JP2011122047A - Rubber composition and pneumatic tire - Google Patents
Rubber composition and pneumatic tire Download PDFInfo
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- JP2011122047A JP2011122047A JP2009280437A JP2009280437A JP2011122047A JP 2011122047 A JP2011122047 A JP 2011122047A JP 2009280437 A JP2009280437 A JP 2009280437A JP 2009280437 A JP2009280437 A JP 2009280437A JP 2011122047 A JP2011122047 A JP 2011122047A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 103
- 239000005060 rubber Substances 0.000 title claims abstract description 103
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000002563 ionic surfactant Substances 0.000 claims abstract description 37
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 11
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 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
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229920003244 diene elastomer Polymers 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 18
- -1 1,3-dimethylbutyl Chemical group 0.000 description 34
- 239000003795 chemical substances by application Substances 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 238000002845 discoloration Methods 0.000 description 17
- 239000001993 wax Substances 0.000 description 17
- 230000003712 anti-aging effect Effects 0.000 description 16
- 150000001412 amines Chemical class 0.000 description 13
- 125000006353 oxyethylene group Chemical group 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- 238000007259 addition reaction Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000004636 vulcanized rubber Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 230000002542 deteriorative effect Effects 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000001180 sulfating effect Effects 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VTEKOFXDMRILGB-UHFFFAOYSA-N bis(2-ethylhexyl)carbamothioylsulfanyl n,n-bis(2-ethylhexyl)carbamodithioate Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=S)SSC(=S)N(CC(CC)CCCC)CC(CC)CCCC VTEKOFXDMRILGB-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 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
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ゴム組成物及び空気入りタイヤに関する。さらに詳しくは、本発明は、耐オゾン性を悪化させることなく、外観を良好に保つことができるタイヤを与えるゴム組成物、及び該ゴム組成物をタイヤ部材に用いてなる、上記性状を有する空気入りタイヤに関するものである。 The present invention relates to a rubber composition and a pneumatic tire. More specifically, the present invention relates to a rubber composition that gives a tire capable of maintaining a good appearance without deteriorating ozone resistance, and air having the above properties, which is obtained by using the rubber composition as a tire member. This relates to the tires inside.
一般に、天然ゴムやジエン系合成ゴムを原料としたゴム物品は、オゾンの存在下で劣化が進行し、表面に亀裂が生じる。この亀裂は、ゴム物品にかかる静的及び動的応力により進行し、その結果、ゴム物品が破壊に至ってしまう。
そこで、このようなオゾンによる亀裂の発生及び進行を抑制するために、ゴム物品、特にタイヤのサイドウォールには、老化防止剤として、Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミンなどのアミン系老化防止剤を配合したゴム組成物が適用されている。また、該ゴム組成物には、オゾンからの静的保護を目的として、ゴム物品の表面に保護膜を形成するためにワックスが配合されている。
In general, a rubber article made from natural rubber or a diene synthetic rubber is deteriorated in the presence of ozone, and a crack occurs on the surface. This crack progresses due to static and dynamic stress applied to the rubber article, and as a result, the rubber article is broken.
Therefore, in order to suppress the occurrence and progression of cracks due to ozone, N- (1,3-dimethylbutyl) -N′-phenyl-is used as an anti-aging agent in rubber articles, particularly tire sidewalls. A rubber composition containing an amine anti-aging agent such as p-phenylenediamine is applied. The rubber composition contains a wax for forming a protective film on the surface of the rubber article for the purpose of static protection from ozone.
しかしながら、上記アミン系老化防止剤及びワックスは、オゾン存在下での亀裂の発生及び進行の抑制に有効であるものの、ゴム成分などのポリマー基質を通って移動しやすく、短期間でゴム物品、特にタイヤの表面に移行し、倉庫保管中及び使用中に該ゴム物品を変色させるなどして外観を悪化させる。ここで、上記アミン系老化防止剤が表面に移行すると該表面が茶変し、ワックスが表面に移行すると該表面が白変してしまう。 However, although the amine-based anti-aging agent and the wax are effective in suppressing the generation and progress of cracks in the presence of ozone, the amine-based anti-aging agent is easy to move through a polymer substrate such as a rubber component, and in a short period of time, particularly a rubber article, It shifts to the surface of the tire and deteriorates the appearance by changing the color of the rubber article during storage and use. Here, when the amine-based anti-aging agent moves to the surface, the surface turns brown, and when the wax moves to the surface, the surface turns white.
これに対し、タイヤサイドウォール用ゴム組成物にポリオキシエチレンエーテル型非イオン系界面活性剤を配合して、アミン系老化防止剤及びワックスによる変色を防止する技術が知られている（例えば、特許文献１及び特許文献２参照）。 On the other hand, a technology for preventing discoloration by an amine anti-aging agent and wax by blending a rubber composition for tire sidewall with a polyoxyethylene ether type nonionic surfactant is known (for example, patents). Reference 1 and Patent Document 2).
ゴム物品、特にタイヤにおいては、適度の光沢を付与し、外観を美しくすることが求められる場合があるが、タイヤサイドウォール用ゴム組成物では、変色を制御する技術はあっても、トレッド部では変色を抑制する技術は、これまで知られていないのが実状である。
本発明は、このような状況下になされたもので、耐オゾン性を悪化させることなく、外観を良好に保つことができるタイヤを与えるゴム組成物、及び該ゴム組成物をタイヤサイドウォールやトレッドなどのタイヤ部材用いてなる、上記性状を有する空気入りタイヤを提供することを目的とするものである。
In rubber articles, particularly tires, it may be required to impart a moderate gloss and beautify the appearance, but in the tire sidewall rubber composition, there is a technique for controlling discoloration, but in the tread part. The technology that suppresses discoloration is not known so far.
The present invention has been made under such circumstances, and provides a rubber composition that gives a tire capable of maintaining a good appearance without deteriorating ozone resistance, and the rubber composition as a tire sidewall or tread. An object of the present invention is to provide a pneumatic tire having the above properties, using a tire member such as.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定の構造を有するイオン系界面活性剤、好ましくは硫酸エステルアンモニウム塩型を、ゴム成分に対して所定の割合で配合してなるゴム組成物により、その目的を達成し得ることを見出した。
本発明は、かかる知見に基づいて完成したものである。
As a result of intensive studies to achieve the above object, the present inventors have formulated an ionic surfactant having a specific structure, preferably a sulfate ammonium salt type, in a predetermined ratio with respect to the rubber component. It has been found that the object can be achieved by the rubber composition.
The present invention has been completed based on such findings.
すなわち、本発明は、
［１］（Ａ）ゴム成分と、（Ｂ）分子内に、オキシアルキレン基を一つ以上有するイオン系界面活性剤とを含有することを特徴とするゴム組成物、
［２］（Ｂ）イオン系界面活性剤が、硫酸エステルアンモニウム塩型である、上記［１］に記載のゴム組成物、
［３］硫酸エステルアンモニウム塩型イオン系界面活性剤が、下記一般式（１）
That is, the present invention
[1] A rubber composition comprising (A) a rubber component and (B) an ionic surfactant having one or more oxyalkylene groups in the molecule;
[2] The rubber composition according to [1], wherein the (B) ionic surfactant is a sulfate ammonium salt type,
[3] A sulfate ammonium salt type ionic surfactant is represented by the following general formula (1):
［式中、Ｒ1は炭素数１〜４のアルキレン基又は環上に炭素数１〜１０のアルキル基を有していてもよいアリーレン基、Ｒ2は水素原子又はメチル基、Ｒ3Ｏは炭素数２〜１２のオキシアルキレン基、Ｒ4、Ｒ5及びＲ6は、それぞれ独立に水素原子、炭素数１〜１８のアルキル基又は炭素数２〜４のアルカノール基を示し、ｋは１〜７０の整数である。Ｒ3Ｏが複数存在する場合、複数のＲ3Ｏは、たがいに同一であってもよく、異なっていてもよい。］
で表される構造を有する化合物である、上記［２］に記載のゴム組成物、
［４］一般式（１）で表される構造を有する化合物が、下記一般式（１−ａ）
[Wherein, R 1 represents an alkylene group having 1 to 4 carbon atoms or an arylene group optionally having an alkyl group having 1 to 10 carbon atoms on the ring, R 2 represents a hydrogen atom or a methyl group, and R 3 O represents An oxyalkylene group having 2 to 12 carbon atoms, R 4 , R 5 and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkanol group having 2 to 4 carbon atoms; It is an integer of 70. If R 3 O there are a plurality, the plurality of R 3 O may be mutually identical or may be different. ]
The rubber composition according to the above [2], which is a compound having a structure represented by:
[4] A compound having a structure represented by the general formula (1) is represented by the following general formula (1-a):
［式中、Ａ1Ｏは炭素数４〜１２のオキシアルキレン基、Ａ2Ｏは炭素数２又は３のオキシアルキレン基を示し、ｎは０〜２０の整数、ｍは１〜５０の整数である。（Ａ1Ｏ）nと（Ａ2Ｏ）mの順序に制限はなく、Ａ2Ｏが複数存在する場合、複数Ａ2Ｏは、たがいに同一であってもよく、異なっていてもよい。Ｒ1、Ｒ2、Ｒ4、Ｒ5及びＲ6は、一般式（１）と同様である。］
で表される構造を有する化合物である、上記［３］に記載のゴム組成物、
［５］一般式（１−ａ）において、ｎが０〜２０の整数、ｍが１〜３０の整数である、上記［４］に記載のゴム組成物、
［６］一般式（１−ａ）において、ｎが０〜１０の整数、ｍが１〜２０の整数である、上記［５］に記載のゴム組成物、
［７］（Ａ）ゴム成分が、ジエン系ゴム及び天然ゴムの中から選らばれる少なくとも一種である、上記［１］〜［６］のいずれかに記載のゴム組成物、
［８］（Ｂ）イオン系界面活性剤が、（Ａ）ゴム成分１００質量部に対して０．１〜１０質量部の割合で含有する上記［１］〜［７］のいずれかに記載のゴム組成物、
［９］空気入りタイヤに用いられる上記［１］〜［８］のいずれかに記載のゴム組成物、［１０］上記［１］〜［９］のいずれかに記載のゴム組成物をタイヤ部材に用いたことを特徴とする空気入りタイヤ、及び
［１１］タイヤ部材がトレッドである、上記［１０］に記載の空気入りタイヤ、
を提供するものである。
[Wherein, A 1 O represents an oxyalkylene group having 4 to 12 carbon atoms, A 2 O represents an oxyalkylene group having 2 or 3 carbon atoms, n is an integer of 0 to 20, and m is an integer of 1 to 50. is there. (A 1 O) n and (A 2 O) order limit of m is not, if A 2 O there are multiple, multiple A 2 O may be mutually identical or may be different. R 1 , R 2 , R 4 , R 5 and R 6 are the same as those in the general formula (1). ]
The rubber composition according to the above [3], which is a compound having a structure represented by:
[5] The rubber composition according to the above [4], wherein in the general formula (1-a), n is an integer of 0 to 20, and m is an integer of 1 to 30.
[6] The rubber composition according to [5], wherein in general formula (1-a), n is an integer of 0 to 10, and m is an integer of 1 to 20,
[7] The rubber composition according to any one of [1] to [6] above, wherein the rubber component (A) is at least one selected from diene rubbers and natural rubbers.
[8] The system according to any one of [1] to [7], wherein the (B) ionic surfactant is contained at a ratio of 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) rubber component. Rubber composition,
[9] The rubber composition according to any one of [1] to [8] used in a pneumatic tire, and [10] the rubber composition according to any one of [1] to [9] described above as a tire member. A pneumatic tire according to claim 10, and [11] the pneumatic tire according to [10], wherein the tire member is a tread.
Is to provide.
本発明によれば、特定の構造を有するイオン系界面活性剤、好ましくは硫酸エステルアンモニウム塩型を含むゴム組成物をタイヤサイドウォールやトレッドなどのタイヤ部材に用いることにより、耐オゾン性を悪化させることなく、外観を良好に保つことができる空気入りタイヤを与えることができる。 According to the present invention, ozone resistance is deteriorated by using a rubber composition containing an ionic surfactant having a specific structure, preferably an ammonium sulfate ester salt type, for a tire member such as a tire sidewall or a tread. Therefore, it is possible to provide a pneumatic tire that can maintain a good appearance.
まず、本発明のゴム組成物について説明する。
［ゴム組成物］
本発明のゴム組成物は、（Ａ）ゴム成分と、（Ｂ）分子内に、オキシアルキレン基を一つ以上有するイオン系界面活性剤とを含有することを特徴とする。
First, the rubber composition of the present invention will be described.
[Rubber composition]
The rubber composition of the present invention is characterized by containing (A) a rubber component and (B) an ionic surfactant having one or more oxyalkylene groups in the molecule.
（（Ａ）ゴム成分）
本発明のゴム組成物においては、（Ａ）ゴム成分として、ジエン系合成ゴム及び天然ゴムの中から選ばれる少なくとも一種が好ましく用いられる。前記ジエン系合成ゴムとしては、イソプレンゴム（ＩＲ）、ポリブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）などが挙げられ、これらゴム成分は、一種を単独で用いても二種以上を組み合わせて用いてもよい。
((A) rubber component)
In the rubber composition of the present invention, as the rubber component (A), at least one selected from diene synthetic rubber and natural rubber is preferably used. Examples of the diene synthetic rubber include isoprene rubber (IR), polybutadiene rubber (BR), and styrene-butadiene copolymer rubber (SBR). These rubber components may be used alone or in combination of two or more. May be used in combination.
（（Ｂ）イオン系界面活性剤）
本発明のゴム組成物において、（Ｂ）成分のイオン系界面活性剤として、分子内に、オキシアルキレン基を一つ以上有するイオン系界面活性剤、好ましくは硫酸エステルアンモニウム塩型の界面活性剤が用いられる。この（Ｂ）成分のイオン系界面活性剤は、以下に示す効果を奏する。
一般に、天然ゴムやジエン系合成ゴムを原料としたゴム物品は、オゾンの存在下で劣化が進行し、表面に亀裂が生じる。この亀裂は、ゴム物品にかかる静的及び動的応力により進行し、その結果、ゴム物品が破壊に至ってしまう。
したがって、上記オゾンによる亀裂の発生及び進行を抑制するために、ゴム物品、特にタイヤ部材には、一般にワックスやアミン系老化防止剤が配合されている。しかしながら、ワックスは表面に移行しやすく、その結果、例えばタイヤ表面に、ワックスの移行による凹凸が形成され、散乱が生じ、白く変色し、さらにアミン系老化防止剤も表面へ移行し、該タイヤ表面は茶色に変色して、外観が損なわれる。
しかし、当該イオン系界面活性剤を配合したゴム組成物をタイヤ部材に用いると、このイオン系界面活性剤が表面に移行して、前記ワックスの移行によって生じる凹凸を滑らかにし、その結果、散乱が生じるのを抑制し、茶色に変色するのを防止することができる。
((B) ionic surfactant)
In the rubber composition of the present invention, as the ionic surfactant of the component (B), an ionic surfactant having at least one oxyalkylene group in the molecule, preferably a sulfate ammonium salt type surfactant is used. Used. This ionic surfactant as the component (B) has the following effects.
In general, a rubber article made from natural rubber or a diene synthetic rubber is deteriorated in the presence of ozone, and a crack occurs on the surface. This crack progresses due to static and dynamic stress applied to the rubber article, and as a result, the rubber article is broken.
Therefore, in order to suppress the occurrence and progress of cracks due to ozone, waxes and amine-based antioxidants are generally blended in rubber articles, particularly tire members. However, the wax easily migrates to the surface. As a result, for example, unevenness due to the migration of the wax is formed on the tire surface, scattering occurs, the color changes to white, and the amine anti-aging agent also migrates to the surface. Turns brown and the appearance is impaired.
However, when a rubber composition containing the ionic surfactant is used for a tire member, the ionic surfactant migrates to the surface and smoothes the unevenness caused by the wax migration, resulting in scattering. Generation | occurence | production can be suppressed and it can prevent changing to brown.
前記硫酸エステルアンモニウム塩型のイオン系界面活性剤としては、下記一般式（１）
［式中、Ｒ1は炭素数１〜４のアルキレン基又は環上に炭素数１〜１０のアルキル基を有していてもよいアリーレン基、Ｒ2は水素原子又はメチル基、Ｒ3Ｏは炭素数２〜１２のオキシアルキレン基、Ｒ4、Ｒ5及びＲ6は、それぞれ独立に水素原子、炭素数１〜１８のアルキル基又は炭素数２〜４のアルカノール基を示し、ｋは１〜７０の整数である。Ｒ3Ｏが複数存在する場合、複数のＲ3Ｏは、たがいに同一であってもよく、異なっていてもよい。］
で表される構造を有する化合物を挙げることができる。
[Wherein, R 1 represents an alkylene group having 1 to 4 carbon atoms or an arylene group optionally having an alkyl group having 1 to 10 carbon atoms on the ring, R 2 represents a hydrogen atom or a methyl group, and R 3 O represents An oxyalkylene group having 2 to 12 carbon atoms, R 4 , R 5 and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkanol group having 2 to 4 carbon atoms; It is an integer of 70. If R 3 O there are a plurality, the plurality of R 3 O may be mutually identical or may be different. ]
The compound which has a structure represented by these can be mentioned.
前記一般式（１）において、Ｒ1のうちの炭素数１〜４のアルキレン基は直鎖状、分岐鎖状のいずれであってもよく、例えばメチレン基、エチレン基、各種プロパンジイル基及び各種ブタンジイル基を挙げることができる。なお、各種プロパンジイル基及び各種ブタンジイル基の「各種」とは、同一炭素数の異性体全てを包含する基を指す。以下、同様である。
一方、Ｒ1のうちの環上に炭素数１〜１０のアルキル基を有してもよいアリーレン基としては、例えばフェニレン基、各種メチルフェニレン基、各種ジメチルフェニレン基、各種ナフチレン基などを挙げることができる。
また、Ｒ3Ｏのうちの炭素数２〜１２のオキシアルキレン基は直鎖状、分岐鎖状のいずれであってもよく、例えばオキシエチレン基、各種オキシプロピレン基、各種オキシブチレン基、各種オキシペンチレン基、各種オキシへキシレン基、各種オキシへプチレン基、各種オキシオクチレン基、各種オキシノニレン基、各種オキシデシレン基、各種オキシウンデシレン基、各種オキシドデシレン基を挙げることができる。
In the general formula (1), the alkylene group having 1 to 4 carbon atoms in R 1 may be linear or branched, such as a methylene group, an ethylene group, various propanediyl groups, and various types. A butanediyl group can be mentioned. “Various” of various propanediyl groups and various butanediyl groups refers to groups including all isomers having the same carbon number. The same applies hereinafter.
On the other hand, examples of the arylene group that may have an alkyl group having 1 to 10 carbon atoms on the ring of R 1 include a phenylene group, various methylphenylene groups, various dimethylphenylene groups, and various naphthylene groups. Can do.
In addition, the oxyalkylene group having 2 to 12 carbon atoms in R 3 O may be either linear or branched, such as oxyethylene group, various oxypropylene groups, various oxybutylene groups, various oxyalkylene groups. Examples thereof include a pentylene group, various oxyhexylene groups, various oxyheptylene groups, various oxyoctylene groups, various oxynonylene groups, various oxydecylene groups, various oxyundecylene groups, and various oxide decylene groups.
分子内に、炭素数２〜１２のオキシアルキレン基を導入する方法としては、水酸基を有する化合物の水酸基に、例えばエチレンオキシド、プロピレンオキシド、各種ブチレンオキシドのほか、炭素数５〜１２の各種アルキレンオキシドから選ばれる少なくとも一種を付加反応させることにより導入することができる。 As a method for introducing an oxyalkylene group having 2 to 12 carbon atoms into the molecule, for example, from a hydroxyl group of a compound having a hydroxyl group, for example, ethylene oxide, propylene oxide, various butylene oxides, and various alkylene oxides having 5 to 12 carbon atoms. At least one selected may be introduced by addition reaction.
前記一般式（１）において、Ｒ4、Ｒ5及びＲ6のうちの炭素数１〜１８のアルキル基は、直鎖状、分岐鎖状、環状のいずれであってもよく、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、各種ペンチル基、各種ヘキシル基、各種オクチル基、各種デシル基、各種ドデシル基、各種テトラデシル基、各種ヘキサデシル基、各種オクタデシル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基などを挙げることができる。
また、Ｒ4、Ｒ5及びＲ6のうちの炭素数２〜４のアルカノール基は直鎖状、分岐鎖状のいずれであってもよく、例えば２−ヒドロキシエチル基、２−ヒドロキシプロピル基、３−ヒドロキシプロピル基、２−ヒドロキシブチル基、３−ヒドロキシブチル基、４−ヒドロキシブチル基を挙げることができる。
ｋは１〜７０の整数であるが、当該イオン系界面活性剤のゴムへの溶解性や性能の観点から、１〜５０の整数であることが好ましく、１〜３０の整数であることがより好ましい。
In the general formula (1), the alkyl group having 1 to 18 carbon atoms of R 4 , R 5 and R 6 may be linear, branched or cyclic, such as a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various types Examples include a tetradecyl group, various hexadecyl groups, various octadecyl groups, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
In addition, the alkanol group having 2 to 4 carbon atoms of R 4 , R 5 and R 6 may be either linear or branched, such as 2-hydroxyethyl group, 2-hydroxypropyl group, Examples thereof include a 3-hydroxypropyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
k is an integer of 1 to 70, but is preferably an integer of 1 to 50 and more preferably an integer of 1 to 30 from the viewpoint of solubility and performance of the ionic surfactant in rubber. preferable.
当該イオン系界面活性剤としては、下記一般式（１−ａ）
［式中、Ａ1Ｏは炭素数４〜１２のオキシアルキレン基、Ａ2Ｏは炭素数２又は３のオキシアルキレン基を示し、ｎは０〜２０の整数、ｍは１〜５０の整数である。（Ａ1Ｏ）nと（Ａ2Ｏ）mの順序に制限はなく、Ａ2Ｏが複数存在する場合、複数のＡ2Ｏは、たがいに同一であってもよく、異なっていてもよい。Ｒ1、Ｒ2、Ｒ4、Ｒ5及びＲ6は、一般式（１）と同様である。］
で表される構造を有する化合物が、製造性及び性能などの観点から、好ましい。
[Wherein, A 1 O represents an oxyalkylene group having 4 to 12 carbon atoms, A 2 O represents an oxyalkylene group having 2 or 3 carbon atoms, n is an integer of 0 to 20, and m is an integer of 1 to 50. is there. (A 1 O) n and (A 2 O) order limit of m is not, if A 2 O there are a plurality, a plurality of A 2 O may be mutually identical or may be different . R 1 , R 2 , R 4 , R 5 and R 6 are the same as those in the general formula (1). ]
Is preferable from the viewpoints of manufacturability and performance.
前記一般式（１−ａ）において、Ａ1Ｏで示される炭素数４〜１２のオキシアルキレン基は直鎖状、分岐鎖状のいずれであってもよく、上記のＲ3Ｏで例示した各種オキシアルキレン基を挙げることができる。このＡ1Ｏは、水酸基を有する化合物の該水酸基に、各種ブチレンオキシドを付加反応させることにより、導入することができる。
一方、Ａ2Ｏで表される炭素数２、３のオキシアルキレン基としては、オキシエチレン基やオキシイソプロピレン基を挙げることができる。水酸基含有化合物の該水酸基に、エチレンオキシドを付加反応させることにより、オキシエチレン基を導入することができ、プロピレンオキシドを付加反応させることにより、オキシイソプロピレン基を導入することができる。
本発明においては、Ａ2Ｏが複数存在する場合、複数のＡ2Ｏは、たがいに同一であってもよく、異なっていてもよい。また、前記Ａ2Ｏは、オキシエチレン基のブロック部と、オキシイソプロピレン基のブロック部とを有するものであってもよく、オキシエチレン基とオキシイソプロピレン基がランダムに混在したものであってもよい。
ｎは０〜２０の整数、ｍは１〜５０の整数であるが、当該イオン系界面活性剤の性能の観点から、ｎが０〜２０の整数であり、かつｍが１〜３０の整数であることが好ましく、ｎが０〜１０の整数であり、かつｍが１〜２０の整数であることがより好ましい。また、（Ａ1Ｏ）nと（Ａ2Ｏ）mの順序については特に制限はない。Ｒ1、Ｒ2、Ｒ4、Ｒ5及びＲ6は、前記一般式（１）と同様である。
In the general formula (1-a), the oxyalkylene group having 4 to 12 carbon atoms represented by A 1 O may be linear or branched, and various examples exemplified for R 3 O above. An oxyalkylene group can be mentioned. This A 1 O can be introduced by addition reaction of various butylene oxides with the hydroxyl group of the compound having a hydroxyl group.
On the other hand, examples of the oxyalkylene group having 2 or 3 carbon atoms represented by A 2 O include an oxyethylene group and an oxyisopropylene group. An oxyethylene group can be introduced by addition reaction of ethylene oxide with the hydroxyl group of the hydroxyl group-containing compound, and an oxyisopropylene group can be introduced by addition reaction of propylene oxide.
In the present invention, if the A 2 O there are a plurality, a plurality of A 2 O may be mutually identical or may be different. The A 2 O may have an oxyethylene group block portion and an oxyisopropylene group block portion, and a mixture of oxyethylene groups and oxyisopropylene groups randomly. Also good.
n is an integer of 0 to 20, and m is an integer of 1 to 50. From the viewpoint of the performance of the ionic surfactant, n is an integer of 0 to 20 and m is an integer of 1 to 30. It is preferable that n is an integer of 0 to 10, and m is more preferably an integer of 1 to 20. Further, no particular limitation is imposed on the order of (A 1 O) n and (A 2 O) m. R 1 , R 2 , R 4 , R 5 and R 6 are the same as those in the general formula (1).
前記一般式（１）又は（１−ａ）で表される硫酸エステルアンモニウム塩型イオン系界面活性剤の製造方法に特に制限はなく、従来公知の製造方法を採用することができる。
前記一般式（１）の化合物は、例えば末端の−（Ｒ3Ｏ）k-1−Ｒ3ＯＨに、硫酸化剤としてクロルスルホン酸、無水硫酸、アミド硫酸などを反応させて−（Ｒ3Ｏ）k-1−Ｒ3ＯＳＯ3Ｈで表される硫酸エステルを得たのち、トリアルキルアミンやトリアルカノールアミンなどで中和してアンモニウム塩化することにより製造することができる。硫酸化剤としては、二重結合基への硫酸基の付加反応や二重結合基の異性化などの副反応を抑制する観点から、アミド硫酸の使用が好ましい。
前記一般式（１）で表される硫酸エステルアンモニウム塩型イオン系界面活性剤は、例えば以下のようにして製造することができる。
Ｈ2Ｃ＝Ｃ（Ｒ2）−Ｒ1−ＯＨ（Ｒ1及びＲ2は前記と同じである。）で表される不飽和アルコールに、触媒の存在下に、エチレンオキシド、プロピレンオキシド、各種ブチレンオキシドのほか、炭素数５〜１２の各種アルキレンオキシドなどの中から選ばれる少なくとも一種を付加反応又は開環付加反応させて、分子内に、炭素数２〜１２のオキシアルキレン基を、合計量で１〜７０個有する不飽和エーテルアルコール及び／又は不飽和エステルアルコールを得る。次いで、このアルコールの水酸基に、クロルスルホン酸、無水硫酸、アミド硫酸などの硫酸化剤、好ましくはアミド硫酸を反応させて硫酸エステルを得たのち、トリアルキルアミンやトリアルカノールアミンで中和することにより、目的の前記一般式（１）で表される硫酸エステルアンモニウム塩型のイオン系界面活性剤を得ることができる。
なお、前記一般式（１−ａ）で表される硫酸エステルアンモニウム塩型イオン系界面活性剤を製造する場合には、前記の製造方法において、ラクトン類を除き、エチレンオキシド、プロピレンピキシド、各種ブチレンオキシドの中から選ばれる少なくとも一種を、不飽和アルコールに付加反応させ、以下、前記と同様な操作を行えばよい。
There is no restriction | limiting in particular in the manufacturing method of a sulfate ester ammonium salt type ionic surfactant represented by the said General formula (1) or (1-a), A conventionally well-known manufacturing method is employable.
The compound of the general formula (1) may, for example, end of - the (R 3 O) k-1 -R 3 OH, is reacted chlorosulfonic acid, sulfuric anhydride, an amide acid as a sulfating agent - (R 3 O) The sulfuric acid ester represented by k-1 -R 3 OSO 3 H can be obtained, and then neutralized with a trialkylamine or trialkanolamine, and then ammonium salted. As the sulfating agent, amidosulfuric acid is preferably used from the viewpoint of suppressing side reactions such as addition reaction of sulfate group to double bond group and isomerization of double bond group.
The sulfate ammonium salt type ionic surfactant represented by the general formula (1) can be produced, for example, as follows.
An unsaturated alcohol represented by H 2 C═C (R 2 ) —R 1 —OH (R 1 and R 2 are the same as described above), ethylene oxide, propylene oxide, and various butylenes in the presence of a catalyst. In addition to the oxide, at least one kind selected from various alkylene oxides having 5 to 12 carbon atoms is subjected to addition reaction or ring-opening addition reaction, and oxyalkylene groups having 2 to 12 carbon atoms are added in the total amount in the molecule. 1 to 70 unsaturated ether alcohols and / or unsaturated ester alcohols are obtained. Then, the hydroxyl group of this alcohol is reacted with a sulfating agent such as chlorosulfonic acid, anhydrous sulfuric acid, amide sulfuric acid, preferably amide sulfuric acid to obtain a sulfate ester, and then neutralized with a trialkylamine or trialkanolamine. Thus, the objective sulfate ammonium salt type ionic surfactant represented by the general formula (1) can be obtained.
In addition, when manufacturing the sulfate ester ammonium salt type ionic surfactant represented by the general formula (1-a), in the above manufacturing method, except for lactones, ethylene oxide, propylene poxide, and various butylenes are used. At least one selected from oxides may be subjected to an addition reaction with an unsaturated alcohol, and then the same operation as described above may be performed.
本発明のゴム組成物においては、（Ｂ）成分のイオン系界面活性剤は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。その含有量は、前述した（Ａ）ゴム成分１００質量部に対して、好ましくは０．１〜１０質量部の範囲で選定される。この含有量が０．１質量部以上であれば、アミン系老化防止剤やワックスによる変色を防止する効果及びゴム物品、特にタイヤ表面に適度の光沢を与える効果が十分に得られ、一方、１０質量部以下であれば、当該イオン系界面活性剤のブルーミングによる過度の光沢が出て、外観が悪化したり、表面粘着性に問題が生じて作業性が悪化することがない。当該イオン系界面活性剤の好ましい含有量は、（Ａ）ゴム成分１００質量部に対して、０．３〜７質量部であり、より好ましくは０．５〜５質量部である。 In the rubber composition of the present invention, the component (B) ionic surfactant may be used alone or in combination of two or more. The content thereof is preferably selected in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component (A) described above. If this content is 0.1 parts by mass or more, the effect of preventing discoloration due to the amine-based anti-aging agent and wax and the effect of giving a moderate gloss to the rubber article, particularly the tire surface can be sufficiently obtained. If the amount is less than or equal to parts by mass, excessive glossiness due to blooming of the ionic surfactant will not occur, and the appearance will not deteriorate, and problems with surface adhesion will not occur and workability will not deteriorate. The preferable content of the ionic surfactant is 0.3 to 7 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the (A) rubber component.
（その他配合剤）
本発明のゴム組成物には、オゾンによる亀裂の発生及び進行を抑制するために、アミン系老化防止剤及びワックスを含有させることが好ましい。
アミン系老化防止剤としては、例えば３Ｃ（Ｎ−イソプロピル−Ｎ’−フェニル−ｐ−フェニレンジアミン、６Ｃ［Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン］、ジフェニルアミンとアセトンの高温縮合物などを挙げることができる。その使用量は、（Ａ）ゴム成分１００質量部に対して、０．１〜７．０質量部が好ましく、さらに好ましくは０．５〜５．０質量部である。
ワックス類は日光亀裂防止剤とも分類され、日光又はオゾンの作用により発生する亀裂を抑制する作用を有する。すなわち、加硫後、ゴム物品の表面にブルームして、ゴム表面と空気とを遮断し、かつ日光を反射して、その効力を発揮する。ワックス類の種類に特に制限はなく、従来慣用されているワックス類の中から、任意のものを適宜選択して用いることができる。その使用量は、（Ａ）ゴム成分１００質量部に対して、０．１〜７．０質量部程度、好ましくは０．５〜５．０質量部である。
(Other ingredients)
The rubber composition of the present invention preferably contains an amine anti-aging agent and a wax in order to suppress the occurrence and progress of cracks due to ozone.
Examples of the amine-based antiaging agent include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine, 6C [N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine], diphenylamine). And a high-temperature condensate of acetone and the like, and the amount used thereof is preferably 0.1 to 7.0 parts by weight, more preferably 0.5 to 5 parts per 100 parts by weight of the rubber component (A). 0.0 part by mass.
Waxes are also classified as sun crack prevention agents, and have an action of suppressing cracks generated by the action of sunlight or ozone. That is, after vulcanization, it blooms on the surface of the rubber article, blocks the rubber surface and air, reflects sunlight and exhibits its effectiveness. There is no restriction | limiting in particular in the kind of wax, Arbitrary things can be suitably selected and used from the conventionally used waxes. The usage-amount is about 0.1-7.0 mass parts with respect to 100 mass parts of (A) rubber components, Preferably it is 0.5-5.0 mass parts.
本発明のゴム組成物には、補強用充填材として、カーボンブラック及び／又はシリカを含有させることができる。
カーボンブラックとしては、特に制限はなく、例えばＧＰＦ、ＦＥＦ、ＳＲＦ、ＨＡＦ、Ｎ３３９、ＩＩＳＡＦ、ＩＳＡＦ、ＳＡＦなどが用いられ、窒素吸着比表面積（Ｎ2ＳＡ、ＪＩＳ Ｋ ６２１７−２：２００１に準拠して測定する）が２０〜２５０ｍ2／ｇであるものが好ましい。
一方、シリカとしては、市販のあらゆるものが使用でき、なかでも湿式シリカ、乾式シリカ、コロイダルシリカを用いるのが好ましく、湿式シリカを用いるのが特に好ましい。シリカのＢＥＴ比表面積（ＩＳＯ ５７９４／１に準拠して測定する）としては１００ｍ2／ｇ以上のものが好ましく、より好ましくは１５０ｍ2／ｇ以上、特に好ましくは１７０ｍ2／ｇ以上である。このようなシリカとしては東ソーシリカ社製、商品名「ニプシルＡＱ」（ＢＥＴ比表面積 ＝１９０ｍ2／ｇ）、「ニプシルＫＱ」、デグッサ社製商品名「ウルトラジルＶＮ３」（ＢＥＴ比表面積 ＝１７５ｍ2／ｇ）などの市販品を用いることができる。
なお、補強用充填材としてシリカを用いる場合には、補強性及び低発熱性をさらに向上させる目的で、シランカップリング剤をシリカに対して１〜２０質量％程度含有させることが好ましい。
カーボンブラック及び／又はシリカの含有量は、（Ａ）ゴム成分１００質量部に対して、通常２０〜１００質量部程度、好ましくは３０〜８０質量部である。
The rubber composition of the present invention can contain carbon black and / or silica as a reinforcing filler.
The carbon black is not particularly limited, and for example, GPF, FEF, SRF, HAF, N339, IISAF, ISAF, SAF and the like are used, and the nitrogen adsorption specific surface area (N 2 SA, conforming to JIS K 6217-2: 2001). Is preferably 20 to 250 m 2 / g.
On the other hand, any commercially available silica can be used, and wet silica, dry silica and colloidal silica are particularly preferable, and wet silica is particularly preferable. The BET specific surface area (measured according to ISO 5794/1) of silica is preferably 100 m 2 / g or more, more preferably 150 m 2 / g or more, particularly preferably 170 m 2 / g or more. Examples of such silicas are those manufactured by Tosoh Silica Co., Ltd., trade names “Nipsil AQ” (BET specific surface area = 190 m 2 / g), “Nipsil KQ”, and Degussa's trade name “Ultra Gil VN3” (BET specific surface area = 175 m 2. / G) can be used.
In addition, when using a silica as a reinforcing filler, it is preferable to contain a silane coupling agent in an amount of about 1 to 20% by mass with respect to silica for the purpose of further improving the reinforcing property and the low exothermic property.
The content of carbon black and / or silica is usually about 20 to 100 parts by mass, preferably 30 to 80 parts by mass with respect to 100 parts by mass of the (A) rubber component.
本発明のゴム組成物には、本発明の効果が損なわれない範囲で、所望により、通常ゴム工業界で用いられる各種薬品、例えば加硫剤、加硫促進剤、軟化剤、アミン系以外の老化防止剤、スコーチ防止剤、亜鉛華、ステアリン酸などを含有させることができる。
上記加硫剤としては、硫黄などが挙げられ、その使用量は、（Ａ）ゴム成分１００質量部に対し、硫黄分として０．１〜１０．０質量部が好ましく、さらに好ましくは１．０〜５．０質量部である。０．１質量部未満では加硫ゴムの破壊強度、耐摩耗性、低発熱性が低下するおそれがあり、１０．０質量部を超えるとゴム弾性が失われる原因となる。
本発明で使用できる加硫促進剤は、特に限定されるものではないが、例えば、Ｍ（２−メルカプトベンゾチアゾール）、ＤＭ（ジベンゾチアゾリルジスルフィド）、ＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド）などのチアゾール系、ＤＰＧ（ジフェニルグアニジン）などのグアニジン系、あるいはＴＯＴ（テトラキス（２−エチルへキシル）チウラムジスルフィド)などのチウラム系の加硫促進剤などを挙げることができ、その使用量は、（Ａ）ゴム成分１００質量部に対し、０．１〜５．０質量部が好ましく、さらに好ましくは０．２〜３．０質量部である。
In the rubber composition of the present invention, various chemicals usually used in the rubber industry, for example, other than vulcanizing agents, vulcanization accelerators, softeners and amines, are used as long as the effects of the present invention are not impaired. An anti-aging agent, an anti-scorch agent, zinc white, stearic acid and the like can be contained.
As said vulcanizing agent, sulfur etc. are mentioned, The usage-amount is 0.1-10.0 mass parts as a sulfur content with respect to 100 mass parts of (A) rubber components, More preferably, it is 1.0. -5.0 parts by mass. If the amount is less than 0.1 parts by mass, the rupture strength, wear resistance, and low heat build-up of the vulcanized rubber may be reduced. If the amount exceeds 10.0 parts by mass, the rubber elasticity is lost.
The vulcanization accelerator that can be used in the present invention is not particularly limited. For example, M (2-mercaptobenzothiazole), DM (dibenzothiazolyl disulfide), CZ (N-cyclohexyl-2-benzothia). Thiazoles such as zolylsulfenamide), guanidines such as DPG (diphenylguanidine), or thiurams such as TOT (tetrakis (2-ethylhexyl) thiuram disulfide), and the like. The amount of use is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight with respect to 100 parts by weight of the rubber component (A).
また、本発明のゴム組成物で使用できる軟化剤としてプロセス油を挙げることができる。このプロセス油としては、例えば、パラフィン系、ナフテン系、アロマチック系などを挙げることができる。引張強度、耐摩耗性を重視する用途にはアロマチック系が、ヒステリシスロス、低温特性を重視する用途にはナフテン系又はパラフィン系が用いられる。その使用量は、（Ａ）ゴム成分１００質量部に対して、０〜１００質量部が好ましく、１００質量部以下であれば加硫ゴムの引張強度、低発熱性(低燃費性)が悪化するのを抑制することができる。 Moreover, a process oil can be mentioned as a softening agent which can be used with the rubber composition of this invention. Examples of the process oil include paraffinic, naphthenic, and aromatic oils. Aromatics are used for applications that emphasize tensile strength and wear resistance, and naphthenic or paraffinic systems are used for applications that emphasize hysteresis loss and low-temperature characteristics. The amount used is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component (A), and if it is 100 parts by mass or less, the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber deteriorate. Can be suppressed.
本発明のゴム組成物は、前述した（Ａ）ゴム成分と、（Ｂ）イオン系界面活性剤と、必要に応じて適宜選択した各種配合剤とを、混練り、熱入れ、押出しなどすることにより、調製することができる。
このようにして調製された本発明のゴム組成物は、アミン系老化防止剤やワックスが、ゴム物品、特にタイヤ表面に移行して変色するのを防止し、表面に適度の光沢を付与する効果を奏する。
The rubber composition of the present invention includes kneading, heating, extruding, etc. the above-described (A) rubber component, (B) ionic surfactant, and various compounding agents appropriately selected as necessary. Can be prepared.
The rubber composition of the present invention thus prepared has the effect of preventing the amine-based anti-aging agent and wax from moving to a rubber article, particularly a tire surface, and discoloring, and imparting an appropriate gloss to the surface. Play.
［空気入りタイヤ］
本発明の空気入りタイヤは、前述した本発明のゴム組成物をタイヤ部材のいずれかに用いたことを特徴とし、タイヤサイドウォールやトレッドに適用したものが好ましく、特にトレッドに適用したものが好ましい。かかるタイヤは、アミン系老化防止剤やワックスがタイヤ表面に移行して変色するのが防止され、かつタイヤ表面に適度の光沢が付与される。
本発明の空気入りタイヤに充填する気体としては、通常の或いは酸素分圧を変えた空気、又は窒素などの不活性ガスが挙げられる。本発明のゴム組成物をトレッドに用いる場合は、例えばトレッド用部材に押出し加工され、タイヤ成形機上で通常の方法により貼り付け成形され、生タイヤが成形される。この生タイヤを加硫機中で加熱加圧して、タイヤが得られる。
[Pneumatic tire]
The pneumatic tire of the present invention is characterized by using the above-described rubber composition of the present invention for any tire member, preferably applied to tire sidewalls and treads, particularly preferably applied to treads. . In such a tire, the amine-based anti-aging agent and wax are prevented from being transferred to the tire surface and discolored, and an appropriate gloss is imparted to the tire surface.
Examples of the gas filled in the pneumatic tire of the present invention include normal or air having a changed oxygen partial pressure, or an inert gas such as nitrogen. When the rubber composition of the present invention is used for a tread, for example, it is extruded on a tread member, and is pasted and molded by a usual method on a tire molding machine to form a raw tire. The green tire is heated and pressed in a vulcanizer to obtain a tire.
次に、本発明を実施例により、さらに詳しく説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、各例で得られたゴム組成物を、１００℃で１４分間加硫処理し、得られた加硫ゴムについて、下記の諸特性を評価した。
（１）引張応力
物性の代表的指標として３００％伸長時の引張応力を測定した。具体的には、ＪＩＳ ３号ダンベル型試験片を用い、ＪＩＳ Ｋ ６２５１−１９９３に従って３００％伸長時の引張応力を測定し、比較例１を１００として指数表示した。指数値が大きい程、３００％伸長時の引張応力が大きいことを示す。
（２）耐オゾン性
ＪＩＳ Ｋ ６３０１に従い、温度４０℃、オゾン濃度５０ｐｐｈｍ、伸び２０％の条件にて、加硫ゴム試験片についてオゾン劣化試験を行った。５０時間後に試験片の劣化状態を目視観察し、亀裂の有無を調べた。
（３）変色度
色度計［日本電色工業株式会社製、機種名「ＮＦ３３３」］を用いて、加硫ゴム試験片の変色度を評価した。測色したデータはＬ*、ａ*、ｂ*表色系で表した。Ｌ*値は明度を示し、ａ*値及びｂ*値はそれぞれ色味を示す。ａ*値とｂ*値は０で無色であり、ａ*値が正の値が大きいほど赤色に近付き、負の値が大きいほど緑色に近付くことを示し、ｂ*値は正の値が大きいほど黄色に近付き、負の値が大きいほど青色に近付くことを示す。
変色度については、加硫直後のｂ*値、目視による加硫直後の変色の度合により加硫直後の変色度を評価し、夏季の屋内放置の環境条件下に加硫ゴム試験片を一ヶ月放置した後のｂ*値及び目視による変色の度合により放置後の変色度を評価した。
なお、変色度の評価は、５段階評価とし、変色がひどく見られる場合を５、変色が見られない場合を１とした。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The rubber composition obtained in each example was vulcanized at 100 ° C. for 14 minutes, and the following properties were evaluated for the obtained vulcanized rubber.
(1) Tensile stress Tensile stress at 300% elongation was measured as a representative indicator of physical properties. Specifically, using a JIS No. 3 dumbbell type test piece, the tensile stress at 300% elongation was measured according to JIS K 6251-1993, and Comparative Example 1 was indicated as 100. A larger index value indicates a greater tensile stress at 300% elongation.
(2) Ozone resistance According to JIS K 6301, an ozone deterioration test was performed on the vulcanized rubber test piece under the conditions of a temperature of 40 ° C., an ozone concentration of 50 pphm, and an elongation of 20%. After 50 hours, the test piece was visually observed for deterioration to check for cracks.
(3) Color change degree The color change degree of a vulcanized rubber test piece was evaluated using the colorimeter [Nippon Denshoku Industries Co., Ltd. make, model name "NF333"]. The colorimetric data was expressed in L * , a * , b * color system. The L * value indicates lightness, and the a * value and b * value indicate color. The a * value and b * value are 0 and colorless. The larger the a * value, the closer to red, and the larger the negative value, the closer to green. The b * value has a larger positive value. The closer it is to yellow, the larger the negative value, the closer it is to blue.
Regarding the degree of discoloration, the b * value immediately after vulcanization and the degree of discoloration immediately after vulcanization were evaluated based on the degree of discoloration immediately after vulcanization. The degree of discoloration after standing was evaluated based on the b * value after standing and the degree of discoloration by visual observation.
The evaluation of the degree of discoloration was made on a five-point scale, with 5 when the discoloration was severely observed and 1 when the discoloration was not observed.
実施例1〜９及び比較例１、２
第１表に示す配合処方に従い、実施例１〜９及び比較例１、２の１１種類のゴム組成物を調製した。これら１１種類のゴム組成物を１６０℃、１４分間の条件で加硫処理して、各加硫ゴムを作製し、その諸特性を評価した。
結果を、用いた界面活性剤の種類と共に、第２表に示す。
また、前記１１種のゴム組成物をタイヤトレッドに配設し、それぞれタイヤサイズ２０５／６５Ｒ１５の乗用車ラジアルタイヤを定法に従って製作した。この場合も、実施例１〜９に係るゴム組成物を用いたタイヤも、引張張力、耐オゾン性及び変色試験（加硫直後のｂ*値及び変色度、放置試験後のｂ*値及び変色度）において優れた結果を示した。
Examples 1 to 9 and Comparative Examples 1 and 2
In accordance with the formulation shown in Table 1, 11 types of rubber compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were prepared. These 11 types of rubber compositions were vulcanized at 160 ° C. for 14 minutes to prepare each vulcanized rubber, and its properties were evaluated.
The results are shown in Table 2 together with the type of surfactant used.
Further, the 11 kinds of rubber compositions were disposed on a tire tread, and passenger car radial tires having tire sizes of 205 / 65R15 were manufactured according to a standard method. In this case, even tire using the rubber composition according to Examples 1 to 9, tensile force, b * values and discoloration after ozone resistance and discoloration test (pressure硫直, b * values and discoloration after storage test Degree).
［注］
１）ＳＢＲ：ＪＳＲ株式会社製「ＳＢＲ＃１５００」
２）ポリブタジエンゴム：ＪＳＲ株式会社製「ＪＳＲ ＢＲ０１」
３）カーボンブラック：東海カーボン株式会社製「シースト７ＨＭ」
４）カーボンブラック：旭カーボン株式会社製「旭＃６５」
５）ワックス：日本精蝋株式会社製「オゾエース０７０１」、マイクロクリスタリンワックス
６）老化防止剤６ＰＰＤ：大内新興化学工業株式会社製「ノクラック６Ｃ」
７）老化防止剤ＴＭＱ：精工化学株式会社製「ノンフレックスＲＤ−Ｓ」
８）アロマオイル：富士興産株式会社製「フッコール アロマックス３Ｂ」
９）加硫促進剤ＤＰＧ：大内新興化学工業株式会社製「ノクセラーＤ」
１０）加硫促進剤ＭＢＴＳ：大内新興化学工業株式会社製「ノクセラーＤＭ」
１１）加硫促進剤ＣＢＳ：三新化学工業株式会社製「サンセラーＣＭ−Ｇ」
[note]
1) SBR: “SBR # 1500” manufactured by JSR Corporation
2) Polybutadiene rubber: “JSR BR01” manufactured by JSR Corporation
3) Carbon black: “Seast 7HM” manufactured by Tokai Carbon Co., Ltd.
4) Carbon black: “Asahi # 65” manufactured by Asahi Carbon Co., Ltd.
5) Wax: “Ozoace 0701” manufactured by Nippon Seiwa Co., Ltd., Microcrystalline wax 6) Anti-aging agent 6PPD: “Nocrack 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.
7) Anti-aging agent TMQ: “Nonflex RD-S” manufactured by Seiko Chemical Co., Ltd.
8) Aroma oil: “Fukkor Aromax 3B” manufactured by Fuji Kosan Co., Ltd.
9) Vulcanization accelerator DPG: “Noxeller D” manufactured by Ouchi Shinsei Chemical Co., Ltd.
10) Vulcanization accelerator MBTS: “Noxeller DM” manufactured by Ouchi Shinsei Chemical Co., Ltd.
11) Vulcanization accelerator CBS: "Sunseller CM-G" manufactured by Sanshin Chemical Industry Co., Ltd.
［注］
界面活性剤の種類
・イオン系Ａ：花王（株）製イオン系界面活性剤；Ｒ1＝Ｃ2Ｈ4、Ｒ2＝ＣＨ3、Ｒ4、Ｒ5及びＲ6＝Ｈ、ｎ＝６、ｍ＝１５、Ａ1Ｏ＝オキシブチレン基、Ａ2Ｏ＝オキシエチレン基
・イオン系Ｂ：花王（株）製イオン系界面活性剤；Ｒ1＝Ｃ2Ｈ4、Ｒ2＝ＣＨ3、Ｒ4、Ｒ5及びＲ6＝エタノール、ｎ＝６、ｍ＝１５、Ａ1Ｏ＝オキシブチレン基、Ａ2Ｏ＝オキシエチレン基
・イオン系Ｃ：花王（株）製イオン系界面活性剤；Ｒ1＝Ｃ2Ｈ4、Ｒ2＝ＣＨ3、Ｒ4＝ステアリル基、Ｒ5及びＲ6＝ＣＨ3、ｎ＝６、ｍ＝１５、Ａ1Ｏ＝オキシブチレン基、Ａ2Ｏ＝オキシエチレン基
・イオン系Ｄ：花王（株）製イオン系界面活性剤；Ｒ1＝Ｃ2Ｈ4、Ｒ2＝ＣＨ3、Ｒ4、Ｒ5及びＲ6＝Ｈ、ｎ＝３、ｍ＝１５、Ａ1Ｏ＝オキシブチレン基、Ａ2Ｏ＝オキシエチレン基
・イオン系Ｅ：花王（株）製イオン系界面活性剤；Ｒ1＝Ｃ2Ｈ4、Ｒ2＝ＣＨ3、Ｒ4、Ｒ5及びＲ6＝Ｈ、ｎ＝３、ｍ＝１０、Ａ1Ｏ＝オキシブチレン基、Ａ2Ｏ＝オキシエチレン基
・イオン系Ｆ：花王（株）製イオン系界面活性剤；Ｒ1＝Ｃ2Ｈ4、Ｒ2＝ＣＨ3、Ｒ4、Ｒ5及びＲ6はそれぞれＨ、ｎ＝７、ｍ＝２０、Ａ1Ｏ＝オキシブチレン基、Ａ2Ｏ＝オキシエチレン基
・イオン系Ｇ：花王（株）製イオン系界面活性剤；Ｒ1＝Ｃ2Ｈ4、Ｒ2＝ＣＨ3、Ｒ4、Ｒ5及びＲ6＝Ｈ、ｎ＝１、ｍ＝１０、Ａ1Ｏ＝ＣＨ2ＣＨ（Ｃ8Ｈ17）Ｏ及びＣＨ2ＣＨ（Ｃ10Ｈ21）Ｏの混合物、Ａ2Ｏ＝オキシエチレン基
・非イオン系Ｈ：花王（株）製非イオン系界面活性剤、商標「レオドールＴＷ−Ｓ１０６」
[note]
Types of surfactants / ionic system A: ionic surfactants manufactured by Kao Corporation; R 1 = C 2 H 4 , R 2 = CH 3 , R 4 , R 5 and R 6 = H, n = 6, m = 15, A 1 O = oxybutylene group, A 2 O = oxyethylene group / ionic system B: ionic surfactant manufactured by Kao Corporation; R 1 = C 2 H 4 , R 2 = CH 3 , R 4 , R 5 and R 6 = ethanol, n = 6, m = 15, A 1 O = oxybutylene group, A 2 O = oxyethylene group, ionic system C: ionic surfactant manufactured by Kao Corporation; R 1 = C 2 H 4, R 2 = CH 3, R 4 = stearyl group, R 5 and R 6 = CH 3, n = 6, m = 15, A 1 O = oxybutylene group, A 2 O = oxyethylene Base / ionic system D: an ionic surfactant manufactured by Kao Corporation; R 1 = C 2 H 4 , R 2 = CH 3 , R 4 , R 5 and R 6 = H, n = 3, m = 15, A 1 = Oxybutylene group, A 2 O = oxyethylene group-ionic E: ionic surface active agent manufactured by Kao (Ltd.); R 1 = C 2 H 4, R 2 = CH 3, R 4, R 5 and R 6 = H, n = 3, m = 10, A 1 O = oxybutylene group, A 2 O = oxyethylene group / ionic system F: ionic surfactant manufactured by Kao Corporation; R 1 = C 2 H 4 , R 2 = CH 3 , R 4 , R 5 and R 6 are H, n = 7, m = 20, A 1 O = oxybutylene group, A 2 O = oxyethylene group / ion system G: Kao Corporation Ionic surfactants: R 1 = C 2 H 4 , R 2 = CH 3 , R 4 , R 5 and R 6 = H, n = 1, m = 10, A 1 O = CH 2 CH (C 8 H 17) O and CH 2 CH (C 10 H 21 ) a mixture of O, a 2 O = oxyethylene group, nonionic H: manufactured by Kao Corporation nonionic surfactant, trademark "Rheodol W-S106 "
第２表から明らかなように、本発明のゴム組成物（実施例１〜９）の加硫ゴム物性は、３００％引張応力については、比較例のものとあまり変わらないが、放置試験後のｂ*値及び変色の度合は、耐オゾン性が悪化することなく、比較例のものよりもはるかに良いことが分かる。また、上記一般式（１）で示される界面活性剤のうち、ゴム表面への移行性、すなわち、ワックスや老化防止剤などの移行によって生じる凹凸を滑らかにし、変色を防止する観点から、上記イオン系Ａ〜Ｇの界面活性剤が好ましく、イオン系Ａ〜Ｃの界面活性剤が特に好ましい。 As is apparent from Table 2, the physical properties of the vulcanized rubbers of the rubber compositions of the present invention (Examples 1 to 9) are not much different from those of the comparative examples with respect to 300% tensile stress, but after the standing test. It can be seen that the b * value and the degree of discoloration are much better than those of the comparative examples without deteriorating the ozone resistance. Further, among the surfactants represented by the general formula (1), from the viewpoint of migrating to the rubber surface, that is, smoothing unevenness caused by migration of wax, anti-aging agent and the like, and preventing discoloration. Surfactants of systems A to G are preferred, and surfactants of ionic systems A to C are particularly preferred.
本発明のゴム組成物は、特定構造のイオン系界面活性剤、好ましくは硫酸エステルアンモニウム塩型の界面活性剤を含み、該ゴム組成物をタイヤ部材、特にトレッドに用いることにより、耐オゾン性を悪化させることなく、外観を良好に保つことができる空気入りタイヤを与えることができる。 The rubber composition of the present invention includes an ionic surfactant having a specific structure, preferably a sulfate ammonium salt type surfactant, and the rubber composition is used for a tire member, particularly a tread, thereby improving ozone resistance. It is possible to provide a pneumatic tire that can maintain a good appearance without deteriorating.
Claims (11)
で表される構造を有する化合物である、請求項２に記載のゴム組成物。 The sulfate ammonium salt type ionic surfactant is represented by the following general formula (1)
The rubber composition according to claim 2, which is a compound having a structure represented by:
で表される構造を有する化合物である、請求項３に記載のゴム組成物。 The compound having the structure represented by the general formula (1) is represented by the following general formula (1-a)
The rubber composition according to claim 3, which is a compound having a structure represented by:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013095857A (en) * | 2011-11-01 | 2013-05-20 | Sumitomo Chemical Co Ltd | Rubber composition and use therefor |
| JP2013095856A (en) * | 2011-11-01 | 2013-05-20 | Sumitomo Chemical Co Ltd | Rubber anti-aging agent |
| JP2013224407A (en) * | 2012-03-22 | 2013-10-31 | Bridgestone Corp | Rubber composition for tire, and tire |
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| JPH08209087A (en) * | 1995-02-01 | 1996-08-13 | Sumika A B S Ratetsukusu Kk | Adhesive composition between rubber and yarn |
| JP2001031938A (en) * | 1999-07-21 | 2001-02-06 | Nippon Zeon Co Ltd | Latex for re-peelable pressure-sensitive adhesive, re- peelable pressure-sensitive adhesive composition using same and material to be recorded using same |
| JP2002146109A (en) * | 2000-11-16 | 2002-05-22 | Bridgestone Corp | Rubber composition and tire |
| JP2003119203A (en) * | 2001-10-10 | 2003-04-23 | Asahi Kasei Corp | Improved copolymer latex with small particle size |
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| JPS5493034A (en) * | 1977-12-29 | 1979-07-23 | Kuraray Co Ltd | Production of liquid polyisoprene emulsion |
| JPH08209087A (en) * | 1995-02-01 | 1996-08-13 | Sumika A B S Ratetsukusu Kk | Adhesive composition between rubber and yarn |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013095857A (en) * | 2011-11-01 | 2013-05-20 | Sumitomo Chemical Co Ltd | Rubber composition and use therefor |
| JP2013095856A (en) * | 2011-11-01 | 2013-05-20 | Sumitomo Chemical Co Ltd | Rubber anti-aging agent |
| JP2013224407A (en) * | 2012-03-22 | 2013-10-31 | Bridgestone Corp | Rubber composition for tire, and tire |
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