CN103012897A - Method for adding high-sulfur-content rubber compound to improve wear-resisting property of tread rubber - Google Patents
Method for adding high-sulfur-content rubber compound to improve wear-resisting property of tread rubber Download PDFInfo
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- CN103012897A CN103012897A CN2012105669060A CN201210566906A CN103012897A CN 103012897 A CN103012897 A CN 103012897A CN 2012105669060 A CN2012105669060 A CN 2012105669060A CN 201210566906 A CN201210566906 A CN 201210566906A CN 103012897 A CN103012897 A CN 103012897A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 99
- 239000005060 rubber Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 title claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000463 material Substances 0.000 claims abstract description 48
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract 9
- 239000011593 sulfur Substances 0.000 claims abstract 9
- 238000010074 rubber mixing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000005864 Sulphur Substances 0.000 description 77
- 238000004513 sizing Methods 0.000 description 48
- 239000003292 glue Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 28
- 239000006229 carbon black Substances 0.000 description 17
- 235000019241 carbon black Nutrition 0.000 description 17
- 239000011159 matrix material Substances 0.000 description 15
- 239000000945 filler Substances 0.000 description 13
- 244000043261 Hevea brasiliensis Species 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229920003052 natural elastomer Polymers 0.000 description 12
- 229920001194 natural rubber Polymers 0.000 description 12
- 238000004073 vulcanization Methods 0.000 description 12
- 238000013329 compounding Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000005062 Polybutadiene Substances 0.000 description 7
- 238000005987 sulfurization reaction Methods 0.000 description 7
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IJJWOSAXNHWBPR-HUBLWGQQSA-N 5-[(3as,4s,6ar)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]-n-(6-hydrazinyl-6-oxohexyl)pentanamide Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)NCCCCCC(=O)NN)SC[C@@H]21 IJJWOSAXNHWBPR-HUBLWGQQSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000005486 sulfidation Methods 0.000 description 1
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Abstract
一种添加高硫磺含量混炼胶提高胎面胶耐磨性能的方法涉及轿车胎或载重胎领域。添加的高硫磺含量混炼胶是指在常规生产的轿车胎或载重胎胎面胶中以橡胶为100份为基准，额外增加1~3份硫磺得到的高硫磺含量混炼胶；将高硫磺含量混炼胶以原料形式加入到常规生产的轿车胎或载重胎胎面胶混炼过程中，添加的高硫磺含量混炼胶的加入量是以其中含有的基础橡胶进行计算的，在新形成的混炼胶100份基础橡胶中含有高硫磺含量混炼胶基础橡胶1-5份；在胶料混炼过程中加入该高硫磺含量混炼胶进行混炼，控制排胶温度为150~170℃。本发明适用范围广，多种乘用车胎和载重胎胎面配方均适用，在提高耐磨性能的同时对胎面胶料所需重要指标基本无影响甚至有一定的提高。工艺简单，易于操作，易于工业化生产。
A method for improving the wear resistance of tread rubber by adding high-sulfur-content mixed rubber relates to the field of car tires or truck tires. The added high-sulfur content compound refers to the high-sulfur content compound obtained by adding 1 to 3 parts of sulfur to the conventionally produced car tire or truck tire tread rubber based on 100 parts of rubber; The content of the mixed rubber is added in the form of raw materials to the conventionally produced car tire or truck tire tread rubber in the mixing process. The added amount of the high sulfur content mixed rubber is calculated based on the base rubber contained in it. 100 parts of the base rubber contains 1-5 parts of high-sulfur-content base rubber; add the high-sulfur-content compound during the mixing process of the rubber, and control the discharge temperature at 150-170 ℃. The invention has a wide application range, and is applicable to various tread formulas of passenger car tires and truck tires, and while improving the wear resistance, it basically does not affect or even improves the important indexes required by the rubber material of the tread. The process is simple, easy to operate, and easy to industrialized production.
Description
Technical field
The present invention relates in the tread mix mixing process of car tire or load-carrying tire the rubber unvulcanizate that adds a certain amount of high sulphur content and have certain thermal history, reach and improve tyre surface with the method for the wear resisting property of sizing material.
Background technology
The means that most improves the tread rubber wear resisting property are by changing the methods such as prescription, interpolation novel material mostly, but these methods often exist and are difficult to disperse, laboratory result is difficult to amplify, later stage suitability for industrialized production debugging cycle is long, the prescription change make sizing material other such as degradation problem under the Key Performance Indicators such as mechanical property and heat aging property, therefore need a kind of simple and easy to do pervasive method.
Even be that adsorbed close is in filling surface, have the good solvent effect also to be difficult to the rubber molecule that is drawn out of at normal temperatures in conjunction with glue, owing to the strong interaction between filler and the rubber forms, after mixing through shearing, be in the thermodynamic instability state, the Second Aggregation that filler can occur, form strong filler/rubber network structure, claim again the flocculation of filler.Flocculation is subject to the impact of temperature and time, Choi(Choi S. S. Influence of storage time and temperature and silane coupling agent on bound rubber formation in filled styrene-butadiene rubber compounds[J] .Polymer Testing, 2002,21 (1); 201～208) the association colloid integration number of having studied carbon black/styrene-butadiene rubber(SBR) system and white carbon black/styrene-butadiene rubber(SBR) in the process of storing with the relation of temperature and time, the result shows that the association colloid integration number in the mixing system all occurs obviously to increase along with time increase, temperature raise.Pu (Pu Z. C., Mark J. E., Jethmalani J. M., et al.Effects of dispersion and aggregation of silica in the reinforcement of poly (methyl actylate) elastomers [J] .Chem. Mater, 1997,2442～2447) etc. 9 (8): will in white carbon black and the Acrylic Acid Monomer blend of the silica-based acrylate of surface grafting trimethoxy, then adopt different polymerization processs to prepare filler random dispersion in matrix, regular arrangement, significantly assemble and wait 3 kinds of different filler/rubber composites that disperse grade.The result shows: the dispersiveness of filler is not more even better, and fillers dispersed is better, and the Young's modulus of compound system is higher; Dispersiveness is poorer, and matrix material has higher tensile yield.Mainly be because the strong network structure that filler forms afterwards in certain gathering has higher energy dissemination.When this explanation did not just reach optimum dispersion, matrix material just had best over-all properties.Therefore, need to control the dispersiveness of filler in rubbery system by hybrid technique, could obtain the performance of the filler/rubber composite of expection.Owing to need to control stock in the production process of tire plant, reduce the consideration of the production costs such as mixing energy consumption, and production technology and management thereof is not in place, therefore is difficult to realize effectively control.
In order conveniently to reach the control of fillers dispersed state, we adopt the method for adding high sulphur content sizing material.The method has universality, uses this method in the car tyre of a plurality of tire plant and load-carrying tire tread prescription, has all obtained good effect.
Summary of the invention
Additionally in car tire that routine is produced or load-carrying tire tread glue increase the high sulphur content rubber unvulcanizate that 1 ~ 3 part of sulphur (take rubber as 100 parts) obtains, the high sulphur content sizing material that obtains is joined in the conventional car tire or load-carrying tire tread glue mixing process of producing with raw material form, and the control dump temperature is 150 ~ 170 ℃.In dump temperature 150-170 ℃ scope, the sulfided state that high sulphur content sizing material reaches rapidly T10 namely produces certain incipient scorch structure, and required time is very short.And in the process that adds, matrix glue is not sulfureted sizing material, speed that high sulphur content is reinforced when reaching the T10 sulfided state is fast, and the sulphur efficient vulcanization that can control high sulphur content sizing material divides and obtains the structure that need to obtain rather than had little time sulfuration being distributed in the whole sizing material.
A kind of method of adding high sulphur content rubber unvulcanizate raising tread rubber wear resisting property is characterized in that:
The high sulphur content rubber unvulcanizate that adds refer in the car tire that routine is produced or load-carrying tire tread glue take rubber as 100 parts as benchmark, additionally increase the high sulphur content rubber unvulcanizate that 1 ~ 3 part of sulphur obtains;
High sulphur content rubber unvulcanizate is joined in the conventional car tire or load-carrying tire tread glue mixing process of producing with raw material form, the add-on of the high sulphur content rubber unvulcanizate that adds is that the basic rubber that wherein contains calculates, and contains high sulphur content rubber unvulcanizate basis rubber 1-5 part in new 100 parts of basic rubber of rubber unvulcanizate that form;
The method that adds high sulphur content rubber unvulcanizate is: add this high sulphur content rubber unvulcanizate and carry out mixingly in the rubber compounding process, the control dump temperature is 150 ~ 170 ℃.
The present invention adds the glue stuff compounding of the high sulphur content form with raw material in high temperature section.Because the high sulphur content of high temperature section rubber vulcanization speed is fast, fashionablely should make it be heated evenly to form desired structure and keep it and be not destroyed and be dispersed in the matrix glue adding as far as possible.Disperse excessive being unfavorable for for avoiding monoblock to add local heating, in experimentation, advise in advance high sulphur content sizing material being dispersed in first in the matrix glue that will add.Be that the high sulphur content glue stuff compounding that will add is divided into 10 parts by quality is roughly the same such as what in shop test, adopt, be cut into evenly elongated ribbon.The ribbon sizing material is evenly folded up in the sizing material that will add, and ribbon sizing material adding mode is seen accompanying drawing 1.Calendering process is mixing in the Banbury mixer of comparatively high temps with the sizing material after pre-dispersed routinely again, and the control dump temperature is 150 ~ 170 ℃.Because the large difference that vulcanization rate exists between high sulphur content sizing material and the matrix glue.During to mixing end, high sulphur content sizing material has the high temperature thermal history of for some time, because higher sulphur content can produce certain incipient scorch, and the flocculation that filler occurs makes in conjunction with glue and forms tight aggregate, and this tight aggregate is not destroyed in mixing process of later stage.This aggregate is dispersed in the whole colloid, can play the effect of focal point of stress.Thereby in the process of abrasion, cause crackle termination crackle and reach dissipation energy to improve the effect of wear resistance.Mechanism figure sees accompanying drawing 2.
Beneficial effect of the present invention
(1) applied widely, multiple car tyre and load-carrying tire tread prescription are all applicable.
(2) high sulphur content sizing material and sizing prescription is basically identical, and consistency is good, can be in sizing Uniform Dispersion, when improving wear resisting property on the required important indicator of tread mix substantially without affecting even improving.
(3) technique is simple, and easy handling is easy to suitability for industrialized production.
Description of drawings
The high sulphur content of Fig. 1 strip sizing material adds the mode synoptic diagram.
Fig. 2 adds high sulphur content sizing material with the mechanism introduction figure of the method for raising tread rubber wear resisting property.
Fig. 3 embodiment 1 to embodiment 3 and Comparative Examples 1 glue stuff compounding vulcanization curve figure.
Embodiment
Embodiment 1 to embodiment 3
Adopt the commercially available auspicious strange board engineering tire tread sizing material Q102-10 of Shandong HengYu rubber Co., Ltd, because the concrete prescription of factory is maintained secrecy, only test on the original formulation basis.On the original formulation basis, additionally add 2 parts of high sulphur content sizing materials that sulphur obtains, investigate respectively the cure of its 150 ℃ (embodiment 1), 160 ℃ (embodiment 2), 170 ℃ (embodiment 3) in control dump temperature scope.Gained vulcanization curve comparison diagram is seen accompanying drawing 3, and curing parameter sees Table 1.
Comparative Examples 1
Comparative Examples 1 adopts the high sulphur content sizing material identical with embodiment 1-3, investigates its curability in the time of 100 ℃.Gained vulcanization curve comparison diagram is seen accompanying drawing 3, and curing parameter sees Table 1.
The high sulphur content sizing material differing temps curability parameter of table 1 experiment
From curing parameter as can be known, embodiment 1,2,3 high sulphur content sizing materials reach the T10 state of vulcanization time in high temperature section to reach the T10 state of vulcanization than the Comparative Examples rubber unvulcanizate fireballing many.The high sulphur content sizing material high temperature thermal history time is longer than and reaches T10 state of vulcanization required time among the present invention, forms the incipient scorch state, then can basically form the structure of the tight gathering flocculation of expectation.But the thermal history time, sizing material entered sulfided state, is unfavorable for disperseing in matrix glue during greater than the T50 state of vulcanization.So the present invention controls dump temperature at 150 ℃ to 170 ℃ high temperature ranges, add the high sulphur content sizing material that different sulphur obtain according to different test recipes, should be in basis its thermal history time of control that guarantees dump temperature in its corresponding T10 state of vulcanization between the T50 state of vulcanization required time.
Embodiment 4
Adopt Fengshen Tyres Co., Ltd. to be provided for ASR69,315/80R2.5 test on the BACH tread glue formula basis of type middle-long distance load-carrying tire, because the concrete prescription of factory is maintained secrecy, only know in this prescription 100 parts of natural rubbers, 50 parts of carbon blacks, 1 part in sulphur, 29 parts of other small powders, total amount is 180 parts.The high sulphur content sizing material that 2 parts of sulphur of extra interpolation obtain then is 100 parts of natural rubbers, 50 parts of carbon blacks, and 2 parts in sulphur, 29 parts of other small powders, total amount is 182 parts.
Embodiment 5
Tread glue formula in the embodiment 4 is as example, the add-on of the high sulphur content rubber unvulcanizate that adds is that the basic rubber that wherein contains calculates, in new 100 parts of basic rubber of rubber unvulcanizate that form, contain 2 parts of high sulphur content rubber unvulcanizate basis rubber, the high sulphur content sizing material that namely adds is 2*1.82 part, and sizing is 98*1.80 part.
Embodiment 6 to embodiment 8
Adopt Fengshen Tyres Co., Ltd. to be provided for 295/75R22.5-14PR, the HN267 type is used for engineering tyre guide deflection sheave BEQ tread glue formula to be tested, because the concrete prescription of factory is maintained secrecy, only know that this prescription (represents with NR/BR for NR and BR paralled system in prescription, together lower), and use than the unknown, fill 10 parts of white carbon blacks of 50 parts of carbon blacks, concrete small powder prescription is unknown.On original sizing material basis, add extraly respectively 1,2,3 part of sulphur and make different high sulphur content glue stuff compoundings.The amount of the high sulphur content sizing material that adds in matrix glue is for containing 2 parts of high sulphur content rubber unvulcanizate basis rubber in new 100 parts of basic rubber of rubber unvulcanizate that form.Make embodiment rubber unvulcanizate 6 to embodiment 8.The rubber unvulcanizate of gained is made specimen according to the actual cure conditions sulfuration of factory, and curing temperature is 151 ℃, curing time 30min.Concrete prescription sees Table 2, characterizes performance and sees Table 3.
Comparative Examples 2 is to Comparative Examples 4
Adopt with embodiment 6 identical NR/BR and with the routine that 10 parts of white carbon black systems of 50 parts of carbon blacks of filling obtain and produce tread mix, namely Comparative Examples 2.Additionally add respectively 0.1,5 part of sulphur and make different high sulphur content glue stuff compoundings on original prescription basis, the amount of the high sulphur content sizing material that adds in matrix glue is for containing 2 parts of high sulphur content rubber unvulcanizate basis rubber in new 100 parts of basic rubber of rubber unvulcanizate that form.Make Comparative Examples rubber unvulcanizate 2 and Comparative Examples 3.The rubber unvulcanizate of gained is made specimen according to the actual cure conditions sulfuration of factory, and curing temperature is 151 ℃, curing time 30min.Concrete prescription sees Table 2, characterizes performance and sees Table 3.
Table 2 embodiment of the invention 6-8 and Comparative Examples 2-4 formula table
Table 3 embodiment of the invention 6-8 and Comparative Examples 2-4 performance comparison table
Embodiment 6,7,8 and Comparative Examples 2,3,4 performance comparison results in can find out sulphur in the high sulphur content sizing material content the wear resisting property of whole sizing material is had obvious impact.When the sulphur content that adds during at 1 ~ 3 part, wear resisting property obviously improves, and when add-on is 2 parts, best wear(ing)value occurred, and whole sizing material mechanics and aging resistance are had no significant effect.Sulphur concentration is too low as only adding 0.1 part among the embodiment 3 but add-on is too small, can not form rapidly required tight aggregate structure in the time in short thermal history, and its wear resisting property is almost indifference of Comparative Examples 2 with not adding high sulphur content sizing material.When add-on during greater than 3 parts, such as Comparative Examples 4, subregion sulphur excessive concentration, degradation with aging can occur in sizing material in the sulfidation, has reduced on the contrary its wear resisting property.Therefore, control in the high sulphur content sizing material the extra sulphur amount that adds 1 to 3 part scope, it can form effectively closely aggregate structure and the least possible degradation with aging rapidly guarantee in mixing process.
Embodiment 9 to embodiment 11
Adopt with embodiment 6 identical NR/BR and with filling 10 parts of white carbon black systems of 50 parts of carbon blacks, on original prescription basis, additionally add respectively 2 parts of sulphur and make different high sulphur content glue stuff compoundings.The amount of the high sulphur content sizing material that adds in matrix glue is respectively and contains high sulphur content rubber unvulcanizate basis rubber 1,3,5 parts in new 100 parts of basic rubber of rubber unvulcanizate that form.Make embodiment 9 to 11.The rubber unvulcanizate of gained is made specimen according to the actual cure conditions sulfuration of factory, and curing temperature is 151 ℃, curing time 30min.Concrete prescription sees Table 4, characterizes performance and sees Table 5.
Comparative Examples 5 is to Comparative Examples 6
Adopt with embodiment 6 identical NR/BR and with filling 10 parts of white carbon black systems of 50 parts of carbon blacks, on original prescription basis, additionally add respectively 2 parts of sulphur and make different high sulphur content glue stuff compoundings.The amount of the high sulphur content sizing material that adds in matrix glue is respectively and contains high sulphur content rubber unvulcanizate basis rubber 0,10 parts in new 100 parts of basic rubber of rubber unvulcanizate that form.Make Comparative Examples 5 to 6.The rubber unvulcanizate of gained is made specimen according to the actual cure conditions sulfuration of factory, and curing temperature is 151 ℃, curing time 30min.Concrete prescription sees Table 4, characterizes performance and sees Table 5.
Table 4 embodiment of the invention 9-11 and Comparative Examples 5-6 formula table
Table 5 embodiment of the invention 5-8 and Comparative Examples 5-9 performance comparison table
Embodiment 12 to embodiment 15
The four kinds of different matrix glue car tires or the load-carrying tire tread glue that adopt that Henan Fengshen Tyres Co., Ltd. provides compare, because the concrete prescription of factory is maintained secrecy, only know that main rubber forms.Be respectively commercially available 4.00R25 AE33 specification (E-SBR), 295/75R22.5 HN308+ specification (NR/E-SBR), embodiment 4 ASR69 315/80R2.5 specifications (NR) and embodiment 6295/75R22.5-14PR HN267 specification (NR/BR).On corresponding sizing material basis, additionally add respectively 2 parts of sulphur and make different high sulphur content glue stuff compoundings.The amount of the high sulphur content sizing material that adds in matrix glue is respectively and contains 3 parts of high sulphur content rubber unvulcanizate basis rubber in new 100 parts of basic rubber of rubber unvulcanizate that form.The rubber unvulcanizate that obtains makes specimen, 143 ℃ of embodiment 12 curing temperatures, curing time 60min according to the actual cure conditions sulfuration of factory; 151 ℃ of embodiment 13,15 curing temperatures, curing time 30min; 170 ℃ of embodiment 14 curing temperatures, curing time 30min.Concrete prescription sees Table 6, characterizes performance and sees Table 7.
Comparative Examples 7 is to Comparative Examples 10
Adopt car tire or the load-carrying tire tread glue of the four kind different matrix glue identical with embodiment 12 to embodiment 15 to compare, according to the mixing rubber unvulcanizate that obtains of the conventional calendering process of factory, make specimen according to the actual cure conditions sulfuration of factory, 143 ℃ of Comparative Examples 7 curing temperatures, curing time 60min; 151 ℃ of Comparative Examples 8,10 curing temperatures, curing time 30min; 170 ℃ of Comparative Examples 9 curing temperatures, curing time 30min.Concrete prescription sees Table 6, characterizes performance and sees Table 7.
Table 6 embodiment of the invention 12-15 and Comparative Examples 7-10 formula table
Table 7 embodiment of the invention 12-15 and Comparative Examples 7-10 performance comparison table
High sulphur content sizing material all makes the wear hardness of sizing material improve, and has confirmed universality of the present invention.The present invention is applicable to different car tires and load-carrying tire tread sizing material, to all being suitable for such as rubber such as natural rubber (NR), cis-1,4-polybutadiene rubber (BR), emulsion polymerized styrene butadiene rubber (E-SBR), solution polymerized butadiene styrene rubbers (S-SBR) that tread rubber adopts, these rubber can use separately, also can with wherein two or more the glue kind and use.And infill system no matter be carbon black filled, white carbon black is filled or carbon black/white carbon black common fill etc. all applicable.
Embodiment 16
Produce the ASR69 decorative pattern in Henan Fengshen Tyres Co., Ltd., the upper employing the present invention of specification 315/80R2.5 type middle-long distance load-carrying tire tread glue prescription basis adds the outer high sulphur content glue stuff compounding that adds 2 parts of sulphur of 3 shares.Durable test 80h in the test proloculum, outdoor mileage reaches 250,000 kilometers.
Comparative Examples 11
Henan Fengshen Tyres Co., Ltd. produces ASR69 decorative pattern, specification 315/80R2.5 type middle-long distance load-carrying tire tread.The indoor long duration test test duration is 80h, and outdoor mileage is 16 ~ 170,000 kilometers.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834140A (en) * | 2005-03-18 | 2006-09-20 | 西北工业大学 | Gross rubber for high wearable tyre and its prepn. |
| CN102634078A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Tire shoulder pad rubber composition and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834140A (en) * | 2005-03-18 | 2006-09-20 | 西北工业大学 | Gross rubber for high wearable tyre and its prepn. |
| CN102634078A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Tire shoulder pad rubber composition and preparation method |
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Application publication date: 20130403 |