JP5380962B2 - Pneumatic studless tire - Google Patents
Pneumatic studless tire Download PDFInfo
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- JP5380962B2 JP5380962B2 JP2008232678A JP2008232678A JP5380962B2 JP 5380962 B2 JP5380962 B2 JP 5380962B2 JP 2008232678 A JP2008232678 A JP 2008232678A JP 2008232678 A JP2008232678 A JP 2008232678A JP 5380962 B2 JP5380962 B2 JP 5380962B2
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- 229920001971 elastomer Polymers 0.000 claims description 115
- 239000005060 rubber Substances 0.000 claims description 114
- 239000000203 mixture Substances 0.000 claims description 75
- 239000010419 fine particle Substances 0.000 claims description 45
- 238000004073 vulcanization Methods 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 239000006229 carbon black Substances 0.000 claims description 12
- 239000003094 microcapsule Substances 0.000 claims description 12
- 229920003244 diene elastomer Polymers 0.000 claims description 9
- 239000011859 microparticle Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 description 10
- 230000005484 gravity Effects 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- 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
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 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
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 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
- 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
- 239000002253 acid Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- -1 permanganate Chemical compound 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- Y02T10/862—
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、空気入りスタッドレスタイヤに関し、さらに詳しくは、環境負荷の低減を図るため再生ゴムを配合しながら、ゴム組成物の破断伸びを実用レベルに維持可能にしたタイヤトレッド用ゴム組成物で構成した空気入りスタッドレスタイヤに関する。 The present invention relates to a pneumatic studless tire, more particularly, consists of environment while blending reclaimed rubber order to reduce the load, tire tread rubber composition which enables maintaining the elongation at break a practical level of the rubber composition Related to a pneumatic studless tire .
地球環境を保護する観点から、空気入りタイヤのリサイクル率を高くすることが要求されるようになり、使用済みのタイヤやチューブから回収された再生ゴムを新しいゴム原料中に配合することが提案されている。 From the viewpoint of protecting the global environment, it has become necessary to increase the recycling rate of pneumatic tires, and it has been proposed to incorporate recycled rubber recovered from used tires and tubes into new rubber raw materials. ing.
しかしながら、一般的に再生ゴムを配合するとゴム組成物の破断伸びが低下するため、タイヤの耐久性の低下が懸念され、再生ゴムを不用意に配合することはできなかった。この対策として、本発明者は、再生ゴムを配合しても引張り特性を低下させないように調製したゴム組成物の発明を行ない特許出願を行なった（特願２００８−５２３６０号）。しかし、このように調製したゴム組成物は、生産コストの増加が避けられない状況であった。 However, generally, when reclaimed rubber is blended, the elongation at break of the rubber composition is lowered. Therefore, there is a concern that the durability of the tire is lowered, and the reclaimed rubber cannot be blended carelessly. As a countermeasure against this, the present inventor has filed a patent application (patent application No. 2008-52360) inventing a rubber composition prepared so as not to deteriorate the tensile properties even when recycled rubber is blended. However, the rubber composition prepared in this way was in an unavoidable increase in production cost.
一方、特許文献１は、氷雪路用空気入りタイヤのトレッド用ゴム組成物に、熱膨張性マイクロカプセルを配合し、加硫工程での加熱によって膨張させることにより、トレッドゴム中に多数の気泡を形成してトレッドが氷面に踏み込むとき氷表面の水膜を吸収除去し、氷面から離れると遠心力で離脱させることを繰り返して氷上摩擦力を増大させることを提案している。このようなトレッド用ゴム組成物においてもゴム組成物の破断伸びを実用レベルに維持することが求められていた。
本発明の目的は、引張り特性を補うための特別な配合調整を行なうことなく、ゴム組成物の破断伸びを実用レベルに維持しつつ、再生ゴムを配合することにより環境負荷を低減するようにしたタイヤトレッド用ゴム組成物で構成した空気入りスタッドレスタイヤを提供することにある。 The object of the present invention is to reduce the environmental load by blending recycled rubber while maintaining the breaking elongation of the rubber composition at a practical level without performing any special blending adjustment to supplement the tensile properties. It is providing the pneumatic studless tire comprised with the rubber composition for tire treads.
上記目的を達成する本発明の空気入りスタッドレスタイヤは、タイヤトレッド用ゴム組成物によりトレッドを構成する空気入りスタッドレスタイヤであって、前記タイヤトレッド用ゴム組成物が、ジエン系ゴム１００重量部に対し、再生ゴムを１〜１５重量部、カーボンブラック及び／又はシリカの合計を４０重量部以上及び熱膨張性微粒子を配合したゴム組成物であって、加硫後の前記熱膨張性微粒子の平均直径が２０μｍ〜４００μｍであると共に、ゴム組成物に占める体積割合が８体積％以上であることを特徴とする。 The pneumatic studless tire of the present invention that achieves the above object is a pneumatic studless tire that constitutes a tread with a rubber composition for a tire tread, and the rubber composition for a tire tread is based on 100 parts by weight of a diene rubber. A rubber composition containing 1 to 15 parts by weight of recycled rubber, 40 parts by weight or more of carbon black and / or silica, and thermally expandable fine particles, and an average diameter of the thermally expandable fine particles after vulcanization Is 20 μm to 400 μm, and the volume ratio in the rubber composition is 8% by volume or more.
前記熱膨張性微粒子としては、好ましくは熱膨張性マイクロカプセル及び／又は熱膨張性黒鉛を用いることができる。 As the thermally expandable fine particles, preferably thermally expandable microcapsules and / or thermally expandable graphite can be used.
本発明の空気入りスタッドレスタイヤによれば、ゴム組成物がジエン系ゴム１００重量部に対し、再生ゴムを１〜１５重量部、カーボンブラック及び／又はシリカの合計を４０重量部以上及び熱膨張性微粒子を配合し、その熱膨張性微粒子が加硫後において平均直径が２０μｍ〜４００μｍであると共に、ゴム組成物中に８体積％以上の体積を占めるタイヤトレッド用ゴム組成物によりトレッドを構成するようにしたので、この熱膨張性微粒子が再生ゴムによるゴム組成物の破断伸びの低下作用よりも大きく支配し、再生ゴムを１〜１５重量部も配合しながら、それに起因する破断伸びの低下を回避し、タイヤの耐久性を実用レベルに維持することができる。 According to the pneumatic studless tire of the present invention, the rubber composition is 1 to 15 parts by weight of recycled rubber, 40 parts by weight or more in total of carbon black and / or silica, and 100% by weight of the diene rubber. Fine particles are blended so that the thermally expandable fine particles have an average diameter of 20 μm to 400 μm after vulcanization, and the rubber composition for tire tread occupies a volume of 8% by volume or more in the rubber composition. As a result, the thermally expandable fine particles have a greater control over the lowering of the breaking elongation of the rubber composition due to the reclaimed rubber, while avoiding the lowering of the breaking elongation due to the addition of 1 to 15 parts by weight of the reclaimed rubber. In addition, the durability of the tire can be maintained at a practical level.
本発明を構成するタイヤトレッド用ゴム組成物において、ゴム成分はジエン系ゴムとし、そのジエン系ゴムは、天然ゴム、イソプレンゴム、ブタジエンゴム、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、ブチルゴムから選ばれる少なくとも１種であるようにする。好ましくは天然ゴム、ブタジエンゴム、スチレンブタジエンゴムがよい。このようなジエン系ゴムは、単独又は複数のブレンドとして使用することができる。 In the rubber composition for a tire tread constituting the present invention, the rubber component is a diene rubber, and the diene rubber is at least selected from natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile-butadiene rubber, and butyl rubber. Make it one type. Natural rubber, butadiene rubber, and styrene butadiene rubber are preferable. Such diene rubbers can be used alone or as a plurality of blends.
本発明を構成するタイヤトレッド用ゴム組成物に配合する再生ゴムは、廃棄タイヤのリサイクル率を高くするため環境負荷を低減する。上述したように、再生ゴムは、ゴム組成物に配合すると破壊の起点となるため破断伸びを低下させる。しかし、この再生ゴムに起因する破断伸びの低下は、後述する熱膨張性微粒子の加硫後の状態での粒子径と含有体積を調整することにより支配することが可能になり、破断伸びの低下を回避することができる。 The recycled rubber blended in the tire tread rubber composition constituting the present invention reduces the environmental load in order to increase the recycling rate of the discarded tire. As described above, when recycled rubber is blended in the rubber composition, it becomes a starting point of fracture, and therefore the elongation at break is lowered. However, the decrease in elongation at break resulting from the recycled rubber can be controlled by adjusting the particle size and volume in the state after vulcanization of the thermally expandable fine particles described later, and the decrease in elongation at break Can be avoided.
このようにしてゴム組成物に配合可能にする再生ゴムの配合量は、ジエン系ゴム１００重量部に対し１〜１５重量部、好ましくは３〜１０重量部にする。再生ゴムの配合量が１重量部未満では、環境負荷の低減が十分でない。また、再生ゴムの配合量が１５重量部を超える場合には、タイヤトレッド用ゴム組成物の破断伸び低下が生じる。 The amount of the recycled rubber that can be blended in the rubber composition in this way is 1 to 15 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of the diene rubber. If the amount of recycled rubber is less than 1 part by weight, the environmental load is not sufficiently reduced. Moreover, when the compounding quantity of a recycled rubber exceeds 15 weight part, the fracture | rupture elongation fall of the rubber composition for tire treads arises.
本発明で使用する再生ゴムは、市販の再生ゴムを使用することができる。再生ゴムとは、ＪＩＳ Ｋ６３１３に規定された自動車用タイヤ、チューブ及びその他のゴム製品の使用済みのゴムなどを脱硫処理により再生したもの並びにこれと同等の性状を有するものとする。再生ゴムの種類は、チューブ再生ゴム、タイヤ再生ゴム、その他の再生ゴムから選ばれるいずれでもよく、複数の種類を組合わせることもできる。 Commercially available recycled rubber can be used as the recycled rubber used in the present invention. Recycled rubber is obtained by regenerating used rubber of automobile tires, tubes, and other rubber products defined in JIS K6313 by desulfurization treatment, and has equivalent properties. The type of recycled rubber may be any one selected from tube recycled rubber, tire recycled rubber, and other recycled rubbers, and a plurality of types may be combined.
本発明において使用する熱膨張性微粒子とは、ゴム組成物の加硫時に膨張機能により体積が膨張して中空或いは気泡を形成する粒子体をいう。この熱膨張性微粒子は、スタッドレスタイヤのトレッドにおいて、表面に露出することにより、氷の表面の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を発生するため、氷上摩擦力を向上する作用を行なう。同時に、この熱膨張性微粒子は、ゴム組成物における破壊の起点となり、ゴム組成物の破断伸びの低下を支配する。このため、再生ゴムの配合量を上述した範囲内にする限りにおいて、再生ゴムに起因する破断伸びの低下の影響が現れないようにすることができる。 The heat-expandable fine particles used in the present invention refer to a particle body whose volume is expanded by an expansion function during the vulcanization of a rubber composition and forms a hollow or a bubble. The thermally expandable fine particles are exposed to the surface of the tread of the studless tire, thereby efficiently absorbing and removing the water film on the ice surface and generating a micro edge effect, thereby improving the frictional force on ice. Perform the action. At the same time, the thermally expandable fine particles serve as a starting point of fracture in the rubber composition and govern the decrease in elongation at break of the rubber composition. For this reason, as long as the amount of the recycled rubber is within the above-described range, it is possible to prevent the influence of the decrease in elongation at break resulting from the recycled rubber from appearing.
熱膨張性微粒子は、タイヤトレッド用ゴム組成物を加硫したときにゴム組成物中の体積割合が８体積％以上、好ましくは８〜２５体積％になるようにする。熱膨張性微粒子が８体積％未満であると、氷上摩擦力を向上することができない。熱膨張性微粒子の体積割合の上限は、ゴム組成物の破断伸びを実用レベルに維持するため２５体積％にするとよい。 The thermally expandable fine particles are adjusted so that the volume ratio in the rubber composition is 8% by volume or more, preferably 8 to 25% by volume, when the rubber composition for a tire tread is vulcanized. If the thermally expandable fine particles are less than 8% by volume, the frictional force on ice cannot be improved. The upper limit of the volume ratio of the thermally expandable fine particles is preferably 25% by volume in order to maintain the breaking elongation of the rubber composition at a practical level.
なお、本発明において、加硫後のゴム組成物中の熱膨張性微粒子の体積割合とは、加硫後のゴム組成物の全体積に対する加硫後の熱膨張性微粒子の体積の割合である。加硫後の熱膨張性微粒子の体積は、加硫後のゴム組成物の全体積から、熱膨張性微粒子を除いた成分の加硫後の体積を、差し引いた体積とする。また、加硫後のゴム組成物の全体積は、加硫後のゴム組成物の全重量を加硫後のゴム組成物の比重で割った値とし、熱膨張性微粒子を除いた成分の加硫後の体積は、熱膨張性微粒子を除いた成分の加硫後の重量を、熱膨張性微粒子を除いた成分の加硫後の比重で割った値とする。したがって、加硫後のゴム組成物中の熱膨張性微粒子の体積割合φは、下記の計算式により求めたものとする。
φ［体積％］＝（（Ｗ／Ｐ）−（ｗ／ρ））／（Ｗ／Ｐ）×１００
In the present invention, the volume ratio of thermally expandable fine particles in the rubber composition after vulcanization is the ratio of the volume of thermally expandable fine particles after vulcanization to the total volume of the rubber composition after vulcanization. . The volume of the heat-expandable fine particles after vulcanization is the volume obtained by subtracting the volume after vulcanization of the components excluding the heat-expandable fine particles from the entire volume of the rubber composition after vulcanization. In addition, the total volume of the rubber composition after vulcanization is a value obtained by dividing the total weight of the rubber composition after vulcanization by the specific gravity of the rubber composition after vulcanization, and adding the components excluding the thermally expandable fine particles. The volume after vulcanization is a value obtained by dividing the weight after vulcanization of the component excluding the heat-expandable fine particles by the specific gravity after vulcanization of the component excluding the heat-expandable fine particles. Therefore, the volume ratio φ of the thermally expandable fine particles in the rubber composition after vulcanization is obtained by the following calculation formula.
φ [volume%] = ((W / P) − (w / ρ)) / (W / P) × 100
式中、φは加硫後のゴム組成物中の熱膨張性微粒子の体積割合、Ｗは加硫後のゴム組成物の全重量、Ｐは加硫後のゴム組成物の比重、ｗは熱膨張性微粒子を除いた成分の加硫後の重量、ρは熱膨張性微粒子を除いた成分の加硫後の比重である。ここで、加硫後のゴム組成物の全重量Ｗ、比重Ｐ及び熱膨張性微粒子を除いた成分の加硫後の比重ρは、測定により求められる。熱膨張性微粒子を除いた成分の加硫後の重量ｗは、加硫後のゴム組成物の全重量Ｗとゴム組成物の配合量（全重量部）に対する熱膨張性微粒子を除いた成分の配合量（重量部）の比との積から求められる。 Where φ is the volume ratio of thermally expandable fine particles in the rubber composition after vulcanization, W is the total weight of the rubber composition after vulcanization, P is the specific gravity of the rubber composition after vulcanization, and w is the heat The weight after vulcanization of the component excluding the expandable fine particles and ρ is the specific gravity after vulcanization of the component excluding the heat expandable fine particles. Here, the total weight W of the rubber composition after vulcanization, the specific gravity P, and the specific gravity ρ after vulcanization of the components excluding the thermally expandable fine particles are determined by measurement. The weight w after vulcanization of the component excluding the heat-expandable fine particles is the total weight W of the rubber composition after vulcanization and the component excluding the heat-expandable fine particles with respect to the blending amount (total weight part) of the rubber composition. It is calculated | required from the product with the ratio of a compounding quantity (weight part).
上記熱膨張性微粒子の大きさは、タイヤトレッド用ゴム組成物を加硫した後のゴム組成物中の平均直径が２０μｍ〜４００μｍ、好ましくは２０μｍ〜３００μｍになるようにする。熱膨張性微粒子の平均直径が２０μｍ未満であると、氷上摩擦力の向上が不十分になる。また、熱膨張性微粒子の平均直径が４００μｍを超えると、ゴム組成物の破断伸びを実用レベルに維持することが難しくなる。 The size of the thermally expandable fine particles is such that the average diameter in the rubber composition after vulcanizing the tire tread rubber composition is 20 μm to 400 μm, preferably 20 μm to 300 μm. When the average diameter of the thermally expandable fine particles is less than 20 μm, the frictional force on ice is not sufficiently improved. Further, if the average diameter of the thermally expandable fine particles exceeds 400 μm, it becomes difficult to maintain the breaking elongation of the rubber composition at a practical level.
なお、本発明において、熱膨張性微粒子の平均直径は、加硫したゴム組成物の断面を１６５倍で拡大観察し、画像処理により観察面内に存在するすべての熱膨張性微粒子の直径を１０視野について測定したときの平均値である。 In the present invention, the average diameter of the heat-expandable fine particles is 10 times the diameter of all the heat-expandable fine particles existing in the observation plane by magnifying the cross section of the vulcanized rubber composition at 165 times. It is an average value when measuring about a visual field.
熱膨張性微粒子の配合量は、加硫後の体積割合が８体積％以上になれば特に制限されるものではなく、その膨張率にもよるが、ジエン系ゴム１００重量部に対し熱膨張性微粒子を好ましくは２〜１０重量部、より好ましくは３〜７重量部配合するとよい。熱膨張性微粒子の配合量が２重量部未満では、氷上性能を向上することができない。また、熱膨張性微粒子の配合量が１０重量部を超える場合には、加硫後の体積割合が過大になり破断伸びを実用レベルに維持することができない。 The blending amount of the heat-expandable fine particles is not particularly limited as long as the volume ratio after vulcanization is 8% by volume or more. Although it depends on the expansion coefficient, the heat-expandable content is 100 parts by weight of the diene rubber. The fine particles are preferably added in an amount of 2 to 10 parts by weight, more preferably 3 to 7 parts by weight. When the amount of the thermally expandable fine particles is less than 2 parts by weight, the performance on ice cannot be improved. Moreover, when the compounding quantity of a thermally expansible microparticle exceeds 10 weight part, the volume ratio after vulcanization becomes excessive and a fracture | rupture elongation cannot be maintained at a practical level.
本発明に使用する熱膨張性微粒子としては、例えば熱膨張性マイクロカプセル、熱膨張性黒鉛を例示することができる。これらの熱膨張性微粒子は、単独で用いてもよく、複数種を組合わせて使用してもよい。また、上述の熱膨張性微粒子を共に使用してもよい。 Examples of the heat-expandable fine particles used in the present invention include heat-expandable microcapsules and heat-expandable graphite. These thermally expandable fine particles may be used alone or in combination of two or more. Moreover, you may use together the above-mentioned thermally expansible microparticles | fine-particles.
本発明で好適に使用する熱膨張性マイクロカプセルは、熱可塑性樹脂で形成された殻材中に、熱膨張性物質を内包した構成からなる。このため、未加硫タイヤの加硫時にゴム組成物中の熱膨張性マイクロカプセルが加熱されると、殻材に内包された熱膨張性物質が膨張して殻材の粒径を大きくし、トレッドゴム中に多数の樹脂被覆気泡を形成する。これにより、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。 The heat-expandable microcapsule preferably used in the present invention has a structure in which a heat-expandable substance is included in a shell material formed of a thermoplastic resin. For this reason, when the thermally expandable microcapsules in the rubber composition are heated during vulcanization of the unvulcanized tire, the thermally expandable substance contained in the shell material expands to increase the particle size of the shell material, A large number of resin-coated bubbles are formed in the tread rubber. As a result, the water film generated on the surface of the ice is efficiently absorbed and removed, and a micro edge effect is obtained, so that the frictional force on ice is improved.
上述した熱膨張性マイクロカプセルとしては、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。 As the above-mentioned thermally expandable microcapsule, trade name “EXPANCEL 091DU-80” or “EXPANCEL 092DU-120” manufactured by Expancel, Sweden, or the trade name “Microsphere F-” manufactured by Matsumoto Yushi Seiyaku Co., Ltd. 85D "or" Microsphere F-100D "can be used.
本発明で好適に使用する熱膨張性黒鉛とは、層間に熱により気化する物質を内包する粒子であって、その加硫前の平均粒径が好ましくは１０〜３００μｍ、より好ましくは１００〜２００μｍの粉体粒子であり、加硫時の熱によって膨張して黒鉛膨張体となるものをいう。熱膨張性黒鉛は、炭素原子から形成されたシートが層状となった構造をしており、その層間物質の気化によって膨張させることができる。材質が硬いために混合による品質低下が起こりにくく、また一定温度で不可逆的に膨張するため、ゴムマトリクス内部に空間を容易に形成させることができる。このようなゴム組成を用いたタイヤのトレッド部は、摩耗時に凹凸が適度に形成されて表面上の水膜を効率よく除去することによって氷上摩擦力の向上をもたらす。また、熱膨張性黒鉛は、炭素原子からなる骨格構造を有しているためにゴムマトリクスやカーボンブラックとの親和性が良好であり、加硫ゴムの耐摩耗性を低下させないという利点もある。 The heat-expandable graphite preferably used in the present invention is a particle that encloses a substance that is vaporized by heat between layers, and its average particle size before vulcanization is preferably 10 to 300 μm, more preferably 100 to 200 μm. Powder particles, which expand by heat during vulcanization and become a graphite expanded body. Thermally expandable graphite has a structure in which sheets formed from carbon atoms are layered, and can be expanded by vaporization of the interlayer material. Since the material is hard, quality deterioration due to mixing hardly occurs, and irreversibly expands at a constant temperature, so that a space can be easily formed inside the rubber matrix. The tread portion of a tire using such a rubber composition is improved in frictional force on ice by appropriately forming irregularities during wear and efficiently removing the water film on the surface. Further, since the heat-expandable graphite has a skeleton structure composed of carbon atoms, it has a good affinity with a rubber matrix and carbon black and has an advantage that it does not lower the wear resistance of the vulcanized rubber.
このような熱膨張性黒鉛は、スタッドレス用タイヤに通常配合されるものを使用することができる。例えば天然の鱗片状グラファイト、熱分解グラファイト、キッシュグラファイト等を無機酸（濃硫酸又は硝酸等）と強酸化剤（濃硝酸、過塩素酸塩、過マンガン酸塩又は重クロム酸塩等）で処理してグラファイト層間化合物を生成させた炭素の層状構造を維持したままの結晶質化合物を挙げることができる。更に、酸処理した熱膨張性黒鉛を塩基性化合物で中和したものを使用することが好ましい。このような熱膨張性黒鉛としては、巴工業社製の商品名「グラフガード１６０−５０」、「グラフガード１６０−８０」又は「グラフガード１６０−５０Ｎ」等を使用することができる。 As such heat-expandable graphite, it is possible to use what is usually blended in studless tires. For example, natural scaly graphite, pyrolytic graphite, quiche graphite, etc. are treated with an inorganic acid (such as concentrated sulfuric acid or nitric acid) and a strong oxidizing agent (such as concentrated nitric acid, perchlorate, permanganate, or dichromate). Examples thereof include crystalline compounds that maintain the layered structure of carbon from which the graphite intercalation compound is formed. Further, it is preferable to use a heat-expandable graphite that has been acid-treated and neutralized with a basic compound. As such heat-expandable graphite, trade names “Graph Guard 160-50”, “Graph Guard 160-80” or “Graph Guard 160-50N” manufactured by Sakai Kogyo Co., Ltd. can be used.
本発明を構成するタイヤトレッド用ゴム組成物には、上述した配合剤のほか、補強剤としてカーボンブラック及び／又はシリカが配合される。カーボンブラックはトレッドゴムの耐摩耗性を高くする作用を行なうと共に、シリカはトレッドゴムの低温時の柔軟性を維持し、氷面に対する凝着性を高め氷上摩擦力を向上する作用を行なう。カーボンブラック及びシリカは、いずれか一方を配合しても両方を共に配合してもよい。カーボンブラック及び／又はシリカを配合する合計量は、ジエン系ゴム１００重量部に対し、４０重量部以上であり、好ましくは４０〜６０重量部にする。カーボンブラック及びシリカの合計量が４０重量部未満であると耐摩耗性が不足する。また、カーボンブラック及び／又はシリカの合計量が、６０重量部と超えると、トレッドゴムのしなやかさが損なわれ、氷上性能が低下する。 In addition to the above-mentioned compounding agents, carbon black and / or silica are compounded as a reinforcing agent in the tire tread rubber composition constituting the present invention. Carbon black acts to increase the wear resistance of the tread rubber, while silica maintains the flexibility of the tread rubber at low temperatures, increases the adhesion to the ice surface, and improves the frictional force on ice. One or both of carbon black and silica may be blended. The total amount of carbon black and / or silica is 40 parts by weight or more, preferably 40 to 60 parts by weight with respect to 100 parts by weight of the diene rubber. When the total amount of carbon black and silica is less than 40 parts by weight, the wear resistance is insufficient. On the other hand, when the total amount of carbon black and / or silica exceeds 60 parts by weight, the flexibility of the tread rubber is impaired and the performance on ice is lowered.
本発明において、シリカを配合する場合には、シランカップリング剤を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に対する補強性を高めることにより、低温時のゴムの柔軟性を向上することができる。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し低温時のゴムの柔軟性の向上効果は期待することができない。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くなる。 In the present invention, when silica is blended, the silane coupling agent is preferably blended in an amount of 3 to 15% by weight, more preferably 5 to 10% by weight, based on the silica weight. By blending the silane coupling agent, the dispersibility of the silica is improved, and the reinforcement of the rubber is improved, so that the flexibility of the rubber at a low temperature can be improved. When the silane coupling agent is less than 3% by weight of the silica weight, the dispersion of the silica is deteriorated and the effect of improving the flexibility of the rubber at a low temperature cannot be expected. Moreover, when a silane coupling agent exceeds 15 weight%, silane coupling agents will superpose | polymerize and it will become impossible to acquire a desired effect.
シランカップリング剤は、シリカ配合のゴム組成物に使用可能なものであればよいが、なかでも硫黄含有シランカップリング剤が好ましく、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 a rubber composition containing silica. Among them, a sulfur-containing silane coupling agent is preferable, for example, bis- (3-triethoxysilylpropyl) tetrasulfide, bis Examples include (3-triethoxysilylpropyl) disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, γ-mercaptopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, and the like.
本発明を構成するタイヤトレッド用ゴム組成物にはカーボンブラック及びシリカ以外の充填剤を配合してもよい。充填剤としては、例えばクレー、炭酸カルシウム、水酸化アルミニウム、マイカ、タルク等を例示することができる。また、タイヤトレッド用ゴム組成物には、加硫剤、加硫促進剤、老化防止剤、可塑剤、オイル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。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。 You may mix | blend fillers other than carbon black and a silica with the rubber composition for tire treads which comprises this invention. Examples of the filler include clay, calcium carbonate, aluminum hydroxide, mica, talc and the like. In addition, the rubber composition for tire treads can be blended with various additives commonly used in rubber compositions such as vulcanizing agents, vulcanization accelerators, anti-aging agents, plasticizers, and oils, Such additives can be kneaded by a general method to form a rubber composition, which can be used for vulcanization or crosslinking. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used. 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.
本発明を構成するタイヤトレッド用ゴム組成物は、再生ゴムを配合してリサイクル率を高くすると共に、再生ゴムに起因した破断伸びの低下を可及的に小さくすることができる。このゴム組成物は、スタッドレスタイヤのキャップトレッド部に適用する。このゴム組成物から構成されたキャップトレッド部を有するスタッドレスタイヤは、使用済みタイヤを再利用し環境負荷を低減可能にするものである。 The rubber composition for a tire tread constituting the present invention can increase the recycling rate by blending recycled rubber and can reduce the decrease in elongation at break caused by the recycled rubber as much as possible. The rubber composition, that apply to the cap tread portion of studless tires. A studless tire having a cap tread portion made of this rubber composition can reuse an used tire and reduce environmental load.
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１〜３に示す配合からなる１３種類のゴム組成物（実施例１〜５、比較例１〜８）を、それぞれ硫黄、加硫促進剤、熱膨張性微粒子を除く配合成分を秤量し、１.７Ｌ密閉式バンバリーミキサーで４分間混練し、温度１５０℃でマスターバッチを放出し室温冷却した。このマスターバッチを１.７Ｌ密閉式バンバリーミキサーに供し、硫黄、加硫促進剤、熱膨張性微粒子を加え混合し、タイヤトレッド用ゴム組成物を調製した。 13 kinds of rubber compositions (Examples 1 to 5 and Comparative Examples 1 to 8) having the compositions shown in Tables 1 to 3, respectively, were weighed with the ingredients except for sulfur, vulcanization accelerator and thermally expandable fine particles, The mixture was kneaded for 4 minutes with a 1.7 L closed Banbury mixer, and the master batch was discharged at a temperature of 150 ° C. and cooled at room temperature. This master batch was subjected to a 1.7 L hermetic Banbury mixer, and sulfur, a vulcanization accelerator, and thermally expandable fine particles were added and mixed to prepare a rubber composition for a tire tread.
得られた１３種類のゴム組成物（実施例１〜５、比較例１〜８）をそれぞれ所定形状の金型中で、１７０℃、１０分間加硫して試験片を作成し、破断伸びを下記に示す方法により測定した。なお、１３種類のゴム組成物を加硫した試験片について、熱膨張性微粒子の平均直径及び体積割合を下記に示す方法により測定した。 The obtained 13 types of rubber compositions (Examples 1 to 5, Comparative Examples 1 to 8) were each vulcanized in a predetermined shape mold at 170 ° C. for 10 minutes to prepare test pieces, and the elongation at break was measured. It measured by the method shown below. In addition, about the test piece which vulcanized | cured 13 types of rubber compositions, the average diameter and volume ratio of thermally expansible fine particle were measured by the method shown below.
平均直径
各ゴム組成物を加硫した試験片の断面を走査型電子顕微鏡（ＳＥＭ）を使用し、１６５倍で拡大観察し、画像処理により観察面内に存在する熱膨張性マイクロカプセル及び熱膨張性黒鉛の直径を１０視野について測定し、それぞれの平均値を求めた。その結果、熱膨張性マイクロカプセルの加硫後平均直径は１００μｍ、熱膨張性黒鉛の加硫後平均直径は２００μｍであった。
Average diameter Using a scanning electron microscope (SEM), the cross section of the test piece obtained by vulcanizing each rubber composition was magnified at 165 times, and thermally expanded microcapsules and thermal expansion existing in the observation plane by image processing The diameter of the characteristic graphite was measured for 10 visual fields, and the average value of each was obtained. As a result, the average diameter after vulcanization of the thermally expandable microcapsule was 100 μm, and the average diameter after vulcanization of the thermally expandable graphite was 200 μm.
体積割合
各ゴム組成物を加硫した試験片の比重及び加硫後の熱膨張性マイクロカプセル、熱膨張性黒鉛及びその他の構成成分の比重を、ＪＩＳ Ｋ６２６８に準拠して測定した。得られた比重と配合重量とから前述した計算式に基づいて、加硫後のゴム組成物中の熱膨張性マイクロカプセル及び熱膨張性黒鉛の体積割合を求めた。得られた結果を表１〜３に示した。
Volume ratio The specific gravity of the test piece obtained by vulcanizing each rubber composition and the specific gravity of the thermally expandable microcapsule, thermally expandable graphite and other components after vulcanization were measured according to JIS K6268. Based on the obtained specific gravity and blending weight, the volume ratio of the thermally expandable microcapsules and thermally expandable graphite in the rubber composition after vulcanization was determined. The obtained results are shown in Tables 1-3.
破断伸び
ＪＩＳ Ｋ６２５１に準拠し、３号ダンベル型試験片、２０℃、引張り速度５００ｍｍ／分の条件で引張り破断伸びを測定した。得られた結果は、表１では比較例１を１００とし、表２では比較例２を１００とし、表３では比較例６を１００とする指数として表１〜３に示した。この指数が大きいほど破断伸びが高いことを意味する。
Breaking Elongation According to JIS K6251, tensile breaking elongation was measured under the conditions of a No. 3 dumbbell-shaped test piece, 20 ° C., and a tensile speed of 500 mm / min. The obtained results are shown in Tables 1 to 3 as indices in which Comparative Example 1 is 100 in Table 1, Comparative Example 2 is 100 in Table 2, and Comparative Example 6 is 100 in Table 3. The larger this index, the higher the elongation at break.
なお、表１〜３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
再生ゴム：村岡ゴム社製タイヤリク紫線、再生ゴム中のゴム成分の含有量は約５０重量％であった。
カーボンブラック：東海カーボン社製シーストＫＨ（窒素吸着比表面積９３ｍ２／ｇ）
シリカ：東ソー社製ニップシールＡＱ
カップリング剤：シランカップリング剤、デグサ社製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：日油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
ワックス：大内新興化学工業社製サンノック
プロセスオイル：富士興産社製アロマオイル
熱膨張性カプセル：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 Ｆ−１００Ｄ
熱膨張性黒鉛：巴工業社製グラフガード１６０−５０Ｎ
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ＣＺ−Ｇ
In addition, the kind of raw material used in Tables 1-3 is shown below.
NR: natural rubber, RSS # 3
BR: butadiene rubber, Nipol BR1220 manufactured by Nippon Zeon
Recycled rubber: Muraoka Rubber Co., Ltd. tire-like purple wire, the content of rubber component in the recycled rubber was about 50% by weight.
Carbon black: Seast KH (nitrogen adsorption specific surface area 93 m 2 / g) manufactured by Tokai Carbon Co., Ltd.
Silica: NIPSEAL AQ manufactured by Tosoh Corporation
Coupling agent: 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 NOF Co., Ltd. Bead stearic acid anti-aging agent: SANTOFLEX 6PPD manufactured by Flexis
Wax: Sannok Process Oil manufactured by Ouchi Shinsei Chemical Industry Co., Ltd .: Aroma oil manufactured by Fuji Kosan Co., Ltd. Thermally expandable capsule: Thermally expandable microcapsule, Matsumoto Yushi Seiyaku Microsphere F-100D
Thermally expandable graphite: graph guard 160-50N manufactured by Sakai Kogyo Co., Ltd.
Sulfur: Fine powder sulfur vulcanization accelerator with Jinhua seal oil manufactured by Tsurumi Chemical Co., Ltd .: Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
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