CN105400022A - Semi-steel radial ply tire tread rubber composition - Google Patents
Semi-steel radial ply tire tread rubber composition Download PDFInfo
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- CN105400022A CN105400022A CN201510967685.1A CN201510967685A CN105400022A CN 105400022 A CN105400022 A CN 105400022A CN 201510967685 A CN201510967685 A CN 201510967685A CN 105400022 A CN105400022 A CN 105400022A
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of the rubber, and particularly a semi-steel radial ply tire tread rubber composition. The composition is characterized by comprising, calculated by 100 parts by weight of a rubber component, 70-95 parts of a highly dispersed between silica, 5-35 parts of carbon black, 15-55 parts of a rubber processing between softener, 5-13 parts of a silane coupling agent, 5-15 parts of a carbon-white dispersing agent, 3-10 parts of an antioxidant, 0.5-5 parts of sulfur and 1.0-6.5 parts of a promoting agent. The rubber component comprises 75-90 parts of modified solution polymerized styrene-butadiene rubber and 10-25 parts of styrene-butadiene rubber of emulsion polymerization with high styrene content; and the styrene-butadiene rubber of emulsion polymerization contains 40 wt% of bound benzene and 30-55 wt% of ethylene; and the styrene-butadiene rubber of emulsion polymerization is also required to have 40 wt% of bound styrene.
Description
Technical field
The present invention relates to a kind of field of rubber technology, specifically a kind of high braking ability semi-steel radial tire tread rubber composition.
Background technology
As everyone knows, along with the fast development of automotive industry and motorway, people require more and more higher to the safety performance of tire, tire is when highway driving, particularly export to Europe some to the country of motorway not speed limit, when in the process of running at high speed because of burst thing to carry out snub, if poor stop occurs vehicle in braking procedure will bring threat to navigating mate life, especially may there is the Serious Accident of car crash under the condition of running at high speed.For this reason, each giant tyre company all actively drops into exploitation superelevation earth-grasping force and the exsertile high-performance semi-steel radial tire of braking.
The crown of tire is the position of mere contact track, and the cling property therefore improving tread rubber is most important to the braking ability improving tire.Improve the braking ability of tread glue formula and handling, the technology generally adopted in the industry is the tread mix formula of styrene butadiene rubbers in conjunction with high filler loading capacity white carbon black.
Have in the industry solution styrene-divinyl rubber is applied to tire tread technical report in conjunction with the white carbon black of high filler loading capacity, but on tread glue formula on the impact of stopping distance and how to use the styrene butadiene rubbers technical problem of modification high styrenic percentage there is no correlation report.
Summary of the invention
Object of the present invention is exactly to overcome above-mentioned existing technical deficiency, a kind of semi-steel radial tire tread rubber composition is provided, the actual entrucking braking ability of prepared semi-steel radial tire promotes obviously, and effective shortening of stopping distance can reach the object promoting safety performance of running at high speed.。
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of semi-steel radial tire tread rubber composition, it is characterized in that, with the rubber components of 100 weight parts for benchmark, also comprise the Aerosil 200 between 70-95 weight part, carbon black between 5-35 weight part, Rubber processing tenderizer between 15-55 weight part, silane coupling agent between 5 ~ 13 weight parts, White carbon black dispersant between 5 ~ 15 weight parts, the anti-aging agent of 3 ~ 10 weight parts, the sulphur of 0.5 ~ 5 weight part, the promotor of 1.0 ~ 6.5 weight parts; Wherein said rubber components comprises the Emulsion polymerized styrene-divinyl rubber (ESBR) of the part by weight modified solution styrene-divinyl rubber (SSBR) of 75-90,10-25 weight part high styrenic percentage; Described solution styrene-divinyl rubber has the styrene butadiene rubbers of the combined styrene content of 40 quality % and the contents of ethylene of 30 ~ 55 quality %; SBR of emulsion polymerization also requires the combined styrene content with 40 quality %.
The invention has the beneficial effects as follows, the styrene-butadiene rubber(SBR) of the solution polymerization high styrenic percentage of vast scale is used in this formula, formula cling property will be made to promote obviously, the prepared stopping distance of semi-steel radial high-performance tire under wet and slippery condition is shorter, effectively raises the driving safety performance of semi-steel radial high-performance tire.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
The rubber components that the present invention relates to comprises modified solution polymerizing styrene-divinyl rubber, Emulsion polymerized styrene-divinyl rubber.
Modified solution polymerizing styrene-divinyl rubber described in invention has the combined styrene content of more than 40 quality %, the contents of ethylene styrene butadiene rubbers simultaneously containing 30 ~ 65 quality %; The both-end base of modified solution polymerized sbr must carry out end coupling technology process, and such Butadiene-Styrene Rubber is just like the SSBR2438-HM of German Lang Sheng company limited; The HP-755B of Japan JSR synthetic rubber company, the SSBR-2466 etc. of Tai Xiang Synesis Company.
Solution styrene in invention-divinyl rubber SSBR, for ensureing certain processing characteristics, SSBR that can be preferably oil-filled; Non-oil-filled SSBR also can use, and suitably should adjust the usage quantity of corresponding Rubber processing tenderizer during use.
The extending oil type of oil-filled SSBR is the aromatic hydrocarbon oil after TDAE(TreatedDistillateAromaticExtract process) or RAE oil (ResidualAromaticExtracts residual aromatics extract); The loading level of oil product is 35-55 weight part.
The virgin rubber Mooney viscosity value of the solution styrene in the present invention-divinyl rubber SSBR is 45-85, for ensureing certain processing characteristics, the SSBR of low Mooney point can be selected, but for ensureing the abrasion resistance of tire, the SSBR of high Mooney should be selected as far as possible, therefore the selection of Mooney point is depending on processing conditions, is recommended as about 70.
The consumption of the solution styrene in the present invention-divinyl rubber SSBR is preferably not less than 75 weight parts, is more preferably not less than 80 weight parts, and when the consumption of SSBR is lower than 75 weight part, the stopping distance of tire shortens and will fall flat.This technology recommends the consumption of solution styrene-divinyl rubber SSBR to be 100 weight parts.
The virgin rubber second-order transition temperature of the solution styrene in the present invention-divinyl rubber SSBR is not higher than subzero 10 degree, more preferably not higher than subzero 15 degree, for ensureing the low temperature use properties of tire, the SSBR of slightly lower glass transition temperatures can be selected, consider that the styrene content of the wet and slippery performance requriements SSBR improving tire wants high relatively on the other hand, and styrene content directly affects the second-order transition temperature of sizing material, about therefore second-order transition temperature the present invention of Butadiene-Styrene Rubber is recommended as minus 20 degrees.
Consider that the processing performance of solution styrene-divinyl rubber SSBR is poor and relative cost is higher, in rubber components of the present invention except solution styrene-divinyl rubber SSBR, the second sizing material is Emulsion polymerized styrene-divinyl rubber ESBR, the styrene content of the present invention to emulsion polymerized styrene butadiene rubber has clear stipulaties, for improving handling of the present invention, styrene content in butadiene-styrene rubber is required to be 40 quality %, higher technique is required to processing characteristics, the SBR1739 etc. filling 37.5 weight part TDAE oil can be selected.
In invention, the consumption of ESBR rubber is preferably no more than 15 weight parts, is more preferably no more than 10 weight parts, and when the consumption of ESBR rubber is more than 15 weight part, will the rolling resistance of tread mix be caused to increase, this will affect the fuel economy of tire.
In view of the carinogenicity of European Union environmental protection laws and regulations requirement and high viscosity aromatic hydrocarbon oil, the kind of the present invention to Rubber Softener explicitly calls for, the extending oil type of recommendation has the aromatic hydrocarbon oil after the holy company's T DAE(TreatedDistillateAromaticExtract process of the German Chinese), the RAE oil (ResidualAromaticExtracts residual aromatics extract) of company of Total France; Rubber Softener recommends consumption to be 15-55 weight part.
To the carbon black related in formula, the present invention allows to use hard(carbon)black general in tire industry in right amount, is preferably less than 35 weight parts, is more preferably and is less than 30 weight parts.
The silicon-dioxide related in the present invention, it can be any reinforcing silica that those skilled in the art know, particularly BET specific surface area and CTAB specific surface area are all less than 400m2/g precipitated silica, preferably BET specific surface area and the highly dispersible precipitated silica of the equal 60-350m2/g of CTAB specific surface area.
When the present invention is for the production of high-performance semi-steel radial tire, preferred BET specific surface area 100-250m2/g, more preferably the highly dispersible precipitated silica of BET specific surface area 120-230m2/g, if use common precipitated silica will cause its dispersed decline and processing performance instability.
The dispersible precipitated silica of the height related in the present invention, can purchased from the Aerosil 200 1165MP of the Aerosil 200 Ultrasil7000GR of Degussa, French Rhodia1 company, domestic HCSIL-822MP and the HCSIL-833MP Aerosil 200 having Wuxi Heng Chenggui industry company limited.
The SiO2 content (butt) that the height related in the present invention dispersibles precipitated silica must be greater than 90%; The moisture content of 105 degree is 5-10%, is preferably 4-8%; PH is 6-8.
When the present invention is for the production of high-performance semi-steel radial tire, highly dispersible precipitated silica consumption must be greater than 70 weight parts, is preferably greater than 75 weight parts, the wet and slippery performance do not provided when white carbon black is less than 70 weight part; The research on maximum utilized quantity of high-dispersion white carbon black is recommended as and is less than 95 weight parts, is more preferably and is less than 90 weight parts, and too high white carbon black loading level is unfavorable to processing performance, is also unfavorable for the transmission of electrostatic in travelling simultaneously; Moderate dioxide-containing silica is one of feature of the present invention, and this will ensure the wetland earth-catching property that sizing compound formula has had, but turn avoid the disadvantageous effect of high filling white carbon black to processing characteristics simultaneously.
Use silicon-dioxide as in the formula of filler, coupler must be used, it can carry out connecting or bonding between macromolecular chain and silica sphere, carries out chemistry simultaneously and infiltrates, thus play the dispersion in rubber matrix promoting mineral filler to inorganic filler surface.
As many sulfurations silane coupling agent conventional in silica formulations, with triethoxysilicane polysulfide (being abbreviated as TESPT) for general types in the industry, wherein purchased from the Si75(triethoxysilicane based bisulfide of Degussa company) and the silica-based tetrasulfide of Si69(triethoxy) range of application is the widest.
Preferable amount according to coupler TESPT of the present invention is 5-13 weight part, and being more preferably usage quantity is 6-11 weight part, but the usage quantity of TESPT generally should be little as much as possible; If the composition of TESPT comprises a certain amount of inertia dispersion agent, the number that it uses suitably should be adjusted.
For improving the dispersing property of white carbon black in sizing material, the present invention advises using a kind of activation dispersion agent effectively to alleviate this problem, facilitates the dispersion of silicon-dioxide in rubber matrix.Activation dispersion agent is the PLURIOLE4000 purchased from BASF Corp. of Germany.
Making PLURIOLE4000 in the sizing material of filler using white carbon black, as when activating dispersion agent, the impact of white carbon black on sulfuration can be reduced or eliminated, make various auxiliary agent be uniformly dispersed and extend time of scorch, improving the physical and mechanical properties of rubber item.
The present invention advises that the preferred addition of activation dispersion agent is: 10-20 weight part white carbon black adds the PLURIOLE4000 of 1 weight part; The scheme of being more preferably is the PLURIOLE4000 that 12-18 weight part white carbon black adds 1 weight part.
In addition, should notice that the PLURIOLE4000 used in the present invention must measure according to a certain percentage in rubber compounding process and add use with silicon-dioxide simultaneously.
Sulphur powder is not specified especially, can use for the sulphur powder in tire industry.
To the usage quantity of sulphur powder, the system based on 100 weight part synthetical glues, the usage quantity of sulphur powder is no more than 5.0 weight parts, preferably no more than 4.5 weight parts, when powder is more than 5.0 weight part, easily causes the material sulfuring up using this formula; Usage quantity is not less than 0.5 weight part, is preferably not less than 1.0 weight parts, and when powder is lower than 0.5 weight part, it is abundant not that state of vulcanization is carried out, and will have a strong impact on physics and the dynamic property of sizing material.
The alternative chemical classes of vulcanization accelerator is more, wherein uses sulfenamide type accelerators can give the good process safety performance of sizing material and vulcanization rate.
The sulfenamide type accelerators used in the present invention has the N-tertiary butyl-2 benzothiazole sulphenamide (accelerator NS), N-oxygen diethylene-2-benzothiazole sulfonamide (accelerant NOBS), N, N-bis-cyclohexyl benzothiazole sulfonamide (accelerator DZ), N, N '-dicyclohexyl-2-[4-morpholinodithio sulphenamide (accelerant CZ), consider the friendly of environment and the requirement of vulcanization rate, preferred accelerators NS and accelerant CZ.
In invention, based on 100 weight part synthetical glues, the amount of the sulfenamide type accelerators that system uses is no more than 3.8 weight parts, and preferably no more than 3.3 weight parts, when powder is more than 3.8 weight part, the safety performance easily causing sizing material to process the initial stage reduces; Because the dispersible precipitated silica consumption of camber of the present invention is about 85 weight parts, the consumption of promotor is slightly higher than the consumption of ordinary carbon black formula system, minimum amount is not less than 2.0 weight parts, preferably be not less than 2.5 weight parts, when accelerator level is lower than 2.0 weight part, vulcanization rate will reduce, and affect the curing efficiency of finished tire.
In addition, except the sulfenamide type accelerators used is for except primary accelerator in the present invention, generally also need and use a certain amount of secondary accelerator, type has diphenyl disulfide a pair of horses going side by side thiazole (altax), diphenylguanidine (vulkacit D PG), consider the requirement to vulcanization rate, preferred accelerators DPG.
In addition, all the other chemical substances used in the present invention are the general in the industry rubber small powder of tire.
Table one is in conjunction with example, the present invention will be described, but the present invention is not limited to these examples.
Table two is corresponding rubber stock physicals table.
Table one: invention formula coordinates table (unit: weight part)
| Composition no | 1 | 2 | 3 | 4 | 5 |
| SSBR | 100 | 95 | 90 | 85 | 80 |
| ESBR | -- | 5 | 10 | 15 | 20 |
| Carbon black | 15 | 20 | 20 | 25 | 25 |
| Silicon-dioxide | 80 | 75 | 75 | 70 | 70 |
| Rubber processing tenderizer | 38 | 40 | 40 | 42 | 42 |
| Activation dispersion agent | 7 | 6 | 6 | 5 | 5 |
| Silane coupling agent | 6.5 | 6.0 | 6.0 | 5.5 | 5.5 |
| Zinc oxide | 5 | 5 | 5 | 5 | 5 |
| Stearic acid | 2 | 2 | 2 | 2 | 2 |
| Resol | 3 | 3 | 3 | 3 | 3 |
| Antioxidant 4020 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Anti-aging agent RD | 2 | 2 | 2 | 2 | 2 |
| Protection wax | 2 | 2 | 2 | 2 | 2 |
| Sulphur | 2.3 | 2.3 | 2.2 | 2.2 | 2.2 |
| Promotor | 4.1 | 4.1 | 4.0 | 4.0 | 4.0 |
| Scorch retarder | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
Table two: formula physicals table
| 150 DEG C of sulfuration * 30min | 1 | 2 | 3 | 4 | 5 |
| 100% stress at definite elongation/Mpa | 4.3 | 4.0 | 3.9 | 3.7 | 4.0 |
| 300% stress at definite elongation/Mpa | 15 | 16.1 | 15.7 | 14.6 | 16.4 |
| Tensile strength/Mpa | 16.3 | 17.8 | 18 | 18.4 | 18.9 |
| Tensile yield/% | 342 | 383 | 408 | 425 | 414 |
| Shao Er A type hardness tester | 69 | 71 | 69 | 70 | 68 |
| DIN wear index | 118 | 122 | 120 | 130 | 135 |
| Rebound value/% | 25 | 18 | 21 | 20 | 17 |
| Tension set/% | 20 | 22 | 21 | 22 | 21 |
| The hysteretic properties of 0 DEG C | 0.847 | 0.805 | 0.854 | 0.763 | 0.785 |
| The hysteretic properties of 60 DEG C | 0.155 | 0.167 | 0.175 | 0.189 | 0.193 |
Claims (1)
1. a semi-steel radial tire tread rubber composition, it is characterized in that: with the rubber components of 100 weight parts for benchmark, also comprise the Aerosil 200 between 70-95 weight part, carbon black between 5-35 weight part, the Rubber processing tenderizer between 15-55 weight part, the silane coupling agent between 5 ~ 13 weight parts, White carbon black dispersant between 5 ~ 15 weight parts, the anti-aging agent of 3 ~ 10 weight parts, the sulphur of 0.5 ~ 5 weight part, the promotor of 1.0 ~ 6.5 weight parts; Wherein said rubber components comprises the Emulsion polymerized styrene-divinyl rubber of the part by weight modified solution styrene-divinyl rubber of 75-90,10-25 weight part high styrenic percentage; Described solution styrene-divinyl rubber has the styrene butadiene rubbers of the combined styrene content of 40 quality % and the contents of ethylene of 30 ~ 55 quality %; SBR of emulsion polymerization requires the combined styrene content with 40 quality %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510967685.1A CN105400022A (en) | 2015-12-22 | 2015-12-22 | Semi-steel radial ply tire tread rubber composition |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510967685.1A CN105400022A (en) | 2015-12-22 | 2015-12-22 | Semi-steel radial ply tire tread rubber composition |
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| CN105400022A true CN105400022A (en) | 2016-03-16 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801942A (en) * | 2016-04-21 | 2016-07-27 | 江苏华安橡胶科技有限公司 | Formula of tread rubber of low-rolling-resistance semi-steel radial tire |
| CN107383493A (en) * | 2017-08-21 | 2017-11-24 | 万力轮胎股份有限公司 | A kind of rubber composition of tire tread and its application |
| CN109369998A (en) * | 2018-09-30 | 2019-02-22 | 安徽佳通乘用子午线轮胎有限公司 | A kind of high humidity grabs the Tire tread rubber composition of performance and low rolling resistance |
| CN112126138A (en) * | 2020-08-07 | 2020-12-25 | 山东玲珑轮胎股份有限公司 | Antibacterial rubber composition and tire |
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|---|---|---|---|---|
| EP2088169A1 (en) * | 2008-02-08 | 2009-08-12 | Continental Aktiengesellschaft | Rubber composition and tyres made from same |
| CN102634086A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Tread rubber composition for semisteel meridian snow tire used in extremely cold area |
| CN104311932A (en) * | 2014-11-20 | 2015-01-28 | 三角轮胎股份有限公司 | Rubber composite for treads of semi-steel radial tyres |
-
2015
- 2015-12-22 CN CN201510967685.1A patent/CN105400022A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2088169A1 (en) * | 2008-02-08 | 2009-08-12 | Continental Aktiengesellschaft | Rubber composition and tyres made from same |
| CN102634086A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Tread rubber composition for semisteel meridian snow tire used in extremely cold area |
| CN104311932A (en) * | 2014-11-20 | 2015-01-28 | 三角轮胎股份有限公司 | Rubber composite for treads of semi-steel radial tyres |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801942A (en) * | 2016-04-21 | 2016-07-27 | 江苏华安橡胶科技有限公司 | Formula of tread rubber of low-rolling-resistance semi-steel radial tire |
| CN107383493A (en) * | 2017-08-21 | 2017-11-24 | 万力轮胎股份有限公司 | A kind of rubber composition of tire tread and its application |
| CN107383493B (en) * | 2017-08-21 | 2019-06-18 | 万力轮胎股份有限公司 | A kind of rubber composition of tire tread and its application |
| CN109369998A (en) * | 2018-09-30 | 2019-02-22 | 安徽佳通乘用子午线轮胎有限公司 | A kind of high humidity grabs the Tire tread rubber composition of performance and low rolling resistance |
| CN112126138A (en) * | 2020-08-07 | 2020-12-25 | 山东玲珑轮胎股份有限公司 | Antibacterial rubber composition and tire |
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Application publication date: 20160316 |