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    • 专利摘要:
    "RUBBER AND PNEUMATIC COMPOSITION". The present invention relates to a rubber composition that includes a rubber component (A), a farnesene polymer (B) and silica (C). The present invention also relates to a tire that at least partially comprises said rubber composition.
    公开号:BR112014020827B1
    申请号:R112014020827-1
    申请日:2013-02-18
    公开日:2020-10-13
    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 rubber composition containing a rubber component, a farnesene polymer and silica, and to a tire using the rubber composition. BACKGROUND OF THE TECHNIQUE
    [002] So far, in the field of application of tires for which wear resistance and mechanical resistance are required, rubber compositions have been widely used that are enhanced in mechanical resistance by incorporating a reinforcing agent, such as carbon black or silica, in a rubber component, such as a natural rubber and a styrene-butadiene rubber. When the particle size of carbon black or silica used in the rubber composition is as large as about 100 to about 200 nm, it is generally difficult to obtain a sufficient interaction between carbon black or silica and the rubber composition, so that the resulting rubber composition tends to be hardly improved in mechanical strength to a sufficient degree. In addition, tires produced from such a rubber composition tend to exhibit low hardness and therefore tend to be insufficient in steering stability.
    [003] On the other hand, when the carbon black or silica 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 The resulting rubber can be improved in properties such as mechanical strength and wear resistance due to a great interaction between carbon black, etc., and the rubber component. In addition, tires produced from such a rubber composition can be improved in steering stability due to their increased hardness.
    [004] However, in the case where carbon black or silica having such a small medium particle size is used in the rubber composition, it is known that the resulting rubber composition tends to be deteriorated in the dispersibility of carbon black or carbon black. silica in it, due to a high cohesive force between the carbon black or silica particles. The deteriorated dispersibility of carbon black or silica in the rubber composition tends to induce a prolonged mixing stage and therefore tends to have an adverse influence on the productivity of the rubber composition. Also, the deteriorated dispersibility of carbon black or silica tends to cause heat generation in the rubber composition, so tires produced from it tend to deteriorate in rolling resistance performance and can often fail to meet the requirements for low rolling resistance tires (so called low fuel tires). Furthermore, in the case where the carbon black or the silica used in the rubber composition has a small average particle size, such a problem tends to occur that the resulting rubber composition exhibits a high viscosity and, therefore, is deteriorated in processability. .
    [005] Thus, the mechanical strength and the hardness of the rubber composition for tires are properties that have a contradictory relationship with the rolling resistance performance and processability of it, and it is therefore considered that the rubber composition is hardly improved on both properties in a well balanced way.
    [006] In Patent Document 1, as a rubber composition that can be improved on the properties mentioned above in a well balanced way, a tire is described including a rubber component containing a diene-based rubber consisting of a copolymer of modified styrene-butadiene and a modified conjugated diene-based polymer, and a filler, such as carbon black or silica, in a predetermined combination ratio.
    [007] However, even the tire described in Patent Document 1 fails to satisfy not only mechanical strength and toughness, but also rolling resistance performance and processability with a sufficiently high level and therefore there is still a strong demand for tires that are further improved in these properties.
    [008] In addition, Patent Document 2 describes a rubber composition containing a rubber component, silica and a silane coupling agent having a specific molecular structure at a predetermined combination ratio.
    [009] However, the rubber composition described in Patent Document 2 also fails to satisfy a sufficiently high level of processability, rolling resistance performance and hardness and therefore there is still a strong demand for rubber compositions that further improved on these properties.
    [0010] However, Patent Documents 3 and 4 describe a β-farnesene polymer, but fail to have a sufficient study on its practical applications. LIST OF CITATIONS PATENT LITERATURE Patent Document 1: JP 2010-209256A Patent Document 2: JP 2009-120819A Patent Document 3: PCT Brochure WO 2010 / 027463A1 Patent Document 4: PCT Brochure WO 2010 / 027464A1 SUMMARY OF THE INVENTION TECHNICAL PROBLEM
    [0011] The present invention was created in view of the conventional problems mentioned above. The present invention provides a rubber composition that exhibits not only good processability when combining, molding or curing, but also excellent rolling resistance performance due to improved dispersibility of carbon black or silica in it, and in addition hardly suffers from deterioration in mechanical strength and hardness, and a tire obtained using the rubber composition. SOLUTION TO THE PROBLEM
    [0012] As a result of extensive and intensive research, the present inventors have found that when using a conjugated diene-based polymer having a specific structure, the resulting rubber composition can be improved in processability, can exhibit reduced rolling resistance due to an improved dispersibility of the carbon black and the silica in it and, moreover, it hardly suffers from deterioration in mechanical strength and hardness. The present invention was carried out in accordance with the above-mentioned discovery.
    [0013] That is, the present invention relates to a rubber composition including a rubber component (A), a farnesene polymer (B) and silica (C). ADVANTAGE EFFECTS OF THE INVENTION
    [0014] According to the present invention, a rubber composition is provided which not only has good processability when combining, molding or curing, but also an excellent rolling resistance performance due to an improved dispersibility of carbon black and of the silica in it and, moreover, hardly suffers from deterioration in mechanical strength and hardness, and a tire obtained using the rubber composition. DESCRIPTION OF THE MODALITIES [RUBBER COMPOSITION]
    [0015] The rubber composition according to the present invention includes a rubber component (A), a farnesene polymer (B) and silica (C). RUBBER COMPONENT (A)
    [0016] Examples of rubber component (A) include a styrene-butadiene rubber (hereinafter also referred to as "SBR"), a natural rubber, a butadiene rubber, an isoprene rubber, a butyl rubber, a halogenated butyl rubber, an ethylene propylene diene rubber, an acrylonitrile butadiene copolymer rubber and a chloroprene rubber. Among these rubbers, SBR, a natural rubber, a butadiene rubber and an isoprene rubber are preferred, and most preferred is SBR. These rubbers can be used alone or as a mixture of any two or more of them. [SYNTHETIC RUBBER]
    [0017] Examples of the preferred synthetic rubber, used as the rubber component (A), include SBR, a butadiene rubber, an isoprene rubber, a butyl rubber, a halogenated butyl rubber, an ethylene propylene diene rubber, an acrylonitrile butadiene copolymer rubber and a chloroprene rubber. Among these synthetic rubbers, SBR, an isoprene rubber and a butadiene rubber are preferred, and most preferred is SBR. (SBR (A-1))
    [0018] As SBR (A-1), those generally used in tire applications can be used. More specifically, SBR (A-1) preferably has a styrene content of 0.1 to 70% by weight, more preferably from 5 to 50% by weight, and even more preferably from 15 to 35% by weight. Also, SBR (A-1) preferably has a vinyl content of 0.1 to 60% by weight and more preferably from 0.1 to 55% by weight.
    [0019] The average molecular weight (Mw) of the SBR 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 range specified above, the resulting rubber composition can be increased in both processability and mechanical strength.
    [0020] However, in this specification, the weight average molecular weight is the value measured by the method described below, in the Examples.
    [0021] The glass transition temperature (Tg) of the SBR used in the present invention, as measured by the differential thermal analysis method, is preferably from -θδ'C to 0Í and more preferably from - θδ'C to-δ'C . When adjusting the SBR Tg to the range specified above, it is possible to suppress the increase in SBR viscosity and increase its handling property. «METHOD FOR THE PRODUCTION OF SBR»
    [0022] The SBR usable in the present invention can be produced by copolymerizing 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 mass polymerization method. Among these methods of polymerization, an emulsion polymerization method and a solution polymerization method are especially preferred. (i) POLYMERIZED STYRENE-BUTADIENE RUBBER IN EMULSION (E-SBR)
    [0023] 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 subjected to emulsion polymerization using a radical polymerization initiator.
    [0024] As the emulsifying reagent, 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.
    [0025] As a dispersant for the aforementioned emulsion polymerization, it can normally be used in water. The dispersant may also contain a water-soluble organic solvent, such as methanol and ethanol, unless the use of such an organic solvent has a negative influence on the stability of the polymerization.
    [0026] Examples of the radical polymerization initiator include persulfates, such as ammonium persulfate and potassium persulfate, organic peroxides and hydrogen peroxide.
    [0027] To properly adjust a molecular weight of the obtained E-SBR, a chain transfer reagent can be used. Examples of the chain transfer reagent include mercaptan, such as t-dodecyl mercaptan and n-dodecyl mercaptan; and carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, y-terpinene and an α-methyl styrene dimer.
    [0028] The temperature used in emulsion polymerization can be appropriately determined according to the type of radical polymerization initiator used therein, and is normally preferably 0 to WO'C and more preferably 0 to 60 ° C. The polymerization method can be a continuous polymerization method or a batch polymerization method. The polymerization reaction can be stopped by adding a terminating reagent to the reaction system.
    [0029] 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.
    [0030] After interrupting the polymerization reaction, an antioxidant can be added, if required. In addition, after stopping the polymerization reaction, unreacted monomers can be removed from the resulting latex, if required. After that, the obtained polymer is coagulated by adding a salt, such as sodium chloride, calcium chloride and potassium chloride, as a coagulant for it, and, if required, at the same time adjusting a value the pH of the coagulation system to a desired value 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 polymer as a flour. The flour thus recovered is washed with water and dehydrated, and then dried using a band dryer or similar, to obtain the E-SBR. However, by coagulating the polymer, the latex can be previously mixed with an extender oil in the form of an emulsified dispersion, to recover the polymer in the form of an extended rubber with oil. (ii) POLYMERIZED STYRENE-BUTADIENE RUBBER IN SOLUTION (S-SBR)
    [0031] S-SBR can be produced by a method of polymerization in common solution. For example, styrene and butadiene are polymerized in a solvent, using an anion-curable active metal, if required, in the presence of a polar compound.
    [0032] Examples of 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 lanthanoids, such as lanthanum and neodymium. Among these active metals, alkali metals and alkaline earth metals are preferred, and more preferred are alkali metals. Alkali metals are most preferably used in the form of an organic alkali metal compound.
    [0033] 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 can normally be used in such a range that a monomer is dissolved in them, in a concentration of 1 to 50% by mass.
    [0034] 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 beno lithium; polyfunctional organic lithium compounds, such as dilithomethane, 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 organic monolithium compounds are more preferred. The amount of the organic alkali metal compound used can be appropriately determined according to a molecular weight of the S-SBR, as required.
    [0035] The organic alkali metal compound can be used in the form of an organic alkali metal amide by reacting a secondary amine, such as dibutyl amine, dihexyl amine and dibenzyl amine, with it.
    [0036] The polar compound used in solution polymerization is not particularly limited, as long as the compound can normally be used in anion polymerization for the control of a butadiene portion microstructure and the distribution of styrene in a copolymer chain of it, without causing the reaction to deactivate. Examples of the polar compound include ether compounds, such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines, such as tetramethyl ethylenediamine and trimethylamine; and alkali metal alkoxides and phosphine compounds.
    [0037] The temperature used in the aforementioned polymerization reaction is usually in the range of -80 to IδO'C, preferably from 0 to WO'C and more preferably from 30 to θO'C. The polymerization method can be a batch method or a continuous method. Also, to optimize a random copolymerization capacity between styrene and butadiene, styrene and butadiene are preferably provided for a solution of the reaction in a continuous or intermittent mode, such that a compositional ratio between styrene and butadiene in the polymerization system in a specific range.
    [0038] 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, a coupling agent, such as tin tetrachloride, tetrachlorosilane, tetramethoxysilane, tetraglycidyl-1,3-bisaminomethyl cyclohexane and 2.4 diisocyanate, can be added -tolylene, which are capable of reacting with an active end of the polymer chain, or a chain end 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 separation by steam, 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 extended rubber with oil. (iii) MODIFIED STYRENE-BUTADIENE RUBBER (MODIFIED SBR)
    [0039] In the present invention, a modified SBR can also be used, produced by introducing a functional group in the SBR. 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.
    [0040] As the method of producing the modified SBR, for example, the method can be used in which, before adding the terminating reagent, a coupling reagent, such as tin tetrachloride, tetrachlorosilane, dimethyl dichlorosilane , dimethyl diethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyl tri-toxysilane, tetraglycidyl-1,3-bisaminomethyl cyclohexane and 2,4-tolylene diisocyanate, which are capable of reacting with one end of the polymer chain, a chain end modifying reagent such as 4,4'-bis (diethylamino) benzophenone and N-vinyl pyrrolidone or other modifying reagents, as described in JP 2011-132298A, are added to the reaction.
    [0041] In the modified SBR, the location of the polymer into which the functional group is introduced can be an end of the chain or a side chain of the polymer. (ISOPRENE RUBBER (A-ll))
    [0042] Isopropene rubber can be a commercially available isoprene rubber, which can be obtained by polymerization using a Ziegler-based catalyst, such as titanium-trialkyl aluminum tetrahalide-based catalysts, catalysts based on diethyl aluminum-cobalt chloride based, trialkyl aluminum-boron nickel trifluoride based catalysts and diethyl aluminum-nickel chloride based catalysts; a rare earth metal catalyst based on lanthanoids, such as catalysts based on triethyl aluminum-Lewis acid-organic acid neodymium salt; and an organic alkali metal compound, as used similarly for the production of S-SBR. Among these isoprene rubbers, isoprene rubbers obtained by polymerization using the Ziegler-based catalyst are preferred because of their high cis isomer content. In addition, iso-prene rubbers having an ultra-high cis isomer content can also be used, which are produced using the rare earth metal catalyst based on lantanoids.
    [0043] Isopropene rubber preferably has a glass content of 50% by weight or less, more preferably 40% by weight or less, and even more preferably 30% by weight or less. When the vinyl content of isoprene rubber is more than 50% by weight, the resulting rubber composition tends to deteriorate in rolling resistance performance. The lower limit of the vinyl content of 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% or less and more preferably -SO'C or less.
    [0044] The weight average molecular weight of isoprene rubber is preferably from 90,000 to 2,000,000 and more preferably from 150,000 to 1,500,000. When the weight average molecular weight of the isoprene rubber falls within the range specified above, the resulting rubber composition may exhibit good processability and good mechanical strength.
    [0045] 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, silicon tetrachloride, a alkoxysilane containing an epoxy group in a molecule of it, and an alkoxysilane containing an amino group. (BUTADIENE RUBBER (A-lll))
    [0046] Butadiene rubber can be a commercially available butadiene rubber, which can be obtained by polymerization using a Ziegler-based catalyst, such as titanium-trialkyl aluminum tetrahalide-based catalysts, aluminum catalysts diethyl aluminum-cobalt chloride based, trialkyl aluminum-boron nickel trifluoride based catalysts and diethyl aluminum-nickel chloride based catalysts; a rare earth metal catalyst based on lantanoids, such as catalysts based on triethyl aluminum-Lewis acid-organic acid neodymium salt; and an organic alkali metal compound, as used similarly for the production of S-SBR. Among these butadiene rubbers, butadiene rubbers obtained by polymerization using the Ziegler-based catalyst are preferred because of their high cis isomer content. In addition, buta-diene rubbers having an ultra-high cis isomer content, which are produced using the rare earth metal catalyst based on lantanoids, can also be used.
    [0047] Butadiene rubber preferably has a vinyl content of 50% by weight or less, more preferably 40% by weight or less, and even more preferably 30% by weight or less. When the vinyl content of butadiene rubber is more than 50% by weight, the resulting rubber composition tends to deteriorate in rolling resistance performance. The lower limit of the vinyl content of butadiene rubber is not particularly limited. The glass transition temperature of the butadiene rubber can vary, depending on its vinyl content, and is preferably - 40 ° or less and more preferably -δO'C or less.
    [0048] The weight average molecular weight of butadiene rubber is preferably from 90,000 to 2,000,000 and more preferably from 150,000 to 1,500,000. When the average molecular weight of butadiene rubber falls within the range specified above, the resulting rubber composition may exhibit good processability and good mechanical strength.
    [0049] Butadiene 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, silicon tetrachloride, a alkoxysilane containing an epoxy group in a molecule of it, and an alkoxysilane containing an amino group.
    [0050] As the rubber component, in addition to at least one from SBR, isoprene rubber and butadiene rubber, one or more rubbers selected from the group consisting of a butyl rubber, a halogenated butyl rubber can be used , an ethylene propylene diene rubber, an acrylonitrile butadiene copolymer rubber and a chloroprene rubber. The method of producing these rubbers is not particularly limited, and any suitable commercially available rubbers can also be used in the present invention.
    [0051] In the present invention, when using SBR, isoprene rubber, butadiene rubber and other synthetic rubbers in combination with the farnesene polymer (B) mentioned above, it is possible to improve a processability of the resulting rubber composition , a carbon black dispersibility in it and a rolling resistance performance of it.
    [0052] 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, several properties of the resulting rubber composition, such as rolling resistance performance and wear resistance, can be appropriately controlled by selecting an appropriate combination of synthetic rubbers. [NATURAL RUBBER]
    [0053] Examples of natural rubber used as the rubber component (A) in the present invention include TSR, as do SMR, SIR and STR; natural rubbers normally used in the tire industry, such as RSS; high purity natural rubbers; and modified natural rubbers, such as epoxidized natural rubbers, hydroxylated natural rubbers, hydrogenated natural rubbers and grafted natural rubbers. Among these natural rubbers, SMR20 and RSS # 3 are preferred from the point of view of less variation in quality and good availability. These natural rubbers can be used alone or in combination with any two or more of them.
    [0054] However, the method of producing the rubber used as the rubber component (A) in the present invention is not particularly limited, and any suitable commercially available products can be used as the rubber.
    [0055] In the present invention, by using the rubber component (A) in combination with the farnesene polymer (B) mentioned above, the resulting rubber composition can be improved in a processability, a carbon black dispersibility therein, and rolling resistance performance. FARNESEN POLYMER (B)
    [0056] The rubber composition of the present invention contains a farnesene polymer (B) (hereinafter, also referred to merely as "polymer (B)").
    [0057] The farnesene polymer (B) used in the present invention is preferably a polymer produced by polymerizing the β-farnesene represented by the formula (I) below, by the method mentioned below, and is more preferably a homopolymer of β- farnesene.

    [0058] The weight average molecular weight of the polymer (B) 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 most preferably from 15,000 to 300,000. When the weight average molecular weight of the polymer falls within the range specified above, the resulting rubber composition according to the present invention has good processability, and can additionally be improved in the dispersibility of silica (C) and carbon black (D) it can therefore exhibit good rolling resistance performance. However, the weight average molecular weight of the polymer (B) used in this specification is the value measured by the method described in the Examples below.
    [0059] In the present invention, two or more types of polymers (B), which are different in weight average molecular weight from each other, can be used in the form of a mixture of them.
    [0060] The melt viscosity (as measured at 38 ^ 3) of polymer (B) is preferably 0.1 to 3,000 Pa * s, more preferably 0.6 to 3,000 Pa * s, even more preferably 0, 6 to 2,800 Pa * s, even more preferably from 1,5 to 2,600 Pa * s and most preferably of all from 1,5 to 800 Pa * s. When the melt viscosity of the polymer (B) falls within the range specified above, the resulting rubber composition can be easily mixed and can be improved in processability. However, in this specification, the melt viscosity of polymer (B) is the value measured by the method described in the Examples below.
    [0061] The molecular weight distribution (Mw / Mn) of the polymer (B) is preferably 1.0 to 8.0, more preferably 1.0 to 5.0 and even more preferably 1.0 to 3, 0. When the molecular weight distribution (Mw / Mn) of the polymer (B) falls within the range specified above, the resulting polymer (B) can suitably exhibit less variation in its viscosity.
    [0062] The glass transition temperature of the polymer (B) can vary, depending on a vinyl content, or contents, of the other monomers in it, and is preferably from -90 to 013 and more preferably from - 90 to - 1013. When the glass transition temperature of the polymer (B) falls within the range specified above, the resulting rubber composition may exhibit good rolling resistance performance. The vinyl content of the polymer (B) is preferably 99% by weight or less, and more preferably 90% by weight or less.
    [0063] In the present invention, the polymer (B) is preferably combined in an amount of 0.1 to 100 parts by weight, more preferably from 0.5 to 50 parts by weight and even more preferably from 1 to 30 parts by weight , per 100 parts by mass of the rubber component (A). When the amount of the combined polymer (B) falls within the range specified above, the resulting rubber composition may exhibit good processability, mechanical strength and rolling resistance performance.
    [0064] The polymer (B) can be produced by an emulsion polymerization method, by the methods described in PCT Leaflet WO 2010 / 027463A1 and in PCT Leaflet WO 2010 / 027464A1 or similar. Among these methods of polymerization, an emulsion polymerization method and a solution polymerization method are preferred, and a solution polymerization method is more preferred. (EMULSION POLYMERIZATION METHOD)
    [0065] The emulsion polymerization method for producing the polymer (B) can be any conventionally known, suitable method. For example, a predetermined amount of a farnesene monomer is 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.
    [0066] As the emulsifying reagent, 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.
    [0067] As the dispersant for emulsion polymerization, water can normally be used, and the dispersant can also contain a water-soluble organic solvent, such as methanol and ethanol, unless the use of such an organic solvent gives any adverse influence on the stability of the polymerization.
    [0068] Examples of the radical polymerization initiator include persulfates, such as ammonium persulfate and potassium persulfate; and organic peroxides and hydrogen peroxide.
    [0069] To adjust a molecular weight of the resulting polymer (B), a chain transfer reagent can be used. Examples of the chain transfer reagent include mercaptan, such as t-dodecyl mercaptan and n-dodecyl mercaptan; and carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, y-terpinene and an oc-methyl styrene dimer.
    [0070] The temperature used in emulsion polymerization can be appropriately determined according to the type of radical polymerization initiator used therein, and is normally preferably 0 to WO'C and more preferably 0 to 60 ° C. The polymerization method can be a continuous polymerization method or a batch polymerization method. The polymerization reaction can be stopped by adding a terminating reagent to the reaction system.
    [0071] 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.
    [0072] After stopping the polymerization reaction, an antioxidant can be added, if required. In addition, after stopping the polymerization reaction, unreacted monomers can be removed from the resulting latex, if required. After that, the resulting polymer (B) is coagulated by adding a salt, such as sodium chloride, calcium chloride and potassium chloride, as a coagulant for it, and, if required, at the same time adjusting it. if a pH value of the coagulation system to a desired value 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 polymer (B) . The polymer thus recovered is washed with water and dehydrated, and then dried to obtain the polymer (B). However, when coagulating the polymer, the latex can be previously mixed, if required, with an extender oil in the form of an emulsified dispersion, to recover the polymer (B) in the form of an oil-extended rubber. (SOLUTION POLYMERIZATION METHOD)
    [0073] The solution polymerization method to produce the polymer (B) can be any conventionally known, suitable method. For example, a farnesene monomer can be polymerized in a solvent, using a ziegler-based catalyst, a metallocene-based catalyst or an anion-curable active metal, if required, in the presence of a polar compound.
    [0074] Examples of 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 lanthanoids, such as lanthanum and neodymium. Among these active metals, alkali metals and alkaline earth metals are preferred, and more preferred are alkali metals. Alkali metals are most preferably used in the form of an organic alkali metal compound.
    [0075] 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.
    [0076] 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 dilithomethane, dilitionaphthalene, 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 organic monolithium compounds are more preferred. 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, per 100 parts by weight of farnesene.
    [0077] The organic alkali metal compound can be used in the form of an organic alkali metal amide by reacting a secondary amine, such as dibutyl amine, dihexyl amine and dibenzyl amine, with it.
    [0078] The polar compound can be used in anion polymerization to control a microstructure of portions of farnesene, without causing the reaction to deactivate. Examples of the polar compound include ether compounds, such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines, such as tetramethyl ethylenediamine and trimethylamine; and alkali metal alkoxides and phosphine compounds. The polar compound is preferably used in an amount of 0.01 to 1,000 mole equivalents for the organic alkali metal compound.
    [0079] The temperature used in the aforementioned polymerization reaction is normally -80 to IδO'C, preferably 0 to WO'C and more preferably 10 to θO'C. The polymerization method can be a batch method or a continuous method.
    [0080] The polymerization reaction can be stopped by adding a terminating reagent to the reaction system, such as methanol and isopropanol. The resulting polymerization reaction solution can be poured into a weak solvent, such as methanol, to precipitate the polymer (B). Alternatively, the polymerization reaction solution can be washed with water, and then a solid is separated from it and dried to isolate the polymer (B) from it. (MODIFIED POLYMER)
    [0081] The polymer (B) thus obtained can be subjected to the modification treatment. Examples of a functional group used in the treatment of modification include an amino group, an amide group, an imino group, an imidazole group, a urea group, an alkoxysilyl group, a hydroxyl group, an epoxy group, an ether group, a carboxyl group, a carbonyl group, a mercapto group, an isocyanate group, a nitrile group and an acid anhydride group.
    [0082] As the method of producing the modified polymer, for example, the method can be used in which, before adding the terminating reagent, a coupling reagent, such as tin tetrachloride, dibutyl tin chloride, tetrachlorosilane, dimethyl dichlorosilane, dimethyl diethoxysilane, tetramethoxysilane, 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 chain end modifying reagent, such as 4,4'-bis (diethylamino) benzophenone, N-vinyl pyrrolidone, N-methyl pyrrolidone, 4-dimethylaminobenzylidene aniline and dimethyl imidazolidinone , or the other modifying reagents, as described in JP 2011-132298A, are added to the polymerization reaction system. In addition, the isolated polymer, when used, can be grafted with maleic anhydride or similar.
    [0083] In the modified polymer, the location of the polymer into which the functional group is introduced may be an end of the chain or a side chain of the polymer. In addition, these functional groups can be used in combination with any two or more of them. The modifying reagent can be used in an amount of 0.1 to 10 moles equivalent, for the organic alkali metal compound. SILICA
    [0084] Examples of silica (C) include wet silica (hydrated silica), dry silica (anhydrous silica), calcium silicate and aluminum silicate. Of these silicas, from the point of view of further improving processability, mechanical strength and wear resistance of the resulting rubber composition, wet silica is preferred. These silicas can be used alone or as a mixture of any two or more of them.
    [0085] The average particle size of the silica (C) is preferably from 0.5 to 200 nm, more preferably from 5 to 150 nm, and even more preferably from 10 to 100 nm, from the point of view of perfecting a processability, rolling resistance performance, mechanical strength and wear resistance of the resulting rubber composition.
    [0086] However, the average particle size of silica (C) can be determined by measuring the diameters of the silica particles by a transmission electron microscope and calculating an average value of the measured diameters.
    [0087] Silica (C) is combined in the rubber composition in an amount of 0.1 to 150 parts by weight, more preferably from 0.5 to 130 parts by weight and even more preferably from 5 to 100 parts by weight, per 100 parts by mass of the rubber component (A). When the amount of combined silica falls within the range specified above, the resulting rubber composition can be improved in processability, rolling resistance performance, mechanical strength and wear resistance. SMOKE BLACK (D)
    [0088] Examples of carbon black (D) include carbon blacks such as furnace carbon black, channel carbon black, thermal carbon black, acetylene carbon black and carbon black of Ketjen. Among these carbon blacks, from the point of view of a high cure rate and improved mechanical strength of the rubber composition, furnace carbon black is preferred.
    [0089] Carbon black (D) preferably has an average particle size of 5 to 100 nm, more preferably 5 to 80 nm, and even more preferably 5 to 70 nm, from the point of view of increasing an dispersibility, mechanical strength and hardness of the resulting rubber composition.
    [0090] Examples of commercially available furnace carbon black, such as carbon black (D) having an average particle size of 5 to 100 nm, include "DIABLACK", available from Mitsubishi Chemical Corp., and " SEAST ", available from Tokai Carbon Co., Ltd. Examples of commercially available acetylene carbon black, such as carbon black (D) having an average particle size of 5 to 100 nm, include" DENKABLACK ", available from Denki Kagaku Kogyo KK Examples of commercially available Ketjen carbon black, such as carbon black (D) having an average particle size of 5 to 100 nm, include "ECP600JD", available from Lion Corp.
    [0091] Carbon black (D) can be subjected to an acid treatment with nitric acid, sulfuric acid, hydrochloric acid or a mixed acid thereof or it can be subjected to a heat treatment in the presence of air, to conduct a oxidation treatment of its surface, from the point of view of improving the wettability or dispersibility of carbon black (D) in the rubber component (A) and in the polymer (B). In addition, from the point of view of improving the mechanical resistance of the rubber composition of the present invention, carbon black can be subjected to a heat treatment, at a temperature of 2,000 to S.OOO'C, in the presence of a catalyst graffiti. As the graphite catalyst, boron, boron oxides (such as, for example, B2O2, B2O3, B4O3 and B4O5), boron oxo acids (such as, for example, orthoboric acid, metabolic acid and tetrabromic acid) and their salts, boron carbonates (such as, for example, B4C and B6C), Boron nitride (such as BN) and other boron compounds.
    [0092] The particle size of carbon black (D) can be controlled by spraying or the like. To spray the carbon black (D), a high speed rotary mill (such as a hammer mill, pin mill and cage mill) or several ball mills (such as a laminator, mill vibrating and a universal mill), a stirring mill (such as a globule mill, a friction mill, a drain tube mill and an annular mill) or the like.
    [0093] However, the average carbon black particle size (D) can be determined by measuring the diameters of the carbon black particles, using a transmission electron microscope, and calculating an average value of the measured diameters .
    [0094] In the rubber composition of the present invention, carbon black (D) is preferably combined in an amount of 0.1 to 150 parts by weight, more preferably from 0.1 to 130 parts by weight, and even more preferably from 0.1 to 100 parts by mass, per 100 parts by mass of the rubber component (A). When the amount of combined carbon black (D) falls within the range specified above, the resulting rubber composition exhibits good mechanical strength, hardness and processability, and carbon black (D) has good dispersibility in the rubber composition. OPTIONAL COMPONENTS (SILANO COUPLING REAGENT)
    [0095] The rubber composition of the present invention preferably contains a silane coupling reagent. Examples of the silane coupling reagent include a sulfide-based compound, a mercapto-based compound, a vinyl-based compound, an amino-based compound, a glycidoxy-based compound, a nitro-based compound and a chlorine-based compound.
    [0096] Specific examples of the sulfide-based compound include bis (3-triethoxysilyl propyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilyl propyl) tetrasulfide, bis (2- trimethoxysilylethyl), bis (3-trimethoxysilylpropyl) bis (3-trimethoxysilyl propyl), bis (3-triethoxysilyl propyl) disulphide, bis (3-trimethoxysilyl propyl) disulfide, 3- trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxyethylethyl-N, dimethylethylethylethylethylethylethylethylethylethylethoxy-3-trimethoxy, 3- 3-triethoxysilylpropyl methacrylate monosulfide and 3-trimethoxysilyl propyl methacrylate monosulfide.
    [0097] Specific examples of the mercapto-based compound include 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 2-mercaptoethyl trimethoxysilane and 2-mercaptoethyl triethoxysilane.
    [0098] Specific examples of the vinyl based compound include triethoxysilane vinyl and trimethoxysilane vinyl.
    [0099] Specific examples of the amino-based compound include 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3- (2-aminoethyl) aminopropyl triethoxysilane and 3- (2-aminoethyl) aminopropyl trimethoxysilane.
    [00100] Specific examples of the glycidoxy compound include y-glycidoxypropyl triethoxysilane, y-glycidoxypropyl trimethoxysilane, y-glycidoxypropylmethyl diethoxysilane and y-glycidoxypropylmethyl dimethoxysilane.
    [00101] Specific examples of the nitro-based compound include 3-nitropropyl trimethoxysilane and 3-nitropropyl triethoxysilane.
    [00102] Specific examples of the chlorine-based compound include 3-chloropropyl trimethoxysilane, 3-chloropropyl triethoxysilane, 2-chloroethyl trimethoxysilane and 2-chloroethyl triethoxysilane.
    [00103] These silane coupling reagents can be used alone or in the form of a mixture of any two or more of them. Of these silane coupling reagents, bis (3-triethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) tetrasulfide and 3-mercaptopropyl trimethoxysilane are preferred from the point of view of a great addition effect and low costs.
    [00104] The silane coupling reagent is preferably combined in the rubber composition in an amount of 0.1 to 30 parts by weight, more preferably from 0.5 to 20 parts by weight, and even more preferably from 1 to 15 parts by mass, per 100 parts by mass of silica (C). When the amount of the combined silane coupling reagent falls within the range specified above, the resulting rubber composition can be increased in dispersibility, coupling effect, reinforcement property and wear resistance. (OTHER LOADS)
    [00105] For the purposes of increasing the mechanical strength of the rubber composition, improving several properties, such as a thermal resistance and a resistance to weathering of it, controlling its hardness, and additionally improving the economy by adding an extender to it, the rubber composition may also contain a filler other than silica (C) and carbon black (D), if required.
    [00106] The charge other than silica (C) and carbon black (D) can be appropriately selected according to the applications of the obtained rubber composition. For example, as the filler, one or more fillers selected from the group consisting of organic fillers, and inorganic fillers, such as clay, talc, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, sulfate, can be used. barium, titanium oxide, glass fibers, fibrous fillers and glass balloons. The aforementioned filler is preferably combined in the rubber composition of the present invention in an amount of 0.1 to 120 parts by weight, more preferably from 5 to 90 parts by weight and even more preferably from 10 to 80 parts by weight, per 100 mass parts of the rubber component (A). When the amount of the combined load falls within the range specified above, the resulting rubber composition can be further improved in mechanical strength.
    [00107] The rubber composition of the present invention may also contain, if required, a softening reagent for the purpose of improving processability, 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 silicone oil, aroma oil, TDAE (treated distilled aromatic extracts), MES (soft extracted solvates), RAE (residual aromatic extracts), an oil paraffin and a naphthene oil; and a liquid polymer, such as a low molecular weight polybutadiene, a low molecular weight polyisoprene, a low molecular weight styrene-butadiene copolymer and a low molecular weight styrene-isoprene copolymer. However, the aforementioned 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 point of view of good processability of the resulting rubber composition. The aforementioned process oil or liquid polymer, such as the softening reagent, is preferably combined in the rubber composition of the present invention in an amount of less than 50 parts by weight, per 100 parts by weight of the rubber component (A) .
    [00108] The rubber composition of the present invention may also contain, if required, one or more additives selected from the group consisting of an antioxidant, an oxidation inhibitor, a lubricant, a light stabilizer, a fire retardant, a processing aid, a dye, such as pigments and dyestuffs, a flame retardant, an antistatic reagent, a shine removing reagent, an anti-blocking reagent, an ultraviolet absorber, a release reagent, a foaming reagent antimicrobial, a mildew proof reagent and a perfume, for the purposes of improving weathering resistance, thermal resistance, oxidation resistance or the like of the resulting rubber composition, unless the effects of the present invention are adversely influenced .
    [00109] Examples of the oxidation inhibitor include hindered phenol-based compounds, phosphorus-based compounds, lactone-based compounds and hydroxyl-based compounds.
    [00110] Examples of the antioxidant include amine-ketone-based compounds, imidazole-based compounds, amine-based compounds, phenol-based compounds, sulfur-based compounds and compounds based on phosphor.
    [00111] The rubber composition of the present invention is preferably used in the form of 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 derivatives, halogen compounds, aldehyde compounds , alcohol compounds, epoxy compounds, metal halides and organic metal halides, and silane compounds. Among these crosslinking reagents, sulfur and sulfur compounds are preferred. These crosslinking reagents can be used alone or in combination with any two or more of them. The crosslinking reagent is preferably combined in the rubber composition in an amount of 0.1 to 10 parts by weight, per 100 parts by weight of the rubber component (A).
    [00112] When sulfur is used as the crosslinking reagent, a vulcanization aid or a vulcanization accelerator is preferably used in combination with the crosslinking reagent.
    [00113] Examples of the vulcanization aid include fatty acids, such as stearic acid, and metal oxides, such as zinc oxide.
    [00114] Examples of the vulcanization accelerator include guanidine-based compounds, sulfene-based compounds, thiazole-based compounds, thiuram-based compounds, thiourea-based compounds, thiourea-based compounds dithiocarbamic acid, 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 them. The vulcanization aid or the vulcanization accelerator is preferably combined in the rubber composition of the present invention in an amount of 0.1 to 15 parts by weight, per 100 parts by weight of the rubber component (A).
    [00115] 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 with each other. The method of uniformly mixing the respective components can be carried out using a closed type mixer of a tangential type or an entanglement type, such as a mixing rudder, a Brabender, a Banbury mixer and an internal mixer, a mono-screw extruder, an extruder double screw, a mixing roller, a roller or similar, in a temperature range of normally 70 to 270 <C. [PNEUMATIC]
    [00116] The tire of the present invention is produced using the rubber composition of the present invention at least in part of it, and therefore can exhibit good mechanical strength and excellent rolling resistance performance. EXAMPLES
    [00117] The present invention will be described in more detail below 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 them.
    [00118] The respective components used in the Examples and Comparative Examples below are as follows. RUBBER COMPONENT (A): A-1: Styrene-butadiene rubber "JSR1500" (available from JSR Corp.); Weight average molecular weight: 450,000; Styrene content: 23.5% by mass (produced by the emulsion polymerization method) A-2: Butadiene rubber "BR01" (available from JSR Corp.); Weight average molecular weight: 550,000; Cis isomer content: 95% by mass A-3: Natural rubber "SMR20" (Malaysian natural rubber) POLYMER (B): Polyphenols (B-1) a (B-4) and (B-5) a (B -7) produced in Production Examples 1 to 4 and 6 to 8 SILICA (C): C-1: "ULTRASIL 7000GR" (wet silica; average particle size: 14 nm) (available from Evonik Degussa Japan Co., Ltd .) C-2: "AEROSIL 300" (dry silica; average particle size: 7 nm) (available from Nippon Aerosil Co., Ltd.) C-3: "NIPSIL E-74P" (wet silica; particle size medium: 74 nm) (available from Tosoh Silica Corp.) SMOKE BLACK (D): D-1: "DIABLACK H" (available from Mitsubishi Chemical Corp.) (average particle size: 30 nm) D-2: " DIABLACK E "(available from Mitsubishi Chemical Corp.) (average particle size: 50 nm) D-3:" DIABLACK I "(available from Mitsubishi Chemical Corp.) (average particle size: 20 nm) D-4:" SEAST V "(available from Tokai Carbon Co., Ltd.) (average particle size: 60 nm) OPTIONAL COMPONENTS Polyisoprene: Polyisoprene (X-1 ) produced in Production Example 5 Polyisoprene (X-2) produced in Production Example 9 TDAE: "VivaTecõOO" (available from H & R Corp.) Stearic Acid: "LUNAC S-20" (available from Kao Corp. ) Silane Coupling Reagent: "Si75" (available from Evonik Degussa Japan Co., Ltd.) Zinc Oxide: Zinc Oxide (available from Sakai Chemical Industry Co., Ltd.) Antioxidant (1): NOCRAC 6C "(available from Ouchi Shinko Chemical Industrial Co., Ltd.) Antioxidant (2):" ANTAGE RD "(available from Kawaguchi Chemical Industry Co., Ltd.) Sulfur: Fine sulfur powder; 200 mesh (available from Tsurumi Chemical Industry Co., Ltd.) Vulcanization accelerator (1): "NOCCELER CZ-G" (available from Ouchi Shinko Chemical Industrial Co., Ltd.) Vulcanization accelerator (2): "NOCCELER D "(available from Ouchi Shinko Chemical Industrial Co., Ltd.) Vulcanization accelerator (3):" NOCCELER TBT-N "(available from Ouchi Shinko Chemical Industrial Co., Ltd.) Vulcanization accelerator (4):" NOCCELER NS -P "(available from Ouchi Shinko Chemical Industrial Co., Ltd.) PRODUCTION EXAMPLE 1: PRODUCTION OF POLYFARNESENE (B-1)
    [00119] A pressure reaction vessel, previously purged with nitrogen and then dried, was loaded with 1070 g of hexane and 11.5 g of n-butyl lithium (in the form of a 17 wt.% Hexane solution). The contents of the reaction vessel were heated to 50 ° C, and 1755 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was mixed with methanol and then washed with water. After separating the water from the polymerization reaction solution, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a polypharnesene (B-1) having the properties shown in Table 1. PRODUCTION EXAMPLE 2: PRODUCTION OF POLYFARNESENE (B-2)
    [00120] A pressure reaction vessel, previously purged with nitrogen and then dried, was loaded with 900 g of cyclohexane and 164.4 g of sec-butyl lithium (in the form of a 10.5 wt.% Solution of cyclohexane ). The contents of the reaction vessel were heated to δO'C, and 1785 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was mixed with methanol and then washed with water. After separating the water from the polymerization reaction solution, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a polypharnesene (B-2) having the properties shown in Table 1. PRODUCTION EXAMPLE 3: PRODUCTION OF POLYFARNESENE (B-3)
    [00121] A pressure reaction vessel, previously purged with nitrogen and then dried, was loaded with 1370 g of hexane and 5.8 g of n-butyl lithium (in the form of a 17 wt.% Hexane solution). The contents of the reaction vessel were heated to δO'C, and 1359 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was mixed with methanol and then washed with water. After separating the water from the polymerization reaction solution, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a polypharnesene (B-3) having the properties shown in Table 1. PRODUCTION EXAMPLE 4: PRODUCTION OF POLYFARNESENE (B-4)
    [00122] A pressure reaction vessel, previously purged with nitrogen and then dried, was loaded with 313 g of hexane and 0.7 g of n-butyl lithium (in the form of a 17 wt.% Solution of cyclohexane ). The contents of the reaction vessel were heated to δO'O, and 226 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was mixed with methanol and then washed with water. After separating the water from the polymerization reaction solution, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a polypharnesene (B-4) having the properties shown in Table 1. PRODUCTION EXAMPLE 5: PRODUCTION OF POLY-ISOPRENE (X-1)
    [00123] 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 wt.% Hexane solution). The contents of the reaction vessel were heated to 70 °, and 2050 g of isoprene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was mixed with methanol and then washed with water. After separating the water from the polymerization reaction solution, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a polyisoprene (X-1) having the properties shown in Table 1. PRODUCTION EXAMPLE 6: PRODUCTION OF POLYFARNESENE (B-5)
    [00124] 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 wt.% Solution of hexane) as an initiator. The contents of the reaction vessel were heated to δO'C, and 272 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was subsequently 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 poly-farnesene (B-5). The various properties of the polypharnesene (B-5) thus obtained are shown in Table 1. PRODUCTION EXAMPLE 7: PRODUCTION OF POLYFARNESENE (B-6)
    [00125] A pressure reaction vessel, previously purged with nitrogen and then dried, was loaded with 240 g of cyclohexane as a solvent and 1.7 g of n-butyl lithium (in the form of a 17 wt.% Solution of hexane) as an initiator. The contents of the reaction vessel were heated to 500, and 0.5 g of N, N, N ', N'-tetramethyl ethylenediamine and an additional 340 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was subsequently 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 polypharnesene (B-6). The various properties of the polyphennesene (B-6) thus obtained are shown in Table 1. PRODUCTION EXAMPLE 8: PRODUCTION OF POLYFARNESENE (B-7)
    [00126] A pressure reaction vessel was loaded with 500 g of the polypharnesene produced by the same method as described in Production Example 6, 0.5 g of "NOCRAC 6C as an antioxidant, and 2.5 g of maleic anhydride. After purging the reaction vessel with nitrogen, the contents of the reaction vessel were heated to 170 ^ and reacted at this temperature for 10 h, thereby obtaining a poly-sine (B-7) .The various properties of the poly-farnesene (B-7) thus obtained are shown in Table 1. PRODUCTION EXAMPLE 9: PRODUCTION OF POLYO-ISOPRENE (X-2)
    [00127] A pressure reaction vessel, previously purged with nitrogen and then dried, was loaded with 600 g of hexane and 13.9 g of n-butyl lithium (in the form of a 17 wt.% Hexane solution). The contents of the reaction vessel were heated to 700, and 1370 g of isoprene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was mixed with methanol and then washed with water. After separating the water from the polymerization reaction solution, the resulting solution was dried at 700 ° C for 12 h, thereby obtaining a polyisoprene (X-2). The various properties of the polyisoprene (X-2) thus obtained are shown in Table 1.
    [00128] However, the weight average molecular weight and the melt viscosity of each of the polymer (B) and the polyisoprene were measured by the following methods. (METHOD OF MEASURING THE PONDERAL AVERAGE MOLECULAR WEIGHT)
    [00129] The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of each of the polymer (B) and the polyisoprene were measured by GPC (gel permeation chromatography) in terms of a molecular weight of polystyrene as a standard reference substance. The measuring devices and the measuring conditions are as follows. • Device: GPC device "GPC8020", available from Tosoh Corp. • Separation column: "TSKgelG4000HXL", available from Tosoh Corp. • Detector: "RI-8020", available from Tosoh Corp. • Eluent: Tetrahydrofuran • Eluent flow rate: 1.0 ml / min • Sample concentration: 5 mg / 10 ml_ • Column temperature: 40'0 (METHOD OF MEASURING FUSION VISCOSITY)
    [00130] The melt viscosity of the polymer (B) was measured at 380, using a Brookfield viscometer, available from Brookfield Engineering Labs. Inc. (METHOD OF MEASURING VINYL CONTENT)
    [00131] A solution prepared by dissolving 50 mg of polymer (B) in 1 mL of CDCI3 was subjected to 1 H NMR measurement, at 400 MHz, at a cumulative frequency of 512 times. In the graph obtained by the aforementioned measurement, a part of the spectrum in the range of 4.94 to 5.22 ppm was considered to be a spectrum derived from a vinyl structure, while a part of the spectrum in the range of 4.45 to 4, 85 ppm was considered to be a combined spectrum, derived both from the vinyl structure and from a 1,4 bond, and the vinyl content of the polymer (B) was calculated according to the following formula. {Vinyl content} = (integrated value from 4.94 to 5.22 ppm) / 2 / {(integrated value from 4.94 to 5.22 ppm) / 2 + [(integrated value from 4.45 to 4, 85 ppm) - (integrated value from 4.94 to 5.22 ppm)] / 3} (METHOD OF MEASURING THE GLASS TRANSITION TEMPERATURE)
    [00132] Ten milligrams of polymer (B) were sampled in an aluminum casserole, and a sample thermogram was measured, at a temperature rise rate of 10'C / min, by differential scanning calorimetry (DSC), and the peak peak value observed on the DDSC curve was determined and defined as a glass transition temperature of the polymer (B).
    EXAMPLES 1 TO 5 AND COMPARATIVE EXAMPLES 1 TO 3
    [00133] The rubber component (A), the polymer (B), the silica (C), the carbon black (D), the polyisoprene, the silane coupling reagent, the TDAE, the stearic acid, zinc oxide and antioxidant were respectively loaded, in such a combination ratio (part (s) by mass) as shown in Table 2, to a closed Banbury mixer and mixed together for 6 min, so that the start temperature was 75 ° C and the resin temperature reached IβO'C. The resulting mixture was once removed from the mixer, and cooled to room temperature. Then, the mixture was placed on a mixing roller and, after adding the sulfur and the vulcanization accelerator to it, the contents of the mixing roller were mixed at 60 ° for 6 min, thereby obtaining a rubber composition . The Mooney viscosity of the rubber composition thus obtained was measured by the method mentioned below.
    [00134] In addition, the resulting rubber composition was pressure molded (at 145 ° C, for 20 to 40 min) to prepare a sheet (thickness: 2 mm). The sheet thus prepared was evaluated for rolling resistance performance, hardness and tensile strength at break by the methods mentioned below. The results are shown in Table 2.
    [00135] However, the method of measuring and evaluating the respective properties is as follows. (1) MOONEY VISCOSITY
    [00136] As an index of a processability of the rubber composition, the Mooney viscosity (ML1 + 4) of the rubber composition, before curing, was measured at WO'C, according to JIS K6300. The values of the Examples and the respective Comparative Examples are relative values based on 100 as the value of Comparative Example 3. However, the lower Mooney viscosity value indicates more excellent processability. (2) BEARING RESISTANCE PERFORMANCE
    [00137] The sheet of the rubber composition prepared in the Examples and in the respective 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 tanδ measurement as an index of the rolling resistance performance of the rubber composition, using a dynamic viscoelasticity measuring device, available from GABO GmbH, under conditions including a measuring temperature of θO'C, a frequency of 10 Hz, a static distortion of 10% and a dynamic distortion of 2%. The values of the Examples and the respective Comparative Examples are relative values based on 100 as the value of Comparative Example 3. However, the lower value indicates excellent rolling resistance performance of the rubber composition. (3) HARDNESS
    [00138] The sheet hardness of the rubber composition prepared in the Examples and in the respective Comparative Examples was measured using a type A hardness tester, according to JIS K6253, and the hardness thus measured was used as an index of the flexibility of the rubber composition. However, when the hardness value is less than 50, a tire produced from the rubber composition suffers from great deformation and, therefore, deteriorates in the stability of the steering. (4) Tensile strength at break
    [00139] The sheet of the rubber composition prepared in the Examples and in the respective Comparative Examples was perforated in a test piece, in the shape of a dumbbell, according to JIS 3, and the test piece obtained was subjected to the measurement of a resistance tensile strength at break using a tensile tester available from Insert Corp. The values of the Examples and the respective Comparative Examples are relative values based on 100 as the value of Comparative Example 3. However, the higher value indicates greater tensile strength in the rupture of the rubber composition.


    [00140] The rubber compositions obtained in Examples 1 to 5 exhibited low Mooney viscosity and, therefore, good processability. In addition, the rubber compositions obtained in Examples 1, 3, 4 and 5 exhibited poor rolling resistance performance. In particular, the rubber compositions obtained in Examples 1, 3 and 4 were prevented from suffering deterioration in mechanical strength and hardness and, therefore, could be properly used as a rubber composition for tires. EXAMPLES 6 TO 26 AND COMPARATIVE EXAMPLES 4 TO 16
    [00141] The rubber component (A), the polymer (B), the silica (C), the carbon black (D), the polyisoprene, the silane coupling reagent, the TDAE, the stearic acid, zinc oxide and antioxidant were respectively loaded, in such a combination ratio (part (s) by mass) as shown in Tables 3 to 5, to a closed type Banbury mixer and mixed together for 6 min, so such that the start temperature was Tδ'C and the resin temperature reached leCTC. The resulting mixture was once removed from the mixer, and cooled to room temperature. Then, the mixture was placed on a mixing roller and, after adding the sulfur and the vulcanization accelerator to it, the contents of the mixing roller were mixed at 60 ° for 6 min, thereby obtaining a rubber composition . The Mooney viscosity of the rubber composition thus obtained was measured by the method mentioned above.
    [00142] In addition, the resulting rubber composition was pressure molded (at 145 °, for 10 to 45 min) to prepare a sheet (thickness: 2 mm). The sheet thus prepared was evaluated for rolling resistance and hardness performance by the methods mentioned above. The results are shown in Tables 3 to 5.
    [00143] However, the values of Mooney viscosity and rolling resistance performance in the Examples and in the respective Comparative Examples are relative values based on 100 as each value in Comparative Example 3 shown in Table 2.


    [00144] The rubber compositions obtained in Examples 6 to 13 exhibited low Mooney viscosity and, therefore, good processability and, in addition, were prevented from suffering deterioration in hardness. In addition, the rubber compositions exhibited poor rolling resistance performance and therefore could be properly used as a rubber tire composition.
    [00145] Furthermore, from the comparison between Examples 8 to 10 and Comparative Example 4, it was confirmed that, even when using two or more types of polymers (B) or using the polymer (B) in combination with the other optional components, it was also possible to obtain the rubber compositions having an excellent rolling resistance performance, without deterioration in their hardness.
    [00146] Furthermore, from the comparison between Example 1 and Comparative Example 5, between Example 12 and Comparative Example 6, between Example 14 or 15 and Comparative Example 8, and between Example 16 and Comparative Example 9, it was confirmed that, even when using two or more types of rubber components (A), it was also possible to obtain rubber compositions having an excellent rolling resistance performance, without deterioration in their hardness.


    [00147] From the comparison between Example 17 and Comparative Example 10, between Example 18 and Comparative Example 11 and between Example 19 and Comparative Example 12, it was confirmed that when using polymer (B) in an amount of 0.1 part by mass or more, per 100 parts by mass of the rubber component (A), it was possible to obtain the rubber compositions having good processability and excellent rolling resistance performance, which were prevented to suffer deterioration in its hardness.
    [00148] From the comparison between Example 20 or 21 and Comparative Example 12 or 13, it was confirmed that, even when using the modified (vinyl) polymer (B), it was also possible to obtain the effects of the present invention.
    [00149] Furthermore, from Example 22 or 23, it was confirmed that, even when combining the silane coupling reagent in an amount of 0.1 to 30 parts by mass, per 100 parts by mass of silica (C ), it was also possible to obtain the rubber composition having an excellent rolling resistance performance, without deterioration in its hardness.


    [00150] From the comparison between Example 24 and Comparative Example 14, between Example 25 and Comparative Example 15 and between Example 26 and Comparative Example 16, it was confirmed that when the polymer (B) is combined in an amount of 100 parts by mass or less, silica (C) in an amount of 0.1 to 150 parts by mass and carbon black (D) in an amount of 0.1 to 150 parts by mass, all per 100 parts by mass of the rubber component (A), it was possible to obtain the rubber compositions having an excellent rolling resistance performance, which were prevented from suffering deterioration in their hardness. In addition, it was confirmed that when silica (C) having an average particle size of 0.5 to 200 nm or carbon black (D) having an average particle size from 5 to 100 nm is also used it was possible to obtain the effects of the present invention. EXAMPLES 27 TO 30 AND COMPARATIVE EXAMPLES 17 TO 19
    [00151] The rubber component (A), polymer (B), silica (C), polyisoprene, silane coupling reagent, TDAE, stearic acid, zinc oxide and antioxidant respectively loaded, in such a combination ratio as shown in Table 6, to a closed type Banbury mixer and mixed together for 6 min, such that the start temperature was 75 ° C and the resin temperature reached 160 °. The resulting mixture was removed from the mixer, and cooled to room temperature. Then, the mixture was placed on a mixing roller and, after adding the sulfur and the vulcanization accelerator to it, the contents of the mixing roller were mixed at 60 °, for 6 min, thereby obtaining a rubber composition. The Mooney viscosity of the rubber composition thus obtained was measured by the method mentioned below.
    [00152] In addition, the resulting rubber composition was molded by pressure (at 145 ° C, for 20 to 40 min) to prepare a sheet (thickness: 2 mm). The sheet thus prepared was evaluated for rolling resistance and hardness performance by the methods mentioned below. The results are shown in Table 6. (1) MOONEY VISCOSITY
    [00153] As an index of a processability of the rubber composition, the Mooney viscosity (ML1 + 4) of the rubber composition, before curing, was measured at WO'C, according to JIS K6300. The values of the respective Examples and Comparative Examples, as shown in Table 6, are relative values based on 100 as the value of Comparative Example 19. However, the lower Mooney viscosity value indicates more excellent processability. (2) BEARING RESISTANCE PERFORMANCE
    [00154] The sheet of the rubber composition prepared in the Examples and in the respective 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 tanδ measurement as an index of the rolling resistance performance of the rubber composition, using a dynamic viscoelasticity measuring device, available from GABO GmbH, under conditions including a measuring temperature of βO'C, a frequency of 10 Hz, a static distortion of 10% and a dynamic distortion of 2%. The values of the Examples and the respective Comparative Examples are relative values based on 100 as the value of Comparative Example 19. However, the lower value indicates a higher rolling resistance performance of the rubber composition. (3) HARDNESS
    [00155] The sheet hardness of the rubber composition prepared in the Examples and in the respective Comparative Examples was measured SUM using a type A hardness tester, according to JIS K6253, and the hardness thus measured was used as an index of flexibility of the rubber composition. However, when the hardness value is less than 50, a tire produced from the rubber composition suffers from great deformation and, therefore, deteriorates in the stability of the steering.


    [00156] The rubber compositions obtained in Examples 27 to 30 exhibited low Mooney viscosity and good processability. In addition, the rubber compositions obtained in Examples 27 to 30 exhibited poor rolling resistance performance and were prevented from suffering deterioration in hardness, even in comparison with those in Comparative Examples 17 and 18. Among them, the rubber compositions obtained in Examples 27, 29 and 30 they exhibited a good balance between a low rolling resistance and a high hardness and, therefore, could be properly used as a rubber tire composition. On the other hand, the rubber composition obtained in Comparative Example 19 exhibited a high Mooney viscosity and was insufficient in processability. EXAMPLES 31 AND 32 AND COMPARATIVE EXAMPLES 20 TO 22
    [00157] The rubber component (A), the polymer (B), the silica (C), the polyisoprene, the silane coupling reagent, the ADTs, the stearic acid, the zinc oxide and the antioxidant respectively loaded, in such a combination ratio (part (s) by mass) as shown in Table 7, to a Banbury mixer of the closed type and mixed together for 6 min, such that the start temperature was 75 ^ and the temperature of resin reached 160 ^. The resulting mixture was removed from the mixer, and cooled to room temperature. Then, the mixture was placed on a mixing roller and, after adding the sulfur and the vulcanization accelerator to it, the contents of the mixing roller were mixed at 60 °, for 6 min, thereby obtaining a rubber composition. The Mooney viscosity of the rubber composition thus obtained was measured by the method mentioned above.
    [00158] In addition, the resulting rubber composition was molded by pressure (at Mδ'C, for 45 min) to prepare a sheet (thickness: 2 mm). The sheet thus prepared was evaluated for rolling resistance and hardness performance by the methods mentioned above. The results are shown in Table 7.
    [00159] However, the values of Mooney viscosity, rolling resistance performance, tensile strength at break in the Examples and in the respective Comparative Examples are relative values based on 100 as each value in Comparative Example 22 shown in Table 7.

    [00160] The rubber compositions obtained in Examples 31 and 32 exhibited low Mooney viscosity and good processability. In addition, the rubber compositions obtained in Examples 31 and 32 exhibited poor rolling resistance performance and were prevented from suffering deterioration in mechanical strength and hardness, even compared with those in Comparative Examples 20 and 21 and therefore could be properly used as a rubber composition for tires. On the other hand, the rubber composition obtained in Comparative Example 22 exhibited a high Mooney viscosity and was insufficient in processability.
    权利要求:
    Claims (16)
    [0001]
    1. Rubber composition, characterized by comprising a rubber component (A), a farnesene polymer (B) and silica.
    [0002]
    2. Rubber composition according to claim 1, characterized by the fact that the polymer (B) is a homopolymer of β-farnesene.
    [0003]
    Rubber composition according to claim 1 or 2, characterized by the fact that silica (C) has an average particle size of 0.5 to 200 nm.
    [0004]
    Rubber composition according to any one of claims 1 to 3, characterized by the fact that the polymer (B) has a melt viscosity of 0.1 to 3,000 Pa * s (as measured at 3813).
    [0005]
    Rubber composition according to any one of claims 1 to 4, characterized in that the polymer (B) has a weight average molecular weight of 2,000 to 500,000.
    [0006]
    Rubber composition according to any one of claims 1 to 5, characterized in that the content of the polymer (B) in the rubber composition is 0.1 to 100 parts by weight and a content of silica (C ) in the rubber composition is 0.1 to 150 parts by weight, both per 100 parts by weight of the rubber component (A).
    [0007]
    Rubber composition according to any one of claims 1 to 6, characterized in that it additionally comprises carbon black (D).
    [0008]
    Rubber composition according to claim 7, characterized by the fact that carbon black (D) has an average particle size of 5 to 100 nm.
    [0009]
    Rubber composition according to claim 7 or 8, characterized by the fact that a content of polymer (B) in the rubber composition is 0.1 to 100 parts by weight, a content of silica (C) in rubber composition is 0.1 to 150 parts by weight, and a carbon black content (D) in the rubber composition is 0.1 to 150 parts by weight, all per 100 parts by weight of the rubber component ( THE).
    [0010]
    Rubber composition according to any one of claims 1 to 9, characterized in that the rubber component (A) 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.
    [0011]
    11. Rubber composition according to claim 10, characterized by the fact that styrene-butadiene rubber has a weight average molecular weight of 100,000 to 2,500,000.
    [0012]
    Rubber composition according to claim 10 or 11, characterized in that the styrene-butadiene rubber has a styrene content of 0.1 to 70% by weight.
    [0013]
    Rubber composition according to any one of claims 10 to 12, characterized in that the butadiene rubber has a weight average molecular weight of 90,000 to 2,000,000.
    [0014]
    Rubber composition according to any one of claims 10 to 13, characterized in that the butadiene rubber has a vinyl content of 50% by weight or less.
    [0015]
    Rubber composition according to any one of claims 1 to 14, characterized in that the polymer (B) has a molecular weight distribution of 1.0 to 8.0.
    [0016]
    16. Pneumatic, characterized in that it at least partially comprises the rubber composition as defined in any one of claims 1 to 15.
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    同族专利:
    公开号 | 公开日
    CA2865378C|2021-05-11|
    KR101961513B1|2019-03-22|
    JP2013241609A|2013-12-05|
    PT2818507T|2017-03-08|
    KR20140129044A|2014-11-06|
    EP2818507A1|2014-12-31|
    RU2617481C2|2017-04-25|
    EP2818507B1|2017-01-11|
    US9228077B2|2016-01-05|
    WO2013125496A1|2013-08-29|
    KR20190031591A|2019-03-26|
    CA3073378C|2022-01-04|
    TW201343795A|2013-11-01|
    CN104245818A|2014-12-24|
    RU2014138498A|2016-04-10|
    JP5617040B2|2014-10-29|
    JPWO2013125496A1|2015-07-30|
    EP3156445A1|2017-04-19|
    ES2614822T3|2017-06-02|
    CA3059169A1|2013-08-29|
    TWI565758B|2017-01-11|
    HUE038502T2|2018-10-29|
    US20150051332A1|2015-02-19|
    CA2865378A1|2013-08-29|
    TR201802865T4|2018-03-21|
    CN106317520A|2017-01-11|
    EP3156445B1|2018-01-17|
    PT3156445T|2018-03-20|
    CA3073378A1|2013-08-29|
    EP2818507A4|2015-11-04|
    CN104245818B|2016-10-19|
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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]|
    2019-11-05| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-06-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-10-13| 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 18/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012039414|2012-02-24|
    JP2012-039414|2012-02-24|
    JP2012-039413|2012-02-24|
    JP2012039413|2012-02-24|
    PCT/JP2013/053904|WO2013125496A1|2012-02-24|2013-02-18|Rubber composition and tire|
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