copolymer, rubber composition using that copolymer and tire

专利摘要:
COPOLYMER, RUBBER COMPOSITION WITH THE USE OF THIS COPOLYMER AND TIRE. The present invention relates to a copolymer that includes a monomer unit (a) derived from isoprene and a monomer unit (b) derived from farnesene; a process for producing the copolymer, including at least the step of copolymerizing isoprene with farnesene; a rubber composition that includes (A) the copolymer, (B) a rubber component and (C) carbon black; a rubber composition that includes (A) the copolymer, (B) a rubber component and (D) silica; a rubber composition that includes (A) the copolymer, (B) a rubber component, (C) carbon black and (D) silica; and a tire that uses the rubber composition at least as part of it.
公开号:BR112014024729B1
申请号:R112014024729-3
申请日:2013-04-02
公开日:2021-01-12
发明作者:Daisuke Koda；Kei Hirata
申请人:Kuraray Co., Ltd.；Amyris, Inc；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to a copolymer that contains a monomeric unit derived from farnesene, a rubber composition that contains the copolymer and a tire that uses the rubber composition. BACKGROUND OF THE INVENTION
[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 which are reinforced in terms of mechanical resistance by incorporating a reinforcing agent such as carbon black in a rubber component, such as a natural rubber and a styrene-butadiene rubber. It is known that carbon black exhibits its reinforcing effect by physically or chemically adsorbing the aforementioned rubber component on the 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 generally difficult to achieve a sufficient interaction between the carbon black and the rubber component, so that the resulting rubber composition tends to slightly improve mechanical strength at a sufficient level. In addition, tires made from this rubber composition tend to exhibit low hardness and therefore tend to be insufficient in terms of steering 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 rubber composition resultant can be improved in terms of properties, such as mechanical strength and wear resistance, due to a great interaction between carbon black and the rubber component. In addition, tires made from this rubber composition can be improved in terms of steering stability due to an increase in their hardness.
[004] However, in the case where carbon black with such a small average particle size is used in the rubber composition, it is known that the resulting rubber composition tends to deteriorate in the dispersibility of carbon black in composition, due to a high cohesive force between the carbon black particles. The deteriorated dispersion capacity of carbon black in the rubber composition tends to induce a prolonged crushing stage and therefore tends to confer an adverse influence on the productivity of the rubber composition. In addition, the deteriorated dispersion of carbon black tends to cause heat generation in the rubber composition, so tires made from that composition tend to deteriorate in rolling resistance performance and may often not meet requirements for low rolling resistance tires, ie the so-called low fuel consumption tires. In addition, in the case where the carbon black used in the rubber composition has a small average particle size, a problem tends to occur in which the resulting rubber composition has a high viscosity and therefore deteriorates in the process. - wisdom.
[005] Thus, the mechanical strength and hardness of the rubber tire composition are properties that have a contradictory relationship with the rolling resistance performance and the processability of the composition, and therefore, the composition of rubber is hardly improved in a well balanced way in both properties.
[006] In PTL1, as a rubber composition that can be improved in the above properties in a well balanced way, a rubber composition for tires is described which includes a rubber component containing an isoprene-based rubber and a rubber styrene-butadiene, carbon black and a liquid resin that has a softening point between -20 and 20 ° C, in a specific composition ratio.
[007] In addition, PTL2 describes a tire that includes a rubber component that contains a diene-based rubber consisting of a modified styrene-butadiene copolymer and a modified conjugated diene-based polymer, and a filler such as carbon black. smoke in a specific composition ratio.
[008] However, any of the tires described in these patent literature do not satisfy the mechanical strength and hardness, as well as the performance in terms of rolling resistance and processability, with a sufficiently high level and therefore there is still a great deal looking for tires that show further improvement in these properties.
[009] However, PTL3 and PTL4 describe a β-farnesene polymer, but fail to present a sufficient study in its practical applications. LIST OF CITATIONS PATENT LITERATURE
[0010] PTL1: JP 2011-195804A
[0011] PTL2: JP 2010-209256A
[0012] PTL3: WO 2010 / 027463A
[0013] PTL4: WO 2010 / 027464A SUMMARY OF THE INVENTION TECHNICAL PROBLEM
[0014] The present invention was carried out in view of the above conventional problems. The present invention provides a copolymer capable of increasing the dispersibility of a filler such as carbon black and silica in a rubber composition when using the copolymer as part of the rubber composition; a rubber composition that contains the copolymer and not only has a good processing capacity in terms of composition, molding or curing, but it is also excellent in rolling resistance and wear resistance performance and, moreover, hardly deteriorates in strength mechanics and hardness; and a tire obtained using the rubber composition. SOLUTION TO THE PROBLEM
[0015] As a result of extensive and intensive research, the inventors of the present invention have found that when using a copolymer containing an isoprene-derived monomer unit and a farnesene-derived monomer unit in a rubber composition, the composition The resulting rubber can be improved not only in processability, but also in mechanical strength, wear resistance and rolling resistance performance. The present invention was carried out based on the aforementioned verification.
[0016] That is, the present invention relates to the following aspects.
[0017] [1] A copolymer that includes a monomer unit (a) derived from isoprene and a monomer unit (b) derived from farnesene.
[0018] [2] A process for producing the copolymer that includes at least the step of copolymerization of isoprene with farnesene.
[0019] [3] A rubber composition that includes (A) the above copolymer; (B) a rubber component; and (C) carbon black.
[0020] [4] A rubber composition that includes (A) the above copolymer; (B) a rubber component; and (D) silica.
[0021] [5] A rubber composition that includes (A) the above copolymer; (B) a rubber component; (C) carbon black; and (D) silica.
[0022] [6] A tire that uses rubber composition, at least, as part of it. ADVANTAGE EFFECTS OF THE INVENTION
[0023] According to the present invention, it is possible to provide a copolymer capable of increasing the dispersibility of a filler such as carbon black and silica in a rubber composition when using the copolymer as part of the rubber composition; a rubber composition that contains the copolymer and not only has a good processing capacity in terms of composition, molding and curing, but it is also excellent in rolling resistance and wear resistance performance and, moreover, hardly deteriorates in strength mechanics and hardness; and a tire obtained using the rubber composition. DESCRIPTION OF THE COPOLYMER CARRYING OUT MODALITIES
[0024] The copolymer according to the present invention is a copolymer that includes a monomer unit (a) derived from isoprene and a monomer unit (b) derived from farnesene.
[0025] In the present invention, the monomer unit (b) can be a monomer unit derived from α-farnesene, or a monomer unit derived from β-farnesene, represented by the following formula (I). However, of these monomer units, from the point of view of facilitated copolymer production, the β-farnesene-derived monomer unit is preferred. However, α-farnesene and β-farnesene can be used in combination with each other.

[0026] The 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 average molecular weight of the copolymer is within the range specified above, the rubber composition mentioned below has a good processing capacity and can be further improved in its dispersion capacity of carbon black or silica in the composition; therefore, it can have a good rolling resistance performance. However, the average weight 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 average weight molecular weight, can be used in the form of a mixture thereof.
[0027] The melt viscosity of the copolymer measured at 38 ° C is preferably from 0.1 to 3,000 Pa ^ s, more preferably from 0.6 to 2,800 Pa ^ s, even more preferably from 1.5 to 2,600 Pa even more preferably from 1.5 to 2,000 Pa ^ s. When the melt viscosity of the copolymer falls within the range specified above, the resulting rubber composition can be easily kneaded and can be improved in terms of processing capacity. However, in this specification, the melt viscosity of the copolymer is the value measured by the method described below in the Examples.
[0028] The mass ratio between the monomer unit (a) and the sum of the monomer unit (a) and the monomer unit (b) in the copolymer is preferably from 1 to 99% by weight, more preferably from 10 to 80% by weight, and even more preferably from 15 to 70% by weight, from the point of view of increased processability and rolling resistance performance of the resulting rubber composition.
[0029] The molecular weight distribution (Mw / Mn) of the copolymer is preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0 and even more preferably from 1.0 to 2.0. When the molecular weight distribution (Mw / Mn) of the copolymer falls within the range specified above, the resulting copolymer can adequately exhibit less variation in its viscosity.
The copolymer according to the present invention can be any suitable copolymer, as long as it is produced by co-polymerizing at least isoprene with farnesene, and the copolymer can also be produced by copolymerizing another monomer with the isoprene farnesene.
[0031] Examples of other monomers include conjugated dienes such as butadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3- pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, mircene and chloroprene; and 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. Of these other monomers, butadiene, myrrene, styrene, α-methyl-styrene and 4-methyl-styrene are preferred.
[0032] The content of the other monomer in the copolymer is preferably not more than 50% by weight, more preferably not more than 40% by weight, and even more preferably not more than 30% by weight. COPOLYMER PRODUCTION PROCESS
[0033] 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 copolymerization of isoprene 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 method is the solution polymerization method. EMULSION POLYMERIZATION METHOD
[0034] The emulsion polymerization method for the production of the copolymer can be any suitable known conventional method. For example, a predetermined amount of a farnesene monomer and a predetermined amount of an isoprene monomer are emulsified and dispersed in the presence of an emulsifying reagent, and then the resulting emulsion is subjected to emulsion polymerization using an initiator. of polymerization via radicals.
[0035] As an emulsifying reagent, for example, a long-chain fatty acid salt with 10 or more carbon atoms or a salt of rosinic acid 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.
[0036] As a 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 an organic solvent has any adverse influence on the stability of the polymerization reaction system.
[0037] Examples of the radical polymerization initiator include persulfates, such as ammonium persulfate and potassium persulfate; and organic peroxides and hydrogen peroxide.
[0038] 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-dodecylmercaptan and n-dodecylmercaptan; and carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, Y-terpinene and an α-methyl-styrene dimer.
[0039] The temperature employed in emulsion polymerization can be appropriately determined according to the type of radical polymerization initiator used, and is generally preferably 0 to 100 ° C and more preferably 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.
Examples of the terminating reagent include amine compounds such as isopropyl hydroxylamine, diethyl hydroxylamine and hydroxylamine; quinone-based compounds such as hydroquinone and benzoquinone; and sodium nitrite.
[0041] After stopping the polymerization reaction, an antioxidant can be added to the polymerization reaction system, if necessary. In addition, after interrupting the polymerization reaction, unreacted monomers can be removed from the resulting latex, if necessary. The resulting copolymer is then coagulated by adding a salt such as sodium chloride, calcium chloride and potassium chloride as a coagulant and, if necessary, by adjusting the pH value of the coagulation system by adding an acid such as nitric acid and sulfuric acid, and then the dispersion 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. However, after coagulation of the copolymer, the latex can be previously mixed, if necessary, with a dilution oil in the form of an emulsified dispersion to recover the copolymer in the form of an oil-extended rubber. SOLUTION POLYMERIZATION METHOD
[0042] The solution polymerization method for the production of copolymer can be any suitable conventional known method. For example, a farnesene monomer can be polymerized with an isoprene monomer in a solvent, using a Ziegler-based catalyst, a metallocene-based catalyst or an anion-curable active metal, if necessary, in the presence of a compound polar.
[0043] Examples of the active metal polymerizable via anions 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 lantanoids, 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 alkali metal organic compound.
[0044] Specific examples of the alkali metal organic 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, dilitionaphthalene, 1,4-dilithiobutane, 1,4-dilithium-2-ethylcyclohexane and 1,3,5-trilithiobenzene; naphthalene sodium and naphthalene potassium. Among these organic alkali metal compounds, organic lithium compounds are preferred, and most preferred are organic monolithium compounds. The amount of the alkali metal organic compound employed can be appropriately determined according to the molecular weight of the farnesene polymer, as needed, and is preferably 0.01 to 3 parts by weight, based on 100 parts by weight of farnesene.
[0045] The organic alkali metal compound can be used in the form of an organic alkali metal amide, allowing a secondary amine such as dibutylamine, diexylamine and dibenzylamine to react with the compound.
[0046] 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 methylcyclopentane; and aromatic hydrocarbons such as benzene, toluene and xylene.
[0047] The polar compound can be used in polymerization via anions to control a microstructure of a statistical structure or a portion derived from farnesene or a portion derived from an isoprene, without causing the reaction to deactivate. Examples of the polar compound include ether compounds such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane and ethylene glycol ethyl ether; pyridine; tertiary amines such as tetramethylethylenediamine 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 alkali metal organic compound.
[0048] The copolymer, according to the present invention, is preferably produced by carrying out an anionic polymerization, in the presence of an organic metal initiator such as the organic compounds of alkali metals above the point of view of easy control of a distribution of molecular weights of the resulting copolymer within the aforementioned range.
[0049] The temperature used in the above polymerization reaction is generally -80 to 150 ° C, preferably 0 to 10 0 ° C and more preferably 10 and 90 ° C. The polymerization method can be a batch method or a continuous method. Farnesene and isoprene are fed to the reaction solution respectively in a continuous or intermittent manner, so that the compositional proportion of farnesene and isoprene in the polymerization system is within a specific range, or a mixture of farnesene and isoprene that has previously prepared, so that a compositional proportion of these compounds, controlled in a specific range, is fed to the reaction solution, by means of which it is possible to produce a statistical copolymer. Alternatively, farnesene and isoprene are sequentially polymerized in the reaction solution such that the composition ratio of these compounds in the polymerization system is controlled within a specific range, whereby it is possible to produce a block copolymer.
[0050] The polymerization reaction can be stopped by adding an alcohol such as methanol and isopropanol as the terminating reagent to the reaction system. The resulting polymerization reaction solution can be poured into a poor solvent such as methanol to precipitate the copolymer. Alternatively, the polymerization reaction solution can be washed with water and then a solid is separated and dried to isolate the copolymer. MODIFIED COPOLYMER
[0051] 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 .
[0052] As a method of producing the modified copolymer, for example, the method in which, before adding the terminating reagent, a coupling reagent such as tin tetrachloride is added to the polymerization reaction system. , tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethyl cyclohexane and 2,4-tolylenediisocyanate that are capable of reacting with a polymer chain with an active end of the chain chain end modification such as 4,4'-bis (diethylamino) benzophenone and N-vinylpyrrolidone, or other modifying reagent as described in JP 2011-132298A. In addition, the isolated copolymer can be grafted with maleic anhydride or the like.
[0053] In the modified copolymer, the location of the polymer where the functional group is introduced can be a chain end or a side chain of the polymer. In addition, these functional groups can be used alone or in combination with 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 and 10 molar equivalents based on the alkali metal organic compound. RUBBER COMPOSITION
[0054] 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.
[0055] 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.
[0056] 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)
[0057] Examples of the rubber component (B) used here include a natural rubber, a styrene-butadiene rubber (hereinafter also referred to simply as "SBR"), a butadiene rubber, an isoprene rubber, a rubber butyl, a halogenated butyl rubber, an ethylene-propylene-diene rubber, a butadiene-acrylonitrile copolymer rubber and a chloroprene rubber. Of these rubbers, SBR, a natural rubber, a butadiene rubber and an isoprene rubber are preferred, and more preferred are SBR and a natural rubber. These rubbers can be used alone or in combination with any two or more of these rubbers. NATURAL RUBBER
[0058] Examples of natural rubber used as a rubber component (B) in the present invention include natural rubbers commonly used in the tire industry, for example, TSR such as SMR, SIR and STR; and RSS etc .; 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, STR20, SMR20 and RSS N ° 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 with any two or more of them. SYNTHETIC RUBBER
[0059] Examples of a synthetic rubber used as a rubber component (B) in the present invention include SBR, a butadiene rubber, an isoprene rubber, a butyl rubber, a halogenated butyl rubber, an ethylene- propylene-diene, a butadiene-acrylonitrile copolymer rubber and a chloroprene rubber. Of these rubbers, SBR, isoprene and a butadiene rubber are preferred. SBR
[0060] As SBR, rubbers generally used in tire applications can be used. More specifically, SBR preferably has a styrene content of 0.1 to 70% by weight and more preferably from 5 to 50% by weight. In addition, the SBR preferably has a vinyl content of 0.1 to 60% by weight and more preferably from 0.1 to 55% by weight.
[0061] 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 average molecular weight of SBR falls within the range specified above, the resulting rubber composition can be improved in both processability and mechanical strength. However, in this specification, the average molecular weight is the value measured by the method described below in the Examples.
[0062] 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. By adjusting the SBR Tg in the range specified above, it is possible to suppress the increase in SBR viscosity and improve the handling properties of this rubber. METHOD FOR THE PRODUCTION OF SBR
[0063] 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 . Of these polymerization methods, an emulsion polymerization method and a solution polymerization method are preferred. (i) Emulsion Polymerized Styrene-Butadiene Rubber (E-SBR)
[0064] 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 powder initiator. limerization via radicals.
[0065] As an emulsifying reagent, for example, a long-chain fatty acid salt with 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.
[0066] As a dispersant for the above emulsion polymerization, water can generally be used. The dispersant can also contain an organic solvent soluble in a dissipating agent, such as methanol and ethanol, unless the use of an organic solvent provides any adverse influence on stability during polymerization.
[0067] Examples of the radical polymerization initiator include persulfates, such as ammonium persulfate and potassium persulfate, organic peroxides and hydrogen peroxide.
[0068] In order to properly adjust the molecular weight of the E-SBR obtained, a chain transfer reagent can be used. Examples of the chain transfer reagent include mercaptan such as t-dodecyl-mercaptan and n-dodecylmercaptan; and carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, Y-terpinene and an α-methylstyrene dimer.
[0069] The temperature used in emulsion polymerization can be appropriately determined according to the type of polymerization initiator via radicals used, and is in general 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.
Examples of the terminating reagent include amine compounds such as isopropyl hydroxylamine, diethyl hydroxylamine and hydroxylamine; quinone-based compounds, such as hydroquinone and benzoquinone; and sodium nitrite.
[0071] After stopping the polymerization reaction, an antioxidant can be added to the polymerization reaction system, if necessary. In addition, after interrupting the polymerization reaction, unreacted monomers can be removed from the resulting latex, if necessary. Thereafter, the polymer obtained is coagulated by adding a salt such as sodium chloride, calcium chloride and potassium chloride as a coagulant and, if necessary, by adjusting the pH value of the coagulation system by adding an acid, such as nitric acid and sulfuric acid and then the dispersing solvent is separated from the reaction solution to recover the polymer as fragments. The granulate, thus recovered, is washed with water and dehydrated, and then dried using a band dryer or similar to obtain E-SBR. However, in the coagulation of the polymer, the latex can be previously mixed, if necessary, with a dilution oil, in the form of an emulsified dispersion to recover the polymer in the form of an oil-extended rubber. (ii) Solution Polymerized Styrene-Butadiene Rubber (S-SBR)
[0072] S-SBR can be produced by a polymerization method in common solution. For example, styrene and butadiene are polymerized in a solvent using an anion-curable active metal, if necessary, in the presence of a polar compound.
[0073] Examples of the anion-curable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals, such as beryllium, magnesium, calcium, strontium and barium; and rare earth metals based on lanthanides, 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 alkali metal organic compound.
[0074] Specific examples of the alkali metal organic compound include organic monolithium compounds such as n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium, phenyl lithium and stilbene lithium; organic polyfunctional lithium compounds such as dilithomethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane and 1,3,5-trilithiumbenzene; naphthalene sodium and naphthalene potassium. Among these alkali metal organic compounds, organic lithium compounds are preferred, and most preferred are organic monolithium compounds. The amount of the alkali metal organic compound used can be appropriately determined according to the molecular weight of S-SBR, as needed.
[0075] The organic alkali metal compound can be used in the form of an organic alkali metal amide, allowing a secondary amine such as dibutylamine, diexylamine and dibenzylamine to react with the compound.
[0076] Examples of polar compounds include ether compounds such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane and ethylene glycol ethyl ether; pyridine; tertiary amines such as tetramethylethylenediamine and trimethylamine; and alkali metal alkoxides, such as potassium t-butoxide; and phosphine compounds. The polar compound is preferably used in an amount of 0.01 to 1,000 molar equivalents based on the alkali metal organic compound.
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 methylcyclopentane; and aromatic hydrocarbons such as benzene and toluene. These solvents are preferably used in an amount such that the monomer is normally dissolved in them at a concentration of 1 to 50% by weight.
[0078] The temperature used in the above polymerization reaction is generally -80 to 150 ° C, preferably 0 to 10 0 ° C and more preferably 30 to 90 ° C. The polymerization method can be a batch method or a continuous method. In addition, in order to improve the statistical copolymerization capacity between styrene and butadiene, styrene and butadiene are preferably fed to the reaction solution in a continuous or intermittent manner, so that the composition ratio between styrene and butadiene in the system of polymerization is within a specific range.
[0079] The polymerization reaction can be stopped by adding an alcohol such as methanol and isopropanol as terminating reagents to the reaction system. The solution of the polymerization reaction obtained after the interruption of the polymerization reaction can be directly subjected to drying or separation by steam to remove the solvent, thus recovering the S-SBR, as intended. However, before removing the solvent, the polymerization reaction solution can be previously mixed with a dilution oil to recover the S-SBR in the form of an oil-extended rubber. MODIFIED STYRENE-BUTADIENE RUBBER (MODIFIED SBR)
[0080] In the present invention, a modified SBR can also be employed produced by the introduction of a functional group in SBR. Examples of the functional group to be introduced into SBR include an amino group, an alkoxysilyl group, a hydroxyl group, an epoxy group and a carboxyl group.
[0081] As a method of producing the modified SBR, for example, the method in which before adding the terminating reagent a coupling reagent, such as tin tetrachloride, tetrachlorosilane, dimethyl dichlorosilane, dimethyl diethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tagaglycidyl-1,3-bisaminomethyl cyclohexane and 2,4-tolylene diisocyanate, which are capable of reacting with an active end of the polymer chain, a reagent is added to the polymerization reaction system chain-end modifying agents, such as 4,4'-bis (diethylamino) benzophenone and N-vinylpyrrolidone, or other modifying reagent, as described in JP 2011-132298A.
[0082] In the modified SBR, the location of the polymer where the functional group is introduced may be a chain end or a side chain of the polymer. ISOPRENE RUBBER
[0083] Isopropylene rubber can be a commercially available isoprene rubber that can be obtained, for example, by polymerization using a Ziegler-based catalyst, such as titanium tetralide-trialkylaluminum catalysts, catalysts based on diethylaluminium-cobalt chloride, catalysts based on trialkylaluminium-boron-nickel trifluoride and catalysts based on diethylaluminium-nickel chloride; a rare earth metal catalyst based on lanthanoid such as catalysts based on triethyl aluminum-Lewis acid organic acid-Lewis acid; or an alkali metal organic compound as used in a similar way for the production of S-SBR. Among these isoprene rubbers, isoprene rubbers obtained by polymerization using the Ziegler-based catalyst are preferred due to a high cis isomer content. In addition, those isoprene rubbers with an ultra high cis isomer content can also be used, which are produced using the lanthanoid based rare earth metal catalyst.
[0084] Isopropene rubber has a vinyl content of 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less. When the vinyl content of isoprene rubber is greater than 50% by mass, the resulting rubber composition tends to deteriorate in rolling resistance performance. The lower limit of the vinyl content of isoprene rubber is not particularly limited. The glass transition temperature of the isoprene rubber can vary, depending on its vinyl content, and is preferably -20 ° C or less and more preferably -30 ° C or less.
[0085] The average weight molecular weight of isoprene rubber is preferably 90,000 to 2,000,000 and more preferably 150,000 to 1,500,000. When the average molecular weight of the isoprene rubber falls within the range specified above, the resulting rubber composition may have good processing capacity and good mechanical strength.
[0086] 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, tetrachloride silicon, an alkoxysilane that contains an epoxy group in the molecule and an alkoxysilane that contains an amino group. BUTADIENE RUBBER
[0087] Butadiene rubber can be a commercially available butadiene rubber, which can be obtained, for example, by polymerization using a Ziegler-based catalyst, such as titanium tetralide-trialkylaluminum catalysts, catalysts with based on diethylaluminium-cobalt chloride, catalysts based on trialkylaluminium-boron-nickel trifluoride and catalysts based on diethylaluminium-nickel chloride; a rare earth metal catalyst based on lanthanoid such as catalysts based on triethyl aluminum-Lewis acid organic acid-Lewis acid; or an alkali metal organic compound as used in a similar way for the production of S-SBR. Among these butadiene rubbers, butadiene rubbers obtained by polymerization using the Ziegler-based catalyst are preferred due to a high cis isomer content. In addition, those butadiene rubbers with an ultra high cis isomer content that are produced using the rare earth metal catalyst based on lantanoid can also be used.
[0088] Butadiene rubber has a vinyl content of 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less. When the vinyl content of butadiene rubber is greater 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 ° C or less and more preferably -50 ° C or less.
[0089] The average weight molecular weight of butadiene rubber is preferably from 90,000 to 2,000,000, more preferably from 150,000 to 1,500,000 and even more preferably from 250,000 to 800,000. When the average molecular weight of butadiene rubber falls within the range specified above, the resulting rubber composition may have good processing capacity and good mechanical strength.
[0090] Butadiene rubber may partially have a branched structure or may partially contain a polar functional group, using a type of polyfunctional modifying reagent, for example, a modifying reagent such as tin tetrachloride, silicon tetrachloride, an alkoxysilane that contains an epoxy group in the molecule and an alkoxysilane that contains amino groups.
[0091] 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 rubber can be used -diene, a butadiene-acrylonitrile copolymer rubber and a chloroprene rubber. The method of producing such rubbers is not particularly limited, and any suitable commercially available synthetic rubbers can also be used in the present invention.
[0092] In the present invention, when using the rubber component (B) in combination with the aforementioned copolymer (A), it is possible to improve the processing capacity of the resulting rubber composition, the dispersion capacity of the carbon black, silica etc. composition and rolling resistance performance.
[0093] When using a mixture of two or more types of synthetic rubbers, the combination of the synthetic rubbers can be optionally selected, unless the effects of the present invention are negatively influenced. In addition, various properties of the resulting rubber composition such as rolling resistance and wear resistance performance can be adequately controlled by selecting an appropriate combination of synthetic rubbers.
[0094] However, the method for producing the rubber used as the rubber component (B) in the present invention is not particularly limited, and any commercially available product can also be used as rubber.
[0095] The rubber composition preferably contains the above copolymer (A) 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 mass, based on 100 parts by mass of the rubber component (B) above the point of view of improving the rolling resistance and wear resistance of the rubber composition. SMOKE BLACK (C)
[0096] 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 point of view of a high cure rate and an improved mechanical strength of the rubber composition, furnace black is preferred.
[0097] Examples of commercially available furnace black products include "DIABLACK" available from Mitsubishi Chemical Corp., and "SEAST" available from Tokai Carbon Co., Ltd. Examples of commercially available acetylene black products include "DENKABLACK" available by Denki Kagaku Kogyo KK. Examples of commercially available Ketjen black products include "ECP600JD" available from Lion Corp.
[0098] The 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 thermal treatment in the presence of air to carry out a treatment surface oxidation, from the point of view of improving the wetting or dispersion capacity of carbon black (C) in the copolymer (a) and in the rubber component (B). In addition, from the point of view of improving the mechanical strength of the rubber composition of the present invention, carbon black can be subjected to a heat treatment at a temperature of 2,000 to 3,000 ° C, in the presence of a graphitization catalyst. As a graphitization catalyst, boron, boron oxides (such as, for example, B2O2, B2O3, B4O3 and B4O5), boron oxoacids (such as, for example, orthoboric acid, metabolic acid and tetraboric acid) and their salts, boron carbides (such as, for example, B4C and B6C), boron nitride (such as BN) and other boron compounds.
[0099] The average size of the carbon black particles (C) can be controlled by spraying or similar. In order to pulverize the carbon black (C), a high speed rotary mill (for example, a hammer mill, a pin mill and a cage mill) can be used or several ball mills (such as a lami - generator, a vibration mill and a planetary mill), a stirring mill (such as a ball mill, a friction mill, a flow tube mill and an annular mill) or similar.
[00100] Carbon black (C) preferably has an average particle size of 5 to 100 nm and more preferably 10 to 80 nm, in terms of improving the dispersibility of the rubber composition and the mechanical strength of the composition rubber.
[00101] However, the average particle size of the carbon black (C) can be determined by calculating an average value of the diameter of the carbon black particles measured using a transmission-type electron microscope.
[00102] In the rubber composition of the present invention, carbon black (C) is preferably composed in an amount of 0.1 to 150 parts by weight, more preferably 2 to 150 parts by weight, even more preferably 5 to 90 parts by weight and even more preferably from 20 to 80 parts by weight, based on 100 parts by weight of the rubber component (B). When the amount of carbon black (C) compound falls within the range specified above, the resulting rubber composition is not only excellent in mechanical strength, hardness and processability, but also has a good dispersion capacity of carbon black (C ) on it. SILICA (D)
[00103] 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 point of view of further improvement of processing capacity, mechanical strength and wear resistance of the resulting rubber composition, wet silica is preferred. These silicas can be used alone or in combination with any two or more of them.
[00104] Silica (D) preferably has an average particle size of 0.5 to 200 nm, more preferably 5 to 150 nm, even more preferably 10 to 100 nm, and even more preferably 10 to 60 nm nm, from the point of view of improving processability, rolling resistance performance, mechanical strength and wear resistance of the resulting rubber composition.
[00105] However, the average size of the silica particles (D) can be determined by calculating the average value of the diameter of the measured silica particles, using a transmission-type electron microscope.
[00106] In the rubber composition of the present invention, silica (D) is preferably included in an amount of 0.1 to 150 parts by weight, more preferably from 0.5 to 130 parts by weight, even more preferably from 5 to 100 parts by weight, and even more preferably from 5 to 95 parts by weight, based on 100 parts by weight of the rubber component (B). When the amount of silica (D) included falls within the range specified above, the resulting rubber composition can be improved in processability, rolling resistance performance, mechanical strength and wear resistance.
[00107] The rubber composition according to the present invention, more preferably contains the copolymer (A) above, carbon black (C) and silica (D) in quantities of 0.1 to 100 parts by mass, 0.1 to 150 parts by weight and 0.1 to 150 parts by weight, respectively, based on 100 parts by weight of the above rubber component (B). OPTIONAL COMPONENTS SILANO COUPLING REAGENT
[00108] The rubber composition according to the present invention preferably also contains a silane coupling reagent. As a silane coupling reagent, a sulfide-based compound, a mercapto-based compound, a vinyl-based compound, an amino-based compound, a glycidoxy compound, a compound based on nitro, a chlorine-based compound, etc.
[00109] Examples of the sulfide-based compound include bis (3-triethoxysilylethyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) bis tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, trisulfide bis (3-triethoxysilylpropyl), bis (3-trimethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, 3-trimethoxysilylpropyl-N, N-dimethyl-thiocarbamoyl , 3-triethoxysilylpropyl-N, N-dimethyl-thiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N, dimethyl-thiocarbamoyl tetrasulfide, 3-trimethoxy-ethylethylsilyl-3-triethylsilylethylsilyl, 3-triethoxyethylsilyl-propyl-3-methylethoxy-ethyl-propyl 3-trimethoxysilylpropyl monosulfide monosulfide and methacrylate.
[00110] Examples of the mercapto-based compound include 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, 2-mercaptoethyl-trimethoxysilane and 2-mercaptoethyl-triethoxysilane.
[00111] Examples of the vinyl-based compound include vinyltriethoxysilane and vinyltrimethoxysilane.
[00112] Examples of the amino-based compound include 3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane and 3- (2-aminoethyl) aminopropyl-trimethoxysilane.
[00113] Examples of the glycidoxy compound include Y-glycidoxypropyl-triethoxysilane, Y-glycidoxypropyl-trimethoxysilane, DY-glycidoxypropylmethyl-detoxysilane and Y-glycidoxypropylmethyl-dimethoxysilane.
[00114] Examples of the nitro-based compound include 3-nitropropyl-trimethoxysilane and 3-nitropropyl-triethoxysilane.
[00115] Examples of the chlorine-based compound include 3-chloropropyl-trimethoxysilane, 3-chloropropyl-triethoxysilane, 2-chloroethyl-trimethoxysilane and 2-chloroethyl-triethoxysilane.
[00116] These silane coupling reagents can be used alone or in combination with any two or more of them. Of these silane coupling reagents, from the point of view of a great addition effect and low costs, bis (3-triethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) and 3-mercaptopropyl-trimethoxysilane are preferred.
[00117] The content of the silane coupling reagent in the rubber composition is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1 to 15 parts by weight. mass, based on 100 parts by mass of silica (D). When the content of the silane coupling reagent in the rubber composition falls within the range specified above, the resulting rubber composition can be improved in dispersibility, coupling effect, reinforcement property and wear resistance. Other Loads
[00118] With the purpose of increasing the mechanical resistance of the rubber composition, improving several of its properties such as thermal resistance and weather resistance, controlling its hardness and further improving the economy by adding a dilution oil, the composition of The rubber according to the present invention may also contain a charge other than carbon black (C) and silica (D), if necessary.
[00119] The charge other than carbon black (C) and silica (D) can be appropriately selected according to the applications of the obtained rubber composition. For example, as a 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, glass fibers, fibrous fillers and glass balloons. The content of the above charge in the rubber composition of the present invention, if included therein, is preferably 0.1 to 120 parts by weight, more preferably 5 to 90 parts by weight, and even more preferably 10 to 80 parts by weight. mass, based on 100 parts by mass of the rubber component (B). When the load content in the rubber composition falls within the range specified above, the resulting rubber composition can be further improved in mechanical strength.
[00120] The rubber composition according to the present invention may also contain, if necessary, a softening reagent for the purpose of improving the processability, fluidity or the like of the resulting rubber composition, unless the effects of the present invention are negatively influenced. Examples of the softening reagent include a processing oil, such as a silicone oil, a flavor oil, TDAE (treated distilled aromatic extracts), MES (light extracted solvates), RAE (residual aromatic extracts), a paraffin oil and naphthene oil; a resin component, such as aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, C9-based resins, rosin-based resins, coumarone-indene resins and phenol-based resins; and a liquid polymer, such as a low molecular weight polybutadiene, a low molecular weight polyisoprene, a low molecular weight styrene-butadiene copolymer and a low molecular weight styrene-isoprene copolymer. However, the above copolymers can be in the form of a block copolymer or a statistical copolymer. The liquid polymer preferably has an average molecular weight of 500 and 100,000 from the point of view of good processing capacity of the resulting rubber composition. The above process oil, resin component or liquid polymer as a softening reagent is preferably included in the rubber composition of the present invention in an amount less than 50 parts by weight, based on 100 parts by weight of the rubber (B).
[00121] The rubber composition according to the present invention can also contain a β-farnesene homopolymer, unless the effects of the present invention are negatively influenced. The content of β-farnesene homopolymer in the rubber composition, if mixed with it, is preferably less than 50 parts by weight, based on 100 parts by weight of the rubber component (B).
[00122] 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, an action stabilizer of light, a burning retardant, a processing aid, a dye such as pigments and dyes, a flame retardant, an antistatic reagent, a de-stripping reagent, an anti-blocking reagent, an ultraviolet absorber, a release reagent, a foaming reagent, an antimicrobial reagent, a mold-proof reagent and a perfume, in order to improve the weather resistance, thermal resistance, oxidation resistance or the like, of the resulting rubber composition, unless the effects of the present invention are negatively influenced.
Examples of the oxidation inhibitor include blocked phenol-based compounds, phosphorus-based compounds, lactone-based compounds and hydroxyl-based compounds.
[00124] Examples of the antioxidant include amine-ketone-based compounds, imidazole-based compounds, amine-based compounds, phenol-based compounds, sulfur-based compounds and phosphorus-based compounds.
[00125] The rubber composition of the present invention is preferably used in a cross-linked product, produced by the addition of a cross-linking reagent. Examples of the crosslinking reagent include sulfur and sulfur compounds, oxygen, organic peroxides, phenolic resins and amino resins, quinones and quinone-dioxima derivatives, halogenated compounds, aldehyde compounds, alcohol compounds, epoxy compounds, halides metals and organic metal halides, and silane compounds. Among such cross-linking reagents, sulfur and sulfur compounds are preferred. These cross-linking reagents can be used alone or in combination with any two or more of them. The crosslinking reagent is preferably included in the rubber composition in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the rubber component (B).
[00126] When sulfur is used as a crosslinking reagent, a vulcanization aid or a vulcanization accelerator is preferably used in combination with the crosslinking reagent.
[00127] Examples of the vulcanization aid include fatty acids such as stearic acid and metal oxides such as zinc oxide.
[00128] Examples of the vulcanization accelerator include compounds based on guanidine, compounds based on sulfide amide, compounds based on thiazole, compounds based on thuram, compounds based on thiourea, compounds based on dithiocarbamic acid, compounds based on of 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 vulcanization accelerator is preferably included in the rubber composition of the present invention in an amount of 0.1 to 15 parts by weight, based on 100 parts by weight of the rubber component (B).
[00129] The method for producing the rubber composition of the present invention is not particularly limited, and any suitable method can be used in the present invention, as long as the respective components are mixed uniformly with each other. The method of uniformly mixing the respective components can be carried out, for example, using a closed, contact or mesh type kneader, such as a kneading rudder mixer, a Brabender mixer, a Banbury mixer and a mixer internal, a single screw extruder, a double screw extruder, a mixing cylinder, a cylinder or similar, in a temperature range of usually 70 to 270 ° C. TIRE
[00130] The tire according to the present invention is produced using the rubber composition according to the present invention at least as part of the tire, and, therefore, can have good mechanical strength and excellent resistance performance to the bearing. EXAMPLES
[00131] The present invention will be described in more detail below, referring to the following examples. It should be noted, however, that the examples that follow are illustrative only and are not intended to limit the invention to them.
[00132] The respective components used in the following Examples and Comparative Examples are as follows. Copolymer of (A):
[00133] Copolymers (A-1) to (A-4) obtained in Production Examples 1 to 4, respectively. Rubber Component (B):
[00134] Natural rubber "STR20" (natural rubber from Thailand)
[00135] "JSR1500" styrene-butadiene rubber (available from JSR Corporation)
[00136] Butadiene rubber "BR-01" (available from JSR Corp.)
[00137] Average molecular weight = 550,000
[00138] Cis isomer content = 95% by mass Carbon Black (C-1):
[00139] "DIABLACK H", available from Mitsubishi Chemical Corp .; average particle size: 30 nm Carbon Black (C-2):
[00140] "DIABLACK I", available from Mitsubishi Chemical Corp .; average particle size: 20 nm Carbon Black (C-3):
[00141] "SEAST V", available from Tokai Carbon Co., Ltd .; mean particle size: 60 nm Silica (D-1):
[00142] "ULTRASIL7000GR", available from Evonik Degussa Ja pan Co., Ltd .; wet silica; average particle size: 14 nm Silica (D-2):
[00143] "AEROSIL 300", available from Nippon Aerosil Co., Ltd .; dry silica; average particle size: 7 nm Silica (D-3):
[00144] "NIPSIL E-74P", available from Tosoh Silica Corporation; wet silica; average particle size: 74 nm Polyisoprene:
[00145] Polyisoprene obtained in Production Example 5. Homopolymer of β-farnesene:
[00146] β-farnesene homopolymer obtained in Production Example 6. TDAE:
[00147] "VivaTec500", available from H & R Corp. Silane coupling reagent:
[00148] "Si75" (available from Evonik Degussa Japan Co., Ltd.) Stearic acid:
[00149] "LUNAC S-20" (available from Kao Corp.) Zinc Oxide:
[00150] Zinc oxide (available from Sakai Chemical Industry Co., Ltd.) Antioxidant (1):
[00151] "NOCRAC 6C" (available from Ouchi Shinko Chemical In dustrial Co., Ltd.) Antioxidant (2):
[00152] "ANTAGE RD" (available from Kawaguchi Chemical Indus try Co., Ltd.) Sulfur:
[00153] Fine sulfur powder, 200 mesh (available from Tsurumi Chemical Industry Co., Ltd.) Vulcanization accelerator (1):
[00154] "NOCCELER NS" (available from Ouchi Shinko Chemical Industrial Co., Ltd.) Vulcanization accelerator (2):
[00155] "NOCCELER CZ-G" (available from Ouchi Shinko Chemi cal Industrial Co., Ltd.) Vulcanization accelerator (3):
[00156] "NOCCELER D" (available from Ouchi Shinko Chemical Industrial Co., Ltd.) Vulcanization accelerator (4):
[00157] "NOCCELER TBT-N" (available from Ouchi Shinko Chemi cal Industrial Co., Ltd.) PRODUCTION EXAMPLE 1: B-FARNESENO / ISOPRENO STATISTIC COPOLYMER PRODUCTION (A-1)
[00158] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 1,490 g of cyclohexane as a solvent and 12.4 g of sec-butyl lithium (in the form of a cycle solution -hexane 10.5% by mass) as initiator. The contents of the reaction vessel were heated to 50 ° C and 1,500 g of a mixture of isoprene (a) and β-farnesene (b) (which was previously prepared by mixing 300 g of isoprene (a) and 1,200 g of β - farnesene (b) in a cylinder) was 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 polymerization reaction solution thus washed, the resulting solution was dried at 70 ° C for 12 h, thus obtaining a statistical copolymer β-farnesene / isoprene (A-1). Various properties of the β-farnesene / isoprene β-farnesene isoprene (A-1) statistical copolymer thus obtained are shown in Table 1. PRODUCTION EXAMPLE 2: PRODUCTION OF STATISTICAL COPOLYMER B-FARNESENO / ISOPRENE (A-2)
[00159] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 1,790 g of cyclohexane as a solvent and 10.9 g of sec-butyl lithium (in the form of a cycle solution -hexane 10.5% by mass) as initiator. The contents of the reaction vessel were heated to 50 ° C and 1,200 g of a mixture of isoprene (a) and β-farnesene (b) (which was previously prepared by mixing 480 g of isoprene (a) and 720 g of β - farnesene (b) in a cylinder) was 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 polymerization reaction solution thus washed, the resulting solution was dried at 70 ° C for 12 h, thus obtaining a statistical copolymer β-farnesene / isoprene (A-2). Several properties of the β-farnesene / isoprene (A-2) statistical copolymer thus obtained are shown in Table 1. PRODUCTION EXAMPLE 3: COPOLYMER PRODUCTION IN BLOCK B-FARNESENE / ISOPRENE (A-3)
[00160] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 2,090 g of cyclohexane as a solvent and 8.2 g of sec-butyl lithium (in the form of a cycle solution -hexane 10.5% by mass) as initiator. The contents of the reaction vessel were heated to 50 ° C and 360 g of isoprene (a) were added at a rate of 10 ml / min, and the mixture was polymerized for 1 h. Then, 540 g of β-farnesene (b) were 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 isoprene block copolymer (A-3). Various properties of the β-farnesene / isoprene block copolymer (A-3) thus obtained are shown in Table 1. PRODUCTION EXAMPLE 4: COPOLYMER PRODUCTION IN BLOCK B-FARNESENO / ISOPRENE / B-FARNESENO (A-4)
[00161] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 1,670 g of cyclohexane as a solvent and 10.2 g of sec-butyl lithium (in the form of a cycle solution -hexane 10.5% by mass) as initiator. The contents of the reaction vessel were heated to 50 ° C and 336 g of β-farnesene (b) were added at a rate of 10 ml / min, and the mixture was polymerized for 1 h. Afterwards, 448 g of isoprene (a) were added to the polymerization reaction solution at a rate of 10 ml / min, and the mixture was further polymerized for 1 h. Then, 336 g of β-farnesene (b) were 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 / isoprene / β-farnesene block copolymer (A-4 ). Various properties of the β-farnesene / isoprene / β-farnesene block copolymer (A-4) thus obtained are shown in Table 1. PRODUCTION EXAMPLE 5: POLY-ISOPRENE PRODUCTION
[00162] 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% by weight hexane solution) . The contents of the reaction vessel were heated to 70 ° C and 2,050 g of isoprene were 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 the water from the polymerization reaction solution thus washed, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a polyisoprene with properties as shown in Table 1. PRODUCTION EXAMPLE 6: PRODUCTION OF HOMOPOLYMER OF B-FARNESENO
[00163] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 274 g of hexane as a solvent and 1.2 g of n-butyl lithium (in the form of a 17% hexane solution in mass) 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. Afterwards, 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 homopolymer. Various properties of the β-farnesene homopolymer thus obtained are shown in Table 1.
[00164] However, the average molecular weight and melt viscosity of each copolymer (A), polyisoprene and β-farnesene homopolymer were measured by the following methods. METHOD OF MEASURING AVERAGE PONDERAL MOLECULAR WEIGHT
[00165] The average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of each copolymer (A), polyisoprene and β-farnesene homopolymer were measured by CPG (gel permeation chromatography) in molecular weight terms of polystyrene as a standard reference substance. The measurement devices and conditions are as follows. • Device: CPG device "GPC8020", available from Tosoh Corp. • Separation column: "TSKgelG4000HXL", available from Tosoh Corp. • Detector: "RI-8020", available from Tosoh Corp. • Eluent: Tetrahydrofuran • Flow rate of the eluent: 1.0 mL / min • Sample concentration: 5 mg / mL 10 • Column temperature: 40 ° C METHOD OF FUSION VISCOSITY MEASUREMENT
[00166] The melt viscosity of each copolymer (A), polyisoprene and β-farnesene homopolymer was measured at 38 ° C using a type B viscometer available from Brookfield Engineering Labs. Inc. TABLE 1
EXAMPLES 1 TO 13 AND COMPARATIVE EXAMPLES 1 TO 8
[00167] Copolymer (A), rubber component (B), carbon black (C), silica (D), silane coupling reagent, polyisoprene, TDAEs, stearic acid, the zinc oxide and anti-oxidant were loaded in respective proportions of composition, as shown in Tables 2 to 4, in a closed Banbury mixer, and kneaded together for 6 min, so that the initial temperature was 75 ° C and the resin temperature reached 160 ° C. The resulting mixture was then removed from the mixer and cooled to room temperature. Then, the mixture was placed in a mixing cylinder and after adding sulfur and the vulcanization accelerator, the contents of the mixing cylinder were kneaded at 60 ° C for 6 min, thereby obtaining a rubber composition. The Mooney viscosity of the rubber composition thus obtained was measured by the following method.
[00168] In addition, the resulting rubber composition was molded under pressure (at 145 ° C for 20 to 60 min) to prepare a sheet (thickness: 2 mm). The sheet thus prepared was evaluated for tensile strength at the breaking point, loss by DIN abrasion and rolling resistance performance by the following methods. The results are shown in Tables 2 to 4. (1) Mooney viscosity
[00169] As a processability index of the rubber composition, the Mooney viscosity (ML1 + 4) of the rubber composition before curing was measured at 100 ° C, according to JIS K 6300. The values of the respective Examples and Examples Comparatives 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 6. The values of the respective Examples and Examples Comparatives shown in Table 4 are relative values based on 100 as the value of Comparative Example 8. However, the lower value of Mooney's viscosity indicates more excellent processability.
[00170] A sheet prepared from the rubber composition produced in the respective Examples and Comparative Examples was perforated in a dumbbell test piece according to JIS No. 3, and the obtained test piece was subjected to a measurement of tensile strength at break point, using a tensile tester available from Instron Corporation, 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 the 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 the Comparative Example 6. The values of the respective Examples and Comparative Examples shown in Table 4 are relative values based on 100 as the value of the Comparative Example 8. However, the higher value indicates better tensile strength at the breaking point of the rubber composition. (3) Loss by DIN Abrasion
[00171] The rubber composition was measured in relation to DIN abrasion loss under a 10 N load 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 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 6. The values of the respective Examples and Comparative Examples shown in Table 4 are relative values based on 100 as the value of Comparative Example 8. However, the lower value indicates less abrasion loss of the rubber composition.
[00172] A sheet prepared from the rubber composition produced in the respective Examples and Comparative Examples was cut into a test piece with a size of 40 mm long x 7 mm wide. The test piece thus obtained was subjected to tanδ measurement as a rolling resistance performance index of the rubber composition, using a dynamic viscoelasticity measuring device available from GABO GmbH, under conditions that included a measuring temperature of 60 ° C , a frequency of 10 Hz, a static strain of 10% and a dynamic strain 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 Example Comparative 6. The values of the respective Examples and Comparative Examples shown in Table 4 are relative values based on 100 as the value of Comparative Example 8. However, the lower value indicates excellent rolling resistance performance of the rubber composition. TABLE 2


[00173] The rubber compositions obtained in Examples 1 to 4 exhibited a low Mooney viscosity compared to that of Comparative Example 3 and, therefore, good processability. In addition, the rubber compositions obtained in Examples 1 to 4 were excellent in rolling resistance performance, compared to Comparative Examples 1 and 2, and were also prevented from suffering deterioration in terms of mechanical strength and wear resistance. TABLE 3


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


[00176] The rubber compositions obtained in Examples 10 to 13 showed a low Mooney viscosity compared to that of Comparative Example 8, and, therefore, good processability. In addition, the rubber compositions obtained in Examples 10 to 13 were excellent in rolling resistance performance, compared to Comparative Example 7, and were also prevented from deteriorating in mechanical strength and wear resistance. EXAMPLES 14 TO 20 AND COMPARATIVE EXAMPLES 9 TO 14
[00177] The copolymer (A), the rubber component (B), the carbon black (C), the silica (D), the β-farnesene homopolymer, the polyisoprene, the silane coupling reagent, TDAEs, stearic acid, zinc oxide and antioxidant were loaded in the respective composition proportions as shown in Tables 5 and 6 in a closed Banbury mixer and kneaded together for 6 min, so that the initial temperature was 75 ° C and the resin temperature reached 160 ° C. The resulting mixture was then removed from the mixer and cooled to room temperature. Then, the mixture was placed in a mixing cylinder, and after adding sulfur and the vulcanization accelerator, the contents of the mixing cylinder were kneaded at 60 ° C for 6 min, thereby obtaining a composition of eraser. The Mooney viscosity of the rubber composition thus obtained was measured by the method above.
[00178] In addition, the resulting rubber composition was molded under pressure (at 145 ° C for 25 to 50 min) to prepare a sheet (thickness: 2 mm). The sheet thus prepared was evaluated for tensile strength at break point and rolling resistance performance by the methods above. The results are shown in Tables 5 and 6.
[00179] Furthermore, the rubber compositions obtained in Examples 14 to 19 and Comparative Examples 9 to 13 were measured with respect to DIN abrasion loss by the above method. The results are shown in Table 5.
[00180] However, the values of Mooney's viscosity, tensile strength at break point, 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 the values of Comparative Example 13.
[00181] In addition, the values of Mooney's viscosity, tensile strength at break point and rolling resistance performance of the respective rubber compositions, as shown in Table 6, are relative values based on 100, as each of the values Comparative Example 14. TABLE 5



[00182] From the comparison between Example 14 and Comparative Example 9, it was confirmed that when controlling the amount of copolymer (A) included in the rubber composition in the range of 0.1 to 100 parts by weight based in 100 parts by mass of the rubber component (B), the resulting rubber composition exhibited good processing capacity, was prevented from deteriorating in terms of mechanical strength and wear resistance, and proved to be excellent in performance of rolling resistance.
[00183] The rubber compositions obtained in Examples 15 to 18 exhibited a low Mooney viscosity compared to that of Comparative Example 13, and, therefore, was improved in processability. In addition, the rubber compositions obtained in Examples 15 to 18 showed a tensile strength at break point and a wear resistance that were almost similar to those of Comparative Example 10 or 11, but were excellent in performance rolling resistance compared to Comparative Example 10 or 11, and therefore can be suitably used as a rubber tire composition.
[00184] The rubber composition obtained in Example 19 exhibited a low Mooney viscosity when compared to that of Comparative Example 13 and, therefore, was improved in terms of processability. In addition, the rubber composition obtained in Example 19 showed a tensile strength at break point and a wear resistance that were almost similar to those of Comparative Example 12, but proved to be excellent in rolling resistance performance compared to Comparative Example 12, and therefore can be conveniently used as a rubber tire composition.
[00185] 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 weight, based on 100 parts by weight of rubber component (B), the effects of the present invention could also be exhibited.
[00186] From the comparison between Example 19 and Comparative Example 12, it was confirmed that when carbon black (C) was included in the composition in an amount of 0.1 to 150 parts by weight, based on in 100 parts by mass of the rubber component (B), the effects of the present invention could also be exhibited.
[00187] From the comparison between Example 19 and Comparative Example 12, it was confirmed that when the average particle size of carbon black (C) and silica (D) was controlled in the range of 5 to 100 nm and 0.5 to 200 nm, respectively, the resulting rubber composition exhibited good processing capacity, was prevented from deteriorating in terms of mechanical strength and proved to be excellent in rolling resistance performance and wear resistance.
[00188] From the comparison between Example 19 and Comparative Example 12, it was confirmed that even when using two or more types of rubbers that include natural rubber and synthetic rubber, the effects of the present invention could be noticeably exhibited .
[00189] From the comparison between Examples 16 and 18 and Comparative Example 10 or 11, it was confirmed that even when using copolymer (A) in combination with the other components, the effects of the present invention could be noticeably exhibited . TABLE 6


[00190] 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 weight, based on 100 parts by weight of the rubber component (B), the resulting rubber composition showed good processability and was excellent in rolling resistance performance, without deterioration in mechanical strength and wear resistance.
[00191] 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 weight, based on 100 parts by weight of the component rubber (B), the effects of the present invention could be noticeably exhibited.

权利要求:
Claims (18)
[0001]
1. Copolymer, characterized by the fact that it comprises a monomer unit (a) derived from isoprene and a monomer unit (b) derived from farnesene.
[0002]
2. Copolymer according to claim 1, characterized by the fact that the monomer unit (b) is a monomer unit derived from β-farnesene.
[0003]
3. Copolymer according to claim 1 or 2, characterized in that the mass ratio of the monomer unit (a) to the sum of the monomer unit (a) and the monomer unit (b) in the copolymer is 1 to 99% by weight.
[0004]
4. Copolymer according to any one of claims 1 to 3, characterized by the fact that the copolymer has a molecular weight distribution (Mw / Mn) of 1.0 to 4.0.
[0005]
Copolymer according to any one of claims 1 to 4, characterized by the fact that the copolymer has an average molecular weight (Mw) between 2,000 and 500,000.
[0006]
6. Copolymer according to any one of claims 1 to 5, characterized in that the copolymer has a melt viscosity of 0.1 to 3,000 Pa • s as measured at 38 ° C.
[0007]
7. Copolymer according to any one of claims 1 to 6, characterized by the fact that the copolymer is produced by carrying out an anionic polymerization in the presence of an organic metal initiator.
[0008]
Process for producing the copolymer, as defined in any one of claims 1 to 7, characterized in that it comprises at least the step of copolymerization of isoprene with farnesene.
[0009]
9. Rubber composition, characterized by the fact that it comprises (A) the copolymer as defined in any one of claims 1 to 7; (B) a rubber component; and (C) carbon black.
[0010]
10. Rubber composition, characterized by the fact that it comprises (A) the copolymer as defined in any one of claims 1 to 7; (B) a rubber component; and (D) silica.
[0011]
11. Rubber composition, characterized by the fact that it comprises (A) the copolymer as defined in any one of claims 1 to 7; (B) a rubber component; (C) carbon black; and (D) silica.
[0012]
Rubber composition according to claim 9 or 11, characterized by the fact that carbon black (C) has an average particle size of 5 to 100 nm.
[0013]
Rubber composition according to claim 10 or 11, characterized in that the silica (D) has an average particle size of 0.5 to 200 nm.
[0014]
Rubber composition according to claim 9, characterized by the fact that the levels of copolymer (A) and carbon black (C) in the rubber composition are 0.1 to 100 parts by weight and 0 , 1 to 150 parts by weight, respectively, based on 100 parts by weight of the rubber component (B).
[0015]
Rubber composition according to claim 10, characterized by the fact that the levels of copolymer (A) and silica (D) in the rubber composition are 0.1 to 100 parts by weight and 0.1 to 150 parts by mass, respectively, based on 100 parts by mass of the rubber component (B).
[0016]
16. Rubber composition according to claim 11, characterized by the fact that the levels of copolymer (A), carbon black (C) and silica (D) in the rubber composition are from 0.1 to 100 parts by weight, from 0.1 to 150 parts by weight and from 0.1 to 150 parts by weight, respectively, based on 100 parts by weight of the rubber component (B).
[0017]
17. Rubber composition according to any one of claims 9 to 16, characterized in that the rubber component (B) is at least one rubber selected from the group consisting of a styrene-butadiene rubber, a natural rubber, a butadiene rubber and an isoprene rubber.
[0018]
18. Tire, characterized by the fact that it uses the rubber composition, as defined in any of claims 9 to 17, at least as part of the tire.

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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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2020-02-04| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-12| 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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JP2012085929|2012-04-04|

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JP2012-085929|2012-04-04|

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PCT/JP2013/060128|WO2013151069A1|2012-04-04|2013-04-02|Copolymer, rubber composition using same, and tire|

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