WO2011129168A1 - ゴム組成物及びその用途 - Google Patents
ゴム組成物及びその用途 Download PDFInfo
- Publication number
- WO2011129168A1 WO2011129168A1 PCT/JP2011/055667 JP2011055667W WO2011129168A1 WO 2011129168 A1 WO2011129168 A1 WO 2011129168A1 JP 2011055667 W JP2011055667 W JP 2011055667W WO 2011129168 A1 WO2011129168 A1 WO 2011129168A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- rubber composition
- sih
- molecule
- mass
- Prior art date
Links
- HXZGEZRMZONNIJ-UHFFFAOYSA-N C[N-][NH+](N)N(O)ON Chemical compound C[N-][NH+](N)N(O)ON HXZGEZRMZONNIJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/02—Polysilicates
-
- 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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0284—Organic resins; Organic polymers
-
- 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
- C09K2200/0625—Polyacrylic esters or derivatives thereof
-
- 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
- C09K2200/0642—Copolymers containing at least three different monomers
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to rubber compositions and their uses. Specifically, the present invention relates to a rubber composition that can be used for various gasket materials such as a gasket material for fuel cells and various sealing materials, a gasket material and a sealing material for fuel cells obtained from the rubber composition, and those For the main body that implemented
- Fuel cells are an efficient, clean power generation system that directly extracts electricity by the reverse reaction of water electrolysis, that is, chemically reacting hydrogen and oxygen, and is attracting attention as a new energy system for automobiles and homes. ing.
- a cell seal member of a fuel cell a low-cost material excellent in heat resistance, acid resistance, gas permeation resistance and high-speed formability is required.
- fluorine rubber is applied from heat resistance and acid resistance
- butyl rubber is applied from gas resistance
- silicone rubber is applied from heat resistance and high-speed formability.
- a normal millable material is not sufficient, and a method using liquid silicone rubber and applying LIM (Liquid Injection Molding) molding is considered.
- silicone rubber is excellent in heat resistance and high-speed moldability, it can not be said that acid resistance and gas permeation resistance are sufficient. Further, in the fuel cell, in order to further improve the power generation performance, raising the power generation reaction temperature has been studied, and excellent high temperature durability is required for the gasket material and the sealing material.
- Patent Document 1 a rubber composition excellent in heat resistance, acid resistance, gas permeation resistance and high speed moldability has been proposed (Patent Document 1, Patent Document 2).
- These rubber compositions are liquid rubber compositions that can be molded by LIM, and are suitable for use as gasket materials for fuel cells where a low-hardness seal is required even with high compression, since molded articles with low hardness can be obtained. There is.
- the silicone rubber composition which has self-adhesiveness with organic resin, and is hard to adhere to metal, such as a metallic mold, is proposed (patent documents 3).
- this silicone rubber composition is not sufficient in acid resistance and gas permeation resistance, it is also excellent in acid resistance and gas permeation resistance, and has self-adhesiveness to organic resins such as PET, PEN, PBT, etc. There is a need for rubber compositions.
- Patent document 1 JP 2008-156574
- Patent Document 1 Japanese Patent Application Publication No. 2008-156575 JP-A-6-172738
- the present invention is excellent in heat resistance, acid resistance, gas permeation resistance and high speed moldability, low hardness and low reaction force, excellent in compression set resistance at high temperature, and further a mold It is an object of the present invention to provide a rubber composition having self-adhesiveness to an organic resin, while being difficult to adhere to metals such as
- an ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A] satisfying the following (a) to (e): (A) a copolymer of ethylene, an ⁇ -olefin and a nonconjugated polyene, (B) the carbon number of the ⁇ -olefin is 3 to 20, (C) the mass ratio of ethylene units / ⁇ -olefin units is 35/65 to 95/5, (D) The iodine value is in the range of 0.5 to 50, (E) The intrinsic viscosity [ ⁇ ] measured in a decalin solution at 135 ° C.
- SiH group-containing compound [B-1] having two SiH groups in one molecule represented by the following general formula [II] and / or SiH in one molecule represented by the following general formula [III]
- R 3 is a monovalent group having 1 to 10 carbon atoms, which is an unsubstituted or substituted saturated hydrocarbon group or an aromatic hydrocarbon group, and may be the same or different in one molecule, a is an integer of 0 to 20, b is an integer of 0 to 20, and R 4 is a divalent organic group having 1 to 30 carbon atoms or an oxygen atom.
- R 5 is a monovalent group having 1 to 10 carbon atoms, which is an unsubstituted or substituted saturated hydrocarbon group or aromatic hydrocarbon group, and may be the same or different in one molecule, a, b and c are each independently an integer of 0 to 20, and R 6 is a trivalent organic group having 1 to 30 carbon atoms.
- n is an integer of 0 to 10.
- n is an integer of 0 to 10.
- n is an integer of 0 to 10.
- the rubber composition according to the first aspect of the present invention comprises an ethylene / ⁇ -olefin / non-conjugated polyene copolymer [A] and an SiH group-containing compound having two SiH groups in one molecule as a crosslinking agent B-1] and / or a SiH group-containing compound [B-2] having three SiH groups in one molecule, and the above-mentioned predetermined methacrylic acid ester compound [C] as a self-adhesion imparting component to an organic resin And.
- a second aspect of the present invention is a rubber composition characterized in that the non-conjugated polyene is at least one norbornene compound represented by the following general formula [I].
- n is an integer of 0 to 10
- R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
- R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms .
- the methacrylic acid ester compound [C] is contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A]. Rubber composition.
- an SiH group-containing compound [B-1] having two SiH groups in one molecule and an SiH group-containing compound [B-2] having three SiH groups in one molecule In an embodiment used in combination, an SiH group-containing compound having two SiH groups in one molecule with respect to 100 parts by mass of the ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A] [B-1 Rubber containing 3.0 to 7.0 parts by mass of a SiH group-containing compound [B-2] having three SiH groups in one molecule. It is a composition.
- an SiH group-containing compound [B-1] having two SiH groups in one molecule represented by formulas [II-1], [II-2], [II-3] and It is a rubber composition which is at least one compound selected from the group consisting of [II-4].
- a sixth aspect of the present invention is the rubber composition wherein the SiH group-containing compound [B-2] having three SiH groups in one molecule is a compound represented by the formula [III-1].
- a seventh aspect of the present invention is a fuel cell gasket material comprising the above rubber composition.
- An eighth aspect of the present invention is a fuel cell provided with a fuel cell gasket material comprising a rubber composition.
- a ninth aspect of the present invention is a sealing material comprising the above rubber composition.
- the first aspect of the present invention it is excellent in heat resistance, acid resistance, gas permeation resistance and high speed moldability, low hardness and low reaction force, and excellent in compression set resistance at high temperature, Since it contains the above-mentioned predetermined methacrylic acid ester compound [C], it is difficult to adhere to a metal such as a mold, but has self-adhesiveness to an organic resin.
- the methacrylic acid ester compound [C] is contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A]. By doing this, appropriate mold releasability and adhesion to organic resin can be exhibited.
- the fourth aspect of the present invention by using the above content, it is possible to obtain a molded product having low hardness and low reaction force even at high compression. Further, according to the fifth and sixth aspects of the present invention, it is possible to obtain a molded article having more excellent high-speed moldability, heat resistance, acid resistance, gas permeability resistance and compression set resistance.
- the seventh aspect of the present invention while being excellent in heat resistance, acid resistance, gas permeation resistance and high speed moldability, it is difficult to adhere to metal such as a mold, while it is difficult to organic resin.
- a gasket material for a fuel cell having self-adhesiveness can be obtained, and according to the eighth aspect of the present invention, an excellent fuel cell provided with the gasket material having the above respective characteristics can be obtained.
- the ninth aspect of the present invention while being excellent in heat resistance, acid resistance, gas permeation resistance and high-speed moldability, it is difficult to adhere to metal such as a mold while it is easy to organic resin Can provide a sealing material having a self-adhesive property, and can be applied to sealing materials in all fields.
- the rubber composition according to the present invention comprises a predetermined ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A], a predetermined SiH group-containing compound [B-1] having two SiH groups in one molecule, and And / or a predetermined SiH group-containing compound [B-2] having three SiH groups in one molecule, and a predetermined methacrylic acid ester compound [C].
- the copolymer [A] used in the present invention for an ethylene / ⁇ -olefin / nonconjugated polyene copolymer is at least (A) a copolymer of ethylene, an ⁇ -olefin and a nonconjugated polyene, (B) the carbon number of the ⁇ -olefin is 3 to 20, (C) the mass ratio of ethylene units / ⁇ -olefin units is 35/65 to 95/5, (D) The iodine value is in the range of 0.5 to 50, (E) The intrinsic viscosity [ ⁇ ] measured in a decalin solution at 135 ° C.
- the nonconjugated polyene is at least represented by the following general formula [I] It is a kind of norbornene compound.
- a copolymer of ethylene, an ⁇ -olefin having 3 to 20 carbon atoms, and a nonconjugated polyene is preferably a random copolymer.
- Examples of the ⁇ -olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1- Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like.
- the carbon number of the ⁇ -olefin is preferably 3 to 10, and propylene, 1-butene, 1-hexene and 1-octene are particularly preferable. These ⁇ -olefins may be used alone or in combination of two or more.
- the non-conjugated polyene is not particularly limited, but is preferably a non-conjugated diene, particularly preferably at least one norbornene compound represented by the following general formula [I] from the viewpoint of enabling high-speed vulcanization in crosslinking reaction. .
- n is an integer of 0 to 10
- R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
- R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms Is
- the norbornene compounds of the general formula [I] are, for example, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (1-) Methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene 5- (1-Methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene , 5- (6-Heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3
- non-conjugated polyenes other than the norbornene compounds represented by the general formula [I] can be used without particular limitation, and, for example, chain non-conjugated dienes, alicyclic non-conjugated dienes, triene compounds etc. Can be mentioned. These can be used alone or in combination of two or more.
- non-conjugated polyenes other than the norbornene compound of the above general formula [I] can be used together with the norbornene compound of the above general formula [I].
- chain non-conjugated dienes examples include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5- Dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like can be mentioned.
- cyclic non-conjugated dienes examples include 5-methylene-2-norbornene, 1-methyl-5-methylene-2-norbornene, 1-ethyl-5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5 And -isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, dicyclopentadiene, methyltetrahydroindene and the like.
- examples other than the above include trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene and the like.
- the ethylene unit / ⁇ -olefin unit of the copolymer [A] has a mass ratio of 35/65 to 95/5 in that a molded article excellent in heat resistance, cold resistance, strength characteristics, and high-speed moldability can be obtained. It is preferably 40/60 to 90/10, more preferably 45/55 to 85/15, particularly preferably 50/50 to 80/20.
- the iodine value of the copolymer [A] is 0.5 to 50 (g / 100 g) from the viewpoint of preventing deterioration of mechanical properties such as tensile strength and elongation while obtaining a rubber composition having high crosslinking efficiency. It is preferably 1 to 45 (g / 100 g), more preferably 1 to 43 (g / 100 g), and particularly preferably 3 to 40 (g / 100 g).
- the iodine number is less than 0.5, the crosslinking efficiency is lowered, and when it is 50 or more, the crosslinking density is too high and the mechanical properties are deteriorated.
- the intrinsic viscosity [ ⁇ ] of the copolymer [A] measured in 135 ° C. decalin is 0.01 to 5.0 dl / g, preferably 0.03 to 4.0 dl / g, more preferably 0. It is preferably from 05 to 3.5 dl / g, particularly preferably from 0.07 to 3.0 dl / g.
- an embodiment in which the intrinsic viscosity []] of the copolymer [A] is 0.5 dl / g or less, preferably less than 0.3 dl / g, is particularly suitable for LIM molding of a rubber composition.
- the intrinsic viscosity [ ⁇ ] is in the above-mentioned range, a rubber composition which is excellent in strength properties and compression set resistance and which can provide a crosslinked rubber molded article excellent in processability can be obtained.
- the copolymer [A] according to the present invention is suitably low in viscosity, and has a complex viscosity (25 ° C., strain 1%) measured using a viscoelastic device MCR 301 manufactured by Anton Paar (Australia)
- the upper limit value of) is 10 5 Pa ⁇ S or less, preferably 4000 Pa ⁇ S or less, particularly preferably 2000 Pa ⁇ S or less.
- the copolymer [A] according to the present invention is obtained by copolymerizing ethylene, an ⁇ -olefin, and a nonconjugated polyene containing a norbornene compound represented by the formula [I] in the presence of a polymerization catalyst It can be manufactured.
- a polymerization catalyst for example, “Polymer production process” (published by the Industrial Research Association, pp. 365-378), JP-A-9-71617, JP-A-9-71618, JP-A-9-208615, It can be prepared by a conventionally known method as described in JP-A-10-67823, JP-A-10-67824, JP-A-10-110054 and the like.
- the polymerization catalyst includes, for example, a Ziegler catalyst composed of a transition metal compound such as vanadium (V), zirconium (Zr), titanium (Ti) and an organoaluminum compound (organoaluminum oxy compound), or the periodic table of the elements
- a metallocene catalyst comprising a metallocene compound of a transition metal selected from Group IVB and an organoaluminum oxy compound or an ionizing ionic compound may, for example, be mentioned.
- the method for producing the copolymer [A] according to the present invention may be carried out, for example, at a polymerization temperature of 30 to 60 ° C. in the presence of a catalyst containing the following vanadium compound (a) and organic aluminum compound (b) as main components: 30 to 50 ° C., polymerization pressure 4 to 12 kgf / cm 2 (preferably 5 to 8 kgf / cm 2 ), molar ratio of non-conjugated polyene to ethylene feed amount (non-conjugated polyene / ethylene) 0.01 to 0.
- a catalyst containing the following vanadium compound (a) and organic aluminum compound (b) as main components: 30 to 50 ° C., polymerization pressure 4 to 12 kgf / cm 2 (preferably 5 to 8 kgf / cm 2 ), molar ratio of non-conjugated polyene to ethylene feed amount (non-conjugated polyene / ethylene) 0.01 to 0.
- the copolymerization reaction is preferably carried out in a hydrocarbon medium.
- Vanadium compound (a) is, for example, the general formula VO (OR) a X b or V (OR) c X d (wherein, R is a hydrocarbon group, 0 ⁇ a ⁇ 3,0 ⁇ b ⁇ 3 And vanadium compounds represented by 2 ⁇ a + b ⁇ 3, 0 ⁇ c ⁇ 4, 0 ⁇ d ⁇ 4, 3 ⁇ c + d ⁇ 4), or electron donor adducts thereof.
- VOCl 3 , VO (OC 2 H 5 ) Cl 2 , VO (OC 2 H 5 ) 2 Cl, VO (O-iso-C 3 H 7 ) Cl 2 , VO (O-n-C 4 H 9 ) Cl 2 , VO (OC 2 H 5 ) 3 , VOBr 3 , VCl 4 , VOCl 3 , VO (ON-C 4 H 9 ) 3 , VCl 3 ⁇ 2 OC 6 H 12 OH, etc. be able to.
- organoaluminum compound (b) examples include trialkylaluminums such as triethylaluminum, tributylaluminum and triisopropylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide Etc .; partially alkoxylated alkylaluminum having an average composition represented by R 0.5 Al (OR) 0.5 etc .; dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; ethyl Aluminum sesquichloride, butyl aluminum sesquichloride, ethyl Partially halogenated alkylaluminums such as alkylaluminum sesquihalides such as aluminum sesquibromide, alky
- the rubber composition according to the present invention preferably contains only the above-mentioned ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A] as a resin component, but within the range not impairing the object of the present invention, A resin component other than the ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A] may be suitably contained.
- resin components other than copolymer [A] organopolysiloxane is mentioned, for example. Since the organopolysiloxane improves the heat aging resistance of the rubber composition, it contributes to the improvement of the heat aging resistance of the gasket material for fuel cell and various sealing materials.
- the content of the organopolysiloxane is 99.9: 0.1 to 5:95, preferably 99.9: 0.1 to the mass ratio of ethylene / ⁇ -olefin / nonconjugated polyene copolymer: organopolysiloxane. 60:40, more preferably 99.9: 0.1 to 70:30.
- the SiH group-containing compound [B-1] having two SiH groups in one molecule used in the present invention for the SiH group-containing compound is a compound represented by the following general formula [II].
- R 3 is a monovalent group having 1 to 10 carbon atoms, which is an unsubstituted or substituted saturated hydrocarbon group or an aromatic hydrocarbon group, and may be the same or different in one molecule, a is an integer of 0 to 20, b is an integer of 0 to 20, and R 4 is a divalent organic group having 1 to 30 carbon atoms or an oxygen atom.
- the SiH group-containing compound [B-1] having two SiH groups in one molecule has SiH groups at both molecular terminal ends, and has two SiH groups per molecule.
- R 3 represents, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, amyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, chloromethyl group, 2- Examples thereof include chloroethyl group, 3-chloropropyl group, phenyl group, phenylmethyl group, 2-phenylethyl group, 2-phenylpropyl group and the like, with methyl group, ethyl group and phenyl group being preferable.
- Both a and b are integers of 0 to 20, preferably a and b both are 10 or less integers, more preferably a and b both integers or less, particularly preferably a and b both integers or less, most preferably Are equal integers where a and b are 2 or less.
- SiH group-containing compound [B-1] having two SiH groups in one molecule represented by the general formula [II] examples include, for example, compounds of [II-1] to [II-4] shown below The compound of [II-1] is preferred. These SiH group-containing compounds [B-1] can be used alone or in combination of two or more.
- a gasket material for a fuel cell having improved mechanical properties while maintaining various properties such as excellent heat resistance, acid resistance, gas permeation resistance and high speed moldability by using the above-mentioned [B-1] component for a crosslinking material. And various sealing materials can be obtained.
- the component [B-1] contains 0.2 to 10 hydrogen atoms bonded to a silicon atom per aliphatic unsaturated bond contained in the resin component in the rubber composition. Is preferred.
- the content thereof is ethylene / ⁇ -olefin / nonconjugated polyene copolymer It is 2 to 15 parts by mass from the viewpoint of maintaining the crosslinking density while suppressing the rubber hardness of the molded product to be low with respect to 100 parts by mass of the polymer [A]. Preferably, it is 3 to 8 parts by mass.
- the SiH group-containing compound [B-2] having three SiH groups in one molecule used in the present invention is a compound represented by the following general formula [III].
- R 5 is a monovalent group having 1 to 10 carbon atoms, which is an unsubstituted or substituted saturated hydrocarbon group or aromatic hydrocarbon group, and may be the same or different in one molecule, a, b and c are each independently an integer of 0 to 20, and R 6 is a trivalent organic group having 1 to 30 carbon atoms.
- the SiH group-containing compound [B-2] has SiH groups at three ends of the molecule, and has three SiH groups in one molecule.
- R 5 in the general formula [III] is, for example, the same as R 3 in the general formula [II], and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an amyl group, a cyclopentyl group, And hexyl, cyclohexyl, octyl, chloromethyl, 2-chloroethyl, 3-chloropropyl, phenyl, phenylmethyl, 2-phenylethyl, 2-phenylpropyl and the like.
- Ethyl group and phenyl group are preferable.
- a, b and c each independently represent an integer of 0 to 20, preferably, all of a, b and c are 10 or less, more preferably, all of a, b and c are 5 or less, particularly preferably And a, b and c are all integers of 2 or less, and most preferably, a, b and c are equal integers of 2 or less.
- R 6 in the general formula [III] is a trivalent organic group having 1 to 30 carbon atoms, preferably one containing silicon.
- a rubber composition in which an SiH group-containing compound [B-2] having three SiH groups in one molecule alone is added to an ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A] has three dimensions Since crosslinking is performed, a molded article excellent in mechanical strength is obtained.
- the SiH group-containing compound [B-2] having three SiH groups in one molecule alone is added to the copolymer [A]
- the content is the balance between the mechanical strength and the tensile elongation, and From the viewpoint of compression set characteristics, the amount is 0.1 to 2.0 parts by mass, preferably 0.2 to 1. parts by weight per 100 parts by mass of the ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A]. It is 0 mass part.
- the rubber composition which is added by combining it with the ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A] it is excellent in high-speed moldability and gas permeability, and has low hardness and low reaction force. It is also possible to reduce the compression set at high temperatures (150 ° C.) and low temperatures (-30 ° C.).
- methacrylic acid ester compound [C] used in the present invention is represented by the following formula [IV], [V], [VI], [VII], [VIII], [Ix] Compound.
- n is an integer of 1 to 10.
- n is an integer of 1 to 10.
- n is an integer of 1 to 10.
- the predetermined methacrylic acid ester compound [C] is a compound selected from methacrylate compounds having methacrylic acid at one terminal of the molecule. While this methacrylic acid ester compound [C] imparts good mold releasability to the rubber composition of the present invention, it is difficult to adhere to a self-adhesiveness imparting component, that is, a metal such as a mold.
- the organic resin is used as a component that imparts adhesiveness to organic resin due to its high adhesive strength.
- M and n in the formula [IV], the formula [V] and the formula [Ix], and m and n in the formula [VI] are each an integer of 1 to 10 from the viewpoint of imparting self-adhesiveness, and have low molecular weight
- An integer of 1 to 7 is preferable from the point of balance between preventing self-adhesion deterioration due to bleeding and low molecular weight being better self-adhesion, and from the point of further improving self-adhesion
- the integer of 1 to 4 is particularly preferred.
- the above-mentioned predetermined methacrylic acid ester compound [C] can be obtained by a known methacrylic acid ester synthesis method.
- the lower limit value of the content of the methacrylic acid ester compound [C] is the mold releasability of the rubber composition and the organic resin relative to 100 parts by mass of the ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A].
- the amount is 0.1 parts by mass from the viewpoint of obtaining the adhesiveness, and 0.5 parts by mass is preferable from the viewpoint of the balance between the adhesiveness to the organic resin and the bleeding prevention, and 1.0 part by mass is particularly preferable.
- the upper limit value of the content of the methacrylic acid ester compound [C] is 100% by mass of ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A] to prevent bleeding and prevent adhesion to organic resin.
- the amount is 10 parts by mass from the viewpoint of suppressing a drop, 8.0 parts by mass is preferable from the point of balance between the adhesion to organic resin and the bleed prevention, and 5.0 parts by mass is particularly preferable.
- These methacrylic acid ester compounds [C] can be used alone or in combination of two or more.
- the rubber composition of the present invention is ethylene / ⁇ -olefin / nonconjugated polyene copolymer [A], SiH group-containing compound having two SiH groups in one molecule [B-1] and / or It contains an SiH group-containing compound [B-2] having three SiH groups in one molecule, a predetermined methacrylic acid ester compound [C], and, if necessary, contains components such as a catalyst and a reaction inhibitor described later. doing.
- the rubber composition of the present invention may be prepared, for example, by mixing equipment such as Banbury mixer, kneader, planetary mixer, internal mixer (interclosed mixer) such as intermix, 2-roll, 3-roll, etc.
- mixing equipment such as Banbury mixer, kneader, planetary mixer, internal mixer (interclosed mixer) such as intermix, 2-roll, 3-roll, etc.
- components such as a rubber reinforcing agent, an inorganic filler, a softening agent, etc., preferably at a temperature of 50 to 180 ° C. for 3 to 10 minutes, and then rolls such as open rolls
- the SiH group-containing compound [B-1] and / or [B-2] and the methacrylic acid ester compound [C] are kneaded using a kneader at a roll temperature of 100 ° C. or less for 1 to 30 minutes, and then dispensed.
- you may add and mix the catalyst, reaction inhibitor, etc. which are mentioned later as needed.
- the catalyst used in the crosslinking is an addition reaction catalyst and a copolymer [ Promotes the addition reaction (such as the hydrosilylation reaction of an alkene) of the alkenyl group of A] with the -SiH group of the SiH group-containing compound [B-1] and / or [B2].
- an addition reaction catalyst comprising a platinum group element such as, for example, a platinum-based catalyst, a palladium-based catalyst, a rhodium-based catalyst, etc. is usually used, but in the present invention, a platinum-based catalyst is preferred. It is desirable to use a complex of a periodic table group 8 element metal, particularly preferably platinum, with a compound containing a vinyl group and / or a carbonyl group, including a platinum-based catalyst.
- the catalyst is not particularly limited, but the amount thereof used is that the crosslink density is appropriate and a rubber composition capable of forming a crosslinked rubber molded article excellent in mechanical strength characteristics and extensibility is obtained.
- 0.1 to 100,000 mass ppm, preferably 0.1 to 10,000 mass ppm, based on the total amount of the resin component body, that is, the copolymer [A] and the other resin components optionally added More preferably, it is 1 to 5000 mass ppm, particularly preferably 5 to 1000 mass ppm.
- Use of the catalyst in a proportion exceeding 100,000 mass ppm is disadvantageous in cost.
- An uncrosslinked rubber molded article of a rubber composition not containing a catalyst may be irradiated with light, ⁇ -rays, electron beams or the like to obtain a crosslinked rubber molded article.
- both the addition crosslinking and the radical crosslinking may be performed using an organic peroxide in addition to the above catalyst.
- the content of the organic peroxide is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the copolymer [A] and the other resin components added as needed.
- the organic peroxide conventionally known organic peroxides commonly used in crosslinking of rubber can be used.
- reaction inhibitors include ethynyl group-containing alcohols such as ethynyl cyclohexanol, acrylonitrile, N, N-diallylacetamide, N, N-diallylbenzamide, N, N, N ', N'-tetraallyl-o-phthalate Amide compounds such as acid diamide, N, N, N ', N'-tetraallyl-m-phthalic acid diamide, N, N, N', N'-tetralyl-p-phthalic acid diamide, sulfur, phosphorus, nitrogen, amines Examples thereof include compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, organic peroxides such as tetramethyltetravinylcyclotetrasiloxane and hydroperoxide.
- reaction inhibitors include ethynyl group-containing alcohols such as ethynyl cyclohexanol, acrylonitrile, N, N-diallylace
- the content of the reaction inhibitor is 0.0001 to 50 parts by mass, preferably 0.0001 to 50 parts by mass with respect to a total of 100 parts by mass of the copolymer [A] and the other resin components added as necessary.
- the amount is 30 parts by mass, more preferably 0.0001 to 20 parts by mass, still more preferably 0.0001 to 10 parts by mass, and particularly preferably 0.0001 to 5 parts by mass. If the content exceeds 50 parts by mass, it is not preferable because the production cost is increased.
- rubber reinforcing agents inorganic fillers, softeners, antiaging agents, processing aids, vulcanization accelerators, organic Additives such as peroxides, crosslinking aids, foaming agents, foaming aids, colorants, dispersants, flame retardants and the like can be appropriately blended within the scope of not impairing the object of the present invention.
- Rubber reinforcing agents are used to enhance mechanical properties such as tensile strength, tear strength and abrasion resistance of crosslinked (vulcanized) rubber.
- rubber reinforcing materials include carbon black, differential silicic acid, silica and the like.
- the upper limit value of the content of the rubber reinforcing material is 300 parts by mass, preferably 200 parts by mass, with respect to 100 parts by mass in total of the copolymer [A] and other resin components added as needed. It is.
- These rubber reinforcing agents can be used alone or in combination of two or more.
- Inorganic fillers include, for example, light calcium carbonate, ground calcium carbonate, talc, clay, diatomaceous earth and the like.
- the upper limit value of the content of the inorganic filler is 300 parts by mass, preferably 200 parts by mass, with respect to 100 parts by mass in total of the copolymer [A] and other resin components added as needed. It is.
- These inorganic fillers can be used alone or in combination of two or more.
- An anti-aging agent may be used as needed to improve heat resistance.
- various conventionally known antiaging agents can be used, and examples thereof include amines, hindered phenols and sulfur antiaging agents.
- the content of the antiaging agent is used in the range not to impair the object of the present invention.
- These anti-aging agents can be used alone or in combination of two or more.
- NR natural rubber
- IR isoprene rubber
- conjugated diene rubbers such as butadiene rubber (BR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR) and chloroprene rubber (CR).
- EPR ethylene / propylene random copolymer
- EPDM ethylene / propylene / nonconjugated diene copolymer
- the rubber composition of the present invention described above is excellent in heat resistance, acid resistance, gas permeation resistance, high-speed moldability and compression set rate, and has self-adhesion to organic resins. It can be used for various sealing materials.
- the rubber composition of the present invention is suitable for LIM molding, but moldings can also be produced by other molding methods.
- the fuel cell gasket material and various sealing materials of the present invention can exhibit the most properties when used as a crosslinked rubber molded article. Therefore, usually, the gasket material for a fuel cell and the sealing material according to the present invention are a crosslinked rubber molded article.
- a non-crosslinked rubber composition is prepared by the method for preparing a rubber composition as in the case of general vulcanization (crosslinking) of a general rubber. It is then preferred to crosslink after shaping the rubber composition into the intended shape.
- Crosslinking can be carried out at the same time as molding or by introducing a molding into a vulcanization tank.
- the rubber composition of the present invention mixed using various kneading devices such as three rolls, open rolls, two open rolls, Banbury mixer, internal mixer, kneader, planetary mixer, high shear type mixer, Molded and crosslinked at 80 to 230 ° C., preferably 100 to 180 ° C., for about 0.5 to 24 hours at about 100 to 230 ° C., preferably about 120 to 150 ° C., if necessary.
- the molding and crosslinking can be carried out by heat treatment (secondary vulcanization) in an air oven such as a gear oven or a thermostat.
- a mold may or may not be used in this crosslinking step. When a mold is not used, molding and crosslinking steps are usually carried out continuously.
- a heating method in the vulcanization vessel a heating vessel such as hot air, glass bead fluidized bed, UHF (ultrahigh frequency electromagnetic wave), steam or the like can be used.
- the compounding components of the rubber composition used in Examples 1 to 7 and Comparative Examples 1 to 8 are as follows.
- ⁇ Ethylene ⁇ ⁇ -olefin ⁇ nonconjugated polyene copolymer [A] Ethylene-propylene-5-vinyl-2-norbornene random copolymer (ethylene content: 52.7% by mass, propylene content: 42.6% by mass, 5 to 10) for Examples 1 to 7 and Comparative Examples 1 to 8, respectively.
- -Vinyl-2-norbornene content 4.7% by mass, iodine number 25 g / 100 g, complex viscosity at 25 ° C.
- Rubber reinforcement Rubber reinforcement (1) Carbon black (iodine adsorption: 19 mg / g, an average particle diameter of 85 .mu.m, DBP absorption amount: 110cm 3 / 100g, Asahi Carbon Co., Ltd.
- Tensile test In accordance with JIS K6251, a tensile test was conducted under the conditions of a measuring temperature of 23 ° C. and a tensile speed of 500 mm / min to measure the tensile strength and elongation at break of the crosslinked sheet.
- Adhesive strength A polyethylene terephthalate (PET) resin is placed in a mold using a LIM molding machine, and this PET resin is brought into contact with the prepared rubber composition to set a hot plate setting temperature of 150 ° C. and mold compression 80 MPa. Molding for 5 minutes. The 90 ° C.
- PET polyethylene terephthalate
- peel strength of this molded product to a PET resin was determined in accordance with JIS K 6256-2. Those having an adhesive strength of 0.2 N / mm or more with respect to the PET resin were evaluated as "adhesive" to be an example. (4) Mold Releasability The case where the rubber composition prepared for the mold can be easily peeled is evaluated as “good”, and the case where the rubber composition can not be easily peeled is evaluated as “defective”.
- Examples 1 to 7 in which the methacrylic acid ester compounds of Compounds 1 to 6 were blended the adhesive strength to the organic resin was excellent, and the mold releasability was also good.
- Example 1 in which Compound 1 was blended and Example 3 in which Compound 2 was blended the adhesive strength to the organic resin was more excellent.
- Examples 1 to 6 were also excellent in mechanical strength such as hardness, tensile strength and elongation.
- Comparative Examples 1 to 8 in which the methacrylic acid ester compounds of Compound 7 to Compound 14 were blended the mold releasability was good, but the adhesive strength to the organic resin was extremely inferior.
- the rubber composition of the present invention is excellent in heat resistance, acid resistance, gas permeation resistance and high speed moldability, has low hardness and low reaction force, is excellent also in compression set rate at high temperature, and further, a mold etc. While it is difficult to adhere to metals of the above, it has adhesiveness to organic resins. Therefore, the rubber composition of the present invention can provide, for example, a gasket material having self-adhesiveness to a fuel cell made of an organic resin, and therefore, it is used in the field of gasket materials for fuel cells and other various sealing materials. It is valuable.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Sustainable Development (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Gasket Seals (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
(a)エチレンと、α-オレフィンと、非共役ポリエンとの共重合体であり、
(b)α-オレフィンの炭素数が3~20であり、
(c)エチレン単位/α-オレフィン単位の質量比が35/65~95/5であり、
(d)ヨウ素価が0.5~50の範囲であり、
(e)135℃のデカリン溶液中で測定した極限粘度[η]が0.01~5.0dl/gである;
下記一般式[II]で表される、一分子中にSiH基を2個有するSiH基含有化合物[B-1]、及び/または下記一般式[III]で表される、一分子中にSiH基を3個有するSiH基含有化合物[B-2]と、
下記式[IV]、[V]、[VI]、[VII]、[VIII]及び[Ix]からなる群から選択された少なくとも一つのメタクリル酸エステル化合物[C]と、を含有してなることを特徴とするゴム組成物である。
本発明で用いられる共重合体[A]は、少なくとも、
(a)エチレンと、α-オレフィンと、非共役ポリエンとの共重合体であり、
(b)α-オレフィンの炭素数が3~20であり、
(c)エチレン単位/α-オレフィン単位の質量比が35/65~95/5であり、
(d)ヨウ素価が0.5~50の範囲であり、
(e)135℃のデカリン溶液中で測定した極限粘度[η]が0.01~5.0dl/gを満足し、好ましくは、非共役ポリエンが、下記の一般式[I]で表わされる少なくとも一種のノルボルネン化合物である。また、エチレンと、炭素数3~20のα-オレフィンと、非共役ポリエンとの共重合体は、ランダム共重合体が好ましい。
本発明で用いられる一分子中にSiH基を2個有するSiH基含有化合物[B-1]は、下記一般式[II]で表される化合物である。
本発明で用いられるメタクリル酸エステル化合物[C]は、下記式[IV]、[V]、[VI]、[VII]、[VIII]、[Ix]で表される化合物である。
本発明のゴム組成物は、エチレン・α-オレフィン・非共役ポリエン共重合体[A]、一分子中にSiH基を2個有するSiH基含有化合物[B-1]および/または一分子中にSiH基を3個有するSiH基含有化合物[B-2]、所定のメタクリル酸エステル化合物[C]を含有し、必要に応じて、後述する触媒、反応抑制剤等の成分を含有している。
・エチレン・α-オレフィン・非共役ポリエン共重合体[A]
実施例1~7及び比較例1~8について、それぞれ、エチレン・プロピレン・5-ビニル-2-ノルボルネンランダム共重合体(エチレン含量:52.7質量%、プロピレン含量:42.6質量%、5-ビニル-2-ノルボルネン含量:4.7質量%、よう素価25g/100g、25℃における複素粘度(Anton Paar社製の粘弾性測定装置MCR-301を用いて測定した複素粘度)(歪み1%):1100Pa・sec、135℃のデカリン溶液中で測定した極限粘度[η]:0.28dl/g、三井化学(株)製「PX-062」)を配合した。
・一分子中にSiH基を2個有するSiH基含有化合物[B-1]
実施例1~7及び比較例1~8について、それぞれ、下記式[II-1]のSiH基含有化合物を配合した。
実施例1、2では下記化合物1を、実施例3では下記化合物2を、実施例4では下記化合物3を、実施例5では下記化合物4を、実施例6では下記化合物5を、実施例7では下記化合物6を配合した。また、比較例1では下記化合物7を、比較例2では下記化合物8を、比較例3では下記化合物9を、比較例4では下記化合物10を、比較例5では下記化合物11を、比較例6では下記化合物12を、比較例7では下記化合物13を、比較例8では下記化合物14を配合した。
ゴム補強材(1)
カーボンブラック(よう素吸着量:19mg/g、平均粒子径85μm、DBP吸収量:110cm3/100g、旭カーボン社製「旭♯50HG」)
ゴム補強材(2)
表面処理した沈降法シリカ(BET表面積:50m2/g、二次粒子径(コールターカウンター法により求めた平均粒子径):2.4μm、M値:65、東ソー・シリカ社製「SS-95」)
・老化防止剤
3-(3,5-ジ-t-ブチル-4-ヒドロキシ・フェニル)プロピオン酸ステアレート(チバ・スペシャリティ・ケミカルズ社製「Irganox1076」)
・反応抑制剤
1-エチニル-1-シクロヘキサノール
・触媒
白金-1,3,5,7-テトラビニルメチルシクロシロキサン錯体(白金濃度0.5質量%、末端ビニルシロキサンオイル溶液)
JIS K6253に準拠して、測定温度23℃でデュロメータ法にてA硬さを測定した。
(2)引張試験
JIS K6251に準拠して、測定温度23℃、引張速度500mm/分の条件で引張試験を行い、架橋シートの破断時の引張強度と伸びを測定した。
(3)接着強度
LIM成型機を用いて金型にポリエチレンテレフタレート(PET)樹脂を置き、このPET樹脂が、調製したゴム組成物と接触するようにして、熱板設定温度150℃、型圧縮80MPaにて5分間成形した。この成形物についてJIS K6256-2に準拠してPET樹脂に対する90℃剥離強さを求めた。PET樹脂に対し0.2N/mm以上の接着強度を有するものを「接着性あり」と評価し実施例とした。
(4)金型離型性
金型に対して調製したゴム組成物が容易に剥離可能である場合を「良」、容易に剥離できない場合を「不良」と評価した。
Claims (9)
- 以下の(a)~(e)を満足するエチレン・α-オレフィン・非共役ポリエン共重合体[A]と、
(a)エチレンと、α-オレフィンと、非共役ポリエンとの共重合体であり、
(b)α-オレフィンの炭素数が3~20であり、
(c)エチレン単位/α-オレフィン単位の質量比が35/65~95/5であり、
(d)ヨウ素価が0.5~50の範囲であり、
(e)135℃のデカリン溶液中で測定した極限粘度[η]が0.01~5.0dl/gである;
下記一般式[II]で表される、一分子中にSiH基を2個有するSiH基含有化合物[B-1]、及び/または下記一般式[III]で表される、一分子中にSiH基を3個有するSiH基含有化合物[B-2]と、
下記式[IV]、[V]、[VI]、[VII]、[VIII]及び[Ix]からなる群から選択された少なくとも一つのメタクリル酸エステル化合物[C]と、を含有していることを特徴とするゴム組成物。
- 前記メタクリル酸エステル化合物[C]が、エチレン・α-オレフィン・非共役ポリエン共重合体[A]100質量部に対して、0.1~10質量部含有していることを特徴とする請求項1に記載のゴム組成物。
- 前記エチレン・α-オレフィン・非共役ポリエン共重合体[A]100質量部に対して、
前記一分子中にSiH基を2個有するSiH基含有化合物[B-1]が3.0~7.0質量部含有し、かつ前記一分子中にSiH基を3個有するSiH基含有化合物[B-2]が0.1~2.0質量部含有していることを特徴とする請求項1に記載のゴム組成物。 - 請求項1~6のいずれか1項に記載のゴム組成物からなることを特徴とする燃料電池用ガスケット材。
- 請求項1~6のいずれか1項に記載のゴム組成物からなる燃料電池用ガスケット材を備えたことを特徴とする燃料電池。
- 請求項1~6のいずれか1項に記載のゴム組成物からなることを特徴とするシール材。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/640,721 US20130030103A1 (en) | 2010-04-12 | 2011-03-10 | Rubber composition and use thereof |
JP2011538768A JPWO2011129168A1 (ja) | 2010-04-12 | 2011-03-10 | ゴム組成物及びその用途 |
EP11768689A EP2559728A1 (en) | 2010-04-12 | 2011-03-10 | Rubber composition and use thereof |
CN2011800184052A CN102844370A (zh) | 2010-04-12 | 2011-03-10 | 橡胶组合物及其用途 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-091707 | 2010-04-12 | ||
JP2010091707 | 2010-04-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011129168A1 true WO2011129168A1 (ja) | 2011-10-20 |
Family
ID=44798547
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/055667 WO2011129168A1 (ja) | 2010-04-12 | 2011-03-10 | ゴム組成物及びその用途 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20130030103A1 (ja) |
EP (1) | EP2559728A1 (ja) |
JP (1) | JPWO2011129168A1 (ja) |
CN (1) | CN102844370A (ja) |
WO (1) | WO2011129168A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018235587A1 (ja) * | 2017-06-22 | 2018-12-27 | Nok株式会社 | 防振ゴム用ゴム組成物 |
JP2019175842A (ja) * | 2018-03-28 | 2019-10-10 | 豊田合成株式会社 | 燃料電池用シール部材の製造方法及び成形用ゴム組成物 |
JP2021027001A (ja) * | 2019-08-08 | 2021-02-22 | 三井化学株式会社 | 燃料電池用ガスケット |
US11631915B2 (en) | 2018-02-23 | 2023-04-18 | Lg Energy Solution, Ltd. | Gasket for secondary battery, and secondary battery including the same |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103554803A (zh) * | 2013-11-05 | 2014-02-05 | 天津鹏翎胶管股份有限公司 | 耐生物柴油丙烯酸酯橡胶组合物 |
US10371596B2 (en) * | 2014-08-07 | 2019-08-06 | Exfo Inc. | Testing fiber arrangement in multi-fiber cables |
JP6652353B2 (ja) * | 2015-09-09 | 2020-02-19 | 任天堂株式会社 | 通信装置および電池蓋 |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56118440A (en) * | 1980-02-25 | 1981-09-17 | Mitsui Petrochem Ind Ltd | Rubber composition |
JPH06172738A (ja) | 1992-12-10 | 1994-06-21 | Shin Etsu Chem Co Ltd | 接着性シリコーンゴム組成物 |
JPH0971617A (ja) | 1994-12-20 | 1997-03-18 | Mitsui Petrochem Ind Ltd | エチレン・α−オレフィン・非共役ポリエンランダム共重合体の製造方法、エチレン・α−オレフィン・非共役ポリエンランダム共重合体および該共重合体の用途 |
JPH0971618A (ja) | 1994-12-20 | 1997-03-18 | Mitsui Petrochem Ind Ltd | エチレン・α−オレフィン・非共役ポリエンランダム共重合体、ゴム組成物およびその製造方法 |
JPH09208615A (ja) | 1995-11-28 | 1997-08-12 | Mitsui Petrochem Ind Ltd | 固体状チタン触媒成分の調製方法、触媒およびオレフィンの重合方法 |
JPH1067824A (ja) | 1997-08-22 | 1998-03-10 | Mitsui Petrochem Ind Ltd | 高級α−オレフィン系共重合体 |
JPH1067823A (ja) | 1997-08-22 | 1998-03-10 | Mitsui Petrochem Ind Ltd | 高級α−オレフィン系共重合体およびその加硫物の用途 |
JPH1087913A (ja) * | 1996-09-17 | 1998-04-07 | Japan Synthetic Rubber Co Ltd | エチレン−α−オレフィン−非共役ジエン共重合体組成物 |
JPH10110054A (ja) | 1996-10-04 | 1998-04-28 | Mitsui Petrochem Ind Ltd | スポンジゴム用組成物、並びにそれを用いたウェザーストリップスポンジゴムおよび型成形スポンジゴム |
JP2001026688A (ja) * | 1999-07-15 | 2001-01-30 | Mitsui Chemicals Inc | 架橋可能なゴム組成物および用途 |
JP2001139695A (ja) * | 1999-09-03 | 2001-05-22 | Shin Etsu Polymer Co Ltd | オレフィン系熱可塑性エラストマー組成物及びその製造方法 |
JP2008156574A (ja) | 2006-12-26 | 2008-07-10 | Nok Corp | ゴム組成物およびその用途 |
JP2008156575A (ja) | 2006-12-26 | 2008-07-10 | Nok Corp | ゴム組成物およびその用途 |
JP2009509012A (ja) * | 2005-09-21 | 2009-03-05 | カール・フロイデンベルク・カーゲー | ゴムコンパウンド |
JP2009509011A (ja) * | 2005-09-21 | 2009-03-05 | カール・フロイデンベルク・カーゲー | エラストマーブレンド |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE60216512T2 (de) * | 2001-12-28 | 2007-09-20 | Mitsui Chemicals, Inc. | Die verwendung einer kautschukzusammensetzung zur herstellung von brennstoffzellenabdichtungen |
JP5334409B2 (ja) * | 2006-12-26 | 2013-11-06 | Nok株式会社 | ゴム組成物およびその用途 |
US8232341B2 (en) * | 2007-12-17 | 2012-07-31 | Nok Corporation | Rubber composition and use thereof |
-
2011
- 2011-03-10 WO PCT/JP2011/055667 patent/WO2011129168A1/ja active Application Filing
- 2011-03-10 JP JP2011538768A patent/JPWO2011129168A1/ja active Pending
- 2011-03-10 US US13/640,721 patent/US20130030103A1/en not_active Abandoned
- 2011-03-10 CN CN2011800184052A patent/CN102844370A/zh active Pending
- 2011-03-10 EP EP11768689A patent/EP2559728A1/en not_active Withdrawn
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56118440A (en) * | 1980-02-25 | 1981-09-17 | Mitsui Petrochem Ind Ltd | Rubber composition |
JPH06172738A (ja) | 1992-12-10 | 1994-06-21 | Shin Etsu Chem Co Ltd | 接着性シリコーンゴム組成物 |
JPH0971617A (ja) | 1994-12-20 | 1997-03-18 | Mitsui Petrochem Ind Ltd | エチレン・α−オレフィン・非共役ポリエンランダム共重合体の製造方法、エチレン・α−オレフィン・非共役ポリエンランダム共重合体および該共重合体の用途 |
JPH0971618A (ja) | 1994-12-20 | 1997-03-18 | Mitsui Petrochem Ind Ltd | エチレン・α−オレフィン・非共役ポリエンランダム共重合体、ゴム組成物およびその製造方法 |
JPH09208615A (ja) | 1995-11-28 | 1997-08-12 | Mitsui Petrochem Ind Ltd | 固体状チタン触媒成分の調製方法、触媒およびオレフィンの重合方法 |
JPH1087913A (ja) * | 1996-09-17 | 1998-04-07 | Japan Synthetic Rubber Co Ltd | エチレン−α−オレフィン−非共役ジエン共重合体組成物 |
JPH10110054A (ja) | 1996-10-04 | 1998-04-28 | Mitsui Petrochem Ind Ltd | スポンジゴム用組成物、並びにそれを用いたウェザーストリップスポンジゴムおよび型成形スポンジゴム |
JPH1067823A (ja) | 1997-08-22 | 1998-03-10 | Mitsui Petrochem Ind Ltd | 高級α−オレフィン系共重合体およびその加硫物の用途 |
JPH1067824A (ja) | 1997-08-22 | 1998-03-10 | Mitsui Petrochem Ind Ltd | 高級α−オレフィン系共重合体 |
JP2001026688A (ja) * | 1999-07-15 | 2001-01-30 | Mitsui Chemicals Inc | 架橋可能なゴム組成物および用途 |
JP2001139695A (ja) * | 1999-09-03 | 2001-05-22 | Shin Etsu Polymer Co Ltd | オレフィン系熱可塑性エラストマー組成物及びその製造方法 |
JP2009509012A (ja) * | 2005-09-21 | 2009-03-05 | カール・フロイデンベルク・カーゲー | ゴムコンパウンド |
JP2009509305A (ja) * | 2005-09-21 | 2009-03-05 | Nok株式会社 | 燃料電池の挿入領域における材料としてのゴム化合物の使用 |
JP2009509011A (ja) * | 2005-09-21 | 2009-03-05 | カール・フロイデンベルク・カーゲー | エラストマーブレンド |
JP2008156574A (ja) | 2006-12-26 | 2008-07-10 | Nok Corp | ゴム組成物およびその用途 |
JP2008156575A (ja) | 2006-12-26 | 2008-07-10 | Nok Corp | ゴム組成物およびその用途 |
Non-Patent Citations (1)
Title |
---|
"Polymer Seizo Process", K.K. KOGYO CHOSAKAI, pages: 365 - 378 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018235587A1 (ja) * | 2017-06-22 | 2018-12-27 | Nok株式会社 | 防振ゴム用ゴム組成物 |
JP6504329B1 (ja) * | 2017-06-22 | 2019-04-24 | Nok株式会社 | 防振ゴム用ゴム組成物 |
US11472952B2 (en) | 2017-06-22 | 2022-10-18 | Nok Corporation | Rubber composition for anti-vibration rubber |
US11631915B2 (en) | 2018-02-23 | 2023-04-18 | Lg Energy Solution, Ltd. | Gasket for secondary battery, and secondary battery including the same |
JP2019175842A (ja) * | 2018-03-28 | 2019-10-10 | 豊田合成株式会社 | 燃料電池用シール部材の製造方法及び成形用ゴム組成物 |
JP7031620B2 (ja) | 2018-03-28 | 2022-03-08 | 豊田合成株式会社 | 燃料電池用シール部材の製造方法及び成形用ゴム組成物 |
JP2021027001A (ja) * | 2019-08-08 | 2021-02-22 | 三井化学株式会社 | 燃料電池用ガスケット |
JP7355550B2 (ja) | 2019-08-08 | 2023-10-03 | 三井化学株式会社 | 燃料電池用ガスケット |
Also Published As
Publication number | Publication date |
---|---|
US20130030103A1 (en) | 2013-01-31 |
EP2559728A1 (en) | 2013-02-20 |
JPWO2011129168A1 (ja) | 2013-07-11 |
CN102844370A (zh) | 2012-12-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4932712B2 (ja) | ゴム組成物およびその用途 | |
EP2267071B1 (en) | Rubber composition and use thereof | |
JP5334409B2 (ja) | ゴム組成物およびその用途 | |
JP4241383B2 (ja) | 燃料電池シール部品、ハードディスクドライブトップカバーガスケット部品または電線コネクター用シール部品用ゴム組成物およびその用途 | |
WO2011129168A1 (ja) | ゴム組成物及びその用途 | |
US8232341B2 (en) | Rubber composition and use thereof | |
JP5261034B2 (ja) | 色素増感型太陽電池用封止材 | |
CA2719493C (en) | Rubber composition and use thereof | |
JP4912860B2 (ja) | ゴム組成物およびその用途 | |
JP4912861B2 (ja) | ゴム組成物およびその用途 | |
JP2010126668A (ja) | 未架橋ゴム組成物の製造方法および架橋ゴム成形品 | |
JP4216137B2 (ja) | 屋外用絶縁体用組成物および屋外用絶縁体 | |
JP2002275318A (ja) | オレフィン系熱可塑性エラストマー組成物およびその組成物からなる成形体 | |
JP2005298592A (ja) | 接着用ゴム組成物および接着ゴム | |
JP2005336290A (ja) | 防水材用ゴム組成物 | |
JP2005298593A (ja) | 接着したゴムシ−ル材 | |
JP2001031813A (ja) | 架橋可能なホース用ゴム組成物およびその用途 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180018405.2 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011538768 Country of ref document: JP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11768689 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13640721 Country of ref document: US Ref document number: 2011768689 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |