JP5944778B2 - Rubber composition for tread and pneumatic tire - Google Patents

Description

The present invention relates to a rubber composition for a tread and a pneumatic tire produced using the rubber composition.

In recent years, due to increasing interest in environmental issues, there has been a strong demand for lower fuel consumption for automobiles, and rubber compositions used for automobile tires are also required to have excellent fuel efficiency. . As a rubber composition for an automobile tire, a rubber composition containing a conjugated diene polymer such as polybutadiene or butadiene-styrene copolymer and a filler such as carbon black or silica is used.

As a method for improving fuel economy, for example, Patent Document 1 proposes a method using a diene rubber (modified rubber) modified with an organosilicon compound containing an amino group and an alkoxy group. However, when modified rubber is used, there is room for improvement in that the processability tends to decrease. Further, the performance required for the rubber composition for automobile tires includes wet grip performance and wear resistance, and these performances are generally in contradiction with low fuel consumption. Therefore, a method for improving the fuel economy, wet grip performance, wear resistance and workability in a well-balanced manner is required.

JP 2000-344955 A

An object of the present invention is to solve the above problems and provide a rubber composition for a tread that can improve fuel economy, wet grip performance, and wear resistance in a well-balanced manner, and a pneumatic tire using the same.

（式中、ｌ〜ｎは、独立に、１〜８の整数を表す。） A rubber component, silica (1) having a nitrogen adsorption specific surface area of 100 m ² / g or less, and silica (2) having a nitrogen adsorption specific surface area of 180 m ² / g or more,
It is obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in an hydrocarbon solvent in the presence of a Lewis basic compound in 100% by mass of the rubber component using an alkali metal catalyst. The content of the modified diene polymer rubber obtained by reacting the compound represented by the following formula (I) with respect to the active conjugated diene polymer having an alkali metal terminal is 5% by mass or more,
The total content of the silica (1) and (2) with respect to 100 parts by mass of the rubber component is 10 to 150 parts by mass,
It is related with the rubber composition for treads in which content of the said silica (1) and (2) satisfy | fills the following formula | equation.
(Content of silica (1)) × 0.2 ≦ (content of silica (2)) ≦ (content of silica (1)) × 6.5

(In the formula, l to n independently represent an integer of 1 to 8.)

It is preferable that the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the modified diene polymer rubber is 1.0 to 1.5.

It is preferable that the vinyl bond content of the modified diene polymer rubber is 10 to 70 mol%, where the content of conjugated diene units is 100 mol%.

The present invention also relates to a pneumatic tire produced using the tread rubber composition.

According to the present invention, since it is a rubber composition for a tread in which a predetermined amount of a specific modified diene polymer rubber and silica (1) and (2) having a specific nitrogen adsorption specific surface area are blended, low fuel consumption It is possible to provide a pneumatic tire with improved wet grip performance and wear resistance in a well-balanced manner.

（式中、ｌ〜ｎは、独立に、１〜８の整数を表す。） The modified diene polymer rubber of the present invention is obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of a Lewis basic compound using an alkali metal catalyst. Is a modified diene polymer rubber obtained by reacting a compound represented by the following formula (I) with an active conjugated diene polymer having an alkali metal terminal obtained by:

(In the formula, l to n independently represent an integer of 1 to 8.)

Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene (piperine), 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, and the like. Then, 1,3-butadiene and isoprene are preferred from the viewpoint of the physical properties of the resulting polymer and the availability for industrial implementation.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, divinyl naphthalene and the like. Among these, the physical properties of the resulting polymer, industrial Styrene is preferable from the viewpoint of availability in carrying out.

The hydrocarbon solvent does not deactivate the alkali metal catalyst, and the suitable hydrocarbon solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons, and particularly has 3 to 12 carbon atoms. Propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, cyclohexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1 -Pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. Moreover, these solvents can be used in mixture of 2 or more types.

Examples of the alkali metal catalyst include metals such as lithium, sodium, potassium, rubidium, and cesium, hydrocarbon compounds containing these metals, and complexes of the metal and polar compounds. Preferred examples of the alkali metal catalyst include lithium or sodium compounds having 2 to 20 carbon atoms. Specific examples thereof include ethyl lithium, n-propyl lithium, and iso-propyl lithium. N-butyl lithium, sec-butyl lithium, t-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium 4-cyclopentyl lithium, Examples include 1,4-dilithio-butene-2, sodium naphthalene, sodium biphenyl, potassium-tetrahydrofuran complex, potassium diethoxyethane complex, and sodium salt of α-methylstyrene tetramer.

As the modifying compound to be reacted with the active diene polymer rubber used in the present invention, a compound represented by the above formula (I) is used, and l to n are independently preferably an integer of 1 to 8, and low fuel consumption. In order to improve the property, triglycidyl isocyanurate where 1 to n are all 1 is most preferable.

As the polymerization monomer, only a conjugated diene monomer may be used, or a conjugated diene monomer and an aromatic vinyl monomer may be used in combination. When the conjugated diene monomer and the aromatic vinyl monomer are used in combination, the ratio by weight of the conjugated diene monomer / aromatic vinyl monomer is preferably 50/50 to 90/10, more preferably 55/45 to 85/15. It is. If the ratio is too small, the polymer rubber becomes insoluble in the hydrocarbon solvent, and uniform polymerization may not be possible. On the other hand, if the ratio is too large, the strength of the polymer rubber may decrease.

In the polymerization, it is possible to use commonly used materials such as an alkali metal catalyst, a hydrocarbon solvent, a reagent for improving random polymerizability, and a vinyl bond content regulator for conjugated diene units. The polymerization temperature in the production of the copolymer is not particularly limited, but is usually −80 ° C. to 150 ° C., and preferably 20 to 110 ° C. from the viewpoint of the reaction rate and the stability of the alkali metal catalyst. The polymerization time is not particularly limited, but the alkali metal catalyst is completed within at least 24 hours.

In order to adjust the vinyl bond content of the conjugated diene part, various compounds can be used as the Lewis basic compound. However, ether compounds or tertiary amines are easily available in industrial implementation. preferable. Examples of ether compounds include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, Examples thereof include aliphatic ethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole. Examples of tertiary amine compounds include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N-diethylaniline, pyridine, quinoline and the like. be able to.

The amount used when the modified compound represented by the general formula (I) of the present invention is added to the active conjugated diene polymer having an alkali metal terminal is used for the alkali used when adding the alkali metal. It is 0.06-10 mol normally per 1 mol of metal catalysts, Preferably it is 0.1-5 mol, More preferably, it is 0.2-2 mol. If the amount used is too small, the effect of improving fuel economy is small, and if it is too large, it remains in the polymerization solvent. Therefore, when the solvent is recycled, a separation step from the solvent is required. Etc., not economically desirable.

Since the reaction between the modifying compound and the active conjugated diene polymer having an alkali metal terminal occurs rapidly, the reaction temperature and reaction time can be selected in a wide range, but generally room temperature to 100 ° C., several seconds to A few hours. The reaction may be performed by bringing the alkali metal-containing diene polymer and the modified compound into contact with each other. For example, an alkali metal catalyst is used to polymerize the diene polymer, and the modified compound is placed in the polymer solution. Although the method of adding quantitatively can be illustrated as a preferred embodiment, it is not limited to this method.

By reacting the modified compound represented by the general formula (I) with the active conjugated diene copolymer having an alkali metal terminal, the modified diene polymer rubber is converted into a coagulant from the reaction solvent. The coagulation method used in the production of rubber by ordinary solution polymerization such as addition or steam coagulation is used as it is, and the coagulation temperature is not limited at all.

For drying the crumb separated from the reaction system, a band drier, an extrusion drier or the like used in the production of ordinary synthetic rubber can be used, and the drying temperature is not limited at all.

The Mooney viscosity (ML _{1 + 4} ) of the modified diene polymer rubber is preferably 10 to 200, more preferably 20 to 150. If the Mooney viscosity is too low, mechanical properties such as the tensile strength of the vulcanizate may be reduced. On the other hand, if the viscosity is too high, the miscibility is poor when used in combination with other rubbers, and the processing operability is difficult. Thus, the mechanical properties of the vulcanizate of the obtained rubber composition may be deteriorated.

The vinyl bond content in the conjugated diene part of the modified diene polymer rubber is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, with the content of the conjugated diene unit being 100 mol%. If it is less than 10 mol%, the grip performance may be inferior, and if it exceeds 70 mol%, the fuel efficiency may be inferior.

The molecular weight distribution of the modified diene polymer rubber of the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 1.5, in order to improve fuel economy. The molecular weight distribution is determined by measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) method and dividing Mw by Mn.

The modified diene polymer rubber of the present invention can be used as a conjugated diene polymer composition by blending other polymer components and additives.

The content of the modified diene polymer rubber in 100% by mass of the rubber component is 5% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more. If the amount is less than 5% by mass, the effect of improving fuel economy tends to be difficult to obtain. The content of the modified diene polymer rubber is preferably 90% by mass or less, more preferably 80% by mass or less. When it exceeds 90% by mass, the wear resistance is lowered and the cost tends to be high.

The rubber component that can be used in addition to the modified diene polymer rubber is not limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber ( NBR), chloroprene rubber (CR), butyl rubber (IIR) and the like. These rubber components may be used alone or in combination of two or more. Of these, NR and BR are preferable because they exhibit a good balance between low fuel consumption, wet grip performance, wear resistance, and workability. These rubber components are not particularly limited, and those generally used in the tire industry can be used.

The content of NR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 15% by mass or more. If the amount is less than 5% by mass, sufficient fuel economy tends not to be obtained. The NR content is preferably 60% by mass or less, more preferably 40% by mass or less. When it exceeds 60 mass%, workability tends to deteriorate.

The content of BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 15% by mass or more. When it is less than 5% by mass, sufficient wear resistance tends to be not obtained. Further, the BR content is preferably 60% by mass or less, more preferably 40% by mass or less. When it exceeds 60% by mass, fuel efficiency tends to deteriorate.

The rubber composition of the present invention contains silica (1) having a nitrogen adsorption specific surface area of 100 m ² / g or less and silica (2) having a nitrogen adsorption specific surface area of 180 m ² / g or more. Examples of the silica (1) and (2) include silica prepared by a dry method (anhydrous silicic acid), silica prepared by a wet method (hydrous silicic acid) and the like, and there are many silanol groups on the surface, Silica prepared by a wet method is preferred because it has many reactive sites with the silane coupling agent.
The nitrogen adsorption specific surface area (N ₂ SA) of silica is a value measured by the BET method according to ASTM D3037-93.

N ₂ SA of silica (1) is 100 m ² / g or less, preferably 80 m ² / g or less, more preferably 60 m ² / g or less. When it exceeds 100 m < ² > / g, there exists a possibility that the effect by combined use of a silica (1) and (2) may not fully be acquired. N ₂ SA of silica (1) is preferably 20 m ² / g or more, more preferably 30 m ² / g or more. If it is less than 20 m ² / g, sufficient reinforcing properties cannot be obtained, and the wear resistance tends to decrease.

Although it does not specifically limit as silica (1), For example, Ultrazil 360 by Degussa, Z40 by Rhodia, RP80 by Rhodia, etc. can be used. Silica (1) may be used alone or in combination of two or more.

The content of silica (1) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 1 part by mass, the rolling resistance tends not to be sufficiently reduced. The content of silica (1) is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, still more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less. When it exceeds 150 mass parts, there exists a tendency for abrasion resistance to fall.

N ₂ SA of silica (2) is 180 m ² / g or more, preferably 190 m ² / g or more, more preferably 200 m ² / g or more. If it is less than 180 m ² / g, the effect of the combined use of silica (1) and (2) may not be sufficiently obtained. Also, _N 2 SA of the silica (2) is preferably 300 meters ² / g, more preferably at most 240 m ² / g. If it exceeds 300 m ² / g, fuel economy and processability tend to deteriorate.

Although it does not specifically limit as silica (2), For example, rheodia Zeosyl 1205MP etc. can be used. Silica (2) may be used alone or in combination of two or more.

The content of silica (2) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 1 part by mass, there is a tendency that sufficient wear resistance cannot be obtained. Further, the content of silica (2) is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, still more preferably 100 parts by mass or less, and particularly preferably 60 parts by mass or less. If it exceeds 150 parts by mass, the workability tends to deteriorate.

The total content of silica (1) and (2) is 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 10 mass parts, there exists a tendency for the sufficient reinforcement effect by blending silica (1) and (2) not to be acquired. The total content of silica (1) and (2) is 150 parts by mass or less, preferably 120 parts by mass or less, more preferably 100 parts by mass or less. If it exceeds 150 parts by mass, it will be difficult for silica to be uniformly dispersed in the rubber composition, and the processability, fuel efficiency and wear resistance will tend to deteriorate.

The content of silica (1) and the content of (2) satisfy the following formula.
[Content of silica (1)] × 0.2 ≦ [Content of silica (2)] ≦ [Content of silica (1)] × 6.5
The content of silica (2) is 0.2 times or more, preferably 0.5 times or more of the content of silica (1). If it is less than 0.2 times, the steering stability tends to decrease. The content of silica (2) is not more than 6.5 times the content of silica (1), preferably not more than 4 times, more preferably not more than 1 time (1 time). If it exceeds 6.5 times, there is a tendency that the improvement effect obtained when the above formula is satisfied is not seen.

The rubber composition of the present invention may contain additives other than the above-mentioned chemicals. Known additives can be used, such as sulfur vulcanizing agents; thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, guanidine vulcanization accelerators. Vulcanization accelerators such as stearic acid and zinc oxide; organic peroxides such as dicumyl peroxide and ditertiary butyl peroxide; reinforcing agents such as carbon black; calcium carbonate, talc and alumina Examples thereof include fillers such as clay, aluminum hydroxide and mica; silane coupling agents; extension oils; processing aids; anti-aging agents;

Examples of the sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. The content of sulfur is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. It is.

Examples of the vulcanization accelerator include 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and thiazole vulcanization accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethylthiuram. Thiuram vulcanization accelerators such as disulfides; N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N -Sulfenamide vulcanization accelerators such as oxyethylene-2-benzothiazole sulfenamide and N, N'-diisopropyl-2-benzothiazole sulfenamide; diphenylguanidine, diortolylguanidine, orthotolylbiguanidine What guanidine-based vulcanization accelerator and the like. The content of the vulcanization accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the rubber component.

Examples of the carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. Carbon blacks include channel carbon blacks such as EPC, MPC and CC; furnace carbon blacks such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF; FT and MT Thermal carbon black such as acetylene carbon black is exemplified. One or more of these can be used.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 5 to 200 m ² / g, and the dibutyl phthalate (DBP) absorption amount of carbon black is preferably 5 to 300 ml / 100 g. . The nitrogen adsorption specific surface area is measured according to ASTM D4820-93, and the DBP absorption is measured according to ASTM D2414-93. As a commercial item, Mitsubishi Chemical Corporation trade name Dia Black N339, Tokai Carbon Co., Ltd. trade name SHIEST 6, SEAST 7HM, SEAST KH, Degussa trade name CK 3, Special Black 4A, etc. can be used.

The content of carbon black is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the rubber component. Further, the content is more preferably 3 parts by mass or more, and still more preferably 4 parts by mass or more, in order to increase wear resistance and strength. Moreover, in order to improve low fuel consumption, More preferably, it is 30 mass parts or less, More preferably, it is 10 mass parts or less.

The content of the reinforcing agent is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the rubber component. Further, the content is more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, in order to increase wear resistance and strength. Moreover, in order to improve low fuel consumption, More preferably, it is 120 mass parts or less, More preferably, it is 100 mass parts or less.

The mass ratio of the silica content and the carbon black content used as the reinforcing agent (silica content: carbon black content) is preferably 2: 1 to 50: 1. The mass ratio is more preferably 5: 1 to 20: 1 in order to increase fuel efficiency and enhance reinforcement.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ- Aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxy Cyril) Pills) tetrasulfide, .gamma.-trimethoxysilylpropyl dimethylthiocarbamoyl tetrasulfide, and the like .gamma.-trimethoxysilylpropyl benzothiazyl tetrasulfide. One or more of these are used. As commercial products, trade names Si69, Si75, etc., manufactured by Degussa Corporation can be used.

The content of the silane coupling agent is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and further preferably 5 to 10 parts by mass with respect to 100 parts by mass of silica.

Examples of the extending oil include aromatic mineral oil (viscosity specific gravity constant (VGC value) 0.900 to 1.049), naphthenic mineral oil (VGC value 0.850 to 0.899), paraffinic mineral oil (VGC value 0.790 to 0.849), and the like. The polycyclic aromatic content of the extender oil is preferably less than 3% by mass, more preferably less than 1% by mass. The polycyclic aromatic content is measured according to the British Petroleum Institute 346/92 method. Moreover, the aromatic compound content (CA) of the extending oil is preferably 20% by mass or more. One or more of these extending oils are used.

As a method for producing the rubber composition of the present invention, a known method, for example, a method of kneading each component with a known mixer such as a roll or Banbury can be used.

As kneading conditions, when additives other than the vulcanizing agent and the vulcanization accelerator are blended, the kneading temperature is usually 50 to 200 ° C., preferably 80 to 190 ° C., and the kneading time is usually 30 seconds. -30 minutes, preferably 1-30 minutes. When blending a vulcanizing agent and a vulcanization accelerator, the kneading temperature is usually 100 ° C. or lower, preferably room temperature to 80 ° C. A composition containing a vulcanizing agent and a vulcanization accelerator is usually used after vulcanization treatment such as press vulcanization. The vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.

The rubber composition of the present invention has a high level of good balance between low fuel consumption, wet grip performance and wear resistance.

The rubber composition of the present invention is used for tire treads (cap treads).

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, a rubber composition containing various additives as necessary is extruded in accordance with the shape of the tread of the tire at an unvulcanized stage, molded by a normal method on a tire molding machine, etc. The tire members are bonded together to form an unvulcanized tire. This unvulcanized tire can be heated and pressurized in a vulcanizer to produce the pneumatic tire of the present invention.

The pneumatic tire of the present invention can be suitably used as a tire for passenger cars.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

<Polymer Production Example 1>
A stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and substituted with dry nitrogen, and then 1,3-butadiene 1404 g, styrene 396 g, tetrahydrofuran 328 g, hexane 10.2 kg, n-butyllithium (n-hexane solution 15 0.0 mmol) was added and polymerization was carried out at 65 ° C. for 3 hours with stirring. After completion of the polymerization, 7.5 mmol (2.23 g) of triglycidyl isocyanurate was added. After reacting at 65 ° C. for 30 minutes with stirring, 10 ml of methanol was added, and the mixture was further stirred for 5 minutes. Thereafter, the contents of the polymerization reaction vessel are taken out, 10 g of 2,6-di-t-butyl-p-cresol (Sumitomo Chemical Co., Ltd., Sumitizer BHT: the same applies below) is added, and most of the hexane is evaporated. After that, the polymer 1 was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

<Polymer Production Example 2>
A stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and substituted with dry nitrogen, and then 1,3-butadiene 1404 g, styrene 396 g, tetrahydrofuran 328 g, hexane 10.2 kg, n-butyllithium (n-hexane solution 8 0.7 mmol) was added, and polymerization was carried out at 65 ° C. for 3 hours with stirring. After the completion of the polymerization, 0.17 mmol (0.029 g) of silicon tetrachloride was added and reacted with stirring at 65 ° C. for 45 minutes, 10 ml of methanol was added, and the mixture was further stirred for 5 minutes. Thereafter, the contents of the polymerization reaction vessel are taken out, 10 g of 2,6-di-t-butyl-p-cresol (Sumitomo Chemical Co., Ltd., Sumitizer BHT: the same applies below) is added, and most of the hexane is evaporated. Then, the polymer 2 was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

The obtained polymers 1 and 2 were analyzed by the following method. The results are shown in Table 1.

(Mooney viscosity (ML _{1 + 4} ))
According to JIS K6300 (1994), the Mooney viscosity of the polymer was measured at 100 ° C.

(Vinyl bond amount (unit: mol%))
The amount of vinyl bonds in the polymer was determined from the absorption intensity in the vicinity of 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

(Styrene unit content (unit: mass%))
According to JIS K6383 (1995), the content of styrene units in the polymer was determined from the refractive index.

(Molecular weight distribution (Mw / Mn))
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method under the following conditions (i) to (viii), and the molecular weight distribution (Mw / Mn) was determined.
(I) Apparatus: HLC-8220 manufactured by Tosoh Corporation
(Ii) Separation column: HM-H manufactured by Tosoh Corporation (two in series)
(Iii) Measurement temperature: 40 ° C
(Iv) Carrier: Tetrahydrofuran (v) Flow rate: 0.6 mL / min (vi) Injection volume: 5 μL
(Vii) Detector: differential refraction (viii) Molecular weight standard: Standard polystyrene

Below, various chemical | medical agents used by the Example and the comparative example are demonstrated.
Natural rubber (NR): RSS # 3
Butadiene rubber (BR): Ubepol BR150B manufactured by Ube Industries, Ltd.
Polymers 1 and 2: Polymer silica obtained in Production Examples 1 and 2 (1): Ultrazil 360 manufactured by Degussa (N ₂ SA: 50 m ² / g)
Silica (2): Ultrasil VN3 manufactured by Degussa (N ₂ SA: 200 m ² / g)
Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa
Carbon black: Diablack N220 manufactured by Mitsubishi Chemical Corporation (N ₂ SA: 111 m ² / g, DBP absorption: 115 ml / 100 g)
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Anti-aging agent: Antigen 3C manufactured by Sumitomo Chemical Co., Ltd.
Stearic acid: Beads manufactured by NOF Corporation Zinc stearate Zinc oxide: Zinc flower No. 1 manufactured by Mitsui Kinzoku Mining Co., Ltd. Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. 1: Soxinol CZ manufactured by Sumitomo Chemical Co., Ltd.
Vulcanization accelerator 2: Soxinol D manufactured by Sumitomo Chemical Co., Ltd.

<Examples and Comparative Examples>
According to the blending content shown in Table 2, materials other than sulfur and vulcanization accelerator were kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer manufactured by Kobe Steel Co., Ltd. Obtained. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes under the condition of 80 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized with a 0.5 mm thick mold at 170 ° C. for 20 minutes to obtain a vulcanized rubber composition.
Further, the obtained unvulcanized rubber composition is molded into a tread shape and bonded together with other tire members on a tire molding machine to form an unvulcanized tire, which is vulcanized at 170 ° C. for 12 minutes, and tested. Tires (size: 195 / 65R15) were manufactured.

The following evaluation was performed about the obtained vulcanized rubber composition and the tire for a test. The results are shown in Table 2.

(Tan δ)
A test piece on a strip having a width of 1 mm or 2 mm and a length of 40 mm was punched out from a sheet-like vulcanized molded body (vulcanized rubber composition) and subjected to the test. The measurement was performed by measuring the loss tangent (tan δ (70 ° C.)) of the test piece at a temperature of 70 ° C. under the conditions of a strain of 1% and a frequency of 10 Hz using a viscoelasticity measuring device (manufactured by Ueshima Seisakusho). It was displayed as an index when Comparative Example 3 was taken as 100. A larger index is better (low fuel consumption).

(Rolling resistance)
A rolling resistance tester was used to measure the rolling resistance when the test tire was run at a rim (15 × 6JJ), internal pressure (230 kPa), load (3.43 kN), speed (80 km / h), and a comparative example. Expressed as an index when 3 is taken as 100. A larger index is better (low fuel consumption).

(Wet grip performance)
Each test tire was mounted on all wheels of a vehicle (domestic FF2000cc), and a braking distance from an initial speed of 100 km / h was determined on a wet asphalt road surface. The result is expressed as an index. The larger the number, the better the wet skid performance (wet grip performance). The index was calculated by the following formula.
Wet skid performance = (braking distance of comparative example 3) / (braking distance of each formulation) × 100

(Abrasion resistance)
Using a LAT tester (Laboratory Abrasion and Skid Tester), the volume loss of each vulcanized rubber composition was measured under the conditions of a load of 50 N, a speed of 20 km / h, and a slip angle of 5 °. The numerical value (LAT index) in Table 2 is a relative value when the volume loss amount of Comparative Example 3 is 100. The larger the value, the better the wear resistance.

By combining the specific modified conjugated diene polymer rubber in the present invention with a silica mixture having a low specific surface area and a high specific surface area, the performance balance of low fuel consumption, wet grip performance and wear resistance can be remarkably improved. It was. In particular, from the evaluation results of Comparative Examples 1 to 3 and Example 1, it became clear that the performance balance can be improved synergistically by the combined use.

Claims (4)

A rubber component, silica (1) having a nitrogen adsorption specific surface area of 100 m ² / g or less, and silica (2) having a nitrogen adsorption specific surface area of 180 m ² / g or more,
It is obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in an hydrocarbon solvent in the presence of a Lewis basic compound in 100% by mass of the rubber component using an alkali metal catalyst. The content of the modified diene polymer rubber obtained by reacting the compound represented by the following formula (I) with respect to the active conjugated diene polymer having an alkali metal terminal is 5% by mass or more,
The total content of the silica (1) and (2) with respect to 100 parts by mass of the rubber component is 10 to 150 parts by mass,
A rubber composition for a tread in which the contents of the silicas (1) and (2) satisfy the following formula.
(Content of silica (1)) × 0.2 ≦ (content of silica (2)) ≦ (content of silica (1)) × 6.5

(Wherein, l to m independently represent an integer of 1 to 8) The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the modified diene polymer rubber is 1.0 to 1.5. Tread rubber composition. The rubber composition for a tread according to claim 1 or 2, wherein the vinyl bond content of the modified diene polymer rubber is 10 to 70 mol%, where the content of conjugated diene units is 100 mol%. The pneumatic tire produced using the rubber composition for treads in any one of Claims 1-3.