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    • 专利摘要:
    RUBBER AND TIRE COMPOSITION. The present invention relates to a rubber composition including (A) at least one rubber component selected from the group consisting of a synthetic rubber and a natural rubber; (b) a farnesene polymer having an average molecular weight of not less than 2,000 and less than 25,000; and (C) carbon black.
    公开号:BR112014007430B1
    申请号:R112014007430-5
    申请日:2012-09-21
    公开日:2020-07-28
    发明作者:Shigenao Kuwahara；Kei Hirata；Daisuke Koda
    申请人:Kuraray Co., Ltd.；Amyris, Inc；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [001] The present invention relates to a rubber composition containing a rubber and polypharnesene component and a tire using the rubber composition. BACKGROUND TECHNIQUE
    [002] Tires are required to have not only good steering stability on a dry road surface (dry grip performance) and good steering stability on a wet road surface (wet grip performance), but also low-temperature performance such as driving stability under low temperature conditions or on a snow-covered road surface (ice-grip performance), that is, the tires must have a level of movement stability high under extensive environmental conditions.
    [003] In general, in order to improve the ice-grip performance of a rubber tire composition, it is effective to increase the contact area between the rubber and ice composition - snow. For this reason, it is necessary for the rubber composition to exhibit excellent flexibility in low temperature conditions. In order to provide good flexibility to the rubber composition, it is generally known to reduce the amount of carbon black compound in the rubber composition or to adjust the particle size of the carbon black compound in the range from about 100 to about 200 nm. In these conventional methods, the rubber compositions can be improved in ice bonding performance by providing them with flexibility, that is, by reducing their elastic modulus in low temperature conditions. However, on the other hand, these methods tend to suffer from such a problem that rubber compositions deteriorate in dry grip performance due to hysteresis or reduction in elastic modulus over a common temperature range. On the other hand, in order to improve the adhesion performance in dry conditions, it is known the method of using a rubber having a high glass transition temperature (Tg), for example, a styrene-butadiene rubber in rubber compositions, or the method of composing a large amount of carbon black having an average particle size of from about 5 to about 100 nm in the rubber compositions. However, in these methods, a problem tends to occur that the rubber compositions are deteriorated in processability during production due to an increase in their viscosity as well as in flexibility under low temperature conditions, that is, the rubber compositions are deteriorated in the ice bond performance due to increased elastic modulus.
    [004] In this way, the processability when producing and adhering performance of rubber tire compositions has a contradictory relationship with their dry grip performance, and it is then considered that the rubber compositions are difficult to improve in both properties in a well balanced manner.
    [005] In Patent Document 1, as a rubber composition that can be perfected in these properties in a well balanced manner, the rubber tread composition which is composed with a liquid polymer such as liquid polybutadiene is described.
    [006] However, Patent Documents 2 and 3 describe the polymer obtained through the polymerization of p-farnesene, but fail to have a sufficient study on its practical applications. CITATION LIST PATENT LITERATURE
    [007] Patent Document 1: JP 07-053784A
    [008] Patent Document 2: WO 2010 / 027463A
    [009] Patent Document 3: WO 2010 / 027464a SUMMARY OF THE INVENTION TECHNICAL PROBLEM
    [0010] The rubber composition for tread as described in Patent Document 1 is improved in ice grip performance and dry grip performance in a well balanced manner. However, the improvement is still insufficient, and thus there is still a strong demand for rubber compositions that are further improved in these properties.
    [0011] The present invention was realized in view of the above conventional problems. An objective of the present invention is to provide a rubber composition that is capable of satisfying everyone of processability when producing, ice-grip performance and dry-grip performance at a high level and a tire obtained using the rubber composition . SOLUTION TO THE PROBLEM
    [0012] As a result of extensive and intensive research, the present inventors have found that when using a conjugated diene polymer having a specific structure, the resulting rubber composition can be improved in all processability when producing, adhering performance ice and dry grip performance. The present invention was carried out based on the above finding.
    [0013] That is, the present invention relates to the following aspects: [1] a rubber composition including (A) at least one rubber component selected from the group consisting of a synthetic rubber and a natural rubber; (B) a farnesene polymer having an average molecular weight of not less than 2,000 and less than 25,000; and (C) carbon black, and [2] a tire including at least partially the above rubber composition. ADVANTAGE EFFECTS OF THE INVENTION
    [0014] In accordance with the present invention, a rubber composition is provided which is capable of satisfying all of processability when producing, ice-grip performance and dry-grip performance at a high level and a tire obtained using the rubber composition. DESCRIPTION OF MODALITIES [Rubber Composition]
    [0015] The rubber composition of the present invention includes (A) at least one rubber component selected from the group consisting of a synthetic rubber and a natural rubber; (B) a farnesene polymer having an average molecular weight of not less than 2,000 and less than 25,000; and (C) carbon black. <Rubber component (A)> The. Synthetic rubber
    [0016] Examples of the synthetic rubber used here include a styrene-butadiene rubber (hereinafter occasionally referred to only as "SBR"), an isoprene rubber, a butadiene rubber, a butyl rubber, a halogen butyl rubber nothing, an ethylene propylene diene rubber, an acrylonitrile butadiene copolymer rubber and a chloroprene rubber. Among these synthetic rubbers, preferred are SBR, an isoprene rubber and a butadiene rubber. These synthetic rubbers can be used alone or in combination with any two or more of them. (SBR (A-D)
    [0017] As SBR (A-1) can be used those generally used in tire applications. More specifically, SBR (A-1) preferably has a styrene content of from 0.1 to 70% by weight and more preferably from 5 to 50% by weight.
    [0018] Also, SBR (A-1) preferably has a vinyl content of from 0.1 to 60% by weight and more preferably from 0.1 to 55% by weight.
    [0019] The average molecular weight (Mw) of the SBR (A-1) is preferably from 100,000 to 2,500,000, more preferably from 150,000 to 2,000,000 and even more preferably from 200,000 to 1,500,000. When the average molecular weight of SBR (A-1) falls within the range specified above, the resulting rubber composition can be improved in both processability and mechanical strength.
    [0020] However, in the present application, the average weight molecular weight is the value measured using the method described below in the Examples.
    [0021] The glass transition temperature (Tg) of the SBR used in the present invention as measured by differential thermal analysis is preferably from -95 ^ to 00 C and most preferably from -95 ^ to -S ' Ç. When adjusting the TBR of the SBR to the range specified above, it is possible to suppress the increase in viscosity of the SBR and improve its handling property. «Method for Production of SBR (A-1)»
    [0022] The SBR (A-1) useful in the present invention can be produced by copolymerizing styrene and butadiene. The SBR production method is not particularly limited, and the SBR can be produced using either an emulsion polymerization method, a solution polymerization method, a vapor phase polymerization method and a mass polymerization. Among these polymerization methods, especially preferred are an emulsion polymerization method and a solution polymerization method. Emulsion Polymerized Styrene-Butadiene Rubber (E-SBR)
    [0023] E-SBR (Emulsion-Polymerized Styrene-Butadiene Rubber) can be produced using any common emulsion polymerization method. For example, a predetermined amount of a styrene monomer and a predetermined amount of a butadiene monomer are emulsified and dispersed in the presence of an emulsifying agent and then subjected to emulsion polymerization using a radical polymerization initiator.
    [0024] As the emulsifying agent, a long-chain fatty acid salt having 10 or more carbon atoms or a rosinic acid salt can be used. Specific examples of the emulsifying agent include potassium salts and sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
    [0025] As a dispersant for the above emulsion polymerization, water can generally be used. The dispersant can also contain a water-soluble organic solvent such as methanol and ethanol unless the use of such an organic solvent causes any adverse influence on the stability of the polymerization.
    [0026] Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides and hydrogen peroxide.
    [0027] In order to properly adjust the molecular weight of the obtained E-SBR, a chain transfer agent can be used. Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; and carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, y-terpinene and an α-methyl styrene dimer.
    [0028] The temperature used when emulsion polymerization can be appropriately determined according to the type of radical polymerization initiator used therein is generally preferably from 0 to WO'C and more preferably from 0 to 6CTC. The polymerization method can be either a continuous polymerization method or a batch polymerization method. The polymerization reaction can be stopped by adding a terminating agent to the reaction system.
    Examples of the terminating agent include α-mine compounds such as isopropyl hydroxyl amine, diethyl hydroxyl amine and hydroxyl amine; quinone-based compounds such as hydroquinone and benzoquinone; and sodium nitrite.
    [0030] After completion of the polymerization reaction, an antioxidant can be added, if necessary. In addition, after the completion of the polymerization reaction, unreacted monomers can be removed from the resulting latex, if necessary. Then, the obtained polymer is added by adding a salt such as sodium chloride, calcium chloride and potassium chloride as a coagulant to it and, if necessary, while adjusting the pH value of the coagulation system through addition of an acid such as nitric acid and sulfuric acid to it, and then the dispersion solvent is separated from the reaction solution to recover the polymer as a fragment. The recovered fragment is then washed with water and dehydrated and then dried using a band dryer or similar to obtain E-SBR. However, when the polymer coagulates, the latex can be previously mixed with an extender oil in the form of an emulsified dispersion to recover the polymer in the form of an oil-extended rubber. (ii) Solution Polymerized Styrene-Butadiene Rubber (S-SBR)
    [0031] S-SBR (Solution-Polymerized Styrene-Butadiene Rubber) can be produced using a common solution polymerization method. For example, styrene and butadiene are polymerized in a solvent using an anion-curable active metal, if necessary, in the presence of a polar compound.
    [0032] Examples of the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and i-sooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methyl cyclopentane; and aromatic hydrocarbons such as benzene and toluene. These solvents can generally be used in such a range so that a monomer is dissolved in them at a concentration of from 1 to 50% by mass.
    [0033] Examples of the anion-curable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and rare earth metals based on lanthanoid such as lanthanum and neodymium. Among these active metals, preferred are alkali metals and alkaline earth metals, and more preferred are alkali metals. Alkali metals are most preferably used in the form of an organic alkali metal compound.
    [0034] Specific examples of the organic alkali metal compound include organic monolithium compounds such as n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexyl lithium, phenyl lithium and stilbene lithium; polyfunctional organic lithium compounds such as dilithomethane; 1,4-dilithiobutane, 1,4-dilithio-2-ethyl cyclohexane and 1,3,5-trilithiotiobenzene; and sodium naphthalene and potassium naphthalene. Among these organic alkali metal compounds, preferred are organic lithium compounds, and more preferred are organic monolithium compounds. The amount of organic alkali metal compound used can be appropriately determined according to a molecular weight of S-SBR as required.
    [0035] The organic alkali metal compound can be used in the form of an organic alkali metal amide by allowing a secondary amine such as dibutyl amine, diexyl amine and dibenzyl amine to react with it.
    [0036] The polar compound used in solution polymerization is not particularly limited as long as the compound does not cause reaction deactivation and can generally be used to control a microstructure of the butadiene portions and distribution of styrene in a copolymer chain thereof. Examples of the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethyl ethylene diamine and trimethylamine; and alkali metal alkoxides and phosphine compounds.
    [0037] The temperature used in the above polymerization reaction is generally from -80 to 150 * C, preferably from 0 to 100 * 0 and more preferably from 30 to 90 * 0. The polymerization method can be either a batch method or a continuous method. Also, in order to improve the ability of random copolymerization between styrene and butadiene, styrene and butadiene are preferably supplied to a reaction solution in a continuous or intermittent manner so that a compositional ratio between styrene and butadiene in the polymerization system fits in a specific range.
    [0038] The polymerization reaction can be stopped by adding an alcohol such as methanol and isopropanol as a terminating agent to the reaction system. In addition, before the addition of the terminating agent, a coupling agent such as tin tetrachloride, tetrachlorosilane, tetramethoxysilane, tetraglycidyl-1,3-bisaminomethyl cyclohexane and 2,4-tolylene diisocyanate can be added which are able to react with one end active polymer chain and a chain end modifying agent such as 4,4'-bis (diethylamino) benzophenone and N-vinyl pyrrolidone. The polymerization reaction solution obtained after the completion of the polymerization reaction can be directly subjected to drying or vapor removal to remove the solvent from it, thus recovering the S-SBR according to the objective. However, prior to removal of the solvent, the polymerization reaction solution can be previously mixed with an extender oil to recover the S-SBR in the form of an extended rubber with oil. [Modified Styrene-Butadiene Rubber (Modified SBR)]
    [0039] In the present invention, a modified SBR produced by the introduction of a functional group in SBR can also be used. Examples of the functional group to be introduced include an amino group, an alkoxysilyl group, a hydroxyl group, an epoxy group and a carboxyl group.
    [0040] In the modified SBR, the polymer site into which the functional group is introduced can be either a chain end or a polymer side chain. (Isoprene rubber (A-2))
    [0041] Isopropylene rubber can be a commercially available isoprene rubber that can be obtained through polymerization using a Ziegler-based catalyst such as titanium-trialkyl aluminum tetrahalide-based catalysts, diethyl aluminum chloride-based catalysts -cobalt, trialkyl aluminum-boron nickel trifluoride-based catalysts and catalysts based on diethyl aluminum-nickel chloride; an earth-rare metal catalyst based on lanthanoid such as catalysts based on triethyl aluminum-Lewis acid-organic acid neodymium salt; and an organic alkali metal compound as used similarly for the production of S-SBR. Among these isoprene rubbers, preferred are isoprene rubbers obtained through polymerization using the Ziegler-based catalyst because of its cis-isomer content. In addition, it is also possible to use those isoprene rubbers having an ultra-high cis isomer content which are produced using the lanthanoid based rare earth metal catalyst.
    [0042] Isopropene rubber has a vinyl content of 50% by weight or less, preferably 40% by weight or less and more preferably 30% by weight or less. When the vinyl content of isoprene rubber is greater than 50% by mass, the resulting rubber composition tends to deteriorate in rolling resistance performance. The lower limit of the vinyl content of isoprene rubber is not particularly limited. The glass transition temperature of the isoprene rubber can vary depending on its vinyl content, and is preferably -20 ° C or less and more preferably -SO'C or less.
    [0043] The average molecular weight of isoprene rubber is preferably from 90,000 to 2,000,000 and more preferably from 150,000 to 1,500,000. When the average molecular weight of the isoprene rubber falls within the range specified above, the resulting rubber composition can exhibit good processability and good mechanical strength.
    [0044] Isopropene rubber may partially have a branched structure or may partially contain a polar functional group using a polyfunctional modifying agent, for example, a modifying agent such as tin tetrachloride, silicon tetrachloride, an alkoxysilane containing an epoxy group in a molecule of it and an alkoxysilane containing amino group. (Butadiene rubber (A-30)
    [0045] Butadiene rubber can be a commercially available butadiene rubber that can be obtained through polymerization using a Ziegler-based catalyst such as titanium-trialkyl aluminum tetrahalide-based catalysts, aluminum-diethyl chloride-based catalysts cobalt, catalysts based on trialkyl aluminum-boron-nickel trifluoride and catalysts based on diethyl aluminum-nickel chloride; an earth-rare metal catalyst based on lanthanoid such as catalysts based on triethyl aluminum-Lewis acid-organic acid neodymium salt; and an organic alkali metal compound as used similarly for the production of S-SBR. Among these butadiene rubbers, preferred are butadiene rubbers obtained through polymerization using the Ziegler-based catalyst due to its cis-isomer content. Also, those butadiene rubbers having a cisultra-high isomer content that are produced using the lanthanoid-based rare earth metal catalyst can also be used. Butadiene rubber has a vinyl content of 50% by weight or less, preferably 40% by weight or less and more preferably 30% by weight or less. When the vinyl content of butadiene rubber is more than 50% by weight, the resulting rubber composition tends to deteriorate in rolling resistance performance. The lower limit of the vinyl content of butadiene rubber is not particularly limited. The glass transition temperature of the butadiene rubber can vary depending on its vinyl content, and is preferably -40% or less and more preferably -6% or less.
    [0046] The average weight molecular weight of butadiene rubber is preferably from 90,000 to 2,000,000 and more preferably from 150,000 to 1,500,000. When the average molecular weight of butadiene rubber falls within the range specified above, the resulting rubber composition may exhibit good processability and good mechanical strength.
    [0047] Butadiene rubber may partially have a branched structure or may partially contain a polar functional group using a polyfunctional modifying agent, for example, a modifying agent such as tin tetrachloride, silicon tetrachloride, an alkoxysilane containing an epoxy group in a molecule and an alkoxysilane containing an amino group.
    [0048] As the rubber component other than SBR, isoprene rubber and butadiene rubber, one or more rubbers selected from the group consisting of a butyl rubber can be used; a halogenated butyl rubber; an ethylene-propylene rubber; a butadiene-acrylonitrile copolymer rubber and a chloroprene rubber. The method of producing such rubbers is not particularly limited, and any suitable commercially available rubbers can also be used in the present invention.
    [0049] In the present invention, when using at least one from SBR, isoprene rubber, butadiene rubber, the other synthetic rubber and natural rubber in combination with the farnesene polymer (B) mentioned below, it is possible to improve the pro-cessability of the resulting rubber composition, the dispersibility of the carbon black in it and its rolling resistance performance.
    [0050] When using a mixture of two or more types of synthetic rubbers, the combination of the synthetic rubbers can be optionally selected unless the effects of the present invention are adversely affected. Also, various properties of the resulting rubber composition such as rolling resistance and wear resistance performance can be appropriately controlled by selecting an appropriate combination of synthetic rubbers. (2) Natural Rubber
    [0051] Examples of natural rubber include TSR such as SMR, SIR and STR; natural rubbers commonly used in the tire industries, such as RSS; high purity natural rubbers; and modified natural rubbers such as epoxidized natural rubbers, hydroxylated natural rubbers, hydrogenated natural rubbers and grafted natural rubbers. Among these natural rubbers, SMR20, STR20 and RSS # 3 are preferred from the point of view of less variation in quality and good availability. These natural rubbers can be used alone or in combination with any two or more of them.
    [0052] The rubber component (A) includes at least one rubber selected from the group consisting of a synthetic rubber and a natural rubber. When using both synthetic rubber and natural rubber, the composition ratio between synthetic rubber and natural rubber can be optionally determined. <Farnesene Polymer (B)>
    The rubber composition of the present invention contains a farnesene polymer (B) having an average molecular weight of not less than 2,000 and less than 25,000 (hereinafter referred to as "polymer (B)").
    [0054] The farnesene polymer used in the present invention can be either a α-farnesene polymer or a p-farnesene polymer represented by the formula (I) which follows. From the point of view of ease of production of the polymer, p-farnesene polymer is preferred.
    [0055] However, in the present application, the polymer (B) of farnese-no means a polymer containing a constitutional unit derived from farnesene in an amount of preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, even more preferably 99% by mass or more and, most preferably preferably 100% by mass. The farnesene polymer may also contain a constitutional unit derived from other monomers such as butadiene and iso-prene.

    [0056] When the average molecular weight of the polymer (B) is less than 2,000, the resulting tire tends to deteriorate in mechanical strength, and the polymer (B) tends to drain from the rubber composition, resulting in poor stability the quality of the rubber composition. On the other hand, when the average molecular weight of the polymer (B) is 25,000 or more, the resulting rubber composition tends to deteriorate in dry grip performance.
    [0057] For example, the average molecular weight of the polymer (B) is preferably 2,100 or more, more preferably 2,500 or more and even more preferably 3,000 or more and is also preferably 20,000 or less, more preferably 18,000 or less and even more preferably 15,000 or less.
    More specifically, the average molecular weight of the polymer (B) is preferably from 2,000 to 20,000 and more preferably from 2,000 to 15,000. However, the average molecular weight of the polymer (B) as used in the present application is the value measured using the method described below in the Examples.
    [0059] The melt viscosity (as measured at 38 °) of the polymer (B) is preferably from 0.1 to 3.5 Pa's, more preferably from 0.1 to 2 Pa's and even more preferably from 0.1 to 1.5 Pa's. When the melt viscosity of the polymer falls within the range specified above, the tire obtained using the rubber composition of the present invention can be improved in ice grip performance and dry grip performance, and the resulting rubber composition can be improved. easily kneaded and can be improved in processability. However, in the present application, the melt viscosity of the polymer (B) is the value measured using the method described below in the Examples.
    The molecular weight distribution (Mw / Mn) of the polymer (B) is preferably from 1.0 to 2.0, more preferably from 1.0 to 1.5 and even more preferably from from 1.0 to 1.3. When the molecular weight distribution (Mw / Mn) of the polymer (B) falls within the range specified above, the resulting polymer can adequately exhibit less variation in its viscosity.
    [0061] In the present invention, the polymer (B) is preferably composed in an amount from from 0.1 to 100 parts by weight, more preferably from from 0.5 to 30 parts by weight, even more preferably from from 1 to 20 parts by weight and even more preferably from 3 to 15 parts by weight based on 100 parts by weight of the rubber component (A). When the amount of the composite polymer (B) falls within the range specified above, the resulting rubber composition can be improved in both ice grip performance and dry grip performance.
    [0062] The polymer (B) can be produced using the methods described in WO 2010 / 027463A and WO 2010 / 027464A or similar. Among these methods, preferred are an emulsion polymerization method and a solution polymerization method, and most preferred is a solution polymerization method. (Emulsion Polymerization Method)
    [0063] The emulsion polymerization method for producing the polymer (B) can be any suitable conventionally known method. For example, a predetermined amount of a farnesene monomer is emulsified and dispersed in the presence of an emulsifying agent, and then the resulting emulsion is subjected to emulsion polymerization using a radical polymerization initiator.
    [0064] As the emulsifying agent can be used, for example, a long chain fatty acid salt having 10 or more carbon atoms or a rosinic acid salt. Specific examples of the emulsifying agent include potassium salts and fatty acid sodium salts such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
    [0065] As the dispersant for water emulsion polymerization can generally be used and the dispersant can also contain a water-soluble organic solvent such as methanol and ethanol unless the use of such an organic solvent gives rise to any adverse influence on the stability of polymerization.
    [0066] Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate; and organic peroxides and hydrogen peroxide.
    [0067] In order to adjust the molecular weight of the resulting polymer (B), a chain transfer agent can be used. Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; and carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, y-terpinene and an α-methyl styrene dimer.
    [0068] The temperature used when emulsion polymerization can be appropriately determined according to the type of radical polymerization initiator used therein and is generally preferably from 0 to WO'C and most preferably from 0 to GO 'Ç. The polymerization method can be either a continuous polymerization method or a batch polymerization method. The polymerization reaction can be stopped by adding a terminating agent to the reaction system.
    Examples of the terminating agent include α-mine compounds such as isopropyl hydroxyl amine, diethyl hydroxyl amine and hydroxyl amine; quinone-based compounds such as hydroquinone and benzoquinone; and sodium nitrite.
    [0070] After the completion of the polymerization reaction, an anti-oxidant can be added, if required. In addition, after the completion of the polymerization reaction, unreacted monomers can be removed from the resulting latex, if necessary. Then, the resulting polymer (B) is coagulated by adding a salt such as sodium chloride, calcium chloride and potassium chloride as a coagulant to it and, if necessary, while adjusting the pH value of the coagulation by adding an acid such as nitric acid and sulfuric acid to it, and then the dispersion solvent is separated from the reaction solution to recover the polymer (B). The polymer then recovered is washed with water and dehydrated and then dried to obtain the polymer (B). However, when the polymer coagulates, the latex can be previously mixed, if necessary, with an extender oil in the form of an emulsified dispersion to recover the polymer (B) in the form of an oil-extended rubber. (Solution Polymerization Method)
    [0071] The solution polymerization method for producing the polymer (B) can be any conventionally known suitable method. For example, a p-farnesene monomer can be polymerized in a solvent using a Ziegler-based catalyst, a metallocene-based catalyst or an anion-curable active metal, if necessary, in the presence of a polar compound.
    [0072] Examples of the solvent used in solution polymerization include aliphatic hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane and isocyanate; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methyl cyclopentane; and aromatic hydrocarbons such as benzene, toluene and xylene.
    [0073] Examples of the anion-curable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and rare earth metals based on lanthanoid such as lanthanum and neodymium. Among these active metals, preferred are alkali metals and alkaline earth metals, and more preferred are alkali metals. Alkali metals are most preferably used in the form of an organic alkali metal compound.
    [0074] Specific examples of the organic alkali metal compound include organic monolithic compounds such as methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium, phenyl lithium and stilbene lithium; polyfunctional organic lithium compounds such as dilithiomethane, dilitionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethyl cyclohexane and 1,3,5-trilithiobenzene; and sodium naphthalene and potassium naphthalene. Among these organic alkali metal compounds, preferred are organic lithium compounds and most preferred are organic monolithium compounds. The amount of the organic alkali metal compound used can be appropriately determined according to a molecular weight of the farnesene polymer as needed and is preferably from 0.01 to 3 parts by weight based on 100 parts by weight of farnesene.
    [0075] The organic alkali metal compound can be used in the form of an organic alkali metal amide by allowing a secondary amine such as dibutyl amine, diexyl amine and dibenzyl amine to react with it.
    [0076] The polar compound can be used in anion polymerization to control a microstructure of farnesene portions without causing the reaction to deactivate. Examples of the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethyl ethylenediamine and trimethylamine; and alkali metal alkoxides and phosphine compounds.
    [0077] The temperature used in the above polymerization reaction is generally from -80 to 10 ° CTC, preferably from 0 to WO'C and more preferably from 10 to OO'C. The polymerization method can be either a batch method or a continuous method.
    [0078] The polymerization reaction can be stopped by adding a terminating agent such as methanol and isopropanol to the reaction system. The resulting polymerization reaction solution can be poured into a poor solvent such as methanol to precipitate the polymer (B). Alternatively, the polymerization reaction solution can be washed with water, and then a solid is separated from it and dried to isolate the polymer (B) from it. <Smoke level (C)>
    [0079] The rubber composition of the present invention contains carbon black (C) in addition to the rubber component (A) and the polymer (B) from the point of view of enhancing both ice-bonding performance and adhesion performance dry tire obtained using the rubber composition. The average particle size of the carbon black (C) used in the present invention is preferably from 5 to 100 nm, more preferably from 5 to 70 nm and even more preferably from 5 to 60 nm nm. When the average particle size of carbon black (C) is 5 nm or more, the resulting rubber composition can be improved in dispersibility, whereas when the average particle size of carbon black (C) is 100 nm or less , the resulting rubber composition may exhibit sufficient mechanical strength and hardness.
    [0080] However, the average carbon black particle size (C) can be determined by calculating an average value of carbon black particle diameters measured using a transmission electron microscope.
    [0081] Examples of carbon black (C) useful in the present invention include carbon blacks such as oven carbon black, channel carbon black, thermal carbon black, acetylene carbon black and Ketjen carbon black. Among these carbon blacks, from the point of view of a high cure rate and improved mechanical strength of the rubber composition, oven carbon black is preferred.
    [0082] Examples of commercially available oven carbon black such as carbon black (C) having an average particle size from 5 to 500 nm include "DIABLACK" available from Mitsubishi Chemical Corp, and "SEAST" available from Tokai Carbon Co., Ltd. Examples of commercially available acetylene black as carbon black (C) having an average particle size from 5 to 500 nm include "DENKABLACK" available from Denki Kagaku Kogyo KK Examples of Ketjen black commercially available as carbon black (C) having an average particle size from 5 to 500 nm include "ECP600JD" available from Lion Corp.
    [0083] Carbon black (C) can be subjected to an acid treatment with nitric acid, sulfuric acid, hydrochloric acid or a mixed acid thereof or it can be subjected to a heat treatment in the presence of air for its treatment of surface oxidation, from the point of view of improving the wetting capacity or dispersibility of carbon black (C) in the rubber component (A) and in the polymer (B). Furthermore, from the point of view of improving the mechanical strength of the rubber composition of the present invention, carbon black can be subjected to a heat treatment at a temperature of from 2,000 to 3,000 ° C in the presence of a graphitization catalyst . As the graphitization catalyst, boron, boron oxides (such as, for example, B2O2, B2O3, B4O3, and B4O5), boron oxo acids (such as, for example, orthoboric acid, metabolic acid and tetraboric acid) can be used appropriately and salts thereof, boron carbonates (such as, for example, B4C and B6C), boron nitrite (such as BN) and other boron compounds.
    [0084] The average particle size of carbon black (C) can be controlled by spraying or similar. In order to spray the carbon black (C), a high speed rotating mill (such as a hammer mill, pin mill and cage mill) or several ball mills (such as a rotation, a vibration mill and a planetary mill), a stirring mill (such as a bead mill, an attractor, a flow tube mill and an annular mill) or similar.
    [0085] In the rubber composition of the present invention, carbon black (C) is preferably composed in an amount of 0.1 parts by weight or more, more preferably 5 parts by weight or more and even more preferably 20 parts by weight or more based on 100 parts by weight of the rubber component (A) and also in an amount of 100 parts by weight or less, more preferably 90 parts by weight or less and even more preferably 80 parts by weight or less based on 100 parts by mass of the rubber component (A). More specifically, the amount of carbon black (C) composed in the rubber composition based on 100 parts by weight of the rubber component (A) is preferably from 0.1 to 100 parts by weight, more preferably from 5 to 90 parts by weight and even more preferably from 20 to 80 parts by weight. When the amount of the carbon black (C) compound in the rubber composition falls within the range specified above, the resulting rubber composition can satisfy good mechanical strength, hardness, processability and dispersibility of the carbon black (C) therein, and the tire obtained from the rubber composition can satisfy both good ice grip performance and dry grip performance. <Carqa>
    [0086] In the present invention, for the purposes of increasing the mechanical strength of the rubber composition, improving various properties such as heat resistance and its resistance to climate, controlling its hardness and further improving the economy through the addition of an extender thereupon, the rubber composition may contain a charge other than carbon black (C), if necessary.
    [0087] The load can be appropriately selected according to the applications of the obtained rubber composition. For example, as the filler, one or more fillers selected from the group consisting of organic fillers and silica, clay, talc, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, can be used. glass fibers, fibrous fillers and glass balloons. Among these fillers, silica is preferred. Specific examples of silica include dry silica (anhydrous silicic acid) and wet silica (anhydrous silicic acid). Among these silicas, from the point of view of additionally increasing the mechanical strength of the resulting rubber composition, wet silica is preferred.
    [0088] The above charge is preferably composed in the rubber composition in an amount of from 0.1 to 120 parts by mass, more preferably from 5 to 90 parts by mass and even more preferably from 10 to 80 parts by mass based on 100 parts by mass of the rubber component (A). When the amount of the composite filler falls within the range specified above, the resulting rubber composition can be further improved in mechanical strength.
    [0089] The rubber composition of the present invention may also contain, if necessary, a softening agent for the purpose of improving processability, fluidity or the like of the resulting rubber composition unless the effects of the present invention are adversely influenced. Examples of the softening agent include a process oil such as a silicone oil, TDAE (treated distilled aromatic extracts), MES (residual aromatic extracts), a paraffin oil, a naphthalene oil and an aroma oil; and a liquid polymer such as a low molecular weight polybutadiene, a low molecular weight polyisoprene, a low molecular weight styrene-butadiene copolymer and a low molecular weight styrene-isoprene copolymer. However, the above copolymers can be in the form of either a block copolymer or a random copolymer. The liquid polymer preferably has an average molecular weight of from 2,000 to 80,000 from the point of view of good processability of the resulting rubber composition.
    [0090] The softening agent is preferably composed in the rubber composition in an amount of less than 50 parts by weight based on 100 parts by weight of the rubber component (A).
    [0091] The rubber composition of the present invention may also contain, if necessary, one or more additives selected from the group consisting of an antioxidant, an oxidation inhibitor, a lubricant, a light stabilizer, a yellowing retardant, a processing, a dye such as pigments and coloring materials, a flame retardant, an anti-aesthetic agent, an opacifying agent, an anti-blocking agent, an ultraviolet absorber, a release agent, a foaming agent, an antimicrobial agent, a mold-proof agent, a perfume and a coupling person, for the purposes of further improvement of weather resistance, heat resistance, oxidation resistance or the like of the resulting rubber composition, unless the effects of the present invention adversely influenced.
    [0092] Examples of the oxidation inhibitor include hindered phenol-based compounds, phosphorus-based compounds, lactone-based compounds and hydroxyl-based compounds.
    [0093] Examples of the antioxidant include amine-ketone-based compounds, imidazole-based compounds, amine-based compounds, phenol-based compounds, sulfur-based compounds and phosphorus-based compounds. When composing silica as the filler, it is preferred that the silica is added together with a silane coupling agent.
    [0094] Examples of the silane coupling agent include bis (3-triethoxysilyl-ethyl) tetrasulfide, bis (3-triethoxysilyl-ethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) bis tetrasulfide, bis (3-triethoxysilylpropyl) disulfide bis (3-triethoxysilylpropyl) disulfide. Among these silane coupling agents, bis (3-triethoxysilylpropyl) tetrasulfide is preferred due to the excellent processability of the resulting rubber composition. These additives can be used alone or in combination with any two or more of them. The above additive is preferably composed in the rubber composition in an amount of from 0.1 to 15 parts by weight based on 100 parts by weight of the rubber component (A).
    [0095] The rubber composition of the present invention is preferably used in the form of a crosslinked product produced by the reaction using a crosslinking agent. Examples of the cross-linking agent include sulfur and sulfur compounds, oxygen, organic peroxides, phenol resins and amino resins, quinone and quinone derivatives dioxin, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, halides of metal and organic metal halides and silane compounds. Among these cross-linking agents, sulfur and sulfur compounds are preferred. Such cross-linking agents can be used alone or in combination with any two or more of them. The crosslinking agent is preferably composed in the rubber composition in an amount of from 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component (A).
    [0096] When using sulfur as the crosslinking agent, the crosslinking reaction can be accelerated using the sulfur in combination with a vulcanization aid or vulcanization accelerator.
    [0097] Examples of the vulcanization aid include fatty acids such as stearic acid and metal oxides such as zinc oxide.
    [0098] Examples of the vulcanization accelerator include compounds based on guanidine, compounds based on sulfene amide, compounds based on thiazole, compounds based on thiuram, compounds based on thiourea, compounds based on dithiocarbamic acid, compounds based on of aldehyde-amine, compounds based on aldehyde-ammonia, compounds based on imidazoline and compounds based on xanthate. These vulcanization aids or vulcanization accelerators can be used alone or in combination with any two or more of them. The vulcanization aid or vulcanization accelerator is preferably composed in the rubber composition of the present invention in an amount of from 0.1 to 15 parts by weight based on 100 parts by weight of the rubber component (A).
    [0099] The method for producing the rubber composition of the present invention is not particularly limited, and any suitable method can be used in the present invention as long as the respective components are uniformly mixed with each other. The method of uniform mixing of the respective components can be carried out using a closed type kneader of a tangential type or a meshing type such as a rudder kneader, a Brabender, a Banbury mixer and an internal mixer; a single screw extruder, a double screw extruder, a mixing roller, a roller or the like in a temperature range of generally 70 to 270 'C. [Tire]
    [00100] The tire of the present invention is produced using the rubber composition of the present invention and is therefore excellent in all processability when producing, adhesion performance on ice and adhesion performance on dry roads. EXAMPLES
    [00101] The present invention will be described in more detail below with reference to the following examples. It should be noted, however, that the examples that follow are illustrative only and are not intended to limit the invention to them.
    [00102] The average molecular weight and melting viscosity of the polymer (B) as well as Mooney viscosity, dry adhesion performance and ice adhesion performance of the rubber composition were evaluated using the following methods. (1) Average Weight Molecular Weight
    [00103] The average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of each of the synthetic rubber, polymer (B) and polyisoprene were measured using GPC (permeation chromatography) gel) in terms of a molecular weight of polystyrene as a standard reference substance. The measuring devices and conditions are as follows. • Device: GPC device "GPC8020" available from Tosoh Corp. • Separation column: "TSKgelG4000HXL" available from Tosoh Corp. • Detector: "RI-8020" available from Tosoh Corp. • Eluent: Tetrahydrofuran • Eluent flow rate: 1.0 mL / min • Sample concentration: 5 mg / 10 ml_ • Column temperature: 40cC (2) Fusion viscosity
    [00104] The melt viscosity of the polymer (B) was measured at SSX) using a Brookfield viscometer available from Brookfield Engineering Labs. Inc. (3) Mooney viscosity
    [00105] As a processability index of the rubber composition, the Mooney viscosity (ML1 + 4) of the rubber composition before curing was measured at WO'C according to JIS K6300. The values of the respective Examples and Comparative Examples appearing in Table 2 are relative values based on 100 as the value of Comparative Example 2. Also, the values of the respective E-xamples and Comparative Example appearing in Table 3 are relative values based on 100 as the value of Comparative Example 3; the values of Example and Comparative Example appearing in Table 4 are relative values based on 100 as the value of Comparative Example 4; the values of Example and Comparative Example appearing in Table 5 are relative values based on 100 as the value of Comparative Example 5; the values of Example and Comparative Example appearing in Table 6 are relative values based on 100 as the value of Comparative Example 6; and the values of the E-example and Comparative Example appearing in Table 7 are relative values based on 100 as the value of Comparative Example 7. However, the lower Mooney viscosity value indicates more excellent processability. (4) Dry grip performance
    [00106] The rubber composition was molded in a press to prepare a cured sheet (thickness: 2 mm). The sheet then prepared was cut into a test piece having a size of 40 mm long x 7 mm wide x 2 mm thick. The test piece then obtained was subjected to the measurement of tannins as an index of its dry grip performance using a dynamic viscoelasticity measuring device available from GABO GmbH under conditions including a measuring temperature of 25 °, a frequency of 10 Hz, a static distortion of 0.5% and a dynamic distortion of 0.1%. The values of the respective Examples and Comparative E-xemples appearing in Table 2 are relative values based on 100 as the value of Comparative Example 2. Also, the values of the respective Examples and Comparative Examples appearing in Table 3 are relative values based on at 100 as the value of Comparative Example 3; the values of Example and Comparative Example appearing in Table 4 are relative values based on 100 as the value of Comparative Example 4; the values of Example and Comparative Example appearing in Table 5 are relative values based on 100 as the value of Comparative Example 5; the values of Example and Comparative Example appearing in Table 6 are relative values based on 100 as the value of Comparative Example 6; and the values of the Example and Comparative Example appearing in Table 7 are relative values based on 100 as the value of Comparative Example 7. However, the higher value indicates a higher dry grip performance of the rubber composition. (5) Ice Bond Performance
    [00107] The test piece obtained using the same method as in item (4) above was subjected to E 'measurement using a dynamic viscoelasticity measuring device available from GABO GmbH under conditions including a measuring temperature of -GO' C and 250, a frequency of 10 Hz, an elastic distortion of 0.5% and a dynamic distortion of 0.1% to determine an E '(- 60 <C) / E' (25'C) ratio as an index of a performance of the ice composition of the rubber composition. The values of the respective Examples and Comparative Examples that appear in Table 2 are relative values based on 100 as the value of Comparative Example 2. Also, the values of the respective Examples and Comparative Examples that appear in Table 3 are relative values based on 100. as the value of Comparative Example 3; the values of Example and Comparative Example that appear in Table 4 are relative values based on 100 as the value of Comparative Example 4; the values of Example and Comparative Example that appear in Table 5 are relative values based on 100 as the value of Comparative Example 5; the values of Example and Comparative Example that appear in Table 6 are relative values based on 100 as the value of Comparative Example 6; and the values of the Example and Comparative Example that appear in Table 7 are relative values based on 100 as the value of Comparative Example 7. However, the lower value indicates a higher ice-grip performance of the rubber composition. Production Example 1: Production of polyphenesene (B-1)
    [00108] A pressurized reaction vessel previously purged with nitrogen and then dried was charged with 241 g of cyclohexane as a solvent and 28.3 g of sec-butyl lithium (in the form of a 10.5 wt% cyclohexane solution ) as an initiator. The contents of the reaction vessel were heated to 500 and then 342 g of p-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating water from the polymerization reaction solution then washed, the resulting solution was dried at 700 ° C for 2 h, in this way obtaining a polypharnesene (B-1). Several properties of the polyphennesene (B-1) then obtained are shown in Table 1. Production Example 2: Production of polyphenesene (B-2)
    [00109] A pressurized reaction vessel previously purged with nitrogen and then dried was charged with 120 g of hexane as a solvent and 1.1 g of n-butyl lithium (in the form of a 17% by weight hexane solution) as a initiator. The contents of the reaction vessel were heated to SO'C and then 210 g of p-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating the water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, thus obtaining a polypharnesene (B-2). Various properties of the polyphennesene (B-2) then obtained are shown in Table 1. Production Example 3: Production of polyisoprene
    [00110] A pressurized reaction vessel previously purged with nitrogen and then dried was charged with 206 g of hexane as a solvent and 14.2 g of sec-butyl lithium (in the form of a 10.5 wt% hexane solution) as an initiator. The contents of the reaction vessel were heated to TO'C and then 250 g d and isoprene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating water from the polymerization reaction solution then washed, the resulting solution was dried at TO'C for 12 h, thereby obtaining a polyisoprene. Various polyisoprene properties then obtained are shown in Table 1
    [00111] The rubber component (A), the polymer (B) and the carbon black (C) used in the Examples and Comparative Examples that follow are the following: Natural Rubber (I): SMR20 (Malaysian natural rubber) Rubber Natural (II): STR20 (natural rubber from Thailand) Styrene-Butadiene rubber: "JSR1500" available from JSR Corp .: average weight molecular weight: 450,000; styrene content: 23.5% by weight (produced using the emulsion polymerization method). Butadiene rubber: "BR-01" available from JSR Corp. Polymer (B): Polyphenols (B-1) and (B-2) produced above in Production Examples 1 and 2. Carbon Black (C): C-1: "DIABLACK H" available from Mitsubishi Chemical Corp .; average particle size: 30 nm C-2: "DIABLACK E" available from Mitsubishi Chemical Corp .; average particle size: 50 nm C-3: "DIABLACK I" available from Mitsubishi Chemical Corp .; average particle size: 20 nm C-4: "SEAST V" available from Tokai Carbon Co., Ltd .; average particle size: 60 nm. Optional Components Polyisoprene: Polyisoprene produced in Production Example 3 Stearic Acid: "LUNAC S-20" available from Kao Corp. Zinc Oxide: Zinc oxide available from Sakai Chemical Industry Co., Ltd. Antioxidant (1): "NOCRAC 6C" available from Ouchi Shinko Chemical Industrial Co., Ltd. Antioxidant (2): "ANTAGE RD" available from Kawaguchi Chemical Industry Co., Ltd. Sulfur: 200 mesh fine sulfur powder available from Tsuru-mi Chemical Industry Co., Ltd. Vulcanization accelerator (1): "NOCCELER NS" available from Ouchi Shinko Chemical Industrial Co., Ltd. Accelerator vulcanization (2): "NOCCELER CZ-G" available from Ouchi Shinko Chemical Industrial Co., Ltd. Vulcanization accelerator (3): "NOCCELER D" available from Ouchi Shinko Chemical Industrial Co., Ltd. Examples 1 to 13 and Comparative Examples 1 to 7
    [00112] The rubber component (A), polymer (B), carbon black (C), polyisoprene, stearic acid, zinc oxide and antioxidant (s) were loaded in a composition ratio (part (s) in bulk) as shown in Tables 2 to 7 in a closed Banbury mixer and kneaded together for 6 minutes so that the start temperature was 75 ° and the resin temperature reached 160 °. The resulting mixture was removed once from the mixer and cooled to room temperature. Then, the mixture was put on a mixing roller, and after adding sulfur and the vulcanization accelerator (s) to it, the contents of the mixing roller were kneaded at BO'C for 6 minutes, thus obtaining a rubber composition. The Mooney viscosity of the rubber composition then obtained was measured using the method above.
    [00113] Also, the resulting rubber composition was press-molded (at 145 ° for 20 minutes) while being cured to prepare a sheet (thickness: 2 mm). The sheet then prepared was evaluated for dry grip performance and ice adhesion performance using the above methods. The results are shown in Tables 2 to 7. TABLE 1
    TABLE 2


    [00114] As shown in Table 2, the rubber compositions obtained in Examples 1 and 2 exhibited low Mooney viscosity and good processability, as well as good ice bonding performance. In particular, the rubber composition obtained in Example 1 also exhibited good dry grip performance and could therefore be used appropriately as a rubber tire composition. TABLE 3

    TABLE 4

    TABLE 5

    TABLE 6
    TABLE 7

    [00115] As shown in Table 3, the rubber compositions obtained in Examples 3 to 9 exhibited good processability due to its low Mooney viscosity and were able to satisfy both good dry grip performance and good wet performance. adhesion to ice, and then could be properly used as a rubber tire composition.
    [00116] As shown in Table 4, the rubber compositions obtained in Example 10 were excellent especially in dry grip performance and ice grip performance and could therefore be used appropriately as a rubber tire composition.
    [00117] As shown in Table 5, the rubber compositions obtained in Example 11 were excellent especially in dry grip performance and ice grip performance and could therefore be used appropriately as a rubber tire composition.
    [00118] As shown in Table 6, the rubber compositions obtained in Example 12 were excellent especially in pro-10 cessability and adhesion performance on dry roads and could therefore be suitably used as a rubber tire composition.
    [00119] As shown in Table 7, the rubber compositions obtained in Example 13 were excellent especially in performance in dry grip and ice grip performance and could therefore be used appropriately as a rubber tire composition.
    权利要求:
    Claims (10)
    [0001]
    1. Rubber composition, characterized by the fact that it comprises (A) at least one rubber component selected from the group consisting of synthetic rubber and natural rubber; (B) a farnesene polymer having an average molecular weight of not less than 2,000 and less than 25,000; and (C) carbon black with an average particle size of 5 to 100 nm, a content of polymer (B) in the rubber composition is from 0.1 to 100 parts by mass based on 100 parts by mass of the rubber component (A) and a carbon black content (C) in the rubber composition is from 0.1 to 100 parts by weight based on 100 parts by weight of the rubber component (A).
    [0002]
    Rubber composition according to claim 1, characterized by the fact that the polymer (B) is a p-farnesene homopolymer.
    [0003]
    Rubber composition according to claim 1 or 2, characterized in that the polymer (B) has a melting viscosity of from 0.1 to 3.5 Pa's as measured at 38 ° C.
    [0004]
    Rubber composition according to any one of claims 1 to 3, characterized in that the synthetic rubber is at least one rubber selected from the group consisting of a styrene-butadiene rubber, a butadiene rubber and an isoprene rubber .
    [0005]
    Rubber composition according to claim 4, characterized in that the styrene-butadiene rubber has an average molecular weight of from 100,000 to 2,500,000.
    [0006]
    Rubber composition according to claim 4 or 5, characterized in that the styrene-butadiene rubber has a styrene content of from 0.1 to 70% by weight.
    [0007]
    Rubber composition according to any one of claims 4 to 6, characterized in that the butadiene rubber has an average molecular weight from 90,000 to 2,000,000.
    [0008]
    Rubber composition according to any one of claims 4 to 7, characterized in that the butadiene rubber has a vinyl content of 50% by weight or less.
    [0009]
    Rubber composition according to any one of claims 1 to 8, characterized in that the polymer (B) has a molecular weight distribution (Mw / Mn) of from 1.0 to 2.0.
    [0010]
    10. Tire, characterized in that it comprises at least partially the rubber composition, as defined in any one of claims 1 to 9.
    类似技术:
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    同族专利:
    公开号 | 公开日
    US20140155536A1|2014-06-05|
    CN105646956B|2018-03-02|
    RU2014112226A|2015-11-10|
    KR101414302B1|2014-07-02|
    TWI441867B|2014-06-21|
    JPWO2013047348A1|2015-03-26|
    CN103748159B|2016-01-20|
    JP2013209673A|2013-10-10|
    EP2762524A1|2014-08-06|
    CN103748159A|2014-04-23|
    EP2762524B1|2016-09-14|
    US8785542B2|2014-07-22|
    CA2837547A1|2013-04-04|
    TW201317292A|2013-05-01|
    CA2837547C|2014-06-10|
    PT2762524T|2016-12-14|
    RU2611511C2|2017-02-27|
    BR112014007430A2|2017-04-04|
    WO2013047348A1|2013-04-04|
    KR20130143142A|2013-12-30|
    EP2762524A4|2015-08-12|
    JP5314812B1|2013-10-16|
    CN105646956A|2016-06-08|
    IN2014CN02316A|2015-06-19|
    ES2597039T3|2017-01-13|
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    CN110511448B|2019-09-16|2021-06-11|中交第一公路勘察设计研究院有限公司|Damping support composite material for high-cold high-altitude high-ultraviolet regions and preparation method thereof|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-06-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-07-28| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011218122|2011-09-30|
    JP2011-218122|2011-09-30|
    PCT/JP2012/074169|WO2013047348A1|2011-09-30|2012-09-21|Rubber composition and tire|
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