JP2014105322A - Rubber composition for base tread and pneumatic tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition for a base tread capable of improving fuel consumption property and fracture strength resistance and to provide a pneumatic tire.SOLUTION: A rubber composition for a base tread contains a rubber component and silica and a compound of the formula (1), and the rubber component contains a diene-based polymer rubber modified by the formula (I).

Description

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

Conventionally, a method of blending silica as a filler is known as a technique for reducing rolling resistance of a tire (reducing fuel consumption of a vehicle). For example, rolling resistance can be reduced by blending silica in a tread. At the same time, the WET traction performance can be improved at the same time. Patent Documents 1 to 3 disclose a method of improving fuel efficiency by blending two types of silica having different nitrogen adsorption specific surface areas and particle diameters into a tread. However, there is a limit to the improvement in fuel efficiency when only the tread is improved, and the base tread is also required to have excellent low heat generation.

Unlike the tread, carbon black having a large particle size has been used for the base tread in order to improve fuel efficiency. Therefore, even if part or all of the carbon black is replaced with silica, the effect of reducing rolling resistance is not so great. Moreover, there is also a problem that the fracture strength is reduced by substitution. As another technique capable of reducing the rolling resistance, a method of reducing the content of the filler is also known, but this method also has a problem that the fracture resistance is lowered. Therefore, there is a demand for a method for improving fuel economy and fracture strength in a well-balanced manner.

JP 2006-233177 A JP 2008-50570 A JP 2008-101127 A

The object of the present invention is to solve the above-mentioned problems and to provide a rubber composition for a base tread that can improve fuel economy and fracture strength in a well-balanced manner, and a pneumatic tire using the same.

（式中、Ｅは炭素数２〜１０のアルキレン基、Ｒ^１０１及びＲ^１０２は、同一若しくは異なって、窒素原子を含む１価の有機基を表す。）

（式中、ｌ〜ｎは、独立に、１〜８の整数を表す。） The present invention contains a rubber component, silica, and a compound represented by the following formula (1), and is conjugated in the presence of a Lewis basic compound in a hydrocarbon solvent in 100% by mass of the rubber component. An active conjugated diene polymer having an alkali metal terminal obtained by polymerizing a diene monomer or a conjugated diene monomer and an aromatic vinyl monomer using an alkali metal catalyst is represented by the following formula (I). The content of the modified diene polymer rubber reacted with the compound is 5% by mass or more, and the content of the silica with respect to 100 parts by mass of the rubber component is represented by the following formula (1). The present invention relates to a rubber composition for a base tread having a compound content of 5 to 23 parts by mass.

(In the formula, E represents an alkylene group having 2 to 10 carbon atoms, and R ¹⁰¹ and R ¹⁰² are the same or different and represent a monovalent organic group containing a nitrogen atom.)

(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 rubber composition for a base tread.

According to the present invention, since it is a rubber composition in which a specific modified diene polymer rubber, silica, and a compound represented by the formula (1) are blended, fuel economy and fracture resistance are improved in a well-balanced manner. Pneumatic tires can be provided.

（式中、ｌ〜ｎは、独立に、１〜８の整数を表す。） The modified diene polymer rubber according to the present invention polymerizes a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer using an alkali metal catalyst in the presence of a Lewis basic compound in a hydrocarbon solvent. 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 the above method.

(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 properties, triglycidyl isocyanurate in which 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 according to 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 according to 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 10% by mass or more, more preferably 15% 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. Further, the content of the modified diene polymer rubber is preferably 90% by mass or less, more preferably 70% 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 25% by mass or more, and further preferably 45% 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 90% by mass or less, more preferably 70% by mass or less. When it exceeds 90 mass%, workability tends to deteriorate.

The rubber composition of the present invention uses silica as a reinforcing agent. Examples of the silica include dry silica (anhydrous silicic acid), wet silica (hydrous silicic acid), colloidal silica, precipitated silica, calcium silicate, and aluminum silicate. One or more of these can be used. The BET specific surface area of silica is preferably 50 to 250 m ² / g. The BET specific surface area is measured according to ASTM D1993-03. As a commercial product of silica, the product name Ultrasil VN3-G manufactured by Degussa, the product name VN3, AQ, ER, RS-150 manufactured by Tosoh Silica Co., Ltd., and the product names Zeosil 1115MP, 1165MP manufactured by Rhodia can be used. .

The content of silica is 5 to 150 parts by mass with respect to 100 parts by mass of the rubber component. The content is preferably 15 parts by mass or more, more preferably 25 parts by mass or more, in order to improve fuel efficiency. Moreover, in order to improve fracture strength and workability, Preferably it is 100 mass parts or less, More preferably, it is 50 mass parts or less.

（式中、Ｅは炭素数２〜１０のアルキレン基、Ｒ^１０１及びＲ^１０２は、同一若しくは異なって、窒素原子を含む１価の有機基を表す。） In the present invention, a compound represented by the following formula (1) is used as a crosslinking agent. Thereby, a CC bond with high binding energy and high thermal stability can be retained in the rubber composition.

(In the formula, E represents an alkylene group having 2 to 10 carbon atoms, and R ¹⁰¹ and R ¹⁰² are the same or different and represent a monovalent organic group containing a nitrogen atom.)

The alkylene group for E is not particularly limited, and includes linear, branched, and cyclic groups. Among them, a linear alkylene group is preferable.

Carbon number of the alkylene group of E is 2-10, Preferably it is 4-8. When the number of carbon atoms in the alkylene group is 1, the thermal stability tends to be poor, and the effect of having an alkylene group tends to be insufficient. When the number of carbon atoms is 11 or more, -S-S-E-S- There is a tendency that formation of a crosslinked chain represented by S- becomes difficult.

Examples of the alkylene group satisfying the above conditions include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, decamethylene group and the like. Among these, a hexamethylene group is preferred because a cross-link represented by -S-S-E-SS-S is smoothly formed between the polymers and is thermally stable.

R ¹⁰¹ and R ¹⁰² are not particularly limited as long as they are monovalent organic groups containing a nitrogen atom, but those containing at least one aromatic ring are preferred, and N—C (═S) in which a carbon atom is bonded to a dithio group. )-Is more preferable. R ¹⁰¹ and R ¹⁰² may be the same or different from each other, but are preferably the same for reasons such as ease of production.

Examples of the compound represented by the formula (1) include 1,2-bis (N, N′-dibenzylthiocarbamoyldithio) ethane and 1,3-bis (N, N′-dibenzylthiocarbamoyldithio). Propane, 1,4-bis (N, N′-dibenzylthiocarbamoyldithio) butane, 1,5-bis (N, N′-dibenzylthiocarbamoyldithio) pentane, 1,6-bis (N, N ′) -Dibenzylthiocarbamoyldithio) hexane, 1,7-bis (N, N'-dibenzylthiocarbamoyldithio) heptane, 1,8-bis (N, N'-dibenzylthiocarbamoyldithio) octane, 1,9 -Bis (N, N′-dibenzylthiocarbamoyldithio) nonane, 1,10-bis (N, N′-dibenzylthiocarbamoyldithio) decane and the like. Among these, 1,6-bis (N, N′-dibenzylthiocarbamoyldithio) hexane is preferable because it is thermally stable and has excellent polarizability.

Content of the compound represented by Formula (1) is 5 mass parts or more with respect to 100 mass parts of rubber components, Preferably it is 7 mass parts or more, More preferably, it is 10 mass parts or more. If it is less than 5 parts by mass, the fuel economy and rubber strength may not be sufficiently improved. The content is 23 parts by mass or less, preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and still more preferably 15 parts by mass or less. If it exceeds 23 parts by mass, the rubber strength tends to decrease.

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 Seast 6, Seast 7HM, Seast KH, Degussa Corporation trade name CK3, 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 10 parts by mass or more, and still more preferably 15 parts by mass or more, in order to increase the fracture resistance. Moreover, in order to improve low fuel consumption, More preferably, it is 45 mass parts or less, More preferably, it is 40 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 the fracture resistance. 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 0.1: 1 to 10: 1. The mass ratio is more preferably 0.5: 1 to 2: 1 in order to enhance 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 balance between low fuel consumption and fracture strength.

The rubber composition of the present invention is used for a tire tread.

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, a rubber composition blended with various additives as necessary is extruded according to the shape of the base tread of the tire at an unvulcanized stage, and molded by a normal method on a tire molding machine, Bonding together with other tire members forms 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 replaced with dry nitrogen, and then 1,3-butadiene 1404 g, tetrahydrofuran 328 g, hexane 10.2 kg, n-butyllithium (n-hexane solution 15.0 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 content of the polymerization reaction vessel was taken out, 10 g of 2,6-di-t-phtyl-p-cresol (Sumilyzer BHT manufactured by Sumitomo Chemical Co., Ltd.) was added, and most of hexane was evaporated. 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 replaced with dry nitrogen, and then 1,3-butadiene 1404 g, tetrahydrofuran 328 g, hexane 10.2 kg, n-butyllithium (n-hexane solution 8.5 mmol) Was added and polymerization was carried out at 65 ° C. for 3 hours with stirring. After completion of the polymerization, 0.16 mmol (0.027 g) of silicon tetrachloride was added, and the mixture was reacted at 65 ° C. for 15 minutes with stirring. Further, instead of triglycidyl isocyanurate, 7.65 mmol (1.19 g) of N, N-dimethylaminopropylacrylamide was added, and the mixture was reacted at 65 ° C. for 30 minutes with stirring, and then 10 ml of methanol was added. Stir for 5 minutes. Thereafter, the content of the polymerization reaction vessel was taken out, 10 g of 2,6-di-t-phtyl-p-cresol (Sumilyzer BHT manufactured by Sumitomo Chemical Co., Ltd.) was added, and most of hexane was evaporated. The polymer 2 was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

<Polymer Production Example 3>
The n-butyllithium solution in n-hexane was changed to 8.7 mmol, the silicon tetrachloride was changed to 0.17 mmol (0.029 g), and triglycidyl isocyanurate and N, N-dimethylaminopropylacrylamide were added. A polymer 3 was obtained in the same manner as the polymer 2 except that it was not added.

The obtained polymers 1 to 3 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 near 910 cm ^−1, which is the absorption peak of the vinyl group, by infrared spectroscopy.

(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.
NR: RSS # 3
BR: Ubepol BR150B manufactured by Ube Industries, Ltd.
Polymers 1-3: Carbon black synthesized by the above method: Diablack N220 manufactured by Mitsubishi Chemical Corporation (N ₂ SA: 111 m ² / g, DBP absorption: 115 ml / 100 g)
Silica: Ultrasil VN3 manufactured by Degussa (N ₂ SA: 175 m ² / g)
Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa
Crosslinking agent: Vulcuren VP KA9188 (1,6-bis (N, N′-dibenzylthiocarbamoyldithio) hexane manufactured by LANXESS)
Anti-aging agent: Antigen 3C manufactured by Sumitomo Chemical Co., Ltd.
Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Oil: X-140 manufactured by Japan Energy Co., Ltd.
Stearic acid: Beads manufactured by NOF Corporation Zinc stearate zinc oxide: Zinc flower No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Sulfur powder vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd. CZ: Sumitomo Chemical ( Soxinol CZ manufactured by

(Examples and Comparative Examples)
According to the composition shown in Table 2, materials other than the crosslinking agent, sulfur and vulcanization accelerator were kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer manufactured by Kobe Steel, A kneaded product was obtained. Next, a crosslinking agent, sulfur and a vulcanization accelerator were added to the kneaded product obtained, 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.

The following evaluation was performed about the obtained unvulcanized rubber composition and vulcanized rubber composition. The results are shown in Table 2.

<Evaluation items and test methods>
<Tan δ index (low fuel consumption)>
A strip-shaped test piece having a width of 1 mm or 2 mm and a length of 40 mm was punched out from the sheet-like vulcanized molded body and subjected to the test. The measurement is 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 Co., Ltd.) The reciprocal of tan δ in Example 2 was taken as 100 and displayed as an index. The larger the index, the better the fuel efficiency.

<Destructive strength index>
The vulcanized rubber composition was subjected to a tensile test using a No. 3 dumbbell according to JIS K6251 and measured for breaking strength (TB) and elongation at break (EB) (%). The numerical value of TB × EB / 2 is taken as the fracture resistance, and the index is shown as an index with the fracture strength of Comparative Example 2 as 100. The larger the index, the better the fracture strength.

As shown in Table 2, an example in which a specific modified conjugated diene polymer (polymer 1) and a compound represented by the formula (1) were blended was lower than the rubber composition of the comparative example. The fuel efficiency and the breaking strength were synergistically improved, and these performances were obtained in a high level and in a well-balanced manner.

Claims (4)

Containing a rubber component, silica, and a compound represented by the following formula (1),
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 rubber composition for base treads in which the content of the silica is 5 to 150 parts by mass and the content of the compound represented by the following formula (1) is 5 to 23 parts by mass with respect to 100 parts by mass of the rubber component.

(In the formula, E represents an alkylene group having 2 to 10 carbon atoms, and R ¹⁰¹ and R ¹⁰² are the same or different and represent a monovalent organic group containing a nitrogen atom.)

(In the formula, l to n 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. Rubber composition for base tread. The rubber composition for a base 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 base treads in any one of Claims 1-3.