WO2020175331A1 - 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 - Google Patents

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 Download PDF

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WO2020175331A1
WO2020175331A1 PCT/JP2020/006896 JP2020006896W WO2020175331A1 WO 2020175331 A1 WO2020175331 A1 WO 2020175331A1 JP 2020006896 W JP2020006896 W JP 2020006896W WO 2020175331 A1 WO2020175331 A1 WO 2020175331A1
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fluorine
containing elastomer
fibrous carbon
producing
average diameter
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Japanese (ja)
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慶久 武山
美信 山口
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Zeon Corp
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Zeon Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • 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

  • Fluorine-containing elastomer composition Fluorine-containing elastomer composition, fluororubber molded product, method for producing fluorine-containing elastomer solution, and method for producing fluorine-containing elastomer composition
  • the present invention relates to a fluoroelastomer composition, a fluororubber molded article, a method for producing a fluoroelastomer solution, and a method for producing a fluoroelastomer composition.
  • Fluorine rubber is widely used in various fields such as the automobile industry, the semiconductor industry, and the chemical industry because it has excellent chemical resistance, oil resistance, heat resistance, and the like.
  • a carbon nanotube having a predetermined average diameter, a predetermined average particle diameter and a mouthpiece are used for a fluoroelastomer (a ternary fluororubber).
  • a fluoroelastomer a ternary fluororubber.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2 0 1 6 _ 1 0 8 4 7 6
  • fluororubber moldings formed using a material containing fluororubber have not only heat resistance but also tensile strength and elongation in a high temperature environment exceeding 100 ° C, for example. High and durable due to a good balance between the two ⁇ 2020/175331 2 ⁇ (:171? 2020 /006896
  • an object of the present invention is to provide a technique capable of forming a fluororubber molded article having high tensile strength and high elongation in a high temperature environment.
  • the present inventors have conducted extensive studies to achieve the above object. Then, the present inventors have found that if a composition containing a fibrous carbon nanostructure containing a single-wall carbon nanotube bundle having a predetermined average diameter (mouth) in a predetermined ratio with respect to a fluoroelastomer, The inventors have found that a fluororubber molded article having high tensile strength and high elongation in a high temperature environment can be formed, and completed the present invention.
  • a fluorine-containing elastomer composition of the present invention is a fiber containing a fluorine-containing elastomer and a single-layer carbon nanotube.
  • the fibrous carbon nanostructure includes a single-wall force-bon nanotube bundle that is a bundle of the fibrous carbon nanostructure containing the single-wall force-carbon nanotubes.
  • the average diameter of the carbon nanotube bundle (the mouth is characterized by 20 nm or more and 600 n or less.
  • a single-wall force-bonded carbon nanotube bundle with a given average diameter (the mouth is By using the fluoroelastomer composition containing the fibrous carbon nanostructure containing at a predetermined ratio, it is possible to form a fluororubber molded article having high tensile strength and high elongation under high temperature environment. ..
  • the average diameter of the single-wall carbon nanotube bundle ((2) The average diameter of the fibrous carbon nanostructure containing the single-wall carbon nanotubes ( Ratio to (Hereafter, "ratio Is the average diameter of single-wall carbon nanotube bundles (mouth 8 ), average diameter of fibrous carbon nanostructures Ratio to May be abbreviated as "”. ) Is preferably 5 or more and 200 or less.
  • the fluororubber molded article formed by using the fluoroelastomer composition of the present invention should maintain a good balance of high tensile strength and high elongation in a high temperature environment.
  • the “average diameter of fibrous carbon nanostructures ()” is the diameter (outer diameter) of 100 fibrous carbon nanostructures randomly selected using a transmission electron microscope. It can be determined by measuring.
  • the fibrous carbon nanostructure containing the single-walled carbon nanotubes has a 1-plot obtained from an adsorption isotherm that has a convex shape upward. Is preferred.
  • the flexibility of the fluororubber molded article formed using the fluoroelastomer composition of the present invention can be improved. Can be improved.
  • the fibrous carbon nanostructure containing the single-walled carbon nanotubes has a Mitsumi specific surface area of 600 2 /9 or more. .. If ear Ding specific surface area of the fibrous carbon nanostructures comprising the monolayer force over carbon nanotubes 6 0 0_Rei_1 2/9 or more, fluororubber formed using a fluorine-containing-containing elastomer composition of the present invention The heat resistance of the molded product can be improved.
  • the “specific surface area of Mitsumi” means the nitrogen adsorption specific surface area measured by the method of Mitsumi. ⁇ 2020/175 331 4 ⁇ (: 171? 2020 /006896
  • the fluorine-containing elastomer composition of the present invention may further contain a crosslinking agent.
  • the fluorine-containing elastomer composition of the present invention preferably further contains carbon black.
  • carbon black By further containing carbon black, it is possible to improve the tensile strength of the fluororubber molded article formed by using the fluoroelastomer composition of the present invention while sufficiently ensuring high elongation in a high temperature environment. ..
  • the present invention has an object to advantageously solve the above-mentioned problems, and the fluororubber molded article of the present invention is formed by molding any one of the above-mentioned fluorine-containing elastomer compositions. It is characterized by being a fluororubber molded product.
  • the fluororubber molded article obtained by molding the above-mentioned fluoroelastomer composition has high tensile strength and high elongation under a high temperature environment, and thus can be suitably used for various applications.
  • the present invention has an object to advantageously solve the above-mentioned problems, and a method for producing a fluorine-containing elastomer solution of the present invention is: a fluorine-containing elastomer; A method for producing a fluorine-containing elastomer solution containing: a fibrous carbon nanostructure containing: a fibrous carbon nanostructure containing the fluorine-containing elastomer, a solvent, and the single-layer carbon nanotube.
  • It is a dispersion liquid in which fibrous carbon nanostructures containing carbon nanotubes are dispersed, and the dispersion liquid is a bundle of fibrous carbon nanostructures containing the above-mentioned single-layer carbon nanotubes. Including a carbon nanotube bundle, and the single-layer force-average diameter of the carbon nanotube bundle (mouth 8 ) It is characterized by the following.
  • the fluorine-containing elastomer of the present invention can be obtained by including the dispersion step of dispersing the fluorine-containing elastomer, the solvent, and the fibrous carbon nanostructure containing the single-layer carbon nanotubes using the dispersion medium.
  • the dispersion step of dispersing the fluorine-containing elastomer, the solvent, and the fibrous carbon nanostructure containing the single-layer carbon nanotubes using the dispersion medium.
  • a possible fluorine-containing elastomer solution can be efficiently produced.
  • the dispersing step includes a first step of dissolving the fluorinated elastomer in the solvent to obtain the fluorinated elastomer-dissolved solution, It is preferable that the method further includes a second step of performing the dispersion treatment on the fibrous single-layer nanostructure including the fluoroelastomer dissolving solution and the single-layer force-carbon nanotube.
  • the fluorine-containing elastomer solution can be produced more efficiently by the dispersion step including the step of.
  • the dispersion medium satisfies at least one of the following (1) and (2).
  • the dispersion medium has a Vickers hardness of 600 or more and 1500 or less.
  • the filling factor of the dispersion medium is 40% by volume or more and 70% by volume or less.
  • at least the Vickers hardness of the dispersion medium is 600 or more and 1500 or less, or
  • the filling rate is 40% by volume or more and 70% by volume or less, the fluorine-containing elastomer solution can be more efficiently produced.
  • the “Pickers hardness of the dispersion medium” and the “filling ratio of the dispersion medium” can be measured according to the methods described in the examples of this specification.
  • the dispersion medium has an average diameter of 0.1.
  • the following is preferable. Average diameter is 0.1
  • the “average diameter of the dispersion medium” is the term “implemented in this specification”. ⁇ 2020/175 331 6 ⁇ (: 171-1? 2020 /006896
  • the present invention has an object to advantageously solve the above problems, and a method for producing a fluorine-containing elastomer composition of the present invention is a method for producing any of the above fluorine-containing elastomer solutions.
  • the method is characterized by including a removal step of removing the solvent from the fluorine-containing elastomer solution obtained by.
  • the removal step of removing the solvent from the fluoroelastomer solution obtained by the method for producing a fluoroelastomer solution of the present invention the tensile strength in a high temperature environment is high and the elongation is high.
  • a fluoroelastomer composition that can be suitably used for producing a fluororubber molded article can be efficiently produced. Effect of the invention
  • a fluoroelastomer composition capable of forming a fluororubber molded article having high tensile strength and high elongation under a high temperature environment, and a fluororubber using the fluoroelastomer composition A molded body can be provided. Further, according to the present invention, it is possible to provide a method for producing a fluoroelastomer solution which can be used for producing a fluororubber molded article having a high tensile strength in a high temperature environment and a high elongation.
  • the fluorine-containing elastomer composition of the present invention can be used, for example, when forming the fluororubber molded article of the present invention. Further, the fluorine-containing elastomer composition of the present invention can be manufactured by using the method of manufacturing the fluorine-containing elastomer composition of the present invention. The method for producing a fluorine-containing elastomer composition of the present invention can be produced using the fluorine-containing elastomer solution obtained by the method for producing a fluorine-containing elastomer solution of the present invention.
  • the fluoroelastomer composition of the present invention contains a fluoroelastomer and a fibrous carbon nanostructure containing a single-layer carbon nanotube, and optionally further contains an additive such as a crosslinking agent or carbon black. obtain.
  • an additive such as a crosslinking agent or carbon black.
  • the fibrous carbon nanostructure a fibrous carbon nanostructure containing a single-walled carbon nanotube bundle having a predetermined average diameter (mouth) is prepared. It is used in a predetermined ratio with respect to.
  • the fluoroelastomer is not particularly limited, and known fluororubber can be used.
  • the fluorine-containing elastomer include vinylidene fluoride rubber ([ ⁇ 1 ⁇ /1), tetrafluoroethylene-propylene rubber (Miwa 1 ⁇ /1), tetrafluoroethylene-perme Fluoromethyl vinyl ether-based rubber ([ ⁇ 1 ⁇ /1]), tetrafluoroethylene-based rubber (Tingmi), etc. These may be used alone or in combination of two or more.
  • fluorine-containing elastomer vinylidene fluoride rubber ([ ⁇ 1 ⁇ /1) and tetrafluoroethylene-propylene rubber (Mitsumi 1 ⁇ /1) are preferable. Vinylidene rubber ([ ⁇ 1 ⁇ /1) is more preferable.
  • vinylidene fluoride rubber ([ ⁇ 1 ⁇ /1] is a fluorine-based rubber that has vinylidene fluoride as a main component and is excellent in heat resistance, oil resistance, chemical resistance, solvent resistance, processability, etc. It is rubber. [ ⁇ 1 ⁇ /1 is not particularly limited, but for example, a binary copolymer of vinylidene fluoride and hexafluoropropylene, a ternary copolymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene can be used.
  • Examples thereof include a copolymer and a quaternary copolymer composed of vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, and a vulcanization site monomer.
  • Market products include, for example, “Byton (registered trademark)” from Kemmers Co., Ltd. and “Daiel (registered trademark) ⁇ ” from Daikinye Industry Co., Ltd.
  • a quaternary copolymer composed of and a vulcanized site monomer is preferable.
  • the quaternary copolymer is available, for example, as a commercially available product “Biton Omi 1_ _ 2 0 0 3” (manufactured by Kemers Co., Ltd.).
  • vinylidene fluoride as a main component means that the vinylidene fluoride unit contained in the vinylidene fluoride-based rubber is 50% by mass or more, preferably more than 50% by mass, and more preferably Means 100% by mass
  • the tetrafluoroethylene-propylene rubber (Min IV!) is based on an alternating copolymer of tetrafluoroethylene and propylene, and has heat resistance, chemical resistance, polar solvent resistance, steam resistance, etc. It is an excellent fluororubber.
  • the number 1 ⁇ /1 for example, a binary copolymer of tetrafluoroethylene and propylene, a terpolymer of tetrafluoroethylene, propylene, and vinylidene fluoride, and tetrafluoroethylene Examples thereof include terpolymers composed of ethylene, propylene, and a crosslinking point monomer.
  • Examples of commercially available binary copolymers composed of tetrafluoroethylene and propylene include "Aflas (registered trademark) 100" and “Aflas 150" of 8° ⁇ Co., Ltd., for example.
  • Commercially available terpolymers composed of tetrafluoroethylene, propylene, and vinylidene fluoride include, for example, 0(3) "Aflas 200". Tetrafluoroethylene, propylene, and bridges.
  • Examples of commercially available terpolymers containing point monomers include “Aflas 300” from 800,000 type company.
  • the content ratio of the fluorine-containing elastomer in the fluorine-containing elastomer composition is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. It is more preferable that the content is 92% by mass or less, more preferably 90% by mass or less, and further preferably 86% by mass or less. If the content ratio of the fluorine-containing elastomer in the fluorine-containing elastomer composition is within the above range, a fluorine-containing elastomer formed by using the fluorine-containing elastomer composition is ⁇ 2020/175 331 9 ⁇ (: 171-1? 2020 /006896
  • fibrous carbon nanostructures include cylindrical carbon nanostructures such as force carbon nanotubes (hereinafter, also referred to as "0 ⁇ 1") and carbon six-membered ring networks.
  • a non-cylindrical carbon nanostructure such as a carbon nanostructure formed in a flat tubular shape, may be mentioned.
  • the fibrous carbon nanostructure containing a single layer 0 bundle having a predetermined average diameter (mouth 8 ) is used in a predetermined ratio with respect to the fluorine-containing elastomer.
  • the above-mentioned single layer 0 1 ⁇ 1 bundle is a bundle of fibrous carbon nanostructures including 0 single layer, and specifically, the single layer 0 1 ⁇ 1 bundle includes fibrous carbon nanostructures.
  • the structures are aggregated by the Van der Waalsker between the fibrous carbon nanostructures and formed into a bundle.
  • the tensile strength in a high temperature environment can be improved. It is possible to obtain a fluororubber elastomer composition capable of forming a fluororubber molded product having a high elongation and a high elongation.
  • the content ratio of the fibrous carbon nanostructure in the fluoroelastomer composition must be 0.1 part by mass or more per 100 parts by mass of the fluoroelastomer, and 1 part by mass. It is preferably not less than 6 parts by mass, preferably less than 6 parts by mass, and preferably not more than 5 parts by mass.
  • the fluororubber molded product formed by using the fluoroelastomer composition has a high high temperature environment. Both tensile strength and high elongation can be sufficiently ensured.
  • the content ratio of the fibrous carbon nanostructure is less than 6 parts by mass per 100 parts by mass of the fluorine-containing elastomer, the elongation of the fluororubber molded product formed by using the fluorine-containing elastomer composition of the present invention Can be suppressed.
  • the average diameter of the single-layer 0-bundle contained in the fibrous carbon nanostructure is ⁇ 2020/175331 10 ⁇ (: 171-1? 2020 /006896
  • Single layer ⁇ 1 ⁇ 1 bundle average diameter When the value is at least the above lower limit, the fluororubber formed by using the fluorine-containing elastomer composition of the present invention exhibits good elongation at room temperature. Further, the average diameter of the single layer 0 ⁇ 1 bundle (when 0 is not more than the above upper limit, good flexibility is maintained in the fluororubber molded article formed using the fluoroelastomer composition of the present invention. Be done.
  • a single layer ⁇ ! Average diameter (ratio to the average diameter () of the fibrous carbon nanostructure including the single layer ⁇ ! Is preferably 5 or more, more preferably 10 or more, still more preferably 30 or more, preferably 200 or less, more preferably 150 or less. , 100 or less is more preferable.
  • the average diameter () of the fibrous carbon nanostructure containing the single layer ⁇ 1 bundle is within the above range, in the fluororubber molded article formed using the fluoroelastomer composition of the present invention, Flexibility is improved.
  • the fibrous carbon nanostructure is It is a fibrous carbon nanostructure including a dent and is not particularly limited as long as it is a fibrous carbon nanostructure including a single layer 0 bunching having the above-mentioned predetermined average diameter (mouth). Therefore, the fibrous carbon nanostructure May further include, for example, a multi-layer 0 ⁇ 1 unit, or may further include a fibrous carbon structure other than O ⁇ 1 unit. ⁇ 2020/175 331 1 1 ⁇ (: 171? 2020 /006896
  • the content ratio of the single layer 0 1 ⁇ 1 is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. More preferable.
  • the I-plot obtained from the adsorption isotherm has a convex shape. If the 1- plot obtained from the adsorption isotherm is a fibrous carbon nanostructure showing a convex shape, the flexibility of the fluororubber molded article formed by using the fluoroelastomer composition of the present invention can be improved. Can be improved.
  • the fibrous carbon nanostructure is not subjected to 0 opening treatment and the plot has a convex shape upward.
  • adsorption is a phenomenon in which gas molecules are removed from a gas phase to a solid surface, and is classified into physical adsorption and chemical adsorption based on the cause. Then, in the nitrogen gas adsorption method used to obtain 1-plot, physical adsorption is used. Generally, if the adsorption temperature is constant, the number of nitrogen gas molecules adsorbed on the fibrous carbon nanostructure increases as the pressure increases.
  • the abscissa is the relative pressure (the ratio between adsorption equilibrium pressure? And the saturated vapor pressure? ⁇ ), and the ordinate is the plot of nitrogen gas adsorption amount called “isothermal line”. The case of measuring the gas adsorption amount is called the “adsorption isotherm", and the case of measuring the nitrogen gas adsorption amount while reducing the pressure is called the "desorption isotherm”.
  • the plot is obtained by converting the relative pressure into the average thickness 1 (nm) of the nitrogen gas adsorption layer in the adsorption isotherm measured by the nitrogen gas adsorption method. That is, from the known standard isotherm obtained by plotting the average thickness 1 of the nitrogen gas adsorption layer with respect to the relative pressure / 0, the average thickness of the nitrogen gas adsorption layer corresponding to the relative pressure is obtained and the above conversion is performed. , Plots of fibrous carbon nanostructures can be obtained (( ⁇ 806 "et al. 1: _ plot method)).
  • the growth of the nitrogen gas adsorption layer was as follows. ⁇ 2020/175 331 12 ⁇ (: 171-1? 2020 /006896
  • the 1-plot of the fibrous carbon nanostructure including the single layer 0 has a position where the plot is located on a straight line passing through the origin in the region where the average thickness 1 of the nitrogen gas adsorption layer is small.
  • 1: becomes large it is preferable that the plot is located at a position displaced downward from the straight line and has a convex shape upward.
  • the 1:-shape of the plot indicates that the ratio of the internal specific surface area to the total specific surface area of the fibrous carbon nanostructure is large and many openings are formed in the fibrous carbon nanostructure.
  • the bending point of the I-plot of the fibrous carbon nanostructure including the single layer ⁇ ! ⁇ 1 unit is preferably in the range that satisfies 0.2 £ I ⁇ £1.5. More preferably, it is within a range satisfying 0.45 £ I (nm) £ 1.5, and 0.55 £ I More preferably, it is in the range satisfying £ 1.0. 1:—When the position of the bending point of the plot is within the above range, the characteristics of the fibrous carbon nanostructure are further improved.
  • the “position of the bending point” is the intersection of the approximate straight line of the above process (1) and the approximate straight line of the above process (3) in the plot.
  • the fibrous carbon nanostructure including the single layer 0 is The ratio of the internal specific surface area 3 2 to the total specific surface area 3 1 obtained from the plot (3 2/3 1) is ⁇ .
  • 3 2 is preferably 3 0_Rei ⁇ / 9 or more 5 4 0 2/9 or less.
  • the total specific surface area 31 and the internal specific surface area 32 of the fibrous carbon nanostructure including the claw can be obtained from the 1:_ plot. Specifically, first, the total specific surface area 31 can be obtained from the slope of the approximation line in the process of (1), and the external specific surface area 33 can be obtained from the slope of the approximation line in the process of (3). Then, the internal specific surface area 32 can be calculated by subtracting the external specific surface area 33 from the total specific surface area 31.
  • the surface area 32 is calculated using, for example, a commercially available measuring device.
  • a ratio (3/8) of a value (3 £7) obtained by multiplying the standard deviation () of the diameter by 3 with respect to the average diameter (8) is used. It is preferred to use fibrous carbon nanostructures with V) greater than 0.20 and less than 0.80, more preferably 3 £7 /8 with fibrous carbon nanostructures greater than 0.25. Preferably, it is more preferable to use a fibrous carbon nanostructure having 3/V of less than 0.70. If a fibrous carbon nanostructure containing a single layer 0 1 ⁇ 1 of 3 £7/8 is more than 0.20 and less than 0.80, it was formed using the fluorine-containing elastomer composition of the present invention.
  • the performance of the fluororubber molded article can be improved.
  • the “standard deviation of the diameter of fibrous carbon nanostructures (£7: sample standard deviation)” is the diameter of 100 fibrous carbon nanostructures randomly selected using a transmission electron microscope ( The outer diameter) can be measured and obtained.
  • It may be adjusted by changing the production method or production conditions of the carbon nanostructures, or may be adjusted by combining a plurality of fibrous carbon nanostructures obtained by different production methods.
  • the fibrous carbon nanostructure containing 0 single layers must have a ratio of ⁇ band peak intensity to robo band peak intensity in Raman spectrum ( ⁇ / 0 ratio) of 1 or more and 20 or less. Is preferred.
  • the performance of the fluororubber molded article formed using the fluoroelastomer composition of the present invention can be further improved.
  • the ratio may be 2 or more, 3 or more, 10 or less, or 5 or less.
  • the average length of the fibrous carbon nanostructure at the time of synthesis is preferably 100 or more. Note that the longer the length of the fibrous carbon nanostructure during synthesis, the more easily the fibrous carbon nanostructure is damaged, such as breakage or cutting, during dispersion, so the average length of the structure during synthesis is 5 It is preferably 0 0 0 0 1 or less.
  • the aspect ratio (length/diameter) of the fibrous carbon nanostructure including the claw is preferably more than 10.
  • the aspect ratio of the fibrous carbon nanostructures was obtained by measuring the diameter and length of 100 randomly selected fibrous carbon nanostructures using a transmission electron microscope. It can be obtained by calculating the average value of the ratio (length/diameter) to the.
  • the specific surface area of the fibrous carbon nanostructure including the single layer 0 is 60
  • the specific surface area of the fibrous carbon nanostructure including the single layer 0 1 ⁇ 1 is 60 2 /9 or more, the fluororubber formed by using the fluorine-containing elastomer composition of the present invention The heat resistance of the molded product can be improved.
  • the specific surface area of the fibrous carbon nanostructure including the single-layer ⁇ 1 is less than 250 0 2 /9, ⁇ 0 2020/175 331 15 ⁇ (: 17 2020 /006896
  • a fluororubber molded article formed using a fluoroelastomer composition has a better balance of both high tensile strength and high elongation in a high temperature environment.
  • the fibrous carbon nanostructure including the single layer 0 having the above-mentioned properties is, for example, a raw material compound and a carrier gas on a base material having a catalyst layer for producing carbon nanotubes on its surface.
  • the catalyst layer In the method of dramatically improving the catalytic activity of the catalyst (super-growth method; see International Publication No. WO 206/011655), the formation of the catalyst layer on the surface of the base material is performed by a wet process. By doing so, it is possible to manufacture efficiently.
  • the force-bonded carbon nanotubes obtained by the super growth method may be referred to as "3,001 ⁇ 1".
  • the fibrous carbon nanostructure including the single layer ⁇ 1 pcs produced by the super growth method may be composed of only 3 ⁇ 1 pcs, or It may be composed of ⁇ 1 unit and a non-cylindrical carbon nanostructure.
  • a fibrous carbon nanostructure containing a single layer ⁇ ! ⁇ 1 unit includes a single-layer or multi-layered flat tubular carbon that has a tape-shaped portion with inner walls close to or bonded to each other over the entire length.
  • a nano structure hereinafter, also referred to as “Graph Ennano Tape (0 1 ⁇ 1)” may be included.
  • the fibrous carbon nanostructure including the single layer 0 obtained by the above method is formed into a bundle by aggregation of the fibrous carbon nanostructure due to Van der Waalsca between the fibrous carbon nanostructures. It contains a bundle of fibrous carbon nanostructures containing formed monolayers. Therefore, if the fibrous carbon nanostructure obtained by the above method is subjected to a dispersion treatment by an arbitrary method, the bundle of fibrous carbon nanostructures is unwoven, and the above-mentioned predetermined average diameter (single layer having a mouth is formed. You can get a bundle of 1!
  • the known additives such as a cross-linking agent, a cross-linking aid, an antioxidant, and a reinforcing material can be used without particular limitation.
  • a dispersant may be used for the purpose of suppressing excessive aggregation of the fibrous carbon nanostructure, but the fluorine-containing elastomer composition of the present invention contains the dispersant substantially. It is preferable that it is not included. By containing substantially no dispersant, a fluororubber molded article having higher tensile strength under a high temperature environment can be obtained by using the fluoroelastomer composition of the present invention. “Substantially free of” means that it is not actively compounded unless it is inevitably mixed.
  • the cross-linking agent is not particularly limited, and a known cross-linking agent capable of cross-linking the fluorine-containing elastomer contained in the fluorine-containing elastomer composition can be used. More specifically, as the cross-linking agent, for example, sulfur, 2,5-dimethyl-2,5-di(1:_pentylperoxy)hexane-based cross-linking agent such as hexane, triallyl isocyanurate, etc. may be used. You can
  • crosslinking aid is not particularly limited and, for example, zinc white can be used.
  • the antioxidant is not particularly limited, and an amine-based antioxidant, an imidazole-based antioxidant, or the like can be used.
  • the reinforcing material is not particularly limited, and carbon black, silica, or the like can be used.
  • examples of the force-black include furnace black, acetylene black, thermal black, channel black and graphite.
  • additives may be used alone or in combination of two or more.
  • the amount of the additive compounded may be any amount as long as the desired effect is not impaired.
  • the fluorine-containing elastomer composition comprises a fluorine-containing elastomer, a predetermined average diameter (a fibrous carbon nanostructure including a single layer 0 bundle having a mouth, and an additive as an optional component). It can be prepared by mixing or kneading at a ratio of.
  • the fluorine-containing elastomer composition is not particularly limited, and includes, for example, a fluorine-containing elastomer and a fibrous carbon nanostructure containing a single-layer circular bundle having a predetermined average diameter (mouth). It is possible to prepare the mixture by mixing the obtained mixture with the additive which is an optional component.
  • Preparation of a mixture with fibrous carbon nanostructures containing !1 bundles includes, for example, fibrous carbon nanostructures containing a single average layer of a fluorine-containing elastomer
  • the mixture can be carried out by using any mixing method that can disperse the body, specifically, the mixture is not particularly limited, and may be, for example, a fluorine-containing elastomer prepared by dissolving a fluorine-containing elastomer in a solvent.
  • the obtained dispersion liquid is used as a solvent or a dispersion medium.
  • the solvent or dispersion medium can be removed by, for example, a coagulation method, a casting method or a drying method.
  • the mixture and the additive can be kneaded by using, for example, a mixer, a single-screw kneader, a twin-screw kneader, a throat, a Brabender, an extruder or the like.
  • the fluorine-containing elastomer composition of the invention is preferably produced by using the fluorine-containing elastomer solution obtained by the method for producing a fluorine-containing elastomer solution of the present invention described below.
  • the method for producing a fluorine-containing elastomer solution of the present invention is a method for producing a fluorine-containing elastomer solution containing a fluorine-containing elastomer and a fibrous carbon nanostructure containing a single layer ⁇ !
  • the method for producing a fluorine-containing elastomer solution of the present invention comprises: a fluorine-containing elastomer; a solvent; And a fibrous carbon nanostructure including a knuckle are dispersed using a dispersion medium to obtain a dispersion.
  • the obtained dispersion liquid is a dispersion liquid in which the fibrous carbon nanostructure containing the monolayer 0 ! ⁇ ] is dispersed in the fluorine-containing elastomer dissolving solution obtained by dissolving the fluorine-containing elastomer in the solvent.
  • the dispersion includes a single layer ⁇ 1 ⁇ 1 Chotaba a bundle of the fibrous carbon nanostructures comprising Ding, and the average diameter of the single layer Rei_1 ⁇ 1 Chotaba ( ⁇ 6) 2 0 n 01 or more 6 0 It is less than 0 n 01.
  • the average straight diameter of the single layer ⁇ 1 ⁇ 1 bundle (the mouth is preferably not less than 50 n, more preferably not less than 100 n, preferably not more than 500 n, It is more preferably 400 n or less.
  • the solvent used in the method for producing a fluoroelastomer solution of the present invention is not particularly limited as long as it can dissolve the fluoroelastomer.
  • examples of such solvent include ketones such as methyl ethyl ketone and acetone, polar solvents such as ethers such as tetrahydrofuran, and the like. These solvents may be used alone or in combination of two or more at any ratio.
  • the concentration of the fluorine-containing elastomer in the solution containing the fluorine-containing elastomer obtained by dissolving the fluorine-containing elastomer in a solvent is not particularly limited, but the monolayer ⁇ 1 ⁇ 1 bundle is uniformly dispersed. From the viewpoint, the concentration of the fluoroelastomer in the fluoroelastomer solution is preferably 50% by mass or more, 6 ⁇ 2020/175 331 19 ⁇ (:171? 2020 /006896
  • the content is more preferably 0% by mass or more, preferably 92% by mass or less, and more preferably 90% by mass or less.
  • the dispersion step it is preferable to perform the dispersion treatment without using a dispersant.
  • a dispersant By not using a dispersant, it is possible to obtain a fluorine-containing elastomer solution that can be suitably used when molding a fluororubber molded article having a higher tensile strength in a high temperature environment.
  • the dispersion treatment using the dispersion medium can be suitably performed by using a known wet media dispersion device such as a bead mill.
  • the material forming the dispersion medium is not particularly limited, and examples thereof include glass, alumina, zircon (zirconia-silica ceramics), zirconia, and steel.
  • the dispersion step includes a first step of dissolving the fluoroelastomer in the solvent to obtain a fluoroelastomer solution. It is preferable that the method further comprises a second step of performing the above dispersion treatment on the fibrous carbon nanostructure including the fluoroelastomer solution and the monolayer 0 1 ⁇ 1.
  • the fibrous carbon nanostructure including the dents in an amount of 0.1 part by mass or more, more preferably 0.5 part by mass or more, preferably 6 parts by mass or less, and 4 parts by mass or less. Is more preferable. If the amount of the fibrous carbon nanostructure including the single layer 0 1 ⁇ 1 is within the above range, the bundle of the fibrous carbon nanostructure is well unwoven in the dispersing step, and the predetermined average diameter ( It is possible to efficiently produce a dispersion liquid containing a single-layer 0-bundle having a mouth.
  • the dispersion obtained in the dispersion step may be used as it is as the fluorine-containing elastomer solution of the present invention, or may be optionally mixed with, for example, the above-mentioned additives and used as a fluorine-containing elastomer solution. You may.
  • the distributed media used in the distributed processing are less than the following (1) and (2). ⁇ 2020/175 331 20 ⁇ (:171? 2020 /006896
  • the dispersion medium satisfies at least one of the following (1) and (2), the fluorine-containing elastomer solution can be produced more efficiently.
  • Dispersion media filling rate is 40% or more and 70% or less by volume.
  • the Pickers hardness of the dispersion medium used in the dispersion treatment is preferably 600 or more, more preferably 800 or more, and further preferably 100 or more. It is preferably 150 or less, more preferably 1300 or less.
  • the filling rate of the dispersion medium is preferably 40% by volume or more, more preferably 50% by volume or more, preferably 70% by volume or less, and 60% by volume or less. It is more preferable.
  • the average diameter of the dispersion media is Or more, more preferably 0.30!! or more, more preferably 10!!! or less, 0. The following is more preferable.
  • the average diameter of the dispersion medium is within the above range, the fluorine-containing elastomer solution can be produced more efficiently.
  • the method for producing a fluorine-containing elastomer composition of the present invention is a method for obtaining a fluorine-containing elastomer composition by removing a solvent from the fluorine-containing elastomer solution obtained by the method for producing a fluorine-containing elastomer solution. ..
  • a fluoroelastomer composition that can be suitably used for producing a fluororubber molded article having high tensile strength in a high temperature environment and high elongation can be efficiently prepared. Can be manufactured.
  • the method of removing the solvent from the fluorine-containing elastomer solution is not particularly limited, and, for example, a drying method can be used. ⁇ 2020/175 331 21 ⁇ (: 171? 2020 /006896
  • drying method known drying methods such as spray drying, vacuum drying, reduced pressure drying, and drying by circulating an inert gas can be used.
  • the mixture obtained by removing the solvent may be used as it is as the fluorine-containing elastomer composition of the present invention, or optionally, for example, the above-mentioned additives are mixed or kneaded to form a fluorine-containing elastomer composition. It may be used as an elastomer composition.
  • the fluororubber molded article of the present invention can be obtained by molding the fluoroelastomer composition of the present invention into a desired shape.
  • the fluororubber molded article can be formed, for example, by introducing the fluoroelastomer composition of the present invention into a mold and optionally crosslinking it.
  • the fluororubber molded article formed by using the fluoroelastomer composition of the present invention contains the components derived from the components contained in the fluoroelastomer composition in the same ratio as that of the fluoroelastomer composition. To do.
  • the fluoroelastomer composition of the present invention contains a crosslinking agent
  • the fluoroelastomer composition when the fluoroelastomer composition contains a crosslinking agent, the fluoroelastomer composition has a crosslinked fluoroelastomer and a predetermined average diameter (a single layer ⁇ 1 having a mouth).
  • ⁇ 1 Contains a fibrous carbon nanostructure containing a bundle in a predetermined ratio, and optionally further contains an additive.
  • the shape of the fluororubber molded article of the present invention may be any shape depending on the application, and the shape of the fluororubber molded article may be, for example, an annular shape, a tubular shape, a hollow disc shape, or a sheet shape. It can be belt-shaped.
  • the fluororubber molded article of the present invention comprises a crosslinked product obtained by crosslinking the fluoroelastomer composition of the present invention
  • the crosslinked product preferably has the following physical properties.
  • the crosslinked product preferably has a tensile strength of 6 IV! 3 or higher, more preferably 8 ⁇ 9 a or higher, under an environment at a temperature of 200° IV!
  • the crosslinked product has an elongation of 70% or more in an environment of a temperature of 200 °C. ⁇ 2020/175 331 22 ⁇ (: 171? 2020 /006896
  • the cross-linked product has a tensile product of preferably 600 or more, more preferably 70 or more, and further preferably 800 or more under an environment of a temperature of 200 °. It is more preferable that it is, and it is particularly preferable that it is 900 or more.
  • the breaking energy of the crosslinked product becomes sufficiently high, and thus the crosslinked product can be suitably used for various purposes.
  • the "tensile strength” and “elongation” of the crosslinked product can be measured according to the methods described in Examples of the present specification.
  • the “tensile product” of the crosslinked product can be calculated by the product of "tensile strength” and "elongation”.
  • the fluoroelastomer composition and the fluororubber molded article of the present invention can be used for various purposes.
  • the fluorine-containing elastomer composition of the present invention can be used as a rubber paint by dissolving or dispersing it in a solvent or a dispersion medium used for a conventionally known paint at an arbitrary ratio.
  • the fluorine-containing elastomer composition of the present invention can be used as a coating material by applying it to an arbitrary object to be coated such as an electric wire.
  • a fluorine rubber molded body formed by using the fluorine-containing elastomer composition of the present invention is, for example, an automobile part, an air conditioner, a control device, a water supply/hot water supply device, a high temperature steam device, a semiconductor device, a food processing.
  • the fluororubber molded article formed by using the fluorine-containing elastomer composition of the present invention is used as a hose, a sealant, a belt, a vibration-proof rubber, a diaphragm, a hollow rubber molded article, or the like. You can ⁇ 2020/175 331 23 ⁇ (:171? 2020 /006896
  • the hose is not particularly limited, and examples thereof include fuel hose, evening hose, oil hose, radiator hose, heater hose, water hose, vacuum brake hose, control hose, air con hose, brake hose. , Various types of hoses such as power steering hoses, air hoses, marine hoses, risers and flow lines.
  • the above-mentioned sealing material is not particularly limited, and examples thereof include a ring, a packing, an oil seal, a shaft seal, a bearing seal, a mechanical seal, a well head seal, a seal for electric/electronic equipment, There are various types of seals such as seals for pneumatic equipment.
  • the belt is not particularly limited, and examples thereof include various belts such as a power transmission belt and a conveyance belt.
  • the vibration-proof rubber is not particularly limited, and examples thereof include various vibration-proof rubbers such as a vibration-proof rubber for automobiles.
  • the diaphragm is not particularly limited and includes, for example, diaphragms for automobile engines such as fuel system, exhaust system, brake system, drive system, ignition system, diaphragms for pumps, diaphragms for valves, filter presses.
  • diaphragms such as diaphragms; diaphragms for blowers;
  • the hollow rubber molded body is not particularly limited, and examples thereof include various bladders such as tire manufacturing bladders and tire vulcanizing bladders; various joints such as flexible joints and expansion joints; joints. Boots, rack and pinion steering boots, pin boots, piston boots and other boots; primer valves and other valves;
  • the Pickers hardness of the dispersing medium, the filling factor and the average diameter, and the tensile strength, elongation and tensile product of the crosslinked product were measured or evaluated using the following methods, respectively.
  • cryomicrotome (Le ⁇ ⁇ a company, product name "!_ 6 I ⁇ 3 ⁇ IV! ⁇ 7”) in which the prepared sheet-shaped cross-linked product was cooled to 100 ° ⁇ , use a diamond knife. I made a cross-section. Using a field emission scanning electron microscope (Hitachi High-Tech, product name “3470”), observe the secondary electron image of the cross section obtained under the conditions of accelerating voltage 5 ! ⁇ and magnification of 20,000 times. did. Image analysis software from the obtained secondary electron image (Olympus, product name “A n 3 I I 3”) to randomly measure the diameter of 100 single layer 0 1 ⁇ 1 bundles, and the average diameter of the single layer 0 1 ⁇ 1 bundles ) Asked.
  • Dispersion media of uniform particle size were embedded in thermosetting resin, and the resin was polished until the cut surface of the dispersion media was visible.
  • Measure the Vitzkers hardness of the dispersion media used in the bead mill by arbitrarily selecting 5 dispersion media, measuring any one of the sections of each dispersion media with a Pitzkers hardness tester, and obtaining the average value. ⁇ 2020/175 331 25 ⁇ (:171? 2020 /006896
  • the volume of the dispersion medium was calculated by dividing the filling amount of the dispersion medium by the specific gravity of the dispersion medium. Next, the volume of the dispersion medium was divided by the vessel volume of the bead mill and expressed as a percentage, which was taken as the filling rate of the dispersion medium used in the bead mill.
  • the produced sheet-shaped cross-linked product was punched out in a dumbbell-shaped No. 3 shape to obtain a test piece. Then, with respect to the obtained test piece, the tensile strength at 200° was measured according to “3 [ ⁇ 6 2 5 1 ”.
  • the produced sheet-shaped cross-linked product was punched out in a dumbbell-shaped No. 3 shape to obtain a test piece. Then, with respect to the obtained test piece, the elongations at break at 23° and 200° were measured in accordance with “3 [ ⁇ 6 25 1 ”, and the elongation of the crosslinked product was determined.
  • the elongation at break is a value which is 100% at the initial stage (that is, before the sheet-like crosslinked product is pulled).
  • the tensile product of the produced sheet-shaped crosslinked product was determined.
  • the tensile product is shown as a value rounded to the nearest whole number.
  • Methyl ethyl ketone 900 as a solvent and fluorine-containing elastomer as [ ⁇ 1 ⁇ /1 (Kemers Co., Ltd., trade name "Baiton ⁇ !_-6003")
  • the stoma was dissolved to obtain a fluorine-containing elastomer dissolved solution.
  • the obtained dispersion was added dropwise to methanol of 40009 and solidified to obtain a black solid. Then, the obtained black solid was dried under reduced pressure at 60 ° for 12 hours to obtain a mixture of the fluorine-containing elastomer and 31,000 ⁇ .
  • the obtained fluoroelastomer composition was put into a mold and crosslinked at a temperature of 160 ° ⁇ and a pressure of 101/13 for 20 minutes to obtain a sheet-like crosslinked product (length:
  • the average diameter of the single-layer 0-bundle bundle (mouth) contained in the obtained sheet-like crosslinked product was determined. Using the average diameter of the carbon nanostructures (), and the average diameter of the single layer ⁇ 1 ⁇ 1 bundle (0
  • a bead mill was used instead of a jet mill (manufactured by Yoshida Kikai Kogyo Co., Ltd., trade name "I-_ _ 3 0 0 7") for dispersion processing (dispersion processing conditions: pressure 100 IV!
  • a sheet-like crosslinked product was produced in the same manner as in Example 1 except that the number of passes was 5 times. Then, various measurements were performed in the same manner as in Example 1. The results are shown in Table 1.
  • a sheet-like crosslinked product was produced in the same manner as in Example 1 except that the condition of the dispersion treatment was changed to the peripheral speed of 10/3. Then, various measurements were performed in the same manner as in Example 1. The results are shown in Table 1.
  • a bead mill was used instead of a homogenizer ([3 ⁇ 4 ⁇ IV!
  • a sheet-like crosslinked product was prepared in the same manner as in Example 1 except that the treatment time was 30 minutes), and various measurements were performed in the same manner as in Example 1. It is shown in Table 1.
  • a fluoroelastomer composition capable of forming a fluororubber molded article having high tensile strength and high elongation under a high temperature environment, and a fluororubber using the fluoroelastomer composition
  • a molded article and a method for producing the fluorine-containing elastomer composition can be provided.

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  • Manufacturing & Machinery (AREA)
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Abstract

L'invention concerne une composition d'élastomère contenant du fluor contenant des nanostructures de carbone fibreux dans une proportion de 0,1 partie en masse à moins de 6 parties en masse pour 100 parties en masse d'élastomère contenant du fluor. Les nanostructures de carbone fibreux comprennent des faisceaux de nanotubes de carbone à paroi unique qui sont des faisceaux de nanostructures de carbone fibreux comprenant des nanotubes de carbone à paroi unique. Le diamètre moyen (DB) des faisceaux de nanotubes de carbone à paroi unique est de 20 à 600 nm inclus.
PCT/JP2020/006896 2019-02-28 2020-02-20 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 Ceased WO2020175331A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022181193A1 (fr) * 2021-02-26 2022-09-01 日本ゼオン株式会社 Matériau composite et corps moulé en caoutchouc vulcanisé
WO2023054716A1 (fr) * 2021-09-30 2023-04-06 日本ゼオン株式会社 Composition de caoutchouc fluoré et objet façonné

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008024800A (ja) * 2006-07-20 2008-02-07 Nissin Kogyo Co Ltd 炭素繊維複合材料
JP2011197596A (ja) * 2010-03-24 2011-10-06 Tokai Rubber Ind Ltd 電子写真機器用導電性組成物及びそれを用いた電子写真機器用部材
JP2013227694A (ja) * 2012-04-25 2013-11-07 Mitsuuma:Kk 導電性を有する立体繊維構造体およびその製造方法
JP2016108476A (ja) * 2014-12-08 2016-06-20 日信工業株式会社 炭素繊維複合材料
WO2017175807A1 (fr) * 2016-04-07 2017-10-12 日本ゼオン株式会社 Composition d'élastomère contenant du fluor, et corps moulé
WO2018225789A1 (fr) * 2017-06-06 2018-12-13 日本ゼオン株式会社 Produit réticulé en caoutchouc et son procédé de fabrication

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008024800A (ja) * 2006-07-20 2008-02-07 Nissin Kogyo Co Ltd 炭素繊維複合材料
JP2011197596A (ja) * 2010-03-24 2011-10-06 Tokai Rubber Ind Ltd 電子写真機器用導電性組成物及びそれを用いた電子写真機器用部材
JP2013227694A (ja) * 2012-04-25 2013-11-07 Mitsuuma:Kk 導電性を有する立体繊維構造体およびその製造方法
JP2016108476A (ja) * 2014-12-08 2016-06-20 日信工業株式会社 炭素繊維複合材料
WO2017175807A1 (fr) * 2016-04-07 2017-10-12 日本ゼオン株式会社 Composition d'élastomère contenant du fluor, et corps moulé
WO2018225789A1 (fr) * 2017-06-06 2018-12-13 日本ゼオン株式会社 Produit réticulé en caoutchouc et son procédé de fabrication

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022181193A1 (fr) * 2021-02-26 2022-09-01 日本ゼオン株式会社 Matériau composite et corps moulé en caoutchouc vulcanisé
WO2023054716A1 (fr) * 2021-09-30 2023-04-06 日本ゼオン株式会社 Composition de caoutchouc fluoré et objet façonné

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