KR20170042931A - Composition for tire treads in which the abrasion and braking ability are improved, master batch composition for tire treads and manufacturing method thereof - Google Patents

Composition for tire treads in which the abrasion and braking ability are improved, master batch composition for tire treads and manufacturing method thereof Download PDF

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KR20170042931A
KR20170042931A KR1020150142157A KR20150142157A KR20170042931A KR 20170042931 A KR20170042931 A KR 20170042931A KR 1020150142157 A KR1020150142157 A KR 1020150142157A KR 20150142157 A KR20150142157 A KR 20150142157A KR 20170042931 A KR20170042931 A KR 20170042931A
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South Korea
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composition
rubber
tire tread
master batch
biir
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KR1020150142157A
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Korean (ko)
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김형석
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현대자동차주식회사
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Publication of KR20170042931A publication Critical patent/KR20170042931A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins

Abstract

The present invention relates to a composition for tire treads which comprises bromobutyl rubber highly effective for improving a braking distance in combination with single-walled carbon nanotubes, and thus has improved abrasion and braking performance. The present invention also relates to a master batch composition for tire treads and a method for preparing the same. The composition for tire treads according to the present invention uses a master batch in which single-walled carbon nanotubes having improved chemical and mechanical binding force between the raw material of rubber and the filler in the composition and capable of improving abrasion performance are dispersed in combination with bromobutyl rubber having excellent frictional properties to show high grip force upon the application to tire treads and thus ensuring excellent braking performance. Therefore, it is possible to improve abrasion and braking performance as compared to the conventional composition for tire treads.

Description

FIELD OF THE INVENTION The present invention relates to a composition for a tire tread having improved wear and braking performance, a master batch composition for a tire tread, and a method for manufacturing the same,

The present invention relates to a tire tread composition for improving wear and braking performance of a tire tread, and more particularly, to a tire tread composition for a tire tread, which further comprises a single-walled carbon nanotube with bromobutyl rubber excellent in braking distance improvement, To an improved composition for a tire tread, a master batch composition for a tire tread, and a method of manufacturing the same.

Development of tires is important in recently developed high performance vehicles, and development of high performance tires with improved braking performance and handling performance of tires is particularly demanded. In terms of environmental aspects, it also reduces fuel consumption and CO 2 emissions, reduces fine solid particles such as carbon black and silica that are released when tires are worn, improves stability during braking, and extends the service life of tires. In addition to the performance, we are basically trying not to reduce the braking performance significantly.

In order to improve the performance of such a tire, it is very important to design the rubber composition that basically constitutes the tire so as to satisfy the required characteristics of the tire as well as the manufacturing technology of the tire itself.

In the rubber composition used in the conventional tire manufacturing, solution-styrene-butadiene rubber (SSBR) is used as a raw material rubber, and natural rubber (NR) or butadiene rubber (BR) 1,4-polybutadiene, and silica, the wear performance is improved. On the contrary, the braking performance is decreased, and the braking distance is increased, and the handling performance is deteriorated.

In order to overcome such disadvantages, carbon black or silica is further used as a reinforcing filler. For example, when the silica is highly charged, the process conditions are difficult, and if the silane coupling agent for silica and the surface modification of the silica nanoparticles does not react, the mechanical properties of the tire tread decrease. If carbon black is additionally added, And rubber, it is possible to obtain a rubber composition for tire tread with reduced rolling resistance and abrasion resistance at the same time. However, when the filler is used, the viscosity increases rapidly, There is a drawback that difficulty follows.

In particular, in the case of high performance tires (ultra high performance tires, UHP tires), dispersion of the inorganic fillers used to sufficiently exhibit their performance is very important, and this is basically influenced by the workability of the raw rubber, It is an important factor that has a great influence on tire performance as well as physical properties.

Korean patent application No. 2012-7032346

However, since the excellent braking performance and the abrasion performance of the tire have mutual interest-rate traits, it is very difficult to manufacture a rubber which satisfies both of them at the same time.

In view of the above, the present invention applies bromo butyl rubber (BIIR), which is excellent in improving the braking distance, in order to improve the braking performance of the tire and at the same time to improve the abrasion performance, (SWCNT), and the braking performance and the abrasion performance of the tire are improved. In addition, since the handling performance is lowered due to the lowering of the friction performance, the tire tread And to provide a composition for use in the present invention.

In view of the above, the present invention provides a master for tire tread in which bromo butyl rubber (BIIR) and single-walled carbon nanotubes (SWCNT) are uniformly dispersed so that performance of abrasion, There is a further object in providing batch compositions and methods of making the same.

In order to achieve the above object, the present invention provides a composition for a tire tread comprising a solution-styrene-butadiene rubber (SSBR) as a raw material rubber, wherein the composition comprises a bromo-butyl rubber butyl rubber (BIIR) in which a single-walled carbon nanotube is dispersed.

The content of the bromobutyl rubber (BIIR) is preferably 7 to 14 phr based on 100 parts by weight of the rubber. If the content of the bromobutyl rubber (BIIR) is less than 6 phr, the content of the bromobutyl rubber (BIIR) is insufficient and the wear resistance is insufficient. When the content of the bromobutyl rubber (BIIR) exceeds 14 phr, (BIIR) has lower abrasion performance than conventional natural rubber (NR) or butadiene rubber (BR), which causes abrasion performance to deteriorate rapidly, shortening tire life.

The content of the single-walled carbon nanotubes is preferably 1.0 to 1.5 wt% based on 100 wt% of the total weight of the master batch. If the content of the single-walled carbon nanotubes is 0.5 wt% or less, There is no effect of reinforcing the abrasion performance because the content is small, and when 2 wt% or more is added, the hardness is rapidly increased, so that it is not suitable for use as a composition of a tire tread.

The composition for tire tread may further include carbon black and silica as a filler.

On the other hand, the composition of the masterbatch for tire treads applied in the present invention comprises 7 to 14 phr of bromobutyl rubber (BIIR) based on 100 parts by weight of rubber, and a single wall carbon And 1.0 to 1.5 wt% of the nanotubes.

The masterbatch composition for tire tread may be prepared by mixing a single-walled carbon nanotube with a surfactant and then dispersing the mixture by applying ultrasonic waves (S210), adding a liquid bromobutyl rubber a second step S220 of mixing the single wall carbon nanotubes dispersed in the first step S210 with rubber, BIIR, and a third step S230 of obtaining the master batch composition by drying the mixture of the two steps at a high temperature ).

The masterbatch composition for tire tread according to claim 1, wherein the bromo butyl rubber (BIIR) comprises 7 to 14 phr based on 100 parts by weight of the rubber, and the single wall carbon nanotubes have a total weight And 1.0 to 1.5 wt% based on 100 wt%.

Further, in the first step, carbon black and silica may be further added as a filler.

The surfactant is selected from the group consisting of sodium dodecyl sulfate (SDS), lithium dodecyl sulfate (LDS), sodium dodecylbenzenesulfate (NaDDS), sodium dodecylsulfonate (SDSA), sodium dodecylbenzenesulfonate (SDBS) Pyrrolidone (PVP) may be used, but the present invention is not limited thereto.

As shown in FIG. 1, the master batch composition for a tire tread of the present invention produced through the above-described production method can improve the chemical and mechanical bonding force between the raw rubber and the filler in the composition, Bromobutyl rubber (BIIR) and carbon black, which are capable of achieving excellent braking performance by exhibiting a high grip force when applied to a tire tread due to their excellent friction characteristics, are available as single wall carbon nanotubes (SWCNT) Uniformly dispersed to form a net structure. Therefore, the wear resistance of the bromobutyl rubber (BIIR) is improved and the excellent braking performance can be sufficiently exhibited.

The composition for a tire tread according to the present invention is excellent in friction characteristics with a single-walled carbon nanotube (SWCNT) capable of improving wear and abrasion performance by improving the chemical and mechanical bonding force between a raw rubber and a filler in a composition, By using masterbatches with dispersed bromobutyl rubber (BIIR), which gives high grip force when applied to treads and ensures excellent braking performance, it is applied to treads of tires in particular, Improvement can be achieved.

1 is a schematic view of a master batch composition for a tire tread prepared according to an embodiment of the present invention.
2 is a flowchart of a method of manufacturing a master batch composition for a tire tread according to an embodiment of the present invention.

As used herein, the terms " comprising, " " comprising, " or " added to, " and the like shall not be construed as necessarily including the various components or steps described in the specification, Elements or some steps may not be included and should be interpreted as further including additional elements or steps.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, these examples and comparative examples are merely examples of the present invention, and the scope of the present invention is not limited to these examples and comparative examples, and can be variously modified and changed.

Compositions for tire treads according to Examples and Comparative Examples of the present invention were prepared by mixing the components and the contents shown in Table 1 below. In the following Table 1, the unit of the content of each material is phr (part per hundred rubber), which represents the weight of the mixed material with respect to the weight of the raw rubber 100.

division Raw material Filler SSBR-I SSBR-II BIIR Master batch
(SWCNT wt%) BR NR Silica Carbon black Comparative Example 1 27 52 0 0 14 0 70 5 Comparative Example 2 27 52 0 0 0 14 70 5 Comparative Example 3 27 52 0 0 7 7 70 5 Comparative Example 4 27 52 0 0 0 0 70 5 Comparative Example 5 27 52 6 0 0 0 70 5 Comparative Example 6 27 52 7 0 0 0 70 5 Comparative Example 7 27 52 14 0 0 0 70 5 Comparative Example 8 27 52 15 0 0 0 70 5 Comparative Example 9 27 52 21 0 0 0 70 5 Example 1 27 52 0 14
(0.25 wt%) 0 0 70 5 Example 2 27 52 0 14
(0.5 wt%) 0 0 70 5 Example 3 27 52 0 14
(1.0 wt%) 0 0 70 5 Example 4 27 52 0 14
(1.5 wt%) 0 0 70 5 Example 5 27 52 0 14
(2.0 wt%) 0 0 70 5

In Table 1, SSBR-Ⅰ and SSBR-Ⅱ show the content of solution styrene-butadiene rubber (SSBR) polymerized in the raw rubber solution of the composition for tire tread of the present invention. BR is a butadiene rubber ), And NR represents the content of natural rubber.

Also, the master batch is manufactured through the steps of the first step (S210) to the third step (S230) according to the method of manufacturing the master batch composition for a tire tread of the present invention as shown in FIG. 2, The net structure was formed by dispersing carbon black uniformly with bromobutyl rubber (BIIR), single wall carbon nanotube (SWCNT) and filler. In Examples 1 to 5, the total weight of the master batch was 100 wt% The content of the single-wall carbon nanotube (SWCNT) is differently applied.

Specimens were prepared using the composition for tire tread obtained according to Comparative Examples 1 to 9 and Examples 1 to 5 to prepare test specimens for viscoelasticity, hardness, friction and Lambourn abrasion. The performance evaluation was conducted in the following manner, and the results of these experimental examples are shown in Table 2 below.

First, to measure the viscoelastic properties, test specimens of 6 mm, 30 mm, and 2 mm in width, height, and height were measured using GABO dynamic mechanical thermal analyzer (DMTA) , The storage elastic modulus, the loss elastic modulus and the tan delta value are obtained, and the glass transition temperature (Tg) is measured. Also, at this time, the larger the tan δ value at 0 ° C, the better the braking performance on the wet road surface, and the larger the tan δ value at 25 ° C, the better the braking performance on the dry road surface.

The hardness indicates the steady-state handling stability of the specimen. The higher the value, the better the steering stability. In the present invention, the hardness is measured by a Shore A type hardness tester.

The abrasion characteristics are measured by using a rimbone abrasion tester, which is generally used for abrasion evaluation of tire materials, under the same conditions. The test specimens having a diameter of 49 mm and a thickness of 5 mm are used. 25 mm, surface roughness of 240 pads. The difference in speed between the test specimen and the grinding stone is evaluated under the condition of 5% and load of 70 N for 120 minutes to measure the wear characteristics.

In order to evaluate the friction characteristics, test specimens of 25 mm, 300 mm, and 2 mm in width, height, and height were rubbed at a speed of 30 km / h and a road slip rate of 0 to 40% at 70N using a friction braking tester of UESHIMA Co., .

Further, when the composition for tire tread according to an embodiment of the present invention is applied to a tire, the braking distance of the actual vehicle on the dry road surface and the performance of the headlamp ring are measured through the actual vehicle test to verify the reliability of the tire.

division Viscoelastic properties Hardness Wear characteristics Friction characteristic Actual vehicle test Tg (占 폚) Tanδ @ 0 C Tanδ @ 25 ℃ Shorea Rambo wear Coefficient of friction Braking distance (m) handling Comparative Example 1 -11 0.455 0.207 65 0.287 1.576 44.47 7 Comparative Example 2 -12 0.448 0.205 65 0.279 1.542 44.68 6+ Comparative Example 3 -12 0.441 0.198 65 0.272 1.533 44.80 6+ Comparative Example 4 -11 0.457 0.209 65 0.294 1.581 44.31 6+ Comparative Example 5 -10.5 0.457 0.210 65 0.296 1.582 44.30 7 Comparative Example 6 -10.5 0.459 0.218 65 0.302 1.589 44.18 7 Comparative Example 7 -10 0.463 0.226 65 0.308 1.625 43.31 7+ Comparative Example 8 -9.5 0.475 0.236 65 0.338 1.656 42.61 7+ Comparative Example 9 -9.5 0.485 0.247 65 0.378 1.685 42.31 7+ Example 1 -10 0.460 0.221 65 0.309 1.612 43.61 7+ Example 2 -10 0.461 0.222 66 0.307 1.612 43.57 7+ Example 3 -10 0.458 0.225 67 0.293 1.618 43.46 7+ Example 4 -10 0.467 0.233 68 0.288 1.623 43.34 7+ Example 5 -10 0.453 0.221 75 0.306 1.607 43.77 7+

In Table 2, 'Tg' is the glass transition temperature, 'Tanδ @ 0 ° C' is the Tanδ value at 0 ° C, and 'Tanδ @ 25 ° C' is the Tanδ value at 25 ° C.

Referring to the above Table 2, it can be seen that in the viscoelastic properties, in comparison with compositions using natural rubber (NR) and butadiene rubber (BR) as in Comparative Examples 1 to 3, (SWCNT) is distributed, the viscoelastic characteristics, that is, the braking performance, are improved on the wet road surface and the dry road surface due to the increase of the friction coefficient.

It can also be seen that the wear characteristics and the friction characteristics are maintained or improved at the same level as that of the comparative example. However, when only the bromobutyl rubber (BIIR) was applied as in Comparative Examples 5 to 9, the abrasion performance was deteriorated, and in particular, the composition of the composition in which the bromobutyl rubber (BIIR) was added in an amount of 6 phr or less based on 100 parts by weight of the rubber The effect is insignificant, and there is no difference in physical properties from that when it is not added, and when it is added at 15 phr or more, abrasion performance tends to be drastically lowered according to intrinsic properties of bromobutyl rubber (BIIR). Accordingly, the butyl rubber is preferably added in an amount of 7 to 14 phr based on 100 parts by weight of the rubber.

In the master batch for a tire tread according to the present invention, the single wall carbon nanotube (SWCNT) has no effect of reinforcing the wear performance at 0.5 wt% or less as in Example 1, Is 75, which is not suitable for tire tread. Therefore, the single-walled carbon nanotubes are preferably added in an amount of 1.0 to 1.5 wt% based on the total weight of the master batch of 100 wt%.

In the actual vehicle test, the braking distance on the dry road surface is reduced by about 1.1 m when the comparison example 1 and the example 4 are compared, and it is confirmed that the braking performance is improved. As mentioned above, the handling performance is improved from 7 to +7 by improving the braking performance and the wear performance.

The present invention relates to a solution styrene-butadiene rubber (SSBR) having excellent mechanical properties, easy dispersion of a filler, excellent dispersibility and bonding force with silica, (BIIR) which is excellent in friction characteristics and exhibits a high grip force when applied to a tire tread and which can secure an excellent braking performance, a raw rubber and a filler in the composition, The masterbatch composition in which the single wall carbon nanotubes (SWCNTs) capable of improving the chemical and mechanical bonding force between the carbon nanotubes and the carbon nanotubes capable of improving the abrasion performance are dispersed is characterized in that the bromobutyl rubber (BIIR) and the carbon black are uniformly dispersed Thereby forming a net structure.

Accordingly, by using the composition of the master batch for tire tread according to the present invention, it is possible to provide a composition for a tire tread having improved braking performance and abrasion performance. As a result, the friction coefficient of the tire tread composition of the present invention is improved to 3.5% It was confirmed that the abrasion performance with the improvement of the friction coefficient was improved by 3% or more.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Do. Accordingly, it is intended that the scope of the invention be defined by the claims appended hereto, and that all such equivalent or equivalent modifications are within the scope of the present invention.

Claims (10)

A composition for a tire tread comprising a solution-styrene-butadiene rubber (SSBR) as a raw rubber,
A composition for a tire tread characterized by comprising a master batch in which single walled carbon nanotubes are dispersed in bromo butyl rubber (BIIR). The composition for a tire tread according to claim 1, wherein the content of the bromo butyl rubber (BIIR) is 7 to 14 phr based on 100 parts by weight of the rubber. The composition for a tire tread according to claim 1, wherein the content of the single-walled carbon nanotubes is 1.0 to 1.5 wt% based on 100 wt% of the total weight of the masterbatch. The composition for a tire tread according to claim 1, wherein the composition for tire tread further comprises carbon black and silica as a filler. A master comprising bromo butyl rubber (BIIR) in an amount of 7 to 14 phr based on 100 parts by weight of rubber and 1.0 to 1.5 wt% of single walled carbon nanotubes based on the total weight of the master batch of 100 wt% Batch composition. A first step of mixing single wall carbon nanotubes with a surfactant and dispersing by applying ultrasonic waves;
A second step of mixing a single-walled carbon nanotube dispersed in the first step with bromo butyl rubber (BIIR) in a liquid phase; And
And a third step of drying the mixture of the two steps at a high temperature to obtain a master batch composition. 7. The method of claim 6, wherein the bromo butyl rubber (BIIR) comprises 7 to 14 phr, based on 100 parts by weight of rubber. 7. The method of claim 6, wherein the single walled carbon nanotubes comprise 1.0 to 1.5 wt% based on the total weight of the master batch of 100 wt%. [7] The method of claim 6, wherein carbon black is further added as a filler in the first step. 7. The composition of claim 6, wherein the surfactant is selected from the group consisting of sodium dodecyl sulfate (SDS), lithium dodecyl sulfate (LDS), sodium dodecylbenzene sulfate (NaDDS), sodium dodecylsulfonate (SDSA), sodium dodecylbenzenesulfonate (SDBS), and polyvinylpyrrolidone (PVP). ≪ / RTI >
KR1020150142157A 2015-10-12 2015-10-12 Composition for tire treads in which the abrasion and braking ability are improved, master batch composition for tire treads and manufacturing method thereof KR20170042931A (en)

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Cited By (7)

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KR101985614B1 (en) * 2018-03-29 2019-09-03 한국타이어앤테크놀로지 주식회사 Rubber composition for covering a sensor and tire comprising a sensor
EP3670598A4 (en) * 2017-08-16 2020-06-24 Korea Kumho Petrochemical Co., Ltd. Rubber composition for tires including carbon nanotubes, and method for producing same
WO2020184675A1 (en) * 2019-03-13 2020-09-17 横浜ゴム株式会社 Rubber composition for tire, and pneumatic tire using this
JP2020147663A (en) * 2019-03-13 2020-09-17 横浜ゴム株式会社 Rubber composition for tires and pneumatic tire therewith
KR20200113666A (en) * 2019-03-26 2020-10-07 황용경 Tire tread rubber composition having the improved tire braking effects
KR20200117526A (en) * 2019-04-04 2020-10-14 넥센타이어 주식회사 Tire tread rubber composition with improved anti-abrasion and Tire produced by the same
JP2020169238A (en) * 2019-04-01 2020-10-15 横浜ゴム株式会社 Tire rubber composition and pneumatic tire including the same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3670598A4 (en) * 2017-08-16 2020-06-24 Korea Kumho Petrochemical Co., Ltd. Rubber composition for tires including carbon nanotubes, and method for producing same
US11441006B2 (en) 2017-08-16 2022-09-13 Korea Kumho Petrochemical Co., Ltd. Rubber composition for tires including carbon nanotubes, and method for producing same
KR101985614B1 (en) * 2018-03-29 2019-09-03 한국타이어앤테크놀로지 주식회사 Rubber composition for covering a sensor and tire comprising a sensor
WO2020184675A1 (en) * 2019-03-13 2020-09-17 横浜ゴム株式会社 Rubber composition for tire, and pneumatic tire using this
JP2020147663A (en) * 2019-03-13 2020-09-17 横浜ゴム株式会社 Rubber composition for tires and pneumatic tire therewith
KR20200113666A (en) * 2019-03-26 2020-10-07 황용경 Tire tread rubber composition having the improved tire braking effects
JP2020169238A (en) * 2019-04-01 2020-10-15 横浜ゴム株式会社 Tire rubber composition and pneumatic tire including the same
KR20200117526A (en) * 2019-04-04 2020-10-14 넥센타이어 주식회사 Tire tread rubber composition with improved anti-abrasion and Tire produced by the same

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