rubber tire and composition

专利摘要:
COMPOSITION AND RUBBER TIRE. The present invention relates to a rubber composition, including (A) at least one rubber component selected from the group consisting of a synthetic rubber and a natural rubber; (B) a farnesene polymer; and (C) carbon black having an average particle size from 5 to 100 nm, a carbon black content (C) in the rubber composition being from 20 to 100 parts by weight based on 100 mass parts of the rubber component (A).
公开号:BR112014007431B1
申请号:R112014007431-3
申请日:2012-09-21
公开日:2020-10-13
发明作者:Shigenao Kuwahara；Kei Hirata；Daisuke Koda
申请人:Kuraray Co., Ltd.；Amyris, Inc；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to a rubber composition containing a rubber component, a farnesene polymer and a carbon black, and a tire using the rubber composition. BACKGROUND OF THE INVENTION
[002] So far, in the field of application of tires for which wear resistance and mechanical strength are required, rubber compositions have been used extensively that have improved mechanical strength through the incorporation of a reinforcing agent such as carbon black in a rubber component such as a natural rubber and a styrene-butadiene rubber.
[003] It is known that carbon black exhibits its reinforcing effect by physically or chemically adsorbing the rubber component mentioned above on a surface of the respective carbon black particles.
[004] However, when the particle size of the carbon black used in the rubber composition is as large as from about 100 to about 200 nm, it is generally difficult to obtain a sufficient interaction between the carbon black and the rubber component, so that the resulting rubber composition tends to hardly be improved in mechanical strength to a sufficient degree.
[005] Also, tires produced from such a rubber composition tend to exhibit low hardness and therefore tend to be insufficient in steering stability.
[006] On the other hand, when the carbon black used in the rubber composition has an average particle size as small as from about 5 to about 100 nm and then a large specific surface area, the rubber composition resultant can be improved in properties such as mechanical strength and wear resistance due to a great interaction between carbon black and the rubber component.
[007] Furthermore, tires produced from such a rubber composition can be improved in steering stability due to their increased hardness.
[008] However, in the case where carbon black having such a small medium particle size is used in the rubber composition, it is known that the resulting rubber composition tends to deteriorate in dispersibility of the carbon black therein due to a force high cohesion between the carbon black particles.
[009] The deteriorated dispersibility of carbon black in the rubber composition tends to induce a prolonged kneading step and then tends to produce an adverse influence on the productivity of the rubber composition.
[0010] Also, the deteriorated dispersibility of carbon black 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 needs of low rolling resistance tires (so-called low fuel consumption tires).
[0011] Also, in the case where the carbon black 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 is then deteriorated in processability.
[0012] In this way, resistance and mechanical hardness of the rubber tire composition are properties having a contradictory relationship with the rolling resistance performance and its processability, and it is then considered that the rubber composition is hardly improved in both tire properties. a well balanced way.
[0013] In Patent Document 1, as a rubber composition that can be perfected in the above mentioned properties in a well balanced manner, the rubber tire composition is described which includes a rubber component containing an isoprene-based rubber and a rubber styrene-butadiene, carbon black and a liquid resin having a softening point of from -20 to 20 ° C in a specific composition ratio.
[0014] Also, Patent Document 2 describes the tire including a rubber component containing a diene-based rubber consisting of a modified styrene-butadiene copolymer and a modified conjugated diene-based polymer and a filler such as black smoke in a specific composition ratio.
[0015] However, any of the tires described in these Patent Documents fail to satisfy mechanical strength and toughness as well as the rolling resistance and processability performance at a sufficiently high level, and so there is still a strong demand for tires which are further enhanced in these properties.
[0016] However, Patent Documents 3 and 4 describe a β-farnesene polymer, but fail to have sufficient study on its practical applications. CITATION LIST PATENT LITERATURE
[0017] Patent Document 1: Jp 2011 -195804A
[0018] Patent Document 2: Jp 2010-209256A
[0019] Patent Document 3: VVO 2010 / 027463A
[0020] Patent Document 4: VVO 2010 / 027464A SUMMARY OF THE INVENTION TECHNICAL PROBLEM
[0021] The present invention was made in view of the above conventional problems. The present invention provides a rubber composition that exhibits not only good processability when composing, molding or curing, but also an excellent rolling resistance performance due to an improved carbon black dispersibility therein, and still hardly suffers from deterioration in mechanical resistance and hardness, and a tire obtained using the rubber composition. SOLUTION TO THE PROBLEM
[0022] 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 low rolling resistance due to a improved carbon black dispersibility in it and still hardly suffers from deterioration in mechanical strength and toughness. The present invention was carried out based on the above finding.
[0023] That is, the present invention relates to the following aspects:
[0024] [1] A rubber composition including (A) at least one rubber component selected from the group consisting of a synthetic rubber and a natural rubber; (B) a farnesene polymer; and (C) carbon black having an average particle size from 5 to 100 nm, a carbon black content (C) in the rubber composition being from 20 to 100 parts by weight based on the 100 mass parts of the rubber component (A), and
[0025] [2] A tire including at least partially the above rubber composition. ADVANTAGE EFFECTS OF THE INVENTION
[0026] According to the present invention, a rubber composition is provided which has not only good processability when composing, molding or curing, but also excellent rolling resistance performance due to improved dispersibility of black smoke in it and still hardly suffer from deterioration in mechanical strength and hardness and a tire obtained using the rubber composition. DESCRIPTION OF THE MODALITIES
[Rubber Composition]
[0027] The rubber composition of the present invention includes (A) at least one rubber component selected from the group consisting of a synthetic rubber and a natural rubber; (B) a farnesene polymer; and (C) carbon black having an average particle size from 5 to 100 nm, where the content of carbon black (C) in the rubber composition is from 20 to 100 parts by weight based on 100 parts by mass of the rubber component (A). <Rubber component (A)> Synthetic rubber
[0028] Examples of the synthetic rubber used here include a styrene-butadiene rubber (hereinafter occasionally referred to only as "SBR"), an isoprene rubber, a butadiene rubber, a butyl rubber, a halogen butyl rubber nothing, an ethylene propylene diene rubber, an acrylonitrile butadiene cup-polymer rubber and a chloroprene rubber. Among these synthetic rubbers, preferred are SBR, an isoprene rubber and a butadiene rubber. These synthetic rubbers can be used alone or in combination with any two or more of them. (SBR (A-D)
[0029] As SBR (A-1) can be used those generally used in tire applications. More specifically, SBR (A-1) preferably has a styrene content of from 0.1 to 70% by weight and more preferably from 5 to 50% by weight. Also, SBR (A-1) preferably has a vinyl content of from 0.1 to 60% by weight and more preferably from 0.1 to 55% by weight.
[0030] The average molecular weight (Mw) of the SBR (A-1) is preferably from 100,000 to 2,500,000, more preferably from 150,000 to 2,000,000 and even more preferably from 200,000 to 1,500,000. When the SBR's average molecular weight (A-1) falls within the range specified above, the resulting rubber composition can be improved in both processability and mechanical strength. However, in the present application, the average weight molecular weight is the value measured using the method described below in the Examples.
[0031] 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 - 5th C. When adjusting the TBR of the SBR to the range specified above, it is possible to suppress the increase in viscosity of the SBR and improve its handling property. «Method for Production of SBR (A-1)»
[0032] The SBR (A-1) useful 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 using either an emulsion polymerization method, a solution polymerization method, a vapor phase polymerization method and a polymerization method in pasta. Among these polymerization methods, especially preferred are an emulsion polymerization method and a solution polymerization method. Emulsion Polymerized Styrene-Butadiene Rubber (E-SBR) [0033] E-SBR (Emulsion-Polymerized Styrene-Butadiene Rubber) can be produced using any common emulsion polymerization method. For example, a predetermined amount of a styrene monomer and a predetermined amount of a butadiene monomer are emulsified and dispersed in the presence of an emulsifying agent and then subjected to emulsion polymerization using a radical polymerization initiator.
[0034] As the emulsifying agent, a long-chain fatty acid salt having 10 or more carbon atoms or a rosinic acid salt can be used. Specific examples of the emulsifying agent include potassium salts and sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
[0035] As a dispersant for the above emulsion polymerization, water can generally be used. The dispersant can also contain a water-soluble organic solvent such as methanol and ethanol unless the use of such an organic solvent causes any adverse influence on the stability of the polymerization.
[0036] Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides and hydrogen peroxide.
[0037] In order to properly adjust the molecular weight of the E-SBR obtained, a chain transfer agent can be used. Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; and carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, y-terpinene and an α-methyl styrene dimer.
[0038] The temperature used when emulsion polymerization can be appropriately determined according to the type of radical polymerization initiator used therein is generally preferably from 0 to 100 ° C and more preferably from 0 to 60 ° C. The polymerization method can be either a continuous polymerization method or a batch polymerization method. The polymerization reaction can be stopped by adding a terminating agent to the reaction system.
Examples of the terminating agent 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.
[0040] After finishing the polymerization reaction, an antioxidant can be added, if necessary. In addition, after completion of the polymerization reaction, unreacted monomers can be removed from the resulting latex, if necessary. Then, the obtained polymer is added by adding a salt such as sodium chloride, calcium chloride and potassium chloride as a coagulant to it and, if necessary, while adjusting the pH value of the coagulation system through addition of an acid such as nitric acid and sulfuric acid to it, and then the dispersion solvent is separated from the reaction solution to recover the polymer as a fragment. The recovered fragment is then washed with water and dehydrated and then dried using a band dryer or similar to obtain E-SBR.
[0041] However, when the polymer coagulates, the latex can be previously mixed with an extender oil in the form of an emulsified dispersion to recover the polymer in the form of an extended rubber with oil. (ii) Solution Polymerized Styrene-Butadiene Rubber (S-SBR)
[0042] S-SBR (Solution-Polymerized Styrene-Butadiene Rubber) can be produced using 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.
Examples of the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isoctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methyl cyclopentane; and aromatic hydrocarbons such as benzene and toluene. These solvents can generally be used in such a range so that a monomer is dissolved in them at a concentration of from 1 to 50% by mass.
[0044] Examples of the anion-curable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and rare earth metals based on lanthanoid such as lanthanum and neodymium. Among these active metals, preferred are alkali metals and alkaline earth metals, and more preferred are alkali metals. Alkali metals are most preferably used in the form of an organic alkali metal compound.
[0045] Specific examples of the organic alkali metal compound include organic monolithium compounds such as n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexyl lithium, phenyl lithium and stilbene lithium; polyfunctional organic lithium compounds such as dilithomethane; 1,4-dilithiobutane, 1,4-dilithio-2-ethyl cyclohexane and 1,3,5-trilithiotiobenzene; and sodium naphthalene and potassium naphthalene. Among these organic alkali metal compounds, preferred are organic lithium compounds, and more preferred are organic monolithium compounds. The amount of organic alkali metal compound used can be appropriately determined according to a molecular weight of S-SBR as required.
[0046] The organic alkali metal compound can be used in the form of an organic alkali metal amide by allowing a secondary amine such as dibutyl amine, diexyl amine and dibenzyl amine to react with it.
[0047] The polar compound used in solution polymerization is not particularly limited as long as the compound does not cause reaction deactivation and can generally be used to control a microstructure of the butadiene moieties and distribution of styrene in a copolymer chain thereof. Examples of the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethyl ethylene diamine and trimethylamine; and alkali metal alkoxides and phosphine compounds.
[0048] The temperature used in the above polymerization reaction is generally from -80 to 150 ° C, preferably from 0 to 100 ° C and more preferably from 30 to 90 ° C. The method of polymerization can be either a batch method or a continuous method. Also, in order to improve the random copolymerization capacity between styrene and butadiene, styrene and butadiene are preferably supplied to a reaction solution in a continuous or intermittent manner so that a compositional ratio between styrene and butadiene in the polymerization system fits in a specific range.
[0049] The polymerization reaction can be stopped by adding an alcohol such as methanol and isopropanol as a terminating agent to the reaction system. In addition, prior to the addition of the terminating agent, a coupling agent such as tin tetrachloride, tetrachlorosilane, tetramethoxysilane, tagaglycidyl-1,3-bisaminomethyl cyclohexane and 2,4-tolylene diisocyanate can be added that an active end of the polymer chain and a chain end modifying agent such as 4,4'-bis (diethylamino) benzophenone and N-vinyl pyrrolidone. The polymerization reaction solution obtained after the completion of the polymerization reaction can be directly subjected to drying or steam removal to remove the solvent from it, thus recovering the S-SBR according to the objective. However, prior to removal of the solvent, the polymerization reaction solution can be previously mixed with an extender oil to recover the S-SBR in the form of an extended rubber with oil. Modified Styrene-Butadiene Rubber (Modified SBR)
[0050] In the present invention, a modified SBR produced by the introduction of a functional group in SBR can also be used. Examples of the functional group to be introduced include an amino group, an alkoxysilyl group, a hydroxyl group, an epoxy group and a carboxyl group.
[0051] In the modified SBR, the polymer site into which the functional group is introduced can be either a chain end or a polymer side chain. (Isoprene rubber (A-2))
[0052] Isopropylene rubber can be a commercially available isoprene rubber that can be obtained through polymerization using a Ziegler-based catalyst such as titanium-trialkyl aluminum tetrahalide-based catalysts, diethyl aluminum chloride-based catalysts -cobalt, trialkyl aluminum-boron nickel trifluoride-based catalysts and catalysts based on diethyl aluminum-nickel chloride; an earth-rare metal catalyst based on lanthanoid such as catalysts based on triethyl aluminum-Lewis acid acid-organic acid neodymium; and an organic alkali metal compound as used similarly for the production of S-SBR. Among these isoprene rubbers, isoprene rubber obtained through polymerization using the Ziegler-based catalyst is preferred because of its high c / s isomer content. In addition, it is also possible to use those isoprene rubbers having an ultra high c / s isomer content which are produced using the lanthanoid-based rare earth metal catalyst.
[0053] 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.
[0054] The average weight molecular weight of isoprene rubber is preferably from 90,000 to 2,000,000 and more preferably from 150,000 to 1,500,000. When the average molecular weight of the isoprene rubber falls within the range specified above, the resulting rubber composition can exhibit good processability and good mechanical strength.
[0055] Isopropene rubber may partially have a branched structure or may partially contain a polar functional group using a polyfunctional modifying agent, for example, a modifying agent such as tin tetrachloride, silicon tetrachloride, an alkoxysilane containing an epoxy group in a molecule and an alkoxysilane containing an amino group. (Butadiene rubber (A-3))
[0056] Butadiene rubber can be a commercially available butadiene rubber that can be obtained through polymerisation using a Ziegler-based catalyst such as titanium-trialkyl aluminum tetrahalide-based catalysts, diethyl chloride-based catalysts aluminum-cobalt, catalysts based on trialkyl aluminum-boron-nickel trifluoride and catalysts based on diethyl aluminum-nickel chloride; an earth-rare metal catalyst based on lanthanoid such as catalysts based on triethyl aluminum-Lewis acid-organic acid neodymium salt; and an organic alkali metal compound as used similarly for the production of S-SBR. Among these butadiene rubbers, preferred are butadiene rubbers obtained through po-limerization using the Ziegler-based catalyst due to its cis-isomer content. In addition, those butadiene rubbers having an ultra-high cis isomer content that are produced using the lanthanoid-based earth metal catalyst can also be used.
[0057] Butadiene rubber has a vinyl content of 50% by weight or less, preferably 40% by weight or less and more preferably 30% by weight or less. When the vinyl content of butadiene rubber is more than 50% by weight, the resulting rubber composition tends to deteriorate in rolling resistance performance. The lower limit of the vinyl content of butadiene rubber is not particularly limited. The glass transition temperature of the butadiene rubber can vary depending on its vinyl content, and is preferably -40 ° C or less and more preferably -50 ° C or less.
[0058] The 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 can exhibit good processability and good mechanical strength.
[0059] Butadiene rubber may partially have a branched structure or may partially contain a polar functional group using a polyfunctional modifying agent, for example, a modifying agent such as tin tetrachloride, silicon tetrachloride, an alkoxysilane containing an epoxy group in a molecule and an alkoxysilane containing an amino group.
[0060] As the rubber component other than SBR, isoprene rubber and butadiene rubber, one or more rubbers selected from the group consisting of a butyl rubber can be used; a halogenated butyl rubber; an ethylene-propylene rubber; a butadiene-acrylonitrile copolymer rubber and a chloroprene rubber. The method of producing such rubbers is not particularly limited, and any suitable commercially available rubbers can also be used in the present invention.
[0061] In the present invention, when using SBR, isoprene rubber, butadiene rubber and other synthetic rubber in combination with the farnesene polymer (B) mentioned below, it is possible to improve the processability of the resulting rubber composition, the dispersibility of the carbon black in it and its rolling resistance performance.
[0062] When using a mixture of two or more types of synthetic rubbers, the combination of the synthetic rubbers can be optionally selected unless the effects of the present invention are adversely affected. Also, various properties of the resulting rubber composition such as rolling resistance and wear resistance performance can be appropriately controlled by selecting an appropriate combination of synthetic rubbers. Natural rubber
[0063] Examples of natural rubber include TSR such as SMR, SIR and STR; natural rubbers generally used in the tire industries, such as RSS; high purity natural rubbers; and modified natural rubbers such as epoxidized natural rubbers, hydroxylated natural rubbers, hydrogenated natural rubbers and grafted natural rubbers. Among these natural rubbers, SMR20, STR20 and RSS # 3 are preferred from the point of view of less variation in quality and good availability. These natural rubbers can be used alone or in combination with any two or more of them.
[0064] The rubber component (A) includes at least one rubber selected from the group consisting of a synthetic rubber and a natural rubber. When using both synthetic rubber and natural rubber, the composition ratio between synthetic rubber and natural rubber can be optionally determined. <Farnesene Polymer (B)>
[0065] The rubber composition of the present invention contains a farnesene polymer (B) (hereinafter referred to only as "polymer (B)"). The polymer (B) can be produced, for example, through the polymerization of β-farnesene represented by formula (I) which follows through the method mentioned below.
[0066] The farnesene polymer used in the present invention can be either an α-farnesene polymer or a β-farnesene polymer represented by the formula (I) below. From the point of view of ease of production of the polymer, the β-farnesene polymer is preferred.
However, in the present application, the farnesene polymer means a polymer containing a constitutional unit derived from farnesene in an amount of preferably 90% by weight or more, more preferably 95% by weight or more, even more preferably 98% by weight. mass or more, even more preferably 99% by mass or more and most preferably preferably 100% by mass. The farnesene polymer can also contain a constitutional unit derived from the other monomers such as butadiene and isoprene.
The average weight molecular weight of the polymer (B) is preferably 25,000 or more, more preferably 30,000 or more, even more preferably 35,000 or more and even more preferably 40,000 or more and is also preferably 500,000 or less, more preferably 450,000 or less, even more preferably 400,000 or less and even more preferably 300,000 or less. More specifically, the average molecular weight of the polymer (B) is preferably from 25,000 to 500,000, more preferably from 30,000 to 450,000, even more preferably from 35,000 to 400,000 and even more preferably from from 40,000 to 300,000.
[0069] When the average molecular weight of the polymer (B) falls within the range specified above, the resulting rubber composition according to the present invention has good processability and can be improved in carbon black dispersibility (C ) on it and then can exhibit good rolling resistance performance. However, the average molecular weight of the polymer (B) used in the present application is the value measured using the method mentioned below. In the present invention, two or more types of polymers (B) that are different in weight average molecular weight from each other can be used in the form of a mixture thereof.
[0070] The melt viscosity (as measured at 38 ° C) of polymer B is preferably from 0.1 to 3,000 Pa's, more preferably from 0.6 to 2,800 Pa's, even more preferably from from 1.5 to 2.600 Pa's and above all preferably 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 kneaded and can be improved in processability. However, in the present application, the melt viscosity of the polymer (B) is the value measured using the method described below in the Examples.
[0071] The molecular weight distribution (Mw / Mn) of the polymer (B) is preferably from 1.0 to 8.0, more preferably from 1.0 to 5.0 and even more preferably from from 1.0 to 3.0. When the molecular weight distribution (Mw / Mn) of the polymer falls within the range specified above, the resulting polymer (B) can adequately exhibit a minor variation in its viscosity.
The glass transition temperature of the polymer (B) can vary depending on the vinyl content or the content of the other monomer therein, and is preferably from -90 ° C to 0 ° C and more preferably from -90 ° C to -10 ° C. As the glass transition temperature of the polymer (B) falls within the range specified above, the resulting rubber composition can 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.
[0073] In the present invention, the polymer (B) is preferably composed in an amount of from 0.1 to 100 parts by weight, more preferably from 0.5 to 50 parts by weight and even more preferably from from 1 to 30 parts by weight based on 100 parts by weight of the rubber component (A). When the amount of the composite polymer (B) falls within the range specified above, the resulting rubber composition can exhibit good processability, mechanical strength and rolling resistance performance.
[0074] However, in the case where the carbon black (C) has an average particle size of 60 nm or less, the polymer (B) is preferably composed in an amount of from 0.1 to 100 parts by mass , more preferably from 0.5 to 50 parts by weight and even more preferably from 1 to 30 parts by weight based on 100 parts by weight of the rubber component (A). When the amount of the composite polymer (B) falls within the range specified above, the resulting rubber composition may exhibit more excellent processability, mechanical strength and rolling resistance performance.
[0075] The polymer (B) can be produced using an emulsion polymerization method, the methods described in WO 2010 / 027463A and W02010 / 027464A or similar. Among these methods, preferred are an emulsion polymerization method and a solution polymerization method, and most preferred is a solution polymerization method. (Emulsion Polymerization Method)
[0076] The emulsion polymerization method for producing the polymer (B) can be any suitable conventionally known method. For example, a predetermined amount of a farnesene monomer is emulsified and dispersed in the presence of an emulsifying agent, and then the resulting emulsion is subjected to emulsion polymerization using a radical polymerization initiator.
[0077] As the emulsifying agent, 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 person include potassium salts and fatty acid sodium salts such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
[0078] As the dispersant for water emulsion polymerization can generally be used and the dispersant can also contain a water-soluble organic solvent such as methanol and ethanol unless the use of such an organic solvent gives rise to any adverse influence on the stability of polymerization.
Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate; and organic peroxides and hydrogen peroxide.
[0080] In order to adjust the molecular weight of the resulting polymer (B), a chain transfer agent can be used. Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; and carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, y-terpinene and an α-methyl styrene dimer.
[0081] The temperature used when emulsion polymerization can be appropriately determined according to the type of radical polymerization initiator used therein and is generally preferably from 0 to 100 ° C and more preferably from 0 to 60 ° C. The polymerization method can be either a continuous polymerization method or a batch polymerization method. The polymerization reaction can be stopped by adding a terminating agent to the reaction system.
Examples of the terminating agent 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.
[0083] 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 necessary. Then, the resulting polymer (B) is coagulated by adding a salt such as sodium chloride, calcium chloride and potassium chloride as a coagulant to it and, if necessary, while adjusting the pH value of the coagulation by adding an acid such as nitric acid and sulfuric acid to it, and then the dispersion solvent is separated from the reaction solution to recover the polymer (B). The polymer then recovered is washed with water and dehydrated and then dried to obtain the polymer (B). However, when the polymer coagulates, the latex can be previously mixed, if necessary, with an extender oil in the form of an emulsified dispersion to recover the polymer (B) in the form of an oil-extended rubber. (Solution Polymerization Method)
[0084] The solution polymerization method for the production of the polymer (B) can be any suitable conventionally known 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 necessary, in the presence of a polar compound.
Examples of the solvent used in solution polymerization include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isocyanate; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methyl cyclopentane; and aromatic hydrocarbons such as benzene, toluene and xylene.
Examples of the anion-curable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and rare earth metals based on lanthanoid such as lanthanum and neodymium. Among these active metals, preferred are alkali metals and alkaline earth metals, and more preferred are alkali metals. Alkali metals are most preferably used in the form of an organic alkali metal compound.
[0087] Specific examples of the organic alkali metal compound include organic monolithic compounds such as methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium, phenyl lithium and lithium lithium; polyfunctional organic lithium compounds such as dilithiomethane, dilitionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethyl cyclohexane and 1,3,5-trilithiobenzene; and sodium naphthalene and potassium naphthalene. Among these organic alkali metal compounds, preferred are organic lithium compounds and most preferred are organic monolithium compounds. The amount of the organic alkali metal compound used can be appropriately determined according to a molecular weight of the farnesene polymer as needed and is preferably from 0.01 to 3 parts by weight based on 100 parts by weight of farnesene.
[0088] The organic alkali metal compound can be used in the form of an organic alkali metal amide by allowing a secondary amine such as dibutyl amine, diexyl amine and dibenzyl amine to react with it.
[0089] The polar compound can be used in anion polymerization to control a microstructure of farnesene portions without causing the reaction to deactivate. Examples of the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethyl ethylenediamine and trimethylamine; and alkali metal alkoxides and phosphine compounds. The polar compound is preferably used in an amount from 0.01 to 1000 mol equivalent based on the organic alkali metal compound.
[0090] The temperature used in the above polymerization reaction is generally from -80 to 150 ° C, preferably from 0 to 100 ° C and more preferably from 10 to 90 ° C. The method of polymerization can be either a batch method or a continuous method.
[0091] The polymerization reaction can be stopped by adding a terminating agent such as methanol and isopropanol to the reaction system. The resulting polymerization reaction solution can be poured into a poor solvent such as methanol to precipitate the polymer (B). Alternatively, the polymerization reaction solution can be washed with water, and then a solid is separated from it and dried to isolate the polymer (B) from it. {Modified Polymer}
[0092] The polymer (B) then obtained can be subjected to 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, an urea group, an alkoxysilyl group, a hydroxyl group, an epoxy group, an ether group, an carboxyl group, carboxyl group, mercapto group, isocyanate group, nitrile group and acid anhydride group.
[0093] As the method of production of the modified polymer, for example, the method can be used where before the addition of the terminating agent a coupling agent such as tin tetrachloride, dibutyl tin chloride, tetrachlorosilane, dimethyl dichlorosilane , dimethyl diethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopril triethoxysilane, tetraglycidyl-3-bisaminocyclohexane and diisocyanated 2,4-tolylene which are capable of reacting with an active end of the polymer chain, a chain end modifying agent such as 4 , 4'-bis (dimethylamino) benzophenone, N-vinyl pyrrolidone, N-methyl pyrrolidone, 4-dimethylaminobenzylidene aniline and dimethyl imidazolidinone or other modifying agent as described in JP 2011-132298A is added to the polymerization reaction system. In addition, the isolated polymer can be grafted with maleic anhydride or similar.
[0094] In the modified polymer, the site of the polymer into which the functional group is introduced can be either a chain end or a side chain of the polymer. In addition, these functional groups can be used in combination of any two or more of them. The modifying agent can be used in an amount of from 0.1 to 10 mol equivalents based on the organic alkali metal compound. <Smoke level (C)>
[0095] The carbon black (C) used in the rubber composition of the present invention has an average particle size of from 5 to 100 nm. When the average particle size of carbon black (C) is less than 5 nm, carbon black tends to exhibit a deteriorated dispersion in the rubber composition. When the average particle size of carbon black (C) is greater than 100 nm, the resulting rubber composition may fail to exhibit sufficient mechanical strength and hardness.
[0096] Examples of carbon black (C) useful in the present invention include carbon blacks such as oven carbon black, channel carbon black, thermal carbon black, acetylene carbon black and Ketjen carbon black. Among these carbon blacks, from the point of view of a high cure rate and improved mechanical strength of the rubber composition, oven carbon black is preferred.
[0097] Examples of commercially available oven carbon black such as carbon black (C) having an average particle size from 5 to 500 nm include "DIABLACK" available from Mitsubishi Chemical Corp, and "SEAST" available from Tokai Carbon Co., Ltd. Examples of commercially available acetylene black as carbon black (C) having an average particle size from 5 to 500 nm include "DENKABLACK" available from Denki Kagaku Kogyo KK Examples of Ketjen black commercially available as carbon black (C) having an average particle size from 5 to 500 nm include "ECP600JD" available from Lion Corp.
[0098] Carbon black (C) can be subjected to an acid treatment with nitric acid, sulfuric acid, hydrochloric acid or a mixed acid thereof or it can be subjected to a heat treatment in the presence of air for its treatment of surface oxidation, from the point of view of improving the wetting capacity or dispersibility of carbon black (C) in the rubber component (A) and in the polymer (B). Furthermore, from the point of view of improving the mechanical strength of the rubber composition of the present invention, carbon black can be subjected to a heat treatment at a temperature of from 2,000 to 3,000 ° C in the presence of a graphitization catalyst . As the graphitization catalyst, boron, boron oxides (such as, for example, B2O2, B2O3, B4O3 and B4O5), boron oxo acids (such as, for example, orthoboric acid, metabolic acid and tetraboric acid) and salts thereof, boron carbonates (such as, for example, B4C and B6C), boron nitrite (such as BN) and other boron compounds.
[0099] The average particle size of carbon black (C) can be controlled by spraying or similar. In order to spray the carbon black (C), a high speed rotary mill (such as a hammer mill, pin mill and cage mill) or several ball mills (such as a rotation, a vibration mill and a planetary mill), a stirring mill (such as a bead mill, an attractor, a flow tube mill and an annular mill) or similar.
[00100] However, the average carbon black particle size (C) can be determined by calculating an average value of carbon black particle diameters measured using a transmission electron microscope.
[00101] In the rubber composition of the present invention, carbon black (C) is composed in an amount of from 20 to 100 parts by weight based on 100 parts by weight of the rubber component (A). When the amount of the composite carbon black (C) is more than 100 parts by weight, the resulting rubber composition tends to deteriorate in processability, dispersibility of the carbon black (C) therein and rolling resistance performance. On the other hand, when the amount of carbon black (C) compound is less than 20 parts by weight, the resulting rubber composition tends to deteriorate in mechanical strength and hardness. The amount of carbon black (C) composed in the rubber composition based on 100 parts by weight of the rubber component (A) is preferably 30 parts by weight or more, more preferably 40 parts by weight or more, even more preferably 43 parts by weight or more and even more preferably 45 parts by weight or more, and it is also preferably 95 parts by weight or less, more preferably 90 parts by weight or less, even more preferably 85 parts by weight or less and even more preferably 80 parts in bulk or less.
[00102] More specifically, the amount of carbon black (C) composed in the rubber composition based on 100 parts by weight of the rubber component (A) is preferably from 3 to 100 parts by weight, more preferably from a from 40 to 90 parts by mass and even more preferably from 45 to 80 parts by mass. «Optional Domponents>
[00103] In the present invention, for the purposes of increasing the mechanical strength of the rubber composition, improving various properties such as its heat resistance and weather resistance, controlling its hardness and further improving the economy through the addition of an extender therein, the rubber composition may also contain a charge other than carbon black (C), if necessary.
[00104] The charge other than carbon black (C) 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 silica, clay, talc, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, can be used. titanium oxide, glass fibers, fibrous fillers and glass balloons. Among these charges, silica is preferred. Specific examples of silica include dry silica (anhydrous silicic acid) and wet silica (anhydrous silicic acid). Among these silicas, from the point of view of increasing the mechanical resistance of the resulting rubber composition, wet silica is preferred. The above charge is preferably composed in the rubber composition of the present invention in an amount of from 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 mass based on 100 parts by mass of the rubber component (A). When the amount of the composite load falls within the range specified above, the resulting rubber composition can be further improved in mechanical strength.
[00105] However, when composing silica as an optional component, it is preferred that the silica is added together with a silane coupling agent. Examples of the silane coupling agent include bis (3-triethoxyethylethyl) bis tetrasulfide, bis (3-triethoxyethylethyl) tetrasulfide, bis (3-triethoxyethylpropyl) bis tetrasulfide, bis (3-triethoxysilylpropyl) disulfide - triethoxysilylpropyl). Among these silane coupling agents, bis (3-triethoxysilylpropyl) tetrasulfide is preferred due to the excellent processability of the resulting rubber composition. These silane coupling agents can be used alone or in combination with any two or more of them. The silane coupling agent is preferably composed in the rubber composition in an amount of from 0.1 to 15 parts by weight based on 100 parts by weight of the rubber component (A).
[00106] The rubber composition of the present invention may also contain, if necessary, a softening agent for the purpose of improving processability, fluidity or the like of the resulting rubber composition unless the effects of the present invention are adversely influenced. Examples of the softening agent include a process oil such as a silicone oil, an aroma oil, ADT (Treated Distilled Aromatic Extracts), MES (Mild Extracted Solvates), RAE (residual aromatic extracts) (Residual Aromatic Extracts), a paraffin oil and a naphtha oil; and a liquid polymer such as a low molecular weight polybutadiene, a low molecular weight polyisoprene, a low molecular weight styrene-butadiene copolymer and a low molecular weight styrene-isoprene copolymer. However, the above copolymers can be in the form of either a block copolymer or a random copolymer. The liquid polymer preferably has an average molecular weight of from 2,000 to 80,000 from the point of view of good processability of the resulting rubber composition. The above process oil or liquid polymer as a softening agent is preferably composed in the rubber composition of the present invention in an amount of less than 50 parts by weight based on 100 parts by weight of the rubber component (A).
[00107] The rubber composition of the present invention may also contain, if necessary, one or more additives selected from the group consisting of an antioxidant, an oxidation inhibitor, a lubricant, a light stabilizer, a yellowing retardant, a processing, a dye such as pigments and coloring materials, a flame retardant, an antistatic agent, an opacifying agent, an anti-blocking agent, an ultraviolet absorber, a release agent, a foaming agent, an antimicrobial agent, an mold proof and a perfume, for the purposes of improving weather resistance, heat resistance, oxidation resistance or the like of the resulting rubber composition, unless the effects of the present invention are adversely influenced.
[00108] Examples of the oxidation inhibitor include compounds based on hindered phenol, phosphorus-based compounds, lactone-based compounds and hydroxyl-based compounds.
[00109] 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.
[00110] The rubber composition of the present invention is preferably used in the form of a crosslinked product produced by adding a crosslinking agent to it.
[00111] Examples of the crosslinking agent include sulfur and sulfur compounds, oxygen, organic peroxides, phenol resins and amino resins, quinone derivatives and quinone dioxima, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, halides metal and organic metal halides and silane compounds. Among these cross-linking agents, sulfur and sulfur compounds are preferred. Such cross-linking agents can be used alone or in combination with any two or more of them. The crosslinking agent is preferably composed in the rubber composition in an amount of from 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component (A).
[00112] When using sulfur as the crosslinking agent, a vulcanization aid or a vulcanization accelerator is preferably used in combination with the crosslinking agent.
[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 compounds based on guanidine, compounds based on sulfene amide, compounds based on thiazole, compounds based on thuram, compounds based on thiourea, compounds based on dithiocarbonic acid, compounds based on of aldehyde-amine, compounds based on aldehyde-ammonia, compounds based on imidazoline and compounds based on xanthate. These vulcanization aids or vulcanization accelerators can be used alone or in combination with any two or more of them. The vulcanization aid or vulcanization accelerator is preferably composed in the rubber composition of the present invention in an amount from 0.1 to 15 parts by weight based on 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 as long as the respective components are uniformly mixed with each other.
[00116] The method of uniform mixing of the respective components can be carried out using a kneader of the closed type of a tangential type or a mesh type (meshing) such as a rudder kneader, a Brabender, a Banbury mixer and an internal mixer; a single screw extruder, a double screw extruder, a mixing roller, a roller or the like in a temperature range of generally 70 to 270 ° C. Tire
[00117] 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
[00118] The present invention will be described in more detail below with reference to the following examples. It should be noted, however, that the examples that follow are illustrative only and are not intended to limit the invention to them. <Examples 1 to 23 and Comparative Examples 1 to 15>
[00119] Average molecular weight, melt viscosity, vinyl content and glass transition temperature of the polymer (B), the Mooney viscosity of the rubber composition, the dispersibility of carbon black (C) in the rubber composition and rolling resistance performance, hardness and tensile strength at rupture of the rubber composition were measured using the following methods. (1) Average Weight Molecular Weight
[00120] The average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the polymer (B) were measured using GPC (gel permeation chromatography) in terms of the molecular weight of polystyrene as a standard substance of reference. The devices and the measurement 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 ° C (2) Fusion viscosity
[00121] The melt viscosity of the polymer (B) was measured at 38 ° C using a Brookfield viscometer available from Brookfield Engineering Labs. Inc. (3) Vinyl Content
[00122] A solution prepared by dissolving 50 mg of polymer (B) in 1 mL of CDCI3 was subjected to the measurement of 1H-NMR at 400 MHz at a cumulative frequency of 512 times. From the graph obtained through the above measurement, a portion of spectrum in the range from 4.94 to 5.22 ppm was considered to be a spectrum derived from a vinyl structure, while a portion of spectrum in the range of a from 4.45 to 4.85 ppm it was considered to be a combined spectrum derived from both the vinyl structure and the 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} (4) Glass Transition Temperature
[00123] Ten milligrams of polymer (B) were sampled in an aluminum pan and a sample thermogram was measured at a temperature increase rate of 10 ° C / min using Differential Scanning Calorimetry (DSC) and the value at the top of a peak observed on the DDSC curve was determined as a glass transition temperature of the polymer (B). (5) Mooney viscosity
[00124] 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 K6300. The values of the respective Examples and Comparative Examples appearing in Table 2 are relative values based on 100 as the value of Comparative Example 3. Also, the values of the respective Examples and Comparative Examples that appear in Tables 3 and 4 are relative values based on 100 as the value of Comparative Example 8; and the values of the respective Examples and Comparative Examples appearing in Group 1, Group 2, Group 3, Group 4 and Group 5 in Table 5 are relative values based on 100 as each of the values of Comparative Example 11, Comparative Example 12, Example Comparative 13, Comparative Example 14 and Comparative Example 15, respectively. However, the lower Mooney viscosity value indicates more excellent processability. (6) Carbon Black Dispersibility
[00125] The rubber composition was molded in a press to prepare a cured sheet (thickness: 2 mm). The sheet then prepared was cut into a test piece having a section of 2 mm x 6 mm and the section was observed using an optical microscope and visually evaluated by counting the number of aggregated carbon black masses having a size of 20 pm or more in the section. The evaluation ratings are as follows: [1]: 1 to 7 coagulated carbon black masses were present. [2]: 8 to 14 coagulated carbon black masses were present. [3]: 15 to 21 coagulated carbon black masses were present. [4]: 22 or more masses of coagulated carbon black were present.
[00126] However, the lower value indicates a more excellent dispersibility of carbon black in the rubber composition. (7) Rolling Resistance Performance
[00127] The rubber composition was molded in a press to prepare a cured sheet (thickness: 2 mm). The sheet then prepared was cut into a test piece having a size of 40 mm long x 7 mm wide. The test piece then obtained was subjected to a 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 60 ° C, a frequency of 10 Hz, a static distortion of 10% and a dynamic distortion of 2%. The values of the respective Examples and Comparative Examples appearing in Table 2 are relative values based on 100 as the value of Comparative Example 3. Also, the values of the respective Examples and Comparative Examples appearing in Tables 3 and 4 are relative values based on at 100 as the value of Comparative Example 8; and the values of the respective Examples and Comparative Examples appearing in Group 1, Group 2, Group 3, Group 4 and Group 5 in Table 5 are relative values based on 100 as each of the values of Comparative Example 11, Comparative Example 12, Example Comparative 13, Comparative Example 14 and Comparative Example 15, respectively. However, the smaller volume indicates excellent rolling resistance performance of the rubber composition. (8) Hardness
[00128] According to JIS K6253, the rubber composition was molded in a press to prepare a cured sheet (thickness: 2 mm). The hardness of the sheet then prepared was measured using a type A hardness tester; and the then measured hardness 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 a large deformation and is then deteriorated in direction stability. (9) Tensile Strength at Break
[00129] The rubber composition was molded in a press to prepare a cured sheet (thickness: 2 mm). The sheet then prepared was punctured in a dumbbell-shaped test piece according to JIS 3 and the test piece was subjected to stress resistance measurement at break using a tension tester from Instron Corp. The values of the respective Examples and Comparative Examples appearing in Table 2 are relative values based on 100 as the value of Comparative Example 3. Also, the values of the respective Examples and Comparative Examples appearing in Tables 3 and 4 are relative values based on 100 as the value of Comparative Example 8; and the values of the respective Examples and Comparative Examples appearing in Group 1, Group 2, Group 3, Group 4 and Group 5 in Table 5 are relative values based on 100 as each of the values of Comparative Example 11, Comparative Example 12, Example Comparative 13, Comparative Example 14 and Comparative Example 15, respectively. However, the higher value indicates a higher tensile strength when the rubber composition breaks. Production Example 1: Production of polyphenesene (B-1)
[00130] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 120 g of hexane as a solvent and 1.1 g of n-butyl lithium (in the form of a 17% by weight hexane solution) as an initiator. The contents of the reaction vessel were heated to 50 ° C and 210 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, in this way obtaining a polypharnesene (B-1). Various properties of the polyphennesene (B-1) then obtained are shown in Table 1. Production Example 2: Production of polyphennesene (B-2)
[00131] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 203 g of hexane as a solvent and 7.7 g of n-butyl lithium (in the form of a 17% by weight hexane solution) as an initiator. The contents of the reaction vessel were heated to 50 ° C and 342 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, in this way obtaining a polypharnesene (B-1). Various properties of the polyphennesene (B-1) then obtained are shown in Table 1. Production Example 3: Production of polyphennesene (B-3)
[00132] 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% by weight hexane solution) as an initiator. The contents of the reaction vessel were heated to 50 ° C and 272 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, in this way obtaining a polypharnesene (B-3). Various properties of the polyphennesene (B-3) then obtained are shown in Table 1. Production Example 4: Production of polyphennesene (B-4)
[00133] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 313 g of hexane as a solvent and 0.7 g of n-butyl lithium (in the form of a 17% by weight hexane solution) as an initiator. The contents of the reaction vessel were heated to 50 ° C and 226 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, in this way obtaining a polypharnesene (B-4). Various properties of the polyphennesene (B-4) then obtained are shown in Table 1. Production Example 5: Production of Polyisopropene
[00134] The same procedure as in Production Example 1 was repeated, except for the use of isoprene in place of β-farnesene, thereby obtaining a Polyisopropene. Various properties of the Polyisopropene then obtained are shown in Table 1. Production Example 6: Production of polyphenesene (B-6)
[00135] 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% by weight hexane solution) as an initiator. The contents of the reaction vessel were heated to 50 ° C 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 treated with methanol and then washed with water. After separating water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, thereby obtaining a polypharnesene (B-6). Several properties of the polyphennesene then obtained (B-6) are shown in Table 1. Production example 7: Production of polyphenesene (B-7)
[00136] A pressure reaction vessel was loaded with 500 g of polypharnesene produced using the same method as that described in Production Example 3, 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 ° C and reacted at this temperature for 10 h, thus obtaining a polyphennesene (B-7). Various properties of the polyphennesene (B-7) then obtained are shown in Table 1. Production Example 8: Production of polyphennesene (B-8)
[00137] A pressure reaction vessel previously purged with nitrogen and then dried was charged with 241 g of cyclohexane as a solvent and 28.3 g of sec-butyl lithium (in the form of a 10.5 wt% cyclohexane solution ) as an initiator. The contents of the reaction vessel were heated to 50 ° C and then 342 g of β-farnesene were added to them and polymerized for 1 h. The resulting polymerization reaction solution was treated with methanol and then washed with water. After separating water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, in this way obtaining a polypharnesene (B-8). Various properties of the then polypharnesene (B-8) obtained are shown in Table 1. TABLE 1
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[00138] The respective components including natural rubber (A), polymer (B), carbon black (C) or similar used in the Examples and Comparative Examples that follow are as follows: Natural Rubber:
[00139] SMR20 (natural rubber from Malaysia)
[00140] STR20 (natural rubber from Thailand) Styrene-Butadiene rubber:
[00141] "JSR1500" available from JSR Corp .; average molecular weight weight: 450,000; styrene content: 23.5% by weight (produced using the emulsion polymerization method) Butadiene rubber:
[00142] "BR-01" available from JSR Corp. Polymer (B):
[00143] Polypharnesenes (B-1) to (B-4) and (B-6) to (B-8) produced above in Production Examples 1 to 4 and 6 to 8. Carbon black (C):
[00144] C-1: "DIABLACK H" available from Mitsubishi Chemical Corp .; average particle size: 30 nm
[00145] C-2: "DIABLACK E" available from Mitsubishi Chemical Corp .; average particle size: 50 nm
[00146] C-3: "SEAST TA" available from Tokai Carbon Co., Ltd .; average particle size: 120 nm
[00147] C-4: "DIABLACK I" available from Mitsubishi Chemical Corp .; average particle size: 20 nm
[00148] C-5: "SEAST V" available from Tokai Carbon Co., Ltd .; average particle size: 60 nm Optional Components
[00149] Polyisopropene: Polyisopropene produced in Production Example 5
[00150] TDAE: "VivaTecõOO" available from H & R Corp.
[00151] Resin: "SCOREZ 1102" available from Exxon Mobil Corp.
[00152] Stearic Acid: "LUNAC S-20" available from Kao Corp.
[00153] Zinc Oxide: Zinc oxide available from Sakai Chemi cal Industry Co., Ltd.
[00154] Antioxidant (1): "NOCRAC 6C" available from Ouchi Shinko Chemical Industrial Co., Ltd.
[00155] Antioxidant (2): "ANTAGE Rd" available from Kawaguchi Chemical Industry Co., Ltd.
[00156] Wax: "SUNTIGHT S" available from Seiko Chemical Co., Ltd.
[00157] Sulfur: 200 mesh fine sulfur powder available from Tsuru-mi Chemical Industry Co., Ltd.
[00158] Vulcanization accelerator: "NOCCELER NS" available from Ouchi Shinko Chemical Industry Co., Ltd.
[00159] The component of rubber (A), polymer (B), carbon black (C), stearic acid, zinc oxide and antioxidant (s) were loaded in a composition ratio (mass part (s)) as shown in Tables 2 to 5 in a closed Banbury mixer and kneaded together for 6 minutes so that the start temperature was 75 ° C and the resin temperature reached 160 ° C. The resulting mixture was removed from the mixer at once and cooled to room temperature. Then, the mixture was put on a mixing roller and after adding sulfur and the vulcanization accelerator to it, the contents of the mixing roller were kneaded at 60 ° C for 6 minutes, thus obtaining a rubber composition. The Mooney viscosity of the rubber composition then obtained was measured using the method above.
[00160] Furthermore, the resulting rubber composition was molded by press (at 145 ° C for 20 minutes) while being cured to prepare a sheet (thickness: 2 mm). The sheet then prepared was evaluated for the dispersibility of carbon black in it, performance of rolling resistance, resistance to hardness and stress at break using the methods above. The results are shown in Tables 2 to 5. 5 TABLE 2


Examples Examples Comparatives 1 2 3 4 5 1 2 3 Properties Mooney viscosity (relative value) 76 75 76 84 63 56 80 100 Carbon black dispersibility 1 1 2 2 1 1 3 3 Rolling resistance performance (at 6CTC; tan δ) (relative value) 69 82 69 81 60 55 95 100 Hardness (type A) 58 56 59 61 56 48 60 64 Tensile strength at break (relative value) 92 95 92 94 82 79 100 100
[00161] The rubber compositions obtained in Examples 1 to 5 were prevented from deteriorating in mechanical strength and hardness and increased in carbon black dispersibility. In addition, the rubber compositions obtained in Examples 1 to 3 exhibited low Mooney viscosity and good processability. In addition, the rubber compositions obtained in Examples 1 and 3 exhibited especially low rolling resistance and could therefore be used appropriately as a rubber tire composition. TABLE 3
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45/65 46/65 TABLE 4

TABLE 5 49/65



50/65 51/65 52/65
[00162] As shown in Table 3, the rubber compositions obtained in Examples 6 to 14 exhibited good processability due to their low Mooney viscosity, were improved in carbon black dispersibility therein and were prevented from deteriorating in hardness. In addition, these rubber compositions had low rolling resistance and could therefore be used appropriately as a rubber tire composition.
[00163] Among them, from the comparison between Examples 6 and 7, and Comparative Example 7, it was confirmed that the effects of the present invention could be exhibited regardless of the vinyl content and modification or non-modification of the rubber compositions.
[00164] From the comparison between Example 8 and Comparative Example 5, between Example 10 and Comparative Example 6 and between Example 12 and Comparative Example 7, it was confirmed that when using polymer (B), the compositions of The resulting rubber was excellent in all processability, carbon black dispersibility and rolling resistance performance.
[00165] Still, from the comparison between Example 14 and Comparative Example 4, it was confirmed that when adjusting the carbon black content (C) to 20 parts by weight or more based on 100 parts by weight of rubber component (A), the resulting rubber composition was prevented from deteriorating in hardness and could be properly used as a tire composition.
[00166] As shown in Table 4, from the comparison between Example 15 and Comparative Example 9 and between Example 16 and Comparative Example 10, it was confirmed that when adjusting the carbon black content (C) to 100 parts by weight or less based on 100 parts by weight of the rubber component (A), the resulting rubber compositions were excellent in all processability, carbon black dispersibility and rolling resistance performance.
[00167] As shown in Table 5, from the comparison between Example 17 and Comparative Example 11 and between Example 18 and Comparative Example 12, it was confirmed that when using carbon black (C) having a particle size medium from 5 to 100 nm, the resulting rubber compositions exhibited good processability and were prevented from deteriorating in hardness and could then provide a rubber tire composition having excellent rolling resistance performance.
[00168] Still, from the comparison between Example 19 and Comparative Example 13 and between Example 20 and Comparative Example 14, it was confirmed that even when using a mixture containing two or more types of natural and synthetic rubbers as the rubber component (A), it was possible to obtain the effects of the present invention.
[00169] Still, from the comparison between Examples 21 to 23 and Comparative Example 15, it was confirmed that even when using two or more types of polymers (B) or using polymer (B) in combination with the other optional components, it was also possible to obtain the effects of the present invention. <Examples 24 to 28 and Comparative Examples 16 to 19>
[00170] The respective components including natural rubber (A), polymer (B), carbon black (C) or similar used in Examples 24 to 28 and Comparative Examples 16 to 19 are as follows. Rubber component (A):
[00171] "JSR1500" styrene-butadiene rubber available from JSR Corp .; average molecular weight: 450,000; styrene content: 23.5% by weight (produced using the emulsion polymerization method). Polymer (B):
[00172] Polypharnesenes (B-9) to (B-12) produced in Production Examples 9 to 12. Carbon Black (C):
[00173] C-1: "DIALBLACK H" available from Mitsubishi Chemical Corp .; average particle size: 30 nm
[00174] C-2: "DIALBLACK E" available from Mitsubishi Chemical Corp .; average particle size: 50 nm
[00175] C-3: "SEAST TA" available from Tokai Carbon Co., Ltd ;, medium particle size: 120 nm Optional Components
[00176] Polyisopropene: Polyisopropene produced in Production Example 13
[00177] TDAE: "VivaTec500" available from H & R Corp.
[00178] Stearic Acid: "LUNAC S-20" available from Kao Corp.
[00179] Zinc Oxide: Zinc oxide available from Sakai Chemi cal Industry Co., Ltd.
[00180] Antioxidant (1): "NOCRAC 6C" available from Ouchi Shinko Chemical Industrial Co., Ltd.
[00181] Antioxidant (2): "ANTAGE RD" available from Kawaguchi Chemical Industry Co., Ltd.
[00182] Sulfur: 200 mesh fine sulfur powder available from Tsuru-mi Chemical Industry Co., Ltd.
[00183] Vulcanization accelerator: "NOCCELER CZ-G" available from Ouchi Shinko Chemical Industry Co., Ltd.
[00184] Vulcanization accelerator (2): "NOCCELER D" available from Ouchi Shinko Chemical Industry Co., Ltd. Production example 9: Production of polyphenesene (B-9)
[00185] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 120 g of hexane and 1.1 g of n-butyl lithium (in the form of a 17% by weight hexane solution). The contents of the reaction vessel were heated to 50 ° C and 210 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 water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, thus obtaining a polypharnesene (B-9) having properties shown in Table 6. Production Example 10: Production of polypharnesene (B-10)
[00186] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 241 g of cyclohexane and 28.3 g of sec-butyl lithium (in the form of a 10.5% mass cyclohexane solution). The contents of the reaction vessel were heated to 50 ° C and 342 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 water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, in this way obtaining a polypharnesene (B-9) having properties shown in Table 6. Production Example 11: Production of polypharnesene (B-11)
[00187] A pressure reaction vessel previously purged with nitrogen and then dried was loaded with 274 g of hexane and 1.2 g of n-butyl lithium (in the form of a 17% by weight hexane solution). The contents of the reaction vessel were heated to 50 ° C and 272 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 water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, in this way obtaining a polypharnesene (B-11) having properties shown in Table 6. Production Example 12: Production of polypharnesene (B-12)
[00188] 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% by weight hexane solution). The contents of the reaction vessel were heated to 50 ° C 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 water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, thus obtaining a polypharnesene (B-12) having properties shown in Table 6. Production Example 13: Production of Polyisopropene
[00189] 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 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 water from the polymerization reaction solution then washed, the resulting solution was dried at 70 ° C for 12 h, thus obtaining Polyisopropene having properties shown in Table 6.
[00190] The average molecular weight and melting viscosity of each of the polymer (B) and Polyisopropene were measured using the following methods. (Method of measuring the Average Weight Molecular Weight)
[00191] The average weight molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of each of the polymer (B) and Polyisopropene were measured using GPC (gel permeation chromatography) in terms of a molecular weight of polystyrene as a standard reference substance. The measuring devices and conditions are as follows. • Device: GPC device "GPC8020" available from Tosoh Corp. 5 • Separation column: "TSKgel4000HXL" available from Tosoh Corp. • Detector: "RI-8020" available from Tosoh Corp. • Eluent: Tetrahydrofuran • Eluent flow rate: 1.0 mL / min 10 • Sample concentration: 5 mg / 10 ml_ • Column temperature: 40 ° C (Melting Viscosity Measurement Method)
[00192] The melt viscosity of the polymer (B) was measured at 38 ° C using a Brookfield viscometer available from Brookfield Enginee-15 ring Labs. Inc TABLE 6

[00193] The rubber (A), polymer (B), Polyisopropene, carbon black (C), TDAE, stearic acid, zinc oxide and antioxidants component were loaded in a composition ratio (part (s) ) in bulk) as shown in Table 7 in a closed Banbury mixer and kneaded together for 6 minutes so that the start temperature was 75 ° C and the resin temperature reached 160 ° C. The resulting mixture was removed at once from the mixer and cooled to room temperature. Then, the mixture was put on a mixing roller and after adding sulfur and the vulcanization accelerators to it, the contents of the mixing roller were kneaded at 60 ° C for 6 minutes, thus obtaining a rubber composition. The Mooney viscosity of the rubber composition then obtained was measured using the method mentioned below.
[00194] Also, the resulting rubber composition was molded in a press (at 145 ° C for 20 minutes) to prepare a sheet (thickness: 2 mm). The sheet then prepared was evaluated for dispersibility of carbon black in it, performance of rolling resistance, hardness, elongation at stress at break and resistance to stress at break using the methods mentioned below. The results are shown in Table 7.
[00195] However, the methods of assessing the Mooney viscosity of the rubber composition and the dispersibility of carbon black in the rubber composition and the methods of measuring the rolling resistance, hardness, elongation at break strength and tensile strength performance at rupture of the rubber composition are as follows. Mooney Viscosity
[00196] 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 K6300. The values of the respective Examples and Comparative Examples appearing in Table 7 are relative values based on 100 as the value of Comparative Example 19. However, the lower Mooney viscosity value indicates more excellent processability. Carbon Black Dispersibility
[00197] The sheet obtained from the rubber composition produced in the respective Examples and Comparative Examples was cut into a test piece having a section of 2 mm x 6 mm and the section was observed using an optical microscope and visually evaluated by counting of the number of coagulated carbon black masses having a size of 20 pm or more in the section. The evaluation classifications are as follows: [1]: 1 to 3 co-agglued carbon black masses were present. [2]: 4 to 6 coagulated carbon black masses were present. [3]: 7 to 9 coagulated carbon black masses were present. [4]: 10 or more masses of coagulated carbon black were present.
[00198] The lower value indicates a more excellent carbon black dispersibility in the rubber composition. Rolling Resistance Performance
[00199] The sheet obtained from the rubber composition produced in the respective Examples and Comparative Examples was cut into a test piece having a size of 40 mm long x 7 mm wide. The test piece then obtained was subjected to tanδ measurement as an index of rolling resistance performance of the rubber composition using a dynamic viscoelasticity measuring device available from GABO GmbH under conditions including a measuring temperature of 60 ° C, a frequency of 10 Hz, a static distortion of 10% and a dynamic distortion of 2%. The values of the respective Examples and 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. Toughness
[00200] According to JIS K6253, the hardness of the sheet obtained from the rubber composition produced in the respective Examples and Comparative Examples was measured using a type A hardness tester and the hardness then 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 large deformation and is then deteriorated in direction stability. Stretching under Tension at Break
[00201] The sheet obtained from the rubber composition produced in the respective Examples and Comparative Examples was punctured in a dumbbell-shaped test piece according to JIS 3, and the obtained test piece was subjected to the measurement of a tension elongation in the rupture using a voltage tester available from Instron Corp. The values of the respective Examples and Comparative Examples are relative values based on 100 as the value of Comparative Example 19. However, the higher value indicates a higher stress elongation at rupture of the rubber composition. Tensile Strength at Break
[00202] The sheet obtained from the rubber composition produced in the respective Examples and Comparative Examples was punctured in a dumbbell-shaped test piece according to JIS 3 and the test piece obtained was subjected to the measurement of tensile strength. their rupture using a tension tester from Inserton Corp. The values of the respective Examples and Comparative Examples are relative values based on 100 as the value of Comparative Example 19. However, the higher value indicates a greater tensile strength in the rupture of the rubber composition. TABLE 7



[00203] The rubber compositions obtained in Examples 24 to 28 exhibited low Mooney viscosity and good processability. In addition, the rubber compositions obtained in Examples 24, 26 and 28 had improved carbon black dispersibility therein and exhibited low rolling resistance. In particular, the rubber compositions obtained in Examples 24 and 26 were prevented from deteriorating in mechanical strength and hardness and could therefore be used appropriately as a rubber tire composition.

权利要求:
Claims (10)
[0001]
1. Rubber composition, characterized by the fact that it comprises (A) at least one rubber component selected from the group consisting of a synthetic rubber and a natural rubber; (B) a farnesene polymer having an average molecular weight from 25,000 to 500,000; and (C) carbon black having an average particle size from 5 to 100 nm, a content of polymer (B) in the rubber composition is from 0.1 to 100 parts by weight based on 100 parts by mass of the rubber component (A), and a carbon black content (C) in the rubber composition being from 20 to 100 parts by weight based on 100 parts by mass of the rubber component (A) .
[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 in that the polymer (B) has a melting viscosity of from 0.1 to 3,000 Pa's as measured at 38 ° C.
[0004]
Rubber composition according to any one of claims 1 to 3, characterized in that the synthetic rubber is at least one rubber selected from the group consisting of a styrene-butadiene rubber, a butadiene rubber and a rubber of isoprene.
[0005]
Rubber composition according to claim 4, characterized in that the styrene-butadiene rubber has an average molecular weight of from 100,000 to 2,500,000.
[0006]
Rubber composition according to claim 4 or 5, characterized in that the styrene-butadiene rubber has a styrene content of from 0.1 to 70% by weight.
[0007]
Rubber composition according to any one of claims 4 to 6, characterized in that the butadiene rubber has an average molecular weight from 90,000 to 2,000,000.
[0008]
Rubber composition according to any one of claims 4 to 7, characterized in that the butadiene rubber has a vinyl content of 50% by weight or less.
[0009]
Rubber composition according to any one of claims 1 to 8, characterized in that the polymer (B) has a molecular weight distribution (Mw / Mn) of from 1.0 to 8.0.
[0010]
10. Tire, characterized by the fact that it comprises at least partially the rubber composition, as defined in any one of claims 1 to 9.

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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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2020-06-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-10-13| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/09/2012, 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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JP2011-218119|2011-09-30|

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JP2011218119|2011-09-30|

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JP2012-039412|2012-02-24|

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JP2012039412|2012-02-24|

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PCT/JP2012/074168|WO2013047347A1|2011-09-30|2012-09-21|Rubber composition and tire|

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