WO2009099113A1 - アクリルゴム - Google Patents
アクリルゴム Download PDFInfo
- Publication number
- WO2009099113A1 WO2009099113A1 PCT/JP2009/051908 JP2009051908W WO2009099113A1 WO 2009099113 A1 WO2009099113 A1 WO 2009099113A1 JP 2009051908 W JP2009051908 W JP 2009051908W WO 2009099113 A1 WO2009099113 A1 WO 2009099113A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylic rubber
- parts
- mass
- acrylate
- methacrylate
- Prior art date
Links
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
-
- 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
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1386—Natural or synthetic rubber or rubber-like compound containing
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
Definitions
- An ethylene-acrylic rubber composition in which a specific polytetramethylene glycol compound is blended with an ethylene-acrylic rubber composition is known as an ethylene-acrylic rubber composition having an excellent balance between cold resistance and heat resistance (for example, patents) Reference 1).
- an ozone antiaging agent is also known (for example, refer patent document 2).
- JP 2006-036826 A Japanese Patent Laid-Open No. 2007-110868
- the present invention provides an acrylic rubber composition and a vulcanized product thereof, which do not impair the normal physical properties when used as a vulcanized product, and in particular, have a small residual ratio of tensile strength before and after thermal aging and a small change rate of elongation at break. This is the main issue.
- heat aging refers to the heat aging resistance described in JIS K6257.
- the present invention is an acrylic rubber obtained by copolymerizing 10 to 100 parts by weight of a methacrylic acid alkyl ester and 0.5 to 4 parts by weight of a crosslinkable monomer with respect to 100 parts by weight of the acrylic acid alkyl ester.
- alkyl acrylates include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate , N-lauryl acrylate, and at least one compound selected from the group consisting of n-octadecyl acrylate are preferable.
- Methacrylic acid alkyl esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, n-dodecyl methacrylate.
- N-lauryl methacrylate, and at least one compound selected from the group consisting of n-octadecyl methacrylate are preferable.
- the crosslinkable monomer is preferably at least one compound selected from the group consisting of butenoic acid monobutyl ester and glycidyl methacrylate.
- the acrylic rubber is preferably one obtained by copolymerizing an olefin monomer such as ethylene at a ratio of 10 parts by mass or less with respect to 100 parts by mass of the acrylic acid alkyl ester. Furthermore, this invention is an acrylic rubber composition containing the said acrylic rubber.
- the acrylic rubber composition of the present invention comprises the group consisting of the acrylic rubber, a vulcanizing agent, a vulcanization accelerator, a filler, a reinforcing agent, a plasticizer, a lubricant, an anti-aging agent, a stabilizer, and a silane coupling agent. It is preferable to contain one or more selected.
- the present invention also relates to a vulcanized product obtained by vulcanizing the acrylic rubber composition, and a hose component, a seal component, and a vibration-proof rubber component using the vulcanized product.
- the acrylic rubber composition obtained from the acrylic rubber of the present invention when used as a vulcanized product, it does not impair the normal physical properties, in particular, the residual rate of tensile strength before and after thermal aging and the rate of change in elongation at break are small, hose parts It is useful as seal parts and anti-vibration rubber parts.
- the acrylic acid alkyl ester is the skeleton of the acrylic rubber obtained by polymerization, and the basic properties such as normal properties, cold resistance, and oil resistance of the resulting acrylic rubber composition are adjusted by selecting the type. it can.
- the alkyl acrylate ester is not particularly limited.
- Acrylic rubber has its main chain cut by oxidative degradation due to the influence of hot air and the like, and mechanical properties such as tensile strength and elongation at break are drastically lowered. This is generally called heat aging.
- heat aging By copolymerizing the acrylic acid main chain with the acrylic rubber main chain, when the acrylic rubber is heat-aged, the main chain is prevented from breaking, and the acrylic rubber has a mechanical strength such as tensile strength and elongation at break. Used to maintain strength.
- the methacrylic acid alkyl ester may be used alone or in combination of two or more. By adjusting the blending amount of the methacrylic acid alkyl ester, it is possible to adjust the suppression of the decrease in mechanical strength due to the cleavage of the main chain of the resulting acrylic rubber.
- the methacrylic acid alkyl ester is not particularly limited.
- the methacrylic acid alkyl ester can be copolymerized to impart heat resistance.
- the compounding amount of the methacrylic acid alkyl ester is in the range of 10 to 100 parts by mass, preferably in the range of 10 to 80 parts by mass with respect to 100 parts by mass of the acrylic acid alkyl ester.
- the blending amount of the methacrylic acid alkyl ester is 10 parts by mass or less, the main chain breakage suppressing effect of the acrylic rubber cannot be obtained, and the deterioration of the mechanical properties cannot be suppressed.
- a compounding quantity exceeds 100 mass parts acrylic rubber will harden
- the crosslinkable monomer When the acrylic rubber composition is vulcanized, the crosslinkable monomer is blended to crosslink the main chains of the acrylic rubber.
- the crosslinkable monomer include those containing an epoxy group, active chlorine groups, carboxyl groups, and monomers containing both epoxy groups and carboxyl groups.
- the crosslinkable monomer is not particularly limited, and examples thereof include those having an active chlorine group such as 2-chloroethyl vinyl ether, 2-chloroethyl acrylate, vinyl benzyl chloride, vinyl chloroacetate, and allyl chloroacetate. .
- an active chlorine group such as 2-chloroethyl vinyl ether, 2-chloroethyl acrylate, vinyl benzyl chloride, vinyl chloroacetate, and allyl chloroacetate.
- carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid, itaconic acid, butenoic acid monobutyl ester, cinnamic acid and the like can be mentioned.
- epoxy groups such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methallyl glycidyl ether, is mentioned.
- the addition amount of the crosslinkable monomer is in the range of 0.5 to 4 parts by mass with respect to 100 parts by mass of the alkyl acrylate ester.
- the addition amount of the crosslinkable monomer is less than 0.5 parts by mass, the effect of crosslinking the acrylic rubber is small and the strength of the vulcanizate obtained from the acrylic rubber composition is insufficient.
- the addition amount exceeds 4 parts by mass, the vulcanizate obtained from the acrylic rubber composition is cured and loses rubber elasticity.
- the acrylic rubber can be copolymerized with other monomers copolymerizable with the above-mentioned monomers within the range not impairing the object of the present invention.
- copolymerizable monomers include, but are not limited to, alkyl vinyl ketones such as methyl vinyl ketone; vinyl and allyl ethers such as vinyl ethyl ether and allyl methyl ether; styrene, ⁇ -methyl styrene Vinyl aromatic compounds such as chlorostyrene, vinyl toluene and vinyl naphthalene; vinyl nitriles such as acrylonitrile and methacrylonitrile; acrylamide, propylene, butadiene, isoprene, pentadiene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, fluorine And ethylenically unsaturated compounds such as vinylidene chloride, ethylene, and vinyl propionate.
- the amount is preferably 10 parts by mass or less with respect to 100 parts by mass of the alkyl acrylate ester.
- the acrylic rubber of the present invention is obtained by copolymerizing the above monomers by a known method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like.
- polyamine compound examples include 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diaminodiphenyl sulfide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1, 3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) pentane, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-diaminodiphenylsulfone, bis (4-3-aminophenoxy) phenyl sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 3,4'-diaminodiphenyl ether, 4,4'- Aromatic
- examples of the guanidine compound include guanidine, tetramethylguanidine, dibutylguanidine, diphenylguanidine, di-o-tolylguanidine and the like.
- imidazole compounds include 1-methylimidazole, 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2- Ethyl-5-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole trimellitic acid salt, 1-aminoethylimidazole, 1-aminoethyl-2-methylimidazole, 1-aminoethyl -2-ethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1 -Cyanoethyl-2- Tylimidazo
- the addition amount of the vulcanizing agent is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the acrylic rubber. Necessary and sufficient vulcanization treatment can be performed within this range.
- the vulcanized product of the acrylic rubber composition of the present invention is obtained by kneading an acrylic rubber composition, a vulcanizing agent, a vulcanization accelerator and the like at a temperature below the vulcanization temperature.
- the acrylic rubber composition of the present invention can be molded into various desired shapes and then vulcanized to obtain a vulcanized product, or can be molded into various shapes after vulcanization.
- the vulcanization temperature can be appropriately set depending on the blending ratio of each component in the acrylic rubber composition and the kind of the vulcanizing agent, and is usually 100 to 200 ° C., preferably 130 to 180 ° C.
- the time required for vulcanization is 1 to 10 hours, preferably 2 to 6 hours.
- the apparatus for kneading, molding and vulcanizing the acrylic rubber composition of the present invention and the apparatus for kneading and molding the vulcanized product of the acrylic rubber composition, those usually used in the rubber industry can be used.
- the acrylic rubber composition of the present invention comprises the above-mentioned acrylic rubber, a filler, a reinforcing agent, a plasticizer, a lubricant, an anti-aging agent, a stabilizer, and a silane coupling agent, depending on the purpose when put to practical use. You may contain 1 or more types chosen from a group.
- fillers and reinforcing agents used for usual rubber applications can be added, and examples thereof include carbon black, silica, clay, talc, and calcium carbonate.
- the total amount of these additives is preferably in the range of 20 to 100 parts by mass with respect to 100 parts by mass of the acrylic rubber.
- plasticizers used for normal rubber applications can be added, and examples thereof include ester plasticizers, polyoxyethylene ether plasticizers, and trimellitate plasticizers.
- the addition amount of the plasticizer is preferably in the range of up to about 50 parts by mass with respect to 100 parts by mass of the acrylic rubber.
- the acrylic rubber composition and the vulcanized product thereof according to the present invention are particularly suitably used as rubber hoses; seal parts such as gaskets and packing; vibration-proof rubber parts;
- Examples of rubber hoses include transmission oil cooler hoses, engine oil cooler hoses, air duct hoses, turbo intercooler hoses, hot air hoses, radiator hoses, power steering hoses, fuel system hoses, drain systems for automobiles, construction machinery, hydraulic equipment, etc. There are hoses for use.
- the rubber hose not only a single-layer hose obtained from the acrylic rubber composition and the vulcanized product thereof, but also a layer made of the acrylic rubber composition and the vulcanized product, for example, fluorine rubber, fluorine-modified acrylic rubber,
- a multi-layer hose in which hydrin rubber, nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, ethylene-propylene rubber, silicone rubber, chlorosulfonated polyethylene rubber and the like are combined as an inner layer, an intermediate layer, or an outer layer may be used.
- reinforcing yarns or wires may be provided in the middle of the hose or in the outermost layer of the rubber hose.
- Seal parts include, for example, engine head cover gasket, oil pan gasket, oil seal, lip seal packing, O-ring, transmission seal gasket, crankshaft, camshaft seal gasket, valve stem, power steering seal belt cover seal, etc.
- Anti-vibration rubber parts include, for example, a damper pulley, a center support cushion, and a suspension bush.
- Example 1 A reaction vessel having an internal volume of 40 liters was charged with 120 g of glycidyl methacrylate, 17 kg of an aqueous solution of 4 parts by mass of partially saponified polyvinyl alcohol, and 22 g of sodium acetate, and mixed well beforehand with a stirrer to prepare a uniform suspension.
- This acrylic rubber is composed of 1.2 parts by weight of glycidyl methacrylate monomer unit, 61.1 parts by weight of ethyl acrylate monomer unit, 38.9 parts by weight of n-butyl acrylate monomer unit,
- the copolymer composition was 11.1 parts by mass of the body unit.
- the monomer unit derived from each monomer was quantified by measuring the nuclear magnetic resonance spectrum of the obtained polymer.
- Example 2 Acrylic rubber was produced in the same manner as in Example 1 except that the amount of ethyl acrylate was 2.24 kg, the amount of n-butyl acrylate was 6.72 kg, and the amount of methyl methacrylate was 2.24 kg.
- This acrylic rubber is composed of 1.4 parts by weight of glycidyl methacrylate monomer unit, 25.0 parts by weight of ethyl acrylate monomer unit, 75.0 parts by weight of n-butyl acrylate monomer unit, and methyl methacrylate monomer.
- the copolymer composition was 25.0 parts by mass.
- Example 3 120 g of glycidyl methacrylate, 17 kg of an aqueous solution of 4 parts by weight of partially saponified polyvinyl alcohol, and 22 g of sodium acetate were put into a pressure resistant reaction vessel having an internal volume of 40 liters and mixed well in advance with a stirrer to prepare a uniform suspension. After replacing air in the upper part of the tank with nitrogen, ethylene was injected into the upper part of the tank, and the pressure was adjusted to 35 kg / cm 2 .
- This acrylic rubber is composed of 5.6 parts by mass of ethylene monomer units, 1.2 parts by mass of glycidyl methacrylate monomer units, 61.1 parts by mass of ethyl acrylate monomer units, and n-butyl acrylate monomer. It was a copolymer composition of 38.9 parts by mass of units and 11.1 parts by mass of methyl methacrylate monomer units.
- Example 4 Acrylic rubber was produced in the same manner as in Example 1 except that 1.12 kg of ethyl methacrylate was added without adding methyl methacrylate.
- This acrylic rubber is composed of 1.2 parts by mass of glycidyl methacrylate monomer unit, 61.1 parts by mass of ethyl acrylate monomer unit, 38.9 parts by mass of n-butyl acrylate monomer unit, The copolymer composition was 11.1 parts by mass of the body unit.
- Example 5 Acrylic rubber was produced in the same manner as in Example 1 except that ethyl acrylate and methyl methacrylate were not added, but that 8.06 kg of n-butyl acrylate and 3.14 kg of ethyl methacrylate were added.
- This acrylic rubber had a copolymer composition of 1.5 parts by mass of glycidyl methacrylate monomer unit, 100.0 parts by mass of n-butyl acrylate monomer unit, and 38.9 parts by mass of ethyl methacrylate monomer unit. It was.
- Example 6 Acrylic rubber was produced in the same manner as in Example 3 except that 1.12 kg of ethyl methacrylate was added without adding methyl methacrylate.
- This acrylic rubber is composed of 5.6 parts by mass of ethylene monomer units, 1.2 parts by mass of glycidyl methacrylate monomer units, 61.1 parts by mass of ethyl acrylate monomer units, and n-butyl acrylate monomer units.
- the copolymer composition was 38.9 parts by mass and 11.1 parts by mass of the ethyl methacrylate monomer unit.
- Example 7 Acrylic rubber is produced in the same manner as in Example 1 except that 1.12 kg of n-butyl methacrylate, 7.84 kg of ethyl acrylate, and 2.24 kg of n-butyl acrylate are added without methyl methacrylate. did.
- This acrylic rubber is composed of 1.2 parts by mass of glycidyl methacrylate monomer unit, 77.8 parts by mass of ethyl acrylate monomer unit, 22.2 parts by mass of n-butyl acrylate monomer unit, and n-butyl methacrylate unit.
- the copolymer composition was 11.1 parts by mass of the monomer unit.
- Example 8 An acrylic rubber was produced in the same manner as in Example 1 except that 6.50 kg of n-butyl acrylate and 4.70 kg of n-butyl methacrylate were added without adding ethyl acrylate and methyl methacrylate.
- This acrylic rubber is a copolymer composition of 1.9 parts by mass of glycidyl methacrylate monomer units, 100.0 parts by mass of n-butyl acrylate monomer units, and 72.4 parts by mass of n-butyl methacrylate monomer units. Met.
- Example 9 Acrylic rubber is produced in the same manner as in Example 3 except that 1.12 kg of n-butyl methacrylate, 7.84 kg of ethyl acrylate, and 2.24 kg of n-butyl acrylate are added without adding methyl methacrylate. did.
- This acrylic rubber is composed of 5.6 parts by mass of ethylene monomer units, 1.2 parts by mass of glycidyl methacrylate monomer units, 77.8 parts by mass of ethyl acrylate monomer units, and n-butyl acrylate monomer units.
- the copolymer composition was 22.2 parts by mass and 11.1 parts by mass of n-butyl methacrylate monomer units.
- Acrylic rubber was produced in the same manner as in Example 1 except that 3.36 kg of methyl acrylate and 6.72 kg of n-butyl acrylate were added without adding ethyl acrylate.
- This acrylic rubber is composed of 1.2 parts by mass of glycidyl methacrylate monomer unit, 33.3 parts by mass of methyl acrylate monomer unit, 66.7 parts by mass of n-butyl acrylate monomer unit, and methyl methacrylate monomer.
- the copolymer composition was 11.1 parts by mass of the unit.
- Example 11 Acrylic rubber in the same manner as in Example 1 except that 1.68 kg of methyl acrylate, 7.28 kg of n-butyl acrylate, and 2.24 kg of ethyl methacrylate were added without adding ethyl acrylate and methyl methacrylate.
- This acrylic rubber is composed of 1.4 parts by mass of glycidyl methacrylate monomer unit, 18.8 parts by mass of methyl acrylate monomer unit, 81.3 parts by mass of n-butyl acrylate monomer unit, and ethyl methacrylate monomer.
- the copolymer composition was 25.0 parts by mass.
- Example 12 The same method as in Example 1, except that 2.80 kg of methyl acrylate, 6.16 kg of n-butyl acrylate, and 2.24 kg of n-butyl methacrylate were added without adding ethyl acrylate and methyl methacrylate.
- Acrylic rubber was produced. This acrylic rubber is composed of 1.4 parts by mass of glycidyl methacrylate monomer unit, 31.3 parts by mass of methyl acrylate monomer unit, 68.8 parts by mass of n-butyl acrylate monomer unit, and n-butyl methacrylate unit.
- the copolymer composition had 25.0 parts by mass of a monomer unit.
- Acrylic rubber was produced in the same manner as in Example 3 except that ethylene was injected into the upper part of the tank and the pressure was adjusted to 45 kg / cm 2 .
- This acrylic rubber is composed of 8.9 parts by mass of ethylene monomer units, 1.2 parts by mass of glycidyl methacrylate monomer units, 61.1 parts by mass of ethyl acrylate monomer units, and n-butyl acrylate monomer units.
- the copolymer composition was 38.9 parts by mass and 11.1 parts by mass of the methyl methacrylate monomer unit.
- Acrylic rubber was produced in the same manner as in Example 3 except that ethylene was injected into the upper part of the tank and the pressure was adjusted to 55 kg / cm 2 .
- This acrylic rubber comprises 11.1 parts by mass of ethylene monomer units, 1.2 parts by mass of glycidyl methacrylate monomer units, 61.1 parts by mass of ethyl acrylate monomer units, and n-butyl acrylate monomer units.
- the copolymer composition was 38.9 parts by mass and 11.1 parts by mass of the methyl methacrylate monomer unit.
- Acrylic rubber was produced in the same manner as in Example 1, except that methyl methacrylate was not added, but 7.84 kg of ethyl acrylate and 3.36 kg of n-butyl acrylate were added.
- This acrylic rubber had a copolymer composition of 1.1 parts by mass of glycidyl methacrylate monomer unit, 70.0 parts by mass of ethyl acrylate monomer unit and 30.0 parts by mass of n-butyl acrylate monomer unit. .
- Acrylic rubber was produced in the same manner as in Example 1, except that methyl methacrylate was not added, but 5.60 kg of ethyl acrylate and 5.60 kg of n-butyl acrylate were added.
- This acrylic rubber had a copolymer composition of 1.1 parts by mass of glycidyl methacrylate monomer unit, 50.0 parts by mass of ethyl acrylate monomer unit and 50.0 parts by mass of n-butyl acrylate monomer unit. .
- Acrylic rubber was produced in the same manner as in Example 1 except that ethyl acrylate was not added, n-butyl acrylate was added at 10.27 kg, and methyl methacrylate was added at 0.93 kg.
- This acrylic rubber had a copolymer composition of 1.2 parts by mass of glycidyl methacrylate monomer unit, 100.0 parts by mass of n-butyl acrylate monomer unit, and 9.1 parts by mass of methyl methacrylate monomer unit. .
- Acrylic rubber was produced in the same manner as in Example 1 except that 0.45 kg of glycidyl methacrylate was added.
- This acrylic rubber comprises 4.4 parts by weight of glycidyl methacrylate monomer unit, 61.1 parts by weight of ethyl acrylate monomer unit, 38.9 parts by weight of n-butyl acrylate monomer unit, methyl methacrylate monomer
- the copolymer composition was 11.1 parts by mass of the unit.
- Example 6 An acrylic rubber was produced in the same manner as in Example 1 except that 0.03 kg of glycidyl methacrylate was added.
- This acrylic rubber comprises 0.3 parts by weight of glycidyl methacrylate monomer unit, 61.1 parts by weight of ethyl acrylate monomer unit, 38.9 parts by weight of n-butyl acrylate monomer unit, methyl methacrylate monomer
- the copolymer composition was 11.1 parts by mass of the unit.
- octadecyltrimethylammonium bromide, trimethylthiourea and 1-benzyl-2-methylimidazole were used as vulcanizing agents.
- the carbon black used as the filler is Toe Carbon Co.'s seast 116
- the liquid paraffin used as the lubricant is Kaneda's Hicoll K-230
- the stearylamine used as the lubricant is Kao's Farmin 80. is there.
- Nowguard 445 manufactured by Shiraishi Calcium Co. was used as an anti-aging agent
- Lunac S-90 manufactured by Kao Corporation was used as stearic acid as a lubricant.
- Other reagents used were commercial products.
- the acrylic rubber composition was heat treated at 170 ° C. for 20 minutes with a steam heating type hot press to form a primary vulcanizate, and then heated with hot air (gear oven) at 170 ° C. for 4 hours to obtain acrylic rubber.
- a vulcanizate of the composition was obtained.
- the vulcanizate of the obtained acrylic rubber composition was evaluated for tensile strength, elongation at break, hardness, cold resistance, and heat aging resistance under the following conditions.
- T 100 is a temperature at which the value of the specific modulus of the vulcanizate at 23 ° C. is 100 times.
- Heat aging resistance test In accordance with JIS K6257, the tensile strength and elongation at break of a test piece after heat treatment at 190 ° C. for 288 hours were measured. It can be said that heat resistance is excellent when the residual value of tensile strength and the residual rate of elongation at break under such evaluation conditions are large. Moreover, each residual rate was calculated
- the vulcanized product of the acrylic rubber composition of the present invention is excellent in heat aging resistance, in particular, the residual ratio of tensile strength after heat aging and the residual ratio of elongation at cutting. .
- the vulcanizate obtained from the acrylic rubber composition of the present invention has a low heat aging resistance, in particular, a residual ratio of tensile strength before and after thermal aging and a low rate of change in elongation at the time of cutting, hose parts, seal parts, vibration-proof rubber parts, etc. Can be suitably used.
- a low heat aging resistance in particular, a residual ratio of tensile strength before and after thermal aging and a low rate of change in elongation at the time of cutting, hose parts, seal parts, vibration-proof rubber parts, etc.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Sealing Material Composition (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
また、オゾン老化防止剤との併用も知られている(例えば、特許文献2参照)。
なお、ここでいう熱老化とは、JIS K6257に記載されている耐熱老化性を示す。
さらに、本発明は、前記アクリルゴムを含有するアクリルゴム組成物である。
また、本発明のアクリルゴム組成物は、アクリルゴムと、加硫剤、加硫促進剤、充填剤、補強剤、可塑剤、滑剤、老化防止剤、安定剤、およびシランカップリング剤からなる群から選ばれる一種以上とを含有する
例えば、n-ブチルアクリレートの共重合比率を多くすることで耐寒性を向上させることができ、エチルアクリレートの共重合比率を多くすることで耐油性を向上させることができる。
メタクリル酸アルキルエステルは、アクリルゴムの主鎖に共重合させておくことにより、アクリルゴムが熱老化した際にその主鎖の切断を抑制し、アクリルゴムの引張強さ、破断伸びなどの機械的強度を維持させるために用いる。
メタクリル酸アルキルエステルは、単体だけでなく2種類以上のものを併用してもよい。メタクリル酸アルキルエステルの配合量を調整することにより、得られるアクリルゴムの主鎖の切断による機械的強度低下の抑制を調整できる。
さらに、メタクリル酸アルキルエステルは耐熱性を付与させるために共重合させることができる。
架橋席モノマーとしては、エポキシ基を含有するもの、活性塩素基、カルボキシル基、エポキシ基とカルボキシル基の両方を含有するもの等が挙げられる。
共重合可能な他のモノマーとしては、特に限定するものではないが、例えば、メチルビニルケトンのようなアルキルビニルケトン;ビニルエチルエーテル、アリルメチルエーテルなどのビニル及びアリルエーテル;スチレン、α-メチルスチレン、クロロスチレン、ビニルトルエン、ビニルナフタレンなどのビニル芳香族化合物;アクリロニトリル、メタクリロニトリルなどのビニルニトリル;アクリルアミド、プロピレン、ブタジエン、イソプレン、ペンタジエン、酢酸ビニル、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、エチレン、プロピオン酸ビニルなどのエチレン性不飽和化合物;などがある。
本発明のアクリルゴム組成物は、所望する各種の形状に成形された後に加硫して加硫物としたり、加硫させた後に各種の形状に成形することもできる。加硫温度はアクリルゴム組成物中の各成分の配合割合や加硫剤の種類によって適宜設定でき、通常は100~200℃、好ましくは130~180℃である。また、加硫に要する時間は1~10時間、好ましくは2~6時間である。
<アクリルゴムの製造>
(実施例1)
内容積40リットルの反応容器に、グリシジルメタクリレート120g、部分ケン化ポリビニルアルコール4質量部の水溶液17kg、および酢酸ナトリウム22gを投入し、攪拌機であらかじめよく混合し、均一懸濁液を作製した。槽内上部の空気を窒素で置換した後、槽内を55℃に保持し、その後、別途注入口よりエチルアクリレート6.16kg、n-ブチルアクリレート3.92kg、メチルメタクリレート1.12kg、およびt-ブチルヒドロペルオキシド水溶液(0.25質量%水溶液)2.9kgを別々に投入して重合を開始させた。反応中、槽内温度は55℃に保ち、6時間で反応を終了した。生成した重合液に硼酸ナトリウム水溶液(3質量%水溶液)10kgを添加して重合体を固化し、脱水及び乾燥を行ってアクリルゴムを得た。このアクリルゴムは、グリシジルメタクリレート単量体単位1.2質量部と、エチルアクリレート単量体単位61.1質量部と、n-ブチルアクリレート単量体単位38.9質量部と、メチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
各モノマーに由来する単量体単位は、得られた重合体の核磁気共鳴スペクトルを測定して定量した。
エチルアクリレートの投入量を2.24kg、n-ブチルアクリレートの投入量を6.72kg、メチルメタクリレートの投入量を2.24kgにした以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位1.4質量部と、エチルアクリレート単量体単位25.0質量部と、n-ブチルアクリレート単量体単位75.0質量部と、メチルメタクリレート単量体単位25.0質量部の共重合体組成であった。
内容積40リットルの耐圧反応容器に、グリシジルメタクリレート120g、部分ケン化ポリビニルアルコール4質量部の水溶液17kg、および酢酸ナトリウム22gを投入し、攪拌機であらかじめよく混合し、均一懸濁液を作製した。槽内上部の空気を窒素で置換した後、エチレンを槽内上部に圧入し、圧力を35kg/cm2に調整した。攪拌を続行し、槽内を55℃に保持した後、別途注入口よりエチルアクリレート6.16kg、n-ブチルアクリレート3.92kg、メチルメタクリレート1.12kg、およびt-ブチルヒドロペルオキシド水溶液(0.25質量%水溶液)3.1kgを別々に圧入して重合を開始させた。反応中、槽内温度は55℃に保ち、6時間で反応を終了した。生成した重合液に硼酸ナトリウム水溶液(3質量%水溶液)10kgを添加して重合体を固化し、脱水及び乾燥を行ってアクリルゴムを得た。このアクリルゴムは、エチレン単量体単位5.6質量部と、グリシジルメタクリレート単量体単位1.2質量部と、エチルアクリレート単量体単位61.1質量部と、n-ブチルアクリレート単量体単位38.9質量部と、メチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
メチルメタクリレートを投入せず、エチルメタクリレートを1.12kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムは、グリシジルメタクリレート単量体単位1.2質量部と、エチルアクリレート単量体単位61.1質量部と、n-ブチルアクリレート単量体単位38.9質量部と、エチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
エチルアクリレート、およびメチルメタクリレートを投入せず、n-ブチルアクリレートを8.06kg、およびエチルメタクリレート3.14kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位1.5質量部と、n-ブチルアクリレート単量体単位100.0質量部と、エチルメタクリレート単量体単位38.9質量部の共重合体組成であった。
メチルメタクリレートを投入せず、エチルメタクリレートを1.12kg投入すること以外は、実施例3と同様の方法でアクリルゴムを製造した。このアクリルゴムはエチレン単量体単位5.6質量部と、グリシジルメタクリレート単量体単位1.2質量部と、エチルアクリレート単量体単位61.1質量部と、n-ブチルアクリレート単量体単位38.9質量部と、エチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
メチルメタクリレートを投入せず、n-ブチルメタクリレートを1.12kg、エチルアクリレートを7.84kg、およびn-ブチルアクリレートを2.24kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位1.2質量部と、エチルアクリレート単量体単位77.8質量部と、n-ブチルアクリレート単量体単位22.2質量部と、n-ブチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
エチルアクリレート、およびメチルメタクリレートを投入せず、n-ブチルアクリレートを6.50kg、およびn-ブチルメタクリレートを4.70kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位1.9質量部と、n-ブチルアクリレート単量体単位100.0質量部と、n-ブチルメタクリレート単量体単位72.4質量部の共重合体組成であった。
メチルメタクリレートを投入せず、n-ブチルメタクリレートを1.12kg、エチルアクリレートを7.84kg、およびn-ブチルアクリレートを2.24kg投入すること以外は、実施例3と同様の方法でアクリルゴムを製造した。このアクリルゴムはエチレン単量体単位5.6質量部と、グリシジルメタクリレート単量体単位1.2質量部と、エチルアクリレート単量体単位77.8質量部と、n-ブチルアクリレート単量体単位22.2質量部と、n-ブチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
エチルアクリレートを投入せず、メチルアクリレートを3.36kg、およびn-ブチルアクリレートを6.72kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位1.2質量部と、メチルアクリレート単量体単位33.3質量部と、n-ブチルアクリレート単量体単位66.7質量部と、メチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
エチルアクリレート、およびメチルメタクリレートを投入せず、メチルアクリレートを1.68kg、n-ブチルアクリレートを7.28kg、およびエチルメタクリレートを2.24kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位1.4質量部と、メチルアクリレート単量体単位18.8質量部と、n-ブチルアクリレート単量体単位81.3質量部と、エチルメタクリレート単量体単位25.0質量部の共重合体組成であった。
エチルアクリレート、およびメチルメタクリレートを投入せず、メチルアクリレートを2.80kg、n-ブチルアクリレートを6.16kg、およびn-ブチルメタクリレートを2.24kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位1.4質量部と、メチルアクリレート単量体単位31.3質量部と、n-ブチルアクリレート単量体単位68.8質量部と、n-ブチルメタクリレート単量体単位25.0質量部の共重合体組成であった。
エチレンを槽内上部に圧入し、圧力を45kg/cm2に調整した以外は実施例3と同様の方法でアクリルゴムを製造した。このアクリルゴムはエチレン単量体単位8.9質量部と、グリシジルメタクリレート単量体単位1.2質量部と、エチルアクリレート単量体単位61.1質量部と、n-ブチルアクリレート単量体単位38.9質量部と、メチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
エチレンを槽内上部に圧入し、圧力を55kg/cm2に調整した以外は実施例3と同様の方法でアクリルゴムを製造した。このアクリルゴムはエチレン単量体単位11.1質量部と、グリシジルメタクリレート単量体単位1.2質量部と、エチルアクリレート単量体単位61.1質量部と、n-ブチルアクリレート単量体単位38.9質量部と、メチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
メチルメタクリレートを投入せず、エチルアクリレートを7.84kg、およびn-ブチルアクリレートを3.36kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位1.1質量部と、エチルアクリレート単量体単位70.0質量部とn-ブチルアクリレート単量体単位30.0質量部の共重合体組成であった。
メチルメタクリレートを投入せず、エチルアクリレートを5.60kg、およびn-ブチルアクリレートを5.60kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位1.1質量部と、エチルアクリレート単量体単位50.0質量部とn-ブチルアクリレート単量体単位50.0質量部の共重合体組成であった。
エチルアクリレートを投入せず、n-ブチルアクリレートを5.04kg、およびメチルメタクリレートを6.16kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位2.4質量部と、n-ブチルアクリレート単量体単位100.0質量部とメチルメタクリレート単量体単位122.2質量部の共重合体組成であった。
エチルアクリレートを投入せず、n-ブチルアクリレートを10.27kg、およびメチルメタクリレートを0.93kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位1.2質量部と、n-ブチルアクリレート単量体単位100.0質量部とメチルメタクリレート単量体単位9.1質量部の共重合体組成であった。
グリシジルメタクリレートを0.45kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位4.4質量部と、エチルアクリレート単量体単位61.1質量部と、n-ブチルアクリレート単量体単位38.9質量部と、メチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
グリシジルメタクリレートを0.03kg投入すること以外は、実施例1と同様の方法でアクリルゴムを製造した。このアクリルゴムはグリシジルメタクリレート単量体単位0.3質量部と、エチルアクリレート単量体単位61.1質量部と、n-ブチルアクリレート単量体単位38.9質量部と、メチルメタクリレート単量体単位11.1質量部の共重合体組成であった。
また、充填剤として用いたカーボンブラックは東海カーボン社製のシースト116を、滑剤として用いた流動パラフィンはカネダ社製のハイコールK-230を、滑剤 として用いたステアリルアミンは花王社製のファーミン80である。さらに、老化防止剤としては白石カルシウム社製のナウガード445を、滑剤としてのステアリン酸は花王社製ルナックS-90を用いた。その他の試薬は市販品を使用した。
JIS K6251に準拠して測定した。
(2)硬さ
JIS K6253に準拠してデュロメータ硬さ計を用いて測定した。
(3)耐寒性試験
JIS K6261に準拠してT100の温度を測定した。ここで、T100とは、23℃における加硫物の比モジュラスの値が100倍の値を示す温度である。
(4)耐熱老化性試験
JIS K6257に準拠し、190℃で288時間の熱処理を行った後の試験片の引張強さと切断時伸びを測定した。このような評価条件下での引っ張り強度の残留率と切断時伸びの残留率の値が大きいと耐熱性が優れているといえる。
また、一般式(数1)を用いてそれぞれの残留率を求めた。残留率は、その値が100に近いほど耐熱試験前後での変化がなく耐熱老化性が良いことを示す。
なお、2008年2月5日に出願された日本特許出願2008-024836号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (12)
- アクリル酸アルキルエステル100質量部に対して、メタクリル酸アルキルエステル10~100質量部と、架橋席モノマー0.5~4質量部とを共重合させて得られることを特徴とするアクリルゴム。
- メタクリル酸アルキルエステルが、メチルメタクリレート、エチルメタクリレート、およびn-ブチルメタクリレートからなる群から選ばれる少なくとも一種の化合物であることを特徴とする請求項1に記載のアクリルゴム。
- アクリル酸アルキルエステルが、メチルアクリレート、エチルアクリレート、およびn-ブチルアクリレートからなる群から選ばれる少なくとも一種の化合物であることを特徴とする請求項1または請求項2に記載のアクリルゴム。
- 架橋席モノマーが、エポキシ基を有することを特徴とする請求項1~3のいずれか一項に記載のアクリルゴム。
- 架橋席モノマーが、カルボキシル基を有することを特徴とする請求項1~3のいずれか一項に記載のアクリルゴム。
- さらに、エチレンをアクリル酸アルキルエステル100質量部に対して10質量部以下の割合で共重合させることを特徴とする請求項1~5のいずれか一項に記載のアクリルゴム。
- 請求項1~6のいずれか一項に記載のアクリルゴムを含有することを特徴とするアクリルゴム組成物。
- さらに、加硫剤、加硫促進剤、充填剤、補強剤、可塑剤、滑剤、老化防止剤、安定剤、およびシランカップリング剤からなる群から選ばれる一種以上を含有することを特徴とする請求項7に記載のアクリルゴム組成物。
- 請求項7または8に記載のアクリルゴム組成物を加硫して得られることを特徴とする加硫物。
- 請求項9に記載の加硫物を用いたホース部品。
- 請求項9に記載の加硫物を用いたシール部品。
- 請求項9に記載の加硫物を用いた防振ゴム部品。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200980103360.1A CN102124040B (zh) | 2008-02-05 | 2009-02-04 | 丙烯酸酯橡胶 |
ES09707415.7T ES2635940T3 (es) | 2008-02-05 | 2009-02-04 | Caucho acrílico |
EP09707415.7A EP2246373B1 (en) | 2008-02-05 | 2009-02-04 | Acrylic rubber |
US12/866,330 US8383220B2 (en) | 2008-02-05 | 2009-02-04 | Acrylic rubber |
JP2009552498A JP5715758B2 (ja) | 2008-02-05 | 2009-02-04 | 耐熱老化性に優れたアクリルゴム加硫物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008024836 | 2008-02-05 | ||
JP2008-024836 | 2008-02-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009099113A1 true WO2009099113A1 (ja) | 2009-08-13 |
Family
ID=40952187
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/051908 WO2009099113A1 (ja) | 2008-02-05 | 2009-02-04 | アクリルゴム |
Country Status (8)
Country | Link |
---|---|
US (1) | US8383220B2 (ja) |
EP (1) | EP2246373B1 (ja) |
JP (1) | JP5715758B2 (ja) |
KR (1) | KR101640610B1 (ja) |
CN (1) | CN102124040B (ja) |
ES (1) | ES2635940T3 (ja) |
TW (1) | TWI457351B (ja) |
WO (1) | WO2009099113A1 (ja) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103044830A (zh) * | 2012-11-25 | 2013-04-17 | 马鞍山市中澜橡塑制品有限公司 | 一种蝶阀密封橡胶及其制备方法 |
CN103044832A (zh) * | 2012-11-25 | 2013-04-17 | 马鞍山市中澜橡塑制品有限公司 | 一种汽车梅花垫胶料及其制备方法 |
US20130095328A1 (en) * | 2010-06-09 | 2013-04-18 | Denki Kagaku Kogyo Kabushiki Kaisha | Laminated body and vulcanizate therefor |
WO2016002936A1 (ja) * | 2014-07-04 | 2016-01-07 | 日本ゼオン株式会社 | アクリルゴム、アクリルゴム組成物、アクリルゴム架橋物及びシール部材 |
JP2017116784A (ja) * | 2015-12-25 | 2017-06-29 | エルジー ディスプレイ カンパニー リミテッド | ディスプレイ用フレキシブル基板及びフレキシブルディスプレイ |
WO2018101146A1 (ja) | 2016-11-30 | 2018-06-07 | 株式会社大阪ソーダ | アクリル共重合体、およびその架橋物 |
JPWO2018008473A1 (ja) * | 2016-07-05 | 2019-05-09 | デンカ株式会社 | アクリルゴム組成物 |
JPWO2018008474A1 (ja) * | 2016-07-05 | 2019-05-16 | デンカ株式会社 | アクリルゴム組成物 |
WO2019188527A1 (ja) | 2018-03-26 | 2019-10-03 | 日本ゼオン株式会社 | アクリルゴム、アクリルゴム組成物、アクリルゴム架橋物、シール材、及びホース材 |
WO2019239922A1 (ja) * | 2018-06-11 | 2019-12-19 | デンカ株式会社 | アクリル系エラストマー組成物 |
WO2020032173A1 (ja) | 2018-08-10 | 2020-02-13 | 株式会社大阪ソーダ | アクリル共重合体、及びゴム材料 |
WO2020158132A1 (ja) * | 2019-01-31 | 2020-08-06 | デンカ株式会社 | 架橋性ゴム組成物、アクリルゴム及びゴム硬化物 |
JPWO2019078167A1 (ja) * | 2017-10-16 | 2020-11-05 | デンカ株式会社 | アクリルゴムの製造方法、アクリルゴム、アクリルゴム組成物、その加硫物及び加硫物の用途 |
JPWO2020262495A1 (ja) * | 2019-06-28 | 2020-12-30 | ||
JP6836020B1 (ja) * | 2019-10-16 | 2021-02-24 | デンカ株式会社 | アクリルゴム、ゴム組成物及びその架橋物、ゴムホース、並びにシール部品 |
WO2021065669A1 (ja) * | 2019-09-30 | 2021-04-08 | デンカ株式会社 | アクリルゴム、架橋性ゴム組成物及びゴム硬化物 |
WO2021075093A1 (ja) * | 2019-10-16 | 2021-04-22 | デンカ株式会社 | アクリルゴム、ゴム組成物及びその架橋物、ゴムホース、並びにシール部品 |
WO2021112190A1 (ja) * | 2019-12-05 | 2021-06-10 | デンカ株式会社 | アクリルゴム、アクリルゴム組成物及びその架橋物 |
JP7541022B2 (ja) | 2019-09-30 | 2024-08-27 | デンカ株式会社 | アクリルゴム、架橋性ゴム組成物及びゴム硬化物 |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102408655B (zh) * | 2011-08-22 | 2015-06-24 | 安徽中鼎密封件股份有限公司 | 一种密封垫片及其制备方法 |
CN102617785B (zh) * | 2012-03-23 | 2015-02-25 | 成都道弘实业有限公司 | 双峰分子量分布丙烯酸酯橡胶及其制备方法 |
CN104822765B (zh) * | 2012-11-30 | 2016-10-05 | 日本瑞翁株式会社 | 丙烯酸类橡胶组合物和橡胶交联物 |
WO2014112564A1 (ja) * | 2013-01-17 | 2014-07-24 | 電気化学工業株式会社 | タイヤ加硫用ブラダー |
CN104650275A (zh) * | 2014-06-26 | 2015-05-27 | 柳州市够旺贸易有限公司 | 丙烯酸酯橡胶的制备方法 |
CN104385647B (zh) * | 2014-08-22 | 2017-12-15 | 五行科技股份有限公司 | 低延伸率多层软管及其制造方法 |
WO2016152616A1 (ja) * | 2015-03-20 | 2016-09-29 | Nok株式会社 | アクリルゴム組成物 |
JP6597221B2 (ja) * | 2015-11-24 | 2019-10-30 | 住友ベークライト株式会社 | 構造体および構造体の製造方法 |
CN105440643A (zh) * | 2015-12-28 | 2016-03-30 | 张桂华 | 一种减震合成橡胶及其制备方法 |
CN105801749A (zh) * | 2016-04-25 | 2016-07-27 | 湖北齐圣橡塑有限公司 | 一种新型硼改性丙烯酸酯橡胶材料的制备方法 |
JPWO2018147142A1 (ja) * | 2017-02-09 | 2019-11-21 | 日本ゼオン株式会社 | アクリルゴム |
CN111183163B (zh) * | 2017-10-31 | 2021-10-15 | 优迈特株式会社 | 丙烯酸类橡胶 |
CN110628156A (zh) * | 2018-06-23 | 2019-12-31 | 深圳市宝聚合塑料有限公司 | 复聚合丙烯酸酯橡胶及其制备方法 |
CN108794692B (zh) * | 2018-07-05 | 2020-11-17 | 南京林业大学 | 一种制备高断裂伸长率丙烯酸酯弹性体的方法 |
JP7505492B2 (ja) * | 2019-06-28 | 2024-06-25 | 日本ゼオン株式会社 | アクリルゴム組成物およびゴム架橋物 |
JP6839332B1 (ja) * | 2019-10-16 | 2021-03-03 | デンカ株式会社 | アクリルゴム、ゴム組成物及びその架橋物、ゴムホース、並びにシール部品 |
CN112898711A (zh) * | 2021-03-29 | 2021-06-04 | 梁燕萍 | 一种高强度丙烯酸酯橡胶材料的制备方法 |
US20220389201A1 (en) * | 2021-06-03 | 2022-12-08 | Denka Company Limited | Acrylic rubber composition and crosslinked product thereof |
CN115975277B (zh) * | 2023-03-17 | 2023-06-27 | 河北华密新材科技股份有限公司 | 一种耐寒橡胶及其制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59189109A (ja) * | 1983-04-11 | 1984-10-26 | Nippon Shokubai Kagaku Kogyo Co Ltd | 熱硬化性水性分散体 |
JPS6123614A (ja) * | 1984-03-22 | 1986-02-01 | Daicel Chem Ind Ltd | 高濃度粘着剤組成物及びその製法 |
JPH07196974A (ja) * | 1993-11-15 | 1995-08-01 | Rhone Poulenc Special Chem Co | 水性ペイントおよび木材塗料に有用な周囲温度および昇温硬化性ポリマー組成物 |
JPH10231325A (ja) * | 1997-02-17 | 1998-09-02 | Daicel Chem Ind Ltd | アクリル系重合体およびそれを含む樹脂組成物 |
JP2001131236A (ja) * | 1999-11-05 | 2001-05-15 | Denki Kagaku Kogyo Kk | アクリル系ゴムおよびその組成物 |
JP2006036826A (ja) | 2004-07-23 | 2006-02-09 | Denki Kagaku Kogyo Kk | エチレン−アクリルゴム組成物 |
JP2007110868A (ja) | 2005-10-17 | 2007-04-26 | Matsushita Electric Ind Co Ltd | 永久磁石型モータ |
JP2008214418A (ja) * | 2007-03-01 | 2008-09-18 | Nippon Zeon Co Ltd | アクリルゴム、アクリルゴム組成物およびアクリルゴム架橋物 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6278273A (ja) * | 1985-09-30 | 1987-04-10 | ジェイエスアール株式会社 | バツキング用組成物 |
JPH1143503A (ja) * | 1997-07-25 | 1999-02-16 | Nippon Mektron Ltd | 変性アクリル系ゴムの製造法 |
US6407179B1 (en) * | 1999-11-02 | 2002-06-18 | Denki Kagaku Kogyo Kabushiki Kaisha | Acrylic rubber and its composition |
JP4273671B2 (ja) * | 2001-03-06 | 2009-06-03 | 日本ゼオン株式会社 | アクリルゴム組成物および加硫物 |
JP2003082029A (ja) * | 2001-09-14 | 2003-03-19 | Tokai Rubber Ind Ltd | アクリルゴム組成物及び耐熱ホース |
US6815506B2 (en) * | 2001-10-15 | 2004-11-09 | Jsr Corporation | Oil-resistant thermoplastic elastomer composition and moldings using the same |
JP3875088B2 (ja) * | 2001-12-03 | 2007-01-31 | 株式会社日本触媒 | 酸−エポキシ架橋エマルション組成物 |
JP4143820B2 (ja) * | 2002-11-20 | 2008-09-03 | 日本ゼオン株式会社 | アクリルゴム組成物 |
US7459495B2 (en) * | 2002-10-09 | 2008-12-02 | Zeon Corporation | Acrylic rubber composition and crosslinked object |
WO2004090035A1 (ja) * | 2003-04-10 | 2004-10-21 | Kaneka Corporation | 硬化性組成物 |
JP4064937B2 (ja) * | 2003-09-02 | 2008-03-19 | ローム アンド ハース カンパニー | 熱硬化性組成物の強化剤を調製する方法 |
US8404344B2 (en) * | 2005-05-20 | 2013-03-26 | Nitto Denko Corporation | Pressure sensitive adhesive composition, pressure sensitive adhesive sheet and surface protective film |
JP4851398B2 (ja) | 2007-06-28 | 2012-01-11 | 電気化学工業株式会社 | アクリルゴム組成物 |
-
2009
- 2009-02-04 EP EP09707415.7A patent/EP2246373B1/en active Active
- 2009-02-04 ES ES09707415.7T patent/ES2635940T3/es active Active
- 2009-02-04 JP JP2009552498A patent/JP5715758B2/ja active Active
- 2009-02-04 KR KR1020107014843A patent/KR101640610B1/ko active IP Right Grant
- 2009-02-04 US US12/866,330 patent/US8383220B2/en active Active
- 2009-02-04 WO PCT/JP2009/051908 patent/WO2009099113A1/ja active Application Filing
- 2009-02-04 CN CN200980103360.1A patent/CN102124040B/zh active Active
- 2009-02-05 TW TW098103683A patent/TWI457351B/zh active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59189109A (ja) * | 1983-04-11 | 1984-10-26 | Nippon Shokubai Kagaku Kogyo Co Ltd | 熱硬化性水性分散体 |
JPS6123614A (ja) * | 1984-03-22 | 1986-02-01 | Daicel Chem Ind Ltd | 高濃度粘着剤組成物及びその製法 |
JPH07196974A (ja) * | 1993-11-15 | 1995-08-01 | Rhone Poulenc Special Chem Co | 水性ペイントおよび木材塗料に有用な周囲温度および昇温硬化性ポリマー組成物 |
JPH10231325A (ja) * | 1997-02-17 | 1998-09-02 | Daicel Chem Ind Ltd | アクリル系重合体およびそれを含む樹脂組成物 |
JP2001131236A (ja) * | 1999-11-05 | 2001-05-15 | Denki Kagaku Kogyo Kk | アクリル系ゴムおよびその組成物 |
JP2006036826A (ja) | 2004-07-23 | 2006-02-09 | Denki Kagaku Kogyo Kk | エチレン−アクリルゴム組成物 |
JP2007110868A (ja) | 2005-10-17 | 2007-04-26 | Matsushita Electric Ind Co Ltd | 永久磁石型モータ |
JP2008214418A (ja) * | 2007-03-01 | 2008-09-18 | Nippon Zeon Co Ltd | アクリルゴム、アクリルゴム組成物およびアクリルゴム架橋物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2246373A4 |
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9227380B2 (en) * | 2010-06-09 | 2016-01-05 | Denka Company Limited | Laminated body and vulcanizate therefor |
KR101858275B1 (ko) * | 2010-06-09 | 2018-05-15 | 덴카 주식회사 | 적층체 및 그의 가황물 |
US20130095328A1 (en) * | 2010-06-09 | 2013-04-18 | Denki Kagaku Kogyo Kabushiki Kaisha | Laminated body and vulcanizate therefor |
CN103044830B (zh) * | 2012-11-25 | 2015-04-01 | 马鞍山市中澜橡塑制品有限公司 | 一种蝶阀密封橡胶及其制备方法 |
CN103044830A (zh) * | 2012-11-25 | 2013-04-17 | 马鞍山市中澜橡塑制品有限公司 | 一种蝶阀密封橡胶及其制备方法 |
CN103044832A (zh) * | 2012-11-25 | 2013-04-17 | 马鞍山市中澜橡塑制品有限公司 | 一种汽车梅花垫胶料及其制备方法 |
WO2016002936A1 (ja) * | 2014-07-04 | 2016-01-07 | 日本ゼオン株式会社 | アクリルゴム、アクリルゴム組成物、アクリルゴム架橋物及びシール部材 |
KR20170028315A (ko) | 2014-07-04 | 2017-03-13 | 니폰 제온 가부시키가이샤 | 아크릴 고무, 아크릴 고무 조성물, 아크릴 고무 가교물 및 시일 부재 |
US9840572B2 (en) | 2014-07-04 | 2017-12-12 | Zeon Corporation | Acrylic rubber, acrylic rubber composition, cross-linked acrylic rubber product, and seal member |
JP2017116784A (ja) * | 2015-12-25 | 2017-06-29 | エルジー ディスプレイ カンパニー リミテッド | ディスプレイ用フレキシブル基板及びフレキシブルディスプレイ |
JP7169191B2 (ja) | 2016-07-05 | 2022-11-10 | デンカ株式会社 | アクリルゴム組成物 |
JPWO2018008473A1 (ja) * | 2016-07-05 | 2019-05-09 | デンカ株式会社 | アクリルゴム組成物 |
JPWO2018008474A1 (ja) * | 2016-07-05 | 2019-05-16 | デンカ株式会社 | アクリルゴム組成物 |
JP7043402B2 (ja) | 2016-07-05 | 2022-03-29 | デンカ株式会社 | アクリルゴム組成物 |
JP7001062B2 (ja) | 2016-11-30 | 2022-01-19 | 株式会社大阪ソーダ | アクリル共重合体、およびその架橋物 |
JPWO2018101146A1 (ja) * | 2016-11-30 | 2019-10-24 | 株式会社大阪ソーダ | アクリル共重合体、およびその架橋物 |
WO2018101146A1 (ja) | 2016-11-30 | 2018-06-07 | 株式会社大阪ソーダ | アクリル共重合体、およびその架橋物 |
KR20190085931A (ko) | 2016-11-30 | 2019-07-19 | 가부시키가이샤 오사카소다 | 아크릴 공중합체, 및 그의 가교물 |
US11760821B2 (en) | 2017-10-16 | 2023-09-19 | Denka Company Limited | Method for producing acrylic rubber, acrylic rubber, acrylic rubber composition, vulcanized substance thereof, and application for vulcanized substance |
JP7204657B2 (ja) | 2017-10-16 | 2023-01-16 | デンカ株式会社 | アクリルゴムの製造方法、アクリルゴム、アクリルゴム組成物、その加硫物及び加硫物の用途 |
JPWO2019078167A1 (ja) * | 2017-10-16 | 2020-11-05 | デンカ株式会社 | アクリルゴムの製造方法、アクリルゴム、アクリルゴム組成物、その加硫物及び加硫物の用途 |
WO2019188527A1 (ja) | 2018-03-26 | 2019-10-03 | 日本ゼオン株式会社 | アクリルゴム、アクリルゴム組成物、アクリルゴム架橋物、シール材、及びホース材 |
JPWO2019239922A1 (ja) * | 2018-06-11 | 2021-06-24 | デンカ株式会社 | アクリル系エラストマー組成物 |
JP7196173B2 (ja) | 2018-06-11 | 2022-12-26 | デンカ株式会社 | アクリル系エラストマー組成物 |
WO2019239922A1 (ja) * | 2018-06-11 | 2019-12-19 | デンカ株式会社 | アクリル系エラストマー組成物 |
WO2020032173A1 (ja) | 2018-08-10 | 2020-02-13 | 株式会社大阪ソーダ | アクリル共重合体、及びゴム材料 |
JPWO2020158132A1 (ja) * | 2019-01-31 | 2021-12-02 | デンカ株式会社 | 架橋性ゴム組成物、アクリルゴム及びゴム硬化物 |
WO2020158132A1 (ja) * | 2019-01-31 | 2020-08-06 | デンカ株式会社 | 架橋性ゴム組成物、アクリルゴム及びゴム硬化物 |
JP7353309B2 (ja) | 2019-01-31 | 2023-09-29 | デンカ株式会社 | 架橋性ゴム組成物、アクリルゴム及びゴム硬化物 |
JPWO2020262495A1 (ja) * | 2019-06-28 | 2020-12-30 | ||
JP7480782B2 (ja) | 2019-06-28 | 2024-05-10 | 日本ゼオン株式会社 | アクリルゴム、アクリルゴム組成物、およびゴム架橋物 |
CN114174355A (zh) * | 2019-09-30 | 2022-03-11 | 电化株式会社 | 丙烯酸类橡胶、交联性橡胶组合物及橡胶固化物 |
WO2021065669A1 (ja) * | 2019-09-30 | 2021-04-08 | デンカ株式会社 | アクリルゴム、架橋性ゴム組成物及びゴム硬化物 |
CN114174355B (zh) * | 2019-09-30 | 2023-08-22 | 电化株式会社 | 丙烯酸类橡胶、交联性橡胶组合物及橡胶固化物 |
JP7541022B2 (ja) | 2019-09-30 | 2024-08-27 | デンカ株式会社 | アクリルゴム、架橋性ゴム組成物及びゴム硬化物 |
JP6836020B1 (ja) * | 2019-10-16 | 2021-02-24 | デンカ株式会社 | アクリルゴム、ゴム組成物及びその架橋物、ゴムホース、並びにシール部品 |
WO2021075093A1 (ja) * | 2019-10-16 | 2021-04-22 | デンカ株式会社 | アクリルゴム、ゴム組成物及びその架橋物、ゴムホース、並びにシール部品 |
WO2021112190A1 (ja) * | 2019-12-05 | 2021-06-10 | デンカ株式会社 | アクリルゴム、アクリルゴム組成物及びその架橋物 |
Also Published As
Publication number | Publication date |
---|---|
CN102124040A (zh) | 2011-07-13 |
KR20100126659A (ko) | 2010-12-02 |
JP5715758B2 (ja) | 2015-05-13 |
TWI457351B (zh) | 2014-10-21 |
EP2246373A4 (en) | 2014-04-30 |
CN102124040B (zh) | 2014-04-09 |
US8383220B2 (en) | 2013-02-26 |
KR101640610B1 (ko) | 2016-07-18 |
US20100323141A1 (en) | 2010-12-23 |
TW200951147A (en) | 2009-12-16 |
JPWO2009099113A1 (ja) | 2011-05-26 |
EP2246373B1 (en) | 2017-07-19 |
EP2246373A1 (en) | 2010-11-03 |
ES2635940T3 (es) | 2017-10-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5715758B2 (ja) | 耐熱老化性に優れたアクリルゴム加硫物 | |
JP5340143B2 (ja) | アクリルゴム組成物ならびにその加硫ゴム及びその用途 | |
JP5022165B2 (ja) | アクリルゴム組成物 | |
JP5814343B2 (ja) | クロロプレンゴム組成物およびその加硫ゴム、並びに該加硫ゴムを用いたゴム型物、防振ゴム部材、エンジンマウントおよびホース | |
WO2012090941A1 (ja) | ゴム組成物およびゴム架橋物 | |
JPWO2018008474A1 (ja) | アクリルゴム組成物 | |
US10266681B2 (en) | Cross-linkable nitrile rubber composition and cross-linked rubber product, and method for manufacturing cross-linkable nitrile rubber composition | |
JP2010174217A (ja) | アクリルゴム組成物及びその用途 | |
EP4015545B1 (en) | Acrylic rubber, crosslinkable rubber composition, and rubber cured product | |
JP7169191B2 (ja) | アクリルゴム組成物 | |
JP6267652B2 (ja) | アクリル系エラストマー、アクリル系エラストマー組成物、積層体、架橋物及び成形部材 | |
JP6293503B2 (ja) | アクリルエラストマー、アクリルエラストマー組成物および積層体 | |
JP2011006509A (ja) | アクリルゴム組成物 | |
JP5313135B2 (ja) | アクリルゴム組成物ならびにその加硫ゴムおよびその用途 | |
JP7196173B2 (ja) | アクリル系エラストマー組成物 | |
JP7541022B2 (ja) | アクリルゴム、架橋性ゴム組成物及びゴム硬化物 | |
JP2022186670A (ja) | アクリルゴム組成物及びその架橋物 | |
JPH11322853A (ja) | アクリル系ゴムおよびその組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980103360.1 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09707415 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20107014843 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009552498 Country of ref document: JP |
|
REEP | Request for entry into the european phase |
Ref document number: 2009707415 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009707415 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12866330 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |