WO2023054716A1 - Composition de caoutchouc fluoré et objet façonné - Google Patents

Composition de caoutchouc fluoré et objet façonné Download PDF

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Publication number
WO2023054716A1
WO2023054716A1 PCT/JP2022/036854 JP2022036854W WO2023054716A1 WO 2023054716 A1 WO2023054716 A1 WO 2023054716A1 JP 2022036854 W JP2022036854 W JP 2022036854W WO 2023054716 A1 WO2023054716 A1 WO 2023054716A1
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fluororubber
fluororubber composition
mass
tensile strength
walled
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PCT/JP2022/036854
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English (en)
Japanese (ja)
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真寛 上野
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日本ゼオン株式会社
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Priority to JP2023551929A priority Critical patent/JPWO2023054716A1/ja
Publication of WO2023054716A1 publication Critical patent/WO2023054716A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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 a composition containing fluororubber and a molded article obtained by molding the composition.
  • Fluorororubber is known to have excellent performance such as chemical resistance, oil resistance, heat resistance, and cold resistance, and is used for various purposes. Conventionally, attempts have been made to add a carbon material to the fluororubber in order to improve the performance of the fluororubber.
  • Patent Document 1 describes a fluororubber composition obtained by adding carbon black as a carbon material to a fluororubber having predetermined properties.
  • the fluororubber composition containing the fluororubber and the carbon black is subjected to a dynamic viscoelasticity test conducted under predetermined conditions.
  • a dynamic viscoelasticity test conducted under predetermined conditions.
  • carbon nanotubes such as single-walled carbon nanotubes (hereinafter sometimes abbreviated as "CNT") have been attracting attention as carbon materials that are excellent in various properties such as electrical conductivity and thermal conductivity.
  • a molded article formed from the fluororubber composition exhibits excellent extensibility in a high-temperature environment (e.g., 200°C or higher). In this respect, there is room for improvement.
  • an object of the present invention is to provide a new technology that can form a molded body that can exhibit excellent extensibility at high temperatures using fluororubber and single-walled CNTs.
  • the inventor of the present invention has diligently studied in order to achieve the above purpose.
  • the present inventor focused on dynamic viscoelasticity of a fluororubber composition obtained by using fluororubber and single-walled CNTs.
  • the ratio of the complex elastic modulus when the dynamic strain is 0.1% to the complex elastic modulus when the dynamic strain is 630% is a predetermined value or more
  • the fluororubber composition can be used to obtain a molded article having excellent extensibility at high temperatures, and the present invention has been completed.
  • an object of the present invention is to advantageously solve the above problems, and according to the present invention, the following fluororubber compositions [1] to [7] and the following [8] molded article is provided.
  • [1] A fluororubber composition containing fluororubber and carbon nanotubes, wherein the carbon nanotubes include single-walled carbon nanotubes, and the measurement frequency is 1 Hz and the measurement temperature is 40°C.
  • a molded article formed using any one of the above-described fluororubber compositions containing a cross-linking agent can exhibit excellent extensibility at high temperatures.
  • a molded article that contains fluororubber and single-walled carbon nanotubes and that can exhibit excellent extensibility at high temperatures, and a fluororubber composition that can form the molded article.
  • the fluorororubber composition of the present invention can be used for forming the molded article of the present invention. And the molded article of the present invention is formed using the fluororubber composition of the present invention.
  • the fluororubber composition of the present invention contains at least fluororubber and single-walled carbon nanotubes, and optionally at least one selected from the group consisting of multi-walled carbon nanotubes, reinforcing fillers, cross-linking agents, and other components. further includes
  • the fluororubber composition of the present invention has a complex elastic modulus of G *
  • L (kPa) and G * H (kPa) is the complex elastic modulus at a dynamic strain of 630%
  • the following formula (I): ⁇ G * G * L /G * H (I) ⁇ G * calculated by is 20 or more. If a fluororubber composition having a ⁇ G * of 20 or more, which is calculated as the ratio of the complex elastic modulus at a dynamic strain of 0.1% to the complex elastic modulus at a dynamic strain of 630%, is used, A molded article having excellent extensibility can be obtained.
  • the reason why the ⁇ G * of the fluororubber composition is equal to or higher than the above-described value can improve the extensibility of the molded article at high temperatures is presumed as follows. First, the extensibility of the molded body at high temperatures is excellent in a network structure composed of single-walled CNTs, multi-walled CNTs, and reinforcing fillers (hereinafter collectively referred to as “single-walled CNTs, etc.”). It is thought that it will be improved by being formed. According to the study of the present inventor, it is possible to use ⁇ G * as a factor that correlates with the degree of formation of this network structure.
  • a network structure composed of single-walled CNTs or the like is maintained when the dynamic strain is small (eg, 0.1%), while the dynamic strain is large (eg, 630 %) in which case it will be destroyed. That is, the complex elastic modulus at a dynamic strain of 0.1% corresponds to the complex elastic modulus when the network structure is maintained, and the complex elastic modulus at a dynamic strain of 630% corresponds to that when the network structure is destroyed. corresponds to the complex elastic modulus in the flattened state. Therefore, if ⁇ G * , which is calculated as the ratio of the complex elastic modulus (dynamic strain: 0.1%) to the complex elastic modulus (dynamic strain: 630%), is 20 or more, the network structure is maintained.
  • the complex elastic modulus (dynamic strain: 0.1%) is sufficiently larger than the complex elastic modulus (dynamic strain: 630%) in the state where the network structure is destroyed, and the single-walled CNT etc. in the fluororubber composition It can be judged that the network structure composed of is well formed. It is believed that the molded article formed from the fluororubber composition can exhibit excellent extensibility at high temperatures due to the favorable network structure of single-walled CNTs and the like.
  • the fluorororubber is not particularly limited, and examples thereof include tetrafluoroethylene-propylene rubber (FEPM), vinylidene fluoride rubber (FKM), tetrafluoroethylene-perfluoromethyl vinyl ether rubber (FFKM), tetrafluoro Ethylene-based rubber (TFE) can be mentioned.
  • FEPM tetrafluoroethylene-propylene rubber
  • FKM vinylidene fluoride rubber
  • FEPM tetrafluoroethylene-propylene rubber
  • FKM tetrafluoroethylene-propylene rubber
  • fluororubber may be used individually by 1 type, and may be used in combination of 2 or more types.
  • 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.
  • FEPM Polytetrafluoroethylene-propylene rubber
  • FEPM is a fluororubber based on an alternating copolymer of tetrafluoroethylene and propylene, and has excellent heat resistance, chemical resistance, polar solvent resistance, and steam resistance.
  • examples of FEPM include, but are not limited to, a binary copolymer consisting of tetrafluoroethylene and propylene, a terpolymer consisting of tetrafluoroethylene, propylene and vinylidene fluoride, and tetrafluoroethylene, propylene and a cross-linking point. a terpolymer consisting of a monomer and the like.
  • Examples of commercially available binary copolymers 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.
  • the content of the fluororubber in the fluororubber composition is preferably 80% by mass or more, more preferably 85% by mass or more, with the mass of the entire fluororubber composition being 100% by mass. It is more preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less. If the content of the fluororubber in the fluororubber composition is within the range described above, the extensibility of the molded article at high temperatures can be sufficiently improved while ensuring the workability of the fluororubber composition.
  • the fluororubber composition of the present invention contains at least single-walled CNTs as CNTs.
  • the average diameter of single-walled CNTs is preferably 0.5 nm or more, more preferably 1 nm or more, preferably 15 nm or less, more preferably 10 nm or less, and 5 nm or less. is more preferable, and 3.5 nm or less is particularly preferable. If the average diameter (Av) of the single-walled CNTs is within the range described above, it is possible to further improve the extensibility at high temperatures of the molded article formed using the fluororubber composition.
  • single-walled CNTs preferably show an upward convex shape in the t-plot obtained from the adsorption isotherm. Among them, it is more preferable that the single-walled CNTs are not subjected to the opening treatment and that the t-plot exhibits an upwardly convex shape. If single-walled CNTs exhibiting a convex shape in the t-plot obtained from the adsorption isotherm are used, the extensibility at high temperatures of the molded article formed using the fluororubber composition can be further improved. can.
  • adsorption is generally a phenomenon in which gas molecules are removed from the gas phase onto a solid surface, and is classified into physical adsorption and chemisorption according to the cause.
  • the nitrogen gas adsorption method used to obtain the t-plot utilizes physical adsorption. Normally, if the adsorption temperature is constant, the number of nitrogen gas molecules adsorbed on CNT increases as the pressure increases.
  • the relative pressure on the horizontal axis the ratio of the adsorption equilibrium state pressure P and the saturated vapor pressure P0
  • the nitrogen gas adsorption amount on the vertical axis are called “isothermal lines", and nitrogen gas adsorption is performed while increasing the pressure.
  • the case where the amount is measured is called the “adsorption isotherm”
  • the case where the nitrogen gas adsorption amount is measured while decreasing the pressure is called the "desorption 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 measured by the nitrogen gas adsorption method. 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. gives a t-plot of CNTs (t-plot method by de Boer et al.).
  • 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 A CNT having such a t-plot shape has a large ratio of the internal specific surface area to the total specific surface area of the CNT, indicating that many openings are formed in the CNT.
  • the t-plot inflection point of the single-walled CNTs used in the present invention preferably falls within a range that satisfies 0.2 ⁇ t (nm) ⁇ 1.5, and 0.45 ⁇ t (nm) ⁇ 1.5. 5, more preferably 0.55 ⁇ t(nm) ⁇ 1.0.
  • the position of the inflection point of the t-plot is within the above range, the properties of the single-walled CNTs are further improved, so that the extensibility at high temperatures of the molded body formed using the fluororubber composition is further improved. can be done.
  • the "position of the inflection point" is the intersection of the approximate straight line A in the process (s-1) described above and the approximate straight line B in the process (s-3) described above in the t-plot. .
  • the ratio (S2/S1) of the internal specific surface area S2 to the total specific surface area S1 obtained from the t-plot is preferably 0.05 or more, and 0.06 or more. It is more preferably 0.08 or more, and preferably 0.30 or less. If S2/S1 is 0.05 or more and 0.30 or less, the properties of the single-walled CNTs can be further improved, so that the extensibility at high temperatures of the molded body formed using the fluororubber composition can be improved. can be further enhanced.
  • the measurement of the adsorption isotherm of CNT, 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 using a commercially available measurement device "BELSORP (registered (trademark)-mini” (manufactured by Bell Japan).
  • BELSORP registered (trademark)-mini
  • the ratio (3 ⁇ /Av) of the value (3 ⁇ ) obtained by multiplying the standard deviation ( ⁇ ) of the diameter by 3 to the average diameter (Av) is single It is preferable to use layered CNTs, more preferably to use single-walled CNTs with 3 ⁇ /Av of more than 0.25, even more preferably to use single-walled CNTs with 3 ⁇ /Av of more than 0.40, and 3 ⁇ /Av of It is particularly preferred to use single-walled CNTs greater than 0.50.
  • average diameter of CNT (Av) and “standard deviation of diameter of CNT ( ⁇ : sample standard deviation)” are the diameters of 100 CNTs randomly selected using a transmission electron microscope (outer diameter ) can be obtained by measuring The average diameter (Av) and standard deviation ( ⁇ ) of CNTs may be adjusted by changing the CNT production method or production conditions, or by combining multiple types of CNTs obtained by different production methods.
  • the single-walled CNTs used in the present invention preferably have 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 1600 m 2 /g or more. 2 /g or less is more preferable.
  • the BET specific surface area of the single-walled CNT is 600 m 2 /g or more, the physical properties of the compact can be further improved.
  • the BET specific surface area of the single-walled CNTs is 2000 m 2 /g or less, the single-walled CNTs can be satisfactorily dispersed in the compact. Therefore, if the BET specific surface area of the single-walled CNTs is within the above range, it is possible to further improve the extensibility at high temperatures of the molded article formed using the fluororubber composition.
  • the average length of the single-walled CNTs used in the present invention is preferably 10 ⁇ m or longer, more preferably 15 ⁇ m or longer, and even more preferably 20 ⁇ m or longer. If the average length of the single-walled CNTs is 10 ⁇ m or more, it is possible to further improve the extensibility at high temperatures of the molded article formed using the fluororubber composition. Although the upper limit of the average length of single-walled CNTs is not particularly limited, it is usually 800 ⁇ m or less.
  • the average length of single-walled CNTs can be obtained by measuring the length of 100 single-walled CNTs and calculating the average value thereof. A scanning electron microscope (SEM) or known image processing can be used for observation of single-walled CNTs.
  • Single-walled CNTs having the properties described above can be produced, for example, by chemical vapor deposition (CVD) by supplying a raw material compound and a carrier gas onto a substrate having a catalyst layer for CNT production on its surface.
  • CVD chemical vapor deposition
  • a method of dramatically improving the catalytic activity of the catalyst layer by allowing a small amount of oxidizing agent (catalyst activating substance) to exist in the system when synthesizing CNTs (super-growth method; International Publication No. 2006/011655 ), the formation of the catalyst layer on the substrate surface by a wet process enables efficient production.
  • the carbon nanotube obtained by the super growth method may be called "SGCNT.”
  • the content of single-walled CNTs in the fluororubber composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, per 100 parts by mass of the fluororubber. It is more preferably 2 parts by mass or more, particularly preferably 2 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 6 parts by mass or less. It is preferably 4 parts by mass or less, and particularly preferably 4 parts by mass or less. If the content of the single-walled CNTs in the fluororubber composition is 0.1 parts by mass or more per 100 parts by mass of the fluororubber, the extensibility of the molded article at high temperatures can be further improved.
  • the content of the single-walled CNTs in the fluororubber composition is 10 parts by mass or less per 100 parts by mass of the fluororubber, it is possible to suppress the increase in viscosity of the fluororubber composition and to ensure sufficient workability.
  • CNT aggregates Carbon nanotubes in the form of CNT aggregates may also be used.
  • CNTs in the form of CNT aggregates for example, CNT aggregates satisfying at least one of conditions (1) to (3) described later can be used.
  • the CNT aggregate used when forming the fluororubber composition it is preferable to use a CNT aggregate that satisfies at least one of the following conditions (1) to (3).
  • At least one peak in the two-dimensional spatial frequency spectrum of the electron microscope image of the aggregate of carbon nanotubes exists in the range of 1 ⁇ m ⁇ 1 to 100 ⁇ m ⁇ 1 .
  • the condition (1) is "a carbon nanotube dispersion obtained by dispersing aggregates of carbon nanotubes so that the bundle length is 10 ⁇ m or more.
  • the carbon nanotube dispersion At least one peak based on the plasmon resonance of is present in the wavenumber range of more than 300 cm ⁇ 1 and 2000 cm ⁇ 1 or less.
  • a strong absorption characteristic in the far-infrared region has been widely known as an optical characteristic of CNTs. Such strong absorption properties in the far-infrared region are believed to be due to the diameter and length of CNTs.
  • T.M the above-mentioned T.M.
  • the upper limit for determining the presence or absence of a peak based on plasmon resonance of the CNT dispersion under condition (1) is 2000 -1 cm or less.
  • condition (1) in obtaining a spectrum by Fourier transform infrared spectroscopy, it is necessary to obtain a CNT dispersion by dispersing the CNT aggregates so that the bundle length is 10 ⁇ m or more.
  • a CNT aggregate, water, and a surfactant for example, sodium dodecylbenzenesulfonate
  • a surfactant for example, sodium dodecylbenzenesulfonate
  • the bundle length of the CNT dispersion can be obtained by analyzing it with a wet image analysis type particle size measuring device. Such a measuring device calculates the area of each dispersion from the image obtained by photographing the CNT dispersion, and the diameter of the circle having the calculated area (hereinafter also referred to as the ISO area diameter). ) can be obtained.
  • the bundle length of each dispersion is defined as the value of the ISO circle diameter thus obtained.
  • Condition (2) defines that "the maximum peak in the pore distribution curve is in the range of pore diameters greater than 100 nm and less than 400 nm.”
  • the pore size distribution of the aggregate of carbon nanotubes can be determined based on the Barrett-Joyner-Halenda method (BJH method) from the adsorption isotherm of liquid nitrogen at 77K.
  • BJH method Barrett-Joyner-Halenda method
  • the fact that the peak in the pore distribution curve obtained by measuring the carbon nanotube aggregate is in the range of more than 100 nm means that there are voids of a certain size between the CNTs in the carbon nanotube aggregate, and the CNTs are It means that it is not in an excessively densely agglomerated state.
  • the upper limit of 400 nm is the measurement limit when, for example, BELSORP-mini II is used as a measurement device.
  • Condition (3) stipulates that "at least one peak in the two-dimensional spatial frequency spectrum of the electron microscope image of the aggregate of carbon nanotubes exists in the range of 1 ⁇ m -1 to 100 ⁇ m -1 ".
  • the sufficiency of such conditions can be determined in the following manner. First, the CNT aggregate to be determined is magnified (e.g., 10,000 times) using an electron microscope (e.g., field emission scanning electron microscope), and a plurality of electron microscope images ( For example, 10 sheets) are obtained. A plurality of electron microscope images obtained are subjected to fast Fourier transform (FFT) processing to obtain a two-dimensional spatial frequency spectrum.
  • FFT fast Fourier transform
  • a two-dimensional spatial frequency spectrum obtained for each of a plurality of electron microscope images is binarized to obtain an average value of peak positions appearing on the highest frequency side. If the average value of the obtained peak positions is within the range of 1 ⁇ m ⁇ 1 or more and 100 ⁇ m ⁇ 1 or less, it can be determined that the condition (3) is satisfied.
  • the "peak" used in the above determination a clear peak obtained by executing the isolated point extraction process (that is, the inverse operation of the isolated point removal) is used. Therefore, if a clear peak is not obtained within the range of 1 ⁇ m ⁇ 1 to 100 ⁇ m ⁇ 1 when performing the isolated point extraction process, it can be determined that the condition (3) is not satisfied.
  • the peak of the two-dimensional spatial frequency spectrum exists in the range of 2.6 ⁇ m ⁇ 1 or more and 100 ⁇ m ⁇ 1 or less.
  • the CNT aggregate preferably satisfies at least two of the above conditions (1) to (3), and more preferably satisfies all of the conditions (1) to (3).
  • the CNT aggregate that can be used in producing the fluororubber composition of the present invention preferably has the following properties in addition to the above conditions (1) to (3).
  • the tap bulk density of the CNT aggregate is preferably 0.001 g/cm 3 or more and 0.2 g/cm 3 or less.
  • a CNT aggregate having such a density range does not excessively strengthen the bonds between CNTs, so that it is excellent in dispersibility and can be molded into various shapes. If the tapped bulk density of the CNT aggregate is 0.2 g/cm 3 or less, the bonds between the CNTs become weak, so that when the CNT aggregate is stirred in a solvent or the like, it becomes easy to uniformly disperse it. Further, when the tap bulk density of the CNT aggregate is 0.001 g/cm 3 or more, the integrity of the CNT aggregate is improved and handling is facilitated.
  • the tapped bulk density is the apparent bulk density in a state in which the powdery CNT aggregate is filled in a container, and then the voids between the powder particles are reduced by tapping or vibration, etc., to close-pack.
  • a method for producing a CNT aggregate is not particularly limited, and production conditions can be adjusted according to desired properties.
  • a CNT aggregate that satisfies at least one of the above conditions (1) to (3) can be produced, for example, according to the method described in WO2021/172078.
  • the fluororubber composition of the present invention preferably contains, as CNTs, multi-walled CNTs in addition to the single-walled CNTs described above.
  • a fluororubber composition containing both single-walled CNTs and multi-walled CNTs ensures sufficient processability, and according to the fluororubber composition, it is possible to form a molded article that can exhibit even better extensibility at high temperatures. can be done.
  • the multilayer CNT preferably has a BET specific surface area of 50 m 2 /g or more, more preferably 150 m 2 /g or more, preferably 800 m 2 /g or less, and 500 m 2 /g or less. It is more preferable to have If the BET specific surface area of the multi-layered CNT is within the above range, it is possible to further improve the extensibility at high temperatures of the molded article formed using the fluororubber composition.
  • multilayer CNTs having the properties described above can be produced by known methods.
  • the content of the multilayer CNT in the fluororubber composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 3 parts by mass or more per 100 parts by mass of the fluororubber. More preferably 4 parts by mass or more, particularly preferably 5 parts by mass or more, preferably 15 parts by mass or less, more preferably 12 parts by mass or less, It is more preferably 8 parts by mass or less, and particularly preferably 6 parts by mass or less. If the content of multi-walled CNTs in the fluororubber composition is 0.5 parts by mass or more per 100 parts by mass of the fluororubber, the extensibility of the molded article at high temperatures can be further improved.
  • the content of multi-walled CNTs in the fluororubber composition is 15 parts by mass or less per 100 parts by mass of the fluororubber, thickening of the fluororubber composition can be suppressed to ensure sufficient workability.
  • the ratio of the multi-walled CNTs to the total CNTs in the fluororubber composition is 40% by mass or more, with the mass of the entire CNTs (that is, the sum of the mass of the single-walled CNTs and the multi-walled CNTs) being 100% by mass. preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, preferably 95% by mass or less, 91% by mass % or less, more preferably 90 mass % or less, even more preferably 85 mass % or less, and particularly preferably 80 mass % or less. If the proportion of multilayer CNTs in the total CNTs is 40% by mass or more, the extensibility of the molded article at high temperatures can be further improved. On the other hand, if the ratio of multi-walled CNTs to the total CNTs is 95% by mass or less, it is possible to suppress thickening of the fluororubber composition and sufficiently ensure workability.
  • the fluororubber composition of the present invention preferably contains a reinforcing filler from the viewpoint of further improving the extensibility of the molded article at high temperatures.
  • reinforcing fillers examples include carbon black, graphene, graphite, and silica.
  • carbon black and silica are preferable from the viewpoint of further improving the extensibility of the molded article at high temperatures.
  • Carbon black is more preferable from the viewpoint of further improving extensibility of molded articles at high temperatures while sufficiently ensuring workability by suppressing thickening of the fluororubber composition.
  • the reinforcing filler may be used singly or in combination of two or more.
  • carbon black examples include furnace black, acetylene black, thermal black, channel black, and ketjen black.
  • the particle size of carbon black is not particularly limited, and can be within the known particle size range of carbon black.
  • silica examples include colloidal silica, wet silica, amorphous silica, fumed silica, silica sol, and silica gel.
  • the surface of silica may be modified with functional functional groups such as hydrophilicity and hydrophobicity.
  • the particle size of silica is not particularly limited, and can be within the range of known silica particle sizes.
  • the content of the reinforcing filler in the fluororubber composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and 6 parts by mass or more per 100 parts by mass of the fluororubber. More preferably 8 parts by mass or more, preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and even more preferably 30 parts by mass or less. If the content of the reinforcing filler in the fluororubber composition is 1 part by mass or more per 100 parts by mass of the fluororubber, the extensibility of the molded article at high temperatures can be further improved.
  • the content of the reinforcing filler in the fluororubber composition is 40 parts by mass or less per 100 parts by mass of the fluororubber, thickening of the fluororubber composition can be suppressed to ensure sufficient workability.
  • the cross-linking agent that the fluororubber composition of the present invention may optionally contain is not particularly limited.
  • a known cross-linking agent capable of cross-linking the fluororubber contained in the fluororubber composition can be used.
  • examples of cross-linking agents include peroxide-based cross-linking agents (2,5-dimethyl-2,5-di(t-butylperoxy)hexane, etc.), triallyl isocyanurate, bisphenol AF (4, 4'-(Hexafluoroisopropylidene)diphenol), bisphenol A and the like can be used.
  • crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the cross-linking agent in the fluororubber composition of the present invention is not particularly limited, but is preferably 1 part by mass or more, more preferably 3 parts by mass or more per 100 parts by mass of the fluororubber. , more preferably 5 parts by mass or more, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.
  • ⁇ Other ingredients Components other than the fluororubber, single-walled CNTs, multi-walled CNTs, reinforcing fillers, and cross-linking agents (other components) that the fluororubber composition of the present invention may optionally contain include, for example, rubbers other than fluororubbers, Additives are included. Rubber other than fluororubber is not particularly limited.
  • Rubber natural rubber (NR), ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR), and their hydrides (hydrogenated acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-isoprene rubber, hydrogenated acrylonitrile- butadiene-isoprene rubber, hydrogenated styrene-butadiene rubber, hydrogenated butadiene rubber, hydrogenated isoprene rubber, hydrogenated natural rubber, hydrogenated ethylene-propylene-diene rubber, hydrogenated butyl rubber).
  • the content of the rubber other than the fluororubber in the fluororubber composition is not particularly limited, and can be appropriately set according to the use of the fluororubber composition.
  • additives include, but are not limited to, cross-linking aids, acid acceptors, dispersants, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, pigments, colorants, foaming agents, and antistatic agents. , flame retardants, lubricants, softeners, tackifiers, plasticizers, mold release agents, deodorants, perfumes, and other known additives that can be blended in fluororubber compositions can be used.
  • the content of the additive in the fluororubber composition is not particularly limited, and may be the amount normally used in known fluororubber compositions.
  • the fluororubber composition of the present invention may contain a compound A described later as another component.
  • another component may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the fluororubber composition of the present invention has a ⁇ G * calculated as a ratio of a complex elastic modulus (dynamic strain: 0.1%) to a complex elastic modulus (dynamic strain: 630%) of 20 or more. It is preferably 24 or more, more preferably 30 or more, and even more preferably 35 or more. If ⁇ G * is less than 20, it is presumed that the network structure composed of single-walled CNTs and the like is not well formed in the fluororubber composition, and the extensibility of the molded article at high temperatures is reduced. .
  • the upper limit of ⁇ G * is not particularly limited, it can be set to 150 or less, for example.
  • ⁇ G * of the fluororubber composition can be controlled by changing the type and/or content of the fluororubber, single-walled CNTs, multi-walled CNTs, and/or reinforcing filler in the fluororubber composition. can.
  • ⁇ G * of the fluororubber composition can be improved by producing the fluororubber composition using the method described later in the section ⁇ Production method of fluororubber composition>.
  • the fluororubber composition of the present invention contains a reinforcing filler and a cross-linking agent
  • T X (MPa) of the cross-linked rubber sheet X obtained by cross-linking the rubber composition and the carbon A test rubber composition excluding nanotubes and a reinforcing filler (that is, a fluororubber composition containing at least a fluororubber, CNTs, a reinforcing filler, and a cross-linking agent, excluding CNTs and a reinforcing filler.
  • the tensile strength ratio calculated by is preferably 3.0 or more, more preferably 3.5 or more, even more preferably 4.0 or more, especially 4.5 or more preferable.
  • the tensile strength ratio calculated by the above formula (II) is the ratio of the tensile strength of the crosslinked rubber sheet containing CNTs and reinforcing filler to the tensile strength of the crosslinked rubber sheet not containing CNTs and reinforcing filler.
  • the higher the tensile strength ratio the higher the durability of the molded article obtained using the fluororubber composition. In addition, since the durability is improved, it becomes possible to reduce the size of various members composed of the molded article.
  • the upper limit of the tensile strength ratio calculated by the above formula (II) is not particularly limited, it can be, for example, 10.0 or less.
  • the tensile strength ratio of the fluororubber composition can be controlled by changing the types and/or contents of single-walled CNTs, multi-walled CNTs, and/or reinforcing fillers in the fluororubber composition. Further, the tensile strength ratio of the fluororubber composition can be improved by producing the fluororubber composition using the method described later in the section ⁇ Production method of fluororubber composition>.
  • the fluororubber composition of the present invention which contains at least fluororubber and single-walled CNTs and has ⁇ G * equal to or greater than the above-mentioned value, contains, for example, fluororubber and single-walled CNTs, and optionally compound A described later.
  • a step of preparing a masterbatch (masterbatch preparation step), and optionally selected from the group consisting of the masterbatch, multi-walled CNTs, reinforcing fillers, cross-linking agents, and other components (excluding compound A) Through a step of kneading at least one of them (kneading step), it can be produced efficiently.
  • the masterbatch is preferably prepared by the following preparation method (i) or (ii). Since single-walled CNTs have a small outer diameter, they are easily bundled (easily bundled). On the other hand, by using the following preparation method (i) or (ii), the bundle structure of single-walled CNTs can be fibrillated and the single-walled CNTs can be well dispersed in the fluororubber. By dispersing the single-walled CNTs, it is speculated that a network structure such as the above-described single-walled CNTs can be formed satisfactorily.
  • a solvent capable of dissolving the fluororubber and dispersing the single-walled CNTs is preferably used.
  • Methyl ethyl ketone is preferred as such a solvent.
  • a solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the fluororubber and single-walled CNTs are added to the above solvent, and the resulting composition is subjected to dispersion treatment by bead building.
  • the conditions of the dispersion treatment are not particularly limited, and can be appropriately set from the viewpoint of dispersing the single-walled CNTs well in the solvent.
  • the method for removing the solvent from the composition after dispersion treatment is not particularly limited, and known methods such as coagulation, casting, and drying can be used.
  • compound A has a freezing point of 40° C. or lower.
  • the distance R1 of the Hansen solubility parameter between the single-walled CNT and the compound A is 6.0 MPa 1/2 or less, and the distance R2 of the Hansen solubility parameter between the fluororubber and the compound A is larger than R1.
  • a masterbatch in which single-walled CNTs are satisfactorily dispersed can be obtained by setting the freezing point of compound A to the above value or less, and having the above relationship between the single-walled CNTs, the fluororubber, and the Hansen solubility parameter of compound A. .
  • the reason for this is not clear, but is presumed to be as follows. First, compound A has sufficient fluidity because it has a freezing point of 40° C.
  • the compound A since the value of R1 is equal to or less than the predetermined value, the compound A has excellent affinity with the single-walled CNT, and the compound A, which has excellent fluidity, is impregnated inside the bundle structure of the single-walled CNT. Promotes disentanglement of the bundle structure.
  • the value of R2 is larger than the value of R1, compound A can have a better affinity with single-walled CNTs than fluororubber, and the presence of fluororubber causes the above-mentioned compound A to excessively defibrate the bundle structure. It does not interfere with Therefore, it is considered that the bundle structure of single-walled CNTs can be sufficiently fibrillated and the single-walled CNTs can be well dispersed in the fluororubber.
  • the “freezing point” of compound A must be 40° C. or lower as described above, and is preferably 35° C. or lower from the viewpoint of ensuring the fluidity of compound A more sufficiently.
  • the lower limit of the freezing point of compound A is not particularly limited, it can be, for example, 5°C or higher.
  • the "freezing point" of compound A is a value measured by the following method. That is, the sample is sealed in an aluminum cell, the aluminum cell is inserted into a sample holder of a differential scanning calorimeter (manufactured by Hitachi High-Tech Science, product name "DSC7000X”), and the sample holder is heated at 10 ° C. in a nitrogen atmosphere. An endothermic peak is observed while heating up to 150° C./min, and the obtained endothermic peak can be taken as the freezing point of the sample.
  • the distance R1 of the Hansen solubility parameter between compound A and single-walled CNTs must be 6.0 MPa 1/2 or less as described above, preferably 5.5 MPa 1/2 or less. It is more preferably 0 MPa 1/2 or less, further preferably 4.5 MPa 1/2 or less, even more preferably 4.0 MPa 1/2 or less, and 3.5 MPa 1/2 or less. is particularly preferred. It is speculated that if R1 is 6.0 MPa 1/2 or less, the affinity of compound A with single-walled CNTs is improved, and compound A easily impregnates inside the bulk structure of single-walled CNTs. Layer CNTs can be well dispersed in the fluororubber.
  • the lower limit of the value of R1 is not particularly limited, but it is preferably 0.5 MPa 1/2 or more, more preferably 1.0 MPa 1/2 or more.
  • the distance R1 (MPa 1/2 ) of the Hansen solubility parameter between single-walled CNT and compound A can be calculated using the following formula (III).
  • R1 ⁇ 4 ⁇ ( ⁇ d3 ⁇ d2 ) 2 +( ⁇ p3 ⁇ p2 ) 2 +( ⁇ h3 ⁇ h2 ) 2 ⁇ 1/2
  • ⁇ d2 Dispersion term of compound A ⁇ d3 : Dispersion term of single-walled CNT ⁇ p2 : Polarity term of compound A ⁇ p3 : Polarity term of single-walled CNT ⁇ h2 : Hydrogen bond term of compound A ⁇ h3 : Single-walled CNT hydrogen bond term
  • the distance R2 of the Hansen solubility parameter between the compound A and the fluororubber must be larger than R1 as described above. If R2 is R1 or more, compound A does not excessively increase affinity with the fluororubber, and it is presumed that the inside of the CNT bulk structure is easily impregnated. can be well dispersed in
  • R2 is preferably 4.0 MPa 1/2 or more, more preferably 4.5 MPa 1/2 or more, and still more preferably more than 5.5 MPa 1/2 . It is more preferably 0 MPa 1/2 or more, particularly preferably 7.0 MPa 1/2 or more, preferably 16.0 MPa 1/2 or less, and preferably 9.0 MPa 1/2 or less. more preferred. If R2 is within the above range, the single-walled CNTs can be dispersed more favorably in the fluororubber.
  • the distance R2 of the Hansen solubility parameter between the fluororubber and the compound A can be calculated using the following formula (IV).
  • R2 ⁇ 4 ⁇ ( ⁇ d1 ⁇ d2 ) 2 +( ⁇ p1 ⁇ p2 ) 2 +( ⁇ h1 ⁇ h2 ) 2 ⁇ 1/2
  • ⁇ d1 Dispersion term of fluororubber
  • ⁇ d2 Dispersion term of compound A
  • ⁇ p1 Polarity term of fluororubber
  • ⁇ p2 Polarity term of compound A
  • ⁇ h1 Hydrogen bond term of fluororubber ⁇ h2 : Hydrogen bond term of compound A
  • Hansen solubility parameter The definition and calculation method of the Hansen solubility parameter are described in the following document. Charles M. Hansen, "Hansen Solubility Parameters: A Users Handbook", CRC Press, 2007.
  • Hansen solubility parameter can be easily estimated from the chemical structure by using computer software (Hansen Solubility Parameters in Practice (HSPiP)). Specifically, for example, using HSPiP version 3, the values are used for compounds registered in the database, and the estimated values are used for compounds that are not registered.
  • HSPiP Hanesen Solubility Parameters in Practice
  • the compound A is not particularly limited as long as it has a freezing point equal to or lower than the above-described value and satisfies the above-described conditions regarding the distance of the Hansen Solubility Parameter, and any organic compound can be used.
  • an ester compound having a cyclic hydrocarbon (a compound having a cyclic hydrocarbon and an ester group) is preferable, an ester compound having an aromatic ring is more preferable, and an ester compound having a benzene ring is still more preferable. Phenyl ester compounds are more preferred.
  • compounds having cyclic hydrocarbons include methyl p-toluate (methyl 4-methylbenzoate), methyl o-toluate (methyl 2-methylbenzoate), methyl benzoate, and benzoic acid.
  • benzoic acid ester compounds such as benzyl and phenyl benzoate; alkyl 3-phenylpropionates such as methyl 3-phenylpropionate; and ethyl cinnamate.
  • methyl o-toluate is particularly preferred.
  • compound A can be used individually by 1 type or in mixture of 2 or more types.
  • the amount of compound A used is not particularly limited, it should be 0.1 parts by mass or more per 100 parts by mass of the fluororubber used for preparing the masterbatch from the viewpoint of better dispersing the single-walled CNTs in the fluororubber. is preferably 1 part by mass or more, more preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more, preferably 60 parts by mass or less, and 40 parts by mass or less is more preferably 35 parts by mass or less, and particularly preferably 30 parts by mass or less.
  • the mixing of the single-walled CNT and the compound A is not particularly limited. Any mixing method such as application of A or spraying of compound A onto single-walled CNTs can be used. Above all, from the viewpoint of better dispersing the single-walled CNTs in the later-described dispersion treatment, it is preferable to mix the single-walled CNTs with the compound A by impregnating the single-walled CNTs with the compound A.
  • the time for which the compound A is impregnated into the single-walled CNTs can be any time, but from the viewpoint of dispersing the single-walled CNTs even better in the dispersion treatment described later, it is preferably at least 1 hour, and at least 10 hours. more preferred.
  • the temperature at which the single-walled CNTs are impregnated with the compound A is not particularly limited. Impregnation of single-walled CNTs with compound A is not particularly limited, but is usually performed under normal pressure (1 atm).
  • - Distributed processing - A dispersion treatment is applied to a composition containing the mixture obtained by mixing the single-walled CNTs and the compound A as described above and the fluororubber.
  • the composition may optionally contain multi-walled CNTs, reinforcing fillers, cross-linking agents and/or other components (excluding compound A). It is preferably added to a masterbatch.
  • the dispersion treatment is not particularly limited as long as the single-walled CNTs can be dispersed in the fluororubber, and any known dispersion treatment can be used.
  • Such dispersion treatment includes, for example, dispersion treatment by shear stress, dispersion treatment by collision energy, and dispersion treatment by which a cavitation effect is obtained.
  • Apparatuses that can be used for dispersion treatment using shear stress include a two-roll mill, a three-roll mill, a kneader, a rotor/stator type disperser, and the like.
  • Apparatuses that can be used for dispersion treatment by collision energy include bead mills, ball mills, and the like.
  • a jet mill, an ultrasonic disperser, and the like can be used as devices that can be used for the dispersion treatment to obtain the cavitation effect.
  • the conditions for the dispersion processing are not particularly limited, and can be set as appropriate within the range of normal dispersion conditions for the above-described apparatus, for example.
  • the masterbatch obtained in the above masterbatch preparation step may be used as it is as the fluororubber composition of the present invention, but in addition to single-walled CNTs and fluororubber, multi-layered CNTs, a cross-linking agent, and / or other components (
  • a fluororubber may be additionally added to the masterbatch.
  • kneading for example, a mixer, single-screw kneader, twin-screw kneader, roll, Brabender, extruder, or the like can be used. Kneading conditions can be appropriately adjusted.
  • the masterbatch and multi-layer CNT and/or reinforcing filler are first kneaded, and then the resulting mixture and cross-linking agent are mixed. is preferable from the viewpoint that ⁇ G * can be well controlled within the desired range.
  • the molded article of the present invention is formed using the fluororubber composition of the present invention containing the cross-linking agent described above. And since the molded article of the present invention is formed from the fluororubber composition of the present invention, it is excellent in extensibility at high temperatures.
  • the use of the molded article of the present invention is not particularly limited.
  • the molded article of the present invention can be suitably used, for example, as a sealing material for oil gas or as an engine peripheral member. Further, the shape of the molded article of the present invention can be appropriately set according to the application.
  • the molding method for obtaining a molded article by molding the fluororubber composition is not particularly limited, and any molding method such as injection molding, extrusion molding, press molding, roll molding, etc. may be used. can be done.
  • the obtained fluororubber composition was subjected to primary cross-linking at a temperature of 160° C. and a pressure of 10 MPa for 20 minutes. Then, it was heated in a gear oven at 232° C. for 2 hours for secondary crosslinking to obtain a crosslinked rubber sheet X (length: 150 mm, width: 150 mm, thickness: 2 mm). This crosslinked rubber sheet X was punched into a dumbbell test piece (JIS No. 3) to prepare a test piece X.
  • the fluororubber, the crosslinker, and the additive (acid acceptor) are mixed at the same mass ratio as the mass ratio of the fluororubber: crosslinker: additive (acid acceptor) contained in the above-described fluororubber composition. ) to prepare a test rubber composition. That is, the test rubber composition corresponds to a composition obtained by removing the CNTs and the reinforcing filler from the fluororubber composition containing the cross-linking agent. The resulting test rubber composition was subjected to primary cross-linking and secondary cross-linking in the same manner as in the preparation of the cross-linked rubber sheet X to obtain a cross-linked rubber sheet Y.
  • This crosslinked rubber sheet Y was punched into a dumbbell test piece (JIS No. 3) to prepare a test piece Y.
  • the tensile strength of the test piece Y was measured in the same manner as when the tensile strength T X of the test piece X was measured. This tensile strength was defined as T Y (MPa).
  • T Y MPa
  • T X tensile strength
  • T Y tensile strength
  • Example 1 ⁇ Preparation of single-walled CNT> SGCNTs ("ZEONANO SG101" manufactured by Nippon Zeon Co., Ltd.) were prepared as single-walled CNTs. In the measurement of SGCNTs with a Raman spectrophotometer, a radial breathing mode (RBM) spectrum was observed in the low wavenumber region of 100 to 300 cm ⁇ 1 characteristic of single-walled CNTs. Further, the BET specific surface area of SGCNT measured using a BET specific surface area meter (BELSORP (registered trademark)-max, manufactured by Bell Japan Co., Ltd.) was 1325 m 2 /g (unopened).
  • BELSORP registered trademark
  • the diameter and length of 100 randomly selected SGCNTs were measured using a transmission electron microscope, and the average diameter (Av) of the SGCNTs, the standard deviation of the diameter ( ⁇ ) and the average length were obtained.
  • the average diameter (Av) is 3.5 nm
  • the standard deviation ( ⁇ ) multiplied by 3 (3 ⁇ ) is 2.1 nm
  • their ratio (3 ⁇ /Av) is 0.6
  • the average The length was 450 ⁇ m.
  • the t-plot of SGCNT was measured using “BELSORP (registered trademark)-mini” manufactured by Bell Japan Co., Ltd., the t-plot was curved in a convex shape.
  • a masterbatch was prepared as follows by the preparation method (i) described above. To 1900 g of methyl ethyl ketone as a solvent, 100 g of a vinylidene fluoride rubber (FKM, manufactured by Chemours, product name "Viton GBL-600S”) as a fluororubber was added and stirred for 24 hours to dissolve the fluororubber.
  • FKM vinylidene fluoride rubber
  • a masterbatch which is a mixture of fluororubber and SGCNT.
  • a fluororubber composition obtained by excluding single-walled CNTs from a fluororubber composition containing a cross-linking agent vinylidene fluoride-based rubber as a fluororubber, zinc white as an acid acceptor, and triallyl as a cross-linking agent
  • a test rubber composition containing isocyanurate and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane in the same weight ratio as the fluororubber composition containing the cross-linking agent was prepared.
  • the test rubber composition was crosslinked under the conditions described above in the section ⁇ Tensile strength ratio> to prepare a crosslinked rubber sheet Y, and the tensile strength TY was measured. Then, the tensile strength ratio was calculated. Table 1 shows the tensile strength ratio results.
  • the distance R1 of the Hansen solubility parameter between the single-walled CNT (SGCNT) and the compound A (methyl o-toluate) is 6.0 MPa 1/2 or less, and the fluororubber (FKM) and the compound A (methyl o-toluate) ) was greater than the distance R1 of the Hansen solubility parameter.
  • FKM fluororubber
  • a fluororubber composition containing a cross-linking agent was obtained in the same manner as in Example 1 except that the masterbatch obtained above (fluororubber: 100 g, SGCNT: 4 g, the total amount of the masterbatch was adjusted to contain 4 g) was used. rice field.
  • This fluororubber composition was subjected to a dynamic viscoelasticity test to determine ⁇ G * and viscosity. Table 1 shows the results.
  • the crosslinked rubber sheet Y prepared in the same manner as in Example 1 was measured to measure the tensile strength TY . Then, the tensile strength ratio was calculated. Table 1 shows the tensile strength ratio results.
  • Example 3 ⁇ Preparation of single-walled CNT> SGCNTs similar to those in Example 1 were prepared.
  • a fluororubber composition was obtained. This fluororubber composition was subjected to a dynamic viscoelasticity test to determine ⁇ G * and viscosity. Table 1 shows the results.
  • the crosslinked rubber sheet Y prepared in the same manner as in Example 1 was measured to measure the tensile strength TY . Then, the tensile strength ratio was calculated. Table 1 shows the tensile strength ratio results.
  • Example 4 Single-walled CNTs were prepared in the same manner as in Example 3, except that silica (hydrophobic, manufactured by Evonik, product name "Aerosil (registered trademark) R972V”) was used instead of carbon black as the reinforcing filler. A fluororubber composition and a molded article were produced and various evaluations were performed. Table 1 shows the results.
  • Example 5 ⁇ Preparation of single-walled CNT> SGCNTs similar to those in Example 1 were prepared. ⁇ Preparation of fluororubber composition> [Preparation of masterbatch] A masterbatch, which is a mixture of fluororubber and SGCNT, was obtained in the same manner as in Example 1.
  • a fluororubber composition was obtained. This fluororubber composition was subjected to a dynamic viscoelasticity test to determine ⁇ G * and viscosity. Table 1 shows the results.
  • the crosslinked rubber sheet Y prepared in the same manner as in Example 1 was measured to measure the tensile strength TY . Then, the tensile strength ratio was calculated. Table 1 shows the tensile strength ratio results.
  • Example 6 In the same manner as in Example 5, except that 5 g of multi-layered CNT (manufactured by KUMHO, product name “K-nanos 100P”; BET specific surface area: 260 m 2 /g) was used instead of 30 g of carbon black as a reinforcing filler. Single-walled CNTs were prepared, fluororubber compositions and moldings were produced, and various evaluations were performed. Table 1 shows the results.
  • Example 7 ⁇ Preparation of CNT2> CNT2 was produced in the CNT synthesis process by a method of supplying raw material gas while continuously conveying a particulate catalyst support by rotating a screw. Specifically, one manufactured in the same manner as in Example 1 of International Publication No. 2021/172078 was used.
  • a masterbatch was obtained in the same manner as in Example 2 except that the above CNT2 was used as the single-walled CNT, a fluororubber composition and a molded body were produced, and various evaluations were performed. Table 1 shows the results.
  • a fluororubber composition containing a cross-linking agent was obtained in the same manner as in Example 1, except that the masterbatch obtained above was used. This fluororubber composition was subjected to a dynamic viscoelasticity test to determine ⁇ G * and viscosity. Table 1 shows the results.
  • a crosslinked rubber sheet Y prepared in the same manner as in Example 1 was measured, and the tensile strength TY was measured. Then, the tensile strength ratio was calculated. Table 1 shows the tensile strength ratio results.
  • Example 2 Single-walled CNTs were prepared in the same manner as in Example 1 except that the amount of single-walled CNTs was changed from 4 g to 2 g during [preparation of masterbatch], and a fluororubber composition and a molded article were produced, Various evaluations were performed. Table 1 shows the results.
  • This fluororubber composition was subjected to a dynamic viscoelasticity test to determine ⁇ G * and viscosity. Table 1 shows the results.
  • the crosslinked rubber sheet Y prepared in the same manner as in Example 1 was measured to measure the tensile strength TY . Then, the tensile strength ratio was calculated. Table 1 shows the tensile strength ratio results.
  • a molded article that contains fluororubber and single-walled carbon nanotubes and that can exhibit excellent extensibility at high temperatures, and a fluororubber composition that can form the molded article.

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Abstract

Le but de la présente invention est de fournir une nouvelle technique grâce à laquelle un objet façonné susceptible de présenter une excellente aptitude à l'étirage à des températures élevées peut être formé à l'aide d'un caoutchouc fluoré et de nanotubes de carbone (CNT) monocouches. La composition de caoutchouc fluoré selon la présente invention comprend un caoutchouc fluoré et des nanotubes de carbone. Les nanotubes de carbone comprennent des CNT monocouches. Cette composition de caoutchouc fluoré, dans un essai de viscoélasticité dynamique mené dans les conditions de mesure correspondant à une fréquence de 1 Hz et à une température de 40 °C, présente un γG*, tel que calculé par l'équation (I) ci-après, de 20 ou plus. Équation (I) : γG*=G* L/G* H (G* L (kPa) étant le module complexe à une déformation dynamique de 0,1 % et G* H (kPa) étant le module complexe à une déformation dynamique de 630 %).
PCT/JP2022/036854 2021-09-30 2022-09-30 Composition de caoutchouc fluoré et objet façonné WO2023054716A1 (fr)

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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
WO2021172555A1 (fr) * 2020-02-26 2021-09-02 日本ゼオン株式会社 Composition d'élastomère, son procédé de production, substance réticulée et corps moulé

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