time T 90 and the required time T 10 for the mass M 1 of the polymer-removed body to decrease to M 1 ⁇ 0.90 is 60 or less. Sufficient rubber performance can be exhibited even at high temperatures.
  • a further object of the present invention is to advantageously solve the above problems, and the vulcanized rubber molded article of the present invention is a composite material containing a fluorine-containing elastomer and a fibrous carbon nanostructure.
  • a vulcanized rubber molded body obtained by removing a polymer component and a polymer carbide from a sheet having a thickness of 500 ⁇ m formed using the vulcanized rubber molded body, and a polymer-removed body obtained by removing the polymer component and polymer carbide in an air atmosphere.
  • V 80/( T90 - T10)
  • the polymer-removed body obtained by removing the polymer component and the polymer carbide from the 500 ⁇ m thick sheet formed using the vulcanized rubber molded body was subjected to thermogravimetric analysis under the condition of 700° C. in an air atmosphere. Until the mass M 1 of the polymer-removed body decreases to M 1 ⁇ 0.90 in the thermogravimetric curve obtained from the values of the mass of the polymer-removed body and the elapsed time when measuring the change in the mass of the polymer-removed body over time.
  • the weight reduction rate V obtained by the above relational expression is A vulcanized rubber molded article having a value of 1.4 or more can exhibit sufficient rubber performance even at high temperatures.
  • the fibrous carbon nanostructures preferably contain single-walled carbon nanotubes. If the fibrous carbon nanostructure contains single-walled carbon nanotubes, the properties of the vulcanized rubber molding can be improved.
  • the carbon nanotube has a G/D ratio of 1 or more and 30 or less. If the G/D ratio of the single-walled carbon nanotubes is 1 or more and 30 or less, the properties of the vulcanized rubber molding can be further improved.
  • the single-walled carbon nanotubes preferably have an average diameter of 1.5 nm or more and 5 nm or less. If the average diameter of the single-walled carbon nanotubes is within the above range, the properties of the vulcanized rubber molding can be further improved.
  • the fluorine-containing elastomer is preferably tetrafluoroethylene-perfluoroalkyl vinyl ether rubber (FFKM). If the fluorine-containing elastomer is tetrafluoroethylene-perfluoroalkylvinylether rubber (FFKM), a vulcanized rubber molding having excellent heat resistance, chemical resistance and plasma resistance can be obtained.
  • FFKM tetrafluoroethylene-perfluoroalkyl vinyl ether rubber
  • FIG. 1 is a graph showing the results of thermogravimetric analysis of a polymer-removed composite material.
  • a composite material of the present invention includes a fluorine-containing elastomer and a fibrous carbon nanostructure.
  • the vulcanized rubber molded article of the present invention is obtained by vulcanizing a composite material containing a fluorine-containing elastomer and a fibrous carbon nanostructure. Then, the composite material and the vulcanized rubber molded article of the present invention show predetermined results when the polymer-removed body obtained from the composite material and the vulcanized rubber molded article of the present invention is subjected to thermogravimetric analysis under predetermined conditions. show. As a result, the composite material and the vulcanized rubber molding of the present invention can exhibit sufficient rubber performance even at high temperatures.
  • the composite material and the vulcanized rubber molding of the present invention will be described below in order.
  • the composite material of the present invention contains a fluorine-containing elastomer and a fibrous carbon nanostructure, and may optionally further contain various additives depending on the application of the composite material.
  • fluorine-containing elastomers include, for example, fluorine-containing elastomers containing hydrogen atoms such as vinylidene fluoride rubber (FKM) and tetrafluoroethylene-propylene rubber (FEPM); fluorine-containing elastomers containing no hydrogen atoms such as ethylene-perfluoroalkyl vinyl ether rubber (FFKM) and tetrafluoroethylene rubber (TFE); Among these, tetrafluoroethylene-perfluoroalkyl vinyl ether rubber (FFKM) is preferred. These may be used individually by 1 type, and may use 2 or more types together.
  • FKM vinylidene fluoride rubber
  • FEPM tetrafluoroethylene-propylene rubber
  • FFKM ethylene-perfluoroalkyl vinyl ether rubber
  • TFE tetrafluoroethylene-perfluoroalkyl vinyl ether rubber
  • FFKM tetrafluoroethylene-perfluoro
  • the vinylidene fluoride rubber is a fluororubber that has vinylidene fluoride as its main component and is excellent in heat resistance, oil resistance, chemical resistance, solvent resistance, workability, and the like.
  • FKM include, but are not limited to, a binary copolymer of vinylidene fluoride and hexafluoropropylene, a terpolymer of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene, and vinylidene fluoride. , hexafluoropropylene, tetrafluoroethylene, and a vulcanization site monomer.
  • quaternary copolymer composed of vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene and a vulcanization site monomer is preferred.
  • the quaternary copolymer is available, for example, as a commercial product "Viton GBL-200S” (manufactured by Chemours Co., Ltd.).
  • "mainly composed of vinylidene fluoride” means that the vinylidene fluoride unit contained in the vinylidene fluoride rubber is 50% by mass or more, preferably more than 50% by mass.
  • Tetrafluoroethylene-propylene rubber is a fluororubber based on an alternating copolymer of tetrafluoroethylene and propylene, and has excellent heat resistance, chemical resistance, polar solvent resistance, steam resistance, etc. .
  • FEPM is not particularly limited.
  • terpolymers composed of point monomers and the like Examples of commercial products of binary copolymers composed of tetrafluoroethylene and propylene include "Afras (registered trademark) 100" and "Afras 150" manufactured by AGC Corporation.
  • Commercially available terpolymers composed of tetrafluoroethylene, propylene and vinylidene fluoride include, for example, "AFRAS 200" manufactured by AGC Corporation.
  • Commercially available terpolymers composed of tetrafluoroethylene, propylene, and cross-linking monomers include, for example, "AFRAS 300" manufactured by AGC Corporation.
  • FFKM tetrafluoroethylene-perfluoroalkyl vinyl ether rubber
  • H hydrogen atoms
  • C carbon-carbon
  • FFKM perfluoroalkyl vinyl ether rubber
  • TFE tetrafluoroethylene
  • PAVE perfluoroalkyl vinyl ether
  • PAOVE perfluoroalkoxyalkyl vinyl ether
  • FFKM may further contain a structural unit having a cross-linking site in addition to the above two structural units.
  • Perfluoroalkyl vinyl ethers having alkyl groups of 1 to 5 carbon atoms can be used.
  • perfluoromethyl vinyl ether PMVE
  • perfluoroethyl vinyl ether PEVE
  • perfluoropropyl vinyl ether PPVE
  • n is an integer of 1 to 5, for example
  • m is an integer of 1 to 3, for example.
  • FFKM examples include "Afras (registered trademark) PM1100", “Afras PM3000” and “Afras PM4000” from AGC Corporation, “Kalrez (registered trademark)” series from DuPont, and “Daiel (registered trademark)” from Daikin Industries, Ltd. (trademark) Perflo” series, Solvay's “Technoflon (registered trademark) PFR” series, and 3M Company's “Dynion (registered trademark)” series.
  • fibrous carbon nanostructures include, but are not limited to, cylindrical carbon nanostructures such as carbon nanotubes, and carbon nanostructures in which a six-membered carbon ring network is formed in a flat cylindrical shape.
  • Non-cylindrical carbon nanostructures, such as, can be used. These may be used individually by 1 type, and may use 2 or more types together.
  • fibrous carbon nanostructures containing carbon nanotubes hereinafter referred to as "CNT"
  • CNT carbon nanotubes
  • the fibrous carbon nanostructures containing CNTs may consist of CNTs alone, or may be a mixture of CNTs and fibrous carbon nanostructures other than CNTs.
  • the CNTs in the fibrous carbon nanostructure are not particularly limited, and single-walled CNTs and/or multi-walled CNTs can be used. is preferred, and single-walled CNTs are more preferred. This is because the smaller the number of CNT layers, the better the properties of the composite material (for example, electrical conductivity, thermal conductivity, strength, etc.) even if the amount is small.
  • the average diameter of the fibrous carbon nanostructure is more preferably 1.5 nm or more, more preferably 2 nm or more, preferably 5 nm or less, and 4 nm or less. is more preferable. If the average diameter of the fibrous carbon nanostructures is within the above range, the properties of the composite material (eg electrical conductivity, thermal conductivity, strength, etc.) can be further improved.
  • the "average diameter of fibrous carbon nanostructures" is the diameter (outer diameter) of, for example, 20 fibrous carbon nanostructures measured on a transmission electron microscope (TEM) image. It can be obtained by calculating the number average value.
  • the ratio (3 ⁇ /Av) of the value (3 ⁇ ) obtained by multiplying the standard deviation of the diameter ( ⁇ : sample standard deviation) by 3 to the average diameter (Av) is greater than 0.20. It is preferable to use fibrous carbon nanostructures with 3 ⁇ /Av of less than 0.80, more preferably use fibrous carbon nanostructures with 3 ⁇ /Av of greater than 0.25, and fibrous carbon nanostructures with 3 ⁇ /Av of greater than 0.50. More preferably, carbon nanostructures are used. As the fibrous carbon nanostructure, a fibrous carbon nanostructure having the ratio (3 ⁇ /Av) of more than 0.20 and less than 0.60 can also be used.
  • the use of fibrous carbon nanostructures with 3 ⁇ /Av greater than 0.20 and less than 0.80 can further improve the performance of the composite material.
  • the average diameter (Av) and standard deviation ( ⁇ ) of the fibrous carbon nanostructures may be adjusted by changing the manufacturing method and manufacturing conditions of the fibrous carbon nanostructures, or obtained by different manufacturing methods. It may be adjusted by combining a plurality of types of fibrous carbon nanostructures.
  • the diameter measured as described above is plotted on the horizontal axis and the frequency is plotted on the vertical axis. be done.
  • the fibrous carbon nanostructure preferably has an average length of 10 ⁇ m or more, more preferably 50 ⁇ m or more, even more preferably 80 ⁇ m or more, and preferably 600 ⁇ m or less, and 550 ⁇ m or more. It is more preferably 500 ⁇ m or less, and even more preferably 500 ⁇ m or less. If the average length of the fibrous carbon nanostructures is within the above range, the properties of the composite material (eg electrical conductivity, thermal conductivity, strength, etc.) can be sufficiently improved.
  • the average length of the "fibrous carbon nanostructure" is obtained by measuring the length of, for example, 20 fibrous carbon nanostructures on a scanning electron microscope (SEM) image, It can be obtained by calculating the average value.
  • fibrous carbon nanostructures usually have an aspect ratio of more than 10.
  • the aspect ratio of fibrous carbon nanostructures was obtained by measuring the diameter and length of 20 randomly selected fibrous carbon nanostructures using a scanning electron microscope or transmission electron microscope. It can be obtained by calculating the average value of the length ratio (length/diameter).
  • the fibrous carbon nanostructure preferably has a BET specific surface area of 600 m 2 /g or more, more preferably 800 m 2 /g or more, preferably 2000 m 2 /g or less, and 1800 m 2 . /g or less, more preferably 1600 m 2 /g or less. If the fibrous carbon nanostructure has a BET specific surface area of 600 m 2 /g or more, the properties of the composite material (eg electrical conductivity, thermal conductivity, strength, etc.) can be sufficiently enhanced with a small amount. Moreover, if the BET specific surface area of the fibrous carbon nanostructures is 2000 m 2 /g or less, the fibrous carbon nanostructures can be dispersed satisfactorily.
  • the fibrous carbon nanostructure preferably exhibits an upward convex shape in the t-plot obtained from the adsorption isotherm.
  • the "t-plot” is obtained by converting the relative pressure to the average thickness t (nm) of the nitrogen gas adsorption layer in the adsorption isotherm of the fibrous carbon nanostructure measured by the nitrogen gas adsorption method. can be done. That is, the average thickness t of the nitrogen gas adsorption layer corresponding to the relative pressure is obtained from a known standard isotherm obtained by plotting the average thickness t of the nitrogen gas adsorption layer against the relative pressure P/P0, and the above conversion is performed. yields a t-plot of fibrous carbon nanostructures (t-plot method by de Boer et al.).
  • the growth of a nitrogen gas adsorption layer on a substance having pores on its surface is classified into the following processes (1) to (3). Then, the slope of the t-plot changes due to the following processes (1) to (3).
  • the t-plot showing an upwardly convex shape is located on a straight line passing through the origin in a region where the average thickness t of the nitrogen gas adsorption layer is small, whereas when t becomes large, the plot is on the straight line.
  • position shifted downward from The fibrous carbon nanostructure having such a t-plot shape has a large ratio of the internal specific surface area to the total specific surface area of the fibrous carbon nanostructure. of openings are formed.
  • the inflection point of the t-plot of the fibrous carbon nanostructure preferably falls within a range satisfying 0.2 ⁇ t(nm) ⁇ 1.5, and 0.45 ⁇ t(nm) ⁇ 1.5. and more preferably 0.55 ⁇ t(nm) ⁇ 1.0. If the inflection point of the t-plot of the fibrous carbon nanostructure is within such a range, the properties of the composite material (eg electrical conductivity, thermal conductivity, strength, etc.) can be enhanced with a small compounding amount.
  • the "position of the bending point" is the intersection of the approximate straight line A in the process (1) described above and the approximate straight line B in the process (3) described above.
  • the fibrous carbon nanostructure preferably has a ratio (S2/S1) of internal specific surface area S2 to total specific surface area S1 obtained from t-plot of 0.05 or more and 0.30 or less. If the value of S2/S1 of the fibrous carbon nanostructure is within such a range, it is possible to enhance the properties (eg electrical conductivity, thermal conductivity, strength, etc.) of the composite material with a small compounding amount.
  • the total specific surface area S1 and internal specific surface area S2 of the fibrous carbon nanostructure can be obtained from the t-plot. Specifically, first, the total specific surface area S1 can be obtained from the slope of the approximate straight line in process (1), and the external specific surface area S3 can be obtained from the slope of the approximate straight line in process (3). By subtracting the external specific surface area S3 from the total specific surface area S1, the internal specific surface area S2 can be calculated.
  • the measurement of the adsorption isotherm of the fibrous carbon nanostructure, the creation of the t-plot, and the calculation of the total specific surface area S1 and the internal specific surface area S2 based on the analysis of the t-plot can be performed, for example, by a commercially available measurement device.
  • "BELSORP (registered trademark)-mini” manufactured by Bell Japan Co., Ltd.
  • fibrous carbon nanostructures containing CNTs which are suitable as fibrous carbon nanostructures, preferably have a Radial Breathing Mode (RBM) peak when evaluated using Raman spectroscopy.
  • RBM Radial Breathing Mode
  • the fibrous carbon nanostructure containing CNTs preferably has a ratio (G/D ratio) of G-band peak intensity to D-band peak intensity in the Raman spectrum of 1 or more and 30 or less. If the G/D ratio is 1 or more and 30 or less, the performance of the composite material can be further improved.
  • G/D ratio refers to the ratio of the G band peak intensity to the D band peak intensity in the Raman spectrum.
  • the fibrous carbon nanostructure containing CNTs is manufactured using known CNT synthesis methods such as an arc discharge method, laser ablation method, and chemical vapor deposition method (CVD method), without any particular limitation. can do.
  • fibrous carbon nanostructures containing CNTs are produced by, for example, supplying a raw material compound and a carrier gas onto a base material having a catalyst layer for producing CNTs on its surface, followed by chemical vapor deposition (CVD method). ) to dramatically improve the catalytic activity of the catalyst layer by allowing a trace amount of oxidizing agent (catalyst activating material) to be present in the system when synthesizing CNTs (super-growth method; International Publication No. 2006/ 011655), it can be produced efficiently.
  • oxidizing agent catalyst activating material
  • the carbon nanotube obtained by the super growth method may be called "SGCNT.”
  • the fibrous carbon nanostructures produced by the super-growth method may be composed only of SGCNTs, or in addition to SGCNTs, other carbon nanostructures such as non-cylindrical carbon nanostructures. may contain
  • the amount of the fibrous carbon nanostructure contained in the composite material is not particularly limited, but is preferably 0.01 parts by mass or more per 100 parts by mass of the fluorine-containing elastomer. It is more preferably 5 parts by mass or more, preferably 12 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.
  • the amount of fibrous carbon nanostructures is at least the above lower limit, the properties of the composite material (eg electrical conductivity, thermal conductivity, strength, etc.) can be sufficiently improved.
  • the amount of the fibrous carbon nanostructures is equal to or less than the above upper limit, the fibrous carbon nanostructures can be well dispersed.
  • Additives that can optionally be included in the composite material of the present invention include, but are not limited to, dispersants, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, pigments, colorants, foaming agents, Antistatic agents, flame retardants, lubricants, softeners, tackifiers, plasticizers, release agents, deodorants, perfumes, and the like can be mentioned.
  • examples of more specific additives include carbon black, silica, talc, barium sulfate, calcium carbonate, clay, magnesium oxide and calcium hydroxide.
  • an additive can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the additive in the composite material is not particularly limited, and can be the amount normally used in known composite materials.
  • the content of the additive in the composite material can be 5 parts by mass or more and 40 parts by mass or less per 100 parts by mass of the fluorine-containing elastomer.
  • the composite material of the present invention is obtained by forming a sheet having a thickness of 500 ⁇ m and a mass of 30 mg containing 4 parts by mass of the fibrous carbon nanostructure with respect to 100 parts by mass of the fluorine-containing elastomer.
  • the polymer-removed body obtained by removing the polymer component and the polymer carbide was subjected to thermogravimetric analysis under the condition of 700° C. in an air atmosphere to measure the change in the mass of the polymer-removed body over time.
  • T 90 ⁇ T 10 the difference between the required time T 10 until the mass M 1 of the polymer - removed body is reduced to M 1 ⁇ 0.90 (T 90 ⁇ T 10 ) is 100 seconds or less, preferably 95 seconds or less. Note that the difference (T 90 ⁇ T 10 ) can be 70 seconds or longer.
  • the polymer-removed body obtained by removing the polymer component and the polymer carbide from the sheet having a thickness of 500 ⁇ m and a mass of 30 mg containing 4 parts by mass of the fibrous carbon nanostructure relative to 100 parts by mass of the fluorine-containing elastomer was placed in an air atmosphere.
  • the composite material of the present invention is obtained by removing the polymer component and the polymer carbide from a sheet having a thickness of 500 ⁇ m formed using the composite material of the present invention.
  • the mass M 1 of the polymer-removed body was M 1 ⁇ 0.
  • the weight loss rate V obtained is 0.8 or more, preferably 0.85 or more.
  • V 80/( T90 - T10)
  • the polymer-removed body obtained by removing the polymer component and the polymer carbide from the 500 ⁇ m-thick sheet formed using the composite material was subjected to thermogravimetric analysis under the condition of 700° C. in an air atmosphere.
  • the weight reduction rate V obtained by the above relational expression using T 10 (seconds) and the required time T 90 (seconds) until the mass M 1 of the polymer-removed body is reduced to M 1 ⁇ 0.10 is 0.8.
  • the fibrous carbon nanostructures are appropriately fibrillated, and sufficient rubber performance can be exhibited even at high temperatures.
  • the polymer-removed body contains fibrous carbon nanostructures and residues.
  • the term "residue” means, for example, inorganic substances such as metals contained in optional additives.
  • the polymer remover typically contains fibrous carbon nanostructures much the same as in the composite.
  • the polymer-removed body is obtained by removing the polymer component and polymer char from the sheet composed of the composite material or vulcanized rubber molding. Then, the removal of the polymer component and polymer char from the sheet can be performed, for example, by heating the sheet.
  • the heating of the sheet is not particularly limited, and can be performed using any device, but is preferably performed using a thermogravimetric analysis device. If a thermogravimetric analyzer is used, the thermogravimetric analysis of the polymer-removed body can be continuously performed after the polymer-removed body is obtained in a single thermogravimetric analyzer, and the polymer component and the polymer charcoal can be removed. You can grasp the situation.
  • the atmosphere for heating the sheet is not particularly limited, but it is preferable to heat in an inert gas atmosphere, and if necessary, it is preferable to further heat in an air atmosphere.
  • the polymer component contained in the sheet can be efficiently removed by thermal decomposition.
  • polymer carbides that may be generated when the sheet is heated in an inert gas atmosphere can be efficiently removed by oxidative decomposition. Note that polymer carbide may occur when a fluorine-containing elastomer containing hydrogen atoms is used.
  • the inert gas is not particularly limited, and for example, nitrogen gas, argon gas, neon gas, helium gas, carbon dioxide gas, etc. can be used. Among them, it is preferable to use nitrogen gas as the inert gas.
  • the temperature and time for heating the sheet are particularly limited as long as the temperature can decompose the polymer component and polymer charcoal contained in the sheet and the fibrous carbon nanostructures are not denatured or decomposed. Any temperature and time can be set depending on the type of fluorine-containing elastomer.
  • the heating temperature can be, for example, 600°C or higher and 800°C or lower, preferably 700°C or lower, and more preferably 700°C.
  • the heating time can be, for example, 5 minutes or more and 30 minutes or less.
  • the heating temperature is 700°C. below, and more preferably 700°C.
  • thermogravimetric analysis of the polymer-removed material is performed at 700° C. in an air atmosphere to measure the change in the mass of the polymer-removed material over time.
  • a thermogravimetric curve is obtained from the values of the mass of the polymer-removed body and the elapsed time.
  • the fluorine-containing elastomer contained in the composite material does not contain hydrogen atoms, for example, using a thermogravimetric analyzer, after heating the sheet at 700° C. in an inert gas atmosphere,
  • the time when the atmosphere is switched to the oxygen atmosphere can be used as a reference for the time-dependent change in the mass of the polymer-removed body.
  • the time-dependent change in the mass of the polymer-removed body was measured with the time when the air atmosphere was switched to 0 minutes as the elapsed time, and the mass M 0 of the polymer-removed body at the elapsed time of 0 minutes was measured at 700 ° C. in the air atmosphere.
  • the fibrous carbon nanostructure at the elapsed time T is defined as 100% by subtracting the mass of the residue when the polymer-removed body is reduced by heating under the conditions (the residue here is the residue of inorganic substances such as metals).
  • a thermogravimetric loss curve for the mass M of the body is obtained and the resulting thermogravimetric loss curve can be used as the thermogravimetric curve.
  • thermogravimetric curve for example, as follows. First, a sheet with a thickness of 500 ⁇ m formed using a composite material was subjected to thermogravimetric analysis under conditions of 700° C. in a nitrogen atmosphere to measure changes in the mass of the sheet over time. Obtain a weight curve. Then, the obtained thermogravimetric curve is fitted using the Doube Boltzmann function represented by the following formula to obtain a thermogravimetric loss curve.
  • thermogravimetric curve is obtained by time-differentiating the thermogravimetric loss curve, and the elapsed time T1 at which the differential thermogravimetric curve takes a minimum value immediately before the peak corresponding to the combustion of the fibrous carbon nanostructure.
  • a thermogravimetric loss curve of the mass of the fibrous carbon nanostructure can be obtained from the time-dependent change in the mass of the sheet after T1, and the obtained thermogravimetric loss curve can be used as the thermogravimetric curve.
  • the final peak of the differential thermogravimetric curve is usually the peak corresponding to the combustion of the fibrous carbon nanostructures.
  • whether or not polymer carbide is generated can be determined by the number of peaks in the differential thermogravimetric curve. Specifically, if the number of peaks is one, no polymer carbide is generated, and in this case, the thermogravimetric curve corresponds to the thermogravimetric loss curve of the fibrous carbon nanostructure. And if the number of peaks is 2 or more, it means that polymer carbide is generated.
  • the method for preparing the composite material of the present invention is not particularly limited. Prepared using a method comprising a dispersing step of treating to obtain a fibrous carbon nanostructure dispersion, and a drying step of removing the solvent from the obtained fibrous carbon nanostructure dispersion to obtain a dried product. can do. Each step will be specifically described below.
  • the dispersing step includes a dissolution step of dissolving a fluorine-containing elastomer in a solvent to obtain a fluorine-containing elastomer solution, and a dissolution step in which fibrous carbon nanostructures are mixed in the obtained fluorine-containing elastomer solution and subjected to dispersion treatment to obtain fibrous carbon. and a dispersion treatment step of obtaining a nanostructure dispersion.
  • the solvent is not particularly limited as long as it can dissolve the fluorine-containing elastomer.
  • solvents include ketones such as methyl ethyl ketone and acetone, ethers such as tetrahydrofuran, and fluorine-based solvents. Among these, fluorine-based solvents are preferred.
  • a solvent having a perfluorohydrocarbon group can be used as the fluorine-based solvent.
  • the perfluorohydrocarbon group may be a chain perfluorohydrocarbon group or a cyclic perfluorohydrocarbon group.
  • the chain-type perfluorohydrocarbon group may be linear or branched.
  • chain perfluorohydrocarbon groups include perfluoroalkyl groups, perfluoroalkylene groups, perfluorovinylalkyl groups, and perfluorovinylalkylene groups.
  • the perfluorohydrocarbon group having the largest number of carbon atoms in the perfluorohydrocarbon group has 3 or more and 7 or less carbon atoms.
  • the solubility of the fluorine-containing elastomer in fluorine-based solvents is excellent.
  • the number of carbon atoms is 7 or less, the fluorine-based solvent is easily available. Further, when the number of carbon atoms is 6 or less, the boiling point of the fluorine-based solvent tends to be low, making it easy to remove the fluorine-based solvent.
  • the boiling point of the fluorine-based solvent is preferably 50°C or higher and 160°C or lower.
  • the dispersion treatment can be stably performed. If the boiling point of the fluorine-based solvent is 160° C. or lower, the fluorine-based solvent can be easily removed.
  • At least one selected from the group consisting of fluorine-containing compounds having a nitrogen atom, hydrofluorocarbons, and hydrofluoroethers is preferable as the fluorine-based solvent.
  • the fluorine-containing solvent is at least one selected from the group consisting of nitrogen-containing fluorine-containing compounds, hydrofluorocarbons, and hydrofluoroethers
  • the fluorine-containing elastomer tends to have excellent solubility in the fluorine-containing solvent.
  • a solvent may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
  • fluorine-containing compound having a nitrogen atom is Fluorinert (registered trademark) FC-770 manufactured by 3M.
  • hydrofluorocarbons include 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,1,2,2,3,3,4,4,5, Examples include 5,6,6-tridecafluorohexane and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane.
  • Commercial products of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane include Asahiklin (registered trademark) AC-2000, 1 manufactured by AGC.
  • 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane is exemplified by Asahiklin (registered trademark) AC-6000 manufactured by AGC. be.
  • hydrofluoroethers include Novec (registered trademark) 7300 manufactured by 3M.
  • the dispersion treatment is preferably carried out using a dispersion medium, and can be preferably carried out using a known wet media dispersion apparatus such as a bead mill.
  • the material constituting the dispersion media is not particularly limited, and examples thereof include glass, alumina, zircon (zirconia-silica-based ceramics), zirconia, and steel.
  • the average diameter of the dispersion media is preferably 0.1 mm or more, more preferably 0.3 mm or more, preferably 1.5 mm or less, more preferably 1 mm or less, and 0 It is more preferably 0.8 mm or less.
  • the drying step can be performed by removing the solvent in the fibrous carbon nanostructure dispersion liquid, and can be performed using a known drying method such as vacuum drying, reduced pressure drying, or drying by flowing an inert gas.
  • the vulcanized rubber molded article of the present invention is obtained by vulcanizing a composite material containing a fluorine-containing elastomer and a fibrous carbon nanostructure. It may further contain additives.
  • fluorine-containing elastomer examples include the same fluorine-containing elastomers as those described in the above section "Composite material”.
  • additives that can optionally be included in the vulcanized rubber molded article of the present invention include the same additives as those described in the above section of "composite material".
  • the vulcanized rubber molded article of the present invention is obtained by removing the polymer component and the polymer carbide from a sheet having a thickness of 500 ⁇ m formed using the vulcanized rubber molded article of the present invention.
  • the change in the mass of the polymer-removed body over time was measured by thermogravimetric analysis at 700 ° C.
  • the mass of the polymer-removed body M 1 is reduced to M 1 ⁇ 0.10 and the difference (T 90 ⁇ T 10 ) is It is 60 seconds or less, preferably 58 seconds or less. Note that the difference (T 90 ⁇ T 10 ) can be 40 seconds or more.
  • the polymer-removed body obtained by removing the polymer component and polymer carbide from a 500 ⁇ m thick sheet formed using vulcanized rubber is subjected to thermogravimetric analysis under the condition of 700° C. in an air atmosphere to remove the polymer.
  • the vulcanized rubber molded article of the present invention is obtained by removing the polymer component and the polymer carbide from a 500 ⁇ m thick vulcanized rubber molded article of the present invention.
  • the change in the mass of the polymer - removed body over time was measured by thermogravimetric analysis under the conditions of Using the time T 90 (seconds) to decrease to 1 ⁇ 0.10 and the time T 10 (seconds) to decrease the mass M 1 of the polymer-removed body to M 1 ⁇ 0.90, the following relational expression
  • the weight reduction rate V obtained in the above is 1.4 or more.
  • V 80/( T90 - T10)
  • the polymer-removed body obtained by removing the polymer component and the polymer carbide from the 500 ⁇ m thick sheet formed using the vulcanized rubber molded body was subjected to thermogravimetric analysis under the condition of 700° C. in an air atmosphere. Until the mass M 1 of the polymer-removed body decreases to M 1 ⁇ 0.90 in the thermogravimetric curve obtained from the values of the mass of the polymer-removed body and the elapsed time when measuring the change in the mass of the polymer-removed body over time.
  • the weight reduction rate V obtained by the above relational expression is A vulcanized rubber molded article having a value of 1.4 or more can exhibit sufficient rubber performance even at high temperatures.
  • thermogravimetric curve can be obtained by a method similar to the method described in the above section "Composite material”.
  • the method for producing the vulcanized rubber molded article of the present invention is not particularly limited. It can be prepared using a method including a cross-linking step of cross-linking to obtain a vulcanized rubber molding and an optional forming step. Each step will be specifically described below.
  • a crosslinkable composition is obtained by kneading the composite material obtained by the method described in the above section "Method for preparing composite material” and a crosslinking agent.
  • the cross-linking agent is a component that imparts sufficient elasticity to the resulting vulcanized rubber molding by cross-linking molecules of the fluorine-containing elastomer contained in the composite material.
  • the cross-linking agent is not particularly limited, and any known cross-linking agent capable of cross-linking the fluorine-containing elastomer contained in the composite material can be used.
  • a cross-linking agent for example, sulfur, a polyol-based cross-linking agent, a peroxide-based cross-linking agent, triallyl isocyanurate, or the like can be used.
  • a peroxide cross-linking agent and triallyl isocyanurate from the viewpoint of enhancing the rubber performance of the vulcanized rubber molded article.
  • these crosslinking agents can be used individually by 1 type or in mixture of 2 or more types.
  • the amount of the cross-linking agent in the vulcanized rubber molded article is not particularly limited, and may be the amount normally used in known vulcanized rubber molded articles.
  • the kneading is not particularly limited, and can be performed using, for example, a twin-screw kneader, an open roll, a Banbury mixer, a pressure kneader, or the like.
  • Cross-linking step the cross-linkable composition is heated to carry out a cross-linking reaction to obtain a vulcanized rubber molding.
  • press molding and the cross-linking step may be performed at the same time, for example, by putting the cross-linkable composition into a mold having a desired shape and heating it.
  • the crosslinkable composition is put into a mold of a desired shape and heated to perform press molding and primary vulcanization at the same time, and then the resulting primary crosslinked product is heated again with a heating device such as a gear oven.
  • Secondary vulcanization may be performed by heating. Conditions such as the temperature and time of the cross-linking reaction can be appropriately set.
  • molding process In the optionally included molding step, a molded article in which the shape of the vulcanized rubber molded article is fixed is obtained.
  • the molding step can be carried out by any method such as injection molding, extrusion molding, press molding, roll molding, and the like.
  • the vulcanized rubber molded article of the present invention can be used, for example, in automotive parts, air conditioning equipment, control equipment, water supply/hot water supply equipment, high-temperature steam equipment, semiconductor equipment, food processing equipment, analytical/physical and chemical equipment, liquid storage equipment, and pressure switch equipment. , paint/coating equipment, printing/coating equipment, OA equipment, fuel cell peripheral equipment, and various parts that require high tensile strength and high elongation in a high-temperature environment, used in fields such as oil drilling and medical fields. It can be preferably used as.
  • the vulcanized rubber molded article of the present invention can be used as a hose, sealing material, belt, anti-vibration rubber, diaphragm, hollow rubber molded article, roll, tube and the like.
  • the hoses are not particularly limited, and examples include fuel hoses, turbo air hoses, oil hoses, radiator hoses, heater hoses, water hoses, vacuum brake hoses, control hoses, air conditioner hoses, brake hoses, power steering hoses, and air hoses. , marine hoses, risers, and flow lines.
  • the sealing material is not particularly limited, and examples include various seals such as O-rings, packings, oil seals, shaft seals, bearing seals, mechanical seals, well head seals, seals for electric/electronic devices, and seals for pneumatic devices.
  • the belt is not particularly limited, and examples thereof include various belts such as power transmission belts and conveyor belts.
  • the anti-vibration rubber is not particularly limited, and examples thereof include various anti-vibration rubbers such as anti-vibration rubber for automobiles.
  • the diaphragm is not particularly limited, and for example, a fuel system, an exhaust system, a brake system, a drive system, a diaphragm for an automobile engine such as an ignition system; a pump diaphragm; a valve diaphragm; a filter press diaphragm; a blower diaphragm; Various diaphragms such as
  • the hollow rubber molding is not particularly limited, and examples include various bladders such as tire manufacturing bladders and tire vulcanizing bladders; various joints such as flexible joints and expansion joints; joint boots, rack and pinion steering boots, and pin boots. , various boots such as a piston boot; various valves such as a primer valve; and the like.
  • the roll is not particularly limited, and includes, for example, a printing roll; a coating roll; a copying roll such as a printer;
  • the tube is not particularly limited, and includes, for example, tubes for analytical instruments; tubes for pumps, reactors, stirrers, mixers; ink tubes for printers; tubes for semiconductor manufacturing equipment pumps; tube; tube requiring high corrosive gas resistance; and the like.
  • thermogravimetric curve is obtained from the change in the mass of the measurement sample and the elapsed time. It was created. The generated thermogravimetric curve is shown in FIG.
  • the required time T 90 (90% reduction time) until the mass M of the measurement sample decreases to M 0 ⁇ 0.10 at the elapsed time T and until it decreases to M 0 ⁇ 0.90
  • the required time T 10 (10% reduction time) is obtained, and the required times T 90 (seconds) until the mass M 1 of the polymer-removed body decreases to M 1 ⁇ 0.10 and The time required for the mass M 1 of the polymer-removed material to decrease to M 1 ⁇ 0.90 was defined as T 10 (seconds).
  • ⁇ (T 90 ⁇ T 10 ) and weight loss rate V> Each of the vulcanized rubber moldings obtained in Examples and Comparative Examples was formed into a sheet having a thickness of 500 ⁇ m and used as a measurement sample. After setting this measurement sample in the same thermogravimetric analyzer as above, the temperature was raised to 700° C. at a temperature elevation rate of 10° C./min in a nitrogen gas atmosphere, and held at 700° C. for 10 minutes. Next, while maintaining the temperature at 700° C., the nitrogen gas atmosphere was switched to the air atmosphere, and the temperature was kept at 700° C. for 20 minutes.
  • the elapsed time was set to 0 minutes, and the mass change of the measurement sample was measured with the elapsed time. Then, the mass M0 obtained by subtracting the mass of the measurement sample after being held at 700 ° C. for 20 minutes from the mass of the measurement sample at the elapsed time of 0 minutes is set to 100%, and the thermogravimetric curve is obtained from the change in the mass of the measurement sample and the elapsed time. It was created.
  • the required time T 90 (90% reduction time) until the mass M of the measurement sample decreases to M 0 ⁇ 0.10 at the elapsed time T and until it decreases to M 0 ⁇ 0.90
  • the required time T 10 (10% reduction time) is obtained, and the required times T 90 (seconds) until the mass M 1 of the polymer-removed body decreases to M 1 ⁇ 0.10 and The time required for the mass M 1 of the polymer-removed material to decrease to M 1 ⁇ 0.90 was defined as T 10 (seconds).
  • test piece was heat-treated in an oven (manufactured by Koyo Thermo Systems Co., Ltd., model "INH-9CD-S") at 330° C. for 70 hours in the atmosphere to prepare a heat-aged test piece.
  • a tensile tester Toyo Seiki Co., Ltd., Strograph VG
  • the test piece after heat aging is tested according to JIS K6251: 2010 at a test temperature of 23 ° C., a test humidity of 50%, and a tensile speed of 500 ⁇ 50 mm / min.
  • the elongation Eb B after heat aging at 330° C.
  • volume resistivity of the vulcanized rubber molding sheets obtained in Examples and Comparative Examples was measured at 10 points at different measurement points, an average value was obtained from the measured values at 10 points, and the average value was taken as the volume resistivity of the vulcanized rubber molding. A smaller value of volume resistivity indicates that the fibrous carbon nanostructure is defibrated.
  • Example 1 ⁇ Preparation of composite material> [Dispersion process] 1899 g of Novec (registered trademark) 7300 manufactured by 3M Corporation as a solvent, and 100 parts of FFKM (tetrafluoroethylene-perfluoroalkyl vinyl ether rubber, manufactured by AGC Co., Ltd., trade name "AFRAS PM1100") as a fluorine-containing elastomer. (100 g) was added and stirred at a temperature of 20° C. for 12 hours to dissolve the fluorine-containing elastomer to obtain a fluorine-containing elastomer solution (dissolving step).
  • FFKM tetrafluoroethylene-perfluoroalkyl vinyl ether rubber, manufactured by AGC Co., Ltd., trade name "AFRAS PM1100”
  • SGCNTs as fibrous carbon nanostructures containing single-walled CNTs (manufactured by Zeon Nanotechnology Co., Ltd., product name “ZEONANO SG101”, average diameter: 3.4 nm, BET specific surface area: 1482 m) were added to the fluorine-containing elastomer solution. 2 /g, t-plot is upward convex) was added, and 4 parts (4 g) was added and stirred at a temperature of 20° C. for 30 minutes.
  • Dispersion treatment was carried out at a temperature of 40° C. for a residence time of 25 minutes (dispersion treatment conditions: peripheral speed of 10 m/s) to obtain a fibrous carbon nanostructure dispersion (dispersion treatment step).
  • the resulting fibrous carbon nanostructure dispersion liquid was added dropwise to 2003 g of methyl ethyl ketone (MEK) and solidified to obtain a black solid.
  • MEK methyl ethyl ketone
  • the obtained black solid was dried under reduced pressure at 150° C. for 12 hours to obtain a mixture of FFKM and SGCNT as a composite material.
  • Various measurements were performed using the obtained composite material. Table 1 shows the results.
  • Crosslinking step The resulting crosslinkable composition was put into a mold and heated at a temperature of 150° C. and a pressure of 10 MPa for 20 minutes to carry out a crosslinking reaction. , width: 150 mm, thickness: 2 mm). Next, a cross-linking reaction was performed by heating in a gear oven (manufactured by Toyo Seiki Co., Ltd., model "S60") at 250°C for 4 hours to obtain a sheet-like vulcanized rubber molding after secondary vulcanization. Various measurements were performed using the obtained vulcanized rubber molding. Table 1 shows the results.
  • Example 2 A composite material and a vulcanized rubber molding were obtained in the same manner as in Example 1, except that the dispersion treatment conditions were changed to a peripheral speed of 8 m/s when the SGCNT-added fluorine-containing elastomer solution was dispersed. Then, the measurement was performed in the same manner as in Example 1. Table 1 shows the results.
  • Example 1 A composite material and a vulcanized rubber molded article were obtained in the same manner as in Example 1, except that the dispersion treatment conditions were changed to a peripheral speed of 6 m/s when the SGCNT-added fluorine-containing elastomer solution was dispersed. Then, the measurement was performed in the same manner as in Example 1. Table 1 shows the results.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Ce matériau composite contient un élastomère contenant du fluor et une nanostructure fibreuse de carbone. Lorsqu'une feuille qui présente une épaisseur de 500 μm et une masse de 30 mg et qui contient 4 parties en masse de la nanostructure fibreuse de carbone par rapport à 100 parties en masse de l'élastomère contenant du fluor est formée à partir du matériau composite, un composant polymère et un carbure de polymère sont éliminés de la feuille pour obtenir un corps à polymère éliminé, et la variation dans le temps de la masse du corps à polymère éliminé est mesurée au moyen d'une analyse thermogravimétrique à 700 °C dans une atmosphère d'air, la différence (T90 - T10) entre le temps (T90) requis pour que la masse M1 du corps à polymère éliminé diminue à M1 × 0,10 et le temps (T10) requis pour que la masse du corps à polymère éliminé diminue à M1 × 0,90 étant inférieure ou égale à 100 secondes.
PCT/JP2022/003160 2021-02-26 2022-01-27 Matériau composite et corps moulé en caoutchouc vulcanisé WO2022181193A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2023502205A JPWO2022181193A1 (fr) 2021-02-26 2022-01-27

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-030615 2021-02-26
JP2021030615 2021-02-26

Publications (1)

Publication Number Publication Date
WO2022181193A1 true WO2022181193A1 (fr) 2022-09-01

Family

ID=83049192

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/003160 WO2022181193A1 (fr) 2021-02-26 2022-01-27 Matériau composite et corps moulé en caoutchouc vulcanisé

Country Status (3)

Country Link
JP (1) JPWO2022181193A1 (fr)
TW (1) TW202239860A (fr)
WO (1) WO2022181193A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019009188A1 (fr) * 2017-07-05 2019-01-10 Nok株式会社 Composition de caoutchouc fluoré, son procédé de production, et article en caoutchouc fluoré réticulé moulé
JP2019085495A (ja) * 2017-11-07 2019-06-06 日本ゼオン株式会社 樹脂組成物の製造方法
WO2019180993A1 (fr) * 2018-03-23 2019-09-26 日本ゼオン株式会社 Procédé de production d'une composition de caoutchouc
JP2019189702A (ja) * 2018-04-20 2019-10-31 Ａｇｃ株式会社 フッ素ゴム組成物、その架橋物およびホース
JP2019199584A (ja) * 2018-05-18 2019-11-21 国立大学法人広島大学 複合材料の製造方法および架橋物の製造方法
WO2020175331A1 (fr) * 2019-02-28 2020-09-03 日本ゼオン株式会社 Composition d'élastomère contenant du fluor, article moulé en caoutchouc fluoré, procédé de production d'une solution d'élastomère contenant du fluor, et procédé de production de composition d'élastomère contenant du fluor
WO2020195799A1 (fr) * 2019-03-28 2020-10-01 日本ゼオン株式会社 Composition d'élastomère et corps moulé

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019009188A1 (fr) * 2017-07-05 2019-01-10 Nok株式会社 Composition de caoutchouc fluoré, son procédé de production, et article en caoutchouc fluoré réticulé moulé
JP2019085495A (ja) * 2017-11-07 2019-06-06 日本ゼオン株式会社 樹脂組成物の製造方法
WO2019180993A1 (fr) * 2018-03-23 2019-09-26 日本ゼオン株式会社 Procédé de production d'une composition de caoutchouc
JP2019189702A (ja) * 2018-04-20 2019-10-31 Ａｇｃ株式会社 フッ素ゴム組成物、その架橋物およびホース
JP2019199584A (ja) * 2018-05-18 2019-11-21 国立大学法人広島大学 複合材料の製造方法および架橋物の製造方法
WO2020175331A1 (fr) * 2019-02-28 2020-09-03 日本ゼオン株式会社 Composition d'élastomère contenant du fluor, article moulé en caoutchouc fluoré, procédé de production d'une solution d'élastomère contenant du fluor, et procédé de production de composition d'élastomère contenant du fluor
WO2020195799A1 (fr) * 2019-03-28 2020-10-01 日本ゼオン株式会社 Composition d'élastomère et corps moulé

Also Published As

Publication number Publication date
JPWO2022181193A1 (fr) 2022-09-01
TW202239860A (zh) 2022-10-16

Similar Documents

Publication Publication Date Title
JP7056556B2 (ja) 含フッ素エラストマー組成物および成形体
JP2017186476A (ja) 含フッ素エラストマー組成物の製造方法およびオイルシール部材の製造方法
JP2019189702A (ja) フッ素ゴム組成物、その架橋物およびホース
WO2020195799A1 (fr) Composition d'élastomère et corps moulé
TWI816861B (zh) 密封材
WO2022210974A1 (fr) Composition élastomère, son procédé de production, produit réticulé et corps moulé
WO2020241601A1 (fr) Procédé d'évaluation et procédé de production de matériau composite et matériau composite
WO2022181193A1 (fr) Matériau composite et corps moulé en caoutchouc vulcanisé
JP5922999B2 (ja) シール部材を用いたバルブ
WO2020175331A1 (fr) Composition d'élastomère contenant du fluor, article moulé en caoutchouc fluoré, procédé de production d'une solution d'élastomère contenant du fluor, et procédé de production de composition d'élastomère contenant du fluor
JP2022086825A (ja) エラストマー組成物およびエラストマー組成物の製造方法
JP7306641B2 (ja) ガスシール部材用組成物、高圧水素機器用ガスシール部材、および、高圧水素機器
CN116057122B (zh) 弹性体组合物、弹性体组合物的制造方法、交联物、以及成型体
JP2021070767A (ja) エラストマー成形体
JP2022136073A (ja) 高圧水素機器用ガスシール部材および高圧水素機器
WO2023162783A1 (fr) Composition élastomère
JP7476613B2 (ja) エラストマー成形体およびその使用方法、ならびに半導体製造装置
JP2022086911A (ja) カーボンナノチューブ分散液およびエラストマー組成物の製造方法
WO2023054716A1 (fr) Composition de caoutchouc fluoré et objet façonné
JPWO2019058911A1 (ja) ゴム組成物
JP7468062B2 (ja) エラストマー組成物の製造方法
WO2019188051A1 (fr) Composition élastomère non réticulée et produit réticulé de celle-ci
JP7243710B2 (ja) 繊維状炭素ナノ構造体分散液の製造方法および複合材料の製造方法
WO2018139570A1 (fr) Composition de caoutchouc, produit en caoutchouc et procédé de production de composition de caoutchouc

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22759235

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2023502205

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22759235

Country of ref document: EP

Kind code of ref document: A1