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WO1999051674A1 - Composition de caoutchouc a diene conjugue - Google Patents

Composition de caoutchouc a diene conjugue Download PDF

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Publication number
WO1999051674A1
WO1999051674A1 PCT/JP1999/001728 JP9901728W WO9951674A1 WO 1999051674 A1 WO1999051674 A1 WO 1999051674A1 JP 9901728 W JP9901728 W JP 9901728W WO 9951674 A1 WO9951674 A1 WO 9951674A1
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weight
rubber
conjugated
group
monomer
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PCT/JP1999/001728
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English (en)
Japanese (ja)
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Yukio Takagishi
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Nippon Zeon Co., Ltd.
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Publication of WO1999051674A1 publication Critical patent/WO1999051674A1/fr

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/006Rubber characterised by functional groups, e.g. telechelic diene polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06Copolymers with styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a rubber composition which provides an automobile tire which has a high crosslinking speed, hardly generates scorch, has excellent strength properties, and has excellent fuel efficiency.
  • conjugated genomics in which a substituent having affinity for silicity is introduced is being studied.
  • a conjugated gen rubber polymerized by an emulsion polymerization method is a conjugated gen rubber having a tertiary amino group introduced therein (Japanese Patent Application Laid-Open No. 11-134344, etc.), and a conjugated gen rubber obtained by an anion polymerization method is alkylsilyl. Group (Japanese Patent Application Laid-Open No.
  • conjugated gen-aromatic vinyl copolymer rubber containing silica has a low crosslinking rate. Therefore, in general, sulfenamide crosslinking accelerators such as N-cyclohexyl-12-benzothiazolesulfenamide and diphenamide are generally used. The cross-linking speed is increased by using a guanidine cross-linking accelerator such as luguanidine. However, the cross-linking using this cross-linking accelerator in combination has a problem that scorch is generated.
  • silica-containing rubber is compounded with a silylating agent to increase the water repellency by hydrophobizing the hydrophilic portion of the rubber composition having active hydrogen such as hydroxyl, amino, and carboxyl groups.
  • a silylating agent to increase the water repellency by hydrophobizing the hydrophilic portion of the rubber composition having active hydrogen such as hydroxyl, amino, and carboxyl groups.
  • active hydrogen such as hydroxyl, amino, and carboxyl groups.
  • it has been proposed to improve the dispersibility of silica for example, Japanese Patent Application Laid-Open Nos. Hei 7-118452, Hei 9-197915.
  • silica is non-conductive, whereas carbon black, which is a typical packing material, is conductive. For this reason, the silica-containing rubber product has a problem that static electricity generated by friction or the like is easily charged.
  • a polar group-containing conjugated rubber, silica, an ether polymer, a rubber containing a silane coupling agent and a silylating agent The composition is found to be excellent in silica dispersibility, fast in crosslinking rate, hard to generate scorch, excellent in strength strength, hard to be charged, and excellent in fuel efficiency when used in tire materials.
  • the present invention has been completed.
  • a rubber component containing a conjugated diene rubber containing a polar group as a main component (b) a reinforcing agent containing silica, (c) an ether polymer, and (d) a silane coupling agent And (e) a conjugated rubber composition containing a silylating agent.
  • the polar group-containing conjugated rubber used in the present invention includes a conjugated diene monomer, a polar group-containing monomer copolymerizable with a conjugated diene monomer, and a polar group copolymerizable with these monomers as necessary. Is a copolymer rubber of a resin monomer containing no.
  • conjugated diene monomer examples include 1,3-butadiene, 2-methyl-11,3-butadiene, 2,3-dimethinole-1,3-butadiene, 2-chlorobuta-1,3-butadiene, 1 , 3-pentagen and the like. Among these, 1,3-butadiene, 2-methyl-1,3-butadiene and the like are preferable, and 1,3-butadiene is more preferable.
  • conjugated gens can be used alone or in combination of two or more.
  • the polar group-containing monomer copolymerizable with the conjugated diene monomer is not particularly limited, Examples thereof include polar group-containing vinyl monomers having atoms drawn from groups 5B and 6B of the second to fourth periods of the periodic table.
  • Examples of atoms selected from Groups 5B and 6B of the second to fourth periods of the periodic table include, for example, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
  • a nitrogen atom and an oxygen atom are preferable, and a nitrogen atom is particularly preferable.
  • polar group having an atom selected from Groups 5B and 6B of the Periodic Tables 2 to 4 include a hydroxyl group, an oxy group, an epoxy group, a carboxy group, a carbonyl group, Oxycarbonyl group, sulfide group, disulfide group, sulfonyl group, sulfininole group, thiocarbonyl group, imino group, amino group, nitrile group, ammonium group, imido group, amide group, hydrazo group, azozo And diazo groups.
  • a hydroxyl group, an oxy group, an epoxy group, a sulfide group, a disulfide group, an imino group, an amino group, and the like are preferable, a hydroxyl group, an amino group, an oxy group, and the like are more preferable, and an amino group is more preferable. preferable.
  • Examples of the polar group-containing monomer having an atom selected from Group 5B and Group 6B of the Periodic Tables 2 to 4 include, for example, an amino group-containing vinyl monomer and a hydroxyl group-containing Examples thereof include a vinyl monomer and an oxy group-containing vinyl monomer. Among these, a hydroxyl group-containing vinyl monomer and an amino group-containing vinyl monomer are preferable, and an amino group-containing vinyl monomer is particularly preferable. Masure, These polar group-containing butyl monomers can be used alone or in combination of two or more.
  • amino group-containing vinyl monomer examples include polymerizable monomers having at least one amino group selected from primary, secondary and tertiary amino groups in one molecule. Among these, a tertiary amino group-containing vinyl monomer is particularly preferred.
  • the primary amino group-containing vinyl monomer examples include acrylamide, methacrylamide, p-aminostyrene, aminomethyl acrylate, aminoethyl acrylate, aminopropyl acrylate, and aminobutyl acrylate. Rate, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, aminobutyl methacrylate and the like.
  • Examples of the secondary amino group-containing vinyl monomer include, for example, anilinostyrene; Linofenyl butadiene; N-methyl acrylamide, N-ethyl acrylamide, N-methylol acrylamide, etc. N-monosubstituted acrylamide; N-methyl methacrylamide, N-ethyl methacrylamide, N-monosubstituted methacrylamides such as N-methylol acrylamide, N- (4-anilinophenyl) methacrylamide; and the like.
  • tertiary amino group-containing vinyl monomer examples include, for example, N, N-disubstituted aminoalkyl acrylate, N, N-disubstituted aminoalkylacrylamide, N, N-disubstituted aminoaromatic biel monomer And a monomer having a pyridyl group.
  • N, N-disubstituted aminoalkyl acrylates and N, N-disubstituted aminoalkyl acrylamides are preferred.
  • N, N-disubstituted aminoacrylate examples include N, N-dimethylaminomethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl phthalate, N, N-dimethyl Aminobutyl acrylate, N, N-Getylaminoethyl acrylate, N, N-Getylaminopropyl pinoleacrylate, N, N-Getinoleaminobutynoleate tallate, N-Methinole-N-ethyl Aminoethyl acrylate, N, N-dipropylaminoethyl acrylate, N, N-dibutynoleaminoethyl acrylate, N, N-dibutynoleaminopropyl acrylate, N, N-dibutylaminobutyl acrylate Creatrate, N, N-Dihex
  • N, N disubstituted aminoalkyl acrylamide examples include N, N dimethylaminomethyl acrylamide, N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminopropynoleacrylamide.
  • N N dimethylaminopropyl methacrylamide, N, N-dimethylaminobutyl methacrylamide, N, N getylaminoethyl methacrylamide, N, N-Jethylaminopropyl methacrylamide N, N dimethylaminobutyl methacrylamide, N methyl-Nethyl aminoethyl methacrylamide, N, N dipropylaminoethyl methacrylamide, N, N-dibutylaminoethyl methacrylamide, N, N dibutylamino methacrylate Propyl methacrylamide, N, N dibutylaminobutyl methacrylamide Acrylamide monomers such as N, N dihexylaminopropyl methacrylamide, N, N dihexylaminopropyl methacrylamide, N, N dioctylaminopropyl methacrylamide; Or methacrylamide monomers, etc.
  • N, N-disubstituted amino aromatic butyl monomers examples include N, N-dimethylaminoethyl styrene, N, N-getylaminoethyl styrene, N, N-dipropynoleaminoethyl styrene, Styrene derivatives such as N, N-dioctynoleaminoethynolestyrene are exemplified.
  • Examples of the vinyl monomer having a pyridyl group include 2-butylpyridin, 4-vinylinolepyridine, 5-methyl-12-bierpyridine, 5-ethyl-2-bulpyridine and the like. Among these, 2-vinylinpyridine, 4-vinyl / leviridine and the like are preferred.
  • hydroxyl group-containing vinyl monomer examples include a polymerizable monomer having at least one primary, secondary or tertiary hydroxyl group in one molecule.
  • hydroxyl group-containing vinyl monomers include, for example, unsaturated carboxylic acid monomers, butyl ether monomers, and vinyl ketone monomers each containing a hydroxyl group.
  • Preferred is a hydroxyl group-containing unsaturated carboxylic acid monomer.
  • hydroxyl group-containing unsaturated carboxylic acid monomer examples include, for example, esters such as atalilic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, derivatives such as amides and anhydrides, and preferably acrylic acid, It is an ester monomer such as methacrylic acid.
  • hydroxyl group-containing vinyl monomers include, for example, hydroxymethyl acrylate, 2-hydroxypropynoleate acrylate, 2-hydroxypropinoleate acrylate, 3-hydroxypropinolate acrylate, 3 —Chloro 1-hydroxypropyl acrylate, 3-phenoxy 1-2—hydroxypropinorea acrylate, glycerone monoacrylate, hydroxybutyl acrylate, 2-chloro-3-hydroxypropinorea Acrylate, hydroxyhexyl acrylate, hydroxy octyl acrylate, hydroxymethyl acrylamide, 2-hydroxy Propylacrylamide, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2—hydroxypropyl methacrylate, 3—hydroxypropyl methacrylate, 3—chloro-2—hydroxypropyl methacrylate, 3-phenoxy 2 — hydroxypropynolemethacrylate, glyceronolemethacrylate, hydroxybutynolemethacrylate,
  • vinyl group-containing vinyl monomers examples include, for example, trimethoxyvinylsilane, triethoxyvinylsilane, 6-trimethoxysilyl 1,2-hexene, p-trimethoxysilylstyrene, and 3-trimethoxysilyl methacrylate.
  • Propyl examples thereof include alkoxysilyl group-containing vinyl monomers such as 3-triethoxysilylpropyl acrylate.
  • Examples of the monomer having no polar group that can be copolymerized with both the conjugated diene monomer and the monomer copolymerizable with the conjugated diene monomer include an aromatic vinyl monomer having no polar group ( Hereinafter, these compounds will be referred to as aromatic butyl monomers. Specific examples thereof include styrene, ⁇ -methinolestyrene, 2-methynolestyrene, 3-methynolestyrene, 4-methynolestyrene, and 2,2.
  • 4-diisopropynolestyrene 2,4-dimethynolethylene, 4-tert-butynolestyrene, 5-tert-butyl-2-methynolethylene, monochlorostyrene, dichlorostyrene, monophnolerostyrene.
  • styrene is preferred.
  • Two or more aromatic vinyl monomers may be used in combination.
  • the conjugated diene rubber having a polar group used in the present invention preferably contains 40 to 99.99% by weight, more preferably 45 to 90% by weight, and particularly preferably 50 to 85% by weight of a conjugated diene monomer unit. / 0 , more preferably 55 to 80% by weight, preferably 0.01 to 20% by weight, more preferably 0.05 to 15% by weight, particularly preferably 0.1 to 10% by weight of the polar group-containing vinyl unit.
  • the polymerizable polar group-free monomer unit is preferably 0 to 59.99% by weight, more preferably 9.95 to 54.95% by weight, and particularly preferably 14.9 to 49.9%. %, More preferably 19.9 to 44.9% by weight.
  • the content of each monomer unit in the polar group-containing conjugated rubber can be appropriately selected from the above ranges in consideration of the low heat generation property, abrasion resistance, and strength characteristics of the tire.
  • the Mooney viscosity (ML 1 + 4 , 100 ° C.) of the conjugated diene rubber having a polar group is in the range of 20 to 200, preferably 30 to 150, more preferably 50 to 120. If the Mooney viscosity of the polar group-containing conjugated gen rubber is low, it is easy to manufacture, but it is difficult to obtain sufficient heat generation characteristics ⁇ ⁇ abrasion resistance, etc. Conversely, if it is large, it is excellent in abrasion resistance, etc. The viscosity of the material becomes too high, resulting in poor processability.
  • the method for producing the conjugated diene rubber having a polar group used in the present invention is not particularly limited, but usually an emulsion polymerization method is employed.
  • the emulsion polymerization method is not particularly limited. And a method of polymerizing with a radical polymerization initiator.
  • the emulsifier used in the emulsion polymerization method is not particularly limited, but the use of an emulsifier having a carboxyl group can further improve the problem of mold contamination in the resulting copolymer at high temperature and short time crosslinking. .
  • Examples of the emulsifier having a carboxyl group include fatty acid soap and rosin soap.
  • the fatty acid soap include long-chain aliphatic carboxylic acids having 12 to 18 carbon atoms, sodium salts of these mixed aliphatic carboxylic acids, and mixed aliphatic carboxylic acid salt salts.
  • Examples of the long-chain aliphatic carboxylic acid having 12 to 18 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid.
  • Examples of the rosin acid soap include sodium salts and potassium salts obtained by disproportionation of natural rosin, and sodium salts and potassium salts obtained by hydrogenating natural rosin.
  • Examples of the natural rosin include abietic acid, levopimaric acid, parastolic acid, dehydroabietic acid, tetrahydroabietic acid, and neoabietic acid, and examples thereof include gum rosin, wood rosin, and tall oil rosin.
  • the amount of the emulsifier is not particularly limited, but is preferably 0.05 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the monomer.
  • radical polymerization initiator examples include a persulfate such as ammonium persulfate and potassium persulfate; a combination of ammonium persulfate and ferric sulfate; a combination of an organic peroxide and ferric sulfate; and Redox initiators such as a combination of hydrogen peroxide and ferric sulfate; and the like.
  • the radical polymerization initiator to be used is not particularly limited, but usually, an organic peroxide, a redox polymerization initiator, an azo compound, a persulfate, or the like is used.
  • the amount of the polymerization initiator to be used is preferably 0.005 to 3 parts by weight per 100 parts by weight of the monomer.
  • the as of the emulsion polymerization can be appropriately selected depending on the kind of the radical polymerization initiator used, but is preferably 0 to 100 ° C, more preferably 0 to 60 ° C.
  • the polymerization mode may be any mode such as continuous polymerization or batch polymerization. As the conversion of emulsion polymerization increases, a tendency to gel is observed. Therefore, heavy The conversion is preferably suppressed to 90% or less, and particularly preferably, the polymerization is stopped within the range of 50 to 80%.
  • the termination of the polymerization reaction is usually performed by adding a polymerization terminator to the polymerization system when a predetermined conversion is reached.
  • an amine compound such as getyl hydroxyloleamine / hydroxylamine, a quinone compound such as hydroquinone or benzoquinone, a compound such as sodium nitrite and sodium dithiocarbamate are used.
  • the rubber component used in the present invention is mainly composed of a conjugated diene rubber having a polar group.
  • other rubbers may be blended within a range that does not impair the effects and objects of the present invention.
  • the other rubber is not particularly limited, and a conjugated rubber other than the polar group-containing conjugated rubber is usually used.
  • conjugated rubbers include natural rubber, polyisoprene rubber, emulsion-polymerized styrene-butadiene copolymer rubber, and solution-polymerized random styrene-butadiene copolymer rubber (for example, styrene unit of 5 to 50% by weight).
  • the rubber other than the conjugated gen rubber for example, butyl rubber, halogenated butizole rubber, ethylene-propylene-gen terpolymer rubber, epichloronohydrin rubber and the like can be used.
  • These rubbers can be used alone or in combination of two or more.
  • a polar group-containing conjugated gen rubber and another rubber are used together as a rubber component, the proportion of each rubber is appropriately selected according to the application and purpose, but among the rubber components, a polar group-containing conjugated gen rubber is preferable. 5 0 weight 0/0 or more, and more preferable properly 7 0 wt% or more, particularly preferably 9 0 wt% or more.
  • the reinforcing agent used in the present invention contains silica as an essential component, and optionally contains other reinforcing agents.
  • the silica is not particularly limited, but examples thereof include dry white carbon, wet white carbon, colloidal silica, and precipitated silica. Among these, wet-process white carbon containing hydrous caustic acid as a main component is particularly preferred. These silicas can be used alone or in combination of two or more.
  • the specific surface area of silica is not particularly limited, a nitrogen adsorption specific surface area (BET method), preferably 5 0 ⁇ 4 0 0 m 2 Z g, more preferably 1 0 0 ⁇ 2 5 0 m 2 g, in particular preferably 1 2 0 ⁇ 1 9 O m 2 Z g.
  • BET method nitrogen adsorption specific surface area
  • the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTM D330-81.
  • the reinforcing agent other than silica is not particularly limited, but usually carbon black is used.
  • carbon black include furnace black and acetylene Racks, thermal black, channel black, graphite, and the like can be used.
  • furnace black is particularly preferable, and specific examples thereof include various types such as SAF, ISAF, ISAF—HS, ISAF—LS, II SAF—HS, HAF, HAF—HS, HAF—LS, and FEF. Grades. These carbon blacks can be used alone or in combination of two or more.
  • the nitrogen adsorption specific surface area (NSA) of Ripbon Black is not particularly limited, but is preferably 5 to 200 ⁇ 2 ⁇ , more preferably 50 to: L 50 m 2 / g, and particularly preferably 80 to 130 m It is in the range of 2 Zg.
  • the amount of DBP adsorbed by the carbon black is not particularly limited, but is preferably in the range of 5 to 300 ml of ZOO g, more preferably 50 to 200 ml / 100 g, and particularly preferably in the range of 80 to 160 ml of ZOO g.
  • the DBP adsorption amount of the carbon black is within this range, the bow I tensile strength / abrasion resistance is improved at a high level, which is preferable.
  • Abrasion resistance can be further improved by using high-structure carbon black having an adsorption amount of DBP (24MDBP) of 110 to 130 ml / 100 g after being repeatedly compressed four times.
  • DBP 24MDBP
  • the content of silica in the reinforcing agent is preferably 10 to 100 weight 0/0, more preferably
  • ether polymer a polymer having an ether bond (-C-0-C-I) in a main chain is used without any particular limitation.
  • an oxysilane monomer such as an alkylene oxide monomer, an epihydric hydrin monomer, an unsaturated epoxide monomer, or the like, alone or in combination of two or more, is added in a block or random manner.
  • a polymerized product is used.
  • Specific examples of the ether polymer obtained by addition-polymerizing an oxysilane monomer alone or in combination of two or more thereof include, for example, a homopolymer of an alkylene oxide monomer and a copolymer of two or more alkylene oxide monomers.
  • Polymer Polymer, copolymer of alkylene oxide monomer and epihalohydrin monomer, copolymer of alkylene oxide monomer and unsaturated epoxide monomer, alkylene oxide monomer and epihalohydrin Copolymer of dolin monomer and unsaturated epoxide monomer, homopolymer of ephalohydrin monomer, copolymer of two or more ephalohydrin monomers, monomeric ephalohydrin monomer and unsaturated epoxide monomer And a homopolymer of an unsaturated epoxide monomer, and a copolymer of two or more unsaturated epoxide monomers.
  • a copolymer of two or more alkylene oxide monomers or a copolymer of an alkylene oxide monomer and an unsaturated epoxide monomer is preferable, and an alkylene oxide monomer and an unsaturated epoxide are preferable. Copolymers with monomers are particularly preferred.
  • alkylene oxide monomer examples include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxymonoisobutane, 2,3-epoxybutane, 1,2-epoxyhexene, 2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-1 Epoxy-1-pentylpropane, 1,2-epoxy-1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycyclododecane, and the like.
  • lower anolexylene oxides such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and amylene oxide are preferred, and ethylene oxide-propylene oxide is particularly preferred.
  • Epiha hydrin monomers include, for example, epichlorohydrin, epibromohydrin, epiohydrin, 2,3-epoxy-1 1,1,1 tripropenolepropane, 1,2-epoxy-1H, 1 H, 2 H, 3 H, 3 H-heptadecafluoroundecane and the like, and usually epichlorohydrin is used.
  • the unsaturated epoxide monomer there is no particular limitation on the unsaturated epoxide monomer as long as it has at least one carbon-carbon unsaturated bond and at least one epoxy group in the molecule.
  • Alkenyl daricidyl ether monomers such as arylglycidyl ether, butenyldaricidyl ether, and octenyldaricidyl ether; to 3,4-epoxy-1-butene, 1,2-epoxy-1-5 Kisen, 1, 2-epoxy
  • Alkenyl epoxide monomers such as 9-decene; aryl epoxide monomers such as styrene epoxide and glycidyl phenyl ether; and the like. Of these, alkenyl dalicidyl ether monomers are preferred, and aryl glycidyl / ether is particularly preferred.
  • oxysilane monomers include, for example, 1,2-epoxy-1-methoxy-2-methylpropane, 2- (3,4-epoxycyclohexyl) ethynoletrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane And so on.
  • oxysilane monomers can be used alone or in combination of two or more.
  • the type and content of the oxysilane monomer in the ether polymer are appropriately selected depending on the purpose of use.
  • an ether polymer (A) obtained by copolymerizing an alkylene oxide monomer and an unsaturated epoxide monomer is generally used.
  • the content of the alkylene O sulfoxide monomer unit in this case is preferably 8 5-9 9. 9 wt 0 I, more preferably 9 0-9 9 wt. /.
  • the content of unsaturated epoxide monomer units is preferably 15 to 0.1% by weight, more preferably 10 to 1% by weight, particularly preferably 95 to 99% by weight.
  • alkylene O sulfoxide monomer units is preferably 5 0 weight 0 /.
  • the ether polymer (B) containing more preferably 70% by weight or more, particularly preferably 90% by weight or more is suitably used.
  • antistatic properties are required.
  • ethylene oxide units are 50% by weight or more, preferably 60% by weight. % Or more, more preferably 70% by weight or more of the ether polymer (C) is suitably used.
  • the alkylene oxide monomer unit in the above ether polymer (A) should be Chirenokishido units preferably 5 0: 1 0 0 wt 0/0, more preferably 6 0 9 9 wt%, particularly preferably a 7 0 9 7 wt%, propylene O carboxymethyl properly 5 0 preferred are de units % To 0% by weight, more preferably 40% to 1% by weight, and particularly preferably 30% to 3% by weight.
  • Preferred copolymers are Echire Nokishido unit 5 0-9 9 wt 0/0, propylene O sulfoxide units 0-4 9 wt 0/0, Contact and ⁇ Li glycidyl ether unit:! It is a copolymer consisting of up to 15% by weight.
  • ether polymers (1) 50 to 98.9% by weight of ethylene oxide unit, preferably 60 to 97.5% by weight, more preferably 70 to 96% by weight, (2) propylene oxide unit 1 to 35 % by weight. Preferably 2-30 weight 0 /.
  • the unsaturated Epokishido monomer is particularly preferably an alkenyl daricidyl ether monomer such as aryl glycidyl ether.
  • the (co) polymer of an oxysilane monomer containing the above terpolymer can be usually obtained by a solution polymerization method or a solvent slurry polymerization method.
  • the catalyst include a catalyst obtained by reacting water and acetylaceton with organoaluminum; a catalyst obtained by reacting phosphoric acid and triethylamine with triisobutylaluminum; a phosphoric acid obtained by reacting triisobutylaluminum; and an organic acid salt of diazabiacycloundecene.
  • a homogeneous catalyst such as a catalyst obtained by the reaction of a compound; a catalyst comprising a partially hydrolyzed product of anolemminium alkoxide and an organic zinc compound; a catalyst comprising an organic zinc conjugate and a polyhydric alcohol; And a heterogeneous catalyst such as a catalyst comprising water.
  • a catalyst previously treated with both a monomer that gives a polymer soluble in the polymerization solution and a monomer that gives a polymer insoluble in the polymerization solvent is used. It is preferable to use it from the viewpoint of the stability of the polymerization reaction system.
  • solvent examples include aromatic hydrocarbons such as toluene; linear hydrocarbons such as n-pentane and n-hexane; alicyclic hydrocarbons such as cyclopentane; You.
  • a solvent slurry polymerization method is employed using a solvent such as n-pentane, n-hexane, or cyclopentane, for example, ethylene oxide that gives a polymer that is insoluble in the solvent and a polymer that is soluble in the solvent are used.
  • Force to treat the catalyst in advance with propylene oxide to give the following: ⁇ As described above, it is preferable from the viewpoint of the stability of the polymerization reaction system.
  • the catalyst component and a small amount of each monomer are mixed, and the mixture is preferably aged at a temperature of 0 to L 0 ° C, more preferably 30 to 50 ° C. .
  • a monomer component, a catalyst component, a polymerization solution, etc. are charged into a reactor, and the temperature is 0 to 100 ° C, preferably 30 to 70 ° C, and is a batch type, a semi-batch type, or a continuous type. Any method can be used.
  • the Mooney viscosity (ML 1 + 4 , 100 ° C.) of the ether polymer is preferably 70 to 150, more preferably 80 to 140, and particularly preferably 85 to 120. . When the Mooney viscosity of the ether polymer is within this range, low heat build-up, tensile strength and workability are highly balanced, which is preferable.
  • ether polymers can be used alone or in combination of two or more.
  • the amount of the ether polymer to be used is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 3 parts by weight, based on 100 parts by weight of the conjugated gen rubber selected as appropriate according to the intended use. 0 parts by weight, particularly preferably 3 to 15 parts by weight. If the amount of the ether polymer is excessively small, the effect of improving the low heat build-up, tensile strength and workability is not sufficient, and if it is excessively large, the low heat build-up is insufficient. Not preferred.
  • the silane coupling agent is not particularly limited, but includes, for example, butyltrichlorosilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxy-1-ethoxy) silane, ⁇ - (3,4-epoxycyclohexinole) -ethynoletrimethoxysilane, ⁇ —Dalicidoxypropyltrimethyoxysilane, ⁇ -methacryloxypropinoletrimethyoxysilane,] —] 3 (aminoethyl) ⁇ -aminopropyltrimethyoxysilane, ⁇ — i3 (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane , ⁇ -phenyl y-aminopropyl trimethyoxysilane, ⁇ -cloth provirt trimethoxysilane, ⁇ mercaptoprovir trimethyoxysilane, ⁇ amino
  • the silinole agent added to change the surface of the sieve to be hydrophobic is, specifically, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyl / reethoxysilane, diphenylinoresethoxysilane.
  • Trifeninoleethoxysilane Triphenylmethoxysilane, ⁇ -Methylphenyltrimethoxysilane, ⁇ -Methynolephenizoletriethoxysilane, 3-Port Propinoletrimethoxysilane, 3-Port Propinoletriethoxysilane, 3, 3,3-Triphnoreo-propynoletrimethoxysilane, 3,3,3-Trifluoropropynoletriethoxysilane, 3-Ditolylpropynoletrimethoxysilane, 3-Nitrilypropynoletriethoxysilane, ⁇ -Bromophene Ninoretrimethoxysilane, ⁇ — Lomopheninoletriethoxysilane, tolyltrimethoxysilane, tonoleinoletriethoxysilane, propyltrimethoxysilane chloride, propyltriethoxysilane
  • R is an alkyl group
  • A is a phenyl group or an alkylphenyl group
  • B is a phenyl group, an alkylphenyl group or an alkoxy group
  • C is a phenyl / alkyl group, It is a kilfenino group or an alkoxy group.
  • silylating agent examples include phenyltriethoxysilane, phenyltrimethoxysilane, diphenylethoxysilane, diphenyldimethoxysilane, triphenylethoxysilane, triphenylmethoxysilane and the like.
  • phenyltriethoxysilane is preferred.
  • the rubber composition of the present invention comprises (a) a rubber component mainly containing a conjugated gen rubber, (b) a reinforcing agent containing silica, (c) an ether polymer, (d) a silane coupling agent, and (e) silylation. Agent.
  • the amount of the reinforcing agent containing (b) silica is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, particularly preferably 100 parts by weight of the rubber component (a). 30 to 120 parts by weight. If it is too large, dispersion may not be successful. If the amount is too small, the reinforcing effect is so small that it may not meet the purpose.
  • the amount of the ether polymer is determined according to the application, but (a) based on 100 parts by weight of the rubber component, preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight, Particularly preferred is 3 to 15 parts by weight. If the amount of the ether polymer is too small, low heat build-up, tensile strength, workability, and the like may be insufficient. If the amount is too large, the low heat build-up may be insufficient.
  • the amount of the silane coupling agent is also determined depending on the application, but is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, particularly preferably 100 parts by weight of silica. Is 1 to 10 parts by weight. If the amount is too large, the effect is not sufficient with respect to the added amount, and the strength may be adversely affected. If the amount is too small, the effect will not be sufficiently exhibited.
  • the amount of the silinolelating agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to: 15 parts by weight, and particularly preferably 1 to 10 parts by weight, per 100 parts by weight of the rubber. Department. If the amount of the silylating agent is too large, the hardness of the rubber composition may decrease, or may be deposited on the surface to reduce the sliding resistance of the rubber composition. If the amount of the silylating agent is too small, the effect may not be sufficiently exhibited.
  • the stabilizer used in the present invention is not particularly limited, and examples thereof include a phenol stabilizer, a zeolite stabilizer, and a phosphorus stabilizer.
  • the phenol stabilizer used in the present invention includes, for example, 2,6-di-tert-butynole 4-methinolephenogre, 2,6-di-tert-butyl-4-butyl-ethyl phenol / re, 2,6-di tert-butynole 4-n-butyl phenol, 2,6-di-tert-butyne 4-iso-butyl phenol, 2-tert-butyl phenol 4,6-dimethynole, 2, 4 , 6-tricyclohexinolephenol, 2,6-ditert-butynole 4-methoxyphenol, 2, 6-diphenol-4, octadecyloxyphenol, n-octadecyl-3- (3 ,,
  • phenol stabilizers such as 6-tris (3,5-ditert-butyl-4-hydroxybenzinole) benzene
  • zeo-containing phenol stabilizers are exemplified.
  • phenol-containing phenol stabilizer examples include 2,4-bis (octylthiomethyl) -1-6-methinolephenol and 2,4-bis (2,, 3,1-hydroxypropynolethiomethinole). Examples thereof include 1,3,6-di-methylphenol and 2,4-bis (2,1-acetylcyclohexylthiomethyl) -1,3-dimethylphenol.
  • the phosphorus stabilizers used in the present invention are also known, for example, tris (nonylphenyl) phosphite, cyclic neopentanetetraylbis (octadecinolephosphite), tris (2,4-di-tert.) —Butylphenyl) phosphite and the like.
  • iodine stabilizer examples include pentaerythritol-tetrakisux (1-lauryl-thio-propionate), Examples thereof include dilauryl-1,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, and distearyl-1,3,3′-thiodipropionate.
  • the crosslinking agent is not particularly limited.
  • sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur
  • sulfur halide such as sulfur monochloride and sulfur dichloride
  • dicumyl par Organic peroxides such as oxoxide and ditertiary butyl peroxide
  • quinone dioximes such as P-quinone dioxime and p, p'-dibenzoyl quinone dioxime
  • 4 Organic polyvalent amine compounds such as 4,4'-methylenebis-o-chloroaniline
  • alkyl phenol resins having methylol groups and the like.
  • These crosslinking agents are used alone or in combination of two or more.
  • the mixing ratio of the cross-linking agent is preferably from 0.3 to 15 parts by weight, more preferably from 0.3 to 0 parts by weight, particularly preferably from 0.3 to 100 parts by weight of the rubber component (a). It is in the range of 5 to 5 parts by weight.
  • the compounding ratio of the cross-linking agent is in this range, it is particularly preferable because it has excellent tensile strength and abrasion resistance, and also has excellent properties such as heat resistance and residual strain.
  • cross-linking accelerator examples include N-cyclohexyl-12-benzothiazoles-norefenamide, Nt-butyl-2-benzothiazolesulfenamide, N-oxyethylene-12-benzothiazo-l / resnolefen Ami de, N- Okishechire Hmm 2-benzothiazyl zone Roh less Honoré Fen Ami de, N, Su ultrasound'ami de crosslinking accelerators such as N r over diisopropylate Honoré one 2-benzothiazole one Rusuru Fen Ami de; Jifue Nirudanijin, Jiorutotoriru Guanidine cross-linking accelerators such as guanidine and o-tolylbiguanidine; thioperia cross-linking accelerators such as thiocarboaureide, dionole tolitol thiourea, ethyl lentiolerea, getyl thiourea, and trimethyl thioure
  • cross-linking accelerators are used alone or in combination of two or more kinds; and those containing at least a sulfenamide cross-linking accelerator are particularly preferred.
  • those containing a sulfenamide cross-linking accelerator those having a sulfenamide cross-linking accelerator in a proportion of 30% by weight or more of all the cross-linking accelerators are preferable, and 50% by weight / 0 .
  • the above compounds are more preferable, and those having 70% by weight or more are particularly preferable.
  • the compounding ratio of the crosslinking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, particularly preferably 0.5 to 100 parts by weight of the solid rubber. It is in the range of ⁇ 5 parts by weight.
  • the cross-linking activator is not particularly limited, and for example, higher lubricating fatty acids such as stearic acid and zinc oxide can be used.
  • zinc oxide having a high surface activity and a particle size of 5 ⁇ or less.
  • an active material having a particle size of 0.05 to 0.2 nm is preferably used.
  • a zinc oxide surface-treated with an amine dispersant or a wetting agent can be used.
  • These crosslinking activators can be used alone or in combination of two or more. The mixing ratio of the crosslinking activator is appropriately selected depending on the type of the crosslinking activator.
  • a higher fatty acid When a higher fatty acid is used, it is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the solid rubber. Mix by weight.
  • zinc oxide When zinc oxide is used, it is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and particularly preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the solid rubber. Mix by weight.
  • the compounding ratio of zinc oxide When the compounding ratio of zinc oxide is in this range, properties such as workability, bow I tensile strength and abrasion resistance are highly balanced and suitable.
  • Examples of other compounding agents include force coupling agents other than silane coupling agents; activators such as methylene glycol, polyethylene glycol, and silicone oil; fillers such as calcium carbonate, tazolex, and clay; process oils and waxes And so on.
  • the rubber composition of the present invention can be obtained by blending each component according to a conventional method. For example, (a) after dispersing each component in an organic solvent in which a rubber component is dissolved or dispersed, the organic solvent is removed by a steam stripping method or a method using a hot roll, And kneading using an extruder.
  • a steam stripping method or a method using a hot roll and kneading using an extruder.
  • the amount of styrene unit in the conjugated gen rubber was measured according to JIS K 6383 (refractive index method).
  • the amount of the amino group-containing monomer unit in the conjugated gen rubber can be determined by dissolving the copolymer in tetrahydrofuran, and reprecipitating and coagulating twice with methanol Zacetone (50/50/50 volume 0 /.). After drying in vacuo, it was measured by 500 MHz 1 H-NMR.
  • the Mooney scorch time (t 5) was determined by measuring the scorch time of an unvulcanized rubber composition at 160 ° C. with an oscillating 'rheometer according to the Japan Rubber Association Standard SR IS 3102.
  • Example:! 5 to 5 and Comparative Examples 2 to 4 are indices based on the Mooney scorch time (t5) of Comparative Example 1 as 100, and are the same as those of Examples 6 to 10;
  • the scorch time ( t 5) is indicated by an index with 100 as the index.
  • Vulcanization rate ⁇ (t 90-t 10) is 90% of the maximum torque at 160 ° C by an oscillating rheometer for unvulcanized rubber composition in accordance with Japan Rubber Association Standard SR IS 3102.
  • the difference ⁇ (t90-t10) between the time to reach (t90) and the time to reach 5% of the maximum torque (t10) was measured.
  • the index was set as an index with the vulcanization rate ⁇ (t90-t10) of Comparative Example 5 being 100.
  • a tank equipped with a stirrer was charged with 200 parts of water, 3 parts of ore diced stone, 0.15 parts of t-dodecyl mercaptan, and a monomer having the composition shown in Table 1.
  • the reactor was kept at 5 ° C, and 0.1 parts of cumenehydride peroxide, 0.2 parts of sodium honolemaldehyde sulfoxylate, and 0.01 parts of ferric sulfate were added as radical polymerization initiators. Started. When the conversion reached 70%, the reaction was stopped by adding getylhydroxylamine.
  • Conjugated gen rubber 2 is a conjugated gen rubber containing a polar group.
  • the autoclave with a stirrer having an internal volume of 3 liters was purged with nitrogen, and charged with 117 g of toluene, 158.7 g of triisobutylaluminum, and 296.4 g of getyl ether.
  • the internal temperature was set at 30 ° C., and 23.5 g of orthophosphoric acid was gradually added with stirring. Further, 122.1 g of triethylamine was added, and the mixture was aged at 60 ° C. for 2 hours to obtain a catalyst solution.
  • Reference example 5 A mixed solution consisting of 240 g of ethylene oxide, 6 g of propylene oxide, and 300 g of n-hexane was mixed with 261 g of ethylene oxide, 30 g of propylene oxide, 9 g of arydaricidyl ether, and 300 g of n-hexane. The same procedure as in Reference Example 4 was carried out except for using the mixed solvent consisting of g, to obtain an ether polymer 2. Table 2 shows the properties of polyether polymer 2. Table 2
  • composition of the composition (parts by weight)
  • Conjugated gen rubber 2 1-1 1 60 60 60 Conjugated gen rubber 3 1 1 ⁇ ⁇ ⁇
  • Siri force is Zeozi 1 1 165MP (Rhone Poulin, nitrogen adsorption specific surface area 175m 2 / g), Sirinorei 1 is phenyltriethoxysilane, Sirenoletting agent 2 is diphenylethoxysilane, silane coupling agent 1 is Si 69 (Degussa, silane coupling agent 2 is mercaptopropyltrimethoxysilane) , Zinc oxide is zinc white # 1 (this chemical cane, particle size 4 ⁇ ), oil is Sansen 410 (Nippon Oil Co., Ltd.), antioxidant is Nocrack 6C (Ouchi Shinko Byeon: fc), and crosslinking is promoted. Noxeller CZ (Ouchi Shiningune) was used as the preparation. Gen rubber used Nipo 1 BR122 (made by Nippon Oil Co., Ltd.), antioxidant is Nocrack 6C (Ouchi Shinko Byeon: fc), and crosslinking is promoted. Noxeller
  • the rubber composition of the present invention is excellent in strength properties because silica is sufficiently dispersed, and excellent in fuel efficiency and high in crosslinking speed because silica is used as a scavenger, and scorch Is unlikely to occur. It can significantly improve the tensile strength, low heat build-up, and abrasion resistance, which were disadvantages without impairing the rolling resistance, which is a characteristic of silica-containing materials, and have excellent properties in terms of workability. Have.
  • the rubber composition of the present invention can be used for tire parts such as treads, carcass, sidewalls, and bead parts, or for rubbers such as hoses, window frames, belts, shoe soles, vibration-isolating rubber, and automobile parts. It can be used for products, and also as resin-resistant rubber such as impact-resistant polystyrene and ABS resin.
  • the rubber composition of the present invention makes use of the above-mentioned properties, and is particularly excellent in tire trails of fuel-efficient tires, but in addition to tires, sidewalls, and tires such as all-season tires, high-performance tires and studless tires. Can be used for under treads, carcass, beats, etc.

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Abstract

Composition de caoutchouc à diène conjugué qui contient les ingrédients suivants: (a) un ingrédient caoutchouc constitué principalement d'un caoutchouc à diène conjugué doté de groupes polaires, (b) un agent de renforcement contenant de la silice, (c) un polymère d'éthylène, (d) un agent de couplage silane et (e) un agent de silylation. Ladite composition de caoutchouc présente d'excellentes propriétés de dispersion de la silice, réticule à un taux élevé, est moins apte au grillage, possède une excellente résistance, est moins apte à se charger d'électricité statique et est efficace pour réduire la consommation de carburant lorsqu'elle est utilisée dans le fabrication de pneus.
PCT/JP1999/001728 1998-04-01 1999-04-01 Composition de caoutchouc a diene conjugue WO1999051674A1 (fr)

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JP2001164051A (ja) * 1999-12-06 2001-06-19 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物およびそれをタイヤトレッドに用いた空気入タイヤ
JP2001214000A (ja) * 2000-02-02 2001-08-07 Bridgestone Corp 重荷重用空気入りタイヤ
JP2002121327A (ja) * 2000-10-16 2002-04-23 Sumitomo Rubber Ind Ltd トレッドゴム組成物およびその製造方法
JP2002201310A (ja) * 2000-12-27 2002-07-19 Bridgestone Corp ゴム組成物
JP4547827B2 (ja) * 2001-04-16 2010-09-22 横浜ゴム株式会社 鉱石運搬用コンベヤベルト
US7132471B2 (en) 2002-04-25 2006-11-07 Asahi Kasei Chemicals Corporation Rubber composition and process for production thereof
KR100476013B1 (ko) * 2002-06-25 2005-03-10 금호타이어 주식회사 실리카를 보강충진제로 하는 타이어 트래드용 고무조성물
JP2006036822A (ja) * 2004-07-22 2006-02-09 Toyo Tire & Rubber Co Ltd ゴム組成物及び空気入りタイヤ
US20070244236A1 (en) * 2004-08-11 2007-10-18 Dow Corning Toray Co., Ltd. Vibration-Damping And Vibration-Isolating Rubber Composition, Method Of Preparation Thereof, And Vibration-Damping And Vibration-Isolating Rubber Products
DE102004061014A1 (de) * 2004-12-18 2006-06-29 Degussa Ag Kautschukmischungen
FR2886303B1 (fr) * 2005-05-26 2007-07-20 Rhodia Chimie Sa Utilisation d'une combinaison particuliere d'un agent de couplage et d'un agent de recouvrement, comme systeme de couplage(charge blanche-elastomere) dans les compositions de caoutchouc comprenant une charge inorganique
JP5085873B2 (ja) * 2006-03-16 2012-11-28 住友ゴム工業株式会社 トレッド用ゴム組成物
JP5085872B2 (ja) * 2006-03-16 2012-11-28 住友ゴム工業株式会社 インナーライナー用ゴム組成物
JP5286642B2 (ja) * 2006-03-31 2013-09-11 横浜ゴム株式会社 タイヤ用ゴム組成物及びそれを用いた空気入りタイヤ
JP4954810B2 (ja) * 2006-08-23 2012-06-20 住友ゴム工業株式会社 サイドウォール用ゴム組成物およびクリンチエイペックス用ゴム組成物、ならびにそれらを用いたタイヤ
JP2008308554A (ja) * 2007-06-13 2008-12-25 Sumitomo Rubber Ind Ltd クリンチ用ゴム組成物および空気入りタイヤ
JP5212782B2 (ja) * 2008-01-28 2013-06-19 住友ゴム工業株式会社 サイド部補強ゴム組成物およびランフラットタイヤ
JP5495153B2 (ja) * 2008-04-22 2014-05-21 住友ゴム工業株式会社 ゴム組成物およびそれを用いた空気入りタイヤ
JP5466447B2 (ja) * 2009-07-21 2014-04-09 住友ゴム工業株式会社 ゴム組成物及びスタッドレスタイヤ
JP5551904B2 (ja) * 2009-08-12 2014-07-16 住友ゴム工業株式会社 トレッド用ゴム組成物及び空気入りタイヤ
JP5612360B2 (ja) * 2010-06-02 2014-10-22 住友ゴム工業株式会社 タイヤ用ゴム組成物及びスタッドレスタイヤ
JP5789968B2 (ja) * 2010-12-06 2015-10-07 横浜ゴム株式会社 タイヤトレッド用ゴム組成物
JP5835351B2 (ja) * 2012-08-30 2015-12-24 横浜ゴム株式会社 タイヤトレッド用ゴム組成物
WO2014054735A1 (fr) * 2012-10-04 2014-04-10 日本ゼオン株式会社 Procédé de production d'une composition de caoutchouc
JP6481370B2 (ja) * 2015-01-06 2019-03-13 横浜ゴム株式会社 スタッドレスタイヤ用ゴム組成物およびそれを用いたスタッドレスタイヤ
JP6504696B2 (ja) * 2015-02-05 2019-04-24 住友ゴム工業株式会社 高減衰組成物および粘弾性ダンパ
JP2016169268A (ja) * 2015-03-11 2016-09-23 株式会社ブリヂストン タイヤ用ゴム組成物の製造方法
JP7535840B2 (ja) * 2018-07-27 2024-08-19 住友ゴム工業株式会社 ゴム組成物及びタイヤ
EP3744777B1 (fr) * 2018-07-27 2023-03-15 Sumitomo Rubber Industries, Ltd. Composition de caoutchouc et pneumatique
JP2020132690A (ja) * 2019-02-14 2020-08-31 住友ゴム工業株式会社 タイヤ用ゴム組成物及びタイヤ
JP2022181089A (ja) * 2021-05-25 2022-12-07 住友ゴム工業株式会社 ゴム組成物の製造方法および医療用ゴム部品の製造方法

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