JP2014141618A - Rubber composition for tire and tire - Google Patents
Rubber composition for tire and tire Download PDFInfo
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- JP2014141618A JP2014141618A JP2013012228A JP2013012228A JP2014141618A JP 2014141618 A JP2014141618 A JP 2014141618A JP 2013012228 A JP2013012228 A JP 2013012228A JP 2013012228 A JP2013012228 A JP 2013012228A JP 2014141618 A JP2014141618 A JP 2014141618A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 77
- 239000005060 rubber Substances 0.000 title claims abstract description 77
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 24
- 239000006229 carbon black Substances 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 16
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 13
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 13
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 13
- 229920001194 natural rubber Polymers 0.000 claims abstract description 13
- 241000872198 Serjania polyphylla Species 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 238000002845 discoloration Methods 0.000 abstract description 18
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 description 18
- 235000019241 carbon black Nutrition 0.000 description 17
- 230000003712 anti-aging effect Effects 0.000 description 15
- -1 fatty acid ester Chemical class 0.000 description 15
- 239000010410 layer Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
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- 239000000047 product Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
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- 229920005549 butyl rubber Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229920003244 diene elastomer Polymers 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- 125000002948 undecyl 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])[H] 0.000 description 4
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 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 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001400 nonyl 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])[H] 0.000 description 3
- 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 3
- 238000004073 vulcanization Methods 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 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 2
- 238000005562 fading Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([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
- JQTYAZKTBXWQOM-UHFFFAOYSA-N 4-n-octan-2-yl-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CCCCCC)=CC=C1NC1=CC=CC=C1 JQTYAZKTBXWQOM-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000006240 Fast Extruding Furnace Substances 0.000 description 1
- 239000006238 High Abrasion Furnace Substances 0.000 description 1
- 239000004169 Hydrogenated Poly-1-Decene Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 235000019383 crystalline wax Nutrition 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 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 1
- 238000005516 engineering process Methods 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 235000019285 ethoxyquin Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 230000020169 heat generation Effects 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
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 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
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 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
- 125000002958 pentadecyl 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])[H] 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、変色を抑制できるタイヤ用ゴム組成物、及び、該ゴム組成物を用いたタイヤに関する。 The present invention relates to a tire rubber composition capable of suppressing discoloration, and a tire using the rubber composition.
天然ゴムやジエン系合成ゴムを原料としたタイヤ等のゴム製品において、アミン系老化防止剤及びワックスを用いた場合、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、ゴム成分等のポリマー基質を通って移動しやすく、短期間でゴム物品の表面に移行するため、倉庫保管中及び使用中に該ゴム物品を変色させる等、外観を悪化させるという問題があった。 In rubber products such as tires made from natural rubber or diene-based synthetic rubber, when using an amine-based anti-aging agent and wax, it is effective in suppressing the generation and progression of cracks in the presence of ozone, but the rubber component Therefore, there is a problem that the appearance of the rubber article is deteriorated, for example, when the rubber article is discolored during storage in a warehouse or during use.
上記課題を解決すべく、本発明者らは、ジエン系合成ゴム及び天然ゴムから選択される少なくとも一種のゴム成分に対し、特定のポリオキシエチレンソルビタンのモノヤシ油脂肪酸エステル類又は脂肪酸エステル及び特定のソルビタンの脂肪酸エステル類から選択される少なくとも一種の５員環又は６員環の環状エーテルを有する特定の非イオン系界面活性剤を配合してなるゴム組成物を開発し、開示している（特許文献１）。 In order to solve the above-mentioned problems, the present inventors, for at least one rubber component selected from diene-based synthetic rubber and natural rubber, have a specific polyoxyethylene sorbitan monococonut oil fatty acid ester or fatty acid ester and a specific A rubber composition comprising a specific nonionic surfactant having at least one 5-membered or 6-membered cyclic ether selected from fatty acid esters of sorbitan has been developed and disclosed (patent) Reference 1).
特許文献１の技術によれば、耐オゾン性を悪化させることなく、アミン系老化防止剤及びワックスによる変色を抑制することが可能となる。
しかしながら、老化防止剤やワックスに起因した変色抑制効果について、タイヤ用ゴム組成物中の他の配合成分との関係性も踏まえて、安定した変色抑制効果が発揮できるように、さらなる改善が望まれていた。
According to the technique of Patent Document 1, it is possible to suppress discoloration due to an amine anti-aging agent and wax without deteriorating ozone resistance.
However, further improvement is desired for the anti-aging effect due to the anti-aging agent and the wax so that the stable anti-coloring effect can be exhibited in consideration of the relationship with other compounding components in the tire rubber composition. It was.
そのため本発明は、良好な耐オゾン性を有するとともに、老化防止剤やワックスに起因した変色を抑制できるタイヤ用ゴム組成物、及び、該ゴム組成物を用いたタイヤを提供することを目的とする。 Therefore, an object of the present invention is to provide a tire rubber composition that has good ozone resistance and can suppress discoloration caused by an anti-aging agent or wax, and a tire using the rubber composition. .
（１）本発明のタイヤ用ゴム組成物は、２０〜８０質量％の天然ゴムを含有するゴム成分１００質量部に対して、下記式（Ｉ）で表される非イオン性界面活性剤を０．１〜１０質量部、及び、カーボンブラックを１５〜４０質量部を含むことを特徴とする。
（２）前記カーボンブラックは、ＧＰＦグレード又はＦＥＦグレードであることが好ましい。さらにまた、前記ゴム成分は、エチレンプロピレンゴムをさらに含むことが好ましい。
（３）前記タイヤ用ゴム組成物の老化防止剤の含有量が、前記ゴム成分１００質量部に対して３質量部を超えることが好ましい。
（４）本発明によるタイヤは、上述したタイヤ用ゴム組成物を、サイドウォール部に用いてなることを特徴とし、該サイドウォール部の最大厚さが２ｍｍ未満であることが好ましい。
(1) The rubber composition for tires of the present invention contains a nonionic surfactant represented by the following formula (I) with respect to 100 parts by mass of a rubber component containing 20 to 80% by mass of natural rubber. 0.1 to 10 parts by mass and 15 to 40 parts by mass of carbon black.
(2) The carbon black is preferably GPF grade or FEF grade. Furthermore, the rubber component preferably further contains ethylene propylene rubber.
(3) It is preferable that content of the antioxidant of the tire rubber composition exceeds 3 parts by mass with respect to 100 parts by mass of the rubber component.
(4) The tire according to the present invention is characterized in that the above-described rubber composition for tire is used for a sidewall portion, and the maximum thickness of the sidewall portion is preferably less than 2 mm.
本発明によれば、良好な耐オゾン性を有するとともに、老化防止剤やワックスに起因した変色を抑制できるタイヤ用ゴム組成物、及び、該ゴム組成物を用いたタイヤを提供できる。 ADVANTAGE OF THE INVENTION According to this invention, while having favorable ozone resistance, the rubber composition for tires which can suppress discoloration resulting from an anti-aging agent and wax, and the tire using this rubber composition can be provided.
以下、本発明の構成と限定理由を具体的に説明する。
（ゴム成分）
本発明のタイヤ用ゴム組成物に含まれるゴム成分は、２０〜８０質量％、好ましくは３０〜７０質量％の天然ゴムを含有する。ゴム成分が天然ゴムを上記の範囲で含有することで、作業性と耐オゾン性能の両立が可能となるからである。前記天然ゴム含有量が２０質量％未満の場合、天然ゴムが少なすぎるため、作業性が悪化する方向であり、一方、前記天然ゴムの含有量が８０質量％を超えると、天然ゴムが多くなりすぎるため、耐オゾン性能が悪化する傾向がある。
Hereinafter, the configuration of the present invention and the reasons for limitation will be described in detail.
(Rubber component)
The rubber component contained in the rubber composition for tires of the present invention contains 20 to 80% by mass, preferably 30 to 70% by mass of natural rubber. This is because when the rubber component contains natural rubber in the above range, both workability and ozone resistance can be achieved. When the content of the natural rubber is less than 20% by mass, the amount of natural rubber is too small and workability is deteriorated. On the other hand, when the content of the natural rubber exceeds 80% by mass, the amount of natural rubber increases. Therefore, ozone resistance tends to deteriorate.
また、前記ゴム成分は、天然ゴム（ＮＲ）の他にも、種々の合成ゴムを含有することができる。ここで、合成ゴムとしては、合成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）等のジエン系ゴム、ブチルゴム（ＩＩＲ）、ハロゲン化ブチルゴム［臭素化ブチルゴム（Ｂｒ−ＩＩＲ）、塩素化ブチルゴム（Ｃｌ−ＩＩＲ）等］、エチレンプロピレンゴム（ＥＰＭ）、エチレンプロピレンジエンゴム（ＥＰＤＭ）等の非ジエン系ゴムが挙げられる。これらゴム成分は一種単独で用いても、二種以上を混合して用いてもよい。
なお、本発明において、非ジエン系ゴムとは、該非ジエン系ゴムを構成するモノマー単位中のジエン系モノマー由来の単位の割合が5mol％以下のゴムを意味する。ここで、ジエン系モノマーとしては、１，３−ブタジエン、イソプレン、１，３−ペンタジエン、２，３−ジメチルブタジエン等が挙げられる。一方、非ジエン系ゴムを構成するジエン系以外（非ジエン系）のモノマーとしては、エチレン、プロピレン、イソブテン等が挙げられる。
The rubber component can contain various synthetic rubbers in addition to natural rubber (NR). Here, as the synthetic rubber, synthetic polyisoprene rubber (IR), styrene butadiene copolymer rubber (SBR), dibutadiene rubber such as polybutadiene rubber (BR), butyl rubber (IIR), halogenated butyl rubber [brominated butyl rubber ( Br-IIR), chlorinated butyl rubber (Cl-IIR, etc.)], non-diene rubbers such as ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), and the like. These rubber components may be used alone or in combination of two or more.
In the present invention, the non-diene rubber means a rubber in which the proportion of units derived from a diene monomer in the monomer units constituting the non-diene rubber is 5 mol% or less. Here, examples of the diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and the like. On the other hand, examples of non-diene-based (non-diene-based) monomers constituting the non-diene rubber include ethylene, propylene, and isobutene.
また、上述したゴムの中でも、前記ゴム成分は、エチレンプロピレンゴムを含むことが好ましい。耐オゾン性を改良することができるからである。さらに、前記エチレンプロピレンゴムの含有量は、前記ゴム成分中、１０〜５０質量％の範囲であることが好ましい。 Among the rubbers described above, the rubber component preferably contains ethylene propylene rubber. This is because the ozone resistance can be improved. Furthermore, it is preferable that content of the said ethylene propylene rubber is the range of 10-50 mass% in the said rubber component.
（カーボンブラック）
本発明のタイヤ用ゴム組成物は、前記ゴム成分１００質量部に対して、カーボンブラックを１５〜４０質量部含むことを特徴とする。
(Carbon black)
The rubber composition for tires of the present invention is characterized by containing 15 to 40 parts by mass of carbon black with respect to 100 parts by mass of the rubber component.
従来からの課題であるゴム製品の外皮の変色は、老化防止剤やワックスがゴム成分等のポリマー基質を通ってゴム表面に移行し、その後、ワックスがゴム製品の表面に析出して凹凸面を形成することで光散乱が起こり、その凹凸面に付着した老化防止剤が酸化し、茶色の着色物色に変わる結果、変色して見えるという現象である。
そのため、特許文献３等に開示された技術では、特定の非イオン性界面活性剤が、表面に析出したワックスの凹凸面を平滑面化することによって、光散乱状態を改善し、変色の改善を図っている。
Discoloration of the outer skin of rubber products, which has been a problem in the past, is that anti-aging agents and wax migrate to the rubber surface through a polymer substrate such as a rubber component, and then the wax precipitates on the surface of the rubber product to create an uneven surface. This is a phenomenon in which light scattering occurs, the anti-aging agent adhering to the uneven surface is oxidized, and the color changes to brown as a result of changing color.
Therefore, in the technology disclosed in Patent Document 3 and the like, the specific nonionic surfactant improves the light scattering state and smoothes the discoloration by smoothing the uneven surface of the wax deposited on the surface. I am trying.
そして、本発明では、上述のようにカーボンブラックの量を１５〜４０質量部に制限することで、前記非イオン性界面活性剤のゴム製品表面への移行速度を高めることができるため、上述したワックスによって形成された凹凸面の平滑化を、従来よりも効果的に行うことが可能となり、より優れた変色抑制効果が得られる。 And in this invention, since the transfer rate to the rubber product surface of the said nonionic surfactant can be improved by restrict | limiting the quantity of carbon black to 15-40 mass parts as mentioned above, it mentioned above. The uneven surface formed by wax can be smoothed more effectively than before, and a more excellent discoloration suppressing effect can be obtained.
また、前記カーボンブラックの量は、前記ゴム成分１００質量部に対して１５〜４０質量部とする必要があり、20〜35部であることがより好ましい。前記カーボンブラックの量が１５質量部未満では、ゴム組成物をタイヤに用いた場合に補強性や耐傷性が悪化する恐れがある。一方、カーボンブラックの量が４０質量部を超えると、前記非イオン性界面活性剤の移行速度を高めることができず、十分な変色抑制効果が得られない。 Moreover, the amount of the carbon black needs to be 15 to 40 parts by mass with respect to 100 parts by mass of the rubber component, and more preferably 20 to 35 parts. When the amount of the carbon black is less than 15 parts by mass, the reinforcing property and scratch resistance may be deteriorated when the rubber composition is used in a tire. On the other hand, when the amount of carbon black exceeds 40 parts by mass, the migration rate of the nonionic surfactant cannot be increased, and a sufficient discoloration suppressing effect cannot be obtained.
さらに、前記カーボンブラックの種類については、特に限定はされず、種々のカーボンブラックを用いることができる。その中でも、ＧＰＦグレード又はＦＥＦグレードのカーボンブラックを用いることが好ましい。上述した前記非イオン性界面活性剤の移行速度を高める効果があるからである。なお、ＦＥＦグレード及びＧＰＦグレードのカーボンブラックについては、各種の市販品があり、これらを用いることができる。 Furthermore, the type of the carbon black is not particularly limited, and various carbon blacks can be used. Among them, it is preferable to use GPF grade or FEF grade carbon black. This is because the above-mentioned nonionic surfactant has an effect of increasing the migration rate. There are various commercially available FEF grade and GPF grade carbon blacks, and these can be used.
（非イオン性界面活性剤）
本発明のタイヤ用ゴム組成物は、前記ゴム成分１００質量部に対して、下記式（Ｉ）で表される非イオン性界面活性剤を０．１〜１０質量部、及び、カーボンブラックを１５〜４０質量部を含む。
なお、前記非イオン性活性剤は、一種単独で使用することもできるし、二種類以上を併用してもよい。
(Nonionic surfactant)
The tire rubber composition of the present invention has 0.1 to 10 parts by mass of a nonionic surfactant represented by the following formula (I) and 15 parts of carbon black with respect to 100 parts by mass of the rubber component. -40 mass parts are included.
In addition, the said nonionic activator can also be used individually by 1 type, and may use 2 or more types together.
また、前記非イオン性界面活性剤の含有量は、０．１〜１０質量部であり、０．５〜７質量部であることが好ましく、０．５〜５質量部であることがより好ましい。含有量が０．１質量部未満の場合、界面活性剤の量が少なすぎるため、十分に変色抑制効果を得ることができず、一方、含有量が１０質量部を超えると、界面活性剤の量が多くなりすぎるため、界面活性剤のブルームによる過度の光沢を抑制できず、表面粘着性による作業性の低下を招く。 Moreover, content of the said nonionic surfactant is 0.1-10 mass parts, It is preferable that it is 0.5-7 mass parts, It is more preferable that it is 0.5-5 mass parts. . When the content is less than 0.1 parts by mass, the amount of the surfactant is too small, so that the effect of suppressing discoloration cannot be sufficiently obtained. On the other hand, when the content exceeds 10 parts by mass, Since the amount is excessively large, excessive gloss due to the surfactant bloom cannot be suppressed, and workability is deteriorated due to surface tackiness.
式（I）のＲ２は、炭素数１〜１５のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は直鎖状、分枝鎖状及び環状の何れでもよい。これらアルキル基及びアルケニル基の炭素数は、主にタック性、接着性及び変色度の観点から、好ましくは６〜１５、更に好ましくは６〜１４、より更に好ましくは８〜１２である。具体的には、ヘキシル基、イソヘプチル基、２−エチルヘキシル基、オクチル基、ノニル基、イソノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、及びペンタデシル基からなる群から選ばれる一種以上のアルキル基が好ましく挙げられ、２−エチルヘキシル基、オクチル基、ノニル基、イソノニル基、デシル基、ウンデシル基、及びドデシル基からなる群から選ばれる一種以上がより更に好ましく、ノニル基、イソノニル基、デシル基、及びウンデシル基からなる群から選ばれる一種以上がより更に好ましい。 R 2 in formula (I) represents an alkyl group or alkenyl group having 1 to 15 carbon atoms, and the alkyl group and alkenyl group may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group and alkenyl group is preferably 6 to 15, more preferably 6 to 14, and still more preferably 8 to 12 mainly from the viewpoint of tackiness, adhesiveness, and discoloration. Specifically, from the group consisting of hexyl, isoheptyl, 2-ethylhexyl, octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, and pentadecyl One or more selected alkyl groups are preferably exemplified, and one or more selected from the group consisting of 2-ethylhexyl group, octyl group, nonyl group, isononyl group, decyl group, undecyl group, and dodecyl group are more preferable, and nonyl group , One or more selected from the group consisting of an isononyl group, a decyl group, and an undecyl group are even more preferable.
また、式（Ｉ）のＲ１は、炭素数２〜４のアルキレン基であり、好ましくは炭素数２又は３のアルキレン基であり、更に好ましくは炭素数２のアルキレン基である。
式（Ｉ）のｎは、主にタック性、接着性，変色度及び加硫速度（生産性）の観点から、１６〜３０であり、好ましくは１６〜２５である。ただし、必ずしも加硫速度（生産性）を考慮しなくてもよいゴム組成物の変色防止方法の場合には、式（Ｉ）のｎは１２〜３０であり、好ましくは１６〜３０、より好ましくは１６〜２５である。
これらから、本発明のゴム組成物に用いられる前記式（Ｉ）の非イオン系界面活性剤において、Ｒ２が炭素数６〜１５のアルキル基又はアルケニル基、Ｒ１が炭素数２又は３のアルキレン基、且つｎが１６〜３０の組み合わせが好ましく、Ｒ２が炭素数８〜１２のアルキル基又はアルケニル基、Ｒ１が炭素数２又は３のアルキレン基、且つｎが１６〜３０の組み合わせがより好ましく、Ｒ２が炭素数８〜１２のアルキル基又はアルケニル基、Ｒ１が炭素数２又は３のアルキレン基、且つｎが１６〜２５の組み合わせが更に好ましい。
また、本発明の変色防止方法に用いられる前記式（I）の非イオン系界面活性剤において、Ｒ２が炭素数６〜１５のアルキル基又はアルケニル基、Ｒ１が炭素数２又は３のアルキレン基、且つｎが１２〜３０の組み合わせが好ましく、Ｒ２が炭素数８〜１２のアルキル基又はアルケニル基、Ｒ１が炭素数２又は３のアルキレン基、且つｎが１２〜３０の組み合わせがより好ましく、Ｒ２が炭素数８〜１２のアルキル基又はアルケニル基、Ｒ１が炭素数２又は３のアルキレン基、且つｎが１６〜３０の組み合わせが更に好ましく、Ｒ２が炭素数８〜１２のアルキル基又はアルケニル基、Ｒ１が炭素数２又は３のアルキレン基、且つｎが１６〜２５の組み合わせがより更に好ましい。
R 1 in formula (I) is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
N in the formula (I) is 16 to 30, and preferably 16 to 25, mainly from the viewpoint of tackiness, adhesiveness, discoloration, and vulcanization rate (productivity). However, in the case of the method for preventing discoloration of the rubber composition, the vulcanization rate (productivity) does not necessarily need to be considered, n in the formula (I) is 12 to 30, preferably 16 to 30, more preferably. Is 16-25.
From these, in the nonionic surfactant of formula (I) used in the rubber composition of the present invention, R 2 is an alkyl group or alkenyl group having 6 to 15 carbon atoms, and R 1 is 2 or 3 carbon atoms. A combination of an alkylene group and n of 16 to 30 is preferable, R 2 is an alkyl group or alkenyl group having 8 to 12 carbon atoms, R 1 is an alkylene group of 2 or 3 carbon atoms, and n is a combination of 16 to 30. More preferred is a combination wherein R 2 is an alkyl group or alkenyl group having 8 to 12 carbon atoms, R 1 is an alkylene group having 2 or 3 carbon atoms, and n is 16 to 25.
In the nonionic surfactant of formula (I) used in the method for preventing discoloration of the present invention, R 2 is an alkyl group or alkenyl group having 6 to 15 carbon atoms, and R 1 is an alkylene having 2 or 3 carbon atoms. And a combination of n and 12 to 30 is preferable, R 2 is an alkyl group or alkenyl group having 8 to 12 carbon atoms, R 1 is an alkylene group having 2 or 3 carbon atoms, and n is a combination of 12 to 30 Preferably, R 2 is an alkyl group or alkenyl group having 8 to 12 carbon atoms, R 1 is an alkylene group having 2 or 3 carbon atoms, and n is more preferably a combination of 16 to 30, and R 2 is 8 to 12 carbon atoms. A combination of an alkyl group or an alkenyl group, R 1 is an alkylene group having 2 or 3 carbon atoms, and n is 16 to 25 is even more preferable.
さらに、上記式（Ｉ）で表される非イオン系界面活性剤は、ＨＬＢ値（親水性と親油性のバランス値）が１０〜１９であることが好ましい。ここで、ＨＬＢ値は、下記に示すグリフィンの式で定義される。
ＨＬＢ＝２０×Ｍｗ／Ｍ
（式中、Ｍは非イオン系界面活性剤の分子量で；Ｍｗは該非イオン系界面活性剤の親水性
部分の分子量である。）
Furthermore, the nonionic surfactant represented by the above formula (I) preferably has an HLB value (balance value between hydrophilicity and lipophilicity) of 10 to 19. Here, the HLB value is defined by the following Griffin equation.
HLB = 20 × Mw / M
(In the formula, M is the molecular weight of the nonionic surfactant; Mw is the molecular weight of the hydrophilic portion of the nonionic surfactant.)
上記式（Ｉ）で表される非イオン系界面活性剤のＨＬＢ値が１０以上では親油性が抑制され、ゴムとの相溶性を抑えて、表面に移行させることができ、１９以下では、ゴムとの相溶性を高めて、混練を容易にし、かつ充填剤への吸着を抑制し、表面に移行させることができる。
上記式（Ｉ）で表される非イオン系界面活性剤のＨＬＢ値は、１５〜１９であるのが更に好ましく、１５〜１８がより更に好ましい。ＨＬＢ値が１５以上では、表面への移行速度を高めて、茶変防止効果を促進することができる。
When the HLB value of the nonionic surfactant represented by the above formula (I) is 10 or more, the lipophilicity is suppressed, the compatibility with rubber can be suppressed, and the surface can be transferred to the surface. The compatibility with can be increased, the kneading can be facilitated, the adsorption to the filler can be suppressed, and the surface can be transferred to the surface.
The HLB value of the nonionic surfactant represented by the above formula (I) is more preferably 15 to 19, and still more preferably 15 to 18. When the HLB value is 15 or more, the transition speed to the surface can be increased, and the effect of preventing browning can be promoted.
（老化防止剤）
本発明のタイヤ用ゴム組成物は、オゾンによるゴム製品の劣化を防ぎ、亀裂の発生及び進行を抑制することを目的として、老化防止剤を含む。
(Anti-aging agent)
The rubber composition for tires of the present invention contains an anti-aging agent for the purpose of preventing the deterioration of rubber products due to ozone and suppressing the occurrence and progression of cracks.
前記老化防止剤としては、例えば、Ｎ−フェニル−Ｎ’−（１，３−ジメチルブチル）−ｐ−フェニレンジアミン（６ＰＰＤ）、２，２，４−トリメチル−１，２−ジヒドロキノリン重合体（ＴＭＤＱ）、６−エトキシ−２，２，４−トリメチル−１，２−ジヒドロキノリン（ＡＷ）、Ｎ，Ｎ’−ジフェニル−ｐ−フェニレンジアミン（ＤＰＰＤ）、Ｎ，Ｎ′−ジ−ｓｅｃ−ブチル−ｐ−フェニレンジアミン、Ｎ−フェニル−Ｎ’−（メチルヘプチル）−ｐ−フェニレンジアミン等のアミン系老化防止剤が挙げられる。 Examples of the antiaging agent include N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (6PPD), 2,2,4-trimethyl-1,2-dihydroquinoline polymer ( TMDQ), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (AW), N, N′-diphenyl-p-phenylenediamine (DPPD), N, N′-di-sec-butyl Examples include amine-based antioxidants such as -p-phenylenediamine and N-phenyl-N '-(methylheptyl) -p-phenylenediamine.
また、前記タイヤ用ゴム組成物における老化防止剤の含有量は、前記ゴム成分100質量部に対して３質量部を超えることが好ましい。前記老化防止剤の含有量を３質量部超えとすることで、十分な耐オゾン性や、耐亀裂進展性を確保できるからである。 Moreover, it is preferable that content of the anti-aging agent in the said rubber composition for tires exceeds 3 mass parts with respect to 100 mass parts of said rubber components. It is because sufficient ozone resistance and crack progress resistance can be ensured by making content of the said anti-aging agent exceed 3 mass parts.
（その他成分）
本発明のタイヤ用ゴム組成物は、上述したゴム成分、カーボンブラック、非イオン性界面活性剤及び老化防止剤の他にも、種々の成分を含むことができる。
例えば、シリカ等の充填材、硫黄等の加硫剤、加硫促進剤、プロセスオイル、スコーチ防止剤、亜鉛華、ステアリン酸等のゴム工業で通常使用される配合剤を、本発明の目的を害しない範囲内で適宜選択して配合することができる。これら配合剤としては、市販品を好適に使用することができる。上記下層ゴムに適用するゴム組成物は、ゴム成分に、必要に応じて適宜選択した各種配合剤を混練り、熱入れ、押出等することにより製造することができる。
(Other ingredients)
The rubber composition for tires of the present invention can contain various components in addition to the rubber component, carbon black, nonionic surfactant and anti-aging agent described above.
For example, a filler such as silica, a vulcanizing agent such as sulfur, a vulcanization accelerator, a process oil, a scorch inhibitor, a zinc white, a stearic acid, and other compounding agents commonly used in the rubber industry, It can be appropriately selected and blended within a range not harming. As these compounding agents, commercially available products can be suitably used. The rubber composition applied to the lower rubber layer can be produced by kneading the rubber component with various compounding agents appropriately selected as necessary, heating, extruding, and the like.
（タイヤ）
本発明によるタイヤは、上述した本発明のタイヤ用ゴム組成物を、サイドウォール部に用いてなることを特徴とする。
例えば、図１に示すように、前記タイヤは、一対のビード部１と、一対のサイドウォール部２と、両サイドウォール部に連なるトレッド部３と、該ビード部１に各々埋設されたビードコア４間にトロイド状に延在させたカーカス５と、該カーカス５のクラウン部のタイヤ半径方向外側に配置したベルト６とを具え、サイドウォール部２のタイヤ外表面の一部に着色層７を具え、該着色層７のタイヤ内面側（図示例では、タイヤ幅方向内側）に隣接して下層ゴム８、タイヤ外面側に保護層９を具える。
(tire)
The tire according to the present invention is characterized in that the above-described rubber composition for a tire according to the present invention is used for a sidewall portion.
For example, as shown in FIG. 1, the tire includes a pair of bead portions 1, a pair of sidewall portions 2, a tread portion 3 connected to both sidewall portions, and a bead core 4 embedded in the bead portion 1. A carcass 5 extending in a toroidal shape, and a belt 6 disposed on the outer side in the tire radial direction of the crown portion of the carcass 5, and a colored layer 7 provided on a part of the tire outer surface of the sidewall portion 2. The lower layer rubber 8 is provided adjacent to the tire inner surface side (in the tire width direction inner side in the illustrated example) of the colored layer 7, and the protective layer 9 is provided on the tire outer surface side.
図示例のカーカス５は、一枚のカーカスプライから構成され、また、一対のビードコア４間にトロイド状に延在する本体部と、各ビードコア４の周りで、タイヤ幅方向の内側から外側に向けて半径方向外方に巻上げた折り返し部とからなるが、本発明のタイヤにおいて、カーカス５のプライ数及び構造は、これに限られるものではない。また、図示例のタイヤにおいては、カーカス５のクラウン部のタイヤ半径方向外側には二枚のベルト層からなるベルト６が配置されており、該ベルト層は、通常、タイヤ赤道面に対して傾斜して延びるスチールコードのゴム引き層からなり、２枚のベルト層は、該ベルト層を構成するスチールコードが互いにタイヤ赤道面を挟んで交差するように積層されてベルト６を構成する。なお、図中のベルト６は、二枚のベルト層からなるが、本発明のタイヤにおいては、ベルト６を構成するベルト層の枚数は、３枚以上であってもよい。また、図１に示すタイヤは、乗用車用タイヤであるが、本発明のタイヤはこれに限定されない。 The carcass 5 in the illustrated example is composed of a single carcass ply, and has a main body portion extending in a toroidal shape between the pair of bead cores 4 and around each bead core 4 from the inside to the outside in the tire width direction. In the tire of the present invention, the number of plies and the structure of the carcass 5 are not limited to this. Further, in the illustrated tire, a belt 6 composed of two belt layers is disposed on the outer side in the tire radial direction of the crown portion of the carcass 5, and the belt layer is usually inclined with respect to the tire equatorial plane. The two belt layers are laminated such that the steel cords constituting the belt layers intersect with each other across the tire equatorial plane to constitute the belt 6. The belt 6 in the figure is composed of two belt layers, but in the tire of the present invention, the number of belt layers constituting the belt 6 may be three or more. Moreover, although the tire shown in FIG. 1 is a tire for passenger cars, the tire of this invention is not limited to this.
また、図１に示すタイヤは、前記サイドウォール部２の最大厚さＴが、２ｍｍ未満であることが好ましい。サイドウォール部２の最大厚さＴが薄いほど、オゾンによる劣化が進むため、本発明による耐オゾン性効果が顕著に発揮されるからである。 In the tire shown in FIG. 1, the maximum thickness T of the sidewall portion 2 is preferably less than 2 mm. This is because as the maximum thickness T of the sidewall portion 2 is thinner, the deterioration due to ozone proceeds, and thus the ozone resistance effect according to the present invention is remarkably exhibited.
以下、実施例を挙げて本発明をより詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.
（実施例１〜１３及び比較例１〜５）
表１に示す原材料を、バンバリーミキサーにより混合して、タイヤ用ゴム組成物を調製した。
その後、調製したタイヤ用ゴム組成物について、タイヤのサイドウォール部に適用し、160℃、30分の条件で加硫を行うことで、サンプルとなるタイヤ（サイズ：195/65R15）を作製した。なお、タイヤのサイドウォール部の最大厚さについては表１に示す。
(Examples 1-13 and Comparative Examples 1-5)
The raw materials shown in Table 1 were mixed by a Banbury mixer to prepare a tire rubber composition.
Thereafter, the prepared tire rubber composition was applied to a sidewall portion of the tire and vulcanized at 160 ° C. for 30 minutes to prepare a sample tire (size: 195 / 65R15). The maximum thickness of the sidewall portion of the tire is shown in Table 1.
（評価）
（１）耐変色性
分光測色計（コニカミノルタ（株）製 ＣＭ−７００Ｄ）を用いて測定することで、退色性の評価を行った。
各実施例及び比較例で得られたサンプルについて、屋外にて暴露評価を行い、暴露３０日後の色差と初期の色差の変化の大きさを評価した 評価については、比較例１の色差を１００としたときの指数値として表示し、数値が大きいほど色差が小さく、退色性が良好となる。評価結果を表１に示す。
(Evaluation)
(1) Discoloration resistance The fading resistance was evaluated by measuring using a spectrocolorimeter (CM-700D manufactured by Konica Minolta Co., Ltd.).
About the sample obtained by each Example and the comparative example, exposure evaluation was performed outdoors and the evaluation of the color difference after 30 days of exposure and the magnitude of the change of the initial color difference was evaluated. The larger the numerical value, the smaller the color difference and the better the color fading. The evaluation results are shown in Table 1.
（２）転がり抵抗（低発熱性）
サンプルのタイヤに対し、室内の一軸転がり抵抗測定ドラム試験機により、８０ｋｍ／ｈでのtanδを測定し、比較例１のtanδを１００としたときの指数として表示した。指数値が小さい程、転がり抵抗が小さいことを示す。
(2) Rolling resistance (low heat generation)
The sample tire was measured for tan δ at 80 km / h using an indoor uniaxial rolling resistance measuring drum tester, and displayed as an index when tan δ of Comparative Example 1 was taken as 100. It shows that rolling resistance is so small that an index value is small.
※１： ＲＳＳ製 ＃１
※２ ＪＳＲ社製 「ＢＲ０１」
※３ ＪＳＲ社製 「ＥＰ１０３ＡＦ」
※４ クリスタリンワックス、精工化学(株)社製
※５：Ｎ−（１，３−ジメチルブチル）−Ｎ’−ｐ−フェニレンジアミン、大内新興化学（株）製 ノックラック６Ｃ
※６： ミヨシ油脂製 ＭＸＳＴ
※７： カーボンブラック、ＧＰＦ、ヨウ素吸着量＝２５ｇ／ｋｇ、ＤＢＰ吸油量＝８７ｍｌ／１００ｇ、Ｎ２ＳＡ（窒素吸着比表面積）＝２５ｍ２／ｇ、旭カーボン（株）製 「旭＃５５」
※８： カーボンブラック、ＦＥＦ、ヨウ素吸着量＝４４ｇ／ｋｇ、ＤＢＰ吸油量＝１１５ｍｌ／１００ｇ、Ｎ２ＳＡ（窒素吸着比表面積）＝４２ｍ２／ｇ、東海カーボン（株）製 「シーストＦ」
※９： カーボンブラック、ＨＡＦ、ヨウ素吸着量＝８０ｇ／ｋｇ、ＤＢＰ吸油量＝１０１ｍｌ／１００ｇ、Ｎ２ＳＡ（窒素吸着比表面積）＝７７ｍ２／ｇ、旭カーボン（株）製 「旭＃７０」
※１０ 非イオン系界面活性剤（ポリオキシエチレンアルキルエーテル）、花王（株）製 「エマルゲン１１１８（登録商標）」、式（Ｉ）におけるＲ2が主としてＣ11Ｈ23で、Ｒ１がＣ2Ｈ4、ｎが１８、ＨＬＢ値が１６．４である。
※１１ 非イオン系界面活性剤（ポリオキシエチレンラウリルエーテル）、花王（株）製 「エマルゲン１２３Ｐ（登録商標）」、式（Ｉ）におけるＲ２がＣ12Ｈ25、Ｒ１がＣ2Ｈ4、ｎが２３、ＨＬＢ値が１６．９である。
※１２ 非イオン系界面活性剤（ポリオキシエチレン２−エチルヘキシルエーテル）、花王株式会社製の試作サンプル、式（Ｉ）におけるＲ２がＣ8Ｈ17、Ｒ１がＣ2Ｈ4、ｎが２０、ＨＬＢ値が１７．７である。
※１３ 非イオン系界面活性剤（ポリオキシエチレン２−エチルヘキシルエーテル）、花王株式会社製 試作サンプル、式（Ｉ）におけるＲ２がＣ8Ｈ17、Ｒ１がＣ2Ｈ4、ｎが３０、ＨＬＢ値が１８．４である。
※１４： 九州白水製 「ハクスイテック」
※１５： 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、大内新興化学（株）製 ノクセラーＣＺ−Ｇ
※１６： ジベンゾチアジルジスルフィド、大内新興化学（株）製 ノクセラーＤＭ−Ｐ
* 1: RSS # 1
* 2 "BR01" manufactured by JSR
* 3 "EP103AF" manufactured by JSR
* 4 Crystalline wax, manufactured by Seiko Chemical Co., Ltd. * 5: N- (1,3-dimethylbutyl) -N'-p-phenylenediamine, Knock Rack 6C manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 6: MXST made by Miyoshi Oil
* 7: Carbon black, GPF, iodine adsorption amount = 25 g / kg, DBP oil absorption amount = 87 ml / 100 g, N 2 SA (nitrogen adsorption specific surface area) = 25 m 2 / g, “Asahi # 55” manufactured by Asahi Carbon Co., Ltd.
* 8: Carbon black, FEF, iodine adsorption amount = 44 g / kg, DBP oil absorption amount = 115 ml / 100 g, N 2 SA (nitrogen adsorption specific surface area) = 42 m 2 / g, “Seast F” manufactured by Tokai Carbon Co., Ltd.
* 9: Carbon black, HAF, iodine adsorption amount = 80 g / kg, DBP oil absorption amount = 101 ml / 100 g, N 2 SA (nitrogen adsorption specific surface area) = 77 m 2 / g, “Asahi # 70” manufactured by Asahi Carbon Co., Ltd.
※ 10 nonionic surfactant (polyoxyethylene alkyl ether), manufactured by Kao Corp., "Emulgen 1118 (registered trademark)", in R2 mainly C11H23 in formula (I), R 1 is C2 H4, n is 18, The HLB value is 16.4.
* 11 Nonionic surfactant (polyoxyethylene lauryl ether), “Emulgen 123P (registered trademark)” manufactured by Kao Corporation, R 2 in formula (I) is C 12 H 25, R 1 is C 2 H 4, n is 23, HLB The value is 16.9.
※ 12 nonionic surfactant (polyoxyethylene 2-ethylhexyl ether), Kao Co. prototype samples, R 2 in formula (I) is C8 H17, R 1 is C2 H4, n is the 20, HLB value 17. 7.
※ 13 nonionic surfactant (polyoxyethylene 2-ethylhexyl ether), Kao Co. trial sample, R 2 is C8H17 in formula (I), R 1 is is C2 H4, n is 30, HLB value 18.4 It is.
* 14: “Hakusuitec” manufactured by Kyushu Hakusui
* 15: N-cyclohexyl-2-benzothiazolylsulfenamide, Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 16: Dibenzothiazyl disulfide, Nouchira DM-P manufactured by Ouchi Shinsei Chemical Co., Ltd.
表１の結果から、本発明の各実施例に係るタイヤは、いずれも耐変色性及び転がり抵抗についてバランスよく優れていることがわかった。一方、比較例のタイヤについては、実施例に比べるといずれかの性能に劣ることがわかった。 From the results shown in Table 1, it was found that all the tires according to the examples of the present invention were excellent in discoloration resistance and rolling resistance with a good balance. On the other hand, the tire of the comparative example was found to be inferior in any performance as compared with the example.
本発明によれば、良好な耐オゾン性を有するとともに、老化防止剤やワックスに起因した変色を抑制できるタイヤ用ゴム組成物を提供できる。その結果、該ゴム組成物をタイヤに用いた場合、より長期間において良好な外観のタイヤを使用することが可能となり、産業上有用な効果を奏する。 ADVANTAGE OF THE INVENTION According to this invention, while having favorable ozone resistance, the rubber composition for tires which can suppress discoloration resulting from anti-aging agent and wax can be provided. As a result, when the rubber composition is used for a tire, it is possible to use a tire having a good appearance for a longer period of time, and an industrially useful effect is obtained.
１ ビード部、２ タイヤ側部、３ トレッド部、４ ビードコア、５ カーカス、６ ベルト
1 bead, 2 tire side, 3 tread, 4 bead core, 5 carcass, 6 belt
Claims (6)
The tire according to claim 5, wherein a maximum thickness of the sidewall portion is less than 2 mm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016208181A1 (en) * | 2015-06-22 | 2016-12-29 | 株式会社ブリヂストン | Rubber composition, laminate, and conveyor belt |
| CN106674626A (en) * | 2016-12-08 | 2017-05-17 | 罗德声 | Novel synthetic rubber material |
| WO2020128329A1 (en) * | 2018-12-21 | 2020-06-25 | Compagnie Generale Des Etablissements Michelin | Tyre provided with an outer sidewall, the composition of which comprises a derivative of polyethylene oxide |
| FR3090667A1 (en) * | 2018-12-21 | 2020-06-26 | Compagnie Generale Des Etablissements Michelin | Tire with an external sidewall, the composition of which comprises a polyethylene oxide derivative |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08231773A (en) * | 1995-02-22 | 1996-09-10 | Sumitomo Rubber Ind Ltd | Pneumatic tire |
| WO2010074286A1 (en) * | 2008-12-26 | 2010-07-01 | 株式会社ブリヂストン | Pneumatic tire |
| JP2012057153A (en) * | 2010-08-11 | 2012-03-22 | Bridgestone Corp | Rubber composition, method for preventing discoloration of rubber composition, and tire |
-
2013
- 2013-01-25 JP JP2013012228A patent/JP6325191B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08231773A (en) * | 1995-02-22 | 1996-09-10 | Sumitomo Rubber Ind Ltd | Pneumatic tire |
| WO2010074286A1 (en) * | 2008-12-26 | 2010-07-01 | 株式会社ブリヂストン | Pneumatic tire |
| JP2012057153A (en) * | 2010-08-11 | 2012-03-22 | Bridgestone Corp | Rubber composition, method for preventing discoloration of rubber composition, and tire |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016208181A1 (en) * | 2015-06-22 | 2016-12-29 | 株式会社ブリヂストン | Rubber composition, laminate, and conveyor belt |
| CN106674626A (en) * | 2016-12-08 | 2017-05-17 | 罗德声 | Novel synthetic rubber material |
| WO2020128329A1 (en) * | 2018-12-21 | 2020-06-25 | Compagnie Generale Des Etablissements Michelin | Tyre provided with an outer sidewall, the composition of which comprises a derivative of polyethylene oxide |
| FR3090667A1 (en) * | 2018-12-21 | 2020-06-26 | Compagnie Generale Des Etablissements Michelin | Tire with an external sidewall, the composition of which comprises a polyethylene oxide derivative |
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