JP2018131501A - Rubber composition for high grip tire tread - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a rubber composition for a high grip tire tread, combining wet grip performance with dry grip performance; a tire tread using the rubber composition partly; and a pneumatic tire for racing.SOLUTION: The rubber composition for a high grip tire tread is provided that contains a farnesene polymer (B) by 0.1 to 90 pts.mass and a filler (C) by 20 to 150 pts.mass per 100 pts.mass of a rubber component (A) containing a styrene butadiene rubber having a styrene content of 20 mass% or more by 60 mass% or more.SELECTED DRAWING: None

Description

  The present invention relates to a rubber composition for a high grip tire tread, a tire tread using the rubber composition at least in part, and a pneumatic tire for racing.

  Pneumatic tires are required to have excellent handling stability on dry road surfaces (dry grip performance) and driving stability on wet road surfaces (wet grip performance), as well as excellent wear resistance. ing. In order to improve the wear resistance, a rubber composition containing carbon black or silica is generally used as a rubber reinforcing agent. However, the rubber composition has a high viscosity, so the processability is poor and the processability improver. Process oils and liquid polymers are used. However, when the conventional processability improver is used, although the processability is improved, there is a problem that the dry grip performance, the wet grip performance and the wear resistance are not sufficiently improved.

  As a rubber composition for improving the above properties in a well-balanced manner, Patent Document 1 includes at least one selected from the group consisting of natural rubber and diene synthetic rubber, carbon black, and acidic and basic functional groups. A rubber composition for a high-performance tire tread containing an amphoteric compound is described. Patent Document 2 describes a rubber composition in which a rubber component, a softening agent, and carbon black are blended by a specific method. Yes.

Patent Document 3 discloses 10 parts by mass of liquid styrene butadiene rubber having a weight average molecular weight of 1000 to 5000 and a hydrogenation rate of 40 to 60% with respect to 100 parts by mass of a rubber component containing styrene butadiene rubber. A rubber composition containing 5 parts by mass or more of an aromatic petroleum resin is described above, and Patent Document 4 discloses a diene system containing 70% by mass or more of styrene butadiene rubber having a styrene content of 30% by mass or more. 80 to 150 parts by mass of specific carbon black, 10 to 50 parts by mass of polyisoprene having a specific number average molecular weight, and 10 to 50 parts by mass of aromatic modified terpene resin having a specific softening point with respect to 100 parts by mass of rubber A blended tire tread rubber composition is described.
Furthermore, Patent Document 5 describes a rubber composition for tire treads that contains a specific styrene butadiene rubber and carbon black.

Japanese Patent Application Laid-Open No. 2014-024912 JP 2001-81239 A JP 2007-137941 A JP 2010-126671 A JP 2013-185090 A

  Although the tire using the rubber composition described in Patent Documents 1 to 5 shows improvement in wet grip performance and dry grip performance, it cannot be said that it is sufficient, and further improvement is desired.

  The present invention has been made in view of the above-described conventional problems, and a rubber composition for a high grip tire tread having both wet grip performance and dry grip performance, a tire tread using the same, and a race An object is to provide a pneumatic tire.

  As a result of intensive studies, the present inventors have found that a rubber composition for a high grip tire tread using a combination of a specific styrene butadiene rubber and a farnesene polymer can solve the above-mentioned problems, thereby completing the present invention. did.

That is, the present invention relates to the following [1] to [3].
[1] 0.1 to 90 parts by mass of a farnesene polymer (B) with respect to 100 parts by mass of a rubber component (A) containing 60% by mass or more of styrene butadiene rubber having a styrene content of 20% by mass or more, filler A rubber composition for a high grip tire tread, containing 20 to 150 parts by mass of (C).
[2] A tire tread using at least a part of the rubber composition for a high grip tire tread according to [1].
[3] A pneumatic tire for racing using at least a part of the rubber composition for a high grip tire tread according to [2].

  ADVANTAGE OF THE INVENTION According to this invention, the rubber composition for high grip tire treads which combines wet grip performance and dry grip performance, the tire tread using this, and the pneumatic tire for a race can be provided.

[Rubber composition for high grip tire tread]
The rubber composition for a high grip tire tread of the present invention has a farnesene polymer (B) based on 100 parts by mass of a rubber component (A) containing 60% by mass or more of styrene butadiene rubber having a styrene content of 20% by mass or more. 0.1 to 90 parts by mass and 20 to 150 parts by mass of filler (C). According to the rubber composition for a high grip tire tread of the present invention, a high grip tire having both wet grip performance and dry grip performance can be produced.
In the present specification, the “rubber composition for high grip tire tread” may be simply referred to as “the rubber composition for tire tread”.

<Rubber component (A)>
[Styrene butadiene rubber]
As the rubber component (A), one containing 60% by mass or more of styrene butadiene rubber having a styrene content of 20% by mass or more is used. Thereby, the wet grip performance and dry grip performance of a tire partially using the rubber composition for a tire tread of the present invention are improved.
The rubber component (A) is not particularly limited as long as it contains 60% by mass or more of styrene butadiene rubber (hereinafter also referred to as “SBR”) having a styrene content of 20% by mass or more. General SBR, synthetic rubber other than SBR, and natural rubber can be mixed and used.

  The styrene content of SBR is 20% by mass or more, preferably 22% by mass or more, more preferably from the viewpoint of improving the wet grip performance and dry grip performance of a tire partially using the tire tread rubber composition. It is 25% by mass or more, more preferably 30% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.

  The content in the rubber component (A) of the styrene butadiene rubber having a styrene content of 20% by mass or more is a viewpoint of improving the wet grip performance and dry grip performance of a tire partially using a rubber composition for a tire tread. Therefore, it is 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and substantially 100% by mass.

The weight average molecular weight (Mw) of SBR having a styrene content of 20% by mass or more is preferably 100,000 to 2,500,000, more preferably 150,000 to 2,000,000, still more preferably 150, 000 to 1,500,000, more preferably 180,000 to 1,000,000. When the weight average molecular weight (Mw) of the SBR is within the above range, the processability of the tire tread rubber composition is improved, and the tire dry grip performance and wet grip performance obtained from the tire tread rubber composition are also improved. improves.
In addition, the weight average molecular weight (Mw) in this specification is the value measured by the method as described in the below-mentioned Example.

  The glass transition temperature (Tg) determined by differential thermal analysis of SBR having a styrene content of 20% by mass or more is preferably −95 to 0 ° C., more preferably −80 to −5 ° C., and still more preferably −70. It is -10 degreeC, More preferably, it is -60 to -15 degreeC, More preferably, it is -50 to -20 degreeC, More preferably, it is -40 degreeC to -20 degreeC. When the glass transition temperature is within the above range, an increase in the viscosity of the tire tread rubber composition can be suppressed, and the handling becomes easy.

The vinyl content of SBR having a styrene content of 20% by mass or more is preferably 0.1 to 80% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 80% by mass. .
In addition, the vinyl content of SBR in this specification represents content of the monomer unit which has a vinyl group among the units derived from all the butadienes contained in SBR. Similarly, the vinyl content of the rubber component (A) represents the content of monomer units actually having a vinyl group with respect to the total amount of monomer units that can have a vinyl group depending on the bonding form.

  The rubber component (A) used in the present invention may be a combination of SBR having a styrene content of 20% by mass or more and SBR having a styrene content of less than 20% by mass. can do.

≪SBR manufacturing method≫
There is no restriction | limiting in particular about the manufacturing method of SBR, and any of an emulsion polymerization method, a solution polymerization method, a gas phase polymerization method, and a bulk polymerization method can be used, and an emulsion polymerization method and a solution polymerization method are especially preferable.

(I) Emulsion polymerization styrene butadiene rubber (E-SBR)
E-SBR can be produced by an ordinary emulsion polymerization method. For example, a predetermined amount of styrene and butadiene monomers are emulsified and dispersed in the presence of an emulsifier, and emulsion polymerization is performed using a radical polymerization initiator.
As the emulsifier, for example, a long chain fatty acid salt or rosin acid salt having 10 or more carbon atoms is used. Specific examples include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
As a dispersion medium, water is usually used, and a water-soluble organic solvent such as methanol and ethanol may be contained as long as stability during polymerization is not hindered.
Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, hydrogen peroxide, and the like.
In order to adjust the molecular weight of the obtained E-SBR, a chain transfer agent can also be used. Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, γ-terpinene, α-methylstyrene dimer, and the like.

Although the temperature of emulsion polymerization can be suitably selected according to the kind of radical polymerization initiator to be used, 0-100 degreeC is preferable normally and 0-60 degreeC is more preferable. The polymerization mode may be either continuous polymerization or batch polymerization. The polymerization reaction can be stopped by adding a polymerization terminator.
Examples of the polymerization terminator include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine, and hydroxylamine; quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.
After termination of the polymerization reaction, an antioxidant may be added as necessary. After the polymerization reaction is stopped, unreacted monomers are removed from the obtained latex as necessary, and then a salt such as sodium chloride, calcium chloride, potassium chloride is used as a coagulant, and nitric acid, sulfuric acid, etc. The polymer can be recovered as crumbs by adding the acid and coagulating the polymer while adjusting the pH of the coagulation system to a predetermined value and then separating the dispersion solvent. E-SBR can be obtained by washing the crumb with water, followed by dehydration and drying with a band dryer or the like. In addition, at the time of coagulation, if necessary, a latex and an extending oil that has been made into an emulsified dispersion may be mixed and recovered as an oil-extended rubber. In addition, in the composition in the rubber composition for tire treads in this specification, the extending oil is not included in the rubber component (A).
Examples of commercially available E-SBR include oil-extended styrene butadiene rubber “JSR1723” manufactured by JSR Corporation.

(Ii) Solution-polymerized styrene butadiene rubber (S-SBR)
S-SBR can be produced by an ordinary solution polymerization method. For example, an active metal capable of anion polymerization in a solvent is used, and styrene and butadiene are polymerized in the presence of a polar compound as desired.
Examples of the anion-polymerizable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium . Of these, alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable. Further, among alkali metals, organic alkali metal compounds are more preferably used.
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; benzene, And aromatic hydrocarbons such as toluene. These solvents are preferably used in a range where the monomer concentration is 1 to 50% by mass.

Examples of the organic alkali metal compound include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; dilithiomethane, 1,4-dilithiobutane, 1,4 -Polyfunctional organic lithium compounds such as dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like. Among these, an organic lithium compound is preferable, and an organic monolithium compound is more preferable. The amount of the organic alkali metal compound used is appropriately determined depending on the required molecular weight of S-SBR.
The organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, and dibenzylamine.
The polar compound is not particularly limited as long as it is usually used to adjust the microstructure of the butadiene site and the distribution of styrene in the polymer chain without deactivating the reaction in anionic polymerization. Examples include ether compounds such as butyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.

The temperature of the polymerization reaction is usually in the range of −80 to 150 ° C., preferably 0 to 100 ° C., more preferably 30 to 90 ° C. The polymerization mode may be either batch polymerization or continuous polymerization. In order to improve the random copolymerization of styrene and butadiene, styrene and butadiene are continuously or intermittently supplied into the reaction solution so that the composition ratio of styrene and butadiene in the polymerization system falls within a specific range. Is preferred.
The polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator. Coupling of tin tetrachloride, tetrachlorosilane, tetramethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylene diisocyanate, etc. that can react with the polymerization active terminal before adding the polymerization terminator An agent, or a polymerization terminal modifier such as 4,4′-bis (diethylamino) benzophenone or N-vinylpyrrolidone may be added. The polymerization solution after termination of the polymerization reaction can recover the target S-SBR by separating the solvent by direct drying, steam stripping or the like. In addition, before removing the solvent, the polymerization solution and the extending oil may be mixed in advance and recovered as an oil-extended rubber.

(Iii) Modified styrene butadiene rubber (modified SBR)
In the present invention, modified SBR in which a functional group is introduced into SBR may be used. Examples of the functional group include an amino group, an alkoxysilyl group, a hydroxy group, an epoxy group, and a carboxyl group.
As a method for producing the modified SBR, for example, before adding a polymerization terminator, tin tetrachloride, tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, which can react with a polymerization active terminal, Coupling agents such as 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylene diisocyanate, 4,4′-bis (diethylamino) benzophenone, N-vinylpyrrolidone, etc. And a method of adding other modifiers described in JP-A-2011-132298.
In this modified SBR, the position of the polymer into which the functional group is introduced may be the polymerization terminal or the side chain of the polymer chain.

  The rubber component (A) used in the present invention may contain two or more kinds of styrene butadiene rubbers having a styrene content of 20% by mass or more, and the styrene butadiene having a styrene content of 20% by mass or more. It may be a mixture of rubber and at least one selected from styrene butadiene rubber having a styrene content of less than 20% by mass, synthetic rubber, and natural rubber.

[Synthetic rubber other than styrene butadiene rubber]
Synthetic rubbers other than styrene butadiene rubber that can be used for the rubber component (A) are preferably butadiene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, ethylene propylene diene rubber, butadiene acrylonitrile polymer rubber, chloroprene rubber, etc. More preferred are isoprene rubber and butadiene rubber. These may be used alone or in combination of two or more.

(Isoprene rubber)
Examples of the isoprene rubber include Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel; -Commercially available isoprene rubber polymerized using a lanthanoid rare earth metal catalyst such as an organic acid neodymium-Lewis acid or the like, or an organic alkali metal compound in the same manner as S-SBR can be used. Isoprene rubber polymerized with a Ziegler catalyst is preferred because of its high cis isomer content. Further, isoprene rubber having an ultra-high cis body content obtained using a lanthanoid rare earth metal catalyst may be used.

  The vinyl content of the isoprene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. If the vinyl content exceeds 50% by mass, the rolling resistance performance (low fuel consumption performance) tends to deteriorate. The lower limit of the vinyl content is not particularly limited. The glass transition temperature varies depending on the vinyl content, but is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.

  The weight average molecular weight (Mw) of isoprene rubber is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000. When the weight average molecular weight of the isoprene rubber is within the above range, the processability of the tire tread rubber composition is improved and the dry grip performance of a tire partially using the tire tread rubber composition is improved.

  Isoprene rubber is partly formed by using a polyfunctional modifier such as tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an amino group-containing alkoxysilane. It may have a branched structure or a polar functional group.

(Butadiene rubber)
Examples of the butadiene rubber include Ziegler catalysts such as titanium tetrahalide-trialkylaluminum, diethylaluminum chloride-cobalt, trialkylaluminum-boron trifluoride-nickel, and diethylaluminum chloride-nickel; -Commercially available butadiene rubber polymerized using a lanthanoid rare earth metal catalyst such as organic acid neodymium-Lewis acid or the like, or an organic alkali metal compound in the same manner as S-SBR can be used. Butadiene rubber polymerized with a Ziegler catalyst is preferred because of its high cis isomer content. Moreover, you may use the butadiene rubber of the ultra high cis body content (for example, cis body content 95% or more) obtained using a lanthanoid type rare earth metal catalyst.

  The vinyl content of the butadiene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. If the vinyl content exceeds 50% by mass, the rolling resistance performance (low fuel consumption performance) tends to deteriorate. The lower limit of the vinyl content is not particularly limited. The glass transition temperature varies depending on the vinyl content, but is preferably −40 ° C. or lower, and more preferably −50 ° C. or lower.

  The weight average molecular weight (Mw) of the butadiene rubber is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000. When the weight average molecular weight (Mw) of the butadiene rubber is within the above range, the processability of the tire tread rubber composition is improved and the dry grip performance of the tire partially using the tire tread rubber composition is also improved. To do.

  Butadiene rubber is partly formed by using a polyfunctional modifier such as tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an amino group-containing alkoxysilane. It may have a branched structure or a polar functional group.

  Along with at least one of SBR, isoprene rubber, and butadiene rubber, one or more of butyl rubber, halogenated butyl rubber, ethylene propylene diene rubber, butadiene acrylonitrile polymer rubber, chloroprene rubber, and the like can be used. Moreover, these manufacturing methods are not specifically limited, What is marketed can be used.

[Natural rubber]
Examples of the natural rubber used for the rubber component (A) include TSR such as SMR, SIR, and STR, natural rubber generally used in the tire industry such as RSS, high-purity natural rubber, epoxidized natural rubber, and hydroxylation. Examples thereof include modified natural rubber such as natural rubber, hydrogenated natural rubber, and grafted natural rubber. Among these, SMR20, STR20, and RSS # 3 are preferable from the viewpoint of little variation in quality and easy availability. These may be used alone or in combination of two or more.

  In the present invention, the strength of the tire partially using the rubber composition for tire tread is improved by using the rubber component (A) described above, the farnesene polymer (B) and filler (C) described later in combination. .

  In the present invention, the content of the rubber component (A) in the rubber composition for a tire tread is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and still more preferably 45% by mass. %, And preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, still more preferably 65% by mass or less, and still more preferably 60% by mass or less. When the content of the rubber component (A) in the tire tread rubber composition is within the above range, the wear resistance of a tire partially using the tire tread rubber composition is improved.

<Farnesene polymer (B)>
The rubber composition for tire treads of the present invention contains a farnesene polymer (B). In the present invention, by using the farnesene polymer (B), a tire excellent in wet grip performance and dry grip performance of a tire partially using a rubber composition for a tire tread can be produced.
In the present invention, the farnesene polymer (B) refers to a polymer containing 5% by mass or more of the monomer unit (b1) derived from farnesene (hereinafter, also simply referred to as “monomer unit (b1)”).

[Monomer unit (b1)]
The monomer unit (b1) is a farnesene-derived monomer unit, may be an α-farnesene-derived monomer unit, and is derived from β-farnesene represented by the following formula (I). It may be a monomer unit, and may include a monomer unit derived from α-farnesene and a monomer unit derived from β-farnesene, but from the viewpoint of ease of production, β-farnesene Derived monomer units are preferred. That is, the farnesene polymer (B) may be a polymer containing monomer units derived from α-farnesene, or may be a polymer containing monomer units derived from β-farnesene. Further, it may be a polymer containing a monomer unit derived from α-farnesene and a monomer unit derived from β-farnesene. Among these, from the viewpoint of ease of production, a polymer containing a monomer unit derived from β-farnesene is preferable, and a homopolymer of β-farnesene is more preferable.

  The content of the monomer unit derived from β-farnesene in the monomer unit (b1) is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass from the viewpoint of ease of production. % Or more, more preferably 95% by mass or more, and still more preferably substantially 100% by mass.

The farnesene polymer (B) in the present invention comprises a monomer unit (b1) derived from farnesene and a monomer unit (b2) derived from a monomer other than farnesene (hereinafter simply referred to as “monomer unit (b2)”). It may also be a copolymer containing "
The monomer other than farnesene constituting the monomer unit (b2) is not particularly limited as long as it is copolymerizable with farnesene. For example, aromatic vinyl compounds, conjugated diene compounds other than farnesene, (Meth) acrylic acid and derivatives thereof, (meth) acrylamide and derivatives thereof, and acrylonitrile.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2- Aromatic vinyl compounds such as vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferable. These aromatic vinyl compounds may be used individually by 1 type, and may use 2 or more types together.

  Examples of conjugated diene compounds other than farnesene include conjugated dienes having 12 or less carbon atoms. Examples of the conjugated diene having 12 or less carbon atoms include butadiene, isoprene, 2,3-dimethyl-butadiene, 2-phenyl-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3- Examples include hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, and chloroprene. Of these, butadiene, isoprene, and myrcene are more preferable. These conjugated diene compounds may be used individually by 1 type, and may use 2 or more types together.

  (Meth) acrylic acid and derivatives thereof include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) T-butyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid tetraethylene glycol, (meth) acrylic acid tripropylene glycol, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic Acid 3-hydroxy-1-adamantyl, (meth) Acrylic acid tetrahydrofurfuryl, methoxyethyl (meth) acrylate, and (meth) acrylic acid N, N-dimethylaminoethyl, and the like. These (meth) acrylic acids and derivatives thereof may be used alone or in combination of two or more.

  Derivatives of (meth) acrylamide include dimethyl (meth) acrylamide, acryloylmorpholine, isopropyl (meth) acrylamide, diethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide methyl chloride quaternary salt , Hydroxyethyl (meth) acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid, and the like. These (meth) acrylamides and derivatives thereof may be used alone or in combination of two or more.

  The monomer unit (b2) is preferably derived from an aromatic vinyl compound from the viewpoint of improving the processability of the tire tread rubber composition and the braking performance of the tire partially using the tire tread rubber composition. It is at least one selected from monomer units and monomer units derived from conjugated diene compounds other than farnesene, more preferably monomer units derived from at least one selected from styrene, isoprene and butadiene. . A monomer unit (b2) may be used individually by 1 type, and may use 2 or more types together.

  When the monomer unit (b2) is an aromatic vinyl compound, the content of the monomer unit (b1) in the sum of the monomer units (b1) and (b2) is the rubber composition for tire treads. From the viewpoint of improving the wet grip performance and the dry grip performance of a tire using a part thereof, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and still more preferably 30% by mass. % Or more, more preferably 35% by weight or more, still more preferably 40% by weight or more, still more preferably 45% by weight or more, and preferably 90% by weight or less, more preferably 80% by weight or less, Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less, More preferably, it is 55 mass% or less, More preferably, it is 50 mass% or less It is.

  In the case where the monomer unit (b2) is a conjugated diene compound other than farnesene, the content of the monomer unit (b1) in the sum of the monomer units (b1) and (b2) is the tire tread rubber. From the viewpoint of improving the wet grip performance and dry grip performance of a tire partially using the composition, it is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and still more preferably. 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, still more preferably 55% by mass or more, still more preferably 58% by mass or more, and preferably 90% by mass. Or less, more preferably 80% by mass or less, further preferably 75% by mass or less, still more preferably 70% by mass or less, and still more preferably. It is less 65 mass%.

[Physical properties of farnesene polymer (B)]
The weight average molecular weight (Mw) of the farnesene polymer (B) is easy to cause crosslinking with the rubber component (A), and the wet grip performance and dry grip performance of a tire using a tire tread rubber composition as a part thereof. From the viewpoint of improving, preferably 2,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, still more preferably 6,000 or more, still more preferably 7,000 or more, and even more preferably. From the viewpoint of improving the processability of the rubber composition for a tire tread, it is preferably 500,000 or less, more preferably 200,000 or less, still more preferably 100,000 or less, and still more preferably. Preferably it is 50,000 or less, More preferably, it is 30,000 or less, More preferably, it is 20,000 Hereinafter, even more preferably 15,000 or less, even more preferably 10,000 or less. In addition, the weight average molecular weight of the farnesene polymer (B) in this specification is the value calculated | required by the method described in the Example mentioned later.
In the present invention, two or more kinds of farnesene polymers (B) having different weight average molecular weights may be used in combination.

  The molecular weight distribution (Mw / Mn) of the farnesene polymer (B) is preferably 1.0 to 8.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 3.0, and still more. Preferably it is 1.0-2.5, More preferably, it is 1.0-2.0, More preferably, it is 1.0-1.5. When the molecular weight distribution (Mw / Mn) is within the above range, it is preferable because variations in the viscosity of the farnesene polymer (B) are reduced.

  The glass transition temperature of the farnesene polymer (B) used in the present invention is preferably −10 ° C. or less from the viewpoint of improving the wet grip performance and dry grip performance of a tire using a rubber composition for a tire tread in part. More preferably, it is −15 ° C. or lower, more preferably −20 ° C. or lower, and preferably −90 ° C. or higher, more preferably −80 ° C. or higher, still more preferably −70 ° C. or higher, still more preferably −60 ° C. As described above, it is more preferably −50 ° C. or higher, and still more preferably −40 ° C. or higher. In addition, the glass transition temperature of a farnesene polymer (B) can be adjusted with the kind, vinyl content, etc. of the monomer unit (b2) of a farnesene polymer (B).

  The melt viscosity at 38 ° C. of the farnesene polymer (B) is preferably 0.1 Pa · s or more, more preferably 0.5 Pa · s or more, still more preferably 5.0 Pa · s or more, and even more preferably 10 Pa · s. Or more, more preferably 50 Pa · s or more, even more preferably 100 Pa · s or more, and from the viewpoint of improving the processability of the rubber composition for a tire tread, preferably 3,000 Pa · s or less, more preferably Is 2,000 Pa · s or less, more preferably 1,000 Pa · s or less, even more preferably 500 Pa · s or less, and still more preferably 400 Pa · s or less. In the present specification, the melt viscosity of the farnesene polymer (B) is a value determined by the method described in Examples described later.

The vinyl content (vinylation degree) of the farnesene polymer (B) is preferably 3% by mass or more, more preferably 15% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less. More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less. When the vinyl content of the farnesene polymer (B) is within the above range, dry grip performance and low fuel consumption performance are improved. In the present specification, the vinyl content is a bond excluding 1,4 bonds among all the β-farnesene-derived monomer units in the polymer (B) containing the monomer units derived from β-farnesene. It is the content of the pattern, and can be measured by using ¹ H-NMR.

  The amount of the farnesene polymer (B) with respect to 100 parts by mass of the rubber component (A) is 0.1 to 90 parts by mass. When the amount of the farnesene polymer (B) is within the above range, the dry grip performance, wet grip performance, and bleed resistance performance of a tire partially using the rubber composition for a tire tread can be improved. Further, mechanical strength and rolling resistance performance can be improved. From the above viewpoint, the amount of the farnesene polymer (B) with respect to 100 parts by mass of the rubber component (A) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more. Is 4 parts by mass or more, more preferably 5 parts by mass or more, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less. More preferably, it is 20 mass parts or less, More preferably, it is 15 mass parts or less.

[Method for producing farnesene polymer (B)]
The farnesene polymer (B) can be produced by an emulsion polymerization method, a method described in International Publication No. 2010/027463, International Publication No. 2010/027464, etc. Among them, an emulsion polymerization method or a solution polymerization method is preferable. The solution polymerization method is more preferable.

(Emulsion polymerization method)
As the emulsion polymerization method for obtaining the farnesene polymer (B), a known method can be applied. For example, a predetermined amount of farnesene monomer is emulsified and dispersed in the presence of an emulsifier, and emulsion polymerization is performed using a radical polymerization initiator.
As the emulsifier, for example, a long chain fatty acid salt or rosin acid salt having 10 or more carbon atoms is used. Specific examples include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
As a dispersion medium, water is usually used, and a water-soluble organic solvent such as methanol and ethanol may be contained as long as stability during polymerization is not hindered.
Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, and hydrogen peroxide.
In order to adjust the molecular weight of the farnesene polymer (B), a chain transfer agent can also be used. Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, γ-terpinene, and α-methylstyrene dimer.

The emulsion polymerization temperature can be appropriately selected depending on the type of the radical polymerization initiator to be used. The polymerization mode may be either continuous polymerization or batch polymerization. The polymerization reaction can be stopped by adding a polymerization terminator.
Examples of the polymerization terminator include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine, and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.

  In the method for producing the farnesene polymer (B), an anti-aging agent may be added as necessary after the polymerization reaction is stopped. After termination of the polymerization reaction, unreacted monomers are removed from the obtained latex as necessary, and then salts such as sodium chloride, calcium chloride, and potassium chloride are used as a coagulant, and nitric acid and sulfuric acid as necessary. The obtained polymer is coagulated while adding the acid such as to adjust the pH of the coagulation system to a predetermined value, and then the unpurified polymer is recovered by separating the dispersion solvent. Next, after washing with water, dehydration and drying, the farnesene polymer (B) can be obtained. In the course of coagulation, if necessary, latex and an extending oil that has been made into an emulsified dispersion may be mixed and recovered as an oil-extended farnesene polymer (B).

(Solution polymerization method)
As a solution polymerization method for obtaining the farnesene polymer (B), a known method can be applied. For example, a method in which a Ziegler catalyst, a metallocene catalyst, an anion-polymerizable active metal is used in a solvent, and polymerization is performed in the presence of a polar compound as necessary.
Examples of the anion-polymerizable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium Is mentioned.
Of these, alkali metals and alkaline earth metals are preferable, alkali metals are more preferable, and alkali metals are preferably used as organic alkali metal compounds.

Examples of the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; dilithiomethane, dilithio Polyfunctional organolithium compounds such as naphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like. Among these, an organic monolithium compound is preferable.
The organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, and dibenzylamine.

  The amount of the organic alkali metal compound used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of farnesene. The molecular weight of the farnesene polymer (B) can be adjusted by adjusting the amount of the organic alkali metal compound used.

The polar compound is used to adjust the microstructure of farnesene in the farnesene polymer (B). For example, ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine An alkali metal alkoxide, a phosphine compound, and the like.
When using a polar compound, the usage-amount is preferably 0.01-1,000 molar equivalent with respect to an organic alkali metal 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; Examples include aromatic hydrocarbons such as benzene, toluene, and xylene.

The temperature of the polymerization reaction is usually −80 to 150 ° C., preferably 0 to 100 ° C., more preferably 10 to 90 ° C. The polymerization mode may be either batch polymerization or continuous polymerization.
The polymerization reaction can be stopped by adding alcohol such as methanol and isopropanol as a polymerization terminator. The obtained polymerization reaction liquid is poured into a poor solvent such as methanol to precipitate the farnesene polymer (B), or the polymerization reaction liquid is washed with water, separated, and dried to obtain a simple farnesene polymer (B). Can be separated.

[Modification method of farnesene polymer (B)]
In this invention, you may use the farnesene polymer (B) modified | denatured by making a specific compound react with the farnesene polymer (B) manufactured by the above-mentioned method.
As a method for modifying the farnesene polymer (B), a modifier such as tetraethoxysilane, carbon dioxide, and ethylene oxide that can react with the polymerization active terminal is added before adding the polymerization terminator in the above-described production method. Examples thereof include a method (I) or a modification method such as a method (II) in which a modification agent such as maleic anhydride is grafted to an unmodified farnesene polymer after adding a polymerization terminator.

  Examples of the functional group introduced into the unmodified farnesene polymer (B) include an amino group, an ammonium group, an amide group, an imino group, an imidazole group, a urea group, an alkoxysilyl group, a silanol group, a hydroxy group, and an epoxy group. , Ether group, carboxy group, carbonyl group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, mercapto group, isocyanate group, nitrile group, silicon halide group, tin halide Groups, pyridine ring groups, and functional groups derived from acid anhydrides. Among these, at least one selected from a carboxy group, an amino group, a hydroxy group, an alkoxysilyl group, an epoxy group, a pyridine ring group, and a functional group derived from an acid anhydride is preferable, and a functional group derived from an acid anhydride is more preferable. A functional group derived from maleic anhydride is more preferable.

The position of the functional group introduced to the unmodified farnesene polymer (B) may be the polymerization terminal or the side chain of the unmodified farnesene polymer (B). From the viewpoint that a functional group can be easily introduced, a side chain of a polymer chain is preferable.
The modified farnesene polymer (B) in the present invention may be one in which one kind of functional group is introduced to the unmodified farnesene polymer (B), and two or more kinds of functional groups are introduced. It may be what you did.

Examples of the modifying agent that can be used in the method (I) include dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2 , 4-tolylene diisocyanate, carbon dioxide, ethylene oxide, succinic anhydride, 4,4′-bis (diethylamino) benzophenone, N-vinylpyrrolidone, N-methylpyrrolidone, vinylpyridine, 4-dimethylaminobenzylideneaniline, and dimethyl Examples include denaturing agents such as imidazolidinone, and denaturing agents described in JP2011-132298A.
The amount of the modifier used in the method (I) is preferably 0.01 to 100 mole equivalent with respect to the organic alkali metal compound.

  Examples of the modifying agent that can be used in the method (II) include unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, and itaconic anhydride; maleic acid, fumaric acid, Unsaturated carboxylic acids such as citraconic acid and itaconic acid; unsaturated carboxylic esters such as maleic acid ester, fumaric acid ester, citraconic acid ester, and itaconic acid ester; maleic acid amide, fumaric acid amide, citraconic acid amide, and Unsaturated carboxylic amides such as itaconic amide; unsaturated carboxylic imides such as maleic imide, fumaric imide, citraconic imide, and itaconic imide; maleimide, bis [3- (triethoxysilyl) propyl] tetrasulfide , Bis [3- (triethoxysilyl) propyl] Sulfide, (3-mercaptopropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, triethoxymethylsilane, hydroxyacetic acid, (3-aminopropyl) triethoxysilane, vinyltrimethoxysilane, and γ-methacryloxy And propyltrimethoxysilane.

In the method (II), the method of grafting the modifying agent onto the unmodified farnesene polymer (B) is not particularly limited. For example, the unmodified farnesene polymer (B), the modifying agent, and a radical catalyst as necessary. And a method of heating in the presence or absence of an organic solvent.
Examples of the organic solvent that can be used in the method (II) include hydrocarbon solvents and halogenated hydrocarbon solvents. Among these organic solvents, hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene are preferable.

The reaction temperature in Method (I) and Method (II) is preferably −80 to 200 ° C., more preferably 0 to 180 ° C.
Moreover, in method (I) and method (II), you may add an anti-aging agent from a viewpoint etc. which suppress a side reaction.

  The amount of the modifier introduced with respect to 100 parts by mass of the unmodified farnesene polymer (B) is the viewpoint of improving the rolling resistance performance of the tire partially using the rubber composition for tire tread, and the elasticity of the tire. From the viewpoint of improving the dry grip performance and the wet grip performance by improving the rate, preferably 0.1 to 100 parts by mass, more preferably 0.1 to 60 parts by mass, and still more preferably 0.5 to 40 parts by mass. It is 0.5-20 mass parts, More preferably, it is 0.5-20 mass parts.

  In the method (I) and the method (II), after introducing a functional group into the unmodified farnesene polymer (B), a modifier capable of reacting with the functional group is further added, and another functional group is polymerized. It may be introduced inside. Specifically, a method of reacting a non-modified farnesene polymer (B) with a carboxylic anhydride and then reacting a compound such as 2-hydroxyethyl methacrylate, methanol, water, ammonia, and an amine. .

<Filler (C)>
The filler (C) is not particularly limited as long as it is generally used for a tire tread rubber composition, but the viewpoint of improving the dispersibility of the filler (C) in the tire tread rubber composition, tire tread From the viewpoint of improving dry grip performance, wet grip performance, and low fuel consumption performance of a tire partially using the rubber composition for rubber, at least one selected from silica and carbon black is preferable.

〔silica〕
Examples of silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. Among these, wet silica is preferable from the viewpoint of further improving the dry grip performance, wet grip performance, and low fuel consumption performance of a tire partially using the rubber composition for tire treads. These may be used alone or in combination of two or more.

  The average particle diameter of the silica is preferably from the viewpoint of improving the processability of the rubber composition for a tire tread, the dry grip performance of a tire partially using the tire tread rubber composition, the wet grip performance, and the low fuel consumption performance. Is 0.5 nm or more, more preferably 2 nm or more, still more preferably 5 nm or more, still more preferably 8 nm or more, still more preferably 10 nm or more, and preferably 200 nm or less, more preferably 150 nm or less, still more preferably The thickness is 100 nm or less, more preferably 50 nm or less, still more preferably 30 nm or less, and still more preferably 20 nm or less. The average particle diameter of silica can be determined by measuring the diameter of the particles with a transmission electron microscope and calculating the average value.

〔Carbon black〕
As the carbon black, for example, carbon black such as furnace black, channel black, thermal black, acetylene black, and ketjen black can be used. Among these, furnace black is preferable from the viewpoint of improving the dry grip performance, wet grip performance, and low fuel consumption performance of a tire partially using the tire tread rubber composition.

  Examples of commercially available furnace blacks that can be used in the present invention include “Dia Black” manufactured by Mitsubishi Chemical Corporation, “Seast” manufactured by Tokai Carbon Co., Ltd., and the like. Examples of commercially available acetylene black include “DENKA BLACK” manufactured by Denki Kagaku Kogyo Co., Ltd. Examples of commercially available ketjen black include “ECP600JD” manufactured by Lion Corporation.

  The average particle size of carbon black is preferably 5 nm or more, more preferably 10 nm or more, from the viewpoint of improving dry grip performance, wet grip performance, and low fuel consumption performance of a tire partially using a tire tread rubber composition. More preferably, it is 15 nm or more, and preferably 100 nm or less, more preferably 80 nm or less, still more preferably 70 nm or less, and still more preferably 60 nm or less. The average particle size of carbon black can be determined by measuring the particle diameter with a transmission electron microscope and calculating the average value.

  The particle size of carbon black can be adjusted by pulverization or the like. For carbon black pulverization, high-speed rotary pulverizer (hammer mill, pin mill, cage mill), various ball mills (rolling mill, vibration mill, planetary mill), stirring mill (bead mill, attritor, distribution pipe mill, annular mill) Etc. can be used.

From the viewpoint of improving wettability and dispersibility to the rubber component (A) and the farnesene polymer (B), the carbon black is acid-treated with nitric acid, sulfuric acid, hydrochloric acid or a mixed acid thereof, or in the presence of air. Surface oxidation treatment by heat treatment may be performed. Moreover, in this invention, you may heat-process at 2,000-3,000 degreeC in presence of a graphitization catalyst from a viewpoint of a mechanical strength improvement. As the graphitization catalyst, boron, boron oxide (for example, B ₂ O ₂ , B ₂ O ₃ , B ₄ O ₃ , B ₄ O _5, etc.), boron oxo acid (for example, orthoboric acid, metaboric acid, Tetraboric acid etc.) and salts thereof, boron carbide (eg B ₄ C, B ₆ C etc.), boron nitride (BN) and other boron compounds are preferably used.

[Other fillers]
In the present invention, other than silica and carbon black for the purpose of improving the mechanical strength of a tire using a rubber composition for a tire tread in part and improving the manufacturing cost by blending a filler as an extender. The filler may be contained.

  Examples of fillers other than silica and carbon black include organic fillers, clay, talc, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, glass fibers, fibrous fillers, and glass balloons. Inorganic fillers such as can be used. These fillers may be used individually by 1 type, and may use 2 or more types together.

  The amount of the filler (C) with respect to 100 parts by mass of the rubber component (A) is 20 to 150 parts by mass. When the amount of the filler (C) is within the above range, the dry grip performance, wet grip performance, and low fuel consumption performance of a tire partially using the tire tread rubber composition are improved. From the above viewpoint, the amount of the filler (C) with respect to 100 parts by mass of the rubber component (A) is more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more, and still more preferably. Is 60 parts by mass or more, and preferably 120 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, still more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less. It is.

  Further, when silica is used as the filler (C), the amount of silica relative to 100 parts by mass of the rubber component (A) is low in dry grip performance, wet grip performance of tires using a rubber composition for tire tread, and low. From the viewpoint of improving fuel efficiency, it is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, still more preferably 35 parts by mass or more, and even more preferably 40 parts by mass or more. More preferably, it is 45 parts by mass or more, and preferably 100 parts by mass or less, more preferably 90 parts by mass or less, still more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, still more preferably 65 parts by mass. Parts or less, more preferably 60 parts by mass or less, and still more preferably 55 parts by mass or less.

  Further, when carbon black is used as the filler (C), the amount of carbon black with respect to 100 parts by mass of the rubber component (A) is the dry grip performance, wet grip performance of a tire partially using the rubber composition for tire tread, And from the viewpoint of improving fuel efficiency, it is preferably at least 25 parts by mass, more preferably at least 30 parts by mass, even more preferably at least 40 parts by mass, even more preferably at least 45 parts by mass, and preferably at least 120 parts by mass. Parts by mass or less, more preferably 100 parts by mass or less, still more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 55 parts by mass or less, even more preferably. Is 50 parts by mass or less.

  When silica and carbon black are used in combination, the ratio of silica to carbon black (mass ratio = silica / carbon black) is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and 30/70. ~ 80/20 is even more preferable.

<Other ingredients>
〔Silane coupling agent〕
In this invention, it is preferable to contain a silane coupling agent. Examples of the silane coupling agent include sulfide compounds, mercapto compounds, vinyl compounds, amino compounds, glycidoxy compounds, nitro compounds, and chloro compounds.

  Examples of sulfide compounds include bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (2-trimethoxy). Silylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) Disulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N, -Dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, etc. Can be mentioned.

Examples of the mercapto compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and the like.
Examples of the vinyl compound include vinyl triethoxysilane and vinyl trimethoxysilane.

Examples of amino compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, and 3- (2-aminoethyl) aminopropyltrimethoxy. Silane etc. are mentioned.
Examples of glycidoxy compounds include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane. Can be mentioned.
Examples of the nitro compound include 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane.
Examples of the chloro compound include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, and the like.

  These silane coupling agents may be used alone or in combination of two or more. Of these, silane coupling agents containing sulfur such as sulfide compounds and mercapto compounds are preferred from the viewpoint of a large reinforcing effect, and bis (3-triethoxysilylpropyl) disulfide and bis (3-triethoxysilylpropyl) tetra Sulfide and 3-mercaptopropyltrimethoxysilane are more preferable.

  When the rubber composition for tire tread contains a silane coupling agent, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 with respect to 100 parts by mass of the rubber component (A). Part by mass, more preferably 1 to 15 parts by mass. When the amount of the silane coupling agent is within the above range, the wear resistance of a tire partially using the tire tread rubber composition is improved.

[Vulcanizing agent]
The tire tread rubber composition preferably contains a vulcanizing agent. Examples of the vulcanizing agent include sulfur and sulfur compounds. These may be used alone or in combination of two or more.

  When the rubber composition for tire tread contains a vulcanizing agent, the amount thereof is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the rubber component (A). Part, more preferably 0.8 to 5 parts by mass.

[Vulcanization accelerator]
The rubber composition for tire tread may contain a vulcanization accelerator. Examples of vulcanization accelerators include guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, thiourea compounds, dithiocarbamic acid compounds, aldehyde-amine compounds, aldehyde-ammonia compounds, and imidazoline compounds. Compounds, xanthate compounds, and the like. These may be used alone or in combination of two or more.

  When the rubber composition for a tire tread contains a vulcanization accelerator, the content thereof is preferably 0.1 to 15 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component (A). Is more preferable.

[Vulcanization aid]
The rubber composition for tire treads may contain a vulcanization aid. Examples of the vulcanization aid include fatty acids such as stearic acid, metal oxides such as zinc white, and fatty acid metal salts such as zinc stearate. These may be used alone or in combination of two or more.

  When the rubber composition for a tire tread contains a vulcanization aid, the content thereof is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the rubber component (A). Part.

[Others]
The rubber composition for tire tread is made of silicon oil, aroma oil, TDAE (Treated Distilled Aromatic Extracts), MES (Mild Extracted Solvates), RAE (Residual Aromatic Extracts) as necessary for the purpose of improving processability and fluidity. ), Process oils such as paraffin oil and naphthenic oil, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, C9 resins, rosin resins, coumarone / indene resins, phenolic resins and other resin components, low molecular weight polybutadiene Liquid polymers such as low molecular weight polyisoprene, low molecular weight styrene butadiene polymer, and low molecular weight styrene isoprene polymer may be contained as a softening agent.
The weight average molecular weight (Mw) of the liquid polymer is preferably 500 to 100,000 from the viewpoint of processability. In the rubber composition for a tire tread of the present invention, since the farnesene polymer (B) plays a role as a softening agent, it is preferable not to contain a softening agent other than the farnesene polymer (B). When the process oil, resin component, and liquid polymer are contained as a softening agent, the amount is preferably 50 parts by mass or less, based on 100 parts by mass of the rubber component (A), from the viewpoint of bleed resistance. Preferably it is 30 mass parts or less, More preferably, it is 15 mass parts or less.

  Rubber compositions for tire treads are used for the purpose of improving weather resistance, heat resistance, oxidation resistance, etc., for anti-aging agents, antioxidants, waxes, lubricants, light stabilizers, scorch inhibitors, processing aids, pigments. 1 type of additives such as coloring agents such as pigments and pigments, flame retardants, antistatic agents, matting agents, antiblocking agents, UV absorbers, mold release agents, foaming agents, antibacterial agents, antifungal agents, and perfumes You may contain 2 or more types.

Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, lactone compounds, hydroxyl compounds, and the like.
Examples of the antiaging agent include amine-ketone compounds, imidazole compounds, amine compounds, phenolic compounds, sulfur compounds, and phosphorus compounds.

  The rubber composition for tire tread may contain a crosslinking agent in addition to the vulcanizing agent. Examples of the crosslinking agent include oxygen, organic peroxide, phenol resin, amino resin, quinone and quinonedioxime derivatives, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, metal halides, organometallic halides, and silanes. Compounds and the like. These may be used alone or in combination of two or more. The amount of the crosslinking agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component (A).

<Method for producing rubber composition for tire tread>
The manufacturing method of the rubber composition for tire treads is not limited as long as the above components can be mixed uniformly. Examples of the uniform mixing method include, for example, a tangential or meshing type closed kneader such as a kneader ruder, a brabender, a banbury mixer, an internal mixer, a single screw extruder, a twin screw extruder, a mixing roll, and a roller. Etc., and can usually be performed in a temperature range of 30 to 270 ° C.

  The rubber composition for tire tread is preferably used as vulcanized rubber by vulcanization. There are no particular restrictions on the conditions and method of vulcanization, but it is preferably carried out using a vulcanization mold under conditions of a vulcanization temperature of 120 to 200 ° C. and a vulcanization pressure of 0.5 to 20 MPa.

[Tire treads and pneumatic tires for racing]
The tire tread of the present invention uses at least a part of the rubber composition for a tire tread and exhibits excellent dry grip performance and wet grip performance. The structure of the tire tread of the present invention is not particularly limited, and may be a single layer structure or a multilayer structure. In the case of a multilayer structure, the tire tread rubber composition is used for a layer in contact with the road surface. It is preferable.

  The racing pneumatic tire of the present invention uses at least a part of the rubber composition for a tire tread, and a racing pneumatic tire using the tire tread is particularly preferable. The pneumatic tire for racing of the present invention exhibits excellent dry grip performance and wet grip performance since the rubber composition for tire tread is partially used.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. Each component used in the examples and comparative examples is as follows.
<(A) component>
SBR (1): JSR1500 manufactured by JSR Corporation
E-SBR
Styrene content: 23.5% by mass
Weight average molecular weight: 370,000
SBR (2): JSR1723 manufactured by JSR Corporation
Oil-extended SBR (oil content 27.3%)
Styrene content: 23.5% by mass
Weight average molecular weight: 480,000
SBR (3): Toughden E580 manufactured by Asahi Kasei Chemicals Corporation
Oil-extended S-SBR (oil content 27.3%)
Styrene content: 35.5% by mass
Weight average molecular weight: 880,000

<(B) component>
Farnesene polymer (B) obtained in Production Examples 1 to 3 to be described later

<(C) component>
Silica: Ultrasil 7000GR manufactured by Evonik
Average particle size 14nm
Carbon black: Diamond Black N234 manufactured by Mitsubishi Chemical Corporation
Average particle size 20nm

<(X) component>
Polyisoprene (X-1) obtained in Comparative Production Example 1 described later
Polybutadiene (X-2) obtained in Comparative Production Example 2 described later

<Other ingredients>
Silane coupling agent: Si75 manufactured by Evonik
Sulfur: Tsurumi Chemical Co., Ltd. Fine sulfur 200 mesh vulcanization accelerator (1): Ouchi Shinsei Chemical Co., Ltd. Noxeller CZ-G
Vulcanization accelerator (2): Nouchira DP manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator (3): Nouchira TBT-N manufactured by Ouchi Shinsei Chemical Co., Ltd.
Stearic acid: Lunac S-20 manufactured by Kao Corporation
Zinc flower: Zinc oxide aging inhibitor manufactured by Sakai Chemical Industry Co., Ltd. (1): Nocrack 6C manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Anti-aging agent (2): ANTAGE RD manufactured by Kawaguchi Chemical Co., Ltd.
Wax: Suntite S manufactured by Seiko Chemical Co., Ltd.

<Production example>
Production Example 1: Production of farnesene homopolymer (B-1) 241 g of cyclohexane as a solvent and 28.3 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an initiator were charged in a dried and nitrogen-substituted pressure vessel, After raising the temperature to 50 ° C., 342 g of β-farnesene was added and polymerized for 1 hour. The obtained polymerization reaction liquid was treated with methanol, and the polymerization reaction liquid was washed with water. The washed polymerization reaction solution was separated from water and dried at 70 ° C. for 12 hours to obtain a farnesene homopolymer (B-1) having physical properties shown in Table 1.

Production Example 2: Production of farnesene copolymer (B-2) A pressure-resistant vessel which had been dried and purged with nitrogen was charged with 1140 g of cyclohexane as a solvent and 56 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an initiator, and 50 ° C. Then, 1800 g of a mixture of butadiene and β-farnesene prepared in advance (mixing 720 g of butadiene and 1080 g of β-farnesene in a cylinder) was added at 10 ml / min and polymerized for 1 hour. The obtained polymerization reaction liquid was treated with methanol, and the polymerization reaction liquid was washed with water. The polymerization reaction solution after washing and water are separated and dried at 70 ° C. for 12 hours, whereby a farnesene copolymer [β-farnesene / butadiene random copolymer] having the physical properties shown in Table 1 (B-2). )

Production Example 3: Production of farnesene copolymer (B-3) A pressure-resistant vessel that had been dried and purged with nitrogen was charged with 1284 g of cyclohexane as a solvent and 156.4 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an initiator, After raising the temperature to 50 ° C., 3.5 g of tetrahydrofuran was added, and 1760 g of a mixture of styrene and β-farnesene prepared in advance (mixing 880 g of styrene and 880 g of β-farnesene in a cylinder) was added at 10 ml / min. Polymerized for 1 hour. The obtained polymerization reaction liquid was treated with methanol, and the polymerization reaction liquid was washed with water. The polymerization reaction solution after washing and water are separated and dried at 70 ° C. for 12 hours, whereby a farnesene copolymer [β-farnesene / styrene random copolymer] having physical properties shown in Table 1 (B-3). )

Comparative production example 1: Production of polyisoprene (X-1) 600 g of hexane and 13.9 g of n-butyllithium (17% by mass hexane solution) were charged in a pressure-resistant container that had been dried and purged with nitrogen, and the temperature was raised to 70 ° C. 1370 g of isoprene was added and polymerized for 1 hour. After adding methanol to the obtained polymerization reaction solution, the polymerization reaction solution was washed with water. Water was separated, and the polymerization reaction solution was dried at 70 ° C. for 12 hours to obtain polyisoprene (X-1) having physical properties shown in Table 1.

Comparative Production Example 2: Production of polybutadiene (X-2) 1100 g of hexane and 100 g of n-butyllithium (17% by mass hexane solution) were charged in a pressure-resistant vessel that had been dried and purged with nitrogen, heated to 70 ° C., and then 1100 g of butadiene was added. In addition, polymerization was performed for 1 hour. After adding methanol to the obtained polymerization reaction solution, the polymerization reaction solution was washed with water. Water was separated, and the polymerization reaction solution was dried at 70 ° C. for 12 hours to obtain polybutadiene (X-2) having physical properties shown in Table 1.

<Method for Measuring Physical Properties of Farnesene Polymer (B) and (X) Component>
(1) Measuring method of weight average molecular weight and molecular weight distribution The weight average molecular weight and molecular weight distribution of a polymer were calculated | required by standard polystyrene conversion molecular weight by GPC (gel permeation chromatography). The measuring apparatus and conditions are as follows.
・ Equipment: GPC device “HLC-8320” manufactured by Tosoh Corporation
-Separation column: Tosoh Corporation column "TSKgelSuperHZM-M"
・ Eluent: Tetrahydrofuran ・ Eluent flow rate: 0.7 ml / min ・ Sample concentration: 5 mg / 10 ml
-Column temperature: 40 ° C

(2) Measuring method of glass transition temperature (Tg) 10 mg of farnesene polymer (B) was collected in an aluminum pan, and a thermogram was measured under a temperature rising rate condition of 10 ° C./min by differential scanning calorimetry (DSC). The value of the peak top of DDSC was taken as the glass transition temperature.
・ Device: Differential scanning calorimeter “DSC6200” manufactured by Seiko Instruments Inc.
・ Detection part: Heat flow rate type ・ Sample weight: 10 mg
・ Rise rate: 10 ° C / min

(3) Method for measuring melt viscosity at 38 ° C. The melt viscosity at 38 ° C. of the farnesene polymer was measured with a Brookfield B-type viscometer (manufactured by BROOKFIELD ENGINEERING LABS. INC.).

<Examples 1-6, Comparative Examples 1-4>
In accordance with the composition of Table 2 and Table 3, each component other than sulfur and vulcanization accelerator was put into a closed Banbury mixer and kneaded for 6 minutes so that the starting temperature was 60 ° C and the resin temperature was 150 ° C. It was taken out of the mixer and cooled to room temperature. Next, this mixture was put into a Banbury mixer again, sulfur and a vulcanization accelerator were added, and kneaded for 75 seconds so that the starting temperature was 50 ° C. and the final temperature was 100 ° C., thereby obtaining a rubber composition for tire tread.
Subsequently, the obtained rubber composition for tire tread is press-molded (pressing conditions: 160 ° C., 30 to 40 minutes, pressure 10 MPa) to produce a crosslinked product having a thickness of 2 mm, and the obtained crosslinked product sheet is evaluated as follows. Went.

<Evaluation>
(1) Wet grip performance A test piece of length 40 mm × width 5 mm was cut out from the cross-linked sheets prepared in Examples and Comparative Examples, and measured using a dynamic viscoelasticity measuring device manufactured by GABO, measuring temperature 0 ° C., frequency 10 Hz, Tan δ was measured under conditions of static strain of 10% and dynamic strain of 2%, and used as an index of wet grip performance.
The numerical values of the examples and comparative examples are shown as relative values in Table 2, in which Comparative Example 1 is set as 100, and in Table 3, the value of Comparative Example 3 is set as 100.
In this evaluation, it shows that the wet grip performance of the tire obtained using the rubber composition for tire treads is so favorable that a numerical value is large.

(2) Dry grip performance A test piece having a length of 40 mm x a width of 5 mm was cut out from the cross-linked sheets prepared in Examples and Comparative Examples, and measured using a dynamic viscoelasticity measuring device manufactured by GABO at a measurement temperature of 25 ° C and a frequency of 10 Hz. Tan δ was measured under the conditions of 10% static strain and 2% dynamic strain, and used as an index of dry grip performance.
The numerical values of the examples and comparative examples are shown as relative values in Table 2, in which Comparative Example 1 is set as 100, and in Table 3, the value of Comparative Example 3 is set as 100.
In this evaluation, the larger the value, the better the dry grip performance of the tire obtained using the rubber composition for tire tread.

  As is clear from the above results, according to the present invention, it is possible to provide a rubber composition for a tire tread capable of producing a high grip tire having both wet grip performance and dry grip performance.

Claims (10)

  0.1 to 90 parts by mass of farnesene polymer (B) and filler (C) with respect to 100 parts by mass of rubber component (A) containing 60% by mass or more of styrene butadiene rubber having a styrene content of 20% by mass or more. 20 to 150 parts by mass of a rubber composition for a high grip tire tread.   The rubber composition for a high grip tire tread according to claim 1, wherein the polymer (B) has a melt viscosity at 38 ° C of 0.1 to 3,000 Pa · s.   The rubber composition for a high grip tire tread according to claim 1 or 2, wherein the polymer (B) has a weight average molecular weight of 2,000 to 500,000.   The rubber composition for a high grip tire tread according to any one of claims 1 to 3, wherein the polymer (B) is a homopolymer of β-farnesene.   The polymer (B) is a copolymer containing a monomer unit (b1) derived from β-farnesene and a monomer unit (b2) derived from a monomer other than β-farnesene. The rubber composition for high grip tire treads according to any one of 1 to 3.   The rubber composition for a high grip tire tread according to any one of claims 1 to 5, wherein the filler (C) is at least one selected from silica and carbon black.   The rubber composition for a high grip tire tread according to claim 6, comprising 5 to 80 parts by mass of the polymer (B) and 20 to 60 parts by mass of the silica with respect to 100 parts by mass of the rubber component (A). object.   The rubber for high grip tire treads according to claim 6, comprising 5 to 80 parts by mass of the polymer (B) and 25 to 120 parts by mass of the carbon black with respect to 100 parts by mass of the rubber component (A). Composition.   A tire tread using at least a part of the rubber composition for a high grip tire tread according to claim 1.   A pneumatic tire for racing using at least a part of the rubber composition for a high grip tire tread according to claim 1.