CN101759890B - Rubbery composition for tire tread - Google Patents

Rubbery composition for tire tread Download PDF

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Publication number
CN101759890B
CN101759890B CN2009102596827A CN200910259682A CN101759890B CN 101759890 B CN101759890 B CN 101759890B CN 2009102596827 A CN2009102596827 A CN 2009102596827A CN 200910259682 A CN200910259682 A CN 200910259682A CN 101759890 B CN101759890 B CN 101759890B
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rubber
mentioned
styrene
weight parts
weight
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CN101759890A (en
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张寿珍
全壹焕
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Hankook Tire and Technology Co Ltd
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Hankook Tire Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00Compositions of natural rubber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60CVEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016Compositions of the tread
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08CTREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00Chemical modification of rubber
    • C08C19/04Oxidation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06Copolymers with styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/10Latex
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/80Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86Optimisation of rolling resistance, e.g. weight reduction 

Abstract

The invention provides rubbery composition for tire tread, which includes crude rubber and styrene-butadiene rubber containing hydroxyl group. The crude rubber contains natural rubber, solution-polymerized styrene-butadiene rubber, and neodymium butadiene rubber. The rubber composition can enhance braking performance on the ice and snow road, has great braking performance on the dry road and the wet road, the rotation resistance is low, therefore it is can be used in difference seasons.

Description

Rubber composition for tire tread
Technical field
The present invention relates to rubber composition for tire tread, in more detail, relate to rubber composition for tire tread, it is applicable to throughout the year.
Background technology
Recently; Acceleration along with global warmingization; Snowfall in 1 year sharply reduces in the world, forms the situation of freezing road though also snowfall is arranged, and snow dissolves and the situation that forms mud (slush) state or form the so moist pavement state of rainfall increases.
The characteristic of the desired rubber combination of braking ability on dry pavement or moist road surface and the ice and snow road is opposite each other, if therefore select a certain performance, then other a kind of performance is become unfavorable.To winter, the braking ability that majority change on the ice and snow road use tire excellent winter, but if during the not snowfall or avenge and dissolve and form the state on moist road surface; Then braking ability becomes very bad; This human consumer's requirement there is the tendency of increase, especially, owing to also direct relation is arranged with the stability of automobile; Thereby become the thing of tiremaker major concern, advance research and development to become present present situation energetically for addressing this problem.
In order to solve such problem, utilized following method at present, promptly; Through in the winter time with using the high styrene-butadiene rubber(SBR) of styrene content in the rubber composition for tire tread; And the second-order transition temperature of rubber combination is raise, and the braking ability on dry or moist road surface is improved, but along with styrene content increases; There are rubber hardness and modulus under the low temperature to raise the problem that the braking ability on the ice and snow road descends.
In addition; Use silicon-dioxide as the method for stiffeners more utilization to be arranged also, silicon-dioxide is compared with carbon black, adds the epistasis excellence; Braking dry or moist road surface is excellent; A little less than temperature dependency during low temperature, the hardness that reduces with temperature and the increment rate of modulus are lower than carbon black, so the also favourable advantage of braking ability on the ice and snow road is arranged.
But, use in the winter time in the rubber composition for tire tread, replace to silicon-dioxide by carbon black simply and be used as stiffeners, the braking ability on the moist road surface may not necessarily obtain the improvement of unusual effect.The winter of having used silicon-dioxide, the raising with the braking ability of tire on moist road surface was very limited, still left following technical problem,, was difficult to carry out the just compromise of the performance of two kinds of contradictions, to reach the degree of the requirement of fully satisfying the human consumer that is.
Summary of the invention
Therefore, the object of the present invention is to provide rubber composition for tire tread, it can improve the braking ability on the ice and snow road, and the braking ability on dry pavement and moist road surface is very excellent, and rotational resistance is low in addition, therefore applicable to throughout the year.
But the technical problem that desire of the present invention realizes is not limited to above-mentioned problem, and other technical problem should can be understood by following record to those skilled in the art clearly.
To achieve these goals; The present invention provides rubber composition for tire tread; It is characterized in that; Contain crude rubber; With with respect to above-mentioned raw materials rubber 100 weight parts be 5~15 weight parts, contain the styrene-butadiene rubber(SBR) gel of hydroxyl with the amount of 30~40mgKOH/g gel, said crude rubber contain (1) tree elastomer 10~30 weight parts, (2) styrene content be 20~30 weight %, contents of ethylene be 60~70 weight %, by solution polymerization styrene-butadiene rubber 30~40 weight parts, (3) neodymium divinyl rubber 30~40 weight parts of continous way method preparation.
Embodiment
The present invention contains 1 through use) tree elastomer 10~30 weight parts, 2) styrene content be 20~30 weight %, contents of ethylene be 60~70 weight %, by solution polymerization styrene-butadiene rubber 30~40 weight parts, 3 of continous way method preparation) crude rubber of neodymium divinyl rubber 30~40 weight parts; And in this crude rubber, add 5~15 weight parts contain hydroxyl (styrene-butadiene rubber(SBR) gel OH) in a large number; Thus rubber composition for tire tread can be provided; It can not cause the decline of winter with tire tread braking ability on ice and snow road, and can improve the braking ability on dry pavement or the moist road surface.
Below, the present invention is described as following in more detail.
The present invention provides rubber composition for tire tread, and it contains crude rubber; Contain the styrene-butadiene rubber(SBR) gel of hydroxyl with amount with 30~40mg KOH/g gel.
Above-mentioned raw materials rubber contain (1) tree elastomer, (2) styrene content be 20~30 weight %, contents of ethylene be 60~70 weight %, by solution polymerization styrene-butadiene rubber, (3) neodymium divinyl rubber of continous way method preparation.
Above-mentioned tree elastomer is the rubber that from nature, obtains, and chemistry TR 301 by name through using with the solution polymerization styrene-butadiene rubber that utilizes the preparation of continous way method, can further improve the braking ability on the moist road surface.
Above-mentioned tree elastomer contains 10~30 weight parts when being benchmark with above-mentioned crude rubber 100 weight parts.When the content of above-mentioned tree elastomer during less than 10 weight parts, the problem that has the persistence of tread-rubber to reduce, when surpassing 30 weight parts, the problem that has the braking ability on the moist road surface to descend.
Styrene-butadiene rubber(SBR) of the present invention can prepare through the continous way method.
Usually, solution polymerization styrene-butadiene rubber prepares through continous way and batch process.The styrene-butadiene rubber(SBR) that utilizes the preparation of continous way method is because a large amount of lower-molecular substances; Comparing with the styrene-butadiene rubber(SBR) that utilizes the batch process preparation, is disadvantageous aspect rotational resistance, but its excellent in workability; Hysteresis loss is high, and the braking ability on dry pavement or the moist road surface is excellent.
For above-mentioned styrene-butadiene rubber(SBR), styrene content is 20~30 weight %, and contents of ethylene is 60~70 weight %.When above-mentioned styrene content and butadiene content are in above-mentioned scope, the advantage of the braking ability on can the moist road surface of best performance is arranged.
Above-mentioned styrene-butadiene rubber(SBR) contains 30~40 weight parts when being benchmark with above-mentioned crude rubber 100 weight parts.When the content of above-mentioned styrene-butadiene rubber(SBR) during, the problem that has the braking ability on the moist road surface to reduce less than 30 weight parts, when surpassing 40 weight parts, the problem that has the braking ability on the ice and snow road to descend on the contrary.
Above-mentioned neodymium divinyl rubber is compared with cobalt divinyl rubber (Co-BR) or nickel divinyl rubber (Ni-BR), narrow molecular weight distribution, and therefore molecular structure is linear (Linear), has the gantry hysteresis of rubber low, rotational resistance is excellent, the advantage of abrasion excellent performance.
Above-mentioned neodymium divinyl rubber contains 30~40 weight parts when being benchmark with above-mentioned crude rubber 100 weight parts.When the content of above-mentioned neodymium divinyl rubber during less than 30 weight parts, the problem that has braking ability and abrasion resistance properties on the ice and snow road to reduce, when surpassing 40 weight parts, the problem that has the braking ability on the moist road surface to descend.
Above-mentioned styrene-butadiene rubber(SBR) gel contains hydroxyl with the amount of 30~40mg KOH/g gel.When the content of above-mentioned hydroxyl during, the problem that has the braking ability on the moist road surface to reduce less than 30mg KOH/g gel, when surpassing 40mg KOH/g gel, the problem that has the braking ability on the ice and snow road to descend.
In addition, the second-order transition temperature of above-mentioned styrene-butadiene rubber(SBR) gel is-20~-10 ℃, and the gel diameter is 30~60mm.
When the second-order transition temperature of above-mentioned styrene-butadiene rubber(SBR) gel is in above-mentioned scope; Can not cause the reduction of braking ability on the ice and snow road, can obtain the excellent effect of braking ability on the moist road surface, in addition; When the gel diameter is in above-mentioned scope, also can obtain above-mentioned effect.
Above-mentioned styrene-butadiene rubber(SBR) gel contains 5~15 weight parts when being benchmark with above-mentioned crude rubber 100 weight parts.When the content of above-mentioned styrene-butadiene rubber(SBR) gel during less than 5 weight parts, the raising effect of braking ability is faint on the moist road surface, when surpassing 15 weight parts; Produce following reverse effect, that is, it is unfavorable that processibility becomes; Braking ability on the ice and snow road significantly reduces, and it is unfavorable that control stability becomes.
For styrene-butadiene rubber(SBR) gel of the present invention; A large amount of hydroxyls is contained on its surface; Carry out chemically bonded through coupling agent and rubber thus, caused increasing in low temperature province (0 ℃~20 ℃) gantry hysteresis by highly cross-linked core, the braking on the dry or moist road surface is excellent.
Situation for common crude rubber; Along with the temperature step-down, hardness and modulus rise, but for above-mentioned styrene-butadiene rubber(SBR) gel; This variation is very little; Therefore even under less than 0 ℃ low temperature, it also has low relatively hardness and modulus value, also produces favourable effect for the braking ability on the ice and snow road.
In addition, utilize chemically bonded, and be created in high-temperature area (50 ℃~80 ℃) gantry hysteresis step-down, in addition the also effect of step-down of rotational resistance through coupling agent and rubber.
The present invention and then contain silicon-dioxide as adding the epistasis weighting agent can use separately, for the dispersiveness that makes silicon-dioxide improves, can use silane coupling agent.
The nitrogen adsorptive capacity of above-mentioned silicon-dioxide is 160~180m 2/ g, the CTAB value is 140~160m 2/ g.Have only the above-mentioned nitrogen adsorptive capacity of use and the silicon-dioxide of TAB value in above-mentioned scope, can obtain effect of the present invention.
Above-mentioned silicon-dioxide contains 60~90 weight parts when being benchmark with crude rubber 100 weight parts.When the content of above-mentioned silicon-dioxide during less than 60 weight parts, there is the epistasis of adding to reduce, the problem that the braking ability on the moist road surface and processing property descend when surpassing 90 weight parts, has raising difficult questions for discussion of braking ability and abrasion resistance properties decline on the ice and snow road.
On the other hand, rubber combination of the present invention can and then contain silane coupling agent, tenderizer, vulcanizing agent, vulcanization accelerator and inhibitor.
Above-mentioned silane coupling agent is used to improve the dispersiveness of silicon-dioxide; In alkoxyl group polysulfide silanes compound; Can enumerate two (trialkoxysilyl propyl group) polysulfides (TESPD) and two-3-triethoxysilylpropyltetrasulfide tetrasulfide (TESPT) etc.; TESPT is sold with trade(brand)name Si75 by デ グ サ society, TESPD by デ グ サ society with trade(brand)name Si69, carbon black 50% and X50S 50% mixed and carries out commerce and sell.
Above-mentioned silane coupling agent contains 10~20 weight parts when being benchmark with above-mentioned crude rubber 100 weight parts.When the content of above-mentioned silane coupling agent is in above-mentioned scope, the maximized advantage of coupling efficiency is arranged.
In addition; For the treated oil that uses as tenderizer of the present invention; The total content of its PAH (PolyCyclicAromatic Hydocarbo) composition is below the 3 weight %, and dynamic viscosity is 95 ℃ (210 ° of FSUS), and the aromatic component in the tenderizer is 15~25 weight %; Naphthenic hydrocarbon is tied to form and is divided into 27~37 weight %, and paraffinic hydrocarbons is tied to form and is divided into 38~58 weight %.When above-mentioned treated oil all satisfies above-mentioned condition, braking ability on moist road surface and the ice and snow road isostatic advantage that becomes is arranged.
When preferably being benchmark with above-mentioned crude rubber 100 weight parts, uses above-mentioned treated oil 20~30 weight parts.When the content of above-mentioned treated oil is in above-mentioned scope, following advantage is arranged, that is, the braking ability on ice and snow and the moist road surface is excellent, and processibility also becomes favourable in addition.
The preferred sulfur vulcanizing agent that uses is as above-mentioned vulcanizing agent.Above-mentioned sulfur vulcanizing agent can be enumerated elementary sulfur or make vulcanizing agent, for example amine disulphide (amine disulfide), the polymer sulphur of sulphur, preferred elements sulphur.
Above-mentioned vulcanizing agent contains 1.5~2.5 weight parts when being benchmark with above-mentioned crude rubber 100 weight parts.When the content of above-mentioned vulcanizing agent is in above-mentioned scope, can form proper crosslinking density, have following advantage thus, that is, braking ability and abrasion resistance properties, rotational resistance can reach best equilibrium.
In addition, vulcanization accelerator can be enumerated amine (Amine), disulphide, guanidine (guanidine), thiocarbamide, thiazole (thiazole), thiuram (thiuram), sulphenamide (sulfene amide) etc.
Above-mentioned vulcanization accelerator contains 0.8~2.0 weight part when being benchmark with above-mentioned crude rubber 100 weight parts.When the content of above-mentioned vulcanization accelerator is in above-mentioned scope, has the advantage that can form suitable cross-linking density.
Above-mentioned inhibitor can be enumerated N-(1, the 3-dimethylbutyl)-N-phenyl-Ursol D (6PPD), N-phenyl-n-sec.-propyl-Ursol D (3PPD), gather (2.2.4-trimethylammonium-1.2-EEDQ (RD) etc.
Above-mentioned inhibitor contains 1~5 weight part when being benchmark with above-mentioned crude rubber 100 weight parts.When above-mentioned ageing-resistant content is in above-mentioned scope, has and to make the advantage that prevents aged effect maximization.
On the other hand, the present invention can also select usually to use at the so various additives of promoting agent, treated oil, vulcanizing agent and vulcanization accelerator that tire tread uses in compsn except the above-mentioned composition of mentioning as required, and this is unquestionable.
Rubber composition for tire tread of the present invention has following advantage, that is, the braking ability on the ice and snow road is improved, and the braking ability on dry pavement and the moist road surface is very excellent, and rotational resistance is low in addition, thereby applicable to throughout the year.
Below, put down in writing the preferred embodiment of the invention and comparative example.But following embodiment only is the preferred embodiment of the present invention, and the present invention is not limited to following embodiment.
[embodiment 1~3 and comparative example 1~5]
Use composition as shown in table 1 below, the rubber composition for tyre of preparation embodiment 1~3 and comparative example 1~5.The rubber composition for tyre utilization is common tire preparation method prepare.
[table 1] (weight part)
Figure 2009102596827100002DEST_PATH_IMAGE002
Figure 2009102596827100002DEST_PATH_IMAGE004
1. tree elastomer: the rubber that from nature, obtains, chemistry TR 301 by name.
2.S-SBR (1): styrene content be the contents of ethylene in the 24 weight %, divinyl be 66 weight %, by the solution polymerization styrene-butadiene rubber (SBR) of batch process preparation.
3.S-SBR (2): styrene content be the contents of ethylene in the 24 weight %, divinyl be 66 weight %, by the solution polymerization styrene-butadiene rubber (SBR) of continous way method preparation.
4.BR (1): the nickel divinyl rubber of Kumho Petrochemical society system, commodity are called KBR01.
5.BR (2): the neodymium divinyl rubber of Lanxess society system, commodity are called CB29MES.
6. divinyl gel rubber: the styrene butadiene gel rubber that contains hydroxyl of Lanxess society system, commodity are called Nanoprene BM15OH.
7. silicon-dioxide: the nitrogen adsorptive capacity is 175m 2/ g, CTAB value are 154m 2The precipitation threshold silicon-dioxide of/g.
8. treated oil: PAH (PolyCyclic Aromatic Hydocarbo) composition total content is below the 3 weight %; Dynamic viscosity is 95 ℃ (210 ° of F SUS); Aromatic component in the tenderizer is 25 weight %; Naphthenic hydrocarbon is tied to form and is divided into 32.5 weight %, and paraffinic hydrocarbons is tied to form the oil that is divided into 47.5 weight %, and commodity are called Vivatec500.
9. inhibitor: UNIBOND (trading company's name), 6PPD (trade(brand)name).
10. vulcanizing agent: Miwon Commerial Co., Ltd. (trading company's name), MIDAS101 (trade(brand)name).
11. promotor: Flexsys (trading company's name), CZ (trade(brand)name).
12. promotor (DPG): Flexsys (trading company's name), DPG (trade(brand)name).
Sample for above-mentioned preparation is implemented physical property test, and its result is shown in following table 2.
[table 2]
Figure DEST_PATH_IMAGE006
1. mooney viscosity (ML1+4 (125 ℃)) is measured according to ASTM specification D1646.
2. hardness is measured according to DIN 53505.
3.300% modulus is measured according to ISO 37 specifications.
4. visco-elasticity uses RDS to measure machine, and G ', G from-60 ℃ to 60 ℃ are measured in the distortion with 0.5% (strain), under the 10Hz frequency ", tan δ.
In above-mentioned table 2, ML1+4 is the value of the viscosity of expression unvulcanized rubber, and numerical value is low more, and the processibility of unvulcanized rubber is more excellent.Hardness is the parameter of expression control stability, and its value is high more, and control stability is more excellent.-40 ℃ of G ' represent the braking characteristic on the ice and snow road, and numerical value is low more, and braking ability is more excellent, and 0 ℃ of tan δ representes the braking characteristic on dry pavement or the moist road surface, and numerical value is high more, and the expression braking ability is more excellent.In addition, 60 ℃ of tan δ represent the rotational resistance characteristic, and numerical value is low more, and the expression performance is more excellent.
Rubber with above-mentioned comparative example and embodiment is made tyre surface; Preparation contains the tire of this tread-rubber as half-finished 205/55R16 specification, and this tire is shown in following table 3 for the relative ratios of stopping distance on dry pavement, moist road surface, the ice and snow road and rotational resistance.
[table 3]
Figure DEST_PATH_IMAGE008
Figure DEST_PATH_IMAGE010
Know by above; During with the solution polymerization styrene-butadiene rubber that uses by batch preparation (comparative example 1) or when using the nickel divinyl rubber (comparative example 2) compare; When using (comparative example 3) by the solution polymerization styrene-butadiene rubber of continous way preparation and neodymium divinyl rubber, can not cause the reduction of the braking ability on the ice and snow road, can improve the braking ability on the moist road surface; When adding the styrene-butadiene rubber(SBR) gel of a large amount of OH bases of containing of 5~15 weight parts therein; Braking ability on the ice and snow road can significantly not reduce, and it is big that braking ability on dry pavement and the moist road surface becomes, in addition yet step-down significantly of rotational resistance.
Simple deformation of the present invention or change can easily be implemented to those skilled in the art fully, and these distortion or change all are included in the field of the invention.

Claims (1)

1. rubber composition for tire tread; It is characterized in that; Contain crude rubber; With with respect to said crude rubber 100 weight parts be styrene-butadiene rubber(SBR) gel 5~15 weight parts, contain hydroxyl with the amount of 30~40mg KOH/g gel; Said crude rubber contain (1) tree elastomer 10~30 weight parts, (2) styrene content be 20~30 weight %, contents of ethylene be 60~70 weight %, by solution polymerization styrene-butadiene rubber 30~40 weight parts, (3) neodymium divinyl rubber 30~40 weight parts of the preparation of continous way method, wherein, the second-order transition temperature of above-mentioned styrene-butadiene rubber(SBR) gel is-10~-20 ℃.
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KR101315110B1 (en) * 2010-11-30 2013-10-07 한국타이어 주식회사 Tread rubber composition and tire manufactured by using the same
JP5097862B1 (en) * 2011-05-25 2012-12-12 住友ゴム工業株式会社 Rubber composition for tire and pneumatic tire
CN102675697B (en) * 2012-06-21 2014-03-12 三角轮胎股份有限公司 Anti-reversion shoulder pad rubber composition
CN104448417A (en) * 2014-12-01 2015-03-25 四川凯力威科技股份有限公司 Special rubber material for tread of all-steel radial tire for ice-snow covered road and preparation method of rubber material
CN104961939B (en) * 2015-06-10 2017-08-15 德州玲珑轮胎有限公司 Four seasons half steel tire tread sizing material and its preparation method and application
FR3045636B1 (en) * 2015-12-22 2017-12-29 Michelin & Cie TIRE FOR VEHICLE CARRYING HEAVY LOADS COMPRISING A NEW BEARING BAND
CN109354725A (en) * 2018-09-04 2019-02-19 潍坊市跃龙橡胶有限公司 A kind of preparation process of snowy day non-skid tyre
CN111205517A (en) * 2020-02-23 2020-05-29 湖北玲珑轮胎有限公司 Neodymium-based butadiene rubber-containing rubber composition
KR102457812B1 (en) * 2021-01-11 2022-10-20 한국타이어앤테크놀로지 주식회사 Rubber composition for tire tread and tire manufactured by using the same
CN113549253B (en) * 2021-06-24 2023-02-24 中策橡胶集团股份有限公司 White carbon black reinforced tread rubber composition with low porosity, and mixing method and application thereof

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