JP2012126852A - Tire rubber composition and racing tire - Google Patents

Tire rubber composition and racing tire Download PDF

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JP2012126852A
JP2012126852A JP2010281019A JP2010281019A JP2012126852A JP 2012126852 A JP2012126852 A JP 2012126852A JP 2010281019 A JP2010281019 A JP 2010281019A JP 2010281019 A JP2010281019 A JP 2010281019A JP 2012126852 A JP2012126852 A JP 2012126852A
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mass
parts
rubber composition
tire
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Koji Fujisawa
Takeo Nakazono
健夫 中園
浩二 藤澤
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Sumitomo Rubber Ind Ltd
住友ゴム工業株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide a tire rubber composition in which wet grip performance, wear resistance and steering stability are improved in a well-balanced state, and a racing tire using the same.SOLUTION: The tire rubber composition comprises a liquid coumarone-indene resin having a softening point of -20 to 20°C, a liquid rosin-based resin having a softening point of -20 to 20°C, and aluminum hydroxide.

Description

The present invention relates to a rubber composition for tires and a racing tire using the same.

Aluminum hydroxide is generally blended for the purpose of improving wet grip performance in treads for competition tires applied to races and the like, particularly wet tires for competition applied to wet road surfaces.

However, when aluminum hydroxide is blended, the wear resistance is lowered, and when it goes around, the grip performance is also deteriorated due to wear appearance defects (ablation, chipping, etc.). In addition, when the traveling distance is extended by traveling for a long time, the tire temperature rises and the steering stability is deteriorated.

On the other hand, an increase in the amount of carbon black improves mechanical strength and improves wear resistance and handling stability, but tends to deteriorate wet grip performance. Thus, it is difficult to improve wet grip performance, wear resistance, and steering stability in a balanced manner.

For example, in Patent Document 1, carbon black, silica and oil having a specific nitrogen specific surface area are blended with styrene-butadiene copolymer rubber and butadiene rubber having a specific styrene content and vinyl content to improve grip performance, hardness, and rigidity. A racing tire is disclosed. However, there is still room for improvement in terms of improving the wet grip performance, wear resistance, and steering stability in a well-balanced manner.

JP 2005-139230 A

An object of the present invention is to solve the above-mentioned problems and provide a rubber composition for tires with improved wet grip performance, wear resistance and steering stability in a well-balanced manner, and a racing tire using the same.

The present invention relates to a tire rubber composition containing a liquid coumarone indene resin having a softening point of -20 to 20 ° C, a liquid rosin resin having a softening point of -20 to 20 ° C, and aluminum hydroxide. Here, the total content of the liquid coumarone indene resin and the liquid rosin resin with respect to 100 parts by mass of the rubber component is preferably 2 to 100 parts by mass.

The acid value of the liquid rosin resin is preferably 10 to 100 mgKOH / g, and the hydroxyl value is preferably 50 to 150 mgKOH / g. The liquid rosin resin is preferably a rosin ester resin.

The tire rubber composition is preferably used as a tread rubber composition.
The present invention also relates to a racing tire produced using the rubber composition.

According to the present invention, since it is a rubber composition for tires containing liquid coumarone indene resin and liquid rosin resin having a specific softening point, and aluminum hydroxide, the rubber composition can be applied to a tread. In addition, it is possible to provide a racing tire with improved wet grip performance, wear resistance and handling stability in a well-balanced manner.

The rubber composition for tires of the present invention contains liquid coumarone indene resin and liquid rosin resin having a specific softening point, and aluminum hydroxide. While the wet grip performance, particularly the initial wet grip performance, can be improved by blending aluminum hydroxide, the wear resistance and steering stability are reduced. About this, even if it mix | blends high melting point (60 degreeC or more) solid resin, temperature dependence becomes large and initial stage grip performance falls. On the other hand, in the present invention, a liquid coumarone indene resin and a liquid rosin resin having a specific softening point in addition to aluminum hydroxide are further blended to maintain a good wet grip performance while maintaining a poor wear appearance (ablation). , Chipping, etc.), can improve steering stability. Therefore, the aforementioned performance can be improved in a well-balanced manner.

Examples of the rubber component used in the present invention include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), and ethylene propylene diene rubber. Examples thereof include diene rubbers such as (EPDM), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), and butyl rubber (IIR). A rubber component may be used independently and may use 2 or more types together. Among these, SBR is preferable because wet grip performance, wear resistance, and steering stability are improved in a well-balanced manner.

The SBR is not particularly limited, and those generally used in the tire industry such as emulsion polymerization styrene butadiene rubber (E-SBR) and solution polymerization styrene butadiene rubber (S-SBR) can be used. Of these, S-SBR is preferable.

The styrene content of SBR is preferably 10% by mass or more, more preferably 25% by mass or more. If it is less than 10% by mass, sufficient wet grip performance may not be obtained. The styrene content is preferably 80% by mass or less, more preferably 55% by mass or less. When it exceeds 80 mass%, rubber | gum will become hard and there exists a tendency for wet grip performance to fall.
In the present invention, the styrene content of SBR is calculated by H 1 -NMR measurement.

The content of SBR in 100% by mass of the rubber component is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass. If it is less than 70% by mass, sufficient wet grip performance cannot be obtained, and the above performance may not be improved in a balanced manner.

The rubber composition of the present invention contains a liquid coumarone indene resin and a liquid rosin resin each having a specific softening point. By using these liquid resins instead of oil, it is possible to obtain good wet grip performance and at the same time improve wear resistance and steering stability.

The liquid coumarone indene resin is a coumarone indene resin having the following softening points. Here, the coumarone indene resin is a resin containing coumarone and indene as a monomer component constituting the skeleton (main chain) of the resin, and monomer components contained in the skeleton other than coumarone and indene include styrene, α- Examples include methylstyrene, methylindene, vinyltoluene and the like.

The softening point of the liquid coumarone indene resin is −20 ° C. or higher, preferably −5 ° C. or higher, more preferably 0 ° C. or higher. When the temperature is lower than -20 ° C, the viscosity becomes too low, so that the kneadability with the rubber component and the dispersibility in the rubber composition are lowered, and the wear resistance and steering stability tend to be deteriorated. Moreover, this softening point is 20 degrees C or less, Preferably it is 18 degrees C or less, More preferably, it is 17 degrees C or less. If it exceeds 20 ° C, the wet grip performance tends to deteriorate.
The softening point of the liquid coumarone indene resin is a temperature at which the sphere descends when the softening point specified in JIS K 6220 is measured with a ring and ball softening point measuring device.

The content of the liquid coumarone indene resin is preferably 1 part by mass or more, more preferably 2 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, the effect of improving the wear resistance tends to be small. Moreover, this content becomes like this. Preferably it is 50 mass parts or less, More preferably, it is 45 mass parts or less, More preferably, it is 30 mass parts or less. When it exceeds 50 parts by mass, the temperature dependency increases and the initial grip performance tends to deteriorate.

The liquid rosin resin is a rosin resin having the following softening points. Here, as rosin resin, raw material rosin such as gum rosin, wood rosin, tall oil rosin; disproportionate of raw material rosin; stabilized rosin obtained by hydrogenating raw material rosin; rosins such as polymerized rosin; Various known products such as esterified products (rosin ester resins), phenol-modified products, unsaturated acid (maleic acid, etc.)-Modified rosins, and formylated rosins obtained by reducing rosins can be used. Among these, a rosin ester resin is preferable from the viewpoint of improving wear resistance and improving the above balance. The rosin ester resin is obtained by an esterification reaction of the rosin and a polyol (polyhydric alcohol such as glycerin or pentaerythritol).

The softening point of the liquid rosin resin is −20 ° C. or higher, preferably −5 ° C. or higher, more preferably 0 ° C. or higher. When the temperature is lower than -20 ° C, the viscosity becomes too low, so that the kneadability with the rubber component and the dispersibility in the rubber composition are lowered, and the wear resistance and steering stability tend to be deteriorated. Moreover, this softening point is 20 degrees C or less, Preferably it is 18 degrees C or less, More preferably, it is 17 degrees C or less. If it exceeds 20 ° C, the wet grip performance tends to deteriorate.
The softening point of the liquid rosin resin is the temperature at which the sphere descends when the softening point specified in JIS K 5902 is measured with a ring and ball softening point measuring device.

The acid value (mgKOH / g) of the liquid rosin resin is preferably 10 or more, more preferably 20 or more, and still more preferably 30 or more. The acid value is preferably 100 or less, more preferably 80 or less, and still more preferably 50 or less. When the acid value is within the above range, wear resistance and steering stability can be improved.
In the present invention, the acid value represents the amount of potassium hydroxide required to neutralize the acid contained in 1 g of the resin in milligrams, and is a value measured by potentiometric titration (JIS K0070). .

The hydroxyl value (mgKOH / g) of the liquid rosin resin is preferably 50 or more, more preferably 60 or more. The hydroxyl value is preferably 150 or less, more preferably 100 or less. When the hydroxyl value is within the above range, wear resistance and steering stability can be improved.
In the present invention, the hydroxyl value is the amount of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of the resin is acetylated. The potentiometric titration method (JIS K0070). It is the value measured by.

The content of the liquid rosin resin is preferably 1 part by mass or more, more preferably 2 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, the effect of improving the wear resistance tends to be small. Moreover, this content becomes like this. Preferably it is 50 mass parts or less, More preferably, it is 45 mass parts or less, More preferably, it is 30 mass parts or less. When it exceeds 50 parts by mass, the temperature dependency increases and the initial grip performance tends to deteriorate.

The total content of the liquid coumarone indene resin and the liquid rosin resin is 2 parts by mass or more, preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 2 parts by mass, the effect of improving wear resistance and steering stability may not be sufficiently obtained. Moreover, the said total content is 100 mass parts or less, Preferably it is 50 mass parts or less. If it exceeds 100 parts by mass, the initial grip performance tends to deteriorate.

The rubber composition of the present invention contains aluminum hydroxide. As a result, the hardness at low temperature is reduced, and good wet grip performance is obtained. It does not specifically limit as aluminum hydroxide, A general thing can be used in the tire industry.

The average primary particle diameter of aluminum hydroxide is preferably 0.5 μm or more, more preferably 0.8 μm or more. If it is less than 0.5 μm, it becomes difficult to disperse aluminum hydroxide, and the wear resistance tends to deteriorate. The average primary particle size is preferably 10 μm or less, more preferably 5 μm or less. When it exceeds 10 μm, aluminum hydroxide becomes a fracture nucleus and wear resistance tends to deteriorate.
In the present invention, the average primary particle diameter of aluminum hydroxide is the number average particle diameter, and is measured by a transmission electron microscope.

The content of aluminum hydroxide is preferably 0.5 parts by mass or more, more preferably 1 part 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 0.5 parts by mass, the effect of improving wet grip performance may be small. Further, the content of the aluminum hydroxide is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less. If it exceeds 50 parts by mass, poor dispersion may occur and the wear resistance may be deteriorated.

The rubber composition of the present invention preferably uses silica. As a result, wet grip performance can be improved, and an effect of improving wear resistance and steering stability can be obtained. Examples of silica include dry method silica (anhydrous silicic acid), wet method silica (hydrous silicic acid), and the like. Of these, wet silica is preferred.

The nitrogen adsorption specific surface area (N 2 SA) of silica is preferably 200 m 2 / g or more, more preferably 250 m 2 / g or more. If it is less than 200 m 2 / g, there is a tendency that sufficient reinforcing properties cannot be obtained. Further, N 2 SA of silica is preferably 350 m 2 / g or less, more preferably 300 m 2 / g or less. When it exceeds 350 m < 2 > / g, the viscosity of an unvulcanized rubber composition will become high and there exists a tendency for workability to deteriorate.
The N 2 SA of silica is a value measured by the BET method in accordance with ASTM D3037-81.

The content of silica is preferably 30 parts by mass or more, more preferably 45 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 30 parts by mass, there is a tendency that sufficient wet grip performance improvement effect cannot be obtained. The content is preferably 200 parts by mass or less, more preferably 190 parts by mass or less, and still more preferably 130 parts by mass or less. If it exceeds 200 parts by mass, the dispersibility tends to deteriorate and the wear resistance tends to decrease.

The rubber composition of the present invention preferably uses a silane coupling agent in combination with silica. As the silane coupling agent, any silane coupling agent conventionally used in combination with silica can be used in the rubber industry. For example, sulfide systems such as bis (3-triethoxysilylpropyl) tetrasulfide, 3 -Mercapto type such as mercaptopropyltrimethoxysilane, vinyl type such as vinyltriethoxysilane, amino type such as 3-aminopropyltriethoxysilane, glycidoxy type of γ-glycidoxypropyltriethoxysilane, 3-nitropropyltri Examples thereof include nitro compounds such as methoxysilane and chloro compounds such as 3-chloropropyltrimethoxysilane. These may be used alone or in combination of two or more. Among these, sulfide type is preferable, and bis (3-triethoxysilylpropyl) tetrasulfide is more preferable.

The content of the silane coupling agent is preferably 8 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of silica. If it is less than 8 parts by mass, the wear resistance tends to deteriorate. Further, the content of the silane coupling agent is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. When it exceeds 40 parts by mass, there is a tendency that an effect commensurate with the increase in cost cannot be obtained.

The rubber composition of the present invention preferably uses carbon black. As a result, wet grip performance can be improved, and an effect of improving wear resistance and steering stability can be obtained. As the carbon black, for example, those generally used in the tire industry such as GPF, HAF, ISAF, and SAF can be used.

The nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 80 m 2 / g or more, more preferably 120 m 2 / g or more. If it is less than 80 m < 2 > / g, there exists a tendency for sufficient reinforcement property not to be acquired. Also, N 2 SA of carbon black is preferably 220 m 2 / g, more preferably at most 180 m 2 / g. When it exceeds 220 m < 2 > / g, the viscosity of an unvulcanized rubber composition will become high and there exists a tendency for workability to deteriorate.
The N 2 SA of carbon black is determined by the A method of JIS K6217.

The content of carbon black is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 5 parts by mass, there is a tendency that sufficient wet grip performance improvement effect cannot be obtained. The content is preferably 200 parts by mass or less, more preferably 190 parts by mass or less, and still more preferably 100 parts by mass or less. If it exceeds 200 parts by mass, the dispersibility tends to deteriorate and the wear resistance tends to decrease.

Further, the total content of aluminum hydroxide, silica and carbon black is preferably 50 parts by mass or more, more preferably 75 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 50 parts by mass, the wet grip performance, wear resistance, and steering stability may not be obtained in a well-balanced manner. The total content is preferably 200 parts by mass or less, more preferably 150 parts by mass or less. If it exceeds 200 parts by mass, the wear resistance and steering stability may be reduced.

The rubber composition of the present invention contains oil. Thereby, favorable wet grip performance is obtained.

The oil is not particularly limited, and examples thereof include process oils such as paraffinic process oil, naphthenic process oil, and aromatic process oil (aromatic oil). Of these, aromatic process oils are preferred because good wet grip performance can be obtained.

The oil content is preferably 50 parts by mass or more, more preferably 60 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 50 parts by mass, the wet grip performance may not be sufficiently improved. The oil content is preferably 150 parts by mass or less, more preferably 100 parts by mass or less. When it exceeds 150 parts by mass, the wear resistance and the steering stability tend to deteriorate.
The oil content includes the amount of oil contained in rubber (oil-extended rubber).

In the rubber composition of the present invention, in addition to the above components, compounding agents generally used in the production of rubber compositions, such as zinc oxide, stearic acid, various anti-aging agents, vulcanizing agents such as wax and sulfur, A vulcanization accelerator or the like can be appropriately blended.

The rubber composition of the present invention is produced by a general method. That is, it can be produced by a method of kneading the above components with a Banbury mixer, kneader, open roll or the like and then vulcanizing.

The rubber composition of the present invention is used for each member of a tire and is suitably used for a tread (particularly a cap tread).

The racing tire of the present invention is manufactured by a normal method using the rubber composition. That is, a rubber composition containing the above components is extruded into a desired shape such as a tread at an unvulcanized stage and molded together with other tire members on a tire molding machine by a normal method. Thus, an unvulcanized tire is formed. A pneumatic tire (competition tire) can be manufactured by heating and pressurizing the unvulcanized tire in a vulcanizer.

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

Hereinafter, various chemicals used in Examples and Comparative Examples will be described together.
SBR: Toughden 4850 manufactured by Asahi Kasei Chemicals Corporation (styrene content: 39% by mass, containing 50 parts by mass of oil with respect to 100 parts by mass of rubber solid content)
Carbon black: Dia Black A (N110, N 2 SA: 142 m 2 / g) manufactured by Mitsubishi Chemical Corporation
Silica: Nipsil VN3 manufactured by Tosoh Silica Corporation (N 2 SA: 270 m 2 / g)
Aluminum hydroxide: Heidilite H-43 (average primary particle size: 1 μm) manufactured by Showa Denko KK
Anti-aging agent 6C: Santoflex 13 manufactured by Flexis Co., Ltd.
Anti-aging agent 224: NOCRACK 224 manufactured by Ouchi Shinsei Chemical Co., Ltd.
Stearic acid: Zinc stearate made by NOF Corporation: Zinc oxide 2 types aroma oil made by Mitsui Mining & Smelting Co., Ltd. Process X-260 made by Japan Energy
Resin: Neopolymer 140 manufactured by Nippon Petrochemical Co., Ltd.
Liquid coumarone indene resin 1: NOVARES C10 (softening point: 5 to 15 ° C.) manufactured by Rutgers Chemicals
Liquid coumarone indene resin 2: L20 (softening point: 20 ° C.) manufactured by Nikko Chemical Co., Ltd.
Liquid rosin resin: ke-364c (rosin ester resin, acid value: 35 mgKOH / g, hydroxyl value: 97 mgKOH / g, softening point: 5 to 15 ° C.) manufactured by Arakawa Chemical Industries, Ltd.
Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator NS manufactured by Tsurumi Chemical Co., Ltd. NS: Noxeller NS manufactured by Ouchi Shinsei Chemical Co., Ltd.

<Examples and Comparative Examples>
In accordance with the formulation shown in Table 1, materials other than sulfur and a vulcanization accelerator were kneaded for 3 minutes at 150 ° C. using a Kobe Steel 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes at 50 ° C. using an open roll to obtain an unvulcanized rubber composition.
The obtained unvulcanized rubber composition was press vulcanized at 170 ° C. for 12 minutes to obtain a vulcanized rubber composition.
The obtained unvulcanized rubber composition was molded into a tread shape, pasted with other tire members, molded into a tire, and vulcanized at 170 ° C. for 12 minutes to produce a test cart tire.

The following evaluation was performed using the obtained vulcanized rubber composition and test cart tire. The results are shown in Table 1.

(SWELL)
The vulcanized rubber composition was extracted with toluene, and the volume change rate (SWELL) before and after extraction was measured. In addition, the smaller the SWELL, the more preferable the variation in crosslinking can be suppressed.

(Viscoelasticity test)
Using a viscoelastic spectrometer manufactured by Iwamoto Seisakusho Co., Ltd., the viscoelasticity (complex elastic modulus E ′ and the elastic modulus E ′) of the vulcanized rubber composition at 0 ° C. and 40 ° C. under conditions of an initial strain of 10% and a vibration frequency of 10 Hz. Loss tangent tan δ) was measured (0 ° C .: dynamic strain 1%, 40 ° C .: dynamic strain 2%). The greater E ′, the better the steering stability, and the greater tan δ, the better the wet grip performance.

(Tensile test)
According to JIS K 6251 “Vulcanized rubber and thermoplastic rubber-Determination of tensile properties”, a tensile test was conducted using a No. 3 dumbbell type rubber test piece made of the above vulcanized rubber composition, and the stress at 300% elongation was (M300) was measured. The M300 index of Comparative Example 1 was set to 100, and M300 of each formulation was displayed as an index by the following calculation formula. The greater the M300 index, the better the abrasion resistance (ablation resistance).
(M300 index) = (M300 of each formulation) / (M300 of Comparative Example 1) × 100

(Actual vehicle evaluation)
The test cart tire is mounted on the test cart, and the test course (wet road surface) of 1 lap is run 8 laps. The initial wet grip performance (1st to 4th lap), steering stability (by the driver's sensory evaluation) 5 to 8 laps) were evaluated. Further, after running for 8 laps, the vehicle was re-traveled 10 more times, and the wear state of the tire after running was visually observed to evaluate the wear resistance. Each evaluation was displayed on a 5-point scale with Comparative Example 1 as 3 points. The larger the value, the better the performance.

From Table 1, in Comparative Example 2 using aluminum hydroxide, although wet grip performance was improved as compared with Comparative Example 1, there was a significant decrease in wear resistance and steering stability. On the other hand, in the examples in which aluminum hydroxide, liquid coumarone indene resin and liquid rosin resin were blended, excellent wet grip performance was obtained, and at the same time, the improvement effect of wear resistance and steering stability was seen. The balance was improved.

Claims (6)

  1. A tire rubber composition comprising a liquid coumarone indene resin having a softening point of -20 to 20 ° C, a liquid rosin resin having a softening point of -20 to 20 ° C, and aluminum hydroxide.
  2. The tire rubber composition according to claim 1, wherein the total content of the liquid coumarone indene resin and the liquid rosin resin is 2 to 100 parts by mass with respect to 100 parts by mass of the rubber component.
  3. The tire rubber composition according to claim 1 or 2, wherein the liquid rosin resin has an acid value of 10 to 100 mgKOH / g and a hydroxyl value of 50 to 150 mgKOH / g.
  4. The rubber composition for tires according to any one of claims 1 to 3, wherein the liquid rosin resin is a rosin ester resin.
  5. The tire rubber composition according to any one of claims 1 to 4, which is used as a tread rubber composition.
  6. A racing tire produced using the rubber composition according to claim 1.
JP2010281019A 2010-12-16 2010-12-16 Tire rubber composition and racing tire Pending JP2012126852A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013053296A (en) * 2011-08-09 2013-03-21 Sumitomo Rubber Ind Ltd Rubber composition for tire and pneumatic tire
WO2016056443A1 (en) * 2014-10-06 2016-04-14 住友ゴム工業株式会社 Rubber composition and pneumatic tire
JP2016074810A (en) * 2014-10-06 2016-05-12 住友ゴム工業株式会社 Rubber composition and pneumatic tire
JP2016094520A (en) * 2014-11-13 2016-05-26 住友ゴム工業株式会社 Rubber composition and pneumatic tire

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013053296A (en) * 2011-08-09 2013-03-21 Sumitomo Rubber Ind Ltd Rubber composition for tire and pneumatic tire
WO2016056443A1 (en) * 2014-10-06 2016-04-14 住友ゴム工業株式会社 Rubber composition and pneumatic tire
JP2016074810A (en) * 2014-10-06 2016-05-12 住友ゴム工業株式会社 Rubber composition and pneumatic tire
US10414906B2 (en) 2014-10-06 2019-09-17 Sumitomo Rubber Industries, Ltd. Rubber composition and pneumatic tire
JP2016094520A (en) * 2014-11-13 2016-05-26 住友ゴム工業株式会社 Rubber composition and pneumatic tire

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