JP4338564B2 - Rubber composition for tire tread and pneumatic tire using the same - Google Patents

Description

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

  In recent years, not only are there concerns about rising oil prices and depletion of oil due to supply problems, but natural materials are being reconsidered from the perspective of environmental issues such as resource conservation and stricter regulations on carbon dioxide emission control. There is no exception in the tire industry, and natural rubber is attracting attention as an alternative to synthetic rubber. Natural rubber has high mechanical strength and excellent wear resistance, so it is often used for large tires such as truck / bus tires. However, natural rubber has only a methyl group with a small molecular weight in the side chain, and has a problem that grip performance is inferior because the glass transition temperature (Tg) is as low as -60 ° C. Moreover, since it is a natural material, there existed a problem that it was inferior in ozone resistance, heat aging resistance, a weather resistance, etc.

  In order to solve these problems, natural rubber derivatives such as cyclized natural rubber, chlorinated natural rubber, and epoxidized natural rubber are used. For example, Patent Literature 1, Patent Literature 2, Patent Literature 3, and Patent Literature 4 propose a method using epoxidized natural rubber as a tire material. The epoxidized natural rubber is obtained by epoxidizing an unsaturated double bond of natural rubber, and has a glass transition temperature (Tg) higher than that of natural rubber because the molecular cohesive force is increased by an epoxy group which is a polar group, and Excellent mechanical strength, wear resistance and gas permeability. In particular, in the rubber composition containing silica, it is said that the silanol group on the silica surface and the epoxy group of the epoxidized natural rubber interact with each other. Therefore, the mechanical strength is comparable to the compound filled with carbon black. Abrasion resistance is obtained. However, the epoxidized natural rubber has a large hysteresis loss and excellent wet grip performance, but has a drawback in that it has poor rolling resistance characteristics even with silica. Furthermore, due to the strong interaction between silica and epoxidized natural rubber, the blending system of epoxidized natural rubber and other diene rubbers causes uneven distribution of silica on the epoxidized natural rubber side, which is inferior in processability. However, there was a problem that the hardness increase, wear resistance, and heat aging resistance deteriorated.

JP-A-6-220254 JP-A-7-90123 JP-A-7-149955 Japanese Patent Laid-Open No. 2001-233959

  An object of the present invention is to provide a rubber composition for a tire tread having improved wear resistance and heat resistance, and a tire obtained using the rubber composition.

The present invention relates to 100 parts by weight of a rubber component containing 5 to 100% by weight of epoxidized natural rubber, 5 to 150 parts by weight of silica having a nitrogen adsorption specific surface area of 100 to 300 m ² / g, an alkaline earth metal stearate. The present invention relates to a rubber composition for a tire tread containing 1 to 10 parts by weight of a salt and 1 to 20 parts by weight of a silane coupling agent represented by the following formula with respect to 100 parts by weight of the silica.
_{(C n H 2n + 1 O} ) 3 -Si- (CH 2) m -S l - (CH 2) m -Si- (C n H 2n + 1 O) 3
(Wherein, n is an integer of 1 to 3, m is an integer of 1 to 4, l is reveal the number of sulfur atoms in the polysulfide part, is 2.1 to 3.5)

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

  According to the present invention, wear resistance and heat resistance can be improved by blending a specific epoxidized natural rubber, silica, silane coupling agent and metal stearate into the rubber composition for tire treads.

  The present invention will be described in detail below.

  The rubber composition for tire treads of the present invention comprises a rubber component, silica, a silane coupling agent and a metal stearate.

  The rubber component contains epoxidized natural rubber. As the epoxidized natural rubber, commercially available epoxidized natural rubber may be used, or natural rubber may be epoxidized. The method for epoxidizing natural rubber is not particularly limited, and can be performed using a method such as a chlorohydrin method, a direct oxidation method, a hydrogen peroxide method, an alkyl hydroperoxide method, a peracid method, for example, Examples include a method of reacting natural rubber with an organic peracid such as peracetic acid or performic acid.

  The epoxidation rate of the epoxidized natural rubber is preferably 5 mol% or more, and more preferably 10 mol% or more. If the epoxidation rate is less than 5 mol%, the modifying effect on the rubber composition tends to be small. The epoxidation rate is preferably 80 mol% or less, and more preferably 60 mol% or less. When the epoxidation rate exceeds 80 mol%, the polymer component is gelled, which is not preferable.

  The content of the epoxidized natural rubber is 5% by weight or more, preferably 10% by weight or more in the rubber component. If the epoxidized natural rubber is less than 5% by weight, a sufficient grip performance cannot be obtained, which is not preferable. The content of the epoxidized natural rubber is 100% by weight or less.

  In the rubber composition for a tire tread of the present invention, examples of the rubber component used in addition to the epoxidized natural rubber include natural rubber and / or diene synthetic rubber. Specific examples of the diene synthetic rubber include styrene-butadiene rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), and acrylonitrile-butadiene rubber. (NBR), butyl rubber (IIR) and the like. These rubbers may be used alone or in combination of two or more.

  The rubber composition for a tire tread of the present invention contains silica. Silica includes silica produced by a wet method or a dry method, but is not particularly limited.

The nitrogen adsorption specific surface area (N ₂ SA) of silica is 100 m ² / g or more, preferably 120 m ² / g or more. When the N ₂ SA of silica is less than 100 m ² / g, the reinforcing effect is small. Further, N ₂ SA of silica is 300 m ² / g or less, preferably 280 m ² / g or less. If the N ₂ SA of silica exceeds 300 m ² / g, the dispersibility is lowered and the exothermic property of the rubber composition is increased, which is not preferable.

  The content of silica is 5 parts by weight or more, preferably 10 parts by weight or more, more preferably 15 parts by weight or more with respect to 100 parts by weight of the rubber component. If the silica content is less than 5 parts by weight, sufficient low heat build-up and wet grip performance cannot be obtained. The silica content is 150 parts by weight or less, preferably 120 parts by weight or less, more preferably 100 parts by weight or less. If the silica content exceeds 150 parts by weight, workability and workability deteriorate, which is not preferable.

The rubber composition for tire treads of the present invention contains a silane coupling agent. The silane coupling agent that can be suitably used in the present invention is represented by the following formula.
_{(C n H 2n + 1 O} ) 3 -Si- (CH 2) m -S l - (CH 2) m -Si- (C n H 2n + 1 O) 3
(In the formula, n is an integer of 1 to 3, m is an integer of 1 to 4, and l represents the number of sulfur atoms in the polysulfide part)

  In the formula, l represents the number of sulfur atoms in the polysulfide part. Here, the average value of l is preferably 2.1 to 3.5. If the average value of l is less than 2.1, the reactivity between the silane coupling agent and the rubber component tends to be inferior, and if it exceeds 3.5, gelation may be promoted during processing.

  Examples of such silane coupling agents include bis (3-triethoxysilylpropyl) polysulfide, bis (2-triethoxysilylethyl) polysulfide, bis (3-trimethoxysilylpropyl) polysulfide, and bis (2-triethoxy). Methoxysilylethyl) polysulfide, bis (4-triethoxysilylbutyl) polysulfide, bis (4-trimethoxysilylbutyl) polysulfide and the like. Among these silane coupling agents, bis (3-triethoxysilylpropyl) disulfide and the like are preferably used from the viewpoint of both the effect of adding the coupling agent and the cost. These silane coupling agents may be used alone or in combination of two or more.

  The content of the silane coupling agent is 1 part by weight or more, preferably 2 parts by weight or more with respect to 100 parts by weight of the silica. When the content of the silane coupling agent is less than 1 part by weight, sufficient effects such as dispersion improvement cannot be obtained. The content of the silane coupling agent is 20 parts by weight or less, preferably 15 parts by weight or less. If the content of the silane coupling agent exceeds 20 parts by weight, the cost is increased, but a sufficient coupling effect cannot be obtained, and the reinforcement and wear resistance are deteriorated. Considering the dispersion effect and the coupling effect, the content of the silane coupling agent is preferably 2 to 15 parts by weight.

  The rubber composition for a tire tread of the present invention contains a stearic acid metal salt. Examples of the metal stearate include magnesium stearate, magnesium 12-hydroxystearate, calcium stearate, calcium 12-hydroxystearate, barium stearate, barium 12-hydroxystearate, zinc stearate, zinc 12-hydroxystearate and the like. can give. Alkaline earth metal salts are preferred from the standpoint of improving heat resistance and compatibility with epoxidized natural rubber, and calcium stearate, 12-hydroxycalcium stearate, barium stearate, and barium 12-hydroxystearate are more preferred.

  The content of the stearic acid metal salt is 1 part by weight or more, preferably 1.5 parts by weight or more with respect to 100 parts by weight of the rubber component. When the content of the stearic acid metal salt is less than 1 part by weight, a sufficient compatibility effect and heat resistance improvement effect cannot be obtained. The content of the stearic acid metal salt is 10 parts by weight or less, preferably 8 parts by weight or less. If the content of the stearic acid metal salt exceeds 10 parts by weight, it is not preferable because the hardness and modulus decrease and the wear resistance deteriorates.

  In addition to the epoxidized natural rubber, diene rubber, silica, silane coupling agent, and stearic acid metal salt, the rubber composition for a tire tread of the present invention includes a reinforcing agent such as carbon black, an oil as necessary. A compounding agent used in a normal rubber industry such as a softening agent such as anti-aging agent, a vulcanizing agent such as sulfur, a vulcanization accelerator, and a vulcanization acceleration aid can be appropriately blended.

  The tire of the present invention is produced by a usual method using the rubber composition for a tire tread of the present invention. That is, if necessary, the rubber composition for a tire tread of the present invention blended with the above compounding agent is extruded in accordance with the shape of each member of the tire at an unvulcanized stage, and is usually used on a tire molding machine. An unvulcanized tire is formed by molding by the method. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this does not limit the objective of this invention.

Examples 1-4 and Comparative Examples 1-3
(1) Description of various chemicals Natural rubber: RSS # 3
Epoxidized natural rubber: ENR-50 (epoxidation rate: 50 mol%) manufactured by Kumplan Guthrie Berhad (Malaysia)
Styrene butadiene rubber: SBR1502 (styrene unit amount: 23.5% by weight) manufactured by JSR Corporation
Silica: Ultrasil VN3 manufactured by Degussa (N ₂ SA: 210 m ² / g)
Silane coupling agent: Si266 (bis (3-triethoxysilylpropyl) disulfide) manufactured by Degussa (average value of l in the formula: 2.2)
_{(C 2 H 5 O) 3} -Si- (CH 2) 3 -S l - (CH 2) 3 -Si- (OC 2 H 5) 3
Calcium stearate: GF200 manufactured by NOF Corporation
Barium stearate: Barium stearate anti-aging agent manufactured by Sakai Chemical Industry Co., Ltd .: NOCRACK 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. Phenylenediamine)
Stearic acid: Zinc stearate oxide manufactured by Nippon Oil & Fats Co., Ltd .: Zinc Hana No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Sulfur powder vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. Noxeller NS (N-tert-butyl-2-benzothiazolylsulfenamide) manufactured by KK
Vulcanization accelerator DPG: Noxeller D (1,3-diphenylguanidine) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

  According to the blending contents of various chemicals shown in Table 1, they were kneaded and blended to obtain various test rubbers. These blends were press vulcanized at 160 ° C. for 20 minutes to obtain vulcanizates, which were tested for the following characteristics.

(2) Explanation of test method <Workability test>
It was measured at 130 ° C. according to the Mooney viscosity measurement method defined in JIS K6300. The Mooney viscosity (ML1 + 4) of Comparative Example 1 was set to 100, and indexed by the following calculation formula. The larger the index, the lower the Mooney viscosity and the better the processability.
(Mooney viscosity index) =
(ML1 + 4 of Comparative Example 1) / (ML1 + 4 of each formulation) × 100

<Abrasion test>
With a Lambourn abrasion tester, the Lambourne wear amount was measured under the conditions of a temperature of 20 ° C., a slip rate of 20% and a test time of 5 minutes, and the volume loss of each formulation was calculated. Expressed as an index using the formula. The higher the index, the better the wear resistance.
(Abrasion index) = (loss amount of Comparative Example 1) / (loss amount of each formulation) × 100

<Rolling resistance test>
Using a viscoelastic spectrometer VES (manufactured by Iwamoto Seisakusho Co., Ltd.), tan δ of each formulation was measured under the conditions of a temperature of 70 ° C., an initial strain of 10%, and a dynamic strain of 2%. The index was expressed by the following formula. The larger the index, the better the rolling resistance characteristics.
(Rolling resistance index) = (tan δ of Comparative Example 1) / (tan δ of each formulation) × 100

<Wet skid index>
Measurement was performed according to the method of ASTM E300-83 using a portable skid tester manufactured by Stanley, and the measured value of Comparative Example 1 was set to 100 and indicated by the following formula. The larger the index, the better the wet grip performance.
(Wet skid index) = (Numerical value of each formulation) / (Numerical value of Comparative Example 1) × 100

(Tensile test)
Based on JIS K6251, the tensile stress at 100% tension (100% modulus), the stress at break, and the elongation at break were measured.

(hardness)
The type A durometer hardness was measured in accordance with JIS K6253.

(Heat aging test)
The vulcanized rubber was allowed to stand at 80 ° C. for 96 hours, and then the tensile test and hardness were measured. The larger the index, the better the heat resistance.
(100% modulus after aging) =
(100% modulus before aging) / (100% modulus after aging) × 100
(Stress at break after aging) =
(Stress at break after aging) / (Stress at break before aging) × 100
(Elongation at break after aging) =
(Elongation at break after aging) / (Elongation at break before aging) × 100
(Hardness after aging) = (Hardness before aging) / (Hardness after aging) × 100

  According to the results in Table 1, it can be seen that the tensile properties, wear resistance, and post-heat aging properties are improved by blending the metal stearate.

  According to the results in Table 2, it can be seen that the wear resistance and rolling resistance characteristics are greatly improved by blending the metal stearate in the blend blend of epoxidized natural rubber and natural rubber. Moreover, it can be seen that the characteristics after heat aging are also improved, and in particular, the improvement range of 100% modulus is large.

  According to the results shown in Table 3, it is understood that the wear resistance and the characteristics after heat aging are improved by blending the metal stearate in the blend blend of epoxidized natural rubber and styrene butadiene rubber.

Claims (2)

For 100 parts by weight of a rubber component containing 5 to 100% by weight of epoxidized natural rubber,
5 to 150 parts by weight of silica having a nitrogen adsorption specific surface area of 100 to 300 m ² / g,
A rubber composition for a tire tread containing 1 to 10 parts by weight of an alkaline earth metal stearate and 1 to 20 parts by weight of a silane coupling agent represented by the following formula with respect to 100 parts by weight of the silica.
_{(C n H 2n + 1 O} ) 3 -Si- (CH 2) m -S l - (CH 2) m -Si- (C n H 2n + 1 O) 3
(Wherein, n is an integer of 1 to 3, m is an integer of 1 to 4, l is reveal the number of sulfur atoms in the polysulfide part, is 2.1 to 3.5) Pneumatic tire using the claim 1 Symbol mounting of the tire tread rubber composition.