JP2009203288A - Rubber composition for tire tread - Google Patents
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- JP2009203288A JP2009203288A JP2008045113A JP2008045113A JP2009203288A JP 2009203288 A JP2009203288 A JP 2009203288A JP 2008045113 A JP2008045113 A JP 2008045113A JP 2008045113 A JP2008045113 A JP 2008045113A JP 2009203288 A JP2009203288 A JP 2009203288A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 41
- 239000005060 rubber Substances 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 29
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 150000002148 esters Chemical class 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 14
- 239000006229 carbon black Substances 0.000 claims abstract description 13
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 8
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 8
- 229920001194 natural rubber Polymers 0.000 claims abstract description 8
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 10
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 6
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 abstract description 16
- 241000872198 Serjania polyphylla Species 0.000 abstract 1
- -1 phthalic acid ester Chemical class 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- IABJHLPWGMWHLX-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)propyl-trimethoxysilane Chemical compound C1=CC=C2SC(CCC[Si](OC)(OC)OC)=NC2=C1 IABJHLPWGMWHLX-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、タイヤトレッド用ゴム組成物に関し、さらに詳しくは、液状ポリブタジエンを含むゴム組成物において、低温性能及び耐摩耗性を維持しながら、ドライグリップ性能とウェットグリップ性能を向上するようにしたオールシーズン用タイヤに好適なタイヤトレッド用ゴム組成物に関する。 The present invention relates to a rubber composition for tire treads, and more particularly, in a rubber composition containing liquid polybutadiene, which improves dry grip performance and wet grip performance while maintaining low temperature performance and wear resistance. The present invention relates to a rubber composition for a tire tread suitable for a tire for a season.
オールシーズン用の空気入りタイヤは、高速走行時における乾燥路面での操縦安定性（ドライグリップ性能）や湿潤路面での操縦安定性（ウェットグリップ性能）を具備することの他に、低温時や積雪路面での操縦安定性（低温グリップ性能）などの低温性能を具備することが必要であるため、広範な条件下で高いレベルの走行安定性と共に、耐摩耗性に優れることが求められている。 Pneumatic tires for all seasons have handling stability on dry roads (dry grip performance) and driving stability on wet roads (wet grip performance) at high speeds, as well as low temperatures and snow cover. Since it is necessary to have low-temperature performance such as steering stability (low-temperature grip performance) on the road surface, it is required to have high level of running stability and excellent wear resistance under a wide range of conditions.
一般に、オールシーズン用空気入りタイヤのドライグリップ性能を向上するためには、ガラス転移温度（Ｔｇ）が高いスチレン−ブタジエンゴムを使用したり、シリカとカーボンブラックを併用したりするが、低温性能や耐摩耗性が悪化するという問題があった。 In general, in order to improve the dry grip performance of pneumatic tires for all seasons, styrene-butadiene rubber having a high glass transition temperature (Tg) is used or silica and carbon black are used in combination. There was a problem that wear resistance deteriorated.
このような低温性能や耐摩耗性を向上する対策として、特許文献１は、液状ポリブタジエンなどの液状ポリマーを配合することを提案している。しかし、この方法では、強度や高温時の硬さが低下するので、ドライグリップ性能及びウェットグリップ性能が悪化するという問題があった。
本発明の目的は、液状ポリブタジエンを含むタイヤトレッド用ゴム組成物において、低温性能及び耐摩耗性を維持しながら、ドライグリップ性能とウェットグリップ性能を向上するようにしたタイヤトレッド用ゴム組成物を提供することにある。 An object of the present invention is to provide a rubber composition for a tire tread containing liquid polybutadiene, which improves dry grip performance and wet grip performance while maintaining low temperature performance and wear resistance. There is to do.
上記目的を達成する本発明のタイヤトレッド用ゴム組成物は、天然ゴム又はブタジエンゴムを４０重量％以上含むジエン系ゴム１００重量部に対し、窒素吸着比表面積が７０〜１３０ｍ２／ｇのカーボンブラックを３〜５０重量部、シリカを７０〜１２０重量部、数平均分子量が２０００〜１００００でビニル結合含有量が５０％以下の液状ポリブタジエンを１〜２０重量部、エステル系可塑剤を１〜１５重量部を配合したことを特徴とする。 The rubber composition for a tire tread of the present invention that achieves the above object is a carbon black having a nitrogen adsorption specific surface area of 70 to 130 m 2 / g based on 100 parts by weight of a diene rubber containing 40% by weight or more of natural rubber or butadiene rubber. 3 to 50 parts by weight, silica 70 to 120 parts by weight, number average molecular weight 2000 to 10,000 and 1 to 20 parts by weight of liquid polybutadiene having a vinyl bond content of 50% or less, and ester plasticizer 1 to 15 parts by weight. It is characterized by blending parts.
前記エステル系可塑剤は、ベンジルブチルフタレート、フタル酸ジイソノニル、フタル酸ビス（２−エチルヘキシル）から選ばれる少なくとも１種にするとよい。 The ester plasticizer may be at least one selected from benzyl butyl phthalate, diisononyl phthalate, and bis (2-ethylhexyl) phthalate.
このタイヤトレッド用ゴム組成物は、空気入りタイヤのトレッド部を構成するのに好適である。 This rubber composition for a tire tread is suitable for constituting a tread portion of a pneumatic tire.
本発明のタイヤトレッド用ゴム組成物は、天然ゴム又はブタジエンゴムを４０重量％以上含むジエン系ゴム１００重量部に対し、窒素吸着比表面積が７０〜１３０ｍ２／ｇのカーボンブラックを３〜５０重量部、数平均分子量が２０００〜１００００でビニル結合含有量が５０％以下の液状ポリブタジエンを１〜２０重量部を配合することにより、低温時のゴム硬さを柔軟にして低温性能及び耐摩耗性を確保することができる。また、上記配合により生じる高温時のゴム硬さの低下を、シリカを７０〜１２０重量部、エステル系可塑剤を１〜１５重量部を配合することにより可及的に小さくし、しかも高いレベルで維持するようにしたので、低温性能及び耐摩耗性を維持しながら、ドライグリップ性能及びウェットグリップ性能を向上することができる。 The rubber composition for a tire tread of the present invention is 3 to 50 weight percent of carbon black having a nitrogen adsorption specific surface area of 70 to 130 m 2 / g with respect to 100 weight parts of diene rubber containing 40% by weight or more of natural rubber or butadiene rubber. By blending 1 to 20 parts by weight of a liquid polybutadiene having a number average molecular weight of 2000 to 10000 and a vinyl bond content of 50% or less, the rubber hardness at low temperature is made flexible and low temperature performance and wear resistance are improved. Can be secured. Moreover, the decrease in rubber hardness at high temperature caused by the above blending is made as small as possible by blending 70 to 120 parts by weight of silica and 1 to 15 parts by weight of an ester plasticizer, and at a high level. Since it is maintained, dry grip performance and wet grip performance can be improved while maintaining low temperature performance and wear resistance.
本発明のタイヤトレッド用ゴム組成物において、ジエン系ゴムは、天然ゴム又はブタジエンゴムを４０重量％以上、好ましくは４０〜７０重量％を含有する。より好ましくはブタジエンゴムを４０〜６０重量％含むとよい。天然ゴム及びブタジエンゴムの含有量が４０重量％未満であると、低温性能及び耐摩耗性が悪化する。 In the rubber composition for a tire tread of the present invention, the diene rubber contains 40% by weight or more, preferably 40 to 70% by weight, of natural rubber or butadiene rubber. More preferably, it is good to contain 40-60 weight% of butadiene rubbers. When the content of natural rubber and butadiene rubber is less than 40% by weight, the low temperature performance and wear resistance are deteriorated.
天然ゴム又はブタジエンゴム以外のジエン系ゴムとしては、特に制限されるものではなく、タイヤトレッド用ゴム組成物に通常用いられるイソプレンゴム、スチレン−ブタジエンゴム、アクリロニトリル−ブタジエンゴム、ブチルゴム等が挙げられる。好ましくはガラス転移温度（Ｔｇ）が高いスチレン−ブタジエンゴムがよい。スチレン−ブタジエンゴムを配合することにより、ドライグリップ性能及びウェットグリップ性能を向上することができる。しかし、スチレン−ブタジエンゴムが多すぎると低温性能及び耐摩耗性が悪化するため、スチレン−ブタジエンゴムの配合量は、３０〜６０重量％にするとよい。これらジエン系ゴムは、単独又は任意のブレンドとして使用することができる。 The diene rubber other than natural rubber or butadiene rubber is not particularly limited, and examples thereof include isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and butyl rubber that are usually used in rubber compositions for tire treads. Styrene-butadiene rubber having a high glass transition temperature (Tg) is preferable. By blending styrene-butadiene rubber, dry grip performance and wet grip performance can be improved. However, if there is too much styrene-butadiene rubber, the low-temperature performance and wear resistance deteriorate, so the blending amount of styrene-butadiene rubber is preferably 30 to 60% by weight. These diene rubbers can be used alone or as any blend.
本発明では、液状ポリブタジエンを配合することにより、タイヤトレッド用ゴム組成物の低温性能及び耐摩耗性をいっそう向上させる。液状ポリブタジエンの数平均分子量は、２０００〜１００００であり、好ましくは２０００〜９０００にするとよい。液状ポリブタジエンの数平均分子量が２０００未満であると、所期の効果が得られない。また、数平均分子量が１００００を超えると、低温での硬度が高くなる傾向がある。なお、液状ポリブタジエンの数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される値とする。 In this invention, the low temperature performance and abrasion resistance of the rubber composition for tire treads are further improved by blending liquid polybutadiene. The number average molecular weight of the liquid polybutadiene is 2000 to 10000, preferably 2000 to 9000. If the number average molecular weight of the liquid polybutadiene is less than 2,000, the desired effect cannot be obtained. Moreover, when the number average molecular weight exceeds 10,000, the hardness at low temperature tends to increase. The number average molecular weight of the liquid polybutadiene is a value measured by gel permeation chromatography (GPC).
液状ポリブタジエンのビニル結合含有量は５０％以下であり、好ましくは２０〜４５％にするとよい。ビニル結合含有量が５０％を超えると、ガラス転移温度が高くなり、低温性能が悪化する。液状ポリブタジエンのビニル結合含有量は、赤外吸収分光法により測定される値とする。 The vinyl bond content of the liquid polybutadiene is 50% or less, preferably 20 to 45%. If the vinyl bond content exceeds 50%, the glass transition temperature increases and the low-temperature performance deteriorates. The vinyl bond content of the liquid polybutadiene is a value measured by infrared absorption spectroscopy.
液状ポリブタジエンの配合量はジエン系ゴム１００重量部に対し１〜２０重量部にし、好ましくは５〜１０重量部にする。液状ポリブタジエンの配合量が１重量部未満では、低温性能及び耐摩耗性を向上することができない。また、液状ポリブタジエンの配合量が２０重量部を超えると、ゴム組成物の強度や高温時の硬さが低下するので、ドライグリップ性能及びウェットグリップ性能が悪化する。 The blending amount of the liquid polybutadiene is 1 to 20 parts by weight, preferably 5 to 10 parts by weight with respect to 100 parts by weight of the diene rubber. When the blending amount of the liquid polybutadiene is less than 1 part by weight, the low temperature performance and the wear resistance cannot be improved. Moreover, since the intensity | strength of a rubber composition and the hardness at the time of high temperature will fall when the compounding quantity of liquid polybutadiene exceeds 20 weight part, dry grip performance and wet grip performance deteriorate.
本発明のタイヤトレッド用ゴム組成物では、エステル系可塑剤を配合することにより、低温時のゴム硬さが過大になるのを防ぎながら、高温時のゴム硬さを高いレベルで維持することができる。すなわち、低温時のゴム硬さが過大になるのを防ぐので低温性能及び耐摩耗性を低下させることがなく、しかも高温時のゴム硬さを高いレベルで維持するためドライグリップ性能及びウェットグリップ性能を向上する。また、ゴム組成物に配合するアロマオイルの一部を置換して配合することができるので、転がり抵抗を低減すること及びカーボンブラックやシリカなどの補強充填剤の配合量を多くすることができる。 In the rubber composition for a tire tread of the present invention, by adding an ester plasticizer, it is possible to maintain the rubber hardness at a high level at a high level while preventing the rubber hardness at a low temperature from becoming excessive. it can. In other words, the rubber hardness at low temperatures is prevented from becoming excessive, so that the low temperature performance and wear resistance are not degraded, and the dry grip performance and wet grip performance are maintained to maintain the rubber hardness at high temperatures at a high level. To improve. In addition, since a part of the aroma oil blended in the rubber composition can be substituted and blended, the rolling resistance can be reduced and the blending amount of the reinforcing filler such as carbon black or silica can be increased.
エステル系可塑剤としては、例えば、フタル酸エステル、アジピン酸エステル、セバシン酸エステル、グルセリンエステル、マレイン酸エステル、フマル酸エステル、ピロメリット酸エステル等を例示することができる。好ましくは、フタル酸エステル、アジピン酸エステル、セバシン酸エステルがよい。これらエステル系可塑剤は、単独又は複数で使用することができる。 Examples of the ester plasticizer include phthalic acid ester, adipic acid ester, sebacic acid ester, glycerin ester, maleic acid ester, fumaric acid ester, and pyromellitic acid ester. Preferably, phthalic acid ester, adipic acid ester, and sebacic acid ester are preferable. These ester plasticizers can be used alone or in combination.
本発明で使用するエステル系可塑剤は、ベンジルブチルフタレート、フタル酸ジイソノニル、フタル酸ビス（２−エチルヘキシル）から選ばれる少なくとも１種にするとよく、とりわけベンジルブチルフタレートが好ましい。 The ester plasticizer used in the present invention may be at least one selected from benzyl butyl phthalate, diisononyl phthalate, and bis (2-ethylhexyl) phthalate, and benzyl butyl phthalate is particularly preferable.
エステル系可塑剤の配合量は、ジエン系ゴム１００重量部に対し１〜１５重量部であり、好ましくは５〜１０重量部にするとよい。エステル系可塑剤の配合量が１重量部未満では、ドライグリップ性能及びウェットグリップ性能を向上することができない。また、エステル系可塑剤が１５重量部を超えると、ブリードが発生する。 The compounding amount of the ester plasticizer is 1 to 15 parts by weight, preferably 5 to 10 parts by weight based on 100 parts by weight of the diene rubber. When the amount of the ester plasticizer is less than 1 part by weight, the dry grip performance and the wet grip performance cannot be improved. If the ester plasticizer exceeds 15 parts by weight, bleeding occurs.
本発明で使用するカーボンブラックは、窒素吸着比表面積（Ｎ２ＳＡ）が、７０〜１３０ｍ２／ｇであり、好ましくは９０〜１３０ｍ２／ｇにするとよい。窒素吸着比表面積が７０ｍ２／ｇ未満のときは、耐摩耗性が不足する。１３０ｍ２／ｇを超えるときは、低温時の硬さが過大になり低温性能が悪化する。窒素吸着比表面積は、ＪＩＳ Ｋ６２１７−２に準拠して、測定するものとする。 The carbon black used in the present invention has a nitrogen adsorption specific surface area (N 2 SA) of 70 to 130 m 2 / g, preferably 90 to 130 m 2 / g. When the nitrogen adsorption specific surface area is less than 70 m 2 / g, the wear resistance is insufficient. When exceeding 130 m < 2 > / g, the hardness at the time of low temperature becomes excessive, and low temperature performance deteriorates. The nitrogen adsorption specific surface area shall be measured according to JIS K6217-2.
カーボンブラックの配合量は、ジエン系ゴム１００重量部に対し、３〜５０重量部であり、好ましくは１０〜４０重量部にするとよい。カーボンブラックが３重量部未満の場合、耐摩耗性が不足する。カーボンブラックが５０重量部を超えると低温時の硬さが過大になり低温性能が悪化する。 The compounding amount of carbon black is 3 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the diene rubber. When carbon black is less than 3 parts by weight, the wear resistance is insufficient. If the carbon black exceeds 50 parts by weight, the hardness at low temperature becomes excessive and the low temperature performance deteriorates.
本発明のゴム組成物は、シリカをジエン系ゴム１００重量部に対し７０〜１２０重量部配合する。好ましくは８０〜１００重量部にするとよい。シリカの配合量が７０重量部未満であると、ドライグリップ性能及びウェットグリップ性能を向上する効果が十分に得られない。また、シリカの配合量が１２０重量部を超えると、混合時の加工性が悪化する。シリカの種類は、特に限定されるものではなく、通常ゴム組成物に配合されるものを使用することができ、例えば湿式法シリカ、乾式法シリカ、表面処理シリカを例示することができる。 In the rubber composition of the present invention, 70 to 120 parts by weight of silica is blended with 100 parts by weight of the diene rubber. Preferably it is 80-100 weight part. When the amount of silica is less than 70 parts by weight, the effect of improving the dry grip performance and the wet grip performance cannot be sufficiently obtained. Moreover, when the compounding quantity of a silica exceeds 120 weight part, the workability at the time of mixing will deteriorate. The kind of silica is not particularly limited, and those usually blended in a rubber composition can be used. Examples thereof include wet method silica, dry method silica, and surface-treated silica.
本発明において、シランカップリング剤をトレッド用ゴム組成物中に配合したシリカ重量に対して好ましくは３〜１５重量％、より好ましくは５〜１０重量％を配合するとよい。シランカップリング剤の配合により、シリカの分散性を向上しゴムとの補強性を高めることができる。シランカップリング剤がシリカ重量の３重量％未満の場合、シリカの分散が悪化する。また、シランカップリング剤が１５重量％を超える場合、シランカップリング剤同士が重合してしまい、所望の効果を得ることができない。 In this invention, it is preferable to mix | blend 3-15 weight% with respect to the silica weight which mix | blended the silane coupling agent in the rubber composition for tread, More preferably, it is good to mix | blend 5-10 weight%. By compounding a silane coupling agent, the dispersibility of silica can be improved and the reinforcement with rubber can be enhanced. When the silane coupling agent is less than 3% by weight of silica, the dispersion of silica is deteriorated. Moreover, when a silane coupling agent exceeds 15 weight%, silane coupling agents will superpose | polymerize and a desired effect cannot be acquired.
シランカップリング剤の種類は、シリカ配合のゴム組成物に使用可能なものであれば特に制限されるものではないが、例えば、ビス−（３−トリエトキシシリルプロピル）テトラサルファイド、ビス（３−トリエトキシシリルプロピル）ジサルファイド、３−トリメトキシシリルプロピルベンゾチアゾールテトラサルファイド、γ−メルカプトプロピルトリエトキシシラン、３−オクタノイルチオプロピルトリエトキシシラン等の硫黄含有シランカップリング剤を例示することができる。 The type of the silane coupling agent is not particularly limited as long as it can be used for the rubber composition containing silica. For example, bis- (3-triethoxysilylpropyl) tetrasulfide, bis (3- Examples thereof include sulfur-containing silane coupling agents such as (triethoxysilylpropyl) disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, γ-mercaptopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane. .
タイヤトレッド用ゴム組成物には、加硫又は架橋剤、加硫促進剤、加工助剤、老化防止剤、可塑剤などのゴム組成物に一般的に使用される各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練してゴム組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 The tire tread rubber composition may contain various additives generally used in rubber compositions such as a vulcanization or crosslinking agent, a vulcanization accelerator, a processing aid, an anti-aging agent, and a plasticizer. Such an additive can be kneaded by a general method to form a rubber composition, which can be used for vulcanization or crosslinking. The blending amounts of these additives may be conventional conventional blending amounts as long as the object of the present invention is not adversely affected.
タイヤトレッド用ゴム組成物は、公知のゴム用混練機械、例えば、バンバリーミキサー、ニーダー、ロール等を使用して、上記各成分を混合することによって製造することができる。 The rubber composition for a tire tread can be produced by mixing each of the above components using a known rubber kneading machine such as a Banbury mixer, a kneader, or a roll.
本発明のタイヤトレッド用ゴム組成物からなるトレッド部を有する空気入りタイヤは、優れた低温性能及び耐摩耗性を維持しながら、ドライグリップ性能とウェットグリップ性能を向上した特性を有し、オールシーズン用タイヤとして好適である。 The pneumatic tire having a tread portion comprising the rubber composition for a tire tread of the present invention has characteristics that improve dry grip performance and wet grip performance while maintaining excellent low temperature performance and wear resistance, It is suitable as a tire.
以下、実施例によって本発明をさらに説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, the scope of the present invention is not limited to these Examples.
表１、２に示す配合からなる１４種類のゴム組成物（実施例１〜６、従来例、比較例１〜７）を、それぞれ硫黄及び加硫促進剤を除く配合成分を秤量し、１.７Ｌのバンバリーミキサーで５分間混練し、温度１６０℃でマスターバッチを放出した。このマスターバッチを８インチのオープンロールに供し、硫黄及び加硫促進剤を加え４分間混合し、タイヤトレッド用ゴム組成物を調製した。 14 kinds of rubber compositions (Examples 1 to 6, Conventional Examples and Comparative Examples 1 to 7) having the compositions shown in Tables 1 and 2 were weighed for the ingredients except sulfur and a vulcanization accelerator, respectively. The mixture was kneaded with a 7 L Banbury mixer for 5 minutes, and the master batch was discharged at a temperature of 160 ° C. This master batch was subjected to an 8-inch open roll, and sulfur and a vulcanization accelerator were added and mixed for 4 minutes to prepare a rubber composition for a tire tread.
得られた１４種類のタイヤトレッド用ゴム組成物（実施例１〜６、従来例、比較例１〜７）により構成したトレッド部を備えた、タイヤサイズ１９５／６５Ｒ１５の空気入りタイヤを製作した。それぞれの空気入りタイヤのドライグリップ性能、ウェットグリップ性能及び耐摩耗性を下記の方法により評価した。 Pneumatic tires having a tire size of 195 / 65R15, each having a tread portion constituted by the obtained 14 types of rubber compositions for tire treads (Examples 1 to 6, conventional examples and comparative examples 1 to 7), were produced. The dry grip performance, wet grip performance and wear resistance of each pneumatic tire were evaluated by the following methods.
また、得られた１４種類のタイヤトレッド用ゴム組成物（実施例１〜６、従来例、比較例１〜７）を、それぞれ所定形状の金型中で、１５０℃、３０分間加硫して試験片を作製し、下記に示す方法により、各種ゴム物性の試験を行った。 Further, the obtained 14 types of rubber compositions for tire treads (Examples 1 to 6, conventional examples, and Comparative Examples 1 to 7) were respectively vulcanized in a mold having a predetermined shape at 150 ° C. for 30 minutes. Test pieces were prepared, and various physical properties of the rubber were tested by the methods shown below.
ドライグリップ性能
空気入りタイヤをサイズ１５×６Ｊのリムにリム組みし、ＪＡＴＭＡイヤーブックに記載の正規空気圧を充填し、国産２．５リットルクラスの車両に装着して、乾燥路面からなるテストコースを走行時のドライグリップ性能を専門パネラー５名が１０点満点でフィーリング評価し、その平均点を求めた。得られた結果は、従来例のタイヤを１００とする指数として表１、２に示した。この値が大きいほどドライグリップ性能が優れている。
Dry grip performance Pneumatic tires are assembled on a rim of size 15x6J, filled with regular air pressure as described in JATMA Yearbook, and mounted on a domestic 2.5 liter class vehicle, a test course consisting of a dry road surface The five expert panelists evaluated the dry grip performance during running with a 10-point scale, and found the average score. The obtained results are shown in Tables 1 and 2 as an index with the conventional tire as 100. The larger this value, the better the dry grip performance.
ウェットグリップ性能
空気入りタイヤをサイズ１５×６Ｊのリムにリム組みし、ＪＡＴＭＡイヤーブックに記載の正規空気圧を充填し、国産２．５リットルクラスの車両に装着して、湿潤路面（水深約１０ｍｍ）からなるテストコースを走行時のウェットグリップ性能を専門パネラー５名が１０点満点でフィーリング評価し、その平均点を求めた。得られた結果は、従来例のタイヤを１００とする指数として表１、２に示した。この値が大きいほどウェットグリップ性能が優れている。
Wet grip performance Pneumatic tires are assembled on a rim of size 15 x 6J, filled with regular air pressure as described in the JATMA Yearbook, and mounted on domestic 2.5 liter class vehicles. Wet road surface (water depth of about 10mm) The five expert panelists evaluated the wet grip performance when driving on the test course consisting of 10 points out of 10 and determined the average score. The obtained results are shown in Tables 1 and 2 as an index with the conventional tire as 100. The larger this value, the better the wet grip performance.
耐摩耗性
空気入りタイヤをサイズ１５×６Ｊのリムにリム組みし、ＪＡＴＭＡイヤーブックに記載の正規空気圧を充填し、国産２．５リットルクラスの車両に装着して、乾燥路面からなるテストコースを５０００ｋｍ走行後の摩耗量を求めた。得られた結果は、従来例のタイヤの逆数を１００とする指数として表１、２に示した。この値が大きいほど耐摩耗性が優れている。
Wear resistance Pneumatic tires are assembled on a rim of size 15x6J, filled with regular air pressure as described in JATMA Yearbook, mounted on domestic 2.5 liter class vehicles, and a test course consisting of a dry road surface The amount of wear after traveling 5000 km was determined. The obtained results are shown in Tables 1 and 2 as an index with the reciprocal of the conventional tire as 100. The larger this value, the better the wear resistance.
低温性能（−２０℃での硬度）
得られた試験片の硬度を、ＪＩＳ Ｋ６２５３に準拠して、デュロメータのタイプＡにより温度−２０℃で測定した。得られた結果は、従来例の逆数を１００とする指数として表１、２に示した。この値が大きいほど低温時の硬度が低く、低温性能が優れている。
Low temperature performance (hardness at -20 ° C)
The hardness of the obtained test piece was measured at a temperature of −20 ° C. with a durometer type A in accordance with JIS K6253. The obtained results are shown in Tables 1 and 2 as indices with the reciprocal of the conventional example as 100. The larger this value, the lower the hardness at low temperature and the better the low temperature performance.
３００％モジュラス
得られた試験片のモジュラスを、ＪＩＳ Ｋ６２５１に準拠して３００％モジュラスを測定した。得られた結果は、従来例を１００とする指数として表１、２に示した。この値が大きいほど強度が大きく優れている。
300% Modulus The modulus of the obtained test piece was measured according to JIS K6251. The obtained results are shown in Tables 1 and 2 as an index with the conventional example as 100. The greater this value, the greater the strength and the better.
高温硬度（６０℃での硬度）
得られた試験片の硬度を、ＪＩＳ Ｋ６２５３に準拠して、デュロメータのタイプＡにより温度６０℃で測定した。得られた結果は、従来例を１００とする指数として表１、２に示した。この値が大きいほど高温時の硬度が高く優れている。
High temperature hardness (hardness at 60 ° C)
The hardness of the obtained test piece was measured at a temperature of 60 ° C. with a durometer type A in accordance with JIS K6253. The obtained results are shown in Tables 1 and 2 as an index with the conventional example as 100. The higher this value, the higher the hardness at high temperature.
転がり抵抗
得られた試験片をＪＩＳ Ｋ６３９４に準拠して、東洋精機製作所社製粘弾性スペクトロメーターを用いて、初期歪み１０％、振幅±２％、周波数２０Ｈｚ、温度６０℃の条件におけるｔａｎδを測定した。得られた結果は、従来例を１００とする指数で表わし表１、２に示した。この指数が小さいほどがｔａｎδが小さく転がり抵抗が低く優れている。
Rolling resistance Based on JIS K6394, tan δ under conditions of initial strain 10%, amplitude ± 2%, frequency 20 Hz, temperature 60 ° C. was measured using the viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd. did. The obtained results are shown in Tables 1 and 2 as an index with the conventional example being 100. The smaller this index is, the smaller the tan δ is, and the lower the rolling resistance is.
なお、表１，２において使用した原材料の種類を下記に示す。
ＮＲ：天然ゴム、ＲＳＳ＃３
ＢＲ：ブタジエンゴム、日本ゼオン社製ＮＩＰＯＬ ＢＲ１２２０
ＳＢＲ：スチレン−ブタジエンゴム、日本ゼオン社製ＮＳ４４０
Ｌ−ＢＲ−１：液状ポリブタジエン、Ｓａｒｔｏｍｅｒ社製ＲＩＣＯＮ１３０（数平均分子量２５００、ビニル結合含有量２８％）
Ｌ−ＢＲ−２：液状ポリブタジエン、Ｓａｒｔｏｍｅｒ社製ＲＩＣＯＮ１３１（数平均分子量４５００、ビニル結合含有量２８％）
Ｌ−ＢＲ−３：液状ポリブタジエン、Ｓａｒｔｏｍｅｒ社製ＲＩＣＯＮ１５２（数平均分子量２９００、ビニル結合含有量８０％）
エステル系可塑剤−１：ベンジルブチルフタレート、バイエル社製ＵＮＩＭＯＬＬ ＢＢ
エステル系可塑剤−２：フタル酸ジイソノニル、ジェイプラス社製ＤＩＮＰ
ＣＢ−１：カーボンブラック、キャボットジャパン社製ショウブラックＮ２３４（窒素吸着比表面積１２６ｍ２／ｇ）
ＣＢ−２：カーボンブラック、キャボットジャパン社製ショウブラックＮ１１０（窒素吸着比表面積１４４ｍ２／ｇ）
ＣＢ−３：カーボンブラック、キャボットジャパン社製ショウブラックＮ５５０（窒素吸着比表面積４２ｍ２／ｇ）
シリカ：ローディア社製Ｚｅｏｓｉｌ １６５ＧＲ
シランカップリング剤：Ｄｅｇｕｓｓａ社製Ｓｉ６９
酸化亜鉛：正同化学工業社製酸化亜鉛３種
ステアリン酸：日本油脂社製ビーズステアリン酸
老化防止剤：フレキシス社製ＳＡＮＴＯＦＬＥＸ ６ＰＰＤ
加工助剤：ラインケミー社製Ａｃｔｉｐｌａｓｔ ＳＴ
アロマオイル：昭和シェル石油社製エキストラクト４号Ｓ
硫黄：鶴見化学工業社製金華印油入微粉硫黄
加硫促進剤−１：大内新興化学工業社製ノクセラーＣＺ−Ｇ
加硫促進剤−２：住友化学社製ソクシノールＤ−Ｇ
The types of raw materials used in Tables 1 and 2 are shown below.
NR: natural rubber, RSS # 3
BR: butadiene rubber, NIPOL BR1220 manufactured by Nippon Zeon Co., Ltd.
SBR: styrene-butadiene rubber, NS440 manufactured by Nippon Zeon Co., Ltd.
L-BR-1: Liquid polybutadiene, RICON 130 manufactured by Sartomer (number average molecular weight 2500, vinyl bond content 28%)
L-BR-2: Liquid polybutadiene, RICON 131 manufactured by Sartomer (number average molecular weight 4500, vinyl bond content 28%)
L-BR-3: Liquid polybutadiene, RICON152 manufactured by Sartomer (number average molecular weight 2900, vinyl bond content 80%)
Ester plasticizer-1: benzyl butyl phthalate, UNIMOL BB manufactured by Bayer
Ester plasticizer-2: diisononyl phthalate, DINP manufactured by J-Plus
CB-1: carbon black, show black N234 manufactured by Cabot Japan (nitrogen adsorption specific surface area 126 m 2 / g)
CB-2: Carbon black, Cabot Japan Show Black N110 (nitrogen adsorption specific surface area 144 m 2 / g)
CB-3: Carbon black, Cabot Japan Show Black N550 (nitrogen adsorption specific surface area 42 m 2 / g)
Silica: Zeosil 165GR manufactured by Rhodia
Silane coupling agent: Si69 manufactured by Degussa
Zinc oxide: 3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd. Stearic acid: Beads manufactured by Nippon Oil & Fats Co., Ltd. Anti-aging agent for stearic acid: SANTOFLEX 6PPD manufactured by Flexis
Processing aid: Actiplast ST manufactured by Rhein Chemie
Aroma oil: Showa Shell Sekiyu Extract 4 S
Sulfur: Fine powder sulfur vulcanization accelerator with Jinhua seal oil manufactured by Tsurumi Chemical Co., Ltd.-1: Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator-2: Soxinol DG manufactured by Sumitomo Chemical Co., Ltd.
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| JP2008045113A Active JP5233317B2 (en) | 2008-02-26 | 2008-02-26 | Rubber composition for tire tread |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011252069A (en) * | 2010-06-01 | 2011-12-15 | Yokohama Rubber Co Ltd:The | Diene-based rubber composition |
| JP2015034219A (en) * | 2013-08-08 | 2015-02-19 | 住友ゴム工業株式会社 | Tread rubber composition for high-performance wet tire and high-performance wet tire |
| JP2015034220A (en) * | 2013-08-08 | 2015-02-19 | 住友ゴム工業株式会社 | Tread rubber composition for high-performance tire and high-performance tire |
| KR20160037478A (en) * | 2014-09-29 | 2016-04-06 | 금호타이어 주식회사 | Tire-rubber composite with excellent tensile strength and appearance |
| JP2016047885A (en) * | 2014-08-27 | 2016-04-07 | 横浜ゴム株式会社 | Rubber composition for studless tire and studless tire |
| JP2016047888A (en) * | 2014-08-27 | 2016-04-07 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire |
| WO2019116804A1 (en) * | 2017-12-15 | 2019-06-20 | 株式会社ブリヂストン | Rubber composition and pneumatic tire |
| WO2019221179A1 (en) * | 2018-05-16 | 2019-11-21 | 横浜ゴム株式会社 | Rubber composition for tire tread for winter and pneumatic tire for winter |
| WO2020100628A1 (en) * | 2018-11-16 | 2020-05-22 | 株式会社ブリヂストン | Rubber composition, vulcanized rubber, and tire |
| EP3907256A1 (en) * | 2020-05-04 | 2021-11-10 | Evonik Operations GmbH | Rubber mixtures with improved properties |
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| JPS60147450A (en) * | 1984-01-11 | 1985-08-03 | Toyo Tire & Rubber Co Ltd | Tire tread rubber composition |
| JPS61101542A (en) * | 1984-10-24 | 1986-05-20 | Idemitsu Petrochem Co Ltd | Rubber composition |
| JPH02167353A (en) * | 1988-03-10 | 1990-06-27 | Sumitomo Rubber Ind Ltd | Rubber composition and tire using the same in tread |
| JP2006249230A (en) * | 2005-03-10 | 2006-09-21 | Bridgestone Corp | Rubber composition for tread and pneumatic tire using the same |
| JP2007510768A (en) * | 2003-11-04 | 2007-04-26 | コンテイネンタル・アクチエンゲゼルシヤフト | Rubber mixture for tire tread |
| JP2007191510A (en) * | 2006-01-17 | 2007-08-02 | Bridgestone Corp | Pneumatic tire |
| JP2007332246A (en) * | 2006-06-14 | 2007-12-27 | Bridgestone Corp | Rubber composition and tire using the same |
| JP2009084495A (en) * | 2007-10-01 | 2009-04-23 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread, and pneumatic tire using it |
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| JPS60147450A (en) * | 1984-01-11 | 1985-08-03 | Toyo Tire & Rubber Co Ltd | Tire tread rubber composition |
| JPS61101542A (en) * | 1984-10-24 | 1986-05-20 | Idemitsu Petrochem Co Ltd | Rubber composition |
| JPH02167353A (en) * | 1988-03-10 | 1990-06-27 | Sumitomo Rubber Ind Ltd | Rubber composition and tire using the same in tread |
| JP2007510768A (en) * | 2003-11-04 | 2007-04-26 | コンテイネンタル・アクチエンゲゼルシヤフト | Rubber mixture for tire tread |
| JP2006249230A (en) * | 2005-03-10 | 2006-09-21 | Bridgestone Corp | Rubber composition for tread and pneumatic tire using the same |
| JP2007191510A (en) * | 2006-01-17 | 2007-08-02 | Bridgestone Corp | Pneumatic tire |
| JP2007332246A (en) * | 2006-06-14 | 2007-12-27 | Bridgestone Corp | Rubber composition and tire using the same |
| JP2009084495A (en) * | 2007-10-01 | 2009-04-23 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread, and pneumatic tire using it |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011252069A (en) * | 2010-06-01 | 2011-12-15 | Yokohama Rubber Co Ltd:The | Diene-based rubber composition |
| JP2015034219A (en) * | 2013-08-08 | 2015-02-19 | 住友ゴム工業株式会社 | Tread rubber composition for high-performance wet tire and high-performance wet tire |
| JP2015034220A (en) * | 2013-08-08 | 2015-02-19 | 住友ゴム工業株式会社 | Tread rubber composition for high-performance tire and high-performance tire |
| JP2016047885A (en) * | 2014-08-27 | 2016-04-07 | 横浜ゴム株式会社 | Rubber composition for studless tire and studless tire |
| JP2016047888A (en) * | 2014-08-27 | 2016-04-07 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire |
| KR20160037478A (en) * | 2014-09-29 | 2016-04-06 | 금호타이어 주식회사 | Tire-rubber composite with excellent tensile strength and appearance |
| KR101674452B1 (en) * | 2014-09-29 | 2016-11-09 | 금호타이어 주식회사 | Tire-rubber composite with excellent tensile strength and appearance |
| JPWO2019116804A1 (en) * | 2017-12-15 | 2020-12-03 | 株式会社ブリヂストン | Rubber composition and pneumatic tire |
| WO2019116804A1 (en) * | 2017-12-15 | 2019-06-20 | 株式会社ブリヂストン | Rubber composition and pneumatic tire |
| CN111465645A (en) * | 2017-12-15 | 2020-07-28 | 株式会社普利司通 | Rubber composition and pneumatic tire |
| CN111465645B (en) * | 2017-12-15 | 2022-11-15 | 株式会社普利司通 | Rubber composition and pneumatic tire |
| JP7218302B2 (en) | 2017-12-15 | 2023-02-06 | 株式会社ブリヂストン | Rubber composition and pneumatic tire |
| US11530318B2 (en) | 2017-12-15 | 2022-12-20 | Bridgestone Corporation | Rubber composition and pneumatic tire |
| WO2019221179A1 (en) * | 2018-05-16 | 2019-11-21 | 横浜ゴム株式会社 | Rubber composition for tire tread for winter and pneumatic tire for winter |
| JP2019199536A (en) * | 2018-05-16 | 2019-11-21 | 横浜ゴム株式会社 | Rubber composition for winter tire tread, and winter pneumatic tire |
| CN112166149A (en) * | 2018-05-16 | 2021-01-01 | 横滨橡胶株式会社 | Rubber composition for winter tire tread and winter pneumatic tire |
| WO2020100628A1 (en) * | 2018-11-16 | 2020-05-22 | 株式会社ブリヂストン | Rubber composition, vulcanized rubber, and tire |
| JPWO2020100628A1 (en) * | 2018-11-16 | 2021-09-30 | 株式会社ブリヂストン | Rubber composition, vulcanized rubber and tires |
| JP7305674B2 (en) | 2018-11-16 | 2023-07-10 | 株式会社ブリヂストン | Rubber composition, vulcanized rubber and tire |
| WO2021223961A1 (en) | 2020-05-04 | 2021-11-11 | Evonik Operations Gmbh | Rubber mixtures with improved properties |
| CN115485329A (en) * | 2020-05-04 | 2022-12-16 | 赢创运营有限公司 | Rubber mixtures with improved properties |
| EP3907256A1 (en) * | 2020-05-04 | 2021-11-10 | Evonik Operations GmbH | Rubber mixtures with improved properties |
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