JP2006206837A - Rubber composition for tire tread - Google Patents
Rubber composition for tire tread Download PDFInfo
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- JP2006206837A JP2006206837A JP2005024234A JP2005024234A JP2006206837A JP 2006206837 A JP2006206837 A JP 2006206837A JP 2005024234 A JP2005024234 A JP 2005024234A JP 2005024234 A JP2005024234 A JP 2005024234A JP 2006206837 A JP2006206837 A JP 2006206837A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 33
- 239000005060 rubber Substances 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 150000004676 glycans Chemical class 0.000 claims abstract description 31
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 31
- 239000005017 polysaccharide Substances 0.000 claims abstract description 31
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000006467 substitution reaction Methods 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 229920003244 diene elastomer Polymers 0.000 claims description 9
- 239000000446 fuel Substances 0.000 abstract description 14
- 229920002907 Guar gum Polymers 0.000 abstract description 13
- 235000010417 guar gum Nutrition 0.000 abstract description 13
- 239000000665 guar gum Substances 0.000 abstract description 13
- 229960002154 guar gum Drugs 0.000 abstract description 13
- 239000001913 cellulose Substances 0.000 abstract description 6
- 229920002678 cellulose Polymers 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 150000001993 dienes Chemical class 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 9
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 150000001720 carbohydrates Chemical class 0.000 description 5
- 235000010980 cellulose Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 229920001285 xanthan gum Polymers 0.000 description 4
- 235000010493 xanthan gum Nutrition 0.000 description 4
- 239000000230 xanthan gum Substances 0.000 description 4
- 229940082509 xanthan gum Drugs 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 229920005549 butyl rubber Polymers 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-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
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical class C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920006978 SSBR Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 240000004584 Tamarindus indica Species 0.000 description 1
- 235000004298 Tamarindus indica Nutrition 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000305 astragalus gummifer gum Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000008266 deoxy sugars Chemical class 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- -1 succinoglucan Polymers 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000010491 tara gum Nutrition 0.000 description 1
- 239000000213 tara gum Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 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
- QPPXVBLDIDEHBA-UHFFFAOYSA-N trimethoxy(3-nitropropyl)silane Chemical compound CO[Si](OC)(OC)CCC[N+]([O-])=O QPPXVBLDIDEHBA-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、空気入りタイヤのトレッドに用いられるタイヤトレッド用ゴム組成物に関するものである。 The present invention relates to a rubber composition for a tire tread used for a tread of a pneumatic tire.
最近、環境あるいは安全への関心が高まるにつれ、タイヤにも低燃費性、湿潤路面におけるグリップ性能を含めた操縦安定性の向上などが強く要請されるようになった。 Recently, with increasing interest in the environment and safety, tires have been strongly demanded to improve fuel economy and handling stability including grip performance on wet roads.
一般に低燃費化を図るため、タイヤトレッド用ゴム組成物にはシリカを配合しており、同時にシランカップリング剤も配合しているが、最近益々高度化される要求に対し、シリカ及びシランカップリング剤のみで低燃費性と操縦安定性を両立させることは難しい。 In general, in order to reduce fuel consumption, silica is blended in the rubber composition for tire treads, and at the same time, a silane coupling agent is blended. It is difficult to achieve both low fuel consumption and handling stability with only the agent.
ところで、下記特許文献1には、ジエン系ゴム100重量部に対して、単糖類、二糖類以上の多糖類並びにこれらの誘導体から選ばれた少なくとも一種の糖類を0.1〜10重量部配合したタイヤトレッド用ゴム組成物が提案されている。そこにおいて上記糖類としては、単糖類としてD−グルコース、D−フルクトースなどが、多糖類としてマルトース、ラクトースなどが、その誘導体としてイノシール等の糖アルコールやデオキシ糖などが、それぞれ列挙されている。そして、このゴム組成物によれば、破壊特性、ウェットグリップ性及び発熱性や加工性を損なうことなく、耐摩耗性及び耐老化性が向上されると記載されている。
上記特許文献1の従来技術では、低燃費性を損なうことなく、タイヤ性能における操縦安定性を向上させることは難しい。実際、同文献に記載された実施例を見ても、糖類を添加することにより、ウェットグリップ性及び発熱性は全く改善されておらず、未添加の場合と同等の性能しか得られていない。 With the prior art of Patent Document 1, it is difficult to improve steering stability in tire performance without impairing fuel efficiency. In fact, even in the examples described in the same document, the wet grip property and the heat generation property are not improved at all by adding the saccharide, and only the performance equivalent to that in the case of no addition is obtained.
本発明は、以上の点に鑑みてなされたものであり、低燃費性を損なうことなく、グリップ性を向上してタイヤの操縦安定性を向上することができるタイヤトレッド用ゴム組成物を提供することを目的とする。 The present invention has been made in view of the above points, and provides a rubber composition for a tire tread capable of improving grip performance and improving steering stability without impairing fuel efficiency. For the purpose.
上記課題を解決する本発明に係るタイヤトレッド用ゴム組成物は、ジエン系ゴム100重量部に対して、エポキシ化合物で変性された変性多糖類を0.1〜10重量部配合してなるものである。 The rubber composition for a tire tread according to the present invention that solves the above problems is obtained by blending 0.1 to 10 parts by weight of a modified polysaccharide modified with an epoxy compound with respect to 100 parts by weight of a diene rubber. is there.
本発明によれば、このような特定の変性多糖類を添加することにより、低燃費性を損なうことなく、操縦安定性を向上することができる。 According to the present invention, by adding such a specific modified polysaccharide, it is possible to improve steering stability without impairing fuel efficiency.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本発明のゴム組成物において、ジエン系ゴムとしては特に限定されず、タイヤトレッド用ゴム組成物において通常使用される各種のジエン系ゴムを用いることができる。例えば、天然ゴム(NR)、ポリイソプレンゴム(IR)、スチレン−ブタジエン共重合体ゴム(SBR)、ポリブタジエンゴム(BR)、アクリロニトリル−ブタジエン共重合体ゴム(NBR)、ブチルゴム(IIR)、ハロゲン化ブチルゴムなどが挙げられ、これらはそれぞれ単独で又は2種以上ブレンドして用いてもよい。 In the rubber composition of the present invention, the diene rubber is not particularly limited, and various diene rubbers usually used in a tire tread rubber composition can be used. For example, natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), butyl rubber (IIR), halogenated Examples thereof include butyl rubber, and these may be used alone or in combination of two or more.
本発明のゴム組成物に使用される変性多糖類は、エポキシ化合物で変性された多糖類であり、即ち、多糖類の持つ水酸基をエポキシ化合物により置換することで変性したものである。このような変性多糖類は、低級アルコールの増粘成分として従来使用されているが(特開2002−212298号公報参照)、これをタイヤトレッド用ゴム組成物に添加することにより、低燃費性を損なうことなく操縦安定性を向上できるという予期せぬ効果が見い出されたのである。このような優れた効果が奏される理由は必ずしも明確ではないが、エポキシ化合物で変性された変性多糖類を用いることにより、ジエン系ゴムとの相溶性を改良できるものと考えられる。これに対し、上記特許文献1に開示された技術では、使用した糖類とジエン系ゴムとの相溶性に問題があるため、操縦安定性の向上に至らないものと考えられる。 The modified polysaccharide used in the rubber composition of the present invention is a polysaccharide modified with an epoxy compound, that is, modified by substituting the hydroxyl group of the polysaccharide with an epoxy compound. Such a modified polysaccharide is conventionally used as a thickening component of a lower alcohol (see JP 2002-212298 A), and by adding this to a rubber composition for a tire tread, low fuel consumption can be achieved. An unexpected effect was found that the steering stability could be improved without loss. The reason why such an excellent effect is exhibited is not necessarily clear, but it is considered that compatibility with the diene rubber can be improved by using a modified polysaccharide modified with an epoxy compound. On the other hand, in the technique disclosed in Patent Document 1, there is a problem in the compatibility between the saccharide used and the diene rubber, and thus it is considered that the steering stability is not improved.
該変性多糖類において、ベースとなる多糖類としては、特に限定されないが、例えば、グアガム(ガラクトマンナン)、キサンタンガム、サクシノグルカン、セルロース、デンプン、タラガム、ローカストビーンガム、アラビアガム、タマリンドガム、トラガントガムなどが挙げられ、これらをそれぞれ単独又は2種以上組み合わせて使用してもよい。 In the modified polysaccharide, the base polysaccharide is not particularly limited. For example, guar gum (galactomannan), xanthan gum, succinoglucan, cellulose, starch, tara gum, locust bean gum, gum arabic, tamarind gum, tragacanth gum These may be used, and these may be used alone or in combination of two or more.
変性剤として使用する上記エポキシ化合物としては、特に限定されるものではないが、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドなどのアルキレンオキサイドを使用することが好ましく、これらはそれぞれ単独又は2種以上組み合わせて使用してもよい。なお、変性多糖類は、エポキシ化合物で変性されたものであれば、エポキシ化合物と他の変性剤とを組み合わせて2種以上の変性剤で変性されたものでも構わない。 Although it does not specifically limit as said epoxy compound used as a modifier, It is preferable to use alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, and these are used individually or in combination of 2 or more types, respectively. May be. As long as the modified polysaccharide is modified with an epoxy compound, the modified polysaccharide may be modified with two or more kinds of modifiers by combining an epoxy compound and another modifier.
本発明において、変性多糖類としては、アルキレンオキサイドによりヒドロキシアルキル化された多糖類、即ちヒドロキシアルキル変性多糖類が好適である。ヒドロキシアルキル変性多糖類の製造方法は、特に限定されないが、従来公知の方法である、苛性ソーダ、苛性カリウムなどのアルカリを触媒として、多糖類にアルキレンオキサイドを付加反応させる方法が使用可能であり、これにより、多糖類の水酸基にアルキレンオキサイドがエーテル結合によって付加され、得られた多糖類はヒドロキシアルキル基を有する。 In the present invention, as the modified polysaccharide, a polysaccharide hydroxyalkylated with an alkylene oxide, that is, a hydroxyalkyl-modified polysaccharide is preferable. The production method of the hydroxyalkyl-modified polysaccharide is not particularly limited, but a conventionally known method of adding an alkylene oxide to a polysaccharide using an alkali such as caustic soda or caustic potassium as a catalyst can be used. Thus, alkylene oxide is added to the hydroxyl group of the polysaccharide by an ether bond, and the resulting polysaccharide has a hydroxyalkyl group.
該変性多糖類の変性量は特に限定されないが、置換度が0.1〜3.0であることが好ましく、より好ましくは0.4〜1.2である。ここで、置換度とは、糖類の環構造1個当たりについてエポキシ化合物により置換された水酸基の数を意味する。置換度が0.1未満では、操縦安定性の向上効果が得られにくい。 The modification amount of the modified polysaccharide is not particularly limited, but the degree of substitution is preferably 0.1 to 3.0, more preferably 0.4 to 1.2. Here, the degree of substitution means the number of hydroxyl groups substituted with an epoxy compound per ring structure of the saccharide. If the degree of substitution is less than 0.1, it is difficult to obtain an effect of improving the steering stability.
該変性多糖類は、ジエン系ゴム100重量部に対して0.1〜10重量部、好ましくは0.5〜8重量部配合される。変性多糖類の配合量が0.1重量部未満では、上記した本発明の効果を十分に発揮させることができず、10重量部を越えると、分散不良による塊ができ、本発明の効果を十分に発揮させることができない。 The modified polysaccharide is blended in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the diene rubber. When the blending amount of the modified polysaccharide is less than 0.1 parts by weight, the above-described effects of the present invention cannot be sufficiently exhibited. It cannot be fully demonstrated.
本発明のゴム組成物には、カーボンブラック、シリカ、酸化チタン、ケイ酸アルミニウム、クレー、タルクなどの各種フィラーを配合することができる。該フィラーとしては、シリカを単独で使用、又はシリカとカーボンブラックを併用することが好ましい。その場合、シリカは、ジエン系ゴム100重量部に対して10〜120重量部配合されることが好ましく、より好ましくは30〜100重量部である。 Various fillers such as carbon black, silica, titanium oxide, aluminum silicate, clay, and talc can be blended with the rubber composition of the present invention. As the filler, it is preferable to use silica alone or to use silica and carbon black in combination. In that case, the silica is preferably blended in an amount of 10 to 120 parts by weight, more preferably 30 to 100 parts by weight, based on 100 parts by weight of the diene rubber.
本発明のゴム組成物には、上記シリカとともにシランカップリング剤を配合することが好ましい。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)テトラスルフィド、ビス(3−トリエトキシシリルプロピル)ジスルフィド、ビス(2−トリエトキシシリルエチル)テトラスルフィド、3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルトリエトキシシラン、3−ニトロプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシランなどが挙げられる。シランカップリング剤の配合量は、シリカ100重量部に対して0.5〜20重量部であることが好ましく、より好ましくは5〜15重量部である。 The rubber composition of the present invention preferably contains a silane coupling agent together with the silica. Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, and 3-mercaptopropyltrimethoxy. Examples thereof include silane, 3-mercaptopropyltriethoxysilane, 3-nitropropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. It is preferable that the compounding quantity of a silane coupling agent is 0.5-20 weight part with respect to 100 weight part of silica, More preferably, it is 5-15 weight part.
本発明のゴム組成物には、上記した成分の他に、軟化剤、老化防止剤、亜鉛華、ステアリン酸、加硫剤、加硫促進剤など、タイヤトレッド用ゴム組成物において一般に使用される各種添加剤を配合することができる。 In addition to the components described above, the rubber composition of the present invention is generally used in rubber compositions for tire treads such as softeners, anti-aging agents, zinc white, stearic acid, vulcanizing agents, and vulcanization accelerators. Various additives can be blended.
本発明のゴム組成物は、空気入りタイヤのトレッドのためのゴム組成物として用いられ、常法に従い加硫成形することにより、トレッドを形成することができる。 The rubber composition of the present invention is used as a rubber composition for a tread of a pneumatic tire, and a tread can be formed by vulcanization molding according to a conventional method.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
(実施例1〜5及び比較例1〜3)
バンバリーミキサーを使用して、下記表1に示す配合に従い、ゴム組成物を調製した。表1の各成分の詳細は以下の通りである。
(Examples 1-5 and Comparative Examples 1-3)
Using a Banbury mixer, a rubber composition was prepared according to the formulation shown in Table 1 below. The detail of each component of Table 1 is as follows.
・SSBR:ランクセス製の溶液重合スチレン−ブタジエン共重合体ゴム「VSL5025−0HM」
・BR:JSR製のブタジエンゴム「BR01」
・シリカ:東ソー・シリカ製「Nipsil AQ」
・シランカップリング剤:デグサ製「Si69」。
SSBR: solution polymerization styrene-butadiene copolymer rubber “VSL5025-0HM” manufactured by LANXESS
・ BR: JSR butadiene rubber “BR01”
・ Silica: “Nipsil AQ” made by Tosoh Silica
Silane coupling agent: “Si69” manufactured by Degussa.
・キサンタンガム:ローディア日華製の未変性キサンタンガム「ロードポール23」
・グアガム:ローディア日華製の未変性グアガム「ジャガーS」
・変性グアガム1:ローディア日華製のヒドロキシプロピル化グアガム(グアガムをプロピレンオキサイドで変性したもの。以下同じ)「ジャガーHP−8」(置換度=0.4)
・変性グアガム2:ローディア日華製のヒドロキシプロピル化グアガム「ジャガーHP−60」(置換度=0.6)
・変性グアガム3:ローディア日華製のヒドロキシプロピル化グアガム「ジャガーHP−120」(置換度=1.2)
・変性セルロース:アクゾ・ノーベル製のヒドロキシエチル化セルロース(セルロースをエチレンオキサイドで変性したもの。)「ベルモコール351」(置換度=0.85)。
Xanthan gum: Rhodia Nikka's unmodified xanthan gum "Lord Pole 23"
・ Guar gum: Rhodia Nikka's unmodified guar gum "Jaguar S"
-Modified guar gum 1: Hydropropylated guar gum manufactured by Rhodia Nikka (Guar gum modified with propylene oxide; the same applies hereinafter) "Jaguar HP-8" (degree of substitution = 0.4)
Modified guar gum 2: Hydropropylated guar gum “Jaguar HP-60” manufactured by Rhodia Nikka (degree of substitution = 0.6)
Modified guar gum 3: hydroxypropylated guar gum “Jaguar HP-120” manufactured by Rhodia Nikka (degree of substitution = 1.2)
Modified cellulose: Hydroxyethylated cellulose manufactured by Akzo Nobel (cellulose modified with ethylene oxide) “Vermocol 351” (degree of substitution = 0.85).
また、各ゴム組成物には、共通の添加剤として、ワックス(日本精鑞製「パラフィンワックス155」)1重量部、老化防止剤(大内新興化学製「ノクラック6C」)1重量部、亜鉛華(三井金属工業製「酸化亜鉛2種」)2重量部、ステアリン酸(花王製「ルナックS−25」)2重量部、加硫促進剤DPG(大内新興化学製「ノクセラーD」)2重量部、加硫促進剤CZ(大内新興化学製「ノクセラーCZ」)1.8重量部、硫黄(鶴見化学工業製「5%油入微粉末硫黄」)2重量部を配合した。 Each rubber composition includes 1 part by weight of a wax (“Paraffin Wax 155” manufactured by Nippon Seiki), 1 part by weight of an anti-aging agent (“NOCRACK 6C” manufactured by Ouchi Shinsei Chemical), and zinc as common additives. 2 parts by weight of Hana (Mitsui Kinzoku "Zinc Oxide 2"), 2 parts by weight of stearic acid (Kao "Lunac S-25"), vulcanization accelerator DPG (Ouchi Shinsei Chemical "Noxeller D") 2 Part by weight, 1.8 parts by weight of a vulcanization accelerator CZ (“Noxeller CZ” manufactured by Ouchi Shinsei Chemical) and 2 parts by weight of sulfur (“5% oil-filled fine powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.) were blended.
得られた各ゴム組成物を用いて空気入りタイヤを作製して、低燃費性と操縦安定性を評価した。タイヤは、キャップ/ベース構造のトレッドを有する205/65R15 94Hの空気入りタイヤのキャップトレッドに各ゴム組成物を適用し、定法に従い加硫成形することにより製造した。使用リムは15×6.5JJとした。各評価方法は次の通りである。 Pneumatic tires were produced using the obtained rubber compositions, and low fuel consumption and steering stability were evaluated. The tire was manufactured by applying each rubber composition to a cap tread of a 205 / 65R15 94H pneumatic tire having a tread with a cap / base structure, and vulcanizing and molding in accordance with a conventional method. The rim used was 15 × 6.5JJ. Each evaluation method is as follows.
・低燃費性:一軸ドラム試験機で、速度80km/h、空気圧230kPa、荷重450kgにて、転がり抵抗を測定し、比較例1を100とした指数で表示した。数値が小さいほど低燃費性に優れることを示す。 -Low fuel consumption: The rolling resistance was measured with a uniaxial drum tester at a speed of 80 km / h, an air pressure of 230 kPa, and a load of 450 kg. The smaller the value, the better the fuel economy.
・操縦安定性:試作タイヤを装着したテスト車を実車フィーリング試験担当ドライバーが運転して乾燥路面及び湿潤路面を走行するときの直進性及びレーンチェンジ性をフィーリングで判定し、比較例1(コントロールタイヤ)より優れるものを「+2」、やや優れるものを「+1」、同等のものを「±0」、やや劣るものを「−1」、劣るものを「−2」の5点法にて評価した。
結果は表1に示す通りであり、比較例1(コントロールタイヤ)に対して、未変性の多糖類(キサンタンガム、グアガム)を添加した比較例2,3では、操縦安定性の改善効果は得られず、低燃費性も若干悪化していた。これに対し、ヒドロキシプロピル化グアガムを添加した実施例1〜4、およびヒドロキシエチル化セルロースを添加した実施例5では、低燃費性を実質的に損なうことなく、操縦安定性が向上していた。 The results are as shown in Table 1, and in Comparative Examples 2 and 3 in which unmodified polysaccharides (xanthan gum and guar gum) were added to Comparative Example 1 (control tire), the effect of improving steering stability was obtained. In addition, the fuel economy was slightly worse. On the other hand, in Examples 1 to 4 to which hydroxypropylated guar gum was added and Example 5 to which hydroxyethylated cellulose was added, steering stability was improved without substantially impairing the fuel economy.
本発明に係るゴム組成物は、低燃費性を損なうことなく、操縦安定性を向上することができるため、空気入りタイヤのトレッドゴムに好適に利用することができる。 Since the rubber composition according to the present invention can improve steering stability without impairing fuel efficiency, it can be suitably used for a tread rubber of a pneumatic tire.
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Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US20100069530A1 (en) * | 2006-12-27 | 2010-03-18 | Michelin Recherche Et Technique, S.A. | Tyre tread having a composition containing a xanthan gum powder |
JP2010514867A (en) * | 2006-12-27 | 2010-05-06 | ソシエテ ド テクノロジー ミシュラン | Tread with composition containing guar gum powder |
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JP2019044115A (en) * | 2017-09-05 | 2019-03-22 | 横浜ゴム株式会社 | Tire rubber composition |
WO2019087570A1 (en) * | 2017-11-06 | 2019-05-09 | 株式会社ブリヂストン | Rubber composition, vulcanized rubber, and tire |
US10336890B2 (en) | 2014-03-17 | 2019-07-02 | Sumitomo Rubber Industries, Ltd. | Rubber composition for studless winter tires, and studless winter tire |
KR20220010680A (en) * | 2020-07-17 | 2022-01-26 | 한국생산기술연구원 | Silica-rubber composite composition containing cellulose derivative dispersant and method for producing the same |
KR20220042945A (en) * | 2020-09-28 | 2022-04-05 | 한국타이어앤테크놀로지 주식회사 | Rubber composition for tire tread and tire comprising the tire tread |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10176082A (en) * | 1996-03-16 | 1998-06-30 | Continental Ag | Rubber mixture for tire |
JPH1171481A (en) * | 1997-06-17 | 1999-03-16 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
JP2001089599A (en) * | 1999-08-06 | 2001-04-03 | Goodyear Tire & Rubber Co:The | Rubber containing reinforcing agent of starch, and tire having the same as component |
JP2002206036A (en) * | 2001-01-10 | 2002-07-26 | Bridgestone Corp | Colored rubber composition and pneumatic tire using the same |
JP2002212298A (en) * | 2001-01-12 | 2002-07-31 | Rhodia Nicca Ltd | Method for increasing viscosity of lower alcohol |
JP2005002287A (en) * | 2003-06-13 | 2005-01-06 | Sumitomo Rubber Ind Ltd | Rubber composition for tire tread |
-
2005
- 2005-01-31 JP JP2005024234A patent/JP4762561B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10176082A (en) * | 1996-03-16 | 1998-06-30 | Continental Ag | Rubber mixture for tire |
JPH1171481A (en) * | 1997-06-17 | 1999-03-16 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
JP2001089599A (en) * | 1999-08-06 | 2001-04-03 | Goodyear Tire & Rubber Co:The | Rubber containing reinforcing agent of starch, and tire having the same as component |
JP2002206036A (en) * | 2001-01-10 | 2002-07-26 | Bridgestone Corp | Colored rubber composition and pneumatic tire using the same |
JP2002212298A (en) * | 2001-01-12 | 2002-07-31 | Rhodia Nicca Ltd | Method for increasing viscosity of lower alcohol |
JP2005002287A (en) * | 2003-06-13 | 2005-01-06 | Sumitomo Rubber Ind Ltd | Rubber composition for tire tread |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
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US8372901B2 (en) * | 2006-12-27 | 2013-02-12 | Michelin Recherche Et Technique S.A. | Tyre tread having a composition containing a xanthan gum powder |
US20100069530A1 (en) * | 2006-12-27 | 2010-03-18 | Michelin Recherche Et Technique, S.A. | Tyre tread having a composition containing a xanthan gum powder |
JP2010514867A (en) * | 2006-12-27 | 2010-05-06 | ソシエテ ド テクノロジー ミシュラン | Tread with composition containing guar gum powder |
JP2010514868A (en) * | 2006-12-27 | 2010-05-06 | ソシエテ ド テクノロジー ミシュラン | Tire tread having a composition containing xanthan gum powder |
US8314165B2 (en) * | 2006-12-27 | 2012-11-20 | Michelin Recherche Et Technique S.A. | Tread having a composition containing a guar gum powder |
JP2009057514A (en) * | 2007-09-03 | 2009-03-19 | Yokohama Rubber Co Ltd:The | Rubber composition |
JP4581116B2 (en) * | 2007-09-10 | 2010-11-17 | 住友ゴム工業株式会社 | Vulcanized rubber composition, pneumatic tire, and production method thereof |
US8022136B2 (en) | 2007-09-10 | 2011-09-20 | Sumitomo Rubber Industries, Ltd. | Vulcanized rubber composition, pneumatic tire and the process of producing the same |
JP2009084564A (en) * | 2007-09-10 | 2009-04-23 | Sumitomo Rubber Ind Ltd | Vulcanized rubber composition, pneumatic tire, and their production methods |
CN101631829B (en) * | 2007-09-10 | 2013-02-20 | 住友橡胶工业株式会社 | Vulcanized rubber composition, pneumatic tire, and their production methods |
WO2009034902A1 (en) * | 2007-09-10 | 2009-03-19 | Sumitomo Rubber Industries, Ltd. | Vulcanized rubber composition, pneumatic tire, and their production methods |
US9181355B2 (en) | 2010-06-10 | 2015-11-10 | Sumitomo Rubber Industries, Ltd. | Modified natural rubber, method for producing same, rubber composition, and pneumatic tire |
JP2012188494A (en) * | 2011-03-09 | 2012-10-04 | Toyo Tire & Rubber Co Ltd | Tire rubber composition |
US9410033B2 (en) | 2011-11-11 | 2016-08-09 | Sumitomo Rubber Industries, Ltd. | Rubber composition for undertread, and pneumatic tire |
FR2984901A1 (en) * | 2011-12-22 | 2013-06-28 | Michelin Soc Tech | RUBBER COMPOSITION COMPRISING A CELLULOSE DERIVATIVE |
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