copolymer, rubber composition using the same, and tire

专利摘要:
COPOLYMER, RUBBER COMPOSITION USING THE SAME, AND TIRE. The present invention relates to a random copolymer that contains monomer units (a) derived from an aromatic vinyl compound and monomer units (b) derived from farnesene. A method for producing the aforementioned copolymer involving copolymerization of at least one aromatic vinyl compound and farnesene. A rubber composition contains the copolymer (A), a rubber component (B) and carbon black (C). One rubber composition contains the copolymer (A), a rubber component (B) and silica (D), and another rubber composition contains the copolymer (A), a rubber component (B), carbon black (C) and silica (D). A tire has at least one part where the rubber composition is used.
公开号:BR112014024788B1
申请号:R112014024788-9
申请日:2013-04-02
公开日:2020-12-22
发明作者:Daisuke Koda；Kei Hirata
申请人:Kuraray Co., Ltd.；Amyris, Inc；
IPC主号:

专利说明:

Technical Field
[001] The present invention relates to a copolymer containing a monomer unit derived from farnesene, a rubber composition containing the copolymer, and a tire using the rubber composition.
[002] Background Technique
[003] Pneumatic tires are required to have not only excellent steering stability on a wet road surface (wet grip performance), but also high wear resistance and excellent durability. In order to improve tire wear resistance, it is conventionally known to use a rubber composition in which carbon black or silica is generally composed as a rubber reinforcing agent. However, the rubber composition tends to have a high viscosity and for that reason to be deteriorated in processability. For this reason, in the rubber composition above, a process oil, a liquid polymer or the like is used as a processability enhancer. When using these conventional processability improvers in the rubber composition, the resulting rubber composition is improved in processability, but fails to be sufficiently improved in the balance between wet grip performance and wear resistance.
[004] In PTL1, as a rubber composition that can be improved in the aforementioned properties in a well balanced way, in this sense a rubber composition for tires is described which includes a rubber component containing a butadiene rubber and a butadiene styrene rubber, and silica in specific composition ratios.
[005] Also, PTL2 describes a rubber composition for tires in which silica, aluminum hydroxide and a specific silane coupling reagent are composed in a specific composition ratio.
[006] However, any of the rubber compositions described in these Patent Literature fail to satisfy a resistance to wear, a wet grip performance and a processability with a sufficiently high level, and for this reason there is still a strong demand for rubber compositions that are also improved in these properties.
[007] However, PTL3 and PTL4 describe a β-farnesene polymer, but fail to have sufficient study in practical applications of these.
[008] Citation List
[009] Patent Literature
[0010] PTL1: JP 2012-031308A
[0011] PTL2: JP 2011-148952A
[0012] PTL3: WO 2010 / 027463A
[0013] PTL4: WO 2010 / 027464A
[0014] Summary of the Invention
[0015] Technical problem
[0016] The present invention was produced in view of the above conventional problems. The present invention provides a copolymer that is improved in processability in composition, molding or curing and is able to enhance wet grip performance, wear resistance and mechanical strength of a rubber composition in a well-balanced manner when using the copolymer as a part of the rubber composition; a rubber composition containing the copolymer; and a tire obtained using the rubber compound.
[0017] Solution to the Problem
[0018] As a result of extensive and intensive research, the present inventors found that when using a copolymer containing a monomer unit derived from an aromatic vinyl compost and a monomer unit derived from farnese in a rubber composition , the resulting rubber composition can be enhanced not only in processability, but also in wet grip performance and also rotation resistance performance while preventing the composition from deteriorating in mechanical strength and wear resistance. The present invention was made based on the above finding.
[0019] That is, the present invention relates to the following aspects.
[0020] [1] A random copolymer including a monomer unit (a) derived from an aromatic vinyl compound and a monomer unit (b) derived from farnesene.
[0021] [2] A process for producing the copolymer, including at least the step of copolymerizing an aromatic vinyl compound with farnesene.
[0022] [3] A rubber composition including (A) the above copolymer; (B) a rubber component; and (C) carbon black.
[0023] [4] A rubber composition including (A) the above copolymer; (B) a rubber component; and (D) silica.
[0024] [5] A rubber composition including (A) the above copolymer; (B) a rubber component; (C) carbon black; and (D) silica.
[0025] [6] A tire using the above rubber composition at least as a part of these.
[0026] Advantageous Effects of the Invention
[0027] In accordance with the present invention, it is possible to provide a copolymer that is improved in processability in composition, molding or curing and is able to enhance wet grip performance, wear resistance and mechanical strength of a rubber composition in a well-balanced manner when using the copolymer as a part of the rubber composition; a rubber composition containing the copolymer; and a tire obtained using the rubber composition.
[0028] Description of Modalities
[0029] Copolymer
[0030] The copolymer according to the present invention is a random copolymer including a monomer unit (a) derived from an aromatic vinyl compound and a monomer unit (b) derived from farnesene.
[0031] The "random copolymer" as used in the present invention means such a random copolymer in which a content of a chain of aromatic vinyl compound containing 3 or less monomer units derived from an aromatic vinyl compound as calculated by NMR method it is not less than 20% by mass based on a total amount of monomer units derived from integral aromatic vinyl compounds. In the present invention, the content of the aromatic vinyl compound chain in the random copolymer is preferably not less than 40% by weight, more preferably not less than 60% by weight and even more preferably not less than 75% by mass. The respective values as mentioned here can be measured by the methods described above in the examples.
[0032] Examples of the aromatic vinyl compound that makes up the monomer unit (a) include aromatic vinyl compounds such as styrene, α-methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene , 4-propyl styrene, 4-t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2,4-dimethyl styrene, 2,4-diisopropyl styrene, 2-styrene , 4,6-trimethyl, 2-ethyl-4-benzyl styrene, 4- (phenyl butyl) styrene, 1-vinyl naphthalene, 2-vinyl naphthalene, vinyl anthracene, N, N-diethyl-4 styrene -aminoethyl, vinyl pyridine, 4-methoxy styrene, monochlorostirene, dichloro-styrene and divinyl benzene. Of these aromatic vinyl compounds, preferred are styrene, α-methyl styrene and 4-methyl styrene.
[0033] In the present invention, the monomer unit (b) can be either a monomer unit derived from α-farnesene or a monomer unit derived from β-farnesene represented by the following formula (I). However, of these monomer units, from the point of view of facilitated copolymer production, the monomer unit derived from β-farnesene is preferred. However, α-farnesene and β-farnesene can be used in combination with each other.

[0034] The average weight molecular weight (Mw) of the copolymer is preferably from 2,000 to 500,000, more preferably from 8,000 to 500,000, even more preferably from 15,000 to 450,000 and even more preferably from 15,000 to 300,000. When the average weight molecular weight of the copolymer falls within the ranges specified above, the aforementioned rubber composition has good processability, and can also be improved in dispersibility of the carbon black or silica compound in this and for this reason can exhibit good rotation resistance performance. However, the weight average molecular weight of the copolymer as used in this specification is the value measured by the method described above in the examples. In the present invention, two or more types of copolymers that are different in molecular weight from the average weight of each other can be used in the form of a mixture of these.
[0035] The melt viscosity of the copolymer as measured at 38 ° C is preferably from 0.1 to 3,000 Pa ^ s, more preferably from 0.6 to 2,800 Pa ^ s, even more preferably from 1.5 to 2,600 Even more preferably 1.5 to 2,000 Pa ^ s. When the melt viscosity of the copolymer falls within the ranges specified above, the resulting rubber composition can be easily kneaded and can be improved in processability. However, in the present specification, the melt viscosity of the copolymer is the value measured by the method described above in the examples.
[0036] The mass ratio of the monomer unit (a) to a sum of the monomer unit (a) and the monomer unit (b) in the copolymer is preferably from 1 to 99% by weight, more preferably from 10 to 80% by weight and even more preferably from 15 to 70% by weight from the point of view of enhancing processability and wet grip performance of the resulting rubber composition.
The molecular weight distribution (Mw / Mn) of the copolymer is preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0 and even more preferably from 1.0 to 2.0. When the molecular weight distribution (Mw / Mn) of the copolymer falls within the ranges specified above, the resulting copolymer can suitably exhibit a smaller variation in its viscosity.
[0038] The copolymer according to the present invention can be any suitable copolymer since it is produced at least by copolymerization of an aromatic vinyl compound with farnesene, and the copolymer can also be produced by copolymerization. the other monomer with the aromatic vinyl compound and farnesene.
[0039] Examples of the other monomer include conjugated dienes such as butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, 3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, mircene and chloroprene.
[0040] The content of the other monomer in the copolymer is preferably not more than 50% by weight, more preferably not more than 40% by weight and even more preferably not more than 30% by weight.
[0041] Process for Copolymer Production
[0042] The copolymer according to the present invention is preferably produced by the production process including at least the step of copolymerizing an aromatic vinyl compound with farnesene. More specifically, the copolymer can be produced by an emulsion polymerization method, a solution polymerization method or the like. Of these methods, the solution polymerization method is preferred.
[0043] Emulsion Polymerization Method
[0044] The emulsion polymerization method used for the production of the copolymer can be any suitable conventionally known method. For example, a predetermined amount of farnesene and a predetermined amount of an aromatic wine compound are emulsified and dispersed in the presence of an emulsifying reagent, and then the resulting emulsion is subjected to emulsion polymerization using a polymerization initiator. radical.
[0045] As the emulsifying reagent, in this sense, for example, 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 reagent include potassium salts and sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
[0046] As the dispersant for emulsion polymerization, in this sense water 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 a organic solvent produces any adverse influence on polymerization stability.
[0047] Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate; and organic peroxides and hydrogen peroxide.
[0048] In order to adjust a molecular weight of the resulting copolymer, a chain transfer reagent can be used in this regard. Examples of the chain transfer reagent include mer-captans such as t-dodecyl mercaptan and n-dodecyl mercaptan; and carbon tetrachloride, thioglycolic acid, diterpene, terpeninolene, Y-terpinene and an α-methyl styrene dimer.
[0049] The temperature used in the emulsion polymerization can be appropriately determined according to the type of radical polymerization initiator used therein, and is generally preferably from 0 to 100 ° C and more preferably from 0 to 60 ° C. 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 reagent to the reaction system.
Examples of the terminating reagent include amine compounds such as isopropyl hydroxyl amine, diethyl hydroxyl amine and hydroxyl amine; quinone-based compounds such as hydroquinone and benzoquinone; and sodium nitrite.
[0051] After interrupting the polymerization reaction, an antioxidant can be added to the polymerization reaction system, if required. In addition, after interrupting the polymerization reaction, unreacted monomers can be removed from the resulting latex, if required. Here afterwards, the resulting copolymer is coagulated by adding a salt such as sodium chloride, calcium chloride and potassium chloride as a coagulant to it and, if required, while adjusting a pH value of the coagulation system by adding an acid such as nitric acid and sulfuric acid to it, and then the dispersing solvent is separated from the reaction solution to recover the copolymer. The copolymer recovered in this way is washed with water and dehydrated, and then dried to obtain the copolymer. However, in the coagulation of the copolymer, the latex can be previously mixed, if required, with an extender oil in the form of an emulsified dispersion to recover the copolymer in the form of an oil-extended rubber.
[0052] Solution Polymerization Method
[0053] The solution polymerization method used for the production of the copolymer can be any suitable conventionally known method. For example, a farnesene monomer can be polymerized with a monomer derived from an aromatic vinasse compound in a solvent using a Zi-egler-based catalyst, one with a metallocene-based catalyst or an anion-curable active metal, if required in the presence of a polar compound.
[0054] 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.
[0055] Specific examples of the organic alkali metal compound include organic monolithium compounds such as methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium, phenyl lithium and lithium stybeno; 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 more 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 required, and is preferably 0.01 to 3 parts by weight based on 100 parts by weight of farnesene.
[0056] The organic alkali metal compound can be used in the form of an organic alkali metal amide leaving a secondary amine such as dibutyl amine, dihexyl amine and dibenzyl amine to react with it.
[0057] Examples of the solvent used in solution polymerization include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methyl cyclopentane; and aromatic hydrocarbons such as benzene, toluene and xylene.
[0058] The polar compound can be used in the polymerization of anion to control a microstructure of a portion of farnesene without causing deactivation of the reaction. Examples of the polar compound include ether compounds such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane and ethylene glycol diethyl ether; pyridine; tertiary amines such as trimethylamine and tetramethyl ethylenediamine; and alkali metal alkoxides such as potassium-t-butoxide; and phosphine compounds.
[0059] The polar compound is preferably used in an amount of 0.01 to 1,000 mol equivalent based on the organic alkali metal compound.
[0060] The copolymer according to the present invention is preferably produced by conducting an anionic polymerization in the presence of an organic metal initiator such as organic alkali metal compounds above the point of view of co-production. polymer capable of satisfying the above mentioned molecular weight distribution range.
[0061] The temperature used in the above polymerization reaction is generally from -80 to 150 ° C, preferably from 0 to 10 0 ° C and more preferably from 10 to 90 ° C. The polymerization method can be either a batch method or a continuous method. The aromatic vinyl compound and farnesene are respectively supplied to the reaction solution in a continuous or intermittent manner so that a compositional relationship of the aromatic vinyl compound and farnesene in the polymerization system is included in a specific range, or a mixture of the compound of aromatic vinyl and farnesene that was previously prepared so that a compositional ratio of these compounds is controlled to a specific range is provided to the reaction solution, by which it is possible to produce a random copolymer.
[0062] The polymerization reaction can be stopped by adding an alcohol such as methanol and isopropanol as a terminating reagent to the reaction system.
[0063] The solution resulting from the polymerization reaction can be poured into a weak solvent such as methanol to precipitate the copolymer. Alternatively, the polymerization reaction solution can be washed with water, and then a solid is separated from it and dried to isolate the copolymer from it.
[0064] Modified Copolymer
[0065] The copolymer according to the present invention can be used in a modified way. Examples of a functional group used for modifying the copolymer include an amino group, an alkoxysilyl group, a hydroxyl group, an epoxy group, a carboxyl group, a carbonyl group, a mercapto group, a group isocyanate and an acid anhydride group.
[0066] As the method of production of the modified copolymer, in this sense, for example, the method in which before adding the terminating reagent, a coupling reagent such as tin tetrachloride, tetrachlorosilane, dimethyl dichlorosilane , dimethyl diethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyl triethoxysilane, tetraglycidyl-1,3-bisaminomethyl cyclohexane and 2,4-tolylene diisocyanate which are capable of reaction with an active terminal of the polymer chain, a chain terminal modifying reagent such as 4,4'-bis (diethylamino) benzophenone and N-vinyl pyrrolidone, or the other modifying reagent as described in JP 2011-132298A is added to the polymerization reaction. Also, the isolated copolymer can be grafted with maleic anhydride or the like.
[0067] In the modified copolymer, the polymer site into which the functional group is introduced can be either a chain terminator or a polymer side chain. In addition, these functional groups can be used alone or in combination with any two or more of these. The modifying reagent can be used in an amount of 0.01 to 100 mol equivalent and preferably 0.1 to 10 mol equivalent based on the organic alkali metal compound.
[0068] Rubber Composition
[0069] The first rubber composition according to the present invention includes (A) the above copolymer according to the present invention; (B) a rubber component; and (C) carbon black.
[0070] The second rubber composition according to the present invention includes (A) the above copolymer according to the present invention; (B) a rubber component; and (D) silica.
[0071] The third rubber composition according to the present invention includes (A) the above copolymer according to the present invention; (B) a rubber component; (C) carbon black; and (D) silica.
[0072] Rubber Component (B)
[0073] Examples of the rubber component (B) used here include a natural rubber, a styrene-butadiene rubber (hereinafter also referred to merely as "SBR"), a butadiene rubber, an isoprene rubber, a butyl rubber, a halogenated butyl rubber, an ethylene propylene diene rubber, an ethylene propylene diene rubber, a butadiene acrylonitrile copolymer rubber and a chloroprene rubber. Of these rubbers, preferred are SBR, a natural rubber, butadiene rubber and isoprene rubber, and most preferred are SBR and natural rubber. These rubbers can be used alone or in combination with any two or more of these.
[0074] Natural Rubber
[0075] Examples of the natural rubber used as the rubber component (B) in the present invention include natural rubbers commonly used in tire industries, for example, TSR such as SMR, SIR and STR; and RSS, etc .; high purity natural rubbers; and modified natural rubbers such as epoxy natural rubbers, hydroxylated natural rubbers, hydrogenated natural rubbers and grafted natural rubbers. Among these natural rubbers, S-TR20, SMR20 and RSS # 3 are preferred from the point of view of less variation in quality and good availability. These natural rubber can be used alone or in combination with any two or more of these.
[0076] Synthetic Rubber
[0077] Examples of a synthetic rubber used as the rubber component (B) in the present invention include SBR, a butadiene rubber, an isoprene rubber, a butyl rubber, a halogenated butyl rubber, a rubber ethylene propylene diene, a butadiene acrylonitrile copolymer rubber and a chloroprene rubber. Of these synthetic rubbers, preference is SBR, an isoprene rubber and a butadiene rubber.
[0078] (SBR)
[0079] As SBR, in this sense, those generally used in tire applications can be used. More specifically, the SBR preferably has a styrene content of 0.1 to 70% by weight and more preferably from 5 to 50% by weight. Also, the SBR preferably has a vinyl content of 0.1 to 60% by weight and more preferably from 0.1 to 55% by weight.
[0080] The average weight molecular weight (Mw) of SBR 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 SBR weight average molecular weight falls within the ranges specified above, the resulting rubber composition can be enhanced in both processability and mechanical strength. However, in the present specification, the average weight molecular weight is the value measured by the method described above in the examples.
[0081] The glass transition temperature (Tg) of the SBR used in the present invention as measured by differential thermal analysis is preferably from -95 ° C to 0 ° C and more preferably from -95 ° C to -5 ° C. When adjusting the TBR of the SBR to the ranges specified above, it is possible to suppress the increase in viscosity of the SBR and to enhance its handling properties.
[0082] Method for SBR Production
[0083] The SBR usable in the present invention can be produced by copolymerization of styrene and butadiene. The production method of SBR is not particularly limited, and SBR can be produced by any of an emulsion polymerization method, a solution polymerization method, a vapor phase polymerization method and a volume polymerization method. Of these polymerization methods, preferred are an emulsion polymerization method and a solution polymerization method.
[0084] E-emulsion Polymerized Styrene-Butadiene Rubber (E-SBR)
[0085] E-SBR can be produced by an ordinary 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 reagent, and then the resulting emulsion is subjected to emulsion polymerization using an emulsion polymerizer. radical polymerization.
[0086] As the emulsifying reagent, in this sense, for example, 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 reagent include potassium salts and sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
[0087] As a dispersant for the above emulsion polymerization, water can generally be used in this regard. The dispersant can also contain a water-soluble organic solvent such as methanol and ethanol unless the use of such an organic solvent produces any adverse influence on polymerization stability.
[0088] Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides and hydrogen peroxide.
[0089] In order to properly adjust a molecular weight of the E-SBR obtained, in this sense a chain transfer reagent can be used. Examples of the chain transfer reagent included in 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.
[0090] The temperature used in the emulsion polymerization can be appropriately determined according to the type of radical polymerization initiator used therein, and is generally preferably from 0 to 100 ° C and more preferably from 0 to 60 ° C. 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 reagent to the reaction system.
Examples of the terminating reagent include amine compounds such as isopropyl hydroxyl amine, diethyl hydroxyl amine and hydroxyl amine; quinone-based compounds such as hydroquinone and benzoquinone; and sodium nitrite.
[0092] After interrupting the polymerization reaction, an antioxidant can be added to the polymerization reaction system, if required. Also, after interrupting the polymerization reaction, unreacted monomers can be removed from the resulting latex, if required. Here later, the polymer obtained is coagulated by adding a salt such as sodium chloride, calcium chloride and potassium chloride as a coagulant to it and, if required, while adjusting a pH value of the coagulation system by adding an acid such as nitric acid and sulfuric acid thereto, and then the dispersing solvent is separated from the reaction solution to recover the polymer as a fragment. The fragment thus recovered is washed with water and dehydrated, and then dried using a tape drier or the like to obtain E-SBR. However, in the coagulation of the polymer, the latex can be pre-mixed, if required, with an extender oil in the form of an emulsified dispersion to recover the polymer in the form of an oil-extended rubber.
[0093] (ii) Solution Polymerized Styrene-Butadiene Rubber (S-SBR)
[0094] S-SBR can be produced by an ordinary solution polymerization method. For example, styrene and butadiene are polymerized in a solvent using an ion-curable active metal, if required, in the presence of a polar compound.
[0095] 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.
[0096] Specific examples of the organic alkali metal compound include organic monolithium compounds such as n-butyl lithium, sec-butyl lithium, t-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-trilithiobenzene; 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 the organic alkali metal compound used can be appropriately determined according to a molecular weight of S-SBR as required.
[0097] The organic alkali metal compound can also be used in the form of an organic alkali metal amide leaving a secondary amine such as dibutyl amine, dihexyl amine and dibenzyl amine to react with it.
Examples of the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methyl cyclopentane; and aromatic hydrocarbons such as benzene and toluene. These solvents are preferably used in such an amount that a monomer is generally dissolved therein in a concentration of 1 to 50% by weight.
[0099] The polar compound used in solution polymerization is not particularly limited since the compound does not cause the reaction to deactivate in anionic polymerization and can ordinarily be used to control a microstructure of a portion of butadiene and distribution of styrene in a chain of the obtained copolymer. Examples of the polar compound include ether compounds such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane and ethylene glycol diethyl ether; pyridine; tertiary amines such as tetramethyl ethylene diamine and trimethylamine; and alkali metal alkoxides such as potassium-t-butoxide; and phosphine compounds. The polar compound is preferably used in an amount of 0.01 to 1,000 mol equivalent based on the organic alkali metal compound.
[00100] The temperature used in the above polymerization reaction is generally -80 to 150 ° C, preferably 0 to 10 0 ° C and more preferably 30 to 90 ° C. The polymerization method can be either a batch method or a continuous method. Also, in order to improve a random copolymerizability between styrene and butadiene, styrene and butadiene are preferably supplied to the reaction solution in a continuous or intermittent manner so that a compositional relationship between styrene and butadiene in the polymerization system is included in a specific range.
[00101] The polymerization reaction can be stopped by adding an alcohol such as methanol and isopropanol as a terminating reagent to the reaction system. In addition, before adding the terminating reagent, an coupling reagent such as tin tetrachloride, tetrachlorosilane, tetrame-toxisilane, tetraglycidyl-1,3-bisaminomethyl cyclohexane and 1,3-bisaminomethyl can be added. 2,4-tolylene which are capable of reaction with an active polymer chain terminal, or a chain terminal modifying reagent such as 4,4'-bis (diethylamino) benzophenone and N-vinyl pyrrolidone. The polymerization reaction solution obtained after interrupting the polymerization reaction can be directly subjected to drying or steam extraction to remove the solvent from it, thereby recovering the S-SBR as planned. However, before removing the solvent, the polymerization reaction solution can be previously mixed with an extender oil to recover the S-SBR in the form of an oil-extended rubber.
[00102] Modified Styrene-Butadiene Rubber (modified SBR)
[00103] In the present invention, in this sense, 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 into SBR include an amino group, an alkoxyethyl group, a hydroxyl group, an epoxy group and a carboxyl group.
[00104] As the production method of the modified SBR, in this sense, for example, the method in which before adding the terminating reagent, a coupling reagent such as tin tetrachloride, tetrachlorosilane, dimethyl dichlorosilane , dimethyl die-toxisilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyl triethoxysilane, tetraglycidyl-1,3-bisaminomethyl cyclohexane and 2,4-tolylene diisocyanate which are capable of reaction with an active end of the chain polymer, a chain terminal modifying reagent such as 4,4'-bis (diethylamino) benzophenone and N-vinyl pyrrolidone, or the other modifying reagent as described in JP 2011-132298A is added to the polymerization reaction system dog.
[00105] In the modified SBR, the polymer site into which the functional group is introduced can be either a chain terminal or a polymer side chain.
[00106] Isoprene rubber
[00107] Isopropylene rubber can be a commercially available isoprene rubber that can be obtained, for example, by polymerization using a Ziegler-based catalyst such as titanium-trialkyl aluminum tetrahalide-based catalysts , catalysts based on diethyl aluminum-cobalt chloride, catalysts based on trialkyl aluminum-boron-nickel trifluoride and catalysts based on diethyl aluminum-nickel chloride; a rare earth metal catalyst based on lanthanoid such as catalysts based on triethyl aluminum-Lewis acid-organic acid neodymium salt; or an organic alkali metal compound as used similarly for the production of S-SBR. Among these isoprene rubbers, isoprene rubbers obtained by polymerization using the Ziegler-based catalyst are preferred because of their high cis isomer content. In addition, it is also possible to use those isoprene rubbers having an ultra high cis isomer content that are produced using the rare earth metal catalyst based on lanthanoid.
[00108] 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 the isoprene rubber is more than 50% by mass, the resulting rubber composition tends to deteriorate in rotation resistance performance. The lower limit of the vinyl content of the 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 -30 ° C or less.
[00109] The average molecular weight of the isoprene rubber weight 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 ranges specified above, the resulting rubber composition can exhibit good processability and good mechanical strength.
[00110] Isopropene rubber may partially have a branched structure or may partially contain a polar functional group using a polyfunctional modifying reagent, for example, a modifying reagent such as tin tetrachloride, te - silicon trachloride, an alkoxysilane containing an epoxy group in a molecule thereof, and an alkoxysilane containing an amino group.
[00111] Butadiene rubber
[00112] Butadiene rubber can be a commercially available butadiene rubber that can be obtained, for example, by polymerization using a Ziegler-based catalyst such as titanium-trialkyl aluminum tetrahalide-based catalysts, ca - talcisers based on diethyl aluminum-cobalt chloride, catalysts based on trialkyl aluminum-boron-nickel trifluoride and catalysts based on diethyl aluminum-nickel chloride; a rare earth metal catalyst based on lanthanoid such as triethyl aluminum-Lewis acid-organic acid neodymium salt catalysts based on; or an organic alkali metal compound as used similarly for the production of S-SBR. Among these butadiene rubbers, preferred are butadiene rubbers obtained by polymerization using the Ziegler-based catalyst because of its high cis isomer content. In addition, those butadiene rubbers having an ultra high cis isomer content that are produced using the rare earth metal catalyst based on lanthanoid can also be used in this regard.
[00113] 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 performance of resistance to rotation. 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 the vinyl content of these, and is preferably -40 ° C or less and more preferably -50 ° C or less.
[00114] The average molecular weight of butadiene rubber is preferably from 90,000 to 2,000,000, more preferably from 150,000 to 1,500,000 and even more preferably from 250,000 to 800,000. When the average weight molecular weight of butadiene rubber falls within the ranges specified above, the resulting rubber composition may exhibit good processability and good mechanical strength.
[00115] Butadiene rubber may partially have a branched structure or may partially contain a polar functional group by using a modifying reagent of the polyfunctional type, for example, a modifying reagent such as tin tetrachloride, silicon tetrachloride , an alkoxysilane containing an epoxy group in such a molecule, and an alkoxysilane containing an amino group.
[00116] As synthetic rubber other than SBR, isoprene rubber and butadiene rubber, in this sense one or more rubbers selected from the group consisting of a butyl rubber, a halogenated butyl rubber, a diene rubber can be used ethylene propylene, a butadiene acrylonitrile copolymer rubber and a chloroprene rubber. The method of producing these rubbers is not particularly limited, and any suitable commercially available synthetic rubbers can also be used in the present invention.
[00117] In the present invention, when using the rubber component (B) in combination with the aforementioned copolymer (A), it is possible to improve a processability of the resulting rubber composition, a dispersibility of carbon black, silica, etc. ., in this and a resistance performance to its rotation.
[00118] When using a mixture of two or more types of synthetic rubber, the combination of synthetic rubbers can be optionally selected unless the effects of the present invention are adversely influenced. Also, various properties of the resulting rubber composition, such as rotation resistance performance and wear resistance, can be appropriately controlled by selecting an appropriate combination of synthetic rubbers.
[00119] However, the method for producing the rubber used as the rubber component (B) in the present invention is not particularly limited, and any commercially available product can also be used as the rubber.
[00120] In the present invention, when using the rubber component (B) in combination with the aforementioned copolymer (A), it is possible to improve a processability of the resulting rubber composition, a dispersibility of silica in it and a performance resistance to its rotation.
[00121] The rubber composition preferably contains the above copolymer (A) in an amount of 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass and even more preferably 1 to 30 parts of mass based on 100 parts of mass of the above rubber component (B) from the point of view of enhancing a rotational strength and wear resistance of the rubber composition.
[00122] Carbon Black (C)
[00123] Examples of carbon black (C) usable in the present invention include carbon black such as oven black, channel black, thermal black, acetylene black and Ketjen black. Of these smoke puffs, from the point of view of enhancing a curing rate and a mechanical strength of the rubber composition, oven black is preferred.
[00124] Examples of commercially available oven black products include "DIABLACK" available from Mitsubishi Chemical Corp., and "SEAST" available from Tokai Carbon Co., Ltd. Examples of commercially available acetyl black products - do not include "DENKABLACK" made available by Denki Kagaku Kogyo KK Examples of commercially available black Ketjen products include "ECP600JD" made available by Lion Corp.
[00125] Carbon black (C) can be subjected to an acid treatment with nitric acid, sulfuric acid, hydrochloric acid or a mixed acid of these or it can be subjected to a thermal treatment in the presence of air to conduct a treatment of surface oxidation of these, from the point of view of improving a wettability or dispersibility of carbon black (C) in the copolymer (A) and the rubber component (B). In addition, 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 2,000 to 3,000 ° C in the presence of a catalyst. - graffiti user. As the graphitization catalyst, boron, boron oxides (such as, for example, B2O2, B2O3, B4O3 and B4O5), oxo boron acids (such as, for example, orthoboric acid, and tetraboric acid) and salts thereof, boron carbides (such as, for example, B4C and B6C), boron nitride (such as BN) and other boron compounds.
[00126] The average particle size of carbon black (C) can be controlled by spraying or the like. In order to spray the smoke cloud (C), a high-speed rotary mill (such as a hammer mill, pin mill and cage mill) or several ball mills (such as such as a rotating mill, a vibrating mill and a planetary mill), a stirring mill (such as a bead mill, an attractor, a flow tube mill and an annular mill) or the like.
[00127] The carbon black (C) used in the rubber composition of the present invention preferably has an average particle size of 5 to 100 nm and more preferably 10 to 80 nm in terms of improving dispersibility and a mechanical strength of the rubber composition.
[00128] 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.
[00129] In the rubber composition of the present invention, carbon black (C) is preferably composed in an amount of 0.1 to 150 pairs per mass, more preferably 2 to 150 parts of mass, even more preferably from 5 to 90 parts by mass and even more preferably from 20 to 80 parts by mass based on 100 parts by mass of the rubber component (B). When the amount of the composite carbon black (C) falls within the ranges specified above, the resulting rubber composition is not only excellent in mechanical strength, hardness and processability, but also exhibits a good dispersibility of the carbon black ( C) in this.
[00130] Silica (D)
[00131] Examples of silica (D) include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate and aluminum silicate. Of these silicas, from the point of view of also enhancing processability, mechanical strength and wear resistance of the resulting rubber composition, wet silica is preferred. These silicas can be used alone or in combination with any two or more of these.
[00132] The silica (D) preferably has an average particle size of 0.5 to 200 nm, more preferably from 5 to 150 nm, even more preferably from 10 to 100 nm and even more preferably from 10 to 60 nm from the point of view of enhancing processability, rotational strength performance, mechanical strength and wear resistance of the resulting rubber composition.
[00133] However, the average particle size of silica (D) can be determined by calculating an average value of diameters of silica particles measured using a transmission-type electron microscope.
[00134] In the rubber composition of the present invention, silica (D) is preferably composed in an amount of 0.1 to 150 pairs by mass, more preferably from 0.5 to 130 parts by mass, even more preferably from 5 to 100 parts by mass and even more preferably from 5 to 95 parts by mass based on 100 parts by mass of the rubber component (B). When the amount of the composed silica (D) falls within the ranges specified above, the resulting rubber composition can be enhanced in processability, rotation resistance performance, mechanical strength and wear resistance.
[00135] The rubber composition according to the present invention most preferably contains the above copolymer (A), carbon black (C) and silica (D) in quantities of 0.1 to 100 parts by mass, from 0 , 1 to 150 parts by mass and 0.1 to 150 parts by mass, respectively, based on 100 parts by mass of the above rubber component (B).
[00136] Optional Components
[00137] Silane coupling reagent
[00138] The rubber composition according to the present invention preferably also contains a silane coupling reagent. As the silane coupling reagent, a sulphide-based compound, a mercapto-based compound, a vinyl-based compound, an amino-based compound, a glycidoxy-based compound, one with - powered by nitro, a chlorine based compound, etc.
[00139] Examples of the sulfide-based compound include bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxyethylethyl) tetrasulfide, bis (3-trimethoxyethylpropyl) tetrasulfide, bis (2-trimethoxyethylethyl) tetrasulfide, bis (3-triethoxysilpropyl) trisulfide , bis (3-trimethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxyethylpropyl) disulfide, 3-trimethoxysilylpropyl-N, N-dimethyl, 3-trimethoxyethyl-3-trimethoxypropyl-3-trimethoxyethyl trisulfide -N, N-dimethyl, 2-trimethoxyethylethyl-thiocarbamoyl tetrasulfide-N, N-dimethyl, 3-trimethoxyethyl-propyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetra-sulphate, 3-triethylethylate methacrylate monoxide of 3-trimethoxysilylpropyl.
[00140] Examples of the mercapto-based compound include 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 2-mercaptoethyl trimethoxysilane and 2-mercaptoethyl triethoxysilane.
[00141] Examples of the vinyl-based compound include vinyl triethoxysilane and vinyl trimethoxysilane.
[00142] Examples of the amino-based compound include 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3- (2-aminoethyl) aminopropyl triethoxysilane and 3- (2-aminoethyl) aminopropyl trimethoxysilane.
[00143] Examples of the glycidoxy-based compound include Y-glycidoxypropyl tri-toxisilane, Y-glycidoxypropyl trimethoxysilane, Y-glycidoxypropyl methyl die-toxisilane and y-glycidoxypropyl methyl dimethoxysilane.
[00144] Examples of the nitro-based compound include 3-nitropropyl trimethoxysilane and 3-nitropropyl triethoxysilane.
[00145] Examples of the chlorine-based compound include 3-chloropropyl trimethoxysilane, 3-chloropropyl triethoxysilane, 2-chloroethyl trimethoxysilane and 2-chloroethyl triethoxysilane.
[00146] These silane coupling reagents can be used alone or in combination with any two or more of these. Of these silane coupling reagents, from the point of view of a great addition effect and low costs, preferred are bis (3-triethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) tetrasulfide and 3-mercaptopropyl trime-toxisilane.
[00147] The content of the silane coupling reagent in the rubber composition is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass and even more preferably from 1 to 15 parts of mass based on 100 parts of silica mass (D). When the content of the silane coupling reagent in the rubber composition falls within the ranges specified above, the resulting rubber composition can be enhanced in dispersibility, coupling effect, reinforcing property and wear resistance.
[00148] Other Loads
[00149] For the purposes of enhancing the mechanical strength of the rubber composition, improvement of various properties such as thermal resistance and weather resistance of this, control of its hardness, and also improvement of economy by adding an extender to this, the rubber composition according to the present invention may also contain a charge other than carbon black (C) and silica (D), if required.
[00150] The charge other than carbon black (C) and silica (D) can be appropriately selected according to the applications of the obtained rubber composition. For example, as the filler, in that sense one or more fillers selected from the group consisting of organic fillers, and inorganic fillers such as clay, talc, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide can be used. , barium sulfate, titanium oxide, glass fibers, fibrous fillers and glass balloons. The content of the above charge in the rubber composition of the present invention, if composed therein, is preferably from 0.1 to 120 parts of dough, more preferably from 5 to 90 parts of dough and even more preferably from 10 to 80 parts of dough based on 100 parts of dough of the rubber component (B). When the load content in the rubber composition falls within the ranges specified above, the resulting rubber composition can also be improved in mechanical strength.
[00151] The rubber composition according to the present invention may also contain, if required, a softening reagent for the purpose of improving processability, fluidity or the like of the resulting rubber composition unless the effects aspects of the present invention are adversely influenced. Examples of the softening reagent include a process oil such as silicone oil, aroma oil, TDAE (treated aromatic extracts), MES (mild extracted solvates), RAE (residual aromatic extracts), a paraffin oil and naphthene oil; a resin component such as aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, C9-based resins, rosin-based resins, chromano-indene-based resins and phenol-based resins; 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 copolymer can be in the form of either a block copolymer or a random copolymer. The liquid polymer preferably has an average molecular weight of 500 to 100,000 from the point of view of good processability of the resulting rubber composition. The above process oil, resin component or liquid polymer as a softening reagent is preferably composed in the rubber composition of the present invention in an amount of less than 50 parts by mass based on 100 parts by mass of the rubber component ( B).
[00152] The rubber composition according to the present invention may also contain a β-farnesene homopolymer unless the effects of the present invention are adversely influenced. The content of the β-farnesene homopolymer in the rubber composition, if composed therefrom, is preferably less than 50 pieces of dough based on 100 dough parts of the rubber component (B).
[00153] The rubber composition according to the present invention may also contain, if required, one or more additives selected from the group consisting of an antioxidant, an oxidation inhibitor, a wax, a lubricant, a light stabilizer, a flame retardant, a processing aid, a dye such as pigments and dyestuffs, a flame retardant, an antistatic reagent, a wear reagent, an anti-blocking reagent, an ultraviolet absorber, a release reagent , a foaming reagent, an antimicrobial reagent, a mildew proof reagent and a perfume, for the purposes of improving weather resistance, thermal resistance, oxidation resistance or similar to the rubber composition resulting, unless the effects of the present invention are adversely influenced.
[00154] Examples of the oxidation inhibitor include compounds based on impaired phenol, compounds based on phosphorus, compounds based on lactone and compounds based on hydroxyl.
[00155] Examples of the antioxidant include compounds based on amine ketone, compounds based on imidazole, compounds based on amine, compounds based on phenol, compounds based on sulfur and compounds based on phosphorus.
[00156] The rubber composition of the present invention is preferably used in a cross-linked product produced by adding a cross-linking reagent to it. Examples of the cross-linking reagent include sulfur and sulfur compounds, oxygen, organic peroxides, phenol resins and amino resins, quinone and quinone dioxide derivatives, halogen compounds, aldehyde compounds, alcohol compounds, compounds of epoxy, metal halides and organic metal halides, and silane compounds. Among these preferred crosslinking agents are sulfur and sulfur compounds. These crosslinking agents can be used alone or in combination with any two or more of these. The crosslinking reagent is preferably composed in the rubber composition in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the rubber component (B).
[00157] When using sulfur as the crosslinking reagent, a vulcanization aid or a vulcanization accelerator is preferably used in combination with the crosslinking reagent.
[00158] Examples of the vulcanization aid include fatty acids such as stearic acid and metal oxides such as zinc oxide.
[00159] Examples of the vulcanization accelerator include compounds based on guanidine, compounds based on sulphine amide, compounds based on thiazole, compounds based on thiuram, compounds based on thiourea, compounds based on acid dithiocarbamic, compounds based on aldehyde-amine or 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 these. The vulcanization aid or vulcanization accelerator is preferably composed in the rubber composition of the present invention in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the rubber component (B).
[00160] 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 since the respective components are uniformly mixed with each other. The method of uniformly mixing the respective components can be carried out, for example, using a closed-type shear from a contact-type shear shovel or a network-type shear, a Brabender, a Banbury mixer and an internal mixer, a single-screw extruder, a double-screw extruder, a mixing cylinder, a cylinder or the like in a temperature range generally from 70 to 270 ° C.
[00161] Tire
[00162] The tire according to the present invention is produced by using the rubber composition according to the present invention at least as a part of these, and for that reason can exhibit good mechanical strength, good adhesion performance in the end - excellent rotation resistance performance.
[00163] Examples
[00164] The present invention will be described in more detail above with reference to the following Examples. It should be noted, however, that the following Examples are illustrative only and are not intended to limit the invention to this.
[00165] The respective components used in the following Examples and Comparative Examples are as follows.
[00166] Copolymer (A):
[00167] Copolymers (A-1) and (A-2) obtained in Production Example 1 and 2, respectively.
[00168] Rubber component (B):
[00169] Natural rubber "STR20" (natural rubber from Thailand)
[00170] "JSR1500" styrene-butadiene rubber (available from JSR Corp.)
[00171] "BR-01" butadiene rubber (available from JSR Corp.)
[00172] Average weight molecular weight = 550,000
[00173] Cis isomer content = 95% by mass
[00174] Carbon black (C-1):
[00175] "DIABLACK H" made available by Mitsubishi Chemical Corp .; average particle size: 30 nm
[00176] Carbon black (C-2):
[00177] "DIABLACK I" made available by Mitsubishi Chemical Corp .; average particle size: 20 nm
[00178] Carbon black (C-3):
[00179] "SEAST V" made available by Tokai Carbono Co., Ltd .; average particle size: 60 nm
[00180] Silica (D-1):
[00181] "ULTRASIL7000GR" provided by Evonik Degussa Japan Co., Ltd .; wet silica; average particle size: 14 nm
[00182] Silica (D-2):
[00183] "AEROSIL 300" provided by Nippon Aerosil Co., Ltd .; dry silica; average particle size: 7 nm
[00184] Silica (D-3):
[00185] "NIPSIL E-74P" provided by Tosoh Sílica Corporatone; wet silica; average particle size: 74 nm
[00186] Polyisoprene:
[00187] Polyisoprene obtained in Production Example 3
[00188] β-Farnesene homopolymer:
[00189] Homopolymer of β-farnesene obtained in Production Example4
[00190] TDAE:
[00191] "VivaTec500" made available by H & R Corp.
[00192] Silane coupling reagent:
[00193] "Si75" (provided by Evonik Degussa Japan Co., Ltd.)
[00194] Stearic acid:
[00195] "LUNAC S-20" (provided by Kao Corp.)
[00196] Zinc oxide:
[00197] Zinc oxide (available from Sakai Chemical Industry Co., Ltd.)
[00198] Antioxidant (1):
[00199] "NOCRAC 6C" (made available by Ouchi Shinko Chemical Industrial Co., Ltd.)
[00200] Antioxidant (2):
[00201] "ANTAGE RD" (made available by Kawaguchi Chemical Industry Co., Ltd.)
[00202] Sulfur:
[00203] Fine 200 mesh sulfur powder (available from Tsurumi Chemical Industry Co., Ltd.)
[00204] Vulcanization accelerator (1):
[00205] "NOCCELER NS" (provided by Ouchi Shinko Chemical Industrial Co., Ltd.)
[00206] Vulcanization accelerator (2):
[00207] "NOCCELER CZ-G" (provided by Ouchi Shinko Chemical Industrial Co., Ltd.)
[00208] Vulcanization accelerator (3):
[00209] "NOCCELER D" (provided by Ouchi Shinko Chemical Industrial Co., Ltd.)
[00210] Vulcanization accelerator (4):
[00211] "NOCCELER TBT-N" (made available by Ouchi Shinko Chemical Industrial Co., Ltd.)
[00212] Production Example 1: Production of random β-farnesene / styrene (A-1) copolymer
[00213] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 1,790 g of cyclohexane as a solvent and 9.0 g of sec-butyl lithium (in the form of a cyclohexane solution of 10.5% by weight) as an initiator. The contents of the reaction vessel were heated to 50 ° C, and after adding 3 g of tetrahydrofuran to the reaction vessel, 1,200 g of a mixture of styrene (a) and β-farnesene (b) (which was previously prepared by mixing 276 g of styrene (a) and 924 g of β-farnesene (b) in a cylinder) were added to it at a rate of 10 mL / min, and the mixture was polymerized for 1 h. The solution resulting from the polymerization reaction was treated with methanol and then washed with water. After separating water from the polymerization reaction solution in this washed manner, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a random β-farnesene / styrene (A-1) copolymer. Various properties of the β-farnesene / styrene (A-1) random copolymer thus obtained are shown in Table 1.
[00214] However, the content of an aromatic vine compound chain containing 3 or less monomer units derived from the aromatic vinyl compound in the copolymer (A-1) was 78% mass, and the transition temperature glass of the copolymer (A-1) was -50 ° C.
[00215] Production Example 2: Production of random β-farnesene / styrene (B-2) copolymer
[00216] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 1,500 g of cyclohexane as a solvent and 112.6 g of sec-butyl lithium (in the form of a 10-cyclohexane solution, 5% by mass) as an initiator. the contents of the reaction vessel were heated to 50 ° C, and after adding 3 g of tetrahydrofuran to the reaction vessel, 1,500 g of a mixture of styrene (a) and β-farnesene (b) (which was previously prepared by mixing 345 g of styrene (a) and 1,155 g of β-farnesene (b) in a cylinder) was added to it at a rate of 10 mL / min, and the mixture was polymerized for 1 h. The solution resulting from the polymerization reaction was treated with methanol and then washed with water. After separating water from the polymerization reaction solution in this washed manner, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a random copolymer of β-farnesene / styrene (A-2). Various properties of the random β-farnesene / styrene (A-2) copolymer thus obtained are shown in Table 1.
[00217] However, the content of an aromatic vine compound chain containing 3 or less monomer units derived from the aromatic vinyl compound in the copolymer (A-2) was 81% mass, and the transition temperature glass of the copolymer (A-2) was -54 ° C.
[00218] Production Example 3: Production of polyisoprene
[00219] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 600 g of hexane and 44.9 g of n-butyl lithium (in the form of a 17% mass hexane solution). the contents of the reaction vessel were heated to 70 ° C, and 2050 g of isoprene was added to it, and the mixture was polymerized for 1 h. the resulting polymerization reaction solution was mixed with methanol and then washed with water. After separating water from the polymerization reaction solution in this washed manner, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a polyisoprene having properties as shown in Table 1.
[00220] Production Example 4: Production of β-farnesene homopolymer
[00221] A pressure reaction vessel previously purged with nitrogen and then dried was charged with 274 g of hexane as a solvent and 1.2 g of n-butyl lithium (in the form of a 17% hexane mass solution) as an initiator . the contents of the reaction vessel were heated to 50 ° C, and 272 g of β-farnesene was added to it, and the mixture was polymerized for 1 h. Subsequently, the solution resulting from the polymerization reaction was treated with methanol and then washed with water. After separating water from the polymerization reaction solution in this washed manner, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a β-farnesene homopolymer. Several properties of this way obtained β-farnesene homopolymer are shown in Table 1.
[00222] However, the average molecular weight and melting viscosity of each of the copolymers (A), polyisoprene and β-farnesene homopolymer were measured by the methods mentioned below.
[00223] Measurement Method Average weight molecular weight
[00224] The average weight molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of each of the copolymers (A), polyisoprene and β-farnesene homopolymer were measured by 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. • Apparatus: GPC device "GPC8020" provided by Tosoh Corp. • Column separation: "TSKgelG4000HXL" made available by Tosoh Corp. • Detector: "RI-8020" available from Tosoh Corp. • Eluent: Tetrahydrofuran • Flow rate of the eluent: 1.0 mL / min • Sample concentration: 5 mg / 10 mL • Column temperature: 40 ° C
[00225] Method of Measurement Melting Viscosity
[00226] The melting viscosity of each of the copolymers (A), polyisoprene and β-farnesene homopolymer was measured at 38 ° C using a type B viscometer provided by Brookfield Engineering Labs. Inc.
[00227] Measurement Method Chain Content of Aromatic Vinyl Compounds Containing 3 or Less Aromatic Vinyl Compound Units
[00228] A solution prepared by dissolving 50 mg of the copolymer (A) in 1 mL of CDCl3 was subjected to NMR measurement at 400 MHz at a cumulative frequency of 512 times. In the diagram obtained, a portion of 6.00 to 7.95 ppm was considered as a content of styrene whole chains, whereas a portion of 6.00 to 6.91 ppm was considered as a content of chains of styrene containing 4 or more styrene units, and the content of styrene chains containing 3 or less styrene units was calculated from the following formula.
[00229] However, when the monomer unit (a) derived from an aromatic vinyl compound is a monomer unit derived from the aromatic vinyl compound other than styrene, the content of the aromatic vinyl compound chain could be calculated in view of changing a chemical shift, depending on a type of functional group in the above mentioned chemical shift range.
[00230] {Content of Styrene Chains Containing 3 or less Styrene Units} = 100 - (Content of styrene chains containing 4 or more styrene units) = 100 - 100 x {(Integrated Value from 6.00 to 7, 95 ppm - Integrated value from 6.91 to 7.95 ppm) / 2} / [(Integrated value from 6.00 to 7.95 ppm - Integrated value from 6.91 to 7.95 ppm) / 2 + {Value Integrated from 6.91 to 7.95 ppm - (Integrated value from 6.00 to 7.95 ppm - Integrated value from 6.91 to 7.95 ppm) / 2 x 3} / 3]
[00231] Glass transition measurement temperature method
[00232] Ten milligrams of copolymer (A) were sampled in an aluminum pan, and subjected to the measurement of a thermogram by differential scanning calorimetry (DDSC) at a temperature rise rate of 10 ° C / min, and the maximum value in DDSC was determined as a glass transition temperature of the copolymer (A).


[00233] Examples 1 to 7 and Comparative Examples 1 to 8
[00234] The copolymer (A), rubber component (B), carbon black (C), silica (D), polyisoprene, TDAE, stearic acid, zinc oxide and antioxidant were loaded in respective ratios of composition as shown in Tables 2 to 4 in a closed Banbury mixer and kneaded together for 6 min so that the initiation temperature was 75 ° C and the resin temperature reached 160 ° C. The resulting mixture was taken out of the mixer once, and cooled to room temperature. Then, the mixture was placed in a mixing cylinder, and after adding sulfur and the vulcanization accelerator to it, the contents of the mixing cylinder were kneaded at 60 ° C for 6 min, thus obtaining a rubber composition. The Mooney viscosity of the rubber composition thus obtained was measured by the following method.
[00235] In addition, the resulting rubber composition was press-molded (at 145 ° C for 20 to 60 min) to prepare a sheet (thickness: 2 mm). The sheet thus prepared was evaluated for tensile strength at break, a loss of DIN abrasion, a wet grip performance and a rotational strength performance by the following methods. The results are shown in Tables 2 to 4.
[00236] (1) Mooney viscosity
[00237] As an index of a processability of the rubber composition, the Mooney viscosity (ML1 + 4) of the rubber composition before curing was measured at 100 ° C according to JIS K 6300. The values of the respective Examples and Comparative Examples shown in Table 2 are relative values based on 100 as the value of Comparative Example 3. Also, the values of the respective Examples and Comparative Examples shown in Table 3 are relative values based on 100 as the value of Comparative Example 6. In addition, the values of the respective Examples and Comparative Examples shown in Table 4 are relative values based on 100 as the value of Comparative Example 8. However, the lower Mooney viscosity value indicates a processability most excellent.
[00238] (2) Tensile force at break
[00239] A sheet prepared from the rubber composition produced in the respective Examples and Comparative Examples was perforated in a JIS No. 3 dumbbell-shaped test piece, and the test piece obtained was subjected to a tensile strength measurement in the rupture of this using a tensile tester made available by Instron Corp., according to JIS K 6251. The values of the respective Examples and Comparative Examples shown in Table 2 are relative values based on 100 as the value of Comparative Example 3. Also, the values of the respective Examples and Comparative Examples shown in Table 3 are relative values based on 100 as the value of Comparative Example 6. In addition, the values of the respective Examples and Comparative Examples shown in Table 4 are relative values with based on 100 as the value of Comparative Example 8. However, the higher value indicates a better tensile strength in the rupture of the rubber composition.
[00240] (3) Loss of DIN abrasion
[00241] The rubber composition was measured for the abrasion loss of DIN under a load of 10 N over an abrasion distance of 40 m according to JIS K 6264. The values of the respective Examples and Comparative Examples shown in Table 2 are relative values based on 100 as the value of Comparative Example 3. Also, the values of the respective Examples and Comparative Examples shown in Table 3 are relative values based on 100 as the value of Comparative Example 6. In addition In addition, the values of the respective Examples and Comparative Examples shown in Table 4 are relative values based on 100 as the value of Comparative Example 8. However, the lower value indicates less abrasion loss of the rubber composition.
[00242] (4) Wet grip performance
[00243] A sheet prepared from the rubber composition produced in the respective Examples and Comparative Examples was cut into a test piece having a size of 40 mm in length x 7 mm in width. The test piece thus obtained was submitted to tanδ measurement as an index of a wet grip performance of the rubber composition using a dynamic viscoelasticity measuring apparatus provided by GABO Gm-bH under conditions including a measuring temperature of 0 ° C, a frequency of 10 Hz, a static voltage of 10% and a dynamic voltage of 2%. The values of the respective Examples and Comparative Examples shown in Table 2 are relative values based on 100 as the value of Comparative Example 3. Also, the values of the respective Examples and Comparative Examples shown in Table 3 are relative values based on 100 as the Comparative Example value 6. In addition, the values of the respective Examples and Comparative Examples shown in Table 4 are relative values based on 100 as the value of Comparative Example 8. However, the higher value indicates a high performance of wet grip of the rubber composition.
[00244] (5) Performance of resistance to rotation
[00245] A sheet prepared from the rubber composition produced in the respective Examples and Comparative Examples was cut into a test piece having a size of 40 mm in length x 7 mm in width. The test piece thus obtained was subjected to the measurement of tanδ as an index of a performance of resistance to rotation of the rubber composition using a dynamic viscoelasticity measuring apparatus provided by GABO Gm-bH under conditions including a measuring temperature of 60 ° C, a frequency of 10 Hz, a static voltage of 10% and a dynamic voltage of 2%. The values of the respective Examples and Comparative Examples shown in Table 2 are relative values based on 100 as the value of Comparative Example 3. Also, the values of the respective Examples and Comparative Examples shown in Table 3 are relative values based on 100 as the Comparative Example value 6. In addition, the values of the respective Examples and Comparative Examples shown in Table 4 are relative values based on 100 as the value of Comparative Example 8. However, the lower value indicates excellent performance of resistance to rotation of the rubber composition.


[00246] The rubber compositions obtained in examples 1 and 2 exhibited a low Mooney viscosity when compared to that of Comparative Example 3 and for this reason a good processability. Also, the rubber composition obtained in example 1 was excellent in performance of resistance to rotation when compared to those of Comparative Examples 1 and 2. In addition, the rubber compositions obtained in examples 1 and 2 had substantially the same wear resistance and wet grip performance like those in Comparative Examples 1 and 2.


[00247] The rubber compositions obtained in examples 3 and 4 exhibited a low Mooney viscosity when compared to that of Comparative Example 6 and for this reason good processability. Also, the rubber compositions obtained in examples 3 and 4 were excellent in wet adhesion performance when compared to that of Comparative Example 4. Furthermore, the rubber compositions obtained in examples 3 and 4 had substantially the same strength wear like that of Comparative Example 4, and also the rubber composition obtained in Example 3 had substantially the same rotational strength performance as that of Comparative Example 4.
[00248] From the comparison between Example 5 and Comparative Example 5, it was confirmed that when controlling an average particle size of carbon black (C) for the range of 5 to 100 nm and an average particle size of silica (D) for the 0.5 to 200 nm range, the resulting rubber composition exhibited good processability, was prevented from deteriorating in mechanical strength and wear resistance, and was excellent in wet grip performance and wet performance. resistance to rotation.


[00249] The rubber compositions obtained in examples 6 and 7 exhibited a low Mooney viscosity when compared to that of Comparative Example 8 and for this reason good processability. Also, the rubber compositions obtained in examples 6 and 7 were excellent in wet performance when compared to that of Comparative Example 7. In addition, the rubber compositions obtained in examples 6 and 7 had substantially the same strength wear like that of Comparative Example 7, and also the rubber composition obtained in Example 6 had substantially the same rotational strength performance as that of Comparative Example 7.
[00250] Examples 8 to 20 and Comparative Examples 9 to 18
[00251] Copolymer (A), rubber component (B), carbon black (C), silica (D), β-farnesene homopolymer, polyisoprene, silane coupling reagent, TDAE, stearic acid , zinc oxide and antioxidant were loaded in respective composition ratios as shown in Tables 5 to 8 in a closed Banbury mixer and kneaded together for 6 min so that the initiation temperature was 75 ° C and the resin temperature reached 160 ° C. The resulting mixture was taken out of the mixer once, and cooled to room temperature. Then, the mixture was placed in a mixing cylinder, and after adding sulfur and the vulcanization accelerator to it, the contents of the mixing cylinder were kneaded at 60 ° C for 6 min, thus obtaining a rubber composition. The Mooney Viscosity of the rubber composition thus obtained was measured by the method above.
[00252] In addition, the resulting rubber composition was press-molded (at 145 ° C for 25 to 50 min) to prepare a sheet (thickness: 2 mm). The sheet prepared in this way was evaluated for tensile strength at break and performance of resistance to rotation by the above methods. The results are shown in Tables 5 to 8.
[00253] Also, the rubber compositions obtained in examples 8 to 17 and Comparative Examples 9 to 14 were measured for their abrasion loss by the above method. The results are shown in Tables 5 and 6.
[00254] However, the values of the respective Examples and Comparative Examples shown in Table 5 are relative values based on 100 as each of those values of Comparative Example 12. The values of the respective Examples and Comparative Examples shown in Table 6 are relative values based on 100 as each of those values of Comparative Example 14. The values of the respective Examples and Comparative Examples shown in Table 7 are relative values based on 100 as each of those values of Comparative Example 17. The values of the respective Examples and Comparative Examples shown in Table 8 are relative values based on 100 as each of those values of Comparative Example 18.


[00255] From the comparison between Example 8 and Comparative Example 9, it was confirmed that when controlling the amount of copolymer (A) copolymer compound (A) in the rubber composition to the range of 0.1 to 100 parts of mass based on 100 parts by mass of the rubber component (B), the resulting rubber composition exhibited good processability, was prevented from deteriorating in mechanical strength and wear resistance, and was excellent in wet grip performance and strength performance the rotation.
[00256] The rubber compositions obtained in examples 9 to 12 exhibited a low Mooney viscosity when compared to that of Comparative Example 12 and for this reason it was improved in processability. Also, the rubber compositions obtained in examples 9 to 12 had a tensile strength at break and a wear resistance that were almost similar to those in Comparative Example 10, but were excellent in wet grip performance and rotation resistance performance. when compared to those in Comparative Example 10, and for that reason could be used properly as a rubber tire composition.
[00257] The rubber composition obtained in example 13 exhibited a low Mooney viscosity when compared to that of Comparative Example 12 and for this reason it was improved in processability. Also, the rubber composition obtained in example 13 had a tensile strength at break and wear resistance that were almost similar to those in Comparative Example 11, but was excellent in wet grip performance and rotation resistance performance when compared to those of Comparative Example 11, and for that reason could be suitably used as a rubber tire composition.
[00258] From the comparison between Example 13 and Comparative Example 11, it was confirmed that when silica (D) was composed in an amount of 0.1 to 150 parts of dough based on 100 parts of dough component rubber (B), the effects of the present invention could be well demonstrated.
[00259] From the comparison between Example 13 and Comparative Example 11, it was confirmed that when carbon black (C) was composed in an amount of 0.1 to 150 parts of mass based on 100 parts of mass of the rubber (B), the effects of the present invention could be well demonstrated.
[00260] From the comparison between Example 13 and Comparative Example 11, it was confirmed that when the average particle sizes of carbon black (C) and silica (D) were controlled for the ranges from 5 to 100 nm and 0.5 at 200 nm, respectively, the resulting rubber composition exhibited good processability, was prevented from deteriorating in mechanical strength, and was excellent in performance of resistance to rotation and resistance to wear.
[00261] From the comparison between Example 13 and Comparative Example 11, it was confirmed that even when using two or more types of rubber-chassis, the effects of the present invention could be well demonstrated.
[00262] From the comparison between Examples 10 to 12 and Comparative Example 10, it was confirmed that even when using copolymer (A) in combination with the other components, the effects of the present invention could be well demonstrated.


[00263] From the comparison between Examples 15 to 17 and Comparative Example 13, it was confirmed that even when the rubber component (B) was a natural rubber and the copolymer (A) was used in combination with the other components, the effects of the present invention could be well demonstrated.


[00264] From the comparison between Example 18 and Comparative Example 15, it was confirmed that when controlling the amount of the copolymer (A) composed in the rubber composition to the range of 0.1 to 100 parts of dough based on 100 parts of mass of the rubber component (B), the resulting rubber composition exhibited good processability, was prevented from deteriorating in mechanical strength, and was excellent in rotation resistance performance.
[00265] From the comparison between Example 19 and Comparative Example 16, it was confirmed that when silica (D) was composed in an amount of 0.1 to 150 parts of mass based on 100 parts of mass of the rubber (B), the effects of the present invention could be well demonstrated.
[00266] From the comparison between Example 19 and Comparative Example 16, it was confirmed that when carbon black (C) was composed in an amount of 0.1 to 150 parts of mass based on 100 parts of mass of the rubber (B), the effects of the present invention could be well demonstrated.
[00267] From the comparison between Example 19 and Comparative Example 16, it was confirmed that when the average particle sizes of carbon black (C) and silica (D) were controlled for the ranges from 5 to 100 nm and 0.5 at 200 nm, respectively, the resulting rubber composition was excellent in wet grip performance and rotation resistance performance.
[00268] From the comparison between Example 19 and Comparative Example 16, it was confirmed that even when using two or more types of rubber including natural rubber and synthetic rubber, the effects of the present invention could be well demonstrated.


[00269] From the comparison between Example 20 and Comparative Example 18, it was confirmed that when the copolymer (A) was composed in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the rubber component (B) , the resulting rubber composition was excellent in wet grip performance and rotation resistance performance without deterioration in mechanical strength.
[00270] From the comparison between Example 20 and Comparative Example 18, it was confirmed that when silica (D) was composed in an amount of 0.1 to 150 parts of dough based on 100 parts of dough component rubber (B), the effects of the present invention could be well demonstrated.

权利要求:
Claims (16)
[0001]
1. Rubber composition, characterized by the fact that it comprises: (A) a random copolymer comprising a monomer unit (a) derived from an aromatic vinyl compound and a monomer unit (b) derived from farnesene; (B) a rubber component; and at least one selected from the group consisting of (C) carbon black and (D) silica.
[0002]
2. Rubber composition according to claim 1, characterized by the fact that the monomer unit (b) is a monomer unit derived from β-farnesene.
[0003]
Rubber composition according to claim 1 or 2, characterized by the fact that a mass ratio of the monomer unit (a) to a sum of the monomer unit (a) and the monomer unit (b) in the copolymer is 1 to 99% by weight.
[0004]
Rubber composition according to any one of claims 1 to 3, characterized by the fact that the copolymer has a molecular weight distribution (Mw / Mn) of 1.0 to 4.0.
[0005]
Rubber composition according to any one of claims 1 to 4, characterized in that the aromatic vinyl compound is at least one compound selected from the group consisting of styrene, α-methyl styrene and 4-methyl styrene .
[0006]
6. Rubber composition according to claim 5, characterized by the fact that the aromatic vinyl compound is styrene.
[0007]
Rubber composition according to any one of claims 1 to 6, characterized by the fact that the copolymer has a weight average molecular weight (Mw) of 2,000 to 500,000.
[0008]
Rubber composition according to any one of claims 1 to 7, characterized in that the copolymer has a melting viscosity of 0.1 to 3,000 Pa ^ s as measured at 38 ° C.
[0009]
Rubber composition according to any one of claims 1 to 8, characterized in that the copolymer is produced by conducting an anionic polymerization in the presence of an organic metal initiator.
[0010]
Rubber composition according to any one of claims 1 to 9, characterized in that the carbon black (C) has an average particle size of 5 to 100 nm.
[0011]
Rubber composition according to any one of claims 1 to 9, characterized by the fact that silica (D) has an average particle size of 0.5 to 200 nm.
[0012]
Rubber composition according to any one of claims 1 to 9, characterized in that the contents of the copolymer (A) and carbon black (C) in the rubber composition are from 0.1 to 100 parts by mass and from 0.1 to 150 parts by mass, respectively, based on 100 parts by mass of the rubber component (B).
[0013]
Rubber composition according to any one of claims 1 to 9, characterized in that the contents of the copolymer (A) and silica (D) in the rubber composition are from 0.1 to 100 parts by mass and 0.1 to 150 parts by mass, respectively, based on 100 parts by mass of the rubber component (B).
[0014]
Rubber composition according to any one of claims 1 to 9, characterized in that the contents of the copolymer (A), carbon black (C) and silica (D) in the rubber composition are 0, 1 to 100 parts by mass, 0.1 to 150 parts by mass and 0.1 to 150 parts by mass, respectively, based on 100 parts by mass of the rubber component (B).
[0015]
Rubber composition according to any one of claims 1 to 14, characterized in that the rubber component (B) is at least one rubber selected from the group consisting of a styrene-butadiene rubber, a natural rubber, a butadiene rubber and an isoprene rubber.
[0016]
16. Tire, characterized by the fact that it uses the rubber composition, as defined in any one of claims 1 to 15, in at least as part of it.

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同族专利:

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WO2013151067A1|2013-10-10|

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KR20150001745A|2015-01-06|

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JP5400989B1|2014-01-29|

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EP2835383A1|2015-02-11|

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JPWO2013151067A1|2015-12-17|

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TW201345936A|2013-11-16|

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CA2869386A1|2013-10-10|

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EP2835383A4|2015-11-04|

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JP2013231196A|2013-11-14|

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RU2014140207A|2016-05-27|

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CN104411734A|2015-03-11|

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TWI605065B|2017-11-11|

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CN111875740A|2020-11-03|

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PT2835383T|2018-03-08|

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KR20190041025A|2019-04-19|

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HUE038300T2|2018-10-29|

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KR101969309B1|2019-04-16|

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CA2869386C|2020-03-31|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2020-02-04| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-10-06| B09A| Decision: intention to grant|

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2020-12-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2012085930|2012-04-04|

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JP2012-085930|2012-04-04|

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PCT/JP2013/060126|WO2013151067A1|2012-04-04|2013-04-02|Copolymer, rubber composition using same, and tire|

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