rubber composition comprising copolymer containing a monomeric unit derived from farnesene and tire

专利摘要:
COPOLYMER, ITS PRODUCTION PROCESS, RUBBER AND TIRE COMPOSITIONS. The present invention relates to a copolymer containing monomeric units (a) derived from a conjugated diene having 12 or less carbon atoms and monomeric units (b) derived from farnesene. A method for producing the aforementioned copolymer which involves copolymerizing at least conjugated dienes having 12 or less carbon atoms and farnesene. A rubber composition contains copolymer (A), a rubber component (B) and carbon black (C). A rubber composition contains copolymer (A), a rubber component (B) and silica (D). A rubber composition contains copolymer (A), a rubber component (B), carbon black (C) and silica (D). A tire has at least one part where the rubber compound is used.
公开号:BR112014021695B1
申请号:R112014021695-9
申请日:2013-04-02
公开日:2021-05-11
发明作者: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 copolymer containing a monomeric unit derived from farnesene, a rubber composition containing the copolymer, and a tire using the rubber composition. Background Technique
[002] Hitherto, in the field of application of tires for which wear resistance and mechanical strength are required, rubber compositions have been extensively used which are reinforced in mechanical strength by incorporating a reinforcing agent such as carbon black. smoke in a rubber component, such as a natural rubber and a styrene-butadiene rubber. It is known that carbon black exhibits its strengthening effect by physically or chemically adsorbing the aforementioned rubber component onto a surface of the respective carbon black particles. Therefore, when the particle size of the carbon black used in the rubber composition is as large as about 100 to about 200 nm, it is often difficult to achieve a sufficient interaction between the carbon black and the rubber component, so that the resulting rubber composition tends to be difficult to improve in its mechanical strength to a sufficient level. Furthermore, tires produced from a rubber composition tend to have a low resistance and therefore tend to be insufficient in driving stability.
[003] On the other hand, when the carbon black used in the rubber composition has an average particle size as small as about 5 to about 100 nm and therefore a large specific surface area, the composition of The resulting rubber can be improved in properties such as mechanical strength and wear resistance, due to a large interaction between carbon black and the rubber component. Furthermore, tires produced from such a rubber composition can be improved in driving stability due to an increase in their resistance.
[004] However, in the case where carbon black having such a small mean particle size is used in the rubber composition, it is known that the resulting rubber composition tends to be deteriorated in the dispersibility of the carbon black, in this particular due to a high cohesive strength between the carbon black particles. The deteriorated dispersibility of carbon black in the rubber composition tends to induce an extended mixing step and therefore tends to provide an adverse influence on the productivity of the rubber composition. Likewise, carbon black's deteriorated dispersibility tends to motivate heat generation in the rubber composition, so tires produced from this tend to deteriorate in rolling resistance performance and may often not have success in meeting the low rolling resistance requirements of tyres, ie so-called fuel-efficient tyres. Furthermore, in the case where the carbon black used in the rubber composition has a small average particle size, such a problem tends to occur where the resulting rubber composition has a high viscosity and therefore deteriorates in processability.
[005] Thus, the mechanical strength and solidity of the rubber composition for tires are properties having a contradictory relationship with the rolling resistance performance and its processing capacity, and it is therefore considered that the rubber composition it is hardly improved in both properties in a well-balanced way.
[006] In Patent Document 1, as a rubber composition that can be improved in the aforementioned properties in a well-balanced manner, the rubber composition for tires is described which includes a rubber component containing an isoprene-based rubber and a styrene-butadiene rubber, carbon black and a liquid resin that has a softening point between -20 and 20 °C in a specific blending ratio.
[007] Also, Patent Document 2 describes the tire including a rubber component containing a diene-based rubber consisting of a modified styrene-butadiene copolymer and a modified conjugated diene-based polymer, and a filler such as black. smoking in a specific combination relationship.
[008] However, any of the tires described in these Patent Literatures cannot satisfy the mechanical strength and solidity, as well as the rolling resistance performance and processability to a sufficiently high level and therefore there is still a strong demand for tires that are further improved in these properties.
[009] Meanwhile, Patent Document 3 and Patent Document 4 describe a β-farnesene polymer, but fail to have a sufficient study in its practical applications. List of citations Patent Literature Patent Document 1: JP 2011-195804A Patent Document 2: JP 2010-209256A Patent Document 3: WO 2010 / 027463A Patent Document 4: WO 2010 / 027464A Invention Summary Technical problem
[0010] The present invention was carried out in view of the above conventional problems. The present invention provides a copolymer capable of enhancing a dispersibility of a filler such as carbon black and silica in a rubber composition when using the copolymer as a part of the rubber composition; a rubber composition containing the copolymer not only exhibits good processability after blending, molding or curing, but is also excellent in rolling resistance performance and wear resistance, and still hardly suffers from deterioration in mechanical strength; and a tire obtained using the rubber composition. Solution to Problem
[0011] As a result of extensive and intensive research, the present inventors have discovered that when using a copolymer containing a monomeric unit derived from a conjugated diene having no more than 12 carbon atoms and a monomeric unit derived from farnesene in a rubber composition, the resulting rubber composition can be improved not only in processability, but also in mechanical strength, wear resistance and rolling resistance performance. The present invention was carried out on the basis of the above discovery.
[0012] That is, the present invention relates to the following aspects. [1] A copolymer including a monomeric unit (a) derived from a conjugated diene having no more than 12 carbon atoms and a monomeric unit (b) derived from farnesene. [2] A process for producing the copolymer, including at least the step of copolymerizing a conjugated diene having no more than 12 carbon atoms with farnesene. [3] A rubber composition including (A) the above copolymer; (B) a rubber component; and (C) carbon black. [4] A rubber composition including (A) the above copolymer; (B) a rubber component; and (D) silica. [5] A rubber composition including (A) the above copolymer; (B) a rubber component; (C) carbon black; and (D) silica. [6] A tire using the above rubber composition as at least a part of it. Advantageous Effects of the Invention
[0013] According to the present invention, it is possible to provide a copolymer capable of enhancing the dispersibility of a filler such as carbon black and silica in a rubber composition when using the copolymer as a part of the rubber composition; a rubber composition containing the copolymer not only exhibits good processability after blending, molding or curing, but is also excellent in rolling resistance and wear resistance performance, and yet hardly suffers from deterioration in mechanical resistance; and a tire obtained using the rubber composition. Description of Modalities Copolymer
[0014] The copolymer according to the present invention is a copolymer which includes a monomeric unit (a) derived from a conjugated diene having no more than 12 carbon atoms and a monomeric unit (b) derived from farnesene.
[0015] Examples of the conjugated diene having no more than 12 carbon atoms that constitute the monomeric unit (a) include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 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, myrcene and chloroprene . Of these conjugated dienes, preferred are butadiene and myrcene. These conjugated dienes can be used alone or in combination of any two or more of these.
[0016] In the present invention, the monomeric unit (b) can be a monomeric unit derived from α-farnesene or a monomeric unit derived from β-farnesene represented by the following formula (I). However, of these monomeric units, from the viewpoint of facilitated production of the copolymer, the monomeric unit derived from β-farnesene is preferable. Meanwhile, α-farnesene and β-farnesene can be used in combination with each other.

The weight average 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 weight average molecular weight of the copolymer is within the range specified above, the rubber composition mentioned below has a good processability, and can be further improved in the dispersibility of the carbon black or silica combined therein and therefore , can exhibit good rolling resistance performance. Meanwhile, the weighted average molecular weight of the copolymer as used in this specification is the value measured by the method described below in the Examples. In the present invention, two or more types of copolymers which are different in weight average molecular weight from each other can be used in the form of a mixture thereof.
The melt viscosity of the copolymer as measured at 38°C is preferably from 0.1 to 3000 Pa^s, more preferably from 0.6 to 2800 Pa^s, even more preferably from 1.5 to 2600 Pa^s if even more preferably from 1.5 to 2000 Pa^s. When the melt viscosity of the copolymer is within the range specified above, the resulting rubber composition can be easily mixed and can be improved in processability. Meanwhile, in the present specification, the melt viscosity of the copolymer is the value measured by the method described below in the Examples.
[0019] The mass ratio of the monomeric unit (a) to a sum of the monomeric unit (a) and the monomeric unit (b) in the copolymer is preferably from 1 to 99% by mass, more preferably from 10 to 80 % by mass, and even more preferably from 15 to 70% by mass, from the standpoint of enhancing the processability and rolling resistance performance of the resulting rubber composition.
[0020] 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 is within the range specified above, the resulting copolymer may suitably exhibit less variation in its viscosity.
[0021] The copolymer according to the present invention can be any suitable copolymer, as long as it is produced at least by copolymerizing a conjugated diene having no more than 12 carbon atoms with farnesene, and the copolymer can also be produced by copolymerizing the other monomer with the conjugated diene having no more than 12 carbon atoms and farnesene.
[0022] Examples of the other monomer include aromatic vinyl compounds such as styrene, α-methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 2,4-diisopropyl styrene, 2,4- dimethyl styrene, 4-tert-butyl styrene and 5-tert-butyl-2-methyl styrene.
[0023] The content of the other monomer in the copolymer is preferably not more than 50% by mass, more preferably not more than 40% by mass, and even more preferably not more than 30% by mass. Process for the Production of Copolymer
[0024] The copolymer according to the present invention is preferably produced by the production process of the present invention which includes at least the step of copolymerizing a conjugated diene having no more than 12 carbon atoms 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 preferred one is the solution polymerization method. Emulsion Polymerization Method
[0025] The emulsion polymerization method for producing the copolymer may be any suitable conventionally known method. For example, a predetermined amount of a farnesene monomer and a predetermined amount of a monomer derived from a conjugated diene having no more than 12 carbon atoms are emulsified and dispersed in the presence of an emulsifying reagent, and then the resulting emulsion is subjected to emulsion polymerization using a radical polymerization initiator.
[0026] As the emulsifying reagent, for example, a long chain fatty acid salt having 10 or more carbon atoms or a rosin 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.
[0027] As the dispersant for emulsion polymerization, generally water can 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 provides any adverse influence on stability after polymerization.
[0028] Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate; and organic peroxides and hydrogen peroxide.
[0029] In order to adjust the molecular weight of the resulting copolymer, a chain transfer reagent can be used. Examples of the chain transfer reagent 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.
[0030] The temperature used after 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 a continuous polymerization method or a batch polymerization process. The polymerization reaction can be stopped by adding a terminating reagent to the reaction system.
[0031] 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.
[0032] After stopping the polymerization reaction, an antioxidant can be added to the polymerization reaction system, if necessary. Furthermore, after stopping the polymerization reaction, unreacted monomers can be removed from the resulting latex, if necessary. Thereafter, the resulting copolymer is coagulated by adding a salt such as sodium chloride, calcium chloride and potassium chloride as a coagulant thereof and, if necessary, while adjusting the 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 copolymer. The copolymer thus recovered is washed with water and dehydrated, and then dried to obtain the copolymer. Meanwhile, after coagulation of the copolymer, the latex can be premixed, if necessary, with a extender oil in the form of an emulsified dispersion to recover the copolymer as an oil-diluted rubber. Solution Polymerization Method
[0033] The solution polymerization method for producing the copolymer may be any suitable conventionally known method. For example, a farnesene monomer can be polymerized with a conjugated diene-derived monomer having no more than 12 carbon atoms in a solvent, using a Ziegler-based catalyst, a metallocene-based catalyst, or an active metal polymerizable by anion, if necessary, in the presence of a polar compound.
[0034] Examples of the anion polymerizable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and lanthanide-based rare earth metals such as lanthanum and neodymium. Among these active metals, preferable are alkali metals and alkaline earth metals, and more preferable are alkali metals. Alkali metals are most preferably used in the form of an organic alkali metal compound.
[0035] 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 stilbene lithium; polyfunctional organic lithium compounds such as dilithiomethane, dilithionaphthalene, 1,4-dilithiobutane, 1,4-dilithium-2-acetate cyclohexane and 1,3,5-trilithiobenzene; and sodium naphthalene and potassium naphthalene. Among these organic alkali metal compounds, organic lithium compounds are preferred, and more preferred are organic monolithium compounds. The amount of organic alkali metal compound used can be appropriately determined in accordance with a molecular weight of the polymer of farnesene as required, and is preferably 0.01 to 3 parts by mass on the basis of 100 parts by mass of farnesene.
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, dihexyl amine and dibenzyl amine to react with it.
[0037] Examples of the solvent used in solution polymerization include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and iso-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methyl cyclopentane; and aromatic hydrocarbons such as benzene, toluene and xylene.
[0038] The polar compound can be used in anion polymerization to control a microstructure of a random structure or a component derived from farnesene or a component derived from conjugated diene having no more than 12 carbon atoms, without causing the 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 tetramethyl ethylenediamine 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 1000 molar equivalents based on the organic alkali metal compound.
[0039] 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 the above organic alkali metal compounds from the standpoint of easily controlling a molecular weight distribution of the resulting copolymer within the aforementioned range.
[0040] The temperature used in the above polymerization reaction is generally from -80 to 150 °C, preferably from 0 to 100 °C and more preferably from 10 to 90 °C. The polymerization method can be a batch method or a continuous method. Conjugated diene having no more than 12 carbon atoms and farnesene are respectively supplied to the reaction solution in a continuous or intermittent manner such that the compositional ratio of conjugated diene having no more than 12 carbon atoms and farnesene in the system of polymerization is within a specific range, or a mixture of the conjugated diene having no more than 12 carbon atoms and farnesene that has been previously prepared in such a way that a compositional ratio of these compounds is controlled in a specific range is provided to the reaction, whereby it is possible to produce a random copolymer. Alternatively, conjugated diene having no more than 12 carbon atoms and farnesene are sequentially polymerized in the reaction solution such that a compositional ratio of these compounds in the polymerization system is controlled in a specific range, whereby it is possible to produce a block copolymer.
[0041] The polymerization reaction can be stopped by adding an alcohol such as methanol and isopropanol as a terminating reagent to the reaction system. The resulting polymerization reaction solution 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. Modified Copolymer
[0042] The copolymer according to the present invention can be used in a modified form. Examples of a functional group used to modify the copolymer include an amino group, an alkoxysilyl group, a hydroxyl group, an epoxy group, a carboxyl group, a carbonyl group, a mercapto group, an isocyanate group and an acid anhydride group.
[0043] As the method of production of the modified copolymer, for example, the method in which before adding the termination reagent, a coupling reagent such as tin tetrachloride, tetrachlorosilane, dimethyl dichlorosilane, dimethyl diethoxysilane, tetramethoxysilane can be used , tetraethoxysilane, 3-aminopropyl triethoxysilane, tetraglycidyl-1,3-bisaminomethyl cyclohexane and 2,4-tolylene diisocyanate, which are capable of reacting with an active end of the polymer chain, a polymer-modifying reagent. chain end 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. Furthermore, the isolated copolymer can be grafted with maleic anhydride, or the like.
[0044] In the modified copolymer, the site of the polymer where the functional group is introduced may be a chain end or a side chain of the polymer. Furthermore, these functional groups can be used alone or in combination of any two or more of them. The modifying reagent can be used in an amount of 0.01 to 100 molar equivalents and preferably between 0.01 to 10 molar equivalents on the basis of the organic alkali metal compound. Rubber Composition
[0045] 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.
[0046] 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.
[0047] 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. Rubber Component (B)
[0048] Examples of the rubber component (B) used herein include a natural rubber, a styrene-butadiene rubber (hereinafter also referred to simply 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, an acrylonitrile butadiene copolymer rubber, and a chloroprene rubber. Of these rubbers, preferable are SBR, a natural rubber, a butadiene rubber and an isoprene rubber, and most preferable are SBR and a natural rubber. These rubbers can be used alone or in combination of any two or more of these. Natural rubber
[0049] Examples of the natural rubber used as the rubber component (B) in the present invention include the natural rubbers commonly used in the tire industries, for example, TSRs such as SMR, SIR and STR; and RSS, etc.; high purity natural rubbers; and modified natural rubbers, such as epoxy-subjected natural rubbers, hydroxylated natural rubbers, hydrogenated natural rubbers, and grafted natural rubbers. Among these natural rubbers, STR20, SMR20 and RSS#3 are preferable from the point of view of less variation in quality and good availability. These natural rubbers can be used alone or in combination of any two or more of these. Synthetic rubber
[0050] 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, an ethylene propyl rubber. lene diene, an acrylonitrile butadiene copolymer rubber, and a chloroprene rubber. Of these rubbers, preferred are SBR, an isoprene rubber and a butadiene rubber. SBR
[0051] As SBR, one can use those generally used in tire applications. More specifically, the SBR preferably has a styrene content from 0.1 to 70% by mass and more preferably from 5 to 50% by mass. Likewise, the SBR preferably has a vinyl content of from 0.1 to 60% by mass and more preferably from 0.1 to 55% by mass.
The weight average molecular weight (Mw) of the 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 weight average molecular weight of SBR is within the range specified above, the resulting rubber composition can be improved in both processability and mechanical strength. Meanwhile, in the present specification, the weighted average molecular weight is the value measured by the method described below in the Examples.
[0053] 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 Tg of the SBR to the range specified above, it is possible to suppress the increase in the viscosity of the SBR and improve its handling property. Method for the Production of SBR
[0054] The SBR (B-1) used in the present invention can be produced through the 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 polymerization method in large scale. Of these polymerization methods, preferable are an emulsion polymerization method and a solution polymerization method.
[0055] (i) Emulsion Polymerized Styrene-Butadiene Rubber (E-SBR)
[0056] E-SBR can be produced by a 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 reagent, and then the resulting emulsion is subjected to emulsion polymerization using a radical polymerization initiator .
[0057] As the emulsifying reagent, for example, a long chain fatty acid salt having 10 or more carbon atoms or a rosin 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.
[0058] As a dispersant for the above emulsion polymerization, water can generally be used. The dispersant may also contain a water-soluble organic solvent such as methanol and ethanol, unless the use of such an organic solvent provides any adverse influence on stability after polymerization.
[0059] Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides and hydrogen peroxide.
[0060] In order to properly adjust the molecular weight of the obtained E-SBR, a chain transfer reagent can be used. Examples of the chain transfer reagent 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.
[0061] The temperature used after 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 a continuous polymerization method or a batch polymerization process. The polymerization reaction can be stopped by adding a terminating reagent to the reaction system.
[0062] 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.
[0063] After stopping the polymerization reaction, an antioxidant can be added to the polymerization reaction system if necessary. Furthermore, after stopping the polymerization reaction, unreacted monomers can be removed from the resulting latex, if necessary. Thereafter, the obtained polymer is coagulated by adding a salt such as sodium chloride, calcium chloride and potassium chloride as a coagulant and, if necessary, while adjusting the pH value of the coagulation system by adding a acid such as nitric acid and sulfuric acid to this, 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 strip dryer or something similar to obtain the E-SBR. Meanwhile, after coagulation of the polymer, the latex can be premixed, if necessary, with a extender oil in the form of an emulsified dispersion to recover the polymer as an oil thinned rubber.
[0064] (ii) Solution Polymerized Styrene-Butadiene Rubber (S-SBR)
[0065] The S-SBR can be produced by a common solution polymerization method. For example, styrene and butadiene are polymerized in a solvent using an anion-polymerizable active metal, if necessary, in the presence of a polar compound.
[0066] Examples of the anion polymerizable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and the rare earth metals based on lanthanides such as lanthanum and neodymium. Among these active metals, preferable are alkali metals and alkaline earth metals, and more preferable are alkali metals. Alkali metals are most preferably used in the form of an organic alkali metal compound.
[0067] 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 dilithiomethane, 1,4-dilithiobutane, 1,4-dilithium-2-ethyl cyclohexane and 1,3,5-trilithiobenzene; and sodium naphthalene and potassium naphthalene. Among these organic alkali metal compounds, organic lithium compounds are preferred, and more preferred are organic monolithium compounds. The amount of organic alkali metal compound used can be appropriately determined in accordance with a molecular weight of the S-SRB as required.
[0068] 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, dihexyl amine and dibenzyl amine to react with it.
[0069] The polar compound used in solution polymerization is not particularly limited, as long as the compound does not cause the deactivation of the reaction in the anionic polymerization and can normally be used to control a microstructure of a butadiene-derived component and the 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 ethylenediamine 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 1000 molar equivalents based on the organic alkali metal compound.
[0070] 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 an amount in which a monomer is generally dissolved in them at a concentration of 1 to 50% by mass.
[0071] The temperature used in the above polymerization reaction is generally from -80 to 150 °C, preferably from 0 to 100 °C and more preferably from 30 to 90 °C. The polymerization method can be a batch method or a continuous method. Also, in order to improve a random copolymerization capability between styrene and butadiene, styrene and butadiene are preferably supplied to the reaction solution in a continuous or intermittent manner, such that a compositional relationship between styrene and butadiene in the polymerization system is within a specific range.
[0072] The polymerization reaction can be stopped by adding an alcohol such as methanol and isopropanol as a terminating reagent to the reaction system. The polymerization reaction solution obtained after stopping the polymerization reaction can be directly subjected to drying or steam extraction to remove its solvent, thus recovering the S-SBR as directed. Meanwhile, prior to solvent removal, the polymerization reaction solution can be pre-mixed with a extender oil to recover the S-SBR as an oil-diluted rubber. Modified Styrene-Butadiene Rubber (Modified SBR)
[0073] In the present invention, a modified SBR produced by introducing a functional group into the SBR can also be used. Examples of the functional group to be introduced into the SBR include an amino group, an alkoxysilyl group, a hydroxyl group, an epoxy group and a carboxyl group.
[0074] As the method of producing the modified SBR, for example, the method in which before adding the termination reagent, a coupling reagent such as tin tetrachloride, tetrachlorosilane, dimethyl dichlorosilane, dimethyl diethoxysilane, tetramethoxysilane can be used , tetraethoxysilane, 3-aminopropyl triethoxysilane, tetraglycidyl-1,3-bisaminomethyl cyclohexane and 2,4-tolylene diisocyanate which are capable of reacting with an active end of the polymer chain, an end-modifying reagent chain 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.
[0075] In modified SBR, the site of the polymer where the functional group is introduced can be a chain end or a side chain of the polymer. Isoprene rubber
[0076] Isoprene rubber can be a commercially available isoprene rubber which can be obtained, for example, by polymerization using a Ziegler-based catalyst such as titanium-trialkyl aluminum tetrahalide-based catalysts, aluminum chloride-diethyl cobalt based catalysts, trialkyl aluminum-boron trifluoride based catalysts and diethyl aluminum chloride-nickel based catalysts; a rare earth metal catalyst based on lanthanide such as triethyl aluminum-organic acid neodymium salt-Lewis acid based catalysts; or an organic alkali metal compound as used similarly for the production of S-SBR. Among these isoprene rubbers, preferred are isoprene rubbers obtained by polymerization using the Ziegler-based catalyst, because of their high cis-isomer content. In addition, those isoprene rubbers having an ultra-high cis-isomer content, which are produced using the lanthanide-based rare earth metal catalyst, can also be used.
[0077] Isoprene rubber has a vinyl content of 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less. When the vinyl content of isoprene rubber is more 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 isoprene rubber can vary depending on its vinyl content, and is preferably -20°C or lower and more preferably -30°C or lower.
[0078] The weight average molecular weight of the isoprene rubber is preferably from 90,000 to 2,000,000 and more preferably from 150,000 to 1,500,000. When the weight average molecular weight of the isoprene rubber is within the range indicated above, the resulting rubber composition can show good processability and good mechanical strength.
[0079] Isoprene rubber may partially have a branched structure or may partially contain a polar functional group by using a polyfunctional type modifying reagent, for example, a modifying reagent such as tin tetrachloride, silicon tetrachloride, a alkoxysilane containing an epoxy group in its molecule, and an alkoxysilane containing amino groups. Butadiene rubber
[0080] Butadiene rubber can be a commercially available butadiene rubber which can be obtained, for example, through polymerization using a Ziegler-based catalyst such as titanium tetrahalide-based catalysts. trialkyl aluminum, aluminum chloride-diethyl cobalt based catalysts, trialkyl aluminum-boron trifluoride based catalysts and diethyl aluminum chloride-nickel based catalysts; a rare earth metal catalyst based on lanthanide such as triethyl aluminum-organic acid neodymium salt-Lewis acid based catalysts; or 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, because of their high cis isomer content. In addition, those butadiene rubbers having an ultra-high cis-isomer content, which are produced using the lanthanide-based rare earth metal catalyst, can also be used.
[0081] Butadiene rubber has a vinyl content of 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less. When the vinyl content of the butadiene rubber is more than 50% by mass, 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 butadiene rubber can vary depending on its vinyl content, and is preferably -40°C or lower and more preferably -50°C or lower.
[0082] The weight average molecular weight of the butadiene rubber is preferably from 90,000 to 2,000,000 and more preferably from 150,000 to 1,500,000 and even more preferably from 250,000 to 800,000. When the weight average molecular weight of butadiene rubber is within the range specified above, the resulting rubber composition can exhibit good processability and good mechanical strength.
[0083] Butadiene rubber may partially have a branched structure or may partially contain a polar functional group through the use of a polyfunctional type modifying reagent, for example, a modifying reagent such as tin tetrachloride, silicon tetrachloride, a alkoxysilane containing an epoxy group in its molecule, and an alkoxysilane containing amino groups.
[0084] As synthetic rubber other than SBR, isoprene rubber and butadiene rubber one or more rubbers selected from the group consisting of a butyl rubber, a halogenated butyl rubber, an ethylene propylene diene rubber can be used , an acrylonitrile butadiene 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.
[0085] In the present invention, when using the rubber component (B) in combination with the aforementioned copolymer (A), it is possible to improve the processability of the resulting rubber composition, a carbon black dispersibility, silica, etc., in that particular and a rolling resistance performance of it.
[0086] When using a mixture of two or more types of synthetic rubbers, the combination of synthetic rubbers can be optionally selected unless the effects of the present invention are adversely influenced. Also, the various properties of the resulting rubber composition such as rolling resistance performance and wear resistance can be adequately controlled by selecting a suitable combination of synthetic rubbers.
[0087] Meanwhile, 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.
[0088] 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 by mass mass, based on 100 mass parts of the above rubber component (B) from the point of view of accentuating the rolling resistance performance and a wear resistance of the rubber composition. Smoke Black (C)
[0089] Examples of carbon black (C) usable in the present invention include carbon blacks such as furnace black, channel black, thermal black, acetylene black and Ketjen black. Of these carbon blacks, from the viewpoints of a high cure rate and improved mechanical strength of the rubber composition, oven black is preferable.
Examples of commercially available products include "DIABLACK" furnace black available from Mitsubishi Chemical Corp, and "SEAST" available from Tokai Carbon Co., Ltd. Examples of commercially available acetylene black products include "DENKA-BLACK" available from Denki Kagaku Kogyo KK Examples of commercially available products of Ketjen Black include "ECP600JD" available from Lion Corp.
[0091] Carbon black (C) can be subjected to a 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 to conduct a treatment of surface oxidation of these, from the point of view of improving the wetting capacity or the dispersibility of the carbon black (C) in the copolymer (A) and the rubber component (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 2000 to 3000 °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, metaboric acid and tetraboric acid can be suitably used ) and its salts, boron carbides (such as, for example, B4C and B6C), boron nitride (such as BN) and other boron compounds.
[0092] The average particle size of carbon black (C) can be controlled by spraying or the like. In order to pulverize the carbon black (C), a high speed rotary mill (such as a hammer mill, a pin mill and a cage mill) or various ball mills (such as a ball mill) can be used. rolling mill, a vibrating mill and a planetary mill), an agitation mill (such as a globule mill, a friction mill, a flow tube mill and an annular mill) or the like.
[0093] 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 from the point of view of improving the ability to dispersion and mechanical strength of the rubber composition.
[0094] Meanwhile, the average particle size of carbon black (C) can be determined by calculating an average value of carbon black particle diameters measured using a transmission-type electron microscope.
[0095] In the rubber composition of the present invention, carbon black (C) is preferably composed of an amount of 0.1 to 150 pairs by mass, more preferably from 2 to 150 parts by mass, even more preferably of 5 to 90 parts by mass and even more preferably from 20 to 80 parts by mass on the basis of 100 parts by mass of the rubber component (B). When the amount of carbon black (C) combined is within the range specified above, the resulting rubber composition is not only excellent in mechanical strength, strength and processability, but also has good carbon black dispersibility. smoke (C) in this particular. Silica (D)
[0096] Examples of silica (D) include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate and aluminum silicate. Of these silicas, from the standpoint of further improving the processability, mechanical strength and wear resistance of the resulting rubber composition, wet silica is preferred. These silicas can be used alone or in combination of any two or more of these.
[0097] Silica (D) preferably has an average particle size from 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 intensifying the processability, rolling resistance performance, mechanical strength and wear resistance of the resulting rubber composition.
[0098] However, the mean particle size of silica (D) can be determined by calculating an average value of the diameters of the silica particles measured using a transmission-type electron microscope.
[0099] In the rubber composition of the present invention, silica (D) is preferably combined with an amount of from 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, on the basis of 100 parts by mass of the rubber component (B). When the combined amount of silica (D) is within the range specified above, the resulting rubber composition can be improved in processability, rolling resistance performance, mechanical strength and wear resistance.
[00100] The rubber composition according to the present invention more preferably contains the above copolymer (A), carbon black (C) and silica (D) in amounts from 0.1 to 100 parts by mass, from 0 .1 to 150 parts by mass and 0.1 to 150 parts by mass, respectively, on the basis of 100 parts by mass of the above rubber component (B). Optional Components Silane Coupling Reagent
[00101] The rubber composition according to the present invention preferably also contains a silane coupling reagent. As the silane coupling reagent, a sulfide-based compound, a mercapto-based compound, a vinyl-based compound, an amine-based compound, a glycidoxy-based compound, a compound based of nitro, a chlorine-based compound, etc.
[00102] Examples of the sulfide-based compound include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide , bis(3-trimethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, 3-trimethoxysilylpropyl-N,N-dimethyl thiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethyl thiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N,N-dimethyl thiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide and 3-trimethoxysilylpropyl methacrylosulfide monosulfide.
[00103] Examples of the mercapto-based compound include 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 2-mercaptoethyl trimethoxysilane and 2-mercaptoethyl triethoxysilane.
[00104] Examples of the vinyl-based compound include vinyl triethoxysilane and vinyl trimethoxysilane.
[00105] Examples of the amino-based compound include 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane and 3-(2-aminoethyl)aminopropyl trimethoxysilane.
[00106] Examples of the glycidoxy-based compound include Y-glycidoxypropyl triethoxysilane, Y-glycidoxypropyl trimethoxysilane, Y-glycidoxypropyl methyl diethoxysilane and Y-glycidoxypropyl methyl dimethoxysilane.
[00107] Examples of the nitro-based compound include 3-nitropropyl trimethoxysilane and 3-nitropropyl triethoxysilane.
[00108] Examples of the chlorine-based compound include 3-chloropropyl trimethoxysilane, 3-chloropropyl triethoxysilane, 2-chloroethyl trimethoxysilane and 2-chloroethyl triethoxysilane.
[00109] These silane coupling reagents can be used alone or in combination of any two or more of these. Of these silane coupling reagents, from the viewpoints of high addition effect and low cost, preferred are bis(3-triethoxysilylpropyl)disulfide, bis(3-triethoxysilylpropyl)tetrasulfide and 3-mercaptopropyl trimethoxysilane.
[00110] 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 by mass in mass based on 100 parts by mass of silica (D). When the content of the silane coupling reagent in the rubber composition is within the range indicated above, the resulting rubber composition can be enhanced in dispersibility, coupling effect, reinforcing property and wear resistance. Other Loads
[00111] For the purposes of enhancing the mechanical strength of the rubber composition, the improvement of various properties such as heat resistance and its resistance to weathering, control of its solidity, and also improve economy by adding a thinner The rubber composition according to the present invention may further contain a charge other than carbon black (C) and silica (D), if necessary.
[00112] The different charge of carbon black (C) and silica (D) can be appropriately selected according to the applications of the rubber composition obtained. For example, as the filler, 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, barium sulfate, oxide can be used. titanium, fiberglass, fibrous fillers and glass balloons. The content of the above filler in the rubber composition of the present invention, if combined therein, is preferably 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 on the basis of 100 parts by mass of the rubber component (B). When the filler content in the rubber composition is within the range indicated above, the resulting rubber composition can be further improved in mechanical strength.
[00113] The rubber composition according to the present invention may also contain, if necessary, a softening reagent for the purpose of improving the processability, the flowability or the like of the resulting rubber composition, unless the effects of the present invention are adversely influenced. Examples of the softening reagent include a process oil such as a silicone oil, an aromatic oil, TDAE (treated distilled aromatic extracts), MES (gently extracted solvates), (RAE residual aromatic extracts), a paraffin oil and a naphthene oil; a resin component such as aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, C9 based resins, rosin based resins, coumarone-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. Meanwhile, the above copolymers can be in the form of a block copolymer or a random copolymer. The liquid polymer preferably has a weight average molecular weight of 500 to 100,000 from the standpoint of good processability of the resulting rubber composition. The above process oil, resin component or liquid polymer as a softening reagent is preferably composed of the rubber composition of the present invention in an amount of less than 50 parts by mass on the basis of 100 parts by mass of the rubber component (B).
[00114] The rubber composition according to the present invention may also contain a homopolymer of β-farnesene unless the effects of the present invention are adversely influenced. The content of β-farnesene homopolymer in the rubber composition, if combined therein, is preferably less than 50 parts by mass, based on 100 parts by mass of the rubber component (B).
[00115] The rubber composition according to the present invention may also contain, if necessary, one or more additives selected from the group consisting of an antioxidant, an oxidation inhibitor, a wax, a lubricant, a light stabilizer, a retarder a burn agent, a processing aid, a dye such as pigments and dyes, a flame retardant, an antistatic reagent, a deglaze reagent, an antiblocking reagent, an ultraviolet absorbent, a release reagent, a foaming reagent , an antimicrobial reagent, a mildew-proof reagent and a perfume, for the purposes of improving the weather resistance, a heat resistance, an oxidation resistance, or the like, of the resulting rubber composition, unless that the effects of the present invention are adversely influenced.
[00116] Examples of the oxidation inhibitor include hindered phenol-based compounds, phosphorus-based compounds, lactone-based compounds and hydroxyl-based compounds.
[00117] Examples of the antioxidant include amine-ketone compounds, imidazole-based compounds, amine-based compounds, phenol-based compounds, sulfur-based compounds and phosphorus-based compounds.
[00118] The rubber composition of the present invention is preferably used in the form of a cross-linked product produced by the addition of a cross-linking reagent. Examples of the crosslinking reagent include sulfur, sulfur compounds, oxygen, organic peroxides, phenolic resins and amino resins, quinone and quinone dioxime derivatives, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, halides metals and organic metal halides, and silane compounds. Among such crosslinking reagents, preferred are sulfur and sulfur compounds. These crosslinking reagents can be used alone or in combination of any two or more of these. The crosslinking reagent is preferably compounded into the rubber composition in an amount of 0.1 to 10 parts by mass on the basis of 100 parts by mass of the rubber component (B).
[00119] When using sulfur as the cross-linking reagent, a vulcanization aid or a vulcanization accelerator is preferably used in combination with the cross-linking reagent.
[00120] Examples of the vulcanizing aid include fatty acids such as stearic acid and metal oxides such as zinc oxide.
[00121] Examples of the vulcanization accelerator include guanidine based compounds, sulphen amide based compounds, thiazole based compounds, thiuram based compounds, thiourea based compounds, dithiocarbamic acid based compounds, based compounds aldehyde-amine or aldehyde-ammonia-based compounds, imidazoline-based compounds and xanthate-based compounds. These vulcanization aids or vulcanization accelerators can be used singly or in combination of any two or more of these. The vulcanizing aid or vulcanizing accelerator is preferably combined with the rubber composition of the present invention in an amount of 0.1 to 15 parts by mass, based on 100 parts by mass of the rubber component (B).
[00122] 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, provided that the respective components are uniformly mixed together. The method of uniformly mixing the respective components can be carried out, for example, using a closed type mixer of a contact type or a gear type such as a kneader rudder, a Brabender, a Banbury mixer and an internal mixer, a single screw extruder, a twin screw extruder, a mixing roller, a roller or the like in a temperature range of generally 70 to 270 °C. Tire
[00123] The tire according to the present invention is produced through the use of the rubber composition according to the present invention, at least as a part thereof, and therefore can exhibit good mechanical strength and excellent strength performance to the bearing. Examples
[00124] The present invention will be described in greater detail below by 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.
[00125] The respective components used in the following Examples and Comparative Examples are as follows. Copolymer of (A):
[00126] Copolymers (A-1) to (A-4) obtained in Production Examples 1 to 4, respectively. Rubber component (B):
[00127] Natural rubber "STR20" (natural rubber from Thailand)
[00128] Styrene-butadiene rubber "JSR1500" (available from JSR Corp.)
[00129] "BR-01" Butadiene Rubber (available from JSR Corp)
[00130] Weighted average molecular weight = 550,000
[00131] Cis isomer content = 95% by mass Carbon Black (C-1):
[00132] "DIABLACK H" available from Mitsubishi Chemical Corp.; average particle size: 30 nm Carbon Black (C-2):
[00133] "DIABLACK I" available from Mitsubishi Chemical Corp.; mean particle size: 20 nm carbon black (C-3):
[00134] "SEAST V" available from Tokai Carbon Co., Ltd.; average particle size: 60 nm Silica (D-1):
[00135] "ULTRASIL7000GR" available from Evonik Degussa Japan Co., Ltd.; wet silica; average particle size: 14 nm Silica (D-2):
[00136] "AEROSIL 300" available from Nippon Aerosil Co., Ltd.; dry silica; average particle size: 7 nm Silica (D-3):
[00137] "NIPSIL E-74P" available from Tosoh Silica Corporation; wet silica; average particle size: 74 nm Polyisoprene:
[00138] Polyisoprene obtained in Production Example 5 β-farnesene homopolymer:
[00139] β-farnesene homopolymer obtained in Production Example 6 TDAE:
[00140] "VivaTec500" available from H & R Corp. Silane Coupling Reagent:
[00141] "Si75" (available from Evonik Degussa Japan Co., Ltd.) Stearic acid:
[00142] "LUNAC S-20" (available from Kao Corp.) Zinc Oxide:
[00143] Zinc Oxide (available from Sakai Chemical Industry Co., Ltd.) Antioxidant (1):
[00144] "NOCRAC 6C" (available from Ouchi Shinko Chemical Industrial Co., Ltd.) Antioxidant (2):
[00145] "ANTAGE RD" (available from Kawaguchi Chemical Industry Co., Ltd.) Sulfur:
[00146] 200 mesh fine sulfur powder (available from Tsurumi Chemical Industry Co., Ltd.) Vulcanization accelerator (1):
[00147] "NOCCELER NS" (available from Ouchi Shinko Chemical Industrial Co., Ltd.) Vulcanization accelerator (2):
[00148] "NOCCELER CZ-G" (available from Ouchi Shinko Chemical Industrial Co., Ltd.) Vulcanization accelerator (3):
[00149] "NOCCELER D" (available from Ouchi Shinko Chemical Industrial Co., Ltd.) Vulcanization accelerator (4):
[00150] "NOCCELER TBT-N" (available from Ouchi Shinko Chemical Industrial Co., Ltd.) Production Example 1: Production of β-phamesene/butadiene random copolymer (A-1)
[00151] A pressure reaction vessel previously purged with nitrogen and then dried was charged with 1490 g of cyclohexane as solvent and 13.3 g of sec-butyl lithium (in the form of a cyclohexane solution of 10, 5% by mass) as an initiator. The contents of the reaction vessel were heated to 50 °C, and 1500 g of a mixture of butadiene (a) and β-farnesene (b) (which was previously prepared by mixing 300 g of butadiene (a) and 1200 g of β-farnesene (b) in a cylinder) were added at a rate of 10 ml/min, and the mixture was polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating the water from the thus washed polymerization reaction solution, the resulting solution was dried at 70 °C for 12 h, thereby obtaining a random β-farnesene/butadiene copolymer (A-1). Various properties of the thus obtained β-phamesene/butadiene random copolymer (A-1) are shown in Table 1. Production Example 2: Production of β-phamesene/butadiene random copolymer (A-2)
[00152] A pressure reaction vessel previously purged with nitrogen and then dried was charged with 1790 g of cyclohexane as solvent and 12.4 g of sec-butyl lithium (in the form of a cyclohexane solution of 10, 5% by mass) as an initiator. The contents of the reaction vessel were heated to 50 °C, and 1200 g of a mixture of butadiene (a) and β-farnesene (b) (which was previously prepared by mixing 480 g of butadiene (a) and 720 g of β-farnesene (b) in a cylinder) were added at a rate of 10 ml/min, and the mixture was polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating the water from the thus washed polymerization reaction solution, the resulting solution was dried at 70 °C for 12 h, thereby obtaining a β-phamesene/butadiene random copolymer (A-2). Various properties of the thus obtained β-farnesene/butadiene random copolymer (A-2) are shown in Table 1. Production Example 3: Production of β-famesene/butadiene block copolymer (A-3)
[00153] A pressure reaction vessel previously purged with nitrogen and then dried was charged with 1790 g of cyclohexane as a solvent and 12.4 g of sec-butyl lithium (in the form of a cyclohexane solution of 10 .5% by mass) as an initiator. The contents of the reaction vessel were heated to 50 °C, and 480 g of butadiene (a) were added at a rate of 10 ml/min, and the mixture was polymerized for 1 h. Successively, 720 g of β-farnesene (b) was added to the polymerization reaction solution at a rate of 10 ml/min, and the mixture was further 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 thus washed, the resulting solution was dried at 70°C for 12 h, thereby obtaining a β-farnesene/butadiene block copolymer (A-3). Various properties of the thus obtained β-farnesene/butadiene block copolymer (A-3) are shown in Table 1. Production Example 4: Production of β-famesene/butadiene/β-farnesene block copolymer (A- 4)
[00154] A pressure reaction vessel previously purged with nitrogen and then dried was charged with 1790 g of cyclohexane as a solvent and 12.4 g of sec-butyl lithium (in the form of a 10 de cyclohexane solution .5% by mass) as an initiator. The contents of the reaction vessel were heated to 50 °C, and 360 g of β-farnesene (b) was added at a rate of 10 ml/min, and the mixture was polymerized for 1 h. Successively, 480 g of butadiene (a) were added to the polymerization reaction solution at a rate of 10 ml/min, and the mixture was further polymerized for 1 h. Successively, 360 g of β-farnesene (b) was added to the polymerization reaction solution at a rate of 10 ml/min, and the mixture was further polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating the water from the thus washed polymerization reaction solution, the resulting solution was dried at 70 °C for 12 h, thus obtaining a copolymer in β-famesene/butadiene/β-farnesene block copolymer (A- 4). Various properties of the thus obtained β-farnesene/butadiene/β-farnesene block copolymer (A-4) are shown in Table 1. Production Example 5: Polyisoprene production
[00155] A pressure reaction vessel previously purged with nitrogen and then dried was charged with 600 g of hexane and 44.9 g of n-butyl lithium (as a 17 wt% hexane solution). The contents of the reaction vessel were heated to 70 °C, and 2050 g of isoprene was added, 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 thus washed, the resulting solution was dried at 70°C for 12 h, thereby obtaining a polyisoprene having properties as shown in Table 1. Production Example 6: Production of β-phamesene homopolymer
[00156] 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 (as a 17 wt% hexane solution) as an initiator. The contents of the reaction vessel were heated to 50 °C, and 272 g of β-farnesene were added, and the mixture was polymerized for 1 h. Successively, the resulting polymerization reaction solution was treated with methanol and then washed with water. After separating the water from the thus washed polymerization reaction solution, the resulting solution was dried at 70 °C for 12 h, thus obtaining a β-farnesene homopolymer. Various properties of the thus obtained homopolymer of β-farnesene are shown in Table 1.
[00157] Meanwhile, the weight average molecular weight and melt viscosity of each of copolymer (A), polyisoprene and β-farnesene homopolymer was measured by the following methods. Weighted Average Molecular Weight Measurement Method
[00158] The weighted average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of each of the copolymer (A), polyisoprene and β-farnesene homopolymer was 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.
[00159] Apparatus: GPC device "GPC8020" available from Tosoh Corp
[00160] Separation column: "TSKgelG4000HXL" available from Tosoh Corp
[00161] Detector: "RI-8020" available from Tosoh Corp
[00162] Eluent: Tetrahydrofuran
[00163] Eluent flow rate: 1.0 ml/min
[00164] Sample concentration: 5 mg/10 ml
[00165] Column temperature: 40°C Melting Viscosity Measurement Method
[00166] The melt viscosity of each of copolymer (A), polyisoprene and β-farnesene homopolymer was measured at 38°C using a type B viscometer available from Brookfield Engineering Labs. Inc.

Examples 1 to 13 and Comparative Examples 1 to 8
[00167] Copolymer (A), rubber component (B), carbon black (C), silica (D), polyisoprene, silane coupling reagent, TDAE, stearic acid, zinc oxide and antioxidant were loaded in the respective composition ratios as shown in Tables 2 to 4 into a closed-type Banbury mixer and mixed together for 6 min such that the onset temperature was 75°C and the resin temperature reached 160°C. The resulting mixture was removed from the blender, and cooled to room temperature. Soon after, the mixture was placed on a mixing roller, and after the addition of sulfur and the vulcanization accelerator, the contents of the mixing roller were mixed 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.
Furthermore, the resulting rubber composition was pressure molded (at 145 °C for 20 to 60 min) to prepare a blade (thickness: 2 mm). The blade thus prepared was evaluated with respect to a tensile strength at break, a loss of DIN abrasion and a rolling resistance performance by the following methods. The results are shown in Tables 2 to 4. Mooney Viscosity
[00169] As an index of a processability of the rubber composition, the Mooney viscosity (ML1+4) of the rubber composition before being cured was measured at 100 °C according to JIS K 6300. respective Examples and Comparative Examples shown in Table 2 are relative values based on 100 as the value of Comparative Example 3. 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 5 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 more indicates more excellent processability. (2) Break Traction Force
[00170] A blade prepared from the rubber composition produced in the respective Examples and Comparative Examples was punched into a test piece in the form of JIS No. 3 dumbbells, and the obtained test piece was subjected to measurement of its tensile force at rupture using a tensile tester available from 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 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 5. The values of the respective Examples and Comparative Examples shown in Table 4 are relative values based on 100 as the value from Comparative Example 8. However, the higher value indicates a better tensile strength at breakage of the rubber composition. (3) DIN Abrasion Loss
[00171] The rubber composition was measured by the DIN abrasion loss under a load of 10 N at 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 values relative values based on 100 as the value of Comparison Example 3. 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 5. 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. Meanwhile, the lower value indicates less abrasion loss from the rubber composition. (4) Bearing Strength Performance
[00172] A blade 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 long x 7 mm wide. The test piece thus obtained was subjected to the measurement of tan um as an index of a rolling resistance performance of the rubber composition, using a dynamic viscoelasticity measuring mechanism available from GABO GmbH under conditions including a measurement temperature of 60° C, a frequency of 10 Hz, a static force of 10% and a dynamic force 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. 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 5. 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. Meanwhile, lower value indicates excellent rolling resistance performance of the rubber composition.

[00173] The rubber compositions obtained in Examples 1 to 4 showed a low Mooney viscosity compared to that of Comparative Example 3 and therefore a good processability. Furthermore, the rubber compositions obtained in Examples 1 to 4 were excellent in rolling resistance performance and wear resistance compared to those of Comparative Examples 1 and 2, and were also prevented from being deteriorated in mechanical strength.


[00174] The rubber compositions obtained in Examples 5 to 8 showed a low Mooney viscosity compared to that of Comparative Example 5 and therefore a good processability. Furthermore, the rubber compositions obtained in Examples 5 to 8 were excellent in rolling resistance performance and wear resistance compared to those of Comparative Example 4, and were also prevented from being deteriorated in mechanical strength.
[00175] From the comparison between Example 9 and Comparative Example 6, it was confirmed that when controlling an average particle size of carbon black (C) in the range of 5 to 100 nm and an average particle size of carbon black silica (D) in the range of 0.5 to 200 nm, the resulting rubber composition exhibited good processability, was prevented from deteriorating in mechanical strength, and was excellent in rolling resistance and wear resistance performance.

[00177] The rubber compositions obtained in Examples 10 to 13 showed a low Mooney viscosity compared to that of Comparative Example 8 and therefore a good processability. Furthermore, the rubber compositions obtained in Examples 10 to 13 were excellent in rolling resistance performance and wear resistance compared to those of Comparative Example 7, and were also prevented from being deteriorated in mechanical strength. Examples 14 to 20 and Comparative Examples 9 to 14
[00178] Copolymer (A), rubber component (B), carbon black (C), silica (D), homopolymer of β-farnesene, polyisoprene, silane coupling reagent, TDAE, stearic acid, zinc oxide and antioxidant were loaded in their respective blending ratios as shown in Tables 5 and 6 into a closed-type Banbury mixer and mixed together for 6 min such that the onset temperature was 75 °C and the resin temperature reached 160 °C. The resulting mixture was then removed from the blender, and cooled to room temperature. After that, the mixture was placed on a mixing roller, and after adding sulfur and the vulcanization accelerator to it, the contents of the mixing roller were mixed 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.
[00179] Furthermore, the resulting rubber composition was pressure molded (at 145 °C for 25 to 50 min) to prepare a blade (thickness: 2 mm). The blade thus prepared was evaluated for a tensile strength at break and a rolling resistance performance by the above methods. The results are shown in Tables 5 and 6.
[00180] Furthermore, the rubber compositions obtained in Examples 14 to 19 and Comparative Examples 9 to 13 were measured by their loss of DIN abrasion by the above method. The results are shown in Table 5.
[00181] In the meantime, the values of Mooney viscosity, tensile strength at break, DIN abrasion loss and rolling resistance performance of the respective rubber compositions as shown in Table 5, are relative values based on 100 as each. of these values from Comparative Example 13.
[00182] Furthermore, the values of Mooney viscosity, tensile strength at break and rolling resistance performance of the respective rubber compositions as shown in Table 6, are relative values based on 100 as each of these values from Comparative Example 14 .

[00184] From the comparison between Example 14 and Comparative Example 9, it was confirmed that when controlling the amount of copolymer (A) combined in the rubber composition in the range of 0.1 to 100 parts by mass based on 100 bulk parts 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 rolling resistance performance.
[00185] The rubber compositions obtained in Examples 15 and 18 showed a low Mooney viscosity compared to that of Comparative Example 13 and therefore was improved in processing capacity. Furthermore, the rubber compositions obtained in Examples 15 to 18 had a tensile strength at break and a wear resistance that were almost similar to those of Comparative Example 10 or 11, but were excellent in rolling resistance performance compared to that. of Comparative Example 10 or 11, and therefore can be suitably used as a rubber tire composition.
[00186] The rubber composition obtained in Example 19 had a low Mooney viscosity compared to that of Comparative Example 13 and therefore was improved in processability. Furthermore, the rubber composition obtained in Example 19 had a tensile strength that was almost similar to that of Comparative Example 12, but was excellent in wear resistance and rolling resistance performance compared to those of Comparative Example 12, and , therefore, it can be suitably used as a rubber compound for tires.
[00187] From the comparison between Example 19 and Comparative Example 12, it was confirmed that when silica (D) was combined in an amount of 0.1 to 150 parts by mass based on 100 parts by mass of the component rubber (B), the effects of the present invention can also be shown.
[00188] From the comparison between Example 19 and Comparative Example 12, it was confirmed that when carbon black (C) was combined in an amount of 0.1 to 150 parts by mass based on 100 parts by mass of the rubber component (B), the effects of the present invention can also be shown.
[00189] From the comparison between Example 19 and Comparative Example 12, it was confirmed that when the average particle sizes of carbon black (C) and silica (D) were controlled in the ranges from 5 to 100 nm and from 0.5 to 200 nm, respectively, the resulting rubber composition showed good processability, was prevented from deteriorating in mechanical strength, and was excellent in rolling resistance performance and wear resistance.
[00190] From the comparison between Example 19 and Comparative Example 12, it was confirmed that even when using two or more types of rubbers, including natural rubber and synthetic rubber, the effects of the present invention can also be shown .
[00191] From the comparison between Examples 16 to 18 and Comparative Example 10 or 11, it was confirmed that even when using the copolymer of (A) in combination with the other components, the effects of the present invention can also be presented.

[00192] From the comparison between Example 20 and Comparative Example 14, it was confirmed that when copolymer (A) was combined in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the component of rubber (B), the resulting rubber composition showed good processability and was excellent in rolling resistance performance, without deterioration in mechanical strength.
[00193] From the comparison between Example 20 and Comparative Example 14, it was confirmed that when silica (D) was combined in an amount of 0.1 to 150 parts by mass based on 100 parts by mass of the component rubber (B), the resulting rubber composition exhibited good processability and was excellent in rolling resistance performance without deterioration in mechanical strength.

权利要求:
Claims (18)
[0001]
1. Rubber composition, characterized in that it comprises: (A) a copolymer comprising a monomeric unit (a) derived from a conjugated diene having no more than 12 carbon atoms and a monomeric unit (b) derived from farnesene; (B) a rubber component; and one or both (C) carbon black and (D) silica.
[0002]
2. Rubber composition according to claim 1, characterized in that the monomeric unit (b) is a monomeric unit derived from β-farnesene.
[0003]
3. Rubber composition according to claim 1 or 2, characterized in that a mass ratio of the monomeric unit (a) to a sum of the monomeric unit (a) and the monomeric unit (b) in the copolymer is 1 to 99% by mass.
[0004]
4. Rubber composition according to any one of claims 1 to 3, characterized in that the copolymer has a molecular weight distribution (Mw/Mn) from 1.0 to 4.0.
[0005]
5. Rubber composition according to any one of claims 1 to 4, characterized in that the conjugated diene having no more than 12 carbon atoms is at least one compound selected from the group consisting of butadiene and myrcene.
[0006]
6. Rubber composition according to claim 5, characterized in that the conjugated diene having no more than 12 carbon atoms is butadiene.
[0007]
7. Rubber composition according to any one of claims 1 to 6, characterized in that the copolymer has a weighted average molecular weight (Mw) of 2,000 to 500,000.
[0008]
8. Rubber composition according to any one of claims 1 to 7, characterized in that the copolymer has a melt viscosity of 0.1 to 3,000 Pa^s as measured at 38°C.
[0009]
9. Rubber composition, characterized in that it comprises (A) the copolymer as defined in any one of claims 1 to 8; (B) the rubber component; and (C) carbon black.
[0010]
10. Rubber composition, characterized in that it comprises (A) the copolymer as defined in any one of claims 1 to 8; (B) the rubber component; and (D) silica.
[0011]
11. Rubber composition, characterized in that it comprises (A) the copolymer as defined in any one of claims 1 to 8; (B) the rubber component; (C) carbon black; and (D) silica.
[0012]
12. Rubber composition according to claim 9 or 11, characterized in that (C) carbon black has an average particle size of 5 to 100 nm.
[0013]
13. Rubber composition according to claim 10 or 11, characterized in that (D) silica has an average particle size of 0.5 to 200 nm.
[0014]
14. Rubber composition according to claim 9, characterized in that the contents of (A) copolymer and (C) carbon black 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 (B) rubber component.
[0015]
15. Rubber composition according to claim 10, characterized in that the contents of (A) copolymer and (D) silica 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 (B) rubber component.
[0016]
16. Rubber composition according to claim 11, characterized in that the contents of (A) copolymer, (C) carbon black and (D) silica in the rubber composition are from 0.1 to 100 parts by mass, from 0.1 to 150 parts by mass and from 0.1 to 150 parts by mass, respectively, based on 100 parts by mass of the (B) rubber component.
[0017]
17. Rubber composition according to any one of claims 1 to 16, characterized in that the (B) rubber component 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.
[0018]
18. Tire, characterized in that it uses the rubber composition as defined in any one of claims 1 to 17, at least as a part of it.

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同族专利:

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公开号 | 公开日

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PT2835386T|2017-03-10|

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JPWO2013151068A1|2015-12-17|

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CN104350075B|2017-06-20|

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CA2869390C|2020-03-24|

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KR20140146091A|2014-12-24|

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CA2869390A1|2013-10-10|

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US20150057403A1|2015-02-26|

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KR102047639B1|2019-11-21|

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ES2618942T3|2017-06-22|

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KR101969310B1|2019-04-16|

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RU2629197C2|2017-08-25|

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TW201402628A|2014-01-16|

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KR20190040376A|2019-04-17|

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WO2013151068A1|2013-10-10|

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EP2835386A1|2015-02-11|

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JP6435016B2|2018-12-05|

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CN104350075A|2015-02-11|

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JP2017145423A|2017-08-24|

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EP2835386B1|2017-01-11|

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RU2014140206A|2016-05-27|

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JP2014058666A|2014-04-03|

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JP2017145422A|2017-08-24|

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JP6435015B2|2018-12-05|

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EP2835386A4|2015-12-30|

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JP5555814B2|2014-07-23|

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US9850336B2|2017-12-26|

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TWI599583B|2017-09-21|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-12-01| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-11| 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 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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JP2012-085928|2012-04-04|

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JP2012085928|2012-04-04|

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PCT/JP2013/060127|WO2013151068A1|2012-04-04|2013-04-02|Copolymer, rubber composition using same, and tire|

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