JP5527014B2 - Rubber composition for tire - Google Patents
Rubber composition for tire Download PDFInfo
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- JP5527014B2 JP5527014B2 JP2010119184A JP2010119184A JP5527014B2 JP 5527014 B2 JP5527014 B2 JP 5527014B2 JP 2010119184 A JP2010119184 A JP 2010119184A JP 2010119184 A JP2010119184 A JP 2010119184A JP 5527014 B2 JP5527014 B2 JP 5527014B2
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- 229920001971 elastomer Polymers 0.000 title claims description 79
- 239000005060 rubber Substances 0.000 title claims description 79
- 239000000203 mixture Substances 0.000 title claims description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 87
- 239000005909 Kieselgur Substances 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 21
- 239000006229 carbon black Substances 0.000 claims description 18
- 229920003244 diene elastomer Polymers 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003094 microcapsule Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 238000004073 vulcanization Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 230000003796 beauty Effects 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000002393 scratching effect Effects 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 239000004636 vulcanized rubber Substances 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 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
- DZZKHFZCOSCMMU-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.S Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.S DZZKHFZCOSCMMU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005096 rolling process Methods 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
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000007704 transition Effects 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
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- -1 γ-mercaptopropyl Chemical group 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、タイヤ用ゴム組成物に関し、さらに詳しくは、耐摩耗性及び引張り強度を維持しながら、氷上摩擦力を従来レベルよりも向上するようにしたタイヤ用ゴム組成物に関する。 The present invention relates to a tire rubber composition, and more particularly to a tire rubber composition in which frictional force on ice is improved from a conventional level while maintaining wear resistance and tensile strength.
氷雪路用空気入りタイヤ（スタッドレスタイヤ）は、水膜に覆われた氷面における制駆動性能（氷上性能）に優れることが求められている。このため特許文献１は、スタッドレスタイヤのトレッド用ゴム組成物に硬度が高い多孔質珪藻土を配合することにより、氷面に対して高硬度粒子による引掻き効果と、多孔質材料による吸水効果とを同時に付与し、氷上摩擦力を向上させることを提案している。 Pneumatic tires (studless tires) for icy and snowy roads are required to have excellent braking / driving performance (performance on ice) on an ice surface covered with a water film. For this reason, Patent Document 1 discloses that a rubber composition for a tread of a studless tire is blended with porous diatomaceous earth having a high hardness, so that the scratching effect by the high hardness particles and the water absorption effect by the porous material are simultaneously applied to the ice surface. It has been proposed to improve the frictional force on ice.
しかしながら、氷上摩擦力を一層向上させるため多孔質珪藻土を増量すると、ゴム組成物の耐摩耗性及び引張り強度が低下することが避けられない。ゴム組成物の耐摩耗性及び引張り強度が低下すると、溝が深くサイプを多数配置したブロックからなるトレッドパターンを有するスタッドレスタイヤの耐久性が低下すると共に、所望の氷上摩擦力が得られないという問題があった。 However, when the amount of porous diatomaceous earth is increased in order to further improve the frictional force on ice, it is inevitable that the wear resistance and tensile strength of the rubber composition are lowered. When the wear resistance and tensile strength of the rubber composition are lowered, the durability of a studless tire having a tread pattern composed of blocks having deep grooves and a large number of sipes is lowered, and a desired frictional force on ice cannot be obtained. was there.
本発明の目的は、耐摩耗性及び引張り強度を維持しながら、氷上摩擦力を従来レベルよりも向上するようにしたタイヤ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 tires that improves the frictional force on ice from the conventional level while maintaining wear resistance and tensile strength.
上記目的を達成する本発明のタイヤ用ゴム組成物は、ジエン系ゴム１００重量部に対し、窒素吸着比表面積が１１０ｍ2／ｇ以上であるカーボンブラックを３５〜６０重量部、珪藻土を１〜１０重量部、硫黄を１．０〜２．５重量部配合すると共に、シリカ及び加硫促進剤を配合し、かつカーボンブラックの配合量をＡ重量部、シリカの配合量をＢ重量部、珪藻土の配合量をＣ重量部、硫黄の配合量をＤ重量部及び加硫促進剤の配合量をＥ重量部とするときに、重量比（Ｂ＋Ｃ）／（Ａ＋Ｂ＋Ｃ）を０．１０〜０．２５、重量比Ｅ／Ｄを０．５０〜１．００にすると共に、前記珪藻土が、メロシラ属に属し、円筒状又は円柱状の多孔質珪藻土であり、その円筒又は円柱の高さが１００μｍ以下であり、前記円筒又は円柱の高さＬと底面の直径Ｄとの比Ｌ／Ｄが０．２〜３．０であることを特徴とする。 In the tire rubber composition of the present invention that achieves the above object, 35 to 60 parts by weight of carbon black having a nitrogen adsorption specific surface area of 110 m 2 / g or more and 1 to 10 diatomaceous earth with respect to 100 parts by weight of diene rubber. parts, the sulfur blending 1.0 to 2.5 parts by weight, blended with silica mosquitoes及 beauty vulcanization accelerator, and a parts by weight amount of carbon black, B parts by weight of the amount of silica, When the blending amount of diatomaceous earth is C parts by weight, the blending amount of sulfur is D parts by weight, and the blending amount of the vulcanization accelerator is E parts by weight, the weight ratio (B + C) / (A + B + C) is 0.10-0. 25, the weight ratio E / D is 0.50 to 1.00, and the diatomaceous earth belongs to the genus Melosilla, and is a cylindrical or columnar porous diatomaceous earth, and the height of the cylinder or column is 100 μm or less. The height L and bottom diameter of the cylinder or cylinder The ratio L / D of is characterized in that 0.2 to 3.0.
またタイヤ用ゴム組成物は、粉砕ゴム、短繊維及び熱膨張性マイクロカプセルから選ばれる少なくとも１種を配合することができ、このとき珪藻土、粉砕ゴム、短繊維及び熱膨張性マイクロカプセルの合計を、前記ジエン系ゴム１００重量部に対し１〜１０重量部にするとよい。前記ジエン系ゴムは、天然ゴム、ポリイソプレンゴム、ポリブタジエンゴム、スチレンブタジエンゴムからなる群から選ばれる少なくとも１種であるとよい。 The tire rubber composition may contain at least one selected from pulverized rubber, short fibers, and thermally expandable microcapsules. At this time, the total of diatomaceous earth, pulverized rubber, short fibers, and thermally expandable microcapsules is calculated. The amount of the diene rubber is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the diene rubber. The diene rubber may be at least one selected from the group consisting of natural rubber, polyisoprene rubber, polybutadiene rubber, and styrene butadiene rubber.
このタイヤ用ゴム組成物を、トレッド部に使用したスタッドレスタイヤは、耐摩耗性及び引張り強度を維持しながら、氷上摩擦力を従来レベルよりも向上することができる。 The studless tire using the tire rubber composition in the tread portion can improve the frictional force on ice from the conventional level while maintaining the wear resistance and the tensile strength.
本発明のタイヤ用ゴム組成物は、ジエン系ゴム１００重量部に対し、窒素吸着比表面積が１１０ｍ2／ｇ以上であるカーボンブラックを３５〜６０重量部、円筒状又は円柱状の多孔質珪藻土であり、その円筒又は円柱の高さＬが１００μｍ以下、円筒又は円柱の底面の直径Ｄに対する高さＬの比Ｌ／Ｄが０．２〜３．０であり、メロシラ属に属する珪藻土を１〜１０重量部及びシリカを配合すると共に、カーボンブラックの配合量をＡ重量部、シリカの配合量をＢ重量部、珪藻土の配合量をＣ重量部にするとき、重量比（Ｂ＋Ｃ）／（Ａ＋Ｂ＋Ｃ）を０．１０〜０．２５にしたので、耐摩耗性の低下を可及的に小さくしながら氷上摩擦力を向上可能にする。また、硫黄の配合量Ｄを１．０〜２．５重量部にすると共に、加硫促進剤の配合量をＥ重量部にするとき、重量比Ｅ／Ｄを０．５０〜１．００にしたので、耐摩耗性及び引張り強度を維持しながら、氷上摩擦力を一層向上することができる。 In the tire rubber composition of the present invention, 35 to 60 parts by weight of carbon black having a nitrogen adsorption specific surface area of 110 m 2 / g or more, cylindrical or columnar porous diatomaceous earth with respect to 100 parts by weight of diene rubber. Yes, the height L of the cylinder or column is 100 μm or less, the ratio L / D of the height L to the diameter D of the bottom of the cylinder or column is 0.2 to 3.0, and diatomaceous earth belonging to the genus Melosilla is 1 to When blending 10 parts by weight and silica, the weight ratio (B + C) / (A + B + C) when the blending amount of carbon black is A parts by weight, the blending amount of silica is B parts by weight, and the blending amount of diatomaceous earth is C parts by weight. Is set to 0.10 to 0.25, so that the frictional force on ice can be improved while reducing the decrease in wear resistance as much as possible. Further, when the blending amount D of sulfur is 1.0 to 2.5 parts by weight and the blending amount of the vulcanization accelerator is E parts by weight, the weight ratio E / D is 0.50 to 1.00. Therefore, the frictional force on ice can be further improved while maintaining the wear resistance and the tensile strength.
本発明のゴム組成物に使用するジエン系ゴムは、特に限定されるものではないが、天然ゴム、ポリイソプレンゴム、ポリブタジエンゴム、スチレンブタジエンゴムからなる群から選ばれる少なくとも１種であるとよい。なかでも、天然ゴム及び／又はブタジエンゴムがより好ましい。これらのジエン系ゴムはガラス転移温度（Ｔｇ）が好ましくは−５０℃以下、より好ましくは−１１０℃〜−７０℃であるとよい。ジエン系ゴムのＴｇを−５０℃以下にすることにより、ゴム組成物の低温状態での硬度が低くなり氷面に対する凝着性を向上し、氷上摩擦力を高くすることができる。なお、本発明において、ジエン系ゴムのＴｇは、示差走査熱量測定（ＤＳＣ）により２０℃／分の昇温速度条件によりサーモグラムを測定し、転移域の中点の温度とした。 The diene rubber used in the rubber composition of the present invention is not particularly limited, but may be at least one selected from the group consisting of natural rubber, polyisoprene rubber, polybutadiene rubber, and styrene butadiene rubber. Of these, natural rubber and / or butadiene rubber are more preferable. These diene rubbers have a glass transition temperature (Tg) of preferably −50 ° C. or lower, more preferably −110 ° C. to −70 ° C. By setting the Tg of the diene rubber to −50 ° C. or less, the hardness of the rubber composition at a low temperature can be lowered, the adhesion to the ice surface can be improved, and the frictional force on ice can be increased. In the present invention, the Tg of the diene rubber was measured by a differential scanning calorimetry (DSC) under a temperature increase rate condition of 20 ° C./min, and was set as the temperature at the midpoint of the transition region.
本発明において、カーボンブラックを配合することにより、ゴム組成物の引張り強度及び耐摩耗性を確保する。カーボンブラックとしては、窒素吸着比表面積（Ｎ２ＳＡ）が１１０ｍ２／ｇ以上、好ましくは１１５〜１５０ｍ２／ｇのものを使用する。カーボンブラックのＮ２ＳＡが１１０ｍ２／ｇ未満であると、ゴム組成物の引張り強度及び耐摩耗性を十分に確保することができない。なお、カーボンブラックのＮ２ＳＡは、ＪＩＳ Ｋ６２１７−２に準拠して求めた。 In the present invention, by blending carbon black, the tensile strength and wear resistance of the rubber composition are ensured. The carbon black, the nitrogen adsorption specific surface area (N 2 SA) of 110m 2 / g or more, preferably used ones 115~150m 2 / g. When the N 2 SA of the carbon black is less than 110 m 2 / g, it is not possible to sufficiently ensure the tensile strength and wear resistance of the rubber composition. Incidentally, N 2 SA of the carbon black was determined 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３５〜６０重量部、好ましくは４０〜５５重量部にする必要がある。カーボンブラックの配合量が３５重量部未満であると、ゴム組成物の引張り強度及び耐摩耗性を十分に確保することができない。また、カーボンブラックの配合量が６０重量部を超えると、引張り強度及び耐摩耗性が低下し、混合加工性も悪化する。 The compounding quantity of carbon black needs to be 35-60 weight part with respect to 100 weight part of diene rubbers, Preferably it is 40-55 weight part. When the blending amount of carbon black is less than 35 parts by weight, the tensile strength and wear resistance of the rubber composition cannot be sufficiently ensured. Moreover, when the compounding quantity of carbon black exceeds 60 weight part, tensile strength and abrasion resistance will fall and mixed workability will also deteriorate.
本発明のゴム組成物において、シリカを配合することにより、ゴム組成物の低温状態の柔軟性を維持し氷面に対する凝着性を高め氷上摩擦力を向上することができる。シリカの配合量は、ジエン系ゴム１００重量部に対し好ましくは１〜１９重量部、より好ましくは５〜１０重量部にするとよい。シリカの配合量が１重量部未満の場合、低温時のゴムの柔軟性を維持し氷面に対する凝着性を高くする効果が十分に得られない。また、シリカの配合量が１９重量部を超えると、引張り強度及び耐摩耗性が著しく低下する。シリカの種類としては、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, by adding silica, the flexibility of the rubber composition at a low temperature can be maintained, the adhesion to the ice surface can be increased, and the frictional force on ice can be improved. The amount of silica is preferably 1 to 19 parts by weight, more preferably 5 to 10 parts by weight, based on 100 parts by weight of the diene rubber. When the amount of silica is less than 1 part by weight, the effect of maintaining the flexibility of rubber at low temperatures and increasing the adhesion to the ice surface cannot be obtained sufficiently. Moreover, when the compounding quantity of silica exceeds 19 weight part, tensile strength and abrasion resistance will fall remarkably. The type 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、珪藻土を配合することにより、氷面に対する引掻き効果と吸水効果とを同時に付与することができる。使用する珪藻土は、円筒状又は円柱状の多孔質珪藻土である。このような形状の多孔質珪藻土を配合することにより、水膜に覆われた氷面に対する引掻き効果を一層高くすると共に、吸水効果を大きくすることができる。なお、通常の珪藻土は、大半が平板状であるため、氷面に対する引掻き効果及び吸水効果が十分に得られない。 In the present invention, by blending diatomaceous earth, a scratching effect on the ice surface and a water absorption effect can be simultaneously imparted. The diatomaceous earth used is a cylindrical or columnar porous diatomaceous earth . By blending such shaped porous diatomaceous earth, it is possible to further enhance the scratching effect on the ice surface covered with the water film and to increase the water absorption effect. In addition, since most normal diatomaceous earth is flat form, the scratching effect with respect to an ice surface and the water absorption effect are not fully acquired.
円筒状又は円柱状の多孔質珪藻土は、その高さＬが１００μｍ以下、好ましくは１〜３０μｍである。高さＬを１００μｍ以下にすることにより、ゴム組成物の引張り強度及び耐摩耗性の低下を抑制することができる。また、円筒状又は円柱状の多孔質珪藻土の底面の直径Ｄに対する高さＬの比Ｌ／Ｄは０．２〜３．０、好ましくは０．３〜２．０である。多孔質珪藻土の比Ｌ／Ｄをこのような範囲内にすることにより、氷面に対する引掻き効果と吸水効果とを同時に付与することができる。このような珪藻土は、メロシラ属に属する多孔質珪藻土である。 Cylindrical or columnar kieselguhr, the height L is 1 00Myuemu less, good Mashiku the Ru 1~30μm der. By making the height L 100 μm or less, it is possible to suppress a decrease in the tensile strength and wear resistance of the rubber composition. The ratio L / D of the height L to the diameter D of the bottom surface of the cylindrical or columnar porous diatomaceous earth is 0 . 2 to 3.0, good Mashiku is Ru 0.3 to 2.0 der. By making the ratio L / D of the porous diatomaceous earth within such a range, a scratching effect on the ice surface and a water absorption effect can be simultaneously imparted. Such diatomaceous earth is kieselguhr belonging to main Roshira genus.
上述した珪藻土の配合量は、ジエン系ゴム１００重量部に対し１〜１０重量部、好ましくは２〜５重量部にする必要がある。珪藻土の配合量が１重量部未満であると、水膜に覆われた氷面に対する引掻き効果及び吸水効果が十分に得られない。また、珪藻土の配合量が１０重量部を超えると、ゴム組成物の引張り強度及び耐摩耗性が低下する。 The blending amount of the diatomaceous earth described above needs to be 1 to 10 parts by weight, preferably 2 to 5 parts by weight with respect to 100 parts by weight of the diene rubber. When the blending amount of diatomaceous earth is less than 1 part by weight, the scratching effect and water absorption effect on the ice surface covered with the water film cannot be sufficiently obtained. Moreover, when the compounding quantity of diatomaceous earth exceeds 10 weight part, the tensile strength and abrasion resistance of a rubber composition will fall.
本発明のゴム組成物は、カーボンブラック、シリカ及び珪藻土を必須成分とするが、カーボンブラックの配合量をＡ重量部、シリカの配合量をＢ重量部、珪藻土の配合量をＣ重量部にするとき、重量比（Ｂ＋Ｃ）／（Ａ＋Ｂ＋Ｃ）を０．１０〜０．２５、好ましくは０．１３〜０．２２にする必要がある。重量比（Ｂ＋Ｃ）／（Ａ＋Ｂ＋Ｃ）が０．１０より小さいと氷上摩擦力が悪化する。また、重量比（Ｂ＋Ｃ）／（Ａ＋Ｂ＋Ｃ）が０．２５より大きいと耐摩耗性及び引張り強度が悪化する。 The rubber composition of the present invention contains carbon black, silica, and diatomaceous earth as essential components. The amount of carbon black is A part by weight, the amount of silica is B part by weight, and the amount of diatomaceous earth is C part by weight. The weight ratio (B + C) / (A + B + C) needs to be 0.10 to 0.25, preferably 0.13 to 0.22. When the weight ratio (B + C) / (A + B + C) is smaller than 0.10, the frictional force on ice is deteriorated. On the other hand, if the weight ratio (B + C) / (A + B + C) is larger than 0.25, the wear resistance and the tensile strength deteriorate.
また、本発明のゴム組成物は、硫黄及び加硫促進剤を配合し、硫黄の配合量をＤ重量部及び加硫促進剤の配合量をＥ重量部とするとき、重量比Ｅ／Ｄを０．５０〜１．００にする必要がある。重量比Ｅ／Ｄが０．５０より小さいとゴム組成物の引張り強度及び耐摩耗性が悪化する。また、重量比Ｅ／Ｄが１．００より大きいとゴム組成物の硬度が高くなり氷上摩擦力が悪化する。またゴム組成物の引張り強度及び耐摩耗性が悪化する。ここで重量比Ｅ／Ｄを好ましくは０．５０〜０．７０、より好ましくは０．５０〜０．６５にすることにより、氷上摩擦力を一層高くすることができる。また重量比Ｅ／Ｄを好ましくは０．６０〜０．９５にすることにより、ゴム組成物の発熱性の悪化を抑制し、タイヤにしたときの耐久性、低転がり抵抗性および氷上摩擦力を高いレベルで兼備することができる。 The rubber composition of the present invention contains sulfur and a vulcanization accelerator, and when the amount of sulfur is D parts by weight and the amount of the vulcanization accelerator is E parts by weight, the weight ratio E / D is It must be 0.50 to 1.00. When the weight ratio E / D is less than 0.50, the tensile strength and wear resistance of the rubber composition are deteriorated. On the other hand, when the weight ratio E / D is larger than 1.00, the hardness of the rubber composition increases and the frictional force on ice deteriorates. Further, the tensile strength and wear resistance of the rubber composition are deteriorated. Here, the frictional force on ice can be further increased by setting the weight ratio E / D to preferably 0.50 to 0.70, more preferably 0.50 to 0.65. Further, by making the weight ratio E / D preferably 0.60 to 0.95, the deterioration of the heat build-up of the rubber composition is suppressed, and the durability, low rolling resistance and frictional force on ice when made into a tire are reduced. Can be combined at a high level.
使用する硫黄及び加硫促進剤としては、通常タイヤ用ゴム組成物に配合可能なものを使用することができる。硫黄の配合量は、ジエン系ゴム１００重量部に対し１．０〜２．５重量部、好ましくは１．３〜２．０重量部にする。 As the sulfur and vulcanization accelerator to be used, those that can be usually blended in a rubber composition for tires can be used. The amount of sulfur, against 100 parts by weight of the diene rubber 1. 0 to 2.5 parts by weight, good Mashiku is you in 1.3 to 2.0 parts by weight.
またタイヤ用ゴム組成物は、粉砕ゴム、短繊維及び熱膨張性マイクロカプセルから選ばれる少なくとも１種を配合することができる。粉砕ゴムを配合すると、粉砕ゴムがトレッドゴムの表面から抜け落ちることにより、トレッドゴム表面に空隙が形成される。このため、吸水効果を発現すると共に、エッジ効果により氷上摩擦力を高くすることができる。このような粉砕ゴムとしては、加硫ゴムや再生ゴムの粉砕品を使用することができる。粉砕ゴムの大きさは特に制限されるものではないが、好ましくは５〜５００μｍ、より好ましくは１５０〜４００μｍにするとよい。 Moreover, the rubber composition for tires can mix | blend at least 1 sort (s) chosen from a ground rubber, a short fiber, and a thermally expansible microcapsule. When the pulverized rubber is blended, the pulverized rubber falls off from the surface of the tread rubber, whereby a void is formed on the surface of the tread rubber. For this reason, while exhibiting a water absorption effect, the frictional force on ice can be increased by the edge effect. As such crushed rubber, pulverized products of vulcanized rubber and recycled rubber can be used. The size of the crushed rubber is not particularly limited, but is preferably 5 to 500 μm, more preferably 150 to 400 μm.
短繊維を配合することにより氷面に対する引掻き効果により氷上摩擦力を高くすることができる。短繊維としては、無機繊維、有機繊維のいずれでもよく、無機繊維としては例えばガラス繊維、炭素繊維、金属繊維等の短繊維を例示することができる。また、有機繊維としては、例えばナイロン繊維、アラミド繊維、ポリエステル繊維、ポリオレフィン繊維、ポリビニルアルコール繊維、セルロース繊維等から選ばれる短繊維を例示することができる。 By blending short fibers, the frictional force on ice can be increased due to the scratching effect on the ice surface. The short fiber may be either an inorganic fiber or an organic fiber, and examples of the inorganic fiber include short fibers such as glass fiber, carbon fiber, and metal fiber. Examples of organic fibers include short fibers selected from nylon fibers, aramid fibers, polyester fibers, polyolefin fibers, polyvinyl alcohol fibers, cellulose fibers, and the like.
また、熱膨張性マイクロカプセルを配合すると、未加硫タイヤの加硫成形時に膨張し、トレッドゴム中に多数の樹脂被覆気泡を形成する。この樹脂被覆気泡により、氷の表面に発生する水膜を効率的に吸収除去すると共に、ミクロなエッジ効果が得られるため、氷上摩擦力を向上させる。このような熱膨張性マイクロカプセルとしては、例えばスェーデン国エクスパンセル社製の商品名「ＥＸＰＡＮＣＥＬ ０９１ＤＵ−８０」又は「ＥＸＰＡＮＣＥＬ ０９２ＤＵ−１２０」等、或いは松本油脂製薬社製の商品名「マイクロスフェアー Ｆ−８５Ｄ」又は「マイクロスフェアー Ｆ−１００Ｄ」等を使用することができる。 Moreover, when a thermally expandable microcapsule is mix | blended, it expand | swells at the time of vulcanization molding of an unvulcanized tire, and many resin-coated bubbles are formed in tread rubber. The resin-coated bubbles efficiently absorb and remove the water film generated on the ice surface, and a micro edge effect is obtained, so that the frictional force on ice is improved. Examples of such thermally expandable microcapsules include trade names “EXPANCEL 091DU-80” and “EXPANEL 092DU-120” manufactured by EXPANSEL, Sweden, or trade names “Microsphere” manufactured by Matsumoto Yushi Seiyaku Co., Ltd. F-85D "or" Microsphere F-100D "can be used.
上述した粉砕ゴム、短繊維及び熱膨張性マイクロカプセルの配合量は、特に制限されるものではないが、ジエン系ゴム１００重量部に対する珪藻土、粉砕ゴム、短繊維及び熱膨張性マイクロカプセルの合計を、好ましくは１〜１０重量部、より好ましくは３〜７重量部になるように配合するとよい。珪藻土、粉砕ゴム、短繊維及び熱膨張性マイクロカプセルの合計が１重量部未満であると氷上摩擦力を高くすることができない。また、珪藻土、粉砕ゴム、短繊維及び熱膨張性マイクロカプセルの合計が１０重量部を超えるとゴム組成物の引張り強度及び耐摩耗性が悪化する。 The blending amount of the above-mentioned crushed rubber, short fiber and thermally expandable microcapsule is not particularly limited, but the total of diatomaceous earth, crushed rubber, short fiber and thermally expandable microcapsule with respect to 100 parts by weight of the diene rubber. The amount is preferably 1 to 10 parts by weight, more preferably 3 to 7 parts by weight. If the total of diatomaceous earth, ground rubber, short fibers, and thermally expandable microcapsules is less than 1 part by weight, the frictional force on ice cannot be increased. On the other hand, if the total of diatomaceous earth, crushed rubber, short fibers, and thermally expandable microcapsules exceeds 10 parts by weight, the tensile strength and wear resistance of the rubber composition are deteriorated.
本発明において、シリカと共にシランカップリング剤を配合することにより、珪藻土及びシリカの分散性を向上しゴムとの補強性を高めことができる。シランカップリング剤の配合量は珪藻土及びシリカ配合量の２〜２０重量％、好ましくは５〜１５重量％にするとよい。シランカップリング剤の配合量が２重量％未満の場合、珪藻土及びシリカの分散を向上する効果が十分に得られないことがある。また、シランカップリング剤の配合量が２０重量％を超える場合、シランカップリング剤同士が凝集・縮合してしまい、所望の効果を得ることができなくなる。 In this invention, by mix | blending a silane coupling agent with a silica, the dispersibility of diatomaceous earth and a silica can be improved, and the reinforcement property with rubber | gum can be improved. The amount of the silane coupling agent is 2 to 20% by weight, preferably 5 to 15% by weight, based on the amount of diatomaceous earth and silica. When the compounding quantity of a silane coupling agent is less than 2 weight%, the effect which improves dispersion | distribution of diatomaceous earth and a silica may not fully be acquired. Moreover, when the compounding quantity of a silane coupling agent exceeds 20 weight%, silane coupling agents will aggregate and condense and it will become impossible to acquire a desired effect.
シランカップリング剤としては、タイヤ用ゴム組成物に使用可能なものであればよく、特に硫黄含有シランカップリング剤が好ましい。硫黄含有シランカップリング剤としては、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を例示することができる。 Any silane coupling agent may be used as long as it can be used in the tire rubber composition, and a sulfur-containing silane coupling agent is particularly preferable. Examples of the sulfur-containing silane coupling agent include bis- (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, and γ-mercaptopropyl. Examples thereof include triethoxysilane and 3-octanoylthiopropyltriethoxysilane.
本発明のタイヤ用ゴム組成物には、上記以外に各種無機充填剤、各種オイル、老化防止剤、可塑化剤（軟化剤）、その他タイヤ用ゴム組成物に一般的に配合されている各種添加剤を配合することができ、これらの添加剤の配合量も、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。本発明のゴム組成物は、通常のゴム用混練機械、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。 In addition to the above, various inorganic fillers, various oils, anti-aging agents, plasticizers (softeners), and other various additives generally blended in tire rubber compositions in addition to the above An additive can be blended, and the blending amount of these additives can be a conventional general blending amount as long as the object of the present invention is not violated. The rubber composition of the present invention can be produced by mixing the above components using a normal rubber kneading machine such as a Banbury mixer, a kneader, or a roll.
本発明のゴム組成物は、耐摩耗性及び引張り強度を維持しながら、氷上摩擦力を従来レベルよりも向上するため、スタッドレスタイヤのトレッド部を構成するのに好適である。本発明のゴム組成物を使用したスタッドレスタイヤは、氷上摩擦力が従来レベルより高く、氷上走行性能が向上すると共に、トレッドゴムの耐摩耗性及び引張り強度が高く、タイヤ耐久性が優れる。 The rubber composition of the present invention is suitable for constituting the tread portion of a studless tire because the frictional force on ice is improved from the conventional level while maintaining wear resistance and tensile strength. The studless tire using the rubber composition of the present invention has a higher frictional force on ice than the conventional level, improves the running performance on ice, has high wear resistance and tensile strength of the tread rubber, and has excellent tire durability.
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に示す配合において、硫黄、加硫促進剤及び熱膨張性マイクロカプセルを除く成分を１６リットル密閉式バンバリーミキサーで１５０℃になるように回転数を調整しながら４分間混練した後、放出して室温冷却した。これに加硫促進剤、硫黄及び熱膨張性マイクロカプセルを配合し、１６リットル密閉式バンバリーミキサーで混合し、１４種類のタイヤ用ゴム組成物（実施例１〜５、比較例１〜９）を調製した。 In the formulation shown in Tables 1 and 2, after kneading the components excluding sulfur, vulcanization accelerator and thermally expandable microcapsule for 4 minutes while adjusting the number of revolutions to 150 ℃ with a 16 liter closed Banbury mixer, Release and cool to room temperature. A vulcanization accelerator, sulfur, and thermally expandable microcapsules are blended into this, and mixed with a 16-liter sealed Banbury mixer, and 14 types of rubber compositions for tires (Examples 1 to 5 and Comparative Examples 1 to 9) are mixed. Prepared.
得られた１４種類のタイヤ用ゴム組成物（実施例１〜５、比較例１〜９）を所定の金型中で１６０℃で２０分間プレス加硫して加硫ゴム試験片を調製した。得られた加硫ゴム試験片の氷上摩擦力、耐摩耗性及び引張り強度を下記に示す方法により評価した。 The obtained 14 types of rubber compositions for tires (Examples 1 to 5, Comparative Examples 1 to 9) were press vulcanized at 160 ° C. for 20 minutes in a predetermined mold to prepare vulcanized rubber test pieces. The resulting vulcanized rubber specimens were evaluated for frictional force on ice, wear resistance, and tensile strength by the following methods.
氷上摩擦力
得られた加硫ゴム試験片を偏平円柱状の台ゴムにはりつけ、インサイドドラム型氷上摩擦試験機を用いて氷上摩擦係数を測定した。測定条件は、温度を−３．０℃、荷重を０．５４ＭＰａ、ドラム回転速度を２５ｋｍ／ｈにした。得られた結果は、比較例１を１００とする指数として表１，２に示した。この指数が大きいほど氷上摩擦力が優れることを意味する。
Friction force on ice The obtained vulcanized rubber specimen was attached to a flat cylindrical base rubber, and the friction coefficient on ice was measured using an inside drum type on-ice friction tester. The measurement conditions were a temperature of −3.0 ° C., a load of 0.54 MPa, and a drum rotation speed of 25 km / h. The obtained results are shown in Tables 1 and 2 as an index with Comparative Example 1 as 100. The larger this index, the better the frictional force on ice.
耐摩耗性
得られた加硫ゴム試験片を、ＪＩＳ Ｋ６２６４に準拠しランボーン摩耗試験機（岩本製作所社製）を使用して、温度２０℃、荷重３９Ｎ、スリップ率３０％、時間４分の条件で摩耗量を測定した。得られた結果は、比較例１の値の逆数を１００とする指数で表わし表１，２に示した。この指数が大きいほど耐摩耗性に優れることを意味する。
Abrasion resistance The obtained vulcanized rubber test piece was conditioned in accordance with JIS K6264 using a Lambourn abrasion tester (manufactured by Iwamoto Seisakusho Co., Ltd.) at a temperature of 20 ° C., a load of 39 N, a slip rate of 30%, and a time of 4 minutes. The amount of wear was measured. The obtained results are shown in Tables 1 and 2 as an index with the reciprocal of the value of Comparative Example 1 as 100. It means that it is excellent in abrasion resistance, so that this index | exponent is large.
引張り強度
得られた加硫ゴム試験片を用いて、ＪＩＳ Ｋ６２５１に準拠し３号型ダンベル試験片を打抜き成形した。この試験片の引張り試験を温度２０℃、引張り速度５００ｍｍ／分の条件で行い、破断時の応力（引張り破断強度）を測定した。得られた結果は、比較例１を１００とする指数として表１，２に示した。この指数が大きいほど引張り強度が優れることを意味する。
Tensile strength No. 3 type dumbbell test piece was punched and molded according to JIS K6251 using the obtained vulcanized rubber test piece. A tensile test of this test piece was performed under the conditions of a temperature of 20 ° C. and a tensile speed of 500 mm / min, and the stress at break (tensile rupture strength) was measured. The obtained results are shown in Tables 1 and 2 as an index with Comparative Example 1 as 100. The larger this index, the better the tensile strength.
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
ＣＢ１：カーボンブラック、窒素吸着比表面積１１７ｍ２／ｇ、新日化カーボン社製ニテロン＃３００
ＣＢ２：カーボンブラック、窒素吸着比表面積１００ｍ２／ｇ、新日化カーボン社製ニテロン＃２００ＩＳ
シリカ：東ソー・シリカ社製ニップシール ＡＱ
珪藻土：円筒状の多孔質珪藻土、イーグルピッチャー社製ＬＣＳ−３、円筒の高さＬ＝３〜１２μｍ（実測値）、円筒のＬ／Ｄ＝０．３〜２（実測値）
粉砕ゴム：日本ピグメント社製粉砕ゴム
短繊維：宇部興産社製ＵＢＥＳＨＰ−ＨＡ１０６０
熱膨張性マイクロカプセル：松本油脂製薬社製マイクロスフェアーＦ１００Ｄ
老化防止剤：住友化学社製アンチゲン６Ｃ
ワックス：大内新興化学工業社製サンノック
亜鉛華：正同化学工業社製酸化亜鉛３種
ステアリン酸：日油社製ビーズステアリン酸
硫黄：鶴見化学工業社製金華印油入微粉硫黄
加硫促進剤：大内新興化学工業社製ノクセラーＮＳ−Ｐ
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
CB1: carbon black, nitrogen adsorption specific surface area of 117 m 2 / g, Niteron # 300 Niteron # 300
CB2: carbon black, nitrogen adsorption specific surface area of 100 m 2 / g, Niteron Carbon Corporation Niteron # 200IS
Silica: NIPSEAL AQ manufactured by Tosoh Silica
Diatomaceous earth: Cylindrical porous diatomaceous earth, LCS-3 manufactured by Eagle Pitcher, cylinder height L = 3 to 12 μm (actual measured value), cylindrical L / D = 0.3 to 2 (actual measured value)
Crush rubber: Nippon Pigment Co., Ltd. Crush rubber short fiber: Ube Kosan Co., Ltd. UBEHP-HA1060
Thermally expandable microcapsule: Microsphere F100D manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
Anti-aging agent: Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.
Wax: Sannok Zinc Hana manufactured by Ouchi Shinsei Chemical Industry Co., Ltd .: Zinc oxide 3 types manufactured by Shodo Chemical Industry Co., Ltd. Stearic acid: Beads sulfur stearate manufactured by NOF Co., Ltd. Nouchira NS-P manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
表１，２の結果から明らかなように、実施例１〜５のタイヤ用ゴム組成物は、耐摩耗性及び引張り強度を維持しながら、氷上摩擦力を従来レベルよりも向上することができる。 As is clear from the results of Tables 1 and 2, the rubber compositions for tires of Examples 1 to 5 can improve the frictional force on ice from the conventional level while maintaining wear resistance and tensile strength.
表１の結果から明らかなように、比較例２のタイヤ用ゴム組成物は、重量比（Ｂ＋Ｃ）／（Ａ＋Ｂ＋Ｃ）が０．１０未満であり、かつシリカを配合せず珪藻土、粉砕ゴム及び短繊維の配合量の合計が１０重量部を超えるので耐摩耗性及び引張り強度が悪化する。比較例３のタイヤ用ゴム組成物は、シリカを配合せず、かつ重量比（Ｂ＋Ｃ）／（Ａ＋Ｂ＋Ｃ）が０．１０未満であるので氷上摩擦力を改良する効果が十分に得られない。比較例４のタイヤ用ゴム組成物は、重量比Ｅ／Ｄが１．００を超えるので氷上摩擦力が悪化すると共に、耐摩耗性及び引張り強度が悪化する。 As is clear from the results in Table 1, the rubber composition for tires of Comparative Example 2 has a weight ratio (B + C) / (A + B + C) of less than 0.10, and does not contain silica and contains diatomaceous earth, crushed rubber, and short Since the total amount of fibers exceeds 10 parts by weight, wear resistance and tensile strength are deteriorated. Since the rubber composition for tires of Comparative Example 3 does not contain silica and the weight ratio (B + C) / (A + B + C) is less than 0.10, the effect of improving the frictional force on ice cannot be sufficiently obtained. Since the rubber composition for tires of Comparative Example 4 has a weight ratio E / D exceeding 1.00, the frictional force on ice deteriorates, and the wear resistance and tensile strength deteriorate.
表２の結果から明らかなように、比較例５のタイヤ用ゴム組成物は、重量比Ｅ／Ｄが０．５０未満であるので耐摩耗性及び引張り強度が悪化する。比較例６のタイヤ用ゴム組成物は、重量比（Ｂ＋Ｃ）／（Ａ＋Ｂ＋Ｃ）が０．２５を超えるので耐摩耗性及び引張り強度が悪化する。比較例７のタイヤ用ゴム組成物は、カーボンブラック２の窒素吸着比表面積が１１０ｍ２／ｇ未満であるので耐摩耗性及び引張り強度が悪化する。比較例８のタイヤ用ゴム組成物は、重量比（Ｂ＋Ｃ）／（Ａ＋Ｂ＋Ｃ）が０．２５を超えるので引張り強度及び耐摩耗性が悪化する。比較例９のタイヤ用ゴム組成物は、重量比Ｅ／Ｄが０．５０未満であるので耐摩耗性及び引張り強度が悪化する。 As is clear from the results in Table 2, since the weight ratio E / D of the tire rubber composition of Comparative Example 5 is less than 0.50, the wear resistance and the tensile strength are deteriorated. In the rubber composition for tires of Comparative Example 6, since the weight ratio (B + C) / (A + B + C) exceeds 0.25, the wear resistance and the tensile strength are deteriorated. Since the rubber composition for tires of Comparative Example 7 has a nitrogen adsorption specific surface area of carbon black 2 of less than 110 m 2 / g, wear resistance and tensile strength are deteriorated. In the rubber composition for tires of Comparative Example 8, the weight ratio (B + C) / (A + B + C) exceeds 0.25, so that the tensile strength and the wear resistance are deteriorated. Since the weight ratio E / D of the rubber composition for tires of Comparative Example 9 is less than 0.50, the wear resistance and the tensile strength are deteriorated.
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| JP2012201879A (en) * | 2011-03-28 | 2012-10-22 | Yokohama Rubber Co Ltd:The | Pneumatic tire for heavy load |
| JP5933497B2 (en) | 2013-09-17 | 2016-06-08 | 住友ゴム工業株式会社 | Pneumatic tire |
| JP2015098561A (en) * | 2013-11-20 | 2015-05-28 | 住友ゴム工業株式会社 | Pneumatic tire |
| JP6344077B2 (en) * | 2014-06-18 | 2018-06-20 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| JP6094614B2 (en) | 2015-03-12 | 2017-03-15 | 横浜ゴム株式会社 | Rubber composition for tire, method for producing thermally expandable microcapsule composite, and pneumatic tire using the composition |
| JP6617011B2 (en) * | 2015-11-20 | 2019-12-04 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for studless tire |
| EP3666821A4 (en) * | 2017-08-10 | 2021-05-19 | Bridgestone Corporation | Rubber composition, production method therefor, and tire |
| WO2019239568A1 (en) * | 2018-06-15 | 2019-12-19 | Compagnie Generale Des Etablissements Michelin | A rubber composition for a tire tread |
| KR102124196B1 (en) * | 2018-12-31 | 2020-06-17 | 넥센타이어 주식회사 | Rubber composition for tire belt and Tire comprising the same |
| JP7183798B2 (en) * | 2019-01-09 | 2022-12-06 | 横浜ゴム株式会社 | Rubber composition and heavy-duty pneumatic tire using the same |
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| CA2181224A1 (en) * | 1995-12-20 | 1997-06-21 | Lawson Gibson Wideman | Silica-filled rubber compositions containing a mixture of dithiodipropionic acid, trithiodipropionic acid and tetrathiodipropionic acid |
| JP3933796B2 (en) * | 1997-08-21 | 2007-06-20 | 宇部興産株式会社 | Rubber mixture and rubber composition |
| JP3106356B2 (en) * | 1997-11-05 | 2000-11-06 | 株式会社テックコーポレーション | How to use diatomaceous earth and surface friction aid |
| JP5164298B2 (en) * | 2000-08-11 | 2013-03-21 | 横浜ゴム株式会社 | Rubber composition and method for producing the same |
| JP4092557B2 (en) * | 2002-06-14 | 2008-05-28 | Ｊｓｒ株式会社 | Conjugated diolefin copolymer rubber, process for producing the copolymer rubber, rubber composition and tire |
| JP2008050449A (en) * | 2006-08-23 | 2008-03-06 | Yokohama Rubber Co Ltd:The | Rubber composition for tire and pneumatic tire using the same composition in cap tread and/or base tread |
| EP2103649B1 (en) * | 2006-12-26 | 2012-09-19 | The Yokohama Rubber Co., Ltd. | Rubber composition for tire |
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