WO2018181373A1 - 高圧ガス用シール部材に用いられるためのゴム組成物、高圧ガス用シール部材、高圧ガス用機器および高圧ガスシール方法 - Google Patents
高圧ガス用シール部材に用いられるためのゴム組成物、高圧ガス用シール部材、高圧ガス用機器および高圧ガスシール方法 Download PDFInfo
- Publication number
- WO2018181373A1 WO2018181373A1 PCT/JP2018/012531 JP2018012531W WO2018181373A1 WO 2018181373 A1 WO2018181373 A1 WO 2018181373A1 JP 2018012531 W JP2018012531 W JP 2018012531W WO 2018181373 A1 WO2018181373 A1 WO 2018181373A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber
- pressure gas
- rubber composition
- pressure
- hydrogen
- Prior art date
Links
Images
Classifications
-
- 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
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/02—Sealings between relatively-stationary surfaces
- F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
- F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/02—Sealings between relatively-stationary surfaces
- F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
- F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
- F16J15/102—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing characterised by material
-
- 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
- C09K2003/1087—Materials or components characterised by specific uses
- C09K2003/1096—Cylinder head gaskets
-
- 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
- C09K2200/0607—Rubber or rubber derivatives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S277/00—Seal for a joint or juncture
- Y10S277/935—Seal made of a particular material
- Y10S277/944—Elastomer or plastic
Definitions
- the present invention relates to a rubber composition for use in a high-pressure gas sealing member, a high-pressure gas sealing member, and a high-pressure gas device including these.
- the present invention also relates to a high pressure gas sealing method.
- the present invention relates to a rubber composition and a sealing member for use in a sealing member for high pressure gas that seals hydrogen or helium, and an apparatus for high pressure gas including these.
- the present invention also relates to a high pressure gas sealing method.
- a fuel cell is a system that generates electricity by reacting hydrogen and oxygen, but there are problems in handling hydrogen.
- FCV fuel cell vehicles
- Patent Documents 1-3, Non-Patent Document 1).
- Patent Document 4 describes a silicone rubber having a specific structure as a rubber composition used as a sealing material for hydrogen gas.
- polystyrene rubber and polystyrene butadiene rubber are known as general-purpose rubbers and are generally used for tires.
- Polybutadiene rubber and polystyrene butadiene rubber are rubbers having relatively high gas permeability.
- EPDM has a problem that even if it is assumed to be used in an environment of ⁇ 40 ° C., if the temperature control becomes severe and the temperature falls down to about ⁇ 45 ° C., leakage immediately occurs.
- Fluoro rubber has insufficient low-temperature characteristics and is difficult to seal in an environment of ⁇ 40 ° C.
- at least butyl rubber, fluororubber, and hydrogenated nitrile rubber have a problem of occurrence of blisters during rapid decompression.
- the silicone rubber disclosed in Patent Document 4 has a problem that the sealing performance is impaired at the sliding portion.
- a seal member used in a hydrogen station has many sliding portions, and it is difficult to use silicone rubber as such a member.
- the cost reduction is naturally required, but the cost of silicone rubber is limited because the material itself is expensive.
- the high-pressure gas sealing member is required to maintain the sealing performance not only at a low temperature but also at a high temperature of about 100 ° C.
- the conventional rubber composition does not have a sufficient sealing performance in a wide temperature range. There was room for improvement. As described above, there is a demand for a sealing member that does not impair sealing performance even in a wide temperature range (particularly at low temperatures) and that can be used even at a sliding portion.
- sealing members special materials such as butyl rubber, fluorine rubber, hydrogenated nitrile rubber, EPDM, and silicone rubber are used. Rubber was used.
- a sealing member there is a tendency to use a material having low gas permeability in order to improve airtightness. For this reason, it has not been considered to divert polybutadiene rubber or polystyrene butadiene rubber, which is a general-purpose rubber and has a relatively high gas permeability, to a sealing member for high-pressure gas.
- an object of the present invention is to provide a rubber composition and a high-pressure gas sealing member for use in a high-pressure gas sealing member that simultaneously satisfy excellent wear resistance, low temperature resistance, heat resistance, and blister resistance. Is to provide. Moreover, it is providing the apparatus for high pressure gas provided with the sealing member for high pressure gas. Furthermore, it is providing the sealing method of a high pressure gas.
- the inventors of the present invention mainly focused on polybutadiene rubber and polystyrene butadiene rubber used as tire applications, and as a result of intensive research to solve the above problems, polybutadiene rubber and polystyrene butadiene rubber are relatively gas permeable. Despite being high, the present inventors have unexpectedly found that the above problems can be solved, and have reached the present invention. That is, the present invention relates to the following inventions.
- a rubber composition for use in a high pressure gas sealing member that seals high pressure gas wherein the rubber component in the rubber composition includes polybutadiene rubber and / or polystyrene butadiene rubber, and the rubber composition A rubber composition having a glass transition point of ⁇ 65 ° C. or lower.
- the high-pressure gas is hydrogen or helium.
- the high-pressure gas is a high-pressure gas of 1 MPa or more.
- ⁇ 4> The rubber composition according to any one of ⁇ 1> to ⁇ 3>, wherein a content of a structural unit derived from butadiene in the rubber component is 70% by mass or more based on the rubber component.
- ⁇ 5> The rubber composition according to any one of ⁇ 1> to ⁇ 4>, wherein the polybutadiene rubber is a low cis type.
- ⁇ 6> The rubber composition according to any one of ⁇ 1> to ⁇ 5>, wherein the rubber composition is a peroxide vulcanizate.
- the extract amount is 12% by mass or less of the rubber composition.
- the high-pressure gas device is any one selected from the group consisting of a high-pressure hydrogen vessel, a high-pressure helium vessel, a high-pressure hydrogen piping device, and a high-pressure helium piping device. High pressure gas equipment.
- the high-pressure gas device is any one selected from the group consisting of a tank, a pressure accumulator, a valve, a joint, a coupler, a safety valve, a check valve, and a pressure regulating valve.
- ⁇ 15> A method of sealing a high-pressure gas of a high-pressure gas device using a seal member, wherein the seal member is molded using a rubber composition, and the rubber component in the rubber composition is A method comprising a polybutadiene rubber and / or a polystyrene butadiene rubber, wherein the rubber composition has a glass transition point of ⁇ 65 ° C. or lower.
- the high-pressure gas is hydrogen or helium.
- the high-pressure gas is a high-pressure gas of 1 MPa or more.
- the present invention it is possible to provide a rubber composition and a high-pressure gas sealing member for use in a high-pressure gas sealing member that simultaneously satisfies excellent wear resistance, low temperature resistance, heat resistance, and blister resistance. .
- the apparatus for high pressure gas provided with the sealing member for high pressure gas can be provided.
- a method for sealing a high-pressure gas can be provided.
- the present invention relates to a rubber composition for use in a high-pressure gas sealing member that seals high-pressure gas, wherein the rubber component in the rubber composition is polybutadiene rubber and / or polystyrene butadiene.
- the present invention relates to a rubber composition (hereinafter, sometimes referred to as “the rubber composition of the present invention”) characterized in that the rubber composition contains rubber and has a glass transition point of ⁇ 65 ° C. or less.
- the “rubber component” is a component composed of a rubber species contained in the rubber composition of the present invention, and is a component obtained by removing a compounding agent such as a filler from the rubber composition of the present invention.
- the rubber type constituting the rubber component includes polybutadiene rubber and / or polystyrene butadiene rubber.
- the rubber composition of the present invention may be constituted by a rubber component alone or may contain a compounding agent such as a filler in addition to the rubber component. Details will be described later.
- glass transition point means a glass transition point obtained by DSC measurement (differential scanning calorimetry) at a temperature rising rate of 20 ° C./min based on JIS K 6240 (2013). .
- DSC measurement it is necessary to perform temperature calibration with a standard substance (cyclohexane) described in Annex JB of JIS K 6240 (2013) and baseline adjustment described in JIS K 7122 (2014) in advance.
- the rubber composition of the present invention is a rubber composition for use in a high-pressure gas sealing member that seals high-pressure gas.
- the rubber composition of the present invention is preferably used for a sealing member that seals hydrogen and helium.
- Hydrogen or helium is a gas that is difficult to seal because it has a smaller molecular size than other gases and easily penetrates the substance, but the rubber composition of the present invention is a molecule such as hydrogen or helium. Excellent sealing properties even for small gas sizes.
- the rubber composition of the present invention is preferably used for sealing a high-pressure gas of 1 MPa or more among high-pressure gases, and particularly preferably used for sealing hydrogen or helium of 1 MPa or more. .
- the rubber composition of the present invention can maintain rubber elasticity even at a low temperature (for example, about ⁇ 40 ° C.) or a high temperature (for example, about 85 ° C.), and is excellent in wear resistance and blister resistance. Excellent sealing performance even when used in sliding parts of equipment used in a wide temperature range.
- the high-pressure gas sealing member is usually disposed between the members and is unlikely to come into contact with the high-pressure gas. Therefore, it is inferred that the gas can be sufficiently sealed even with gas permeability equivalent to that of polybutadiene rubber or polystyrene butadiene rubber. Is done.
- the high pressure gas sealing member is usually disposed between the members and hardly contacts the atmosphere, it contains a rubber type having low weather resistance, ozone resistance, and oil resistance such as polybutadiene rubber and polystyrene butadiene rubber. Even in this case, it is assumed that the rubber composition is not easily deteriorated.
- the high-pressure gas is hydrogen
- hydrogen since hydrogen is a reducing gas, the hydrogen is partially dissolved in the rubber and is not easily subjected to oxidative deterioration typified by ozone resistance.
- the rubber composition of the present invention can simultaneously satisfy excellent wear resistance, low temperature resistance, heat resistance and blister resistance.
- the lower limit temperature of the high pressure gas seal member is about 25 ° C. to 30 ° C. higher than the glass transition point of the rubber composition constituting the high pressure gas seal member. Obtained knowledge. Since the rubber composition of the present invention has a glass transition point of ⁇ 65 ° C. or lower, it can sufficiently withstand a use environment of ⁇ 40 ° C. or lower. When the rubber composition of the present invention has a glass transition point of about -95 ° C, it can be used even in an environment of -70 ° C. As described above, the glass transition point can be adjusted according to the use environment, but in order to maintain an excellent sealing property even at a lower temperature, it is preferably ⁇ 80 ° C. or lower or ⁇ 90 ° C. or lower.
- the rubber composition of the present invention may have a glass transition point at a temperature higher than ⁇ 65 ° C., as long as it has at least one glass transition point at ⁇ 65 ° C. or lower. It may have a transition point.
- the rubber composition of the present invention is configured to include a rubber component alone or a rubber component and a compounding agent such as a filler.
- the content of the rubber component in the rubber composition of the present invention is determined by the method A described in JIS K 6229 (2013) from the total organic components analyzed by the method described in JIS K 6226-2 (2013). It can be calculated by subtracting the obtained solvent (acetone) extraction amount.
- the content of the rubber component in the rubber composition is not particularly limited, but is preferably 20 to 70% by mass and more preferably 20 to 66% by mass when the rubber composition is 100% by mass. Preferably, the content is 35 to 50% by mass.
- the rubber component of the rubber composition of the present invention may include a polybutadiene rubber and / or a polybutadiene styrene rubber, and may be a polybutadiene rubber alone, a polybutadiene styrene rubber alone, a polybutadiene rubber and a polybutadiene styrene rubber. It may be a mixture of the above, and may contain rubber types other than polybutadiene rubber and polybutadiene styrene rubber (hereinafter may be referred to as “other rubber types”) as long as the object of the present invention is not impaired.
- Polybutadiene rubber (hereinafter sometimes referred to as “BR”) is a polymer obtained by addition polymerization of 1,3-butadiene as a conjugated diene monomer. That is, BR is a polymer composed of structural units derived from butadiene. Three structural isomers (cis-1,4 bond (cis), trans-1,4 bond (trans), 1,2 bond (vinyl), depending on the bond mode of the structural unit
- the bonding mode in the polybutadiene main chain is called a microstructure, and the microstructure and stereoregularity can be controlled by selecting a polymerization method.
- the glass transition point (tg) shows a wide range depending on the content of 1,2 bonds (vinyl content), and moves to the high temperature side when the vinyl content increases and to the low temperature side when the vinyl content decreases. For example, if BR has a vinyl content of about 80 mol%, tg is about -35 ° C, and if BR has a vinyl content of about 10 mol%, tg is about -90 ° C.
- BR is classified according to differences in microstructure, polymerization method, and the like
- the type of polybutadiene rubber contained in the rubber composition of the present invention is not particularly limited as long as the object of the present invention is not impaired.
- BR having a vinyl content of 50 mol% or less is preferable, and BR having a vinyl content of 40 mol% or less is more preferable.
- examples of BR having a 1,2 bond (vinyl) content of 50 mol% or less include high cis type polybutadiene rubber (high cis-BR) and low cis type polybutadiene rubber (low cis-BR).
- the high cis type polybutadiene rubber means a polybutadiene rubber having a cis-1,4 bond content (cis content) in the potabutadiene main chain of 90 mol% or more
- the low cis type polybutadiene rubber means a polybutadiene rubber. It means a polybutadiene rubber having a cis content in the main chain of 52 mol% or less.
- the glass transition point (tg) of high cis type BR is about ⁇ 100 to ⁇ 95 ° C. and has excellent low temperature characteristics.
- the low cis type has an advantage that crystallization of cis-1,4 bonds hardly occurs.
- the high cis type and the low cis type can be discriminated by the high pressure gas sealing member after vulcanization molding.
- the cis content can be calculated by NMR measurement using a sample from which unnecessary components such as oil have been removed by Soxhlet extraction, and discrimination between high cis type and low cis type is possible.
- Preferred polybutadiene rubber includes low cis type polybutadiene rubber.
- low cis type polybutadiene rubber By using a low cis type polybutadiene rubber, low temperature characteristics and wear resistance are improved, and blisters are less likely to occur.
- low cis type polybutadiene rubbers include Nipol 1250H from Nippon Zeon, Diene NF35R from Asahi Kasei, liquid polybutadiene from Kuraray: LBR-302B, LBR-302B , Rubber such as LBR-305, LBR-307, LBR-352, LBR-361 It is possible to use a grade like.
- Polystyrene butadiene rubber Polybutadiene styrene rubber (hereinafter sometimes referred to as “SBR”) is a polymer composed of 1,3-butadiene and styrene. That is, it is a polymer composed of a structural unit derived from butadiene and a structural unit derived from styrene.
- SBR emulsion polymerization SBR and solution polymerization SBR are mainly industrialized, and as the SBR contained in the rubber composition of the present invention, solution polymerization SBR having excellent low-temperature characteristics is preferable.
- JSR products JSR1500, JSR1502, JSR1507, JSR0202, JSR1503, and the like can be used.
- Asahi Kasei products Toughden 1000, Toughden 2000R, JSR products JSR SL552, JSR SL563, Nippon Zeon products Nipol NS116R, and the like can be used.
- the rubber component in the rubber composition of the present invention may contain other rubber types, such as polybutadiene rubber and / or polybutadiene styrene rubber, and other rubber types (other than polybutadiene rubber and polybutadiene styrene rubber). Rubber type) may be blended.
- the kind of other rubber type is not particularly limited, and is appropriately selected according to the purpose.
- NBR nitrile rubber
- EPDM ethylene-propylene-diene rubber
- silicone rubber nitrile rubber
- NBR nitrile rubber
- EPDM ethylene-propylene-diene rubber
- silicone rubber silicone rubber
- nitrile rubber having a low glass transition point can be blended and used for improving wear resistance.
- Nitrile rubber is not particularly limited, and for example, JSR product JSR N260S, Nippon Zeon products Nipol DN401, Nipol DN401L, Nipol DN401LL, and the like can be used.
- EPDM ethylene-propylene-diene rubber
- the EPDM is not particularly limited.
- NORDEL IP4570, NORDEL IP5565, Dow Chemical products, Espren 532, Esprene 7456, JSR products T7141, EP342, etc. can be used.
- silicone rubber is not particularly limited.
- KE-136Y-U and KE-186-U of Shin-Etsu Chemical products, DY32-379U of Dow Corning products, and the like can be used.
- fluororubber is possible to improve high temperature characteristics.
- fluororubber For example, DuPont Viton A type, B type, F type, Daikin Co., Ltd. Daiel G700 series, 800 series, 900 series, Asahi Glass Co., Ltd. Afras 100 series, 150 series, etc. Can be used.
- the rubber component in the rubber composition of the present invention includes a mixture of polybutadiene rubber and polybutadiene styrene rubber, or other rubber types
- the blending amount of each rubber type is within a range where the object of the present invention can be achieved, What is necessary is just to determine suitably according to the objective.
- the content of structural units derived from butadiene in the rubber component is 70% by mass or more based on the rubber component. If the content of the structural unit derived from butadiene in the rubber component is 70% by mass or more with respect to the rubber component, it becomes a situation in which breakdown such as blister breakage, protrusion breakage, and buckling failure is less likely to occur. It is also possible to suppress the compression set that is an important evaluation characteristic. More preferably, the content of the structural unit derived from butadiene in the rubber component is 80% by mass or more with respect to the rubber component, and the above-described fracture is less likely to occur, and the compression set can be further reduced. Become. More preferably, it is 90 mass% or more with respect to a rubber component.
- the “structural unit derived from butadiene” means a portion derived from one molecule of 1,3-butadiene, present in a polymer obtained by homopolymerization or copolymerization of 1,3-butadiene (monomer).
- the “content of structural units derived from butadiene in the rubber component” refers to the total amount of structural units derived from butadiene contained in the rubber species constituting the rubber component.
- the structural unit derived from butadiene may be contained not only in polybutadiene rubber and polybutadiene styrene rubber but also in other rubber types.
- the content of the structural unit derived from butadiene in the rubber component is 100% by mass when the rubber component is made of polybutadiene rubber.
- a rubber component consists of polybutadiene styrene rubber, it can calculate based on the copolymer composition ratio of a butadiene and styrene, for example.
- the content of the structural unit derived from butadiene in the rubber component is a structural unit derived from butadiene contained in polybutadiene rubber and polybutadiene styrene rubber. The total amount with the structural unit derived from butadiene contained in other rubber types.
- the content of the structural unit derived from butadiene in the rubber component is, for example, pyrolysis GC or heat after extracting compounding agents such as process oil by Soxhlet extraction (Method A described in JIS K 6229 (2013)).
- a calibration curve and analysis results decomposition of BR-derived pyrolysis products such as butadiene and 4-vinyl-1-cyclohexene, pyrolysis derived from SBR, decomposition using GC / MS with decomposition GC-MS) Detection peaks for butadiene, 4-vinyl-1-cyclohexene, styrene, etc., thermal decomposition products derived from NBR, detection peaks for butadiene, 4-vinyl-1-cyclohexene, acrylonitrile, thermal decomposition products derived from EPDM It can be calculated using a certain C3-C8 paraffin detection peak).
- the content of structural units derived from butadiene in the rubber component can be calculated from detection peaks of butadiene and 4-vinyl-1-cyclohexene, which are thermal decomposition products of structural units derived from butadiene. It is.
- the generation origin of butadiene or 4-vinyl-1-cyclohexene may be a peak derived from any occurrence of BR, SBR, NBR, liquid rubber and the like.
- analysis can be performed using detection peaks whose holding times do not overlap under the analysis conditions described in JIS K 6231 (2013) and JIS K 6231-2 (2013) or in compliance with the conditions.
- the content of structural units derived from butadiene in the rubber component can also be measured from a high-pressure gas sealing member after vulcanization molding.
- the rubber composition of the present invention may be a rubber component alone or a composition containing a rubber component and a compounding agent, but usually contains a rubber component and a compounding agent.
- a known compounding agent generally used in the rubber industry may be used as long as the object of the present invention is not impaired.
- the type and amount of compounding agent are not particularly limited, but depending on the type and amount of compounding agent, when the rubber composition of the present invention is exposed to high-pressure gas for a long time, Since the properties may be changed, the amount of the extract when the rubber composition of the present invention is subjected to Soxhlet extraction based on Method A described in JIS K 6229 (2013) using acetone as a solvent is It is preferably 12% by mass or less, and preferably 10% by mass or less, of the rubber composition of the invention.
- the rubber composition of the present invention may be uncrosslinked, but is usually crosslinked.
- vulcanization may be used as a term synonymous with “crosslinking”. That is, in the present application, “vulcanization” means not only crosslinking of a rubber component using sulfur or sulfur and a vulcanization accelerator, but also using a crosslinking agent other than sulfur such as an organic peroxide. It also means cross-linking the rubber component.
- the crosslinking (vulcanization) method is not particularly limited as long as the object of the present invention is not impaired.
- a more preferable crosslinking (vulcanization) method is peroxide vulcanization which is crosslinked using an organic peroxide. That is, the rubber composition of the present invention is preferably a peroxide vulcanizate.
- Peroxide vulcanizates have improved compression set characteristics and are preferred for FCV applications because there is no concern about sulfur poisoning of the fuel cell catalyst.
- Peroxide vulcanizates can be organically detected when sulfur is not detected by fluorescent X-ray analysis of the rubber composition, or by extracting the rubber composition with Soxhlet and subjecting the extract to GC-MS or FT-IR analysis. This can be confirmed by detecting a peroxide residue (decomposed product).
- the organic peroxide can be used without particular limitation as long as it is generally usable for rubber.
- benzoyl peroxide p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tertiary.
- the compounding amount of the organic peroxide may be appropriately determined according to the kind of the organic peroxide, but is usually 0.2 to 8 parts by mass, preferably 1 to 5 parts per 100 parts by mass of the rubber component. Used in the ratio of parts by mass.
- compounding agents include reinforcing agents such as carbon black and silica, fillers such as talc, clay, graphite, calcium silicate and calcium carbonate, stearic acid, palmitic acid, paraffin wax, and process oil. And processing aids, metal oxides such as zinc oxide and magnesium oxide, anti-aging agents, plasticizers, and scorch inhibitors. These compounding agents may use only 1 type and may use 2 or more types together.
- the rubber composition of the present invention may contain a reinforcing agent such as carbon black or silica. Only 1 type may be used for a reinforcing agent and it may use 2 or more types together.
- the carbon black includes at least one of hard carbon types SAF, ISAF and HAF from the viewpoint of giving strength to the rubber.
- the compression set property of rubber it is preferable for the compression set property of rubber to contain at least one of soft carbon species FEF, GPF, HMF and SRF. It is preferable to use a hard carbon species and a soft carbon species in combination.
- SAF, ISAF, HAF, FEF, GPF, HMF, and SRF are all abbreviations of carbon black classified according to the American ASTM standard D-1765-82a.
- the amount of carbon black added can be appropriately selected according to the purpose, but from the viewpoint of strength, hardness, and abrasion resistance, it is preferable to add 50 parts by mass or more with respect to 100 parts by mass of the rubber component, and more preferably 100 parts by mass or more. preferable.
- the rubber composition of the present invention may contain process oil.
- the process oil is preferably paraffinic or naphthenic oil.
- the addition amount may be appropriately determined within a range that does not impair the object of the present invention, but when exposed to a high-pressure gas for a long time, the process oil may be pushed out, which may cause a change in properties of the rubber composition. Therefore, it is preferably 12% by mass or less, and more preferably 10% by mass or less, based on the rubber composition or the rubber composition after vulcanization, which hardly affects changes in physical properties.
- the amount of process oil can be measured by Soxhlet extraction (Method A described in JIS K 6229 (2013)).
- sub (factis) or liquid rubber as an alternative to process oil.
- the sub (factis) is preferably a sub (factis) treated with a sulfur-free type peroxide
- the liquid rubber is preferably liquid butadiene rubber or liquid styrene butadiene rubber from the viewpoint of compatibility with polybutadiene and / or polybutadiene styrene.
- Liquid rubber that can be used as an alternative to process oil includes, for example, Kuraray's liquid polybutadiene: rubber grades such as LBR-300, LBR-302B, LBR-305, LBR-307, LBR-352, and LBR-361, Kuraray liquid styrene butadiene rubbers: rubber grades such as L-SBR-820 and L-SBR-841 are preferably used.
- Kuraray's liquid polybutadiene rubber grades such as LBR-300, LBR-302B, LBR-305, LBR-307, LBR-352, and LBR-361
- Kuraray liquid styrene butadiene rubbers rubber grades such as L-SBR-820 and L-SBR-841 are preferably used.
- the rubber composition of this invention may contain anti-aging agent, and anti-aging agent may use 1 type (s) or 2 or more types together.
- the anti-aging agent is not particularly limited and conventionally known anti-aging agents can be used, but those containing nitrogen atoms are preferable. Specifically, amine-ketone type, aromatic secondary amine type, imidazole type and the like are preferable. Such an anti-aging agent is preferable because, in addition to the anti-aging effect, when carbon black is added as a compounding agent, the effect of dispersing the carbon black is also enhanced.
- the anti-aging agent when exposed to high-pressure gas for a long time, the anti-aging agent is pushed out, and the property change of the rubber composition may become a problem, so that non-eluting aging having reactive functional groups such as methacrylic groups Inhibitors are preferred.
- the rubber composition of the present invention may contain a co-crosslinking agent.
- the co-crosslinking agent include polyfunctional unsaturated compounds. Only 1 type may be used for a polyfunctional unsaturated compound and it may use 2 or more types together.
- polyfunctional unsaturated compound examples include a quinonedioxime-based polyfunctional unsaturated compound (eg, p-quinonedioxime) and a methacrylate-type polyfunctional unsaturated compound (eg, ethylene glycol dimethacrylate).
- quinonedioxime-based polyfunctional unsaturated compound eg, p-quinonedioxime
- methacrylate-type polyfunctional unsaturated compound eg, ethylene glycol dimethacrylate
- allyl polyfunctional unsaturated compounds eg diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, etc.
- maleimide type examples thereof include polyfunctional unsaturated compounds (for example, maleimide, phenylmaleimide, N, N′-m-phenylenebismaleimide), maleic anhydride, divinylbenzene, vinyltoluene, and 1,2-polybutadiene.
- triallyl isocyanurate and diethylene glycol dimethacrylate are preferable in order to reduce the compression set of the seal member.
- a co-crosslinking agent especially a polyfunctional unsaturated compound
- the amount is preferably 0.1 to 20 parts by mass, particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass of the rubber component.
- One preferred embodiment of the rubber composition of the present invention is a rubber composition containing polybutadiene rubber and / or polystyrene butadiene rubber, a crosslinking agent, and a reinforcing agent.
- a rubber composition includes a rubber composition containing polybutadiene rubber and / or polystyrene butadiene rubber, an organic peroxide, and carbon black.
- the rubber composition further contains carbon black
- the rubber component in the rubber composition is 20 to 66% by mass with respect to the rubber composition.
- examples thereof include rubber compositions in which carbon black is 50 to 400 parts by mass with respect to 100 parts by mass of the rubber component.
- the rubber composition further contains carbon black, the rubber component in the rubber composition is 20 to 66% by mass with respect to the rubber composition, and with respect to 100 parts by mass of the rubber component, Examples thereof include a rubber composition having 50 to 400 parts by mass of carbon black and an acetone extraction amount of the rubber composition of 12% by mass or less.
- Such a rubber composition has a small compression set. Moreover, the physical property change by rapid decompression etc. by high pressure gas exposure is suppressed, and it becomes more excellent and preferable.
- the production method of the rubber composition of the present invention is not particularly limited, and may be selected from conventionally known methods according to the purpose.
- the rubber composition of the present invention is produced by kneading using a kneader such as an intermix, kneader, Banbury mixer or an open roll.
- a kneader such as an intermix, kneader, Banbury mixer or an open roll.
- vulcanization molding for example, an injection molding machine, a compression molding machine, a vulcanization press, or the like is used.
- vulcanization molding is performed by heating at about 150 to 200 ° C. for about 3 to 60 minutes, and if necessary, oven heating (secondary heating at about 80 to 150 ° C. for about 1 to 24 hours. Vulcanization) is performed.
- the present invention relates to a high-pressure gas seal member molded by using the rubber composition of the present invention (hereinafter sometimes referred to as “the seal member of the present invention”). That is, the seal member of the present invention has the rubber composition of the present invention.
- the rubber composition of the present invention may be used as it is depending on the purpose, or may be used after being crosslinked or molded. Moreover, what was shape
- the production method is not particularly limited, and the sealing member of the present invention can be produced by appropriately selecting a conventionally known method according to the purpose. Further, the high-pressure gas sealing member only needs to be able to substantially prevent the gas from leaking, and does not need to be sealed so that the gas does not completely leak from a container such as a tank.
- the sealing member of this invention is a molded object, a shape will not be specifically limited, The shape can be suitably selected according to the objective.
- Specific examples of the seal member of the present invention include O-rings, packings, gaskets, hoses, and the like, and preferably any one selected from the group consisting of O-rings, packings, and gaskets.
- the hardness of the sealing member of the present invention is preferably a durometer A hardness of 60 or more, more preferably a durometer A hardness of 80 or more, from the viewpoint of reducing the volume expansion rate during rapid decompression after high pressure gas exposure and improving wear resistance.
- a durometer A hardness of 85 or more is more preferable.
- the durometer hardness is less than 60, the volume expansion becomes very large at the time of rapid decompression after exposure to high pressure gas. For this reason, for example, in the case of an O-ring, there are “extrusion failure” by protruding from the O-ring groove, “buckling failure” due to expansion in the circumferential direction, “blister failure” in which the rubber locally expands and bursts, etc. It tends to happen.
- the seal member of the present invention has characteristics that it does not generate blisters even when exposed to high-pressure gas and has excellent low-temperature characteristics. Furthermore, the sealing member of the present invention has a small compression set and good wear resistance (sliding characteristics). Therefore, the seal member of the present invention can be used as a seal member for various high-pressure gas equipment, and is particularly suitable as a seal member for equipment handling hydrogen gas or helium gas.
- high-pressure gas equipment examples include high-pressure hydrogen containers for fuel cell vehicles, members for hydrogen stations, high-pressure helium containers for the space industry, and the like, for example, stored high-pressure hydrogen gas (for example, hydrogen gas of 70 MPa or more) ) Storage tank seal member, hydrogen station seal member, and high pressure helium seal seal member for space industry applications.
- stored high-pressure hydrogen gas for example, hydrogen gas of 70 MPa or more
- Storage tank seal member, hydrogen station seal member, and high pressure helium seal seal member for space industry applications The high-pressure gas device will be described in detail later.
- High-pressure gas means a compressed gas or a liquefied gas specified by the High-Pressure Gas Safety Law.
- the “compressed gas” refers to a gas whose pressure (gauge pressure) is 1 MPa or more at ordinary temperature or a gas whose pressure is 1 MPa or more at 35 ° C. (excluding compressed acetylene gas). It is.
- the “liquefied gas” refers to a gas having a pressure of 0.2 MPa or higher at a normal temperature or a gas having a temperature of 35 ° C. or lower when the pressure is 0.2 MPa.
- the sealing member of the present invention can seal such an extremely high pressure gas (particularly hydrogen or helium gas), and has excellent sealing properties. Therefore, the sealing member of the present invention is more preferably used for sealing high-pressure gas (compressed gas) of 1 MPa or more.
- the pressure resistance of the high-pressure gas sealing member of the present invention is preferably intended for use with a high-pressure gas of 1 MPa or more.
- a high-pressure gas of 1 MPa or more.
- excellent pressure-resistant sealing performance is exhibited even under use conditions at 35 MPa or higher (for example, 50 MPa or higher, 70 MPa or higher, 90 MPa or higher) in accordance with the specification of the storage tank.
- “1 MPa” is the pressure in the compressed gas (gas).
- the high-pressure gas sealing member of the present invention exhibits excellent sealing properties even in a wide temperature range (particularly in a low temperature environment), and is preferably used at -70 ° C to 100 ° C (preferably -40 ° C to 85 ° C). .
- the sealing member of the present invention may be sealed alone, or an existing grease may be used in combination, or a backup ring and the sealing member of the present invention may be used. It is also possible to seal by using together.
- the grease is not particularly limited, and silicone-based or fluorine-based grease may be used.
- fluorine-based grease is particularly preferable in terms of suppressing ozone degradation during product storage.
- various grades of Krytox series manufactured by DuPont, various grades of Moricoat manufactured by Toray Dow Corning, etc. are preferably used.
- the ozone resistance improvement effect by fluorine grease application is remarkable, ozone concentration: 50 pphm, test temperature: 40 ° C., no cracking over 120 hours under 20% strain condition (JIS K 6259 (2013) test method) Of durability.
- ozone resistance may be improved by adding wax to rubber used in existing automobile tires and blooming the wax.
- the backup ring When used in conjunction with a backup ring, the backup ring is not particularly limited, and resins for backup rings such as existing fluororesins (PTFE, PFA, PVDF, etc.), nylon (nylon 6, nylon 66, MC nylon), polyester, polyacetal, etc. Further, a backup ring made from a composite of fiber such as glass fiber, resin fiber, carbon fiber and the resin for backup ring may be used.
- resins for backup rings such as existing fluororesins (PTFE, PFA, PVDF, etc.), nylon (nylon 6, nylon 66, MC nylon), polyester, polyacetal, etc.
- a backup ring made from a composite of fiber such as glass fiber, resin fiber, carbon fiber and the resin for backup ring may be used.
- the present invention also relates to an apparatus for high-pressure gas provided with the sealing member of the present invention (hereinafter may be referred to as “the apparatus for high-pressure gas of the present invention”).
- the high-pressure gas device of the present invention is a high-pressure gas device including a sealing member having a rubber composition, and the rubber component in the rubber composition includes polybutadiene rubber and / or polystyrene butadiene rubber,
- the rubber composition is an apparatus for high-pressure gas, which is a rubber composition having a glass transition point of ⁇ 65 ° C. or less.
- the sealing member and rubber composition possessed by the high-pressure gas device are as described above, and the preferred embodiments are also the same.
- Such a device for high-pressure gas of the present invention can be used stably with the leakage of gas suppressed even when used in a wide temperature range or at a sliding part.
- a high-pressure gas device is a device having a location where high-pressure gas contacts.
- the high-pressure gas device of the present invention is preferably a high-pressure gas container or a high-pressure gas piping device.
- the high-pressure gas device of the present invention preferably has a pressure resistance of 1 MPa or more, and more preferably has a pressure resistance of 35 MPa or more. Moreover, it can have pressure resistance, such as 50 MPa or more, 70 MPa or more, 90 MPa or more.
- the sealing member of the present invention can suitably seal hydrogen and helium gas.
- the high-pressure gas device of the present invention is preferably a device having a location where high-pressure hydrogen or high-pressure helium contacts, and is composed of a high-pressure hydrogen container, a high-pressure helium container, a high-pressure hydrogen piping device, and a high-pressure helium piping device. More preferably, it is any one selected from the group. Moreover, it is any one selected from the group consisting of a high-pressure hydrogen container, a high-pressure helium container, a high-pressure hydrogen piping device, and a high-pressure helium piping device, and is preferably a device having a pressure resistance of 1 MPa or more.
- a high-pressure gas container is a gas container filled with high-pressure gas.
- a high-pressure hydrogen container is a container filled with high-pressure hydrogen gas.
- a container filled with high-pressure hydrogen of 1 MPa or more is preferable.
- Examples of the high-pressure hydrogen container include a hydrogen storage tank (for example, a high-pressure hydrogen tank for a fuel cell vehicle) filled with hydrogen of 70 MPa or more, a pressure accumulator for a hydrogen station, and the like.
- a high-pressure helium container is a container filled with high-pressure helium.
- a container filled with high-pressure helium of 1 MPa or more is preferable.
- An example of the high pressure helium vessel is a high pressure helium vessel for the space industry.
- the high-pressure gas piping device is a device provided in a pipe that contacts the high-pressure gas, such as a pipe for transporting the high-pressure gas from the accumulator to the dispenser.
- the high-pressure hydrogen piping device is a device provided in a pipe in contact with high-pressure hydrogen.
- the high-pressure helium piping device is a device provided in a pipe that is in contact with high-pressure helium.
- the high-pressure gas device of the present invention is preferably any one selected from the group consisting of a tank, a pressure accumulator, a valve, a joint, a coupler, a safety valve, a check valve and a pressure regulating valve.
- the high-pressure gas device of the present invention can be a hydrogen station device such as a hydrogen production apparatus, a hydrogen compressor, a pressure accumulator, a hydrogen dispenser, or a high-pressure hydrogen piping device that connects these devices.
- a hydrogen station device such as a hydrogen production apparatus, a hydrogen compressor, a pressure accumulator, a hydrogen dispenser, or a high-pressure hydrogen piping device that connects these devices.
- Each device for the hydrogen station has a different use environment for each device.
- hydrogen for example, in a pressure accumulator, hydrogen of about 90 MPa is stored at about ⁇ 20 ° C. to 50 ° C.
- the temperature is increased when hydrogen is charged, so that it is cooled to ⁇ 40 ° C. as a precool.
- the high-pressure gas device of the present invention can be stably operated by suppressing leakage of high-pressure gas.
- the sealing method of the present invention is also a method of sealing a high-pressure gas of a high-pressure gas device using a sealing member, wherein the sealing member is molded using a rubber composition, and the rubber A method in which the rubber component in the composition contains polybutadiene rubber and / or polystyrene butadiene rubber, and the rubber composition has a glass transition point of ⁇ 65 ° C. or less (hereinafter referred to as “the sealing method of the present invention”). ”).). That is, it is a sealing method for preventing high-pressure gas from leaking from the high-pressure gas equipment using the above-described sealing member of the present invention.
- molds a sealing member and a sealing member is also as having demonstrated above.
- the high-pressure gas device is also as described above, and the preferred embodiment is also the same.
- the high-pressure gas of high-pressure gas equipment used at ⁇ 70 ° C. to 100 ° C. (preferably ⁇ 40 ° C. to 85 ° C.) or high-pressure gas equipment that generates a temperature difference of 65 ° C. to 125 ° C. is sealed. It can be a method to do.
- the sealing member of the present invention is disposed on the sliding portion of the high-pressure gas device to perform sealing.
- the sealing member of the present invention is used in a sliding portion of a high-pressure gas device used at ⁇ 70 ° C. to 100 ° C. (preferably ⁇ 40 ° C. to 85 ° C.) or a temperature difference of 65 ° C. to 125 ° C. It is more preferable to adopt a method of arranging and sealing.
- the seal member of the present invention can maintain rubber elasticity even in a temperature range from low temperature to high temperature, and is excellent in wear resistance and blister resistance.
- the sealing member of the present invention is arranged at the sliding portion of the high-pressure gas equipment, it has been difficult to seal the gas conventionally (especially sliding at low temperature use). The leakage of the high-pressure gas can be suppressed even at the location).
- the sealing method of the present invention is suitable when the high-pressure gas is hydrogen or helium.
- the sealing method of the present invention is suitable when the high-pressure gas is a high-pressure gas of 1 MPa or higher, and more preferable when the high-pressure gas is a high-pressure gas of 35 MPa or higher.
- it can be set as the method of sealing high pressure gas, such as 50 Mpa or more, 70 Mpa or more, 90 Mpa or more.
- Example> 1 Ingredients Each ingredient used in Examples 1 and 2 is listed below.
- Rubber Low cis-BR Nipol BR1250H (vinyl content 7 to 13 mol%) (manufactured by Nippon Zeon), diene NF35R (cis content 35 mol%, trans content 57.5 mol%, vinyl content 7.5 mol% (infrared data) )) (Asahi Kasei Corporation) Solution polymerization SBR: Toughden 2000R (styrene content: 25 wt%) (Asahi Kasei Corporation)
- NBR JSR NBR N260S (acrylonitrile amount: 15 wt%) (manufactured by JSR Corporation)
- EBT Ethylene / Butene Rubber / Diene Copolymer Rubber
- Mitsui EBT-K-9330M Mitsubishi Chemicals
- EPDM Mitsui EPT-3070 (Mitsui Chemicals) Liquid rubber: Claprene L
- Example 1> Production of Rubber Composition and Seal Member Each component was kneaded using a kneader in the mass parts shown in Table 1 to prepare rubber compositions of Examples 1-1 to 1-8. Next, the rubber compositions of Examples 1-1 to 1-8 were press-molded at 170 ° C. with a press-molding device, respectively, to obtain measurement samples and seal members.
- a measurement sample for use in normal property measurement, glass transition point measurement and exposure test was manufactured by punching into a shape corresponding to each evaluation item.
- a measurement sample for evaluation of compression set was produced according to JIS K 6262 (2013).
- the seal member was manufactured to have an O-ring shape.
- Compression set heat resistance / cold resistance Compressed 25% at test temperature (85 ° C or -40 ° C) (compression ratio is based on JIS B 2401-1 Annex JC (2013)) and stored for 24 hours at the same temperature.
- the strain was measured based on JIS K 6262 (2013).
- the compression set is a value measured at a compression temperature of 85 ° C. after 30 minutes of standing at room temperature after releasing the compression.
- a compression temperature of ⁇ 40 ° C. it is a value measured after 30 minutes after being left in an environment of ⁇ 40 ° C. after being released from compression.
- the glass transition temperature of the sealing member was measured using DSC based on JIS K 6240 (2013).
- the measurement conditions are a nitrogen flow rate of 50 mL / min and a temperature increase rate of 20 ° C./min.
- temperature calibration using a standard substance (cyclohexane) described in Annex JB of JIS K 6240 (2013) and baseline adjustment described in JIS K 7122 (2014) were performed in advance.
- the measurement sample was a No. 7 dumbbell shape defined in JIS K 6251 (2013). One side of the measurement sample was measured (L0) in advance at room temperature. Next, a measurement sample is placed in a pressure vessel (capacity 100 mL), exposed to 90 MPa hydrogen for 16 hours at the test temperature (room temperature or ⁇ 40 ° C.), and then rapidly (within 5 seconds) at the same temperature as the exposure temperature. ) Was depressurized. Thereafter, the sample was quickly taken out (room temperature), and a measurement sample for 10 minutes after depressurization was photographed together with the scale at room temperature.
- volume expansion rate (%) (L1 / L0) 3 ⁇ 100 Moreover, the presence or absence of blister destruction was observed by visual observation of the photograph after photography and the actual sample after exposure. The case where there was a blister failure was evaluated as “ ⁇ ”, and the case where there was no blister failure was evaluated as “ ⁇ ”.
- FIG. 1 shows a schematic diagram of a cross section of a pressure test apparatus used in the test.
- FIG. 2 is a photograph of the device before attaching a jig having a gas supply port and a leak detection port
- FIG. 3 is a schematic cross-sectional view of the device before attaching a jig having a gas supply port and a leak detection port. Show.
- the pressure test apparatus used in this test is equipped with a jig having a gas supply port and a leak detection port after fitting an O-ring, thereby preventing high-pressure gas supply and gas leakage. It is possible to detect.
- a seal member was loaded into a pressure test apparatus.
- the test was carried out 6600 times at a test temperature (85 ° C. or ⁇ 40 ° C.) between a normal pressure and 90 MPa in 6 to 8 seconds for one cycle of hydrogen.
- the presence or absence of hydrogen leakage during the test was monitored with a pressure sensor.
- damage of the sealing member after a test was evaluated visually.
- the temperature was adjusted by monitoring the surface temperature of the jig loaded with the seal member. Evaluation was made according to the following criteria depending on hydrogen leakage and the degree of damage of the seal member.
- the temperature was adjusted by monitoring the surface temperature of the casing of the valve loaded with the seal member. Evaluation was made according to the following criteria depending on hydrogen leakage and the degree of damage of the seal member. ⁇ : No hydrogen leak and no damage to the seal member ⁇ : No hydrogen leak, but partial damage to the seal member is noticeable ⁇ : If there is a hydrogen leak, or the seal member is damaged If you are
- Table 1 shows the compositions of the rubber compositions of Examples 1-1 to 1-8 and the evaluation results of the above (5-1) to (5-4).
- the seal members of the examples of the present invention also had good hydrogen resistance at low temperatures, no blister breakage, and a low volume expansion rate in the high-pressure hydrogen exposure test.
- Example 1-1 As shown in Table 1, there was no hydrogen leakage and no damage to the seal member.
- droplets were observed around the seal member after the test. It was.
- this droplet was a part of process oil added as a compounding agent (1.5 wt% loss in 14.5 wt%).
- Example 1-5 Hydrogen pressure cycle test-2
- the seal member of Example 1-5 was evaluated in the same manner as described in (5-2) except that the test temperature was -58 ° C to -50 ° C or 85 ° C to 110 ° C.
- the seal member of Example 1-5 was subjected to a hydrogen resistance pressure cycle test at a test temperature of ⁇ 58 ° C. to ⁇ 50 ° C., and the result was that there was no hydrogen leakage after 1600 tests.
- a hydrogen pressure cycle test was conducted at a test temperature of 85 ° C. to 110 ° C., the result was that there was no hydrogen leakage even after 6600 tests.
- Example 1-5 a hydrogen pressure-resistant cycle test (one cycle of hydrogen pressure reduction between normal pressure and 95 MPa) was performed at each temperature of ⁇ 40 ° C., room temperature, and 85 ° C. The sample was not changed. As a result, 7600 times at ⁇ 40 ° C., 6700 times at room temperature, and 38900 times at 85 ° C., no hydrogen leakage was observed in the same sample (no sample exchange). From this result, it became clear that it was highly durable to withstand a total of 53200 pressure cycles at each temperature.
- Example 2> Production of Rubber Composition and Seal Member Each component shown in Table 2 was kneaded using a kneader to prepare rubber compositions of Examples 2-1 to 2-3. Next, the rubber compositions of Example 2-1 to Example 2-3 were each press-molded at 170 ° C. with a press-molding apparatus to obtain a measurement sample and a seal member.
- ⁇ Comparative Example 1> Production of Rubber Composition and Seal Member Each component was kneaded in a mass part shown in Table 3 using a kneader to prepare rubber compositions of Comparative Examples 1-1 to 1-6. Next, the rubber compositions of Comparative Examples 1-1 to 1-6 were respectively press molded at 170 ° C. with a press molding apparatus to obtain measurement samples and seal members. The shapes of the measurement sample and the seal member are the same as those in the example.
- the rubber compositions of Comparative Examples 1-1 to 1-6 may be damaged at a higher temperature than the rubber compositions of Examples, and therefore, instead of the ⁇ 65 ° C. high pressure hydrogen sealability test.
- a high-pressure hydrogen sealability test was conducted at the test temperature (room temperature, -20 ° C, -30 ° C, or -40 ° C).
- the test method was the same as Example (5-4) except that the test temperature was changed to ⁇ 65 ° C. and changed to the test temperature (room temperature, ⁇ 20 ° C., ⁇ 30 ° C., or ⁇ 40 ° C.).
- Table 3 shows the compositions and evaluation results of the rubber compositions of Comparative Examples 1-1 to 1-6.
- the volume expansion coefficient was a result of decreasing as the hardness increased. Moreover, the volume expansion coefficient was a result of decreasing as the content of structural units derived from butadiene in the rubber component increased. Further, in the high-pressure hydrogen exposure test under the ⁇ 40 ° C. environment, blister breakdown was observed when the test environment temperature was below the glass transition point.
- ⁇ Comparative example 2> As a comparative example of an existing product, using an existing O-ring (low temperature EPDM) compatible with a low temperature of a commercially available valve device (super high pressure hydrogen gas adaptive valve (manufactured by Fujikin)), the same as in Comparative Example 1-5, ⁇ 40 A high-pressure hydrogen-based seal test was conducted at 0 ° C. As a result, when the casing temperature was adjusted (targeted at ⁇ 40 ° C.), when the casing temperature dropped to ⁇ 43 ° C., hydrogen leaked quickly.
- an existing O-ring low temperature EPDM
- a commercially available valve device super high pressure hydrogen gas adaptive valve (manufactured by Fujikin)
- the sealing member of this example did not leak at all under the same conditions, and high-pressure hydrogen sealing was possible even at ⁇ 65 ° C. as described above. As described above, there is a clear difference between the existing seal member and the seal member of this embodiment, and the superiority thereof is clarified.
- Table 4 shows the evaluation results.
- Comparative Example 3-1 brusta destruction was observed at room temperature in the high-pressure hydrogen exposure test.
- Comparative Examples 3-2 to 3-4 no brusta destruction was confirmed in the high-pressure hydrogen exposure test.
- the volume expansion was also the same as or slightly inferior to Examples 1-1 to 1-8.
- hydrogen leakage was confirmed in the hydrogen resistant pressure cycle test at ⁇ 40 ° C.
- Comparative Examples 3-2 to 3-4 hydrogen leakage was confirmed in the hydrogen resistant sliding test at ⁇ 40 ° C.
- the friction at the portion in contact with the shaft of the valve that moves up and down is large, and the fuzz is severe.
- the seal member taken out after the hydrogen-resistant sliding test at 85 ° C. has been confirmed to be in a state in which partial damage (abrasion) of the seal member due to friction has occurred remarkably at the place where it contacts the vertically moving valve shaft. Sexual deficiency was suggested.
- ⁇ Comparative example 4> Production of rubber composition and seal member 100 parts by mass of cryogenic silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KE-136Y-U), 30 parts by mass of silica (manufactured by Tosoh Corporation, VN3), hexamethyldisilazane (Wako Pure)
- a rubber composition of Comparative Example 4 was prepared by kneading 1.5 parts by mass of Yaku Kogyo Co., Ltd. and 1.8 parts by mass of a crosslinking agent (C-8A, manufactured by Shin-Etsu Chemical Co., Ltd.) with a kneader. .
- a measurement sample and a seal member were obtained in the same manner as in Comparative Example 1-1.
- Comparative Example 4 was measured by the same method as in Example 1, and it was 87.
- the glass transition point of Comparative Example 4 was measured by the same method as in Example 1. As a result, it was ⁇ 125 ° C.
- the sealing performance at ⁇ 40 ° C. of the sealing member of Comparative Example 4 was evaluated in the same manner as Comparative Example 1-1.
- the sealing member of Comparative Example 4 could be sealed even at ⁇ 40 ° C.
- an Akron wear amount was determined by an Akron wear test.
- the amount of Akron abrasion of comparative example 4 was 0.101 (cc / 1000 times / 27.0N). Further, for Example 1-3 and Example 1-5, the amount of Akron wear was determined in the same manner as in Comparative Example 4, and 0.011 (cc / 1000 times / 27.0 N) and 0.011 (cc / 1000 times / 27.0 N).
- Table 5 shows the evaluation results of hardness (durometer A), glass transition point, acron wear and -40 ° C. sealability of Examples 1-3, 1-5 and Comparative Example 4. Comparing the results, the amount of abrasion of Akron in Comparative Example 4 was nearly 10 times larger than that in Examples 1-3 and 1-5. It should be noted that the larger the value of the Akron wear amount, the greater the wear. That is, the sealing member of Comparative Example 4 can be sealed with high-pressure hydrogen at low temperatures, but it is likely to be worn and used for applications where wear resistance such as sliding parts is required. Is unsuitable. On the other hand, Examples 1-3 and 1-5 can be suitably used even for applications that require wear resistance such as sliding portions.
- the rubber composition of the present invention is excellent in wear resistance, low temperature resistance, heat resistance and blister resistance, and is used as a seal member for various high-pressure gas equipment, particularly as a seal member for equipment handling hydrogen gas or helium gas. Can be industrially useful.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Gasket Seals (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020197017646A KR102326698B1 (ko) | 2017-03-31 | 2018-03-27 | 고압 가스용 실링 부재에 사용되기 위한 고무 조성물, 고압 가스용 실링 부재, 고압 가스용 기기 및 고압 가스 실링 방법 |
CN201880005313.2A CN110099981A (zh) | 2017-03-31 | 2018-03-27 | 高压气体用密封部件中使用的橡胶组合物、高压气体用密封部件、高压气体用机器和高压气体密封方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017-071804 | 2017-03-31 | ||
JP2017071804A JP6312183B1 (ja) | 2017-03-31 | 2017-03-31 | 高圧ガス用シール部材に用いられるためのゴム組成物および高圧ガス用シール部材 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018181373A1 true WO2018181373A1 (ja) | 2018-10-04 |
Family
ID=61968264
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/012531 WO2018181373A1 (ja) | 2017-03-31 | 2018-03-27 | 高圧ガス用シール部材に用いられるためのゴム組成物、高圧ガス用シール部材、高圧ガス用機器および高圧ガスシール方法 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6312183B1 (zh) |
KR (1) | KR102326698B1 (zh) |
CN (1) | CN110099981A (zh) |
WO (1) | WO2018181373A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021020204A1 (ja) * | 2019-08-01 | 2021-02-04 | 株式会社オートネットワーク技術研究所 | ワイヤーハーネス |
EP3783060A1 (en) | 2019-07-29 | 2021-02-24 | The Goodyear Tire & Rubber Company | Rubber composition and pneumatic tire |
US11441021B2 (en) | 2019-07-29 | 2022-09-13 | The Goodyear Tire & Rubber Company | Pneumatic tire |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7368936B2 (ja) * | 2018-09-27 | 2023-10-25 | 株式会社バルカー | シール部材付き継手 |
JP7182459B2 (ja) * | 2018-12-27 | 2022-12-02 | Toyo Tire株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
JP7411446B2 (ja) * | 2019-02-27 | 2024-01-11 | 旭有機材株式会社 | 流体輸送配管用シール部材に用いられるためのゴム製部材 |
WO2023074312A1 (ja) * | 2021-11-01 | 2023-05-04 | Nok株式会社 | ゴム製品、シール材用の試験治具及び試験装置並びに漏れ検知部材 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000104833A (ja) * | 1998-09-29 | 2000-04-11 | Kureha Elastomer Kk | エアゾール噴霧器用ゴム製シール材 |
JP2005233296A (ja) * | 2004-02-19 | 2005-09-02 | Kumamoto Technology & Industry Foundation | 液体ヘリウムトランスファーライン |
JP2016508082A (ja) * | 2012-12-21 | 2016-03-17 | ランクセス・ドイチュランド・ゲーエムベーハー | 複合材料 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003028302A (ja) | 2001-07-16 | 2003-01-29 | Nok Corp | 密封装置 |
JP2007292235A (ja) * | 2006-04-26 | 2007-11-08 | Toyota Motor Corp | 圧力容器用バルブアッセンブリ及び圧力容器 |
EP2033993B1 (en) | 2006-06-27 | 2013-08-21 | NOK Corporation | Silicone rubber composition |
KR101267942B1 (ko) * | 2011-09-30 | 2013-05-27 | 평화오일씰공업주식회사 | 냉매 압축기용 오링의 고무 조성물 |
JP2014114878A (ja) * | 2012-12-10 | 2014-06-26 | Kawasaki Heavy Ind Ltd | シール構造 |
JP2015108104A (ja) | 2013-12-03 | 2015-06-11 | 高石工業株式会社 | ゴム組成物 |
JP5885131B2 (ja) * | 2013-12-27 | 2016-03-15 | 住友電気工業株式会社 | 耐寒性ゴム組成物 |
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 |
CN107709503B (zh) * | 2015-06-26 | 2019-06-18 | 日本瑞翁株式会社 | 气体密封构件用组合物及气体密封构件 |
-
2017
- 2017-03-31 JP JP2017071804A patent/JP6312183B1/ja active Active
-
2018
- 2018-03-27 KR KR1020197017646A patent/KR102326698B1/ko active IP Right Grant
- 2018-03-27 WO PCT/JP2018/012531 patent/WO2018181373A1/ja active Application Filing
- 2018-03-27 CN CN201880005313.2A patent/CN110099981A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000104833A (ja) * | 1998-09-29 | 2000-04-11 | Kureha Elastomer Kk | エアゾール噴霧器用ゴム製シール材 |
JP2005233296A (ja) * | 2004-02-19 | 2005-09-02 | Kumamoto Technology & Industry Foundation | 液体ヘリウムトランスファーライン |
JP2016508082A (ja) * | 2012-12-21 | 2016-03-17 | ランクセス・ドイチュランド・ゲーエムベーハー | 複合材料 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3783060A1 (en) | 2019-07-29 | 2021-02-24 | The Goodyear Tire & Rubber Company | Rubber composition and pneumatic tire |
US11441021B2 (en) | 2019-07-29 | 2022-09-13 | The Goodyear Tire & Rubber Company | Pneumatic tire |
WO2021020204A1 (ja) * | 2019-08-01 | 2021-02-04 | 株式会社オートネットワーク技術研究所 | ワイヤーハーネス |
JP2021026832A (ja) * | 2019-08-01 | 2021-02-22 | 株式会社オートネットワーク技術研究所 | ワイヤーハーネス |
CN114175403A (zh) * | 2019-08-01 | 2022-03-11 | 株式会社自动网络技术研究所 | 线束 |
JP7419697B2 (ja) | 2019-08-01 | 2024-01-23 | 株式会社オートネットワーク技術研究所 | ワイヤーハーネス |
CN114175403B (zh) * | 2019-08-01 | 2024-02-02 | 株式会社自动网络技术研究所 | 线束 |
Also Published As
Publication number | Publication date |
---|---|
JP2018172538A (ja) | 2018-11-08 |
JP6312183B1 (ja) | 2018-04-18 |
KR20190086519A (ko) | 2019-07-22 |
CN110099981A (zh) | 2019-08-06 |
KR102326698B1 (ko) | 2021-11-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2018181373A1 (ja) | 高圧ガス用シール部材に用いられるためのゴム組成物、高圧ガス用シール部材、高圧ガス用機器および高圧ガスシール方法 | |
JP5244469B2 (ja) | ゴム成分の耐dme性の付与方法 | |
JP5414196B2 (ja) | 高/低温負荷シール性が良好なフッ素ゴム系シール材 | |
JP5223674B2 (ja) | シリコーンゴム組成物 | |
JP6914771B2 (ja) | 過酸化物架橋用フッ素ゴム組成物 | |
WO2007094447A1 (ja) | 水素化nbr組成物 | |
JP2013159632A (ja) | 熱可塑性エラストマー組成物及び発泡体 | |
JP7005745B2 (ja) | 積層体およびその用途 | |
JP5223672B2 (ja) | シリコーンゴム組成物 | |
JP4855199B2 (ja) | 耐急速減圧性シール部材を用いたバルブ | |
US8697782B2 (en) | Rubber composition | |
JP2011168630A (ja) | 耐燃料透過性の良好な耐寒フッ素ゴム組成物 | |
JP2016216549A (ja) | ゴム組成物及びそれを用いたホース | |
JP6034707B2 (ja) | 空気圧機器のシール用ゴム組成物およびそれを用いた空気圧機器用シール | |
JP4651202B2 (ja) | シール材用ゴム組成物を用いたシール材 | |
JP3840230B2 (ja) | ゴム組成物 | |
EP3409742B1 (en) | Rubber composition and high-pressure hydrogen instrument seal component using same | |
JPH11100465A (ja) | 水素化nbr組成物 | |
KR20240079600A (ko) | 혼합냉매에 적용 가능한 냉매호스 | |
CN112708255A (zh) | 一种耐低温弹性体橡胶组合物及其应用 | |
KR20100073605A (ko) | 냉각 및 냉방장치의 압축기의 씰링용 고무 조성물 | |
WO2019181722A1 (ja) | ガスシール用シリコーンゴム組成物 | |
JP2011079974A (ja) | ゴム組成物およびそれを用いたシ−ル部材 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18777432 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20197017646 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 18777432 Country of ref document: EP Kind code of ref document: A1 |