JP2017088898A - Rubber composition for tire tread - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition for tire tread achieving both of low heat generation property and wet brake performance at high level.SOLUTION: There is provided a rubber composition containing a rubber component and a filler and having a temperature at a peak position of a temperature curve of tanδ of -16.0°C to -6.0°C, tanδ at the peak position of larger than 1.13, tanδ at 0°C of 0.95 or more and a value of absolute value of difference between tanδ at -5°C and tanδ at 5°C divided by temperature difference of -5°C and 5°C {|(tanδ at -5°C)-(tanδ at 5°C)|/10}(/°C) of smaller than 0.045/°C. [measurement method of bound styrene content (mass%): calculated from integration ratio ofH-NMR spectrum] [measurement method of tanδ: measuring a value of tanδ at -25°C to 80°C at frequency of 52 Hz, initial strain of 2%, dynamic strain of 1%, temperature rise rate of 3°C/min. by using a dynamic tensile viscoelasticity measurement test machine.SELECTED DRAWING: None

Description

  The present invention relates to a rubber composition for a tire tread that has excellent braking performance on a wet road surface and good fuel efficiency.

  In recent years, due to social demands for energy saving, demands for lower fuel consumption of automobiles are becoming more severe. In order to meet such demands, a reduction in rolling resistance has also been demanded for tire performance. As a method for reducing the rolling resistance of tires, a method by optimizing the tire structure has been studied, but the most common method is to improve low heat generation by using a material that generates less heat as a rubber composition. It is done as

It is also important to secure a braking performance on a wet road surface (hereinafter abbreviated as “wet braking performance”) from the standpoint of improving the safety of driving a vehicle, improving low heat generation and improving wet braking performance. It is also required to secure.
On the other hand, Patent Document 1 proposes a tire using a rubber composition containing a rubber component containing an amine functional group-modified styrene-butadiene copolymer and specific silica as a tread. Furthermore, Patent Document 2 discloses a rubber composition for a tire tread, which includes a rubber component containing three kinds of rubbers composed of emulsion-polymerized styrene-butadiene copolymer rubber, terminal-modified solution-polymerized styrene-butadiene rubber and butadiene rubber, and silica. Has been.
However, there is a demand for a rubber composition that achieves a high degree of compatibility between low heat build-up and wet braking performance.

International Publication No. 2009-084667 JP 2010-275386 A

  Under such circumstances, an object of the present invention is to provide a rubber composition for a tire tread that achieves a high degree of compatibility between low heat build-up and wet braking performance.

  The inventor first improves the dispersibility of the filler, shifts (moves) the tan δ peak to a higher temperature, and increases the tan δ peak value in the tan δ temperature curve of the rubber composition. Tried. Then, the present inventor focused on the variation in wet braking performance due to the seasonal difference in wet braking performance, that is, the difference in road surface temperature between summer and winter, with the aim of further improving the performance of the rubber composition. It has been found that this seasonal difference in wet braking performance is increased by the method of shifting (moving) the tan δ peak to a higher temperature and increasing the tan δ peak value. Furthermore, when the cause of the seasonal difference in the wet braking performance was investigated, it was found that the temperature dependency of the rubber composition near 0 ° C. was remarkable, which caused the seasonal difference.

  Therefore, by appropriately adjusting the temperature range of the peak position of the temperature curve of tan δ, increasing tan δ near 0 ° C. and decreasing the temperature dependence of tan δ near 0 ° C., that is, tan δ at −5 ° C. and 5 ° C. By reducing the absolute value of the difference from tan δ by the temperature difference between −5 ° C. and 5 ° C., it has been found that high wet braking performance can be obtained at any road surface temperature. The present invention has been completed based on such findings.

That is, the present invention contains a rubber component and a filler containing a styrene-butadiene copolymer rubber (A) having a high bound styrene content and a styrene-butadiene copolymer rubber (B) having a low bound styrene content, A rubber composition in which the difference between the bound styrene content of the styrene-butadiene copolymer rubber (A) and the bound styrene content of the styrene-butadiene copolymer rubber (B) is 11% by mass or more, and a temperature of tan δ The temperature at the peak position of the curve is −16.0 ° C. or more and −6.0 ° C. or less, the tan δ of the peak position is larger than 1.13, the tan δ at 0 ° C. is 0.95 or more, and −5 Value obtained by dividing the absolute value of the difference between tan δ at 5 ° C. and tan δ at 5 ° C. by the temperature difference between −5 ° C. and 5 ° C. {| (tan δ at −5 ° C.) − (Tan δ at 5 ° C.) | / 10} ( ° C.) is intended to provide a tire tread rubber composition characterized by less than 0.045 / ° C..
[Measurement method of bound styrene content (mass%): Calculated from integral ratio of ¹ H-NMR spectrum. ]
[Measurement method of tan δ: Using a dynamic tensile viscoelasticity measuring tester, the value of tan δ from −25 ° C. to 80 ° C. at a frequency of 52 Hz, initial strain of 2%, dynamic strain of 1%, and a temperature rising rate of 3 ° C./min. Measure. ]

  According to the present invention, it is possible to provide a rubber composition for a tire tread that can achieve both a low exothermic property and wet braking performance at a higher level and can also reduce the seasonal difference in wet braking performance.

Description illustrating the temperature curve of tan δ of the rubber composition of the present invention and a comparative rubber composition and {| (tan δ at −5 ° C.) − (Tan δ at 5 ° C.) | / 10} of each rubber composition FIG.

[Rubber composition]
The rubber composition for a tire tread of the present invention has a temperature at the peak position of the tan δ temperature curve of −16.0 ° C. or more and −6.0 ° C. or less, and the tan δ of the peak position is larger than 1.13. Tan δ at 0 ° C. is 0.95 or more, and a value obtained by dividing the absolute value of the difference between tan δ at −5 ° C. and tan δ at 5 ° C. by the temperature difference between −5 ° C. and 5 ° C. {| (at −5 ° C. tan δ) − (tan δ at 5 ° C.) | / 10} (/ ° C.) is smaller than 0.045 / ° C.
Here, tan δ is tan δ at −25 ° C. to 80 ° C. at a frequency of 52 Hz, an initial strain of 2%, a dynamic strain of 1%, and a heating rate of 3 ° C./min using a dynamic tensile viscoelasticity measuring tester. The value is measured from the ratio of the dynamic tensile loss modulus E ″ to the dynamic tensile storage modulus E ′ (E ″ / E ′).

When the temperature at the peak position of the tan δ temperature curve of the rubber composition for a tire tread of the present invention is less than −16.0 ° C., the wet braking performance deteriorates, and when it is higher than −6.0 ° C., the low-temperature brittleness of the rubber composition. The chemical properties will deteriorate. From the viewpoint of improving wet braking performance, the temperature at the peak position of the temperature curve of tan δ of the rubber composition for a tire tread of the present invention is preferably −12.0 ° C. or higher and −6.0 ° C. or lower. If the tan δ at the peak position of the temperature curve of tan δ is 1.13 or less, the wet braking performance is deteriorated, but if it is greater than 1.20, the wet braking performance is further improved, which is preferable.
Further, a value obtained by dividing the absolute value of the difference between tan δ at −5 ° C. and tan δ at 5 ° C. by the temperature difference between −5 ° C. and 5 ° C. {| (tan δ at −5 ° C.) − (Tan δ at 5 ° C.) | / 10} (/ ° C.) (hereinafter sometimes abbreviated as “α (/ ° C.)”) less than 0.045 / ° C., and tan δ at 0 ° C. of 0.95 or more. By both, low exothermic property and wet braking performance can be achieved at a higher level, and the seasonal difference in wet braking performance can also be reduced. When the tan δ at 0 ° C. of the rubber composition is less than 0.95, the wet braking performance is lowered.

  The α (/ ° C.) will be described with reference to the drawings. FIG. 1 is an explanatory diagram illustrating a temperature curve of tan δ of a rubber composition of the present invention and a rubber composition as a comparative example and α (/ ° C.) of each rubber composition. In FIG. 1, the temperature curve of tan δ of one example of the rubber composition of the present invention is shown by a solid line. L1 illustrates α (/ ° C.) of the rubber composition of the present invention. On the other hand, the temperature curve of tan δ of the rubber composition as a comparative example is indicated by a broken line. L2 illustrates α (/ ° C.) of the rubber composition as a comparative example. As is apparent from FIG. 1, the tan δ value at 0 ° C. of the rubber composition of the present invention is 1.08, which is larger than the tan δ value at 0 ° C. of the rubber composition as a comparative example. Moreover, α (/ ° C.) of the rubber composition of the present invention is 0.035, which is smaller than α (/ ° C.) of the rubber composition as a comparative example.

  The rubber composition of the present invention has {| (tan δ at −5 ° C.) − (Tan δ at 5 ° C.) | / 10} (/ ° C.), that is, α is greater than 0.025 / ° C. and tan δ at 60 ° C. It is preferable that it is 0.135 or less. This is because if α is greater than 0.025 / ° C., the wet braking performance is further improved, and if tan δ at 60 ° C. is 0.135 or less, the low heat build-up is further improved.

The rubber composition for a tire tread according to the present invention is a styrene-butadiene copolymer rubber (A) having a high bound styrene content and a styrene having a low bound styrene content, from the viewpoint of achieving both a high exothermic property and wet braking performance. -It is preferable to contain a rubber component containing a butadiene copolymer rubber (B) and a filler. The rubber component of the rubber composition for a tire tread according to the present invention contains at least two types of styrene-butadiene copolymer rubbers having different bound styrene contents (mass%), whereby a plurality of styrene-butadiene copolymers in the rubber component are contained. This is because it is possible to give different functions to the combined rubber.
Here, the bound styrene content (% by mass) is calculated from the integral ratio of the ¹ H-NMR spectrum.

In the tire tread rubber composition of the present invention, the filler is unevenly distributed in the styrene-butadiene copolymer rubber (B) having a low bound styrene content from the viewpoint of making α smaller than 0.045 / ° C. Is preferred. As a method for unevenly distributing the styrene-butadiene copolymer rubber (B) having a low bound styrene content, for example, the following method is preferably exemplified.
(1) After kneading the styrene-butadiene copolymer rubber (B) having a low bound styrene content and the filler in the first stage of kneading, the styrene-butadiene copolymer having a high bound styrene content in the second stage of kneading. The combined rubber (A) is kneaded.
(2) A modified styrene-butadiene copolymer rubber having a high affinity with the filler is used as the styrene-butadiene copolymer rubber (B) having a low bound styrene content.
In the present invention, hereinafter, the styrene-butadiene copolymer rubber may be abbreviated as “SBR”.

  In the above method (1), in order to further improve the dispersibility between the styrene-butadiene copolymer rubber (B) having a low bound styrene content and the filler, a first step of kneading the dispersion improver together with the filler. It is preferable to add in. Suitable examples of the dispersion improver include at least one compound selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas, and xanthates. As the guanidines, at least one compound selected from 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine and 1-o-tolylbiguanide is preferably exemplified, and as sulfenamides, N -Cyclohexyl-2-benzothiazolylsulfenamide and / or N-tert-butyl-2-benzothiazolylsulfenamide is preferably exemplified, and as thiazoles, 2-mercaptobenzothiazole and / or di-2 -Benzothiazolyl disulfide is preferably exemplified, and thiurams are preferably exemplified by tetrakis (2-ethylhexyl) thiuram disulfide and / or tetrabenzylthiuram disulfide, and thioureas are exemplified by N, N'-diethylthiourea , Trimethylthiourea, N, N′-diphe Preferred examples include at least one compound selected from ruthiourea and N, N′-dimethylthiourea. Examples of the dithiocarbamate include zinc dibenzyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, and dimethyldithiocarbamate. Suitable examples include at least one compound selected from zinc and copper dimethyldithiocarbamate, and preferred examples of xanthates include zinc isopropylxanthate.

The styrene-butadiene copolymer rubbers (A) and (B) according to the present invention may be emulsion polymerization SBR or solution polymerization SBR.
From the viewpoint of increasing tan δ at 0 ° C. of the rubber composition of the present invention, the styrene-butadiene copolymer rubber (A) having a high styrene content preferably has a bound styrene content St (A) of 40% by mass or more, More preferably, it is 40-60 mass%, It is further more preferable that it is 40-55 mass%, It is especially preferable that it is 40-50 mass%.
In the method (2), the styrene-butadiene copolymer rubber (B) having a low bound styrene content is a modified SBR obtained by modification with a nitrogen-containing compound or a silicon-containing compound. It is preferable from the viewpoint of increasing the affinity.
The modified SBR modified by a nitrogen-containing compound or a silicon-containing compound is preferably solution polymerization SBR, and the polymerization initiator is a lithium amide compound, or a modifier used at the active terminal of SBR is Nitrogen-containing compounds, silicon-containing compounds, and nitrogen- and silicon-containing compounds are preferred, hydrocarbyloxysilane compounds are more preferred, and hydrocarbyloxysilane compounds containing nitrogen and silicon are particularly preferred. By these modified SBR, the dispersibility of the filler such as silica and / or carbon black in the rubber component is improved, and the low heat build-up of the rubber composition is improved.

[Rubber component]
The rubber composition of the rubber composition of the present invention may be composed of only two or more types of SBR having different bound styrene contents (mass%), but other than SBR as long as it does not contradict the solution of the problems of the present invention. The diene rubber may be included. Preferably, the rubber component contains 60 to 100% by mass of SBR having different two or more types of bonded styrene content (% by mass) and 40 to 0% by mass of diene rubber other than SBR. More preferably, SBRs having different (mass%) contain 80 to 100 mass% and diene rubbers other than SBR, 20 to 0 mass%.
Here, diene rubbers other than SBR include natural rubber, polybutadiene rubber, synthetic polyisoprene rubber, styrene-isoprene rubber, ethylene-butadiene copolymer rubber, propylene-butadiene copolymer rubber, ethylene-propylene-butadiene copolymer. Examples thereof include polymer rubber, ethylene-α-olefin-diene copolymer rubber, butyl rubber, halogenated butyl rubber, a copolymer of styrene and isobutylene having a halogenated methyl group, and chloroprene rubber.

[Polymerization of modified SBR]
In the present invention, in order to react and modify a hydrocarbyloxysilane compound, particularly a hydrocarbyloxysilane compound containing nitrogen and silicon, at the active terminal of the styrene-butadiene copolymer, the styrene-butadiene copolymer is at least 10%. Those having a polymer chain having a living property or pseudo-living property are preferred. As such a polymerization reaction having a living property, a reaction in which an organic alkali metal compound is used as an initiator and styrene and butadiene are anionically polymerized in an organic solvent is preferable. By anionic polymerization, a high conjugated diene moiety vinyl bond content can be obtained, and the glass transition temperature Tg can be adjusted to a desired temperature. Heat resistance can be improved by increasing the vinyl bond content, and fuel efficiency and ice / snow performance can be improved by increasing the cis-1,4 bond content.

  As the organic alkali metal compound used as an initiator for the above-mentioned anionic polymerization, an organic lithium compound is preferable. The organolithium compound is not particularly limited, but hydrocarbyl lithium or lithium amide compound is preferably used. When the former hydrocarbyl lithium is used, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal has polymerization activity. A styrene-butadiene copolymer as a site is obtained, and the above-mentioned hydrocarbyloxysilane compound is reacted with the active end as a polymerization active site to be modified.

  When the latter lithium amide compound is used, a styrene-butadiene copolymer having a nitrogen-containing group at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained. In the case of a lithium amide compound, the modified SBR according to the present invention can be obtained without modification with the above-described hydrocarbyloxysilane compound, but the hydrocarbyloxysilane compound, particularly nitrogen and silicon, are included at the active terminal that is the polymerization active site. When the hydrocarbyloxysilane compound is modified by reaction, a so-called both-end-modified styrene-butadiene copolymer is obtained, and the dispersibility and reinforcing property of fillers such as carbon black and silica can be further improved. preferable.

  As the hydrocarbyl lithium which is a polymerization initiator, those having a hydrocarbyl group having 2 to 20 carbon atoms are preferable, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium. N-decyllithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclobenthyllithium, reactive organisms of diisopropenylbenzene and butyllithium, etc. Among them, n-butyllithium is particularly preferable among these.

Examples of the lithium amide compound as a polymerization initiator include lithium hexamethylene imide, lithium pyrrolidide, lithium piperide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, lithium Dipropylamide, lithium diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiverazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide, Examples include lithium methylphenethylamide. Among these, from the viewpoint of the interaction effect on carbon black and the ability of initiating polymerization, cyclic lithium amides such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, and lithium dodecamethylene imide are preferable. In particular, lithium hexamethylene imide and lithium pyrrolidide are suitable.
In general, these lithium amide compounds prepared from a secondary amine and a lithium compound can be used for the polymerization, but they can also be prepared in-polymerization in situ. The amount of the polymerization initiator used is preferably selected in the range of 0.2 to 20 mmol per 100 g of monomer.

There is no restriction | limiting in particular as a method of manufacturing a styrene-butadiene copolymer by anionic polymerization using the said organolithium compound as a polymerization initiator, A conventionally well-known method can be used.
Specifically, the lithium compound is polymerized with a conjugated diene compound and an aromatic vinyl compound in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound. If desired, a styrene-butadiene copolymer having a target active terminal can be obtained by anionic polymerization in the presence of a randomizer used as desired.

The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene and trans-2. -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more.
The monomer concentration in the solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. In addition, when copolymerizing using a conjugated diene compound and an aromatic vinyl compound, the content of the aromatic vinyl compound in the charged monomer mixture is preferably 5 to 55% by mass, and more preferably 6 to 45% by mass. .

  The randomizer used as desired is control of the microstructure of the styrene-butadiene copolymer, for example, an increase in 1,2 bonds in the butadiene portion in the butadiene-styrene copolymer, an increase in 3,4 bonds in the isoprene polymer, etc. Or it is the compound which has the effect | action of control of the composition distribution of the monomer unit in a conjugated diene monoaromatic vinyl copolymer, for example, the randomization of the butadiene unit and styrene unit in a butadiene-styrene copolymer. The randomizer is not particularly limited, and any one of known compounds generally used as a conventional randomizer can be appropriately selected and used. Specifically, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-bis (2-tetrahydrofuryl) -propane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, Examples thereof include ethers such as N′-tetramethylethylenediamine and 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium t-amylate and potassium t-butoxide, and sodium salts such as sodium t-amylate can also be used.

One of these randomizers may be used alone, or two or more thereof may be used in combination. The amount used is preferably selected in the range of 0.01 to 1000 molar equivalents per mole of the lithium compound.
The temperature in this polymerization reaction is preferably selected in the range of 0 to 150 ° C, more preferably 20 to 130 ° C. The polymerization reaction can be carried out under generated pressure, but it is usually desirable to operate at a pressure sufficient to keep the monomer in a substantially liquid phase. That is, the pressure depends on the particular material being polymerized, the polymerization medium used and the polymerization temperature, but higher pressures can be used if desired, such pressure being a gas that is inert with respect to the polymerization reaction. Can be obtained by an appropriate method such as pressurizing.

  Examples of the hydrocarbyloxysilane compound containing nitrogen and silicon used as a modifier for obtaining the modified SBR include N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane and N, N-bis (trimethylsilyl) aminopropylmethyl. Diethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, and 1-trimethylsilyl-2,2-diethoxymethyl-1-aza- 2-silacyclopentane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- {3- (triethoxysilyl) propyl} -4,5-dihydroimidazole N, N-bis (trimethylsilyl) amino B pills triethoxysilane, preferably dimethyl-aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropyl methyl dimethoxy silane being particularly preferred.

Examples of the hydrocarbyloxysilane compound that is a silicon-containing compound used as a modifier for obtaining the modified SBR include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-. Butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltri Ethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxy Orchids, vinyltrimethoxysilane, vinyltriethoxysilane, divinyl dimethoxysilane, there may be mentioned divinyl diethoxy silane, among these, tetraethoxysilane is preferred.
These modifiers may be used alone or in combination of two or more. The modifier may be a partial condensate.
Here, the partial condensate means a product in which a part (not all) of the modifier SiOR is SiOSi bonded by condensation.

  In the modification reaction using the above modifier, the amount of the modifier used is preferably 0.5 to 200 mmol / kg · styrene-butadiene copolymer. The content is more preferably 1 to 100 mmol / kg · styrene-butadiene copolymer, and particularly preferably 2 to 50 mmol / kg · styrene-butadiene copolymer. Here, the styrene-butadiene copolymer means the mass of only a polymer that does not contain an additive such as an anti-aging agent added at the time of production or after production. By making the usage-amount of a modifier into the said range, it is excellent in the dispersibility of a filler, and the mechanical property after abrasion, abrasion resistance, and low fuel consumption are improved.

The method for adding the modifier is not particularly limited, and examples thereof include a batch addition method, a division addition method, and a continuous addition method. preferable.
In addition, the modifier may be bonded to any of the polymerization initiation terminal, polymerization termination terminal, polymer main chain, and side chain, but it can improve fuel economy by suppressing energy loss from the polymer terminal. Therefore, it is preferably introduced at the polymerization initiation terminal or the polymerization termination terminal.

[Condensation accelerator]
In the modified SBR according to the present invention, it is preferable to use a condensation accelerator in order to accelerate the condensation reaction involving the aforementioned modifier.
Examples of such a condensation accelerator include a compound containing a tertiary amino group, or among group 3, 4, 5, 12, 13, 14, and 15 of the periodic table (long period type). An organic compound containing one or more elements belonging to any of the above can be used. Further, as a condensation accelerator, an alkoxide, a carboxyl containing at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn). It is preferably an acid salt or an acetylacetonate complex salt. Among these condensation accelerators, tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-ethylhexoxy) titanium, titanium di-n-butoxide (bis-2,4-pentanedionate), etc. Titanium condensation accelerators are particularly preferred.
The condensation accelerator used here is preferably added to the modification reaction system during and / or after the modification reaction. When added before the denaturation reaction, a direct reaction with the active end occurs, and for example, a hydrocarboxy group having a protected primary amino group at the active end may not be introduced.
The addition time of the condensation accelerator is usually 5 minutes to 5 hours after the start of the modification reaction, preferably 15 minutes to 1 hour after the start of the modification reaction.

  The SBR (A) and (B) used in the rubber composition of the present invention preferably has a weight average molecular weight (Mw) before or after modification of 100,000 to 800,000, preferably 150,000 to 700. Is more preferable. The rubber composition containing SBR (A) and (B) can be obtained by controlling the decrease in elastic modulus of the vulcanizate and the increase in hysteresis loss by setting the weight average molecular weight within the above range, and obtaining excellent fracture resistance. Excellent kneading workability can be obtained. A weight average molecular weight is obtained by standard polystyrene conversion based on GPC method.

[Filler]
The rubber composition of the present invention preferably contains 30 to 150 parts by mass, more preferably 40 to 120 parts by mass with respect to 100 parts by mass of the rubber component as the filler. If it is 30 parts by mass or more, the wear resistance is improved, and if it is 150 parts by mass or less, the fuel efficiency is improved.
This filler is preferably silica and / or carbon black. In particular, the filler is preferably silica alone or silica and carbon black, and the content ratio of silica to carbon black (silica: carbon black) is (100: 0) to (30:70) in mass ratio. It is preferable that it is (100: 0)-(50:50). The compounding amount of silica is preferably 10 to 100 parts by mass and more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the rubber component. If it is this range, low-fuel-consumption property, ice-snow performance, and abrasion resistance will become more favorable, and wet braking performance can be improved more.

Examples of silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. Among them, wet is most effective in achieving both wet performance and wear resistance. Silica is preferred.
The BET specific surface area (measured in accordance with ISO 5794/1) of silica is preferably 80 m ² / g or more, more preferably 120 m ² / g or more, and particularly preferably 150 m ² / g or more. Although there is no restriction | limiting in particular in the upper limit of a BET specific surface area, Usually, it is about 450 m < ² > / g. Examples of such silica include Tosoh Silica Co., Ltd., trade name “Nip Seal AQ” (BET specific surface area = 205 m ² / g), “Nip Seal KQ”, and Degussa product name “Ultra Gil VN 3” (BET specific surface area = 175 m ² / g) can be used.

There is no restriction | limiting in particular as carbon black, For example, HAF, N339, IISAF, 1 SAF, SAF etc. are used.
The nitrogen adsorption method specific surface area (measured in accordance with N ₂ SA, JIS K 6217-2: 2001) of carbon black is preferably 70 to 180 m ² / g, more preferably 80 to 180 m ² / g. Moreover, DBP oil absorption (measured based on JISK6217-4: 2008) becomes like this. Preferably it is 70-160 cm < ³ > / 100g, More preferably, it is 90-160 cm < ³ > / 100g. By using carbon black, improvement effects such as fracture resistance and wear resistance are increased. N339, IISAF, ISAF, and SAF, which are excellent in wear resistance, are particularly preferable.
One type of silica and / or carbon black may be used, or two or more types may be used in combination.

[Silane coupling agent]
In the rubber composition of the present invention, if desired, when silica is used as one of the reinforcing fillers, it is preferable to add a silane coupling agent for the purpose of further improving the reinforcing property and fuel efficiency. .
Examples of silane coupling agents include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxysilyl). Ethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltri Methoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarba Yl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilyl Propyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide , Dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, 3-octanoylthiopropyltriethoxysilane, and the like. From the viewpoint of reinforcing effect of improving al, bis (3-triethoxysilylpropyl) polysulfide, 3-octanoylthiopropyl propyltriethoxysilane and 3-trimethoxysilylpropyl benzothiazyl tetrasulfide are preferable.
One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

  From the viewpoints of the effect as a coupling agent and the prevention of gelation, the preferable blending amount of this silane coupling agent is such that the mass ratio (silane coupling agent / silica) is (1/100) to (20/100). It is preferable. If it is (1/100) or more, the effect of improving the low heat build-up of the rubber composition will be more suitably exhibited. If it is (20/100) or less, the cost of the rubber composition will be reduced, and the economic efficiency This is because it improves. Furthermore, the mass ratio (3/100) to (20/100) is more preferable, and the mass ratio (4/100) to (10/100) is particularly preferable.

Further, the rubber composition according to the present invention includes various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, and an aging, as long as the effects of the present invention are not impaired. An inhibitor, a scorch inhibitor, zinc white, stearic acid and the like can be contained.
As said vulcanizing agent, sulfur etc. are mentioned, The usage-amount is 0.1-10.0 mass parts as a sulfur content with respect to 100 mass parts of rubber components, More preferably, it is 1.0-5. 0 parts by mass. If the amount is less than 0.1 parts by mass, the fracture strength, wear resistance, and fuel efficiency of the vulcanized rubber may be reduced. If the amount exceeds 10.0 parts by mass, the rubber elasticity is lost.

  The vulcanization accelerator that can be used in the present invention is not particularly limited, and examples thereof include M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazyl). Thiophene vulcanization accelerators such as thiazoles such as sulfenamide), guanidines such as DPG (diphenylguanidine), or thiurams such as TOT (tetrakis (2-ethylhexyl) thiuram disulfide). The amount used is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, with respect to 100 parts by weight of the rubber component.

  As the process oil used as a softening agent that can be used in the rubber composition according to the present invention, an aromatic oil is used from the viewpoint of compatibility with SBR. In addition, naphthenic oil or paraffinic oil is used from the viewpoint of emphasizing low temperature characteristics. The amount used is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component, and if it is 100 parts by mass or less, the deterioration of the tensile strength and low fuel consumption (low heat generation) of the vulcanized rubber is suppressed. can do.

  Further, examples of the anti-aging agent that can be used in the rubber composition according to the present invention include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine, 6C [N- (1,3-dimethylbutyl) -N ′). -Phenyl-p-phenylenediamine], AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), high-temperature condensate of diphenylamine and acetone, etc. 0.1-5.0 mass parts is preferable with respect to 100 mass parts of rubber components, More preferably, it is 0.3-3.0 mass parts.

[Preparation of rubber composition, production of pneumatic tire]
The rubber composition of the present invention is obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer or the like according to the above compounding prescription, vulcanizing after molding, It is suitably used as a tread, particularly as a tread grounding portion.
A tire is manufactured by a normal tire manufacturing method using the rubber composition of the present invention for a tread. That is, as described above, the rubber composition of the present invention containing various chemicals is processed into each member at an unvulcanized stage, pasted and molded by a normal method on a tire molding machine, and a raw tire is molded. The The green tire is heated and pressed in a vulcanizer to obtain a tire.
In this way, a tire, particularly a pneumatic tire, with low heat build-up and good wet braking performance can be obtained.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples. Various measurements in the examples were performed by the following methods.
<Measurement method of bound styrene content (mass%)>
^It was calculated from the integral ratio of ¹ H-NMR spectrum.
<Measurement method of tan δ>
Using a spectrometer (dynamic tensile viscoelasticity measuring tester) manufactured by Ueshima Seisakusho Co., Ltd., with a frequency of 52 Hz, initial strain of 2%, dynamic strain of 1%, and a temperature increase rate of 3 ° C./min. The value of tan δ at 0 ° C. was measured from the ratio (E ″ / E ′) of the dynamic tensile loss elastic modulus E ″ to the dynamic tensile storage elastic modulus E ′.

[Tire performance evaluation]
<Wet braking performance>
Four test tires with a tire size of 195 / 65R15 were mounted on a passenger car with a displacement of 2000 cc, and the passenger car was run on a wet evaluation road where the road surface temperature of the test course was set to 10 ° C. and 30 ° C., at a speed of 80 km / hr. The brake pedal was pressed to lock the tire, and the distance to stop was measured. As a result, the reciprocal of the braking distance at a road surface temperature of 10 ° C. was displayed as an index with the tire of Comparative Example 1 as 100, and the reciprocal of the braking distance at a road surface temperature of 30 ° C. was displayed as an index as 100. The larger the index value, the better the wet braking performance.
Wet braking performance index = {(distance until the tire of Comparative Example 1 or Example 4 stops) / (distance until the test tire stops)} × 100
<Low heat generation>
A tire having a tire size of 195 / 65R15 was rotated at a speed of 80 km / h by a rotating drum, and the rolling resistance was measured at a load of 4.41 kN. The reciprocal of the rolling resistance of the control tire (Comparative Example 1) was expressed as an index with the reciprocal being 100. The larger the index value, the lower the rolling resistance and the lower the heat buildup.
Low exothermic index = {(rolling resistance of tire of Comparative Example 1) / (rolling resistance of test tire)} × 100

Synthesis Example 1 Synthesis of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane 36 g of 3-aminopropylmethyldiethoxy as an aminosilane moiety in 400 mL of dichloromethane solvent in a glass flask equipped with a stirrer under nitrogen atmosphere After adding silane (manufactured by Gelest), 48 mL of trimethylsilane chloride (manufactured by Aldrich) and 53 mL of triethylamine were further added to the solution as protective sites, and the mixture was stirred at room temperature for 17 hours, and then the reaction solution was applied to an evaporator. The solvent was removed to obtain a reaction mixture, and the obtained reaction mixture was distilled under reduced pressure under a pressure of 665 Pa to obtain 40 g of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane as a 130-135 ° C. fraction. Obtained.

Production Example 1 Production of Unmodified SBR (B-1) An autoclave reactor having an internal volume of 5 L (liter) purged with nitrogen was charged with 2,750 g of cyclohexane, 16.8 mmol of tetrahydrofuran, 125 g of styrene, and 365 g of 1,3-butadiene. It is. After adjusting the temperature of the reactor contents to 10 ° C., 1.2 mmol of n-butyllithium was added to initiate polymerization. The polymerization was carried out under adiabatic conditions and the maximum temperature reached 85 ° C.
When the polymerization conversion rate reached 99%, 10 g of butadiene was added, and polymerization was further performed for 5 minutes. Next, an isopropanol solution of 2,6-di-tert-butyl-p-cresol (BHT) was added to the polymerization reaction system to stop the polymerization reaction. Thereafter, vacuum-dried to obtain unmodified SBR (B-1). The bound styrene content was 25% by mass, the weight average molecular weight was 158,000, and the molecular weight distribution was 1.05.

Production Example 2 Production of Modified SBR (B-2) Polymerization was carried out in the same manner as unmodified SBR (B-1). When the polymerization conversion reached 99%, 10 g of butadiene was added, and the polymerization was further continued for 5 minutes. It was. Next, a small amount of the polymer solution from the reactor was sampled in 30 g of cyclohexane solution added with 1 g of methanol, and 1.1 mmol of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane obtained in Synthesis Example 1 was added. The denaturation reaction was performed for 15 minutes. Thereafter, 0.6 mmol of tetrakis (2-ethyl-1,3-hexanediolato) titanium was added and further stirred for 15 minutes. Finally, 2,6-di-tert-butyl-p-cresol was added to the polymer solution after the reaction. Next, the solvent was removed by steam stripping and the protected primary amino group was deprotected, and the rubber was dried with a ripening roll adjusted to 110 ° C. to obtain modified SBR (B-2). The obtained modified SBR (B-2) had a bound styrene content of 25% by mass, a vinyl content in the conjugated diene part of 56 mol%, a Mooney viscosity of 32, a weight average molecular weight before modification of 158,000, and before modification. The molecular weight distribution was 1.05.

Production Example 3 Production of Modified SBR (B-3) In a dry, nitrogen-substituted 800 mL pressure-resistant glass container, 32.5 g of butadiene in cyclohexane solution (16 mol%) and styrene in cyclohexane solution (21 mol%) were added. Styrene 17.5 g, 2,4-ditetrahydrofurylpropane 0.44 mmol was injected, n-butyllithium (BuLi) 0.48 mmol was added thereto, and then in a hot water bath at 50 ° C. For 1.5 hours. The polymerization conversion was almost 100%.
After adding 0.43 mmol of tetraethoxysilane to this polymerization system, a modification reaction was further performed at 50 ° C. for 30 minutes. Thereafter, 1.26 mmol of tetrakis (2-ethylhexoxy) titanium and 1.26 mmol of water were added to the polymerization system, followed by a condensation reaction at 50 ° C. for 30 minutes. Thereafter, 0.5 mL of a 5 wt% isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) was further added to the polymerization system to stop the reaction. Then, the modified SBR (B-3) which is tetraethoxysilane modification was obtained by drying according to a conventional method. The obtained modified SBR had a bound styrene content of 35 mass%, a vinyl content of the conjugated diene part of 52 mol%, a Mooney viscosity of 64, a weight average molecular weight before modification of 186,000, and a molecular weight distribution before modification of 1. 07.

Examples 1-6 and Comparative Examples 1-2
Eight types of rubber compositions having the compounding compositions shown in Table 1 were prepared, and the rubber compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were applied to the tread contact portion of a pneumatic radial tire for passenger cars having a tire size of 195 / 65R15. 8 kinds of pneumatic radial tires for passenger cars were prepared, and vulcanized rubber physical properties tan δ, wet braking performance and low heat generation were evaluated. The evaluation results are shown in Table 1. The tan δ was evaluated by cutting a vulcanized rubber test piece from the tire.

[note]
* 1: Emulsion polymerization SBR: manufactured by JSR Corporation, trade name “JSR 0202”, bound styrene content = 46 mass%, non-oil-extended * 2: Emulsion polymerization SBR: manufactured by Nippon Zeon Co., Ltd., trade name “Nipol 1739”, Bonded styrene content = 40% by weight, 37.5 parts by weight with respect to 100 parts by weight of rubber * 3: Emulsion polymerization SBR: manufactured by JSR Corporation, trade name "JSR 0122", bound styrene content = 37% by weight, rubber 37.5 parts by mass of oil for 100 parts by mass * 4: solution polymerization SBR: unmodified SBR (B-1) obtained in Production Example 1, bound styrene content = 25% by mass
* 5: Solution polymerization SBR: N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane modified SBR (B-2) obtained in Production Example 2, bound styrene content = 25% by mass
* 6: Solution polymerization SBR: modified SBR (B-3) obtained in Production Example 3, which is tetraethoxysilane-modified, bound styrene content = 35% by mass
* 7: Carbon black: N234, manufactured by Tokai Carbon Co., Ltd., trade name “SEAST 7HM”
* 8: Silica: Tosoh Silica Co., Ltd., trade name “Nip Seal AQ”
* 9: Silane coupling agent: bis (3-triethoxysilylpropyl) tetrasulfide, manufactured by Evonik, trade name “Si69” (registered trademark)
* 10: Process oil: Processed distillate aromatic extract (TDAE), manufactured by JX Nippon Oil & Energy Corporation, trade name “TDAE”
* 11: Vulcanization accelerator DPG: Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller D”
* 12: Anti-aging agent 6PPD: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “NOCRACK 6C”
* 13: Vulcanization accelerator DM: Di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller DM”
* 14: Vulcanization accelerator NS: N-tert-butyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller NS”

  As is clear from Table 1, the rubber compositions of Examples 1 to 6 were compared with the rubber compositions of Comparative Examples 1 and 2, and both rubber compositions were wet braking performance and road surface at a road surface temperature of 10 ° C. The wet braking performance at a temperature of 30 ° C. and the low heat build-up were well balanced.

  The rubber composition for a tire tread of the present invention can achieve both a low exothermic property and wet braking performance at a higher level, and can also reduce the seasonal difference in wet braking performance. Suitable for tread members such as pneumatic tires, pneumatic tires for passenger cars such as pneumatic tires for summer, pneumatic tires for light vehicles, pneumatic tires for light trucks, pneumatic tires for trucks and buses, especially tread grounding members Used for.

Claims (18)

A rubber composition containing a rubber component and a filler, wherein the temperature at the peak position of the tan δ temperature curve is −16.0 ° C. or more and −6.0 ° C. or less, and the tan δ of the peak position is 1.13. Tan δ at 0 ° C. is 0.95 or more, and the value obtained by dividing the absolute value of the difference between tan δ at −5 ° C. and tan δ at 5 ° C. by the temperature difference between −5 ° C. and 5 ° C. {| A tire tread rubber composition, wherein (tan δ at -5 ° C)-(tan δ at 5 ° C) | / 10} (/ ° C) is smaller than 0.045 / ° C.
[Measurement method of tan δ: Using a dynamic tensile viscoelasticity measuring tester, the value of tan δ from −25 ° C. to 80 ° C. at a frequency of 52 Hz, initial strain of 2%, dynamic strain of 1%, and a temperature rising rate of 3 ° C./min. Measure. ]   The tire tread rubber composition according to claim 1, wherein tan δ at 60 ° C is 0.135 or less.   The rubber composition for a tire tread according to claim 1 or 2, wherein {| (tan δ at -5 ° C)-(tan δ at 5 ° C) | / 10} (/ ° C) is greater than 0.025 / ° C.   The rubber composition for a tire tread according to any one of claims 1 to 3, wherein a temperature at a peak position of the temperature curve of tan δ is -12.0 ° C or higher.   The filler contains silica and carbon black, and the content ratio of the silica and the carbon black in the filler is (100: 0) to (30:70) in mass ratio (silica: carbon black). The rubber composition for tire treads of any one of Claims 1-4.   The rubber composition for a tire tread according to claim 5, wherein the silica in the filler is 10 to 100 parts by mass with respect to 100 parts by mass of the rubber component.   The rubber composition for a tire tread according to claim 6, wherein the silica in the filler is 30 to 80 parts by mass with respect to 100 parts by mass of the rubber component.   The rubber composition for a tire tread according to any one of claims 1 to 7, comprising 30 to 55 parts by mass of the filler with respect to 100 parts by mass of the rubber component.   9. The rubber component according to claim 1, wherein the rubber component includes a styrene-butadiene copolymer rubber (A) having a high bound styrene content and a styrene-butadiene copolymer rubber (B) having a low bound styrene content. The rubber composition for a tire tread as described. The rubber component includes the styrene-butadiene copolymer rubber (A) having a bound styrene content of 37 to 60% by mass and the styrene-butadiene copolymer rubber (B) having a bound styrene content of 25 to 35% by mass. The rubber composition for a tire tread according to claim 9, comprising 60 to 100% by mass.
[Measurement method of bound styrene content (mass%): Calculated from integral ratio of ¹ H-NMR spectrum. ]   The tire according to claim 9 or 10, wherein the difference between the bound styrene content of the styrene-butadiene copolymer rubber (A) and the bound styrene content of the styrene-butadiene copolymer rubber (B) is 11% by mass or more. Tread rubber composition. The BET specific surface area of the silica in the filler is a tire tread rubber composition according to any one of claims 5 to 11 is 150 meters ² / g or more.   The rubber composition for a tire tread according to any one of claims 9 to 12, wherein the filler is unevenly distributed in the styrene-butadiene copolymer rubber (B) having a low bound styrene content.   The rubber component comprises 60 to 100% by mass of the styrene-butadiene copolymer rubber (A) and the styrene-butadiene copolymer rubber (B), and a diene rubber other than the styrene-butadiene copolymer rubber. The rubber composition for tire treads of any one of Claims 9-13 containing 40-0 mass%.   The rubber component comprises 80-100% by mass of the styrene-butadiene copolymer rubber (A) and the styrene-butadiene copolymer rubber (B), and a diene rubber other than the styrene-butadiene copolymer rubber. The rubber composition for a tire tread according to claim 14, containing 20 to 0% by mass.   The styrene-butadiene copolymer rubber (B) having a low bound styrene content is modified with at least one compound selected from nitrogen-containing compounds, silicon-containing compounds, and nitrogen and silicon-containing compounds. The rubber composition for a tire tread according to any one of 9 to 15.   The rubber composition for a tire tread according to claim 16, wherein at least one compound selected from the nitrogen-containing compound, the silicon-containing compound, and the nitrogen- and silicon-containing compound is a hydrocarbyloxysilane compound.   The rubber composition for tire tread according to any one of claims 9 to 17, wherein the styrene-butadiene copolymer rubber (A) having a high styrene content has a bound styrene content St (A) of 40% by mass or more.