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WO2024135527A1 - Composition de matériau d'étanchéité pour hydrogène gazeux à haute pression - Google Patents

Composition de matériau d'étanchéité pour hydrogène gazeux à haute pression Download PDF

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Publication number
WO2024135527A1
WO2024135527A1 PCT/JP2023/044833 JP2023044833W WO2024135527A1 WO 2024135527 A1 WO2024135527 A1 WO 2024135527A1 JP 2023044833 W JP2023044833 W JP 2023044833W WO 2024135527 A1 WO2024135527 A1 WO 2024135527A1
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Prior art keywords
sealing material
hydrogen gas
pressure hydrogen
material composition
mass
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English (en)
Japanese (ja)
Inventor
浩文 圖師
彰 上田
憲 鈴木
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Valqua Ltd
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Valqua Ltd
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Priority to KR1020257023929A priority Critical patent/KR20250124870A/ko
Priority to CN202380088001.3A priority patent/CN120530180A/zh
Publication of WO2024135527A1 publication Critical patent/WO2024135527A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • 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
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/10—Homopolymers or copolymers of unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0204—Elements
    • C09K2200/0208—Carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0247—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/04—Non-macromolecular organic compounds
    • C09K2200/0458—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0635—Halogen-containing polymers, e.g. PVC
    • C09K2200/0637—Fluoro-containing polymers, e.g. PTFE

Definitions

  • the present invention relates to a sealing material composition for high-pressure hydrogen gas, and also to a sealing material for high-pressure hydrogen gas.
  • EPDM ethylene-propylene-diene rubber
  • Patent Document 1 JP 2015-206002 A
  • Patent Document 2 JP 2015-108104 A
  • Patent Document 3 JP 2020-51540 A
  • Patent Document 4 JP 2020-158602 A
  • sealing materials containing ethylene-propylene-diene rubber do not have sufficient heat resistance and are often unable to be used in high-temperature environments of 150°C or higher.
  • sealing materials using perfluoroelastomers have excellent heat resistance and can be used in high-temperature environments, but they tend to be prone to blistering when used with high-pressure hydrogen.
  • the object of the present invention is to provide a sealing material composition for high-pressure hydrogen gas and a sealing material for high-pressure hydrogen gas that have good blister resistance and heat resistance.
  • the present invention provides the following sealing material composition for high-pressure hydrogen gas and sealing material for high-pressure hydrogen gas.
  • a composition comprising 100 parts by mass of a perfluoroelastomer and 5 to 60 parts by mass of a filler; The filler comprises silica; The content of the silica in the composition is 5 to 50 parts by mass.
  • the sealing material for high-pressure hydrogen gas according to [11] having a Shore A hardness of 85 or more.
  • the present invention provides a sealing material composition for high-pressure hydrogen gas and a sealing material for high-pressure hydrogen gas that have good blister resistance and heat resistance.
  • the sealing material composition of the present invention contains 100 parts by mass of a perfluoroelastomer and 5 to 60 parts by mass of a filler. By containing the perfluoroelastomer and the filler in the above-mentioned amounts, a sealing material composition having excellent heat resistance and less susceptible to blistering can be obtained.
  • the heat resistance of the sealing material composition tends to be improved by including a perfluoroelastomer.
  • the perfluoroelastomer may be, for example, a tetrafluoroethylene-perfluorovinyl ether system.
  • the tetrafluoroethylene-perfluorovinyl ether system may be composed of a structural unit derived from tetrafluoroethylene and a structural unit derived from perfluorovinyl ether, and may be copolymerized with a small amount of a crosslinking site monomer.
  • the perfluorovinyl ether is preferably at least one selected from the group consisting of perfluoro(alkyl vinyl ether)s and perfluoro(alkoxyalkyl vinyl ethers).
  • the number of carbon atoms in the alkyl group in the perfluoro(alkyl vinyl ether) may be, for example, 1 to 5.
  • Examples of perfluoro(alkyl vinyl ether) include perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(propyl vinyl ether). Of these, perfluoro(methyl vinyl ether) is preferred.
  • n is, for example, 1 to 5
  • m is, for example, 1 to 3.
  • the crosslinking site monomer is a monomer having a group that provides a crosslinking site, and in the present invention, may be any monomer that provides peroxide crosslinkability to the perfluoroelastomer.
  • a group that provides a crosslinking site is a halogen atom (e.g., an iodine atom).
  • the viscosity of the perfluoroelastomer is preferably 50 to 100 in terms of Mooney viscosity [ML (1+4) 121°C]. If the viscosity is too low, the fluidity of the perfluoroelastomer composition will be excessively high, and the sealing material composition will deform under its own weight on the mold during molding, which will tend to cause defects such as dents in the resulting crosslinked molded product. If the viscosity of the perfluoroelastomer is too high, the fluidity of the sealing material composition will be excessively low, which will tend to reduce moldability.
  • perfluoroelastomers Commercially available perfluoroelastomers can also be used, and specific examples include “Kalrez (registered trademark)” manufactured by DuPont, “Dai-el (registered trademark) Perflo” manufactured by Daikin, “Tecnoflon (registered trademark)” manufactured by Solvay, “Dyonin” manufactured by Sumitomo 3M, and “AFLAS (registered trademark)” manufactured by AGC.
  • the content of the filler is 5 to 60 parts by mass relative to 100 parts by mass of the perfluoroelastomer. If the content of the filler is less than 5 parts by mass relative to 100 parts by mass of the perfluoroelastomer, the blister resistance tends to be difficult to improve. If the content of the filler is more than 60 parts by mass relative to 100 parts by mass of the perfluoroelastomer, the molding processability tends to decrease, rubber elasticity is not exhibited, and it tends to be difficult to function as a sealing material.
  • the content of the filler is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass, and even more preferably 20 to 40 parts by mass relative to 100 parts by mass of the perfluoroelastomer.
  • the filler includes silica.
  • silica those known to have a reinforcing effect on general-purpose rubber can be used.
  • examples of silica include, but are not limited to, dry white carbon produced by the thermal decomposition of halogenated silicic acid or organic silicon compounds, or by the air oxidation of SiO vaporized by heating and reducing silica sand, and wet white carbon produced by the thermal decomposition of sodium. In the present invention, it is preferable to use dry white carbon. Only one type of silica may be used, or two or more types may be used in combination.
  • the silica content is 5 to 50 parts by mass per 100 parts by mass of perfluoroelastomer, and from the viewpoints of moldability, blister resistance of the sealing material, and rubber elasticity, it is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, and even more preferably 20 to 40 parts by mass.
  • the sealing material composition of the present invention is preferably filled with a relatively high amount of silica.
  • silica has a lower hydrogen adsorption capacity than carbon black, it is more useful to use silica to improve blister resistance.
  • the silica may contain at least 70% by mass of silica component (SiO 2 ).
  • the specific surface area of the silica is preferably 10 to 120 m 2 /g, more preferably 15 to 40 m 2 /g.
  • the silica is preferably spherical, and more preferably non-porous and spherical. When the silica is spherical, friction between silica particles is less than that of silica of other shapes (e.g., chain-like), and dispersibility is improved, so that the silica can be highly loaded into the sealing material composition. Note that "spherical” includes not only perfect spheres but also slightly distorted spheres.
  • the average particle size of the silica is preferably 5 nm to 5 ⁇ m, more preferably 10 nm to 1 ⁇ m, even more preferably 30 nm to 500 nm, and particularly preferably 50 nm to 300 nm, from the viewpoints of suppressing aggregation and achieving smoothness. If the average particle size of the silica is too large, the blister resistance of the sealing material may decrease.
  • the average particle size can be determined, for example, by observing the morphology using a microscope, measuring the particle size of the silica within the observation field by image analysis, and calculating the number average of the measured values.
  • the composition for the sealing material may further contain a silane coupling agent to facilitate high loading of silica.
  • Silane coupling agents have reactive groups in their molecules that chemically bond with inorganic materials and reactive groups that chemically bond with organic materials, so they act as a binder that binds organic materials and inorganic materials that are normally difficult to bond.
  • the surface of the silica is coated with a silane coupling agent, the surface of the silica becomes hydrophobic, and the aggregation of silica can be prevented. This makes it possible to disperse the silica more in the rubber composition for the sealing member and to load it more, making it easier to improve the blister resistance of the sealing material.
  • the silane coupling agent also makes it easier to improve the blister resistance by increasing the bonding strength between the silica and the rubber component.
  • the silane coupling agent in the present invention is not particularly limited, but examples thereof include vinyl-based, acrylic-based, epoxy-based, methacryl-based, mercapto-based, and amino-based silane coupling agents.
  • vinyl-based silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, and vinyltriethoxysilane.
  • acrylic-based silane coupling agents include 3-acryloxypropyltrimethoxysilane.
  • Examples of epoxy-based silane coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane.
  • Examples of methacryl-based silane coupling agents include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.
  • the content of the silane coupling agent may be, for example, 0.1 to 10 parts by mass per 100 parts by mass of perfluoroelastomer, and from the viewpoint of blister resistance, is preferably 1 to 8 parts by mass, and more preferably 3 to 6 parts by mass.
  • the filler may further include a filler that is generally used as a filler that exhibits a reinforcing effect in general-purpose rubber.
  • the filler preferably further includes carbon black.
  • the content of carbon black is preferably 3 to 50 parts by mass, more preferably 4 to 30 parts by mass, and even more preferably 5 to 20 parts by mass per 100 parts by mass of perfluoroelastomer, from the viewpoints of moldability, mechanical strength of the sealing material, and blister resistance.
  • the carbon black is preferably spherical. If the carbon black is closer to a perfect sphere (smaller specific surface area), the carbon black is less likely to aggregate, and the mechanical properties of the sealing material composition at low temperatures tend not to deteriorate.
  • Carbon black may be conductive or non-conductive, and examples of carbon black include furnace black, channel black, acetylene black, ketjen black, thermal black, and lamp black, depending on the manufacturing method. Carbon black may be of the following types: SAF, ISAF, ISAF-HF, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, MAF, FEF, FEF-LS, GPF, GPF-HS, GPF-LS, SRF, SRF-HS, SRF-LM, FT, and MT.
  • the average particle size of carbon black may vary depending on the manufacturer, but for example, SAF is 19 nm, ISAF is 23 nm, HAF is 28 nm, MAF is 38 nm, FEF is 43 nm, GPF is 62 nm, SRF is 66 nm, and FT is 122 nm. From the perspective of reinforcing properties, it is preferable for the carbon black particle size to be small.
  • One type of carbon black may be used alone, or two or more types may be used in combination.
  • the carbon black may contain two or more types of carbon black.
  • the difference between the average particle size of the large-diameter carbon black and the average particle size of the small-diameter carbon black is not particularly limited, but can be, for example, 7 nm or more and 330 nm or less.
  • the sealing material composition may further contain a composite crosslinking agent.
  • the composite crosslinking agent may contain an organic peroxide and a nitroxide compound as a crosslinking agent for crosslinking the crosslinkable rubber component (perfluoroelastomer).
  • organic peroxides can be used as the organic peroxides that make up the composite crosslinking agent.
  • dicumyl peroxide ⁇ , ⁇ '-bis(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and n-butyl-4,4-bis(t-butylperoxy)valerate are preferred. Only one type of organic peroxide may be used, or two or more types may be used in combination.
  • nitroxide compounds that constitute the composite crosslinking agent include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,5,5-tetramethylpiperidine-1-oxyl, bis(2,2,6,6-tetramethyl-1-piperdinyloxy-4-yl)sebacate, and 4,4'-[(1,10-dioxo-1,10-decanediyl)bis(oxy)]bis(2,2,6,6-tetramethyl).
  • nitroxide compounds may be used alone or in combination of two or more.
  • the composite crosslinking agent is added to the perfluoroelastomer composition so that the organic peroxide content is 0.5 to 10 parts by mass, preferably 0.8 to 6 parts by mass, per 100 parts by mass of perfluoroelastomer.
  • the amount of composite crosslinking agent added may be, for example, about 0.6 to 20 parts by mass, about 1 to 15 parts by mass, or about 1 to 10 parts by mass, per 100 parts by mass of perfluoroelastomer.
  • keeping the organic peroxide content at 10 parts by mass or less per 100 parts by mass of perfluoroelastomer tends to be advantageous in that it can suppress or prevent foaming and stickiness in the resulting crosslinked molded product (sealing material, etc.), and can improve the heat resistance and sealing properties of the resulting sealing material.
  • the content of the nitroxide compound in the composite crosslinking agent is preferably within the range of 1 to 10 mass% of the organic peroxide content, and more preferably within the range of 2 to 8 mass%. By keeping the content of the nitroxide compound within this range, it is possible to obtain a good effect of extending the initial flow time and shortening the crosslinking time.
  • the composite crosslinking agent may be composed of only organic peroxides and nitroxide compounds, but may also contain other components such as filler components.
  • filler components include the above-mentioned silica and carbon black, other inorganic pigments (calcium carbonate, clay, talc, etc.), organic pigments, resin components, etc.
  • the form of the composite crosslinking agent is not particularly limited, and it can be liquid, powder, or molded (e.g., granules, pellets, sheets, etc.). Only one type of filler component may be used alone, or two or more types may be used in combination.
  • the content of silica in the composite crosslinking agent is included in the content of the above-mentioned filler.
  • the content of silica in the composite crosslinking agent can be, for example, 10 parts by mass or less per 100 parts by mass of perfluoroelastomer.
  • "Luperox 101XL45-SP2" is preferably
  • the sealing material composition may further contain a co-crosslinking agent.
  • co-crosslinking agent examples include quinone dioxime, ethylene glycol dimethacrylate, divinylbenzene, diallyl phthalate, triallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, 1,2-polybutadiene, metal methacrylate, and metal acrylate. Only one type of co-crosslinking agent may be used, or two or more types may be used in combination.
  • the co-crosslinking agent may be either liquid or solid, and when roll kneading is performed, a solid is preferred from the viewpoints of workability and dispersibility.
  • the sealing material composition contains a co-crosslinking agent
  • the content can be about 1 to 10 parts by mass per 100 parts by mass of perfluoroelastomer.
  • the sealing material composition may contain other components other than the above-mentioned components as necessary.
  • the other components include fillers other than silica and carbon black, crosslinking assistants, polyhydric alcohols, surfactants other than silane coupling agents, tackifiers, flame retardants, release agents, processing assistants, stabilizers, waxes, lubricants, and other additives.
  • the additives may be used alone or in combination of two or more.
  • fillers other than silica and carbon black include alumina, zinc oxide, titanium dioxide, clay, talc, diatomaceous earth, barium sulfate, calcium carbonate, magnesium carbonate, calcium oxide, mica, graphite, aluminum hydroxide, aluminum silicate, hydrotalcite, granular or powdered resins (such as fluororesins), metal powders, glass powders, ceramic powders, etc.
  • the sealing material composition contains fillers other than silica and carbon black, the content thereof can be about 1 to 10 parts by mass per 100 parts by mass of perfluoroelastomer.
  • cross-linking aids examples include zinc oxide.
  • polyhydric alcohol is diethylene glycol.
  • the sealing material composition may contain a plasticizer, but the content of the plasticizer is preferably as small as possible (for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less per 100 parts by mass of perfluoroelastomer), and it is extremely preferable that the composition does not contain a plasticizer. If the fluidity of the sealing material composition becomes excessively high due to the inclusion of a plasticizer, the sealing material composition will deform under its own weight on the hot press mold, and the resulting sealing material will tend to have defects such as dents. Furthermore, the inclusion of a plasticizer tends to reduce the heat resistance of the sealing material, and there is a risk of contamination of objects that come into contact with the sealing material.
  • the content of other additives that may cause contamination of objects that come into contact with the sealing material such as release agents, waxes, lubricants, liquid processing aids, etc., as low as possible (for example, 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 2 parts by weight or less, and even more preferably 1 part by weight or less per 100 parts by weight of the crosslinkable rubber component), and it is even more preferable to not contain such additives.
  • plasticizer includes plasticizers in the narrow sense (such as silicone-based, phthalate-based, adipate-based, aliphatic dibasic acid ester-based, phosphate-based, citrate-based, and trimellit-based plasticizers), as well as oils (such as silicone-based oils, naphthenic process oils, paraffinic process oils, aromatic process oils, fluorine-based oils, vegetable oils, and epoxidized vegetable oils).
  • oils such as silicone-based oils, naphthenic process oils, paraffinic process oils, aromatic process oils, fluorine-based oils, vegetable oils, and epoxidized vegetable oils.
  • the sealing material composition can be prepared by uniformly kneading the perfluoroelastomer, silica, carbon black, and other compounding ingredients that are added as necessary.
  • a kneading machine for example, a roll kneader such as an open roll; a mixer such as a pressure kneader or an internal mixer (Banbury mixer), or other conventionally known kneading machines can be used.
  • These compounding ingredients may be mixed and kneaded at once, or may be kneaded in multiple stages, such that some of the compounding ingredients are kneaded and then the remaining compounding ingredients are kneaded, so that all of the compounding ingredients are kneaded.
  • the above-mentioned sealing material composition can be crosslinked and molded to produce a sealing material, which is a crosslinked molded product.
  • the crosslinking molding method can be a conventionally known method such as hot press molding, feed press molding, or injection molding.
  • the crosslinking molding temperature is, for example, about 100 to 200°C, and preferably 150 to 190°C. If necessary, secondary crosslinking (heat treatment) can be performed at a temperature equal to or higher than the crosslinking molding temperature.
  • the sealant containing the cross-linked product of the above-mentioned sealing material composition has excellent blister resistance and heat resistance, making it suitable as a sealant for high-pressure hydrogen gas.
  • the shape of the sealant is selected appropriately depending on the application, but a typical example is a ring shape such as an O-ring.
  • the high-pressure hydrogen gas sealing material of the present invention can function as a sealing material in a high-temperature environment, for example, at a temperature of 150°C or higher, and preferably functions as a sealing material in a high-temperature environment at a temperature of 180°C or higher, and more preferably functions as a sealing material in a high-temperature environment at a temperature of 200°C or higher.
  • the high-pressure hydrogen gas sealing material of the present invention does not cause blistering even under high-pressure water gas of at least 90 MPa.
  • the Shore A hardness of the sealing material for high-pressure hydrogen gas of the present invention may be, for example, 85 to 95.
  • the sealing material for high-pressure hydrogen gas of the present invention does not contain sulfur. If sulfur is contained, the sulfur released from the sealing material will react with hydrogen, generating toxic hydrogen sulfide. The generated hydrogen sulfide may contaminate hydrogen gas and have adverse effects on the human body. In addition, when oxidized in the air, it becomes sulfuric acid, which may corrode pipes, etc.
  • Examples 1 and 2 and Comparative Examples 1 to 4 The components shown in Table 2 were mixed in the ratios shown in Table 2 using an 8-inch roll to obtain a sealing material composition.
  • the obtained sealing material composition was placed in a mold set at a temperature of 160 to 180°C and molded using a pressure press for 3 to 20 minutes. Thereafter, secondary vulcanization was performed in an oven set at 200 to 300°C for 2 to 8 hours to obtain each evaluation test sample. The results are shown in Table 3.
  • Rubber component A FFKM: Tetrafluoroethylene-perfluorovinyl ether perfluoroelastomer Rubber component B: FKM: Fluorine rubber Rubber component C: EPDM: Ethylene-propylene-diene rubber
  • Crosslinking agent zinc oxide (JIS standard type 2)
  • Antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline copolymer
  • Filler A Silica manufactured by Elkem (SiDISTAR), average particle size: 0.15 ⁇ m Filler B: Carbon black-1 Diablack H HAF carbon Filler C: Carbon black-2 Seast GSO FEF carbon
  • Silane coupling agent vinyltrimethoxysilane
  • Polyhydric alcohol ethylene glycol
  • Co-crosslinking agent-1 triallyl isocyanurate
  • Crosslinking agent-1 Composite crosslinking agent: manufactured by Arkema (Luperox 101 XL45-SP2E)
  • Crosslinker-2 bis(t-butyldioxyisopropyl)benzene
  • Crosslinker-3 2,5-dimethyl-2,5-di(t-butylperoxy)hexane
  • sealing materials were obtained that had excellent blister resistance and a small compression set rate.
  • the sealing materials in Comparative Examples 1 to 4 had a large compression set rate, and in Comparative Examples 3 and 4, the blister resistance was insufficient.
  • the sealing material composition of the present invention can provide a sealing material for high-pressure hydrogen gas that has good blister resistance and heat resistance.

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

Abstract

La présente divulgation concerne une composition de matériau d'étanchéité pour hydrogène gazeux à haute pression, la composition de matériau d'étanchéité contenant 100 parties en masse d'un élastomère perfluoré et 5 à 60 parties en masse d'une charge, la charge contenant de la silice et la teneur en silice étant de 5 à 50 parties en masse. La présente divulgation concerne également un matériau d'étanchéité pour hydrogène gazeux à haute pression, le matériau d'étanchéité contenant un produit réticulé de la composition de matériau d'étanchéité pour hydrogène gazeux à haute pression. La présente divulgation concerne une composition de matériau d'étanchéité pour hydrogène gazeux à haute pression, la composition de matériau d'étanchéité ayant une bonne résistance au cloquage et une bonne résistance à la chaleur, et un matériau d'étanchéité pour hydrogène gazeux à haute pression, le matériau d'étanchéité contenant un produit réticulé de la composition de matériau d'étanchéité pour hydrogène gazeux à haute pression.
PCT/JP2023/044833 2022-12-22 2023-12-14 Composition de matériau d'étanchéité pour hydrogène gazeux à haute pression Pending WO2024135527A1 (fr)

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KR1020257023929A KR20250124870A (ko) 2022-12-22 2023-12-14 고압 수소 가스용 시일재 조성물
CN202380088001.3A CN120530180A (zh) 2022-12-22 2023-12-14 高压氢气用密封件组合物

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JP2022205538A JP2024089962A (ja) 2022-12-22 2022-12-22 高圧水素ガス用シール材組成物
JP2022-205538 2022-12-22

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JP (1) JP2024089962A (fr)
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WO (1) WO2024135527A1 (fr)

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JPH06302527A (ja) * 1993-04-19 1994-10-28 Mitsubishi Cable Ind Ltd 半導体製造装置用シール
JP2007502890A (ja) * 2003-08-15 2007-02-15 デュポン パフォーマンス エラストマーズ エルエルシー 硬化性パーフルオロエラストマー組成物
JP2008057711A (ja) * 2006-09-01 2008-03-13 Toyota Motor Corp 高圧水素容器
JP2013529710A (ja) * 2010-06-25 2013-07-22 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 硬化性パーフルオロエラストマー組成物を調製する方法
JP2015174988A (ja) * 2014-03-18 2015-10-05 日本バルカー工業株式会社 パーフルオロエラストマー組成物及びシール材
JP2016090050A (ja) * 2014-10-30 2016-05-23 株式会社ジェイテクト シール材
WO2018151099A1 (fr) * 2017-02-14 2018-08-23 国立大学法人九州大学 Élément d'étanchéité au gaz destiné à un dispositif à hydrogène haute pression et dispositif à hydrogène haute pression
JP2020051540A (ja) * 2018-09-27 2020-04-02 株式会社バルカー シール部材付き継手
WO2020195696A1 (fr) * 2019-03-26 2020-10-01 株式会社バルカー Composition de caoutchouc pour matériau d'étanchéité et matériau d'étanchéité l'utilisant

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015108104A (ja) 2013-12-03 2015-06-11 高石工業株式会社 ゴム組成物
JP2015206002A (ja) 2014-04-22 2015-11-19 三菱電線工業株式会社 ゴム組成物および高圧水素機器用シール部材

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06302527A (ja) * 1993-04-19 1994-10-28 Mitsubishi Cable Ind Ltd 半導体製造装置用シール
JP2007502890A (ja) * 2003-08-15 2007-02-15 デュポン パフォーマンス エラストマーズ エルエルシー 硬化性パーフルオロエラストマー組成物
JP2008057711A (ja) * 2006-09-01 2008-03-13 Toyota Motor Corp 高圧水素容器
JP2013529710A (ja) * 2010-06-25 2013-07-22 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 硬化性パーフルオロエラストマー組成物を調製する方法
JP2015174988A (ja) * 2014-03-18 2015-10-05 日本バルカー工業株式会社 パーフルオロエラストマー組成物及びシール材
JP2016090050A (ja) * 2014-10-30 2016-05-23 株式会社ジェイテクト シール材
WO2018151099A1 (fr) * 2017-02-14 2018-08-23 国立大学法人九州大学 Élément d'étanchéité au gaz destiné à un dispositif à hydrogène haute pression et dispositif à hydrogène haute pression
JP2020051540A (ja) * 2018-09-27 2020-04-02 株式会社バルカー シール部材付き継手
WO2020195696A1 (fr) * 2019-03-26 2020-10-01 株式会社バルカー Composition de caoutchouc pour matériau d'étanchéité et matériau d'étanchéité l'utilisant

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KR20250124870A (ko) 2025-08-20
JP2024089962A (ja) 2024-07-04
TW202440866A (zh) 2024-10-16

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