JP2009007549A - Rubber composition for coating tire cord - Google Patents
Rubber composition for coating tire cord Download PDFInfo
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- JP2009007549A JP2009007549A JP2008067292A JP2008067292A JP2009007549A JP 2009007549 A JP2009007549 A JP 2009007549A JP 2008067292 A JP2008067292 A JP 2008067292A JP 2008067292 A JP2008067292 A JP 2008067292A JP 2009007549 A JP2009007549 A JP 2009007549A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 62
- 239000005060 rubber Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000011248 coating agent Substances 0.000 title abstract description 5
- 238000000576 coating method Methods 0.000 title abstract description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 18
- 229920001194 natural rubber Polymers 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 229920003049 isoprene rubber Polymers 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- WHCIAGVVOCLXFV-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-ylsulfanyl)-1,3-benzothiazole Chemical group C1=CC=C2SC(SC=3SC4=CC=CC=C4N=3)=NC2=C1 WHCIAGVVOCLXFV-UHFFFAOYSA-N 0.000 claims abstract description 7
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 229960001755 resorcinol Drugs 0.000 claims description 8
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 6
- 229930003836 cresol Natural products 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 abstract description 35
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 229920002857 polybutadiene Polymers 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 239000005062 Polybutadiene Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- -1 2-ethylhexyl Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 4
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229920005683 SIBR Polymers 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 0 *N(*)Sc1nc2ccccc2[s]1 Chemical compound *N(*)Sc1nc2ccccc2[s]1 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 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
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- UTBVIMLZIRIFFR-UHFFFAOYSA-N CSc1nc2ccccc2[s]1 Chemical compound CSc1nc2ccccc2[s]1 UTBVIMLZIRIFFR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XMEKHKCRNHDFOW-UHFFFAOYSA-N O.O.[Na].[Na] Chemical compound O.O.[Na].[Na] XMEKHKCRNHDFOW-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- QXYKBSYRGILOTK-UHFFFAOYSA-L disodium;1,6-bis(sulfonatosulfanyl)hexane Chemical compound [Na+].[Na+].[O-]S(=O)(=O)SCCCCCCSS([O-])(=O)=O QXYKBSYRGILOTK-UHFFFAOYSA-L 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- URMSIZAJUFVFFU-UHFFFAOYSA-N hydroxy-(6-hydroxysulfonothioyloxyhexoxy)-oxo-sulfanylidene-lambda6-sulfane Chemical compound OS(=O)(=S)OCCCCCCOS(O)(=O)=S URMSIZAJUFVFFU-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- UBHUJVKAJQRWRR-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-ethyl-n-(2-ethylhexyl)hexan-1-amine Chemical compound C1=CC=C2SC(SN(CC(CC)CCCC)CC(CC)CCCC)=NC2=C1 UBHUJVKAJQRWRR-UHFFFAOYSA-N 0.000 description 1
- VUPGMBVHOLNANB-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methyl-n-(2-methylhexyl)hexan-1-amine Chemical compound C1=CC=C2SC(SN(CC(C)CCCC)CC(C)CCCC)=NC2=C1 VUPGMBVHOLNANB-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
本発明は、タイヤコード被覆用ゴム組成物および該ゴム組成物により被覆されたタイヤコードに関する。 The present invention relates to a rubber composition for covering a tire cord and a tire cord coated with the rubber composition.
通常、タイヤコードはタイヤ内部に配置されることが多く、タイヤコード近隣のゴムは、タイヤ加硫工程において熱源から離れた場所に位置し、加硫されにくいので、加硫促進のためにN，Ｎ−ジシクロヘキシル−２−ベンゾチアゾールスルフェンアミド（ＤＣＢＳ）などが使用されている（特許文献１）。 Normally, tire cords are often placed inside the tire, and the rubber in the vicinity of the tire cord is located in a location away from the heat source in the tire vulcanization process and is difficult to vulcanize. N-dicyclohexyl-2-benzothiazolesulfenamide (DCBS) and the like are used (Patent Document 1).
このようなＤＣＢＳの代わりに、他のスルフェンアミド系促進剤、チアゾール系促進剤などを使用することも知られている。これらの加硫促進剤では、スチールコードとの初期接着性が充分でなく、また湿熱劣化時に、スチールコードとの接着を回復する効果が小さいので、レゾルシノール、ハイブリッド架橋剤、または多量のコバルトを配合して改善するという試みも行われている（特許文献２）。 It is also known to use other sulfenamide accelerators, thiazole accelerators and the like instead of such DCBS. These vulcanization accelerators do not have sufficient initial adhesion to steel cords, and are less effective in restoring adhesion to steel cords when wet heat deteriorates, so they contain resorcinol, a hybrid cross-linking agent, or a large amount of cobalt. Attempts have also been made to improve (Patent Document 2).
しかしながら、これらの試みによっても、自動車用タイヤの製造時の高温加硫条件下では良好な接着性が得られず、ＤＣＢＳと比較して充分でないという問題がある。多量のコバルトを使用すれば、熱酸化劣化によりゴムの破断強度が低下し、レゾルシノールを使用するとゴムの破断強度が低くなるという問題がある。 However, even with these attempts, there is a problem in that good adhesiveness cannot be obtained under high temperature vulcanization conditions at the time of production of automobile tires, which is not sufficient as compared with DCBS. When a large amount of cobalt is used, there is a problem that the breaking strength of the rubber is lowered due to thermal oxidation deterioration, and when resorcinol is used, the breaking strength of the rubber is lowered.
本発明は、初期加硫速度を維持したままで、タイヤコードとの接着性を改善し、湿熱劣化時にもタイヤコードとの接着性を回復する作用を有するタイヤコード被覆用ゴム組成物を提供することを目的とする。 The present invention provides a rubber composition for covering a tire cord which has an action of improving the adhesion with a tire cord while maintaining the initial vulcanization speed and recovering the adhesion with the tire cord even when wet heat is deteriorated. For the purpose.
本発明は、天然ゴムおよび／またはイソプレンゴムを６０重量％以上含むゴム成分１００重量部に対して、化学式（１）：
レゾルシン樹脂およびクレゾール樹脂を含まないことが好ましい。 It is preferable not to contain resorcin resin and cresol resin.
タイヤコードがタイヤスチールコードであることが好ましい。 The tire cord is preferably a tire steel cord.
また、本発明は、前記タイヤコード被覆用ゴム組成物により被覆したタイヤコードに関する。 The present invention also relates to a tire cord coated with the tire cord covering rubber composition.
本発明によれば、特定の加硫促進剤を使用することによって、環境に配慮して、タイヤコードとの湿熱接着性を改善し、破断強度も向上させることができる。 According to the present invention, by using a specific vulcanization accelerator, in consideration of the environment, wet heat adhesion with the tire cord can be improved, and the breaking strength can be improved.
本発明のタイヤコード被覆用ゴム組成物は、天然ゴムおよび／またはイソプレンゴムを６０重量％以上含むゴム成分１００重量部に対して、
化学式（１）：
Chemical formula (1):
天然ゴムには、天然ゴムそのものだけでなく、エポキシ化天然ゴム（ＥＮＲ）や脱タンパク天然ゴム（ＤＰＮＲ）も含まれる。天然ゴム（ＮＲ）および／またはイソプレンゴム（ＩＲ）は、他のゴム成分と混合して使用することもできる。他のゴム成分としては、スチレン−ブタジエンゴム（ＳＢＲ）、スチレン−イソプレン−ブタジエンゴム（ＳＩＢＲ）、ブタジエンゴム（ＢＲ）、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）、クロロプレンゴム（ＣＲ）、ブチルゴム（ＩＩＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）などがあげられる。中でも、ハイシスＢＲ、変性ＢＲ、変性ＳＢＲが好ましい。変性ＢＲとしては、特開２００６−１２４５０３号公報および特開２００６−６３１４３号公報に記載されているように、１，２−シンジオタクチックポリブタジエン結晶を含むポリブタジエンゴム（ａ）（ＢＲ（ａ））、スズ変性ポリブタジエンゴム（ｂ）（ＢＲ（ｂ））などが挙げられる。 Natural rubber includes not only natural rubber itself but also epoxidized natural rubber (ENR) and deproteinized natural rubber (DPNR). Natural rubber (NR) and / or isoprene rubber (IR) can also be used by mixing with other rubber components. Other rubber components include styrene-butadiene rubber (SBR), styrene-isoprene-butadiene rubber (SIBR), butadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), and butyl rubber (IIR). And acrylonitrile-butadiene rubber (NBR). Among these, high cis BR, modified BR, and modified SBR are preferable. As modified BR, as described in JP-A-2006-124503 and JP-A-2006-63143, a polybutadiene rubber (a) containing 1,2-syndiotactic polybutadiene crystals (BR (a)) And tin-modified polybutadiene rubber (b) (BR (b)).
他のゴム成分と混合する場合には、ＮＲおよび／またはＩＲはゴム成分中に６０重量％以上が好ましく、７０重量％以上がより好ましく、１００％が最も好ましい。６０重量％未満では、破断強度が低くなる傾向がある。 When mixed with another rubber component, NR and / or IR is preferably 60% by weight or more, more preferably 70% by weight or more, and most preferably 100% in the rubber component. If it is less than 60% by weight, the breaking strength tends to be low.
本発明では、化学式（１）で表されるベンゾチアゾリルスルフェンアミドまたはベンゾチアゾリルスルフェンイミドを加硫促進剤として使用する。化学式（１）におけるＲ１は炭素数３〜１６の分岐構造を有する直鎖のアルキル基であって、Ｒ２は炭素数３〜１６の分岐構造を有する直鎖のアルキル基またはベンゾチアゾリルスルフィド基である。直鎖のアルキル基は、炭素数３〜１６からなるが、４〜１６が好ましく、６〜１２がより好ましい。２以下では、初期加硫速度が速く、接着性が悪くなり、１７以上では、初期加硫速度が遅すぎ、またゴム硬度が低くなる。Ｒ１およびＲ２における好ましいアルキル基としては、ｔ−ブチル基、２−エチルヘキシル、２−メチルヘキシル、３−エチルヘキシル、３−メチルヘキシル、２−エチルプロピル、２−エチルブチル、２−エチルペンチル、２−エチルヘプチル、２−エチルオクチルなどがあげられる。また、製造原料数を減らし、製造収率を高く、純度を高め、コストを低減できるという理由から、Ｒ１とＲ２は同じであることが好ましい。 In the present invention, benzothiazolylsulfenamide or benzothiazolylsulfenimide represented by the chemical formula (1) is used as a vulcanization accelerator. R 1 in the chemical formula (1) is a linear alkyl group having a branched structure having 3 to 16 carbon atoms, and R 2 is a linear alkyl group having a branched structure having 3 to 16 carbon atoms or benzothiazolyl It is a sulfide group. The linear alkyl group is composed of 3 to 16 carbon atoms, preferably 4 to 16 and more preferably 6 to 12. If it is 2 or less, the initial vulcanization speed is high and the adhesiveness is poor, and if it is 17 or more, the initial vulcanization speed is too slow and the rubber hardness is low. Preferred alkyl groups for R 1 and R 2 include t-butyl group, 2-ethylhexyl, 2-methylhexyl, 3-ethylhexyl, 3-methylhexyl, 2-ethylpropyl, 2-ethylbutyl, 2-ethylpentyl, 2 -Ethyl heptyl, 2-ethyl octyl, etc. are mentioned. Also, reducing the number of manufacturing raw materials, high manufacturing yield, increase the purity, since they can reduce the cost, it is preferred that R 1 and R 2 are the same.
化学式（１）におけるＲ２として、下記式：
化学式（１）で表されるベンゾチアゾリルスルフェンアミドまたはベンゾチアゾリルスルフェンイミドとしては、川口化学工業（株）製のＢＥＨＺ（Ｎ，Ｎ−ジ（２−エチルヘキシル）−２−ベンゾチアゾリルスルフェンアミド）、川口化学工業（株）製のＢＭＨＺ（Ｎ，Ｎ−ジ（２−メチルヘキシル）−２−ベンゾチアゾリルスルフェンアミド）、フレキシス（株）製のサントキュアーＴＢＳＩ（Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアゾリルスルフェンイミド）などが挙げられる。 As the benzothiazolylsulfenamide or benzothiazolylsulfenimide represented by the chemical formula (1), BEHZ (N, N-di (2-ethylhexyl) -2-benzothiazoli manufactured by Kawaguchi Chemical Industry Co., Ltd. Rusulfenamide), BMHZ (N, N-di (2-methylhexyl) -2-benzothiazolylsulfenamide) manufactured by Kawaguchi Chemical Industry Co., Ltd., Santocure TBSI (N-tert) manufactured by Flexis Co., Ltd. -Butyl-2-benzothiazolylsulfenimide) and the like.
化学式（１）で表されるベンゾチアゾリルスルフェンアミドまたはベンゾチアゾリルスルフェンイミドの配合量の下限は、ＮＲおよび／またはＩＲを６０重量％以上含むゴム成分１００重量部に対して、０．７重量部以上、好ましくは０．８重量部以上である。配合量が０．７重量部未満では、ゴムの硬度が低く、破断強度が低くなる。また、配合量の上限は、３重量部以下、好ましくは２．７重量部以下である。配合量が２．７重量部をこえると、コードとの接着性が低下する。 The lower limit of the amount of benzothiazolyl sulfenamide or benzothiazolyl sulfenimide represented by the chemical formula (1) is 0.000 parts by weight with respect to 100 parts by weight of the rubber component containing 60% by weight or more of NR and / or IR. 7 parts by weight or more, preferably 0.8 parts by weight or more. If the blending amount is less than 0.7 parts by weight, the hardness of the rubber is low and the breaking strength is low. The upper limit of the amount is 3 parts by weight or less, preferably 2.7 parts by weight or less. When the blending amount exceeds 2.7 parts by weight, the adhesiveness with the cord decreases.
硫黄の配合量は、ＮＲおよび／またはＩＲ１００重量部に対して、３重量部以上、好ましくは３．５重量部以上である。硫黄の配合量が３重量部未満では、得られたゴム組成物とコードとの接着が充分でなくなる。また、硫黄（Ｂ）の配合量は、７重量部以下、好ましくは６．５重量部以下である。硫黄の配合量が７重量部をこえると、ブルーミングにより隣接部材との粘着性が悪化し、硫黄の濃度が均一でなくなる。 The compounding amount of sulfur is 3 parts by weight or more, preferably 3.5 parts by weight or more with respect to 100 parts by weight of NR and / or IR. When the compounding amount of sulfur is less than 3 parts by weight, the obtained rubber composition and the cord are not sufficiently adhered. Moreover, the compounding quantity of sulfur (B) is 7 weight part or less, Preferably it is 6.5 weight part or less. When the amount of sulfur exceeds 7 parts by weight, the adhesion with the adjacent member is deteriorated by blooming, and the concentration of sulfur is not uniform.
本発明のタイヤコード被覆用ゴム組成物では、破断強度を高くするために、レゾルシン樹脂およびクレゾール樹脂を含まないことが好ましい。ここで、レゾルシン樹脂には変性レゾルシン樹脂が、クレゾール樹脂には変性クレゾール樹脂が含まれるので、レゾルシン樹脂およびクレゾール樹脂を含まないこととは、レゾルシン樹脂、変性レゾルシン樹脂、クレゾール樹脂、変性クレゾール樹脂の全てを含まないことを意味する。 The rubber composition for covering a tire cord of the present invention preferably contains no resorcin resin and cresol resin in order to increase the breaking strength. Here, the resorcin resin includes the modified resorcin resin, and the cresol resin includes the modified cresol resin. Therefore, the resorcin resin, the modified resorcin resin, the cresol resin, and the modified cresol resin do not include the resorcin resin and the cresol resin. It means not including everything.
本発明のゴム組成物には、前記ゴム成分、硫黄および加硫促進剤のほかにも、必要に応じて、カーボンブラック、シリカ、炭酸カルシウムなどの充填剤、可塑剤、酸化亜鉛、加硫助剤、発泡剤、老化防止剤、ワックスなどの添加剤を配合することができる。 In addition to the rubber component, sulfur, and vulcanization accelerator, the rubber composition of the present invention includes, if necessary, a filler such as carbon black, silica, calcium carbonate, plasticizer, zinc oxide, vulcanization aid. Additives such as agents, foaming agents, anti-aging agents, and waxes can be blended.
カーボンブラックの配合量の下限は、ＮＲおよび／またはＩＲを６０重量％以上含むゴム成分１００重量部に対して、好ましくは４０重量部以上、より好ましくは４５重量部以上である。配合量が４０重量部未満では、ゴム硬度が低くなり、破断強度が不足する傾向がある。また、配合量の上限は、好ましくは７０重量部以下、より好ましくは６５重量部以下である。配合量が７０重量部をこえると、発熱性が高くなり、耐久性が低下する傾向がある。 The lower limit of the amount of carbon black is preferably 40 parts by weight or more, more preferably 45 parts by weight or more with respect to 100 parts by weight of the rubber component containing 60% by weight or more of NR and / or IR. If the blending amount is less than 40 parts by weight, the rubber hardness tends to be low and the breaking strength tends to be insufficient. The upper limit of the amount is preferably 70 parts by weight or less, more preferably 65 parts by weight or less. If the blending amount exceeds 70 parts by weight, the exothermicity increases and the durability tends to decrease.
シリカの配合量の下限は、ＮＲおよび／またはＩＲを６０重量％以上含むゴム成分１００重量部に対して、好ましくは４重量部以上、より好ましくは５重量部以上である。配合量が４重量部未満では、破断伸びＥＢの向上効果は小さくなる傾向がある。また、配合量の上限は、好ましくは２０重量部以下、より好ましくは１５重量部以下である。配合量が２０重量部をこえると、加硫速度が遅くなり、コード接着性が低下し、かつゴム硬度Ｈｓが低下する傾向がある。 The lower limit of the amount of silica is preferably 4 parts by weight or more, more preferably 5 parts by weight or more with respect to 100 parts by weight of the rubber component containing 60% by weight or more of NR and / or IR. If the blending amount is less than 4 parts by weight, the effect of improving the breaking elongation EB tends to be small. Moreover, the upper limit of the amount is preferably 20 parts by weight or less, more preferably 15 parts by weight or less. When the blending amount exceeds 20 parts by weight, the vulcanization rate is slowed, the cord adhesiveness is lowered, and the rubber hardness Hs tends to be lowered.
シランカップリング剤としては、特に限定されず、公知のカップリング剤を使用することができる。シランカップリング剤の配合量の下限は、シリカ１００重量部に対して、好ましくは４重量部以上、より好ましくは６重量部以上である。配合量が４重量部未満では、ｔａｎδが高くなる傾向がある。また、配合量の上限は、好ましくは１０重量部以下、より好ましくは８重量部以下である。配合量が１０重量部をこえると、経済的にコストが高くなり、破断伸びが低下する傾向がある。 It does not specifically limit as a silane coupling agent, A well-known coupling agent can be used. The lower limit of the amount of the silane coupling agent is preferably 4 parts by weight or more, more preferably 6 parts by weight or more with respect to 100 parts by weight of silica. If the blending amount is less than 4 parts by weight, tan δ tends to be high. Moreover, the upper limit of the amount is preferably 10 parts by weight or less, more preferably 8 parts by weight or less. If the blending amount exceeds 10 parts by weight, the cost is increased economically and the elongation at break tends to decrease.
加硫助剤としては有機酸コバルトがあげられ、コードとゴムとを架橋する役目を果たすため、有機酸コバルトを配合することにより、コードとゴムとの接着性を向上させることができる。有機酸コバルトとしては、例えば、ステアリン酸コバルト、ナフテン酸コバルト、ネオデカン酸コバルトなどがあげられ、ステアリン酸コバルトが好ましい。有機酸コバルトの含有量は、ＮＲおよび／またはＩＲ１００重量部に対して、コバルトに換算して０．０５重量部以上、好ましくは０．１重量部以上である。該含有量が０．０５重量部未満では、スチールコードのメッキ層とゴムの接着性が充分ではない。また、該含有量は、０．８重量部以下、好ましくは０．２重量部以下である。該含有量が０．８重量部をこえると、ゴムの酸化劣化が顕著になり、破断特性が悪化する。 Examples of the vulcanization aid include organic acid cobalt, which serves to crosslink the cord and the rubber. By blending the organic acid cobalt, the adhesion between the cord and the rubber can be improved. Examples of the organic acid cobalt include cobalt stearate, cobalt naphthenate, and cobalt neodecanoate, and cobalt stearate is preferable. The content of the organic acid cobalt is 0.05 parts by weight or more, preferably 0.1 parts by weight or more in terms of cobalt with respect to 100 parts by weight of NR and / or IR. If the content is less than 0.05 parts by weight, the adhesion between the steel cord plating layer and the rubber is not sufficient. The content is 0.8 parts by weight or less, preferably 0.2 parts by weight or less. When the content exceeds 0.8 parts by weight, the oxidative deterioration of the rubber becomes remarkable, and the breaking property is deteriorated.
新品タイヤにおいて、タイヤコードに対して接着することは重要であるが、そのために初期加硫速度が重要な要因となる。本発明のゴム組成物では、特定の加硫促進剤を使用するので、初期加硫速度が適度になり、加硫中に、タイヤコードのメッキ表面上の銅、ゴム中の硫黄やコバルトが適度な流動性下に移動し、結合することが可能となる。また、リバージョンも大きくないので、形成された銅−硫黄−ゴムの結合が切断することがなく、たとえば、ゴム成分として天然ゴムのみを使用した場合における、破断伸びの低下も抑制し、ゴムの耐久性を向上させることができる。 In a new tire, it is important to adhere to a tire cord, but the initial vulcanization speed is an important factor for that purpose. In the rubber composition of the present invention, since a specific vulcanization accelerator is used, the initial vulcanization speed becomes moderate, and copper on the plated surface of the tire cord, sulfur and cobalt in the rubber are moderate during vulcanization. It is possible to move and bond under the proper fluidity. In addition, since the reversion is not large, the formed copper-sulfur-rubber bond is not broken. For example, when only natural rubber is used as a rubber component, the decrease in elongation at break is suppressed, and the rubber Durability can be improved.
発明のゴム組成物は、タイヤコードを該ゴム組成物で被覆してベルト層を成形したのち、他のタイヤ部材と貼りあわせて未加硫タイヤを成形し、加硫することによって、空気入りタイヤ（ラジアルタイヤなど）を得ることができる。ここで、ベルト層とは、ブレーカー層のなかでもラジアルタイヤに用いるものであり、カーカスを強く締め付け、トレッドの剛性を高めるという役割をはたすものである。ベルトは、タイヤ空気圧により発生する張力が大きく、隣接し、かつ角度が交差するもう１枚のベルトとの間に転動時に大きな歪みが発生するという点から、本発明のゴム組成物をベルト層においてスチールコードを被覆するために用いることが最も好ましい。 The rubber composition of the invention is a pneumatic tire obtained by coating a tire cord with the rubber composition to form a belt layer, and then bonding to another tire member to form an unvulcanized tire and vulcanizing it. (Radial tires, etc.) can be obtained. Here, the belt layer is used for a radial tire among the breaker layers, and plays a role of strongly tightening the carcass and increasing the rigidity of the tread. The belt has a large tension generated by the tire air pressure, and a large strain is generated at the time of rolling between the belt and another belt that is adjacent and intersects at an angle. And most preferably used for coating steel cords.
本発明のタイヤコード被覆用ゴム組成物は、タイヤコードのトッピング、エッジストリップおよびインスレーションに用いられる。エッジストリップ、インスレーションは、コードに隣接して配置され、コードトッピングゴムと同じ配合であるか、もしくは類似の物性を呈する。 The rubber composition for covering a tire cord of the present invention is used for topping, edge strip and insulation of a tire cord. The edge strip and insulation are arranged adjacent to the cord and have the same composition as the cord topping rubber or similar physical properties.
また、本発明は、タイヤコード被覆用ゴム組成物により被覆したタイヤコードに関する。タイヤコードとしては、カーカスコード、フィラー、バンド、ブレーカー（ベルト）などがあげられる。スチールとしては、タイヤ用スチールコード、２＋２／０．２３（線経０．２３ｍｍの２本と２本のコードを和して撚り合せたタイヤコード）、黄銅メッキ付高張力コードなどがあげられる。 The present invention also relates to a tire cord coated with a rubber composition for covering a tire cord. Examples of the tire cord include a carcass cord, a filler, a band, and a breaker (belt). Examples of the steel include steel cords for tires, 2 + 2 / 0.23 (tire cords obtained by adding and twisting two cords having a wire diameter of 0.23 mm), high tension cords with brass plating, and the like.
以下、実施例に基づいて本発明を詳細に説明するが、本発明はこれらのみに制限されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not restrict | limited only to these.
実施例１〜１１および比較例１〜１０
（材料）
ＮＲ：ＴＳＲ２０（タイ産）
ＢＲ１２５０Ｈ：日本ゼオン（株）製のブタジエンゴム（開始剤としてリチウムを使用して重合）
カーボンブラックＮ３３０：昭和キャボット（株）製のカーボンブラックＮ３３０
カーボンブラックＮ３２６：昭和キャボット（株）製のカーボンブラックＮ３２６
シリカＺ１１５Ｇ：ローディア社製のＺ１１５Ｇｒ
シランカップリング剤：デグッサ社製のＳｉ６９
ステアリン酸コバルト：大日本インキ化学工業（株）製のステアリン酸コバルト
オイル処理不溶性硫黄：フレキシス社製のクリステックス（不溶性硫黄８０％、およびオイル２０％含有、表中にはオイルを含んだ全オイル処理不溶性硫黄の配合量を記載した）
加硫促進剤ＤＣＢＳ：川口化学工業（株）製のアクセルＤＺ−Ｇ（Ｎ，Ｎ−ジシクロヘキシルベンゾチアゾリルスルフェンアミド）
加硫促進剤ＢＥＨＺ：川口化学工業（株）製のＢＥＨＺ（Ｎ，Ｎ−ジ（２−エチルヘキシル）−２−ベンゾチアゾリルスルフェンアミド）
加硫促進剤ＴＢＢＳ：大内新興化学工業（株）製のノクセラーＮＳ
加硫促進剤ＤＭ：大内新興化学工業（株）製のノクセラーＤＭ
加硫促進剤ＴＢＳＩ：フレキシス（株）製のサントキュアーＴＢＳＩ（Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアゾリルスルフェンイミド）
スミカノール６２０：住友化学（株）製の変性レゾルシン樹脂
スミカノール５０７Ａ：住友化学（株）製のＨＭＭＰＭＥ（（ヘキサメチロールメラミン）ペンタメチルエーテル）
ＨＴＳ：フレキシス（株）製のデュラリンクＨＴＳ（ヘキサメチレンビスチオサルフェート２ナトリウム２水和物）
アロマオイル：（株）ジャパンエナジー製のプロセスＸ−１４０
老化防止剤：大内新興化学工業（株）製のノクラック６Ｃ
酸化亜鉛：東邦亜鉛（株）製の銀嶺Ｒ
Examples 1-11 and Comparative Examples 1-10
(material)
NR: TSR20 (Thailand)
BR1250H: butadiene rubber manufactured by Nippon Zeon Co., Ltd. (polymerized using lithium as an initiator)
Carbon Black N330: Carbon Black N330 manufactured by Showa Cabot Corporation
Carbon Black N326: Carbon Black N326 manufactured by Showa Cabot Corporation
Silica Z115G: Z115Gr made by Rhodia
Silane coupling agent: Si69 manufactured by Degussa
Cobalt stearate: Cobalt stearate oil manufactured by Dainippon Ink and Chemicals Co., Ltd. Processed insoluble sulfur: Kristex manufactured by Flexis (containing 80% insoluble sulfur and 20% oil, all oils including oil in the table) (The amount of treated insoluble sulfur is listed)
Vulcanization accelerator DCBS: Axel DZ-G (N, N-dicyclohexylbenzothiazolylsulfenamide) manufactured by Kawaguchi Chemical Industry Co., Ltd.
Vulcanization accelerator BEHZ: BEHZ (N, N-di (2-ethylhexyl) -2-benzothiazolylsulfenamide) manufactured by Kawaguchi Chemical Industry Co., Ltd.
Vulcanization accelerator TBBS: Noxeller NS manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Vulcanization accelerator DM: Noxeller DM manufactured by Ouchi Shinsei Chemical
Vulcanization accelerator TBSI: Suntocure TBSI (N-tert-butyl-2-benzothiazolylsulfenimide) manufactured by Flexis Co., Ltd.
Sumikanol 620: Modified Resorcin Resin resin manufactured by Sumitomo Chemical Co., Ltd. Sumikanol 507A: HMMPME manufactured by Sumitomo Chemical Co., Ltd. ((hexamethylolmelamine) pentamethyl ether)
HTS: Duralink HTS (Hexamethylenebisthiosulfate disodium dihydrate) manufactured by Flexis Co., Ltd.
Aroma oil: Process X-140 manufactured by Japan Energy Co., Ltd.
Anti-aging agent: NOCRACK 6C manufactured by Ouchi Shinsei Chemical Co., Ltd.
Zinc oxide: Silver candy R made by Toho Zinc Co., Ltd.
（製造方法）
表１および２に示す配合内容のうち、硫黄および加硫促進剤を除く各種薬品を、バンバリーミキサーにて混練し、得られた混練り物に、オイル処理不溶性硫黄および各種加硫促進剤を加えて、オープンロールにて混練し、未加硫ゴム組成物を得た。該未加硫ゴム組成物を、１５０℃で３０分間プレス加硫し、加硫ゴムサンプルを得た。なお、アロマオイル、老化防止剤、および酸化亜鉛については、表１および２には記載していないが、それぞれ２重量部、１重量部、１０重量部としてすべての実施例および比較例で配合し、加硫促進剤はＤＣＢＳ１重量部と等モルになるように配合した。
(Production method)
Of the contents shown in Tables 1 and 2, various chemicals excluding sulfur and vulcanization accelerator were kneaded with a Banbury mixer, and oil-treated insoluble sulfur and various vulcanization accelerators were added to the obtained kneaded product. And kneading with an open roll to obtain an unvulcanized rubber composition. The unvulcanized rubber composition was press vulcanized at 150 ° C. for 30 minutes to obtain a vulcanized rubber sample. Aroma oils, anti-aging agents, and zinc oxide are not described in Tables 1 and 2, but are blended in all Examples and Comparative Examples as 2 parts by weight, 1 part by weight, and 10 parts by weight, respectively. The vulcanization accelerator was blended so as to be equimolar with 1 part by weight of DCBS.
（試験方法）
＜加硫試験＞
ＪＩＳ Ｋ ６３００に記載されている振動式加硫試験機（キュラストメーター）を用い、測定温度１６０℃で加硫試験を行なって、時間とトルクとをプロットした加硫速度曲線を得た。加硫速度曲線のトルクの最小値をＭＬ、最大値をＭＨ、その差（ＭＨ−ＭＬ）をＭＥとしたとき、ＭＬ＋０．１ＭＥに到達する時間Ｔ10（分）を読み取った。
(Test method)
<Vulcanization test>
A vulcanization test was performed at a measurement temperature of 160 ° C. using a vibration type vulcanization tester (curast meter) described in JIS K 6300 to obtain a vulcanization rate curve in which time and torque were plotted. When the minimum value of the torque of the vulcanization speed curve is ML, the maximum value is MH, and the difference (MH−ML) is ME, time T 10 (min) for reaching ML + 0.1ME was read.
＜引張り試験（破断抗力および破断時伸び）＞
ＪＩＳ Ｋ６２５１に準じ、３号ダンベルを用いて引張り試験を実施し、室温における破断時伸び（％）を測定した。
<Tensile test (breaking resistance and elongation at break)>
According to JIS K6251, a tensile test was carried out using a No. 3 dumbbell, and elongation at break (%) at room temperature was measured.
＜接着試験＞
接着試験を実施し、ゴム組成物のゴム被覆率（％）をそれぞれ測定した。ゴム被覆率は、スチールコードとゴム間を剥離したときの剥離面のゴムの覆われている割合を指数表示した。５は１００％全面が覆われ、０は全く覆われていない状態を示す。また、ゴム組成物を温度８０℃、湿度９５％の条件下で１５０時間、湿熱劣化したのちのゴム組成物についても、同様にゴム被覆率を測定した。
<Adhesion test>
An adhesion test was performed, and the rubber coverage (%) of the rubber composition was measured. For the rubber coverage, the ratio of the rubber covered on the peeled surface when the steel cord and the rubber were peeled was indicated by an index. 5 indicates that 100% of the entire surface is covered, and 0 indicates that the surface is not covered at all. In addition, the rubber coverage was measured in the same manner for the rubber composition after the heat and heat degradation of the rubber composition under conditions of a temperature of 80 ° C. and a humidity of 95% for 150 hours.
＜粘弾性試験＞
前記加硫ゴム組成物から、所定サイズの試験片を作製し、（株）岩本製作所製の粘弾性スペクトロメータＶＥＳを用いて、所期歪１０％、動歪２％、および周波数１０Ｈｚの条件下で、７０℃におけるゴム試験片の複素弾性率（Ｅ*）および損失正接（ｔａｎδ）を測定した。Ｅ*が大きいほど剛性に優れている。
<Viscoelasticity test>
A test piece of a predetermined size was prepared from the vulcanized rubber composition, and was subjected to the conditions of an intended strain of 10%, a dynamic strain of 2%, and a frequency of 10 Hz using a viscoelastic spectrometer VES manufactured by Iwamoto Seisakusho Co., Ltd. The complex elastic modulus (E *) and loss tangent (tan δ) of the rubber test piece at 70 ° C. were measured. The greater E *, the better the rigidity.
それぞれの試験結果を表１および２に示す。 The respective test results are shown in Tables 1 and 2.
表１および２の評価結果から、加硫促進剤ＢＥＨＺを使用した場合には、比較例１のＤＣＢＳと比較して、破断伸びおよびコード接着性に優れていることがわかる。 From the evaluation results of Tables 1 and 2, it can be seen that when the vulcanization accelerator BEHZ is used, the elongation at break and the cord adhesion are excellent as compared with the DCBS of Comparative Example 1.
実施例１２〜２１および比較例１１〜１９
（製造方法）
表３および４に示す配合内容のうち、硫黄および加硫促進剤を除く各種薬品を、バンバリーミキサーにて混練し、得られた混練り物に、オイル処理不溶性硫黄および各種加硫促進剤を加えて、オープンロールにて混練し、未加硫ゴム組成物を得た。該未加硫ゴム組成物を、１５０℃で３０分間プレス加硫し、加硫ゴムサンプルを得た。なお、アロマオイル、老化防止剤、および酸化亜鉛については、表３および４には記載していないが、それぞれ２重量部、１重量部、１０重量部としてすべての実施例および比較例で配合し、加硫促進剤はＤＣＢＳ１重量部と等モルになるように配合した。
Examples 12 to 21 and Comparative Examples 11 to 19
(Production method)
Of the contents shown in Tables 3 and 4, various chemicals excluding sulfur and a vulcanization accelerator were kneaded with a Banbury mixer, and oil-treated insoluble sulfur and various vulcanization accelerators were added to the obtained kneaded product. And kneading with an open roll to obtain an unvulcanized rubber composition. The unvulcanized rubber composition was press vulcanized at 150 ° C. for 30 minutes to obtain a vulcanized rubber sample. Aroma oils, anti-aging agents, and zinc oxide are not described in Tables 3 and 4, but they are blended in all examples and comparative examples as 2 parts by weight, 1 part by weight, and 10 parts by weight, respectively. The vulcanization accelerator was blended so as to be equimolar with 1 part by weight of DCBS.
前記試験方法と同様の方法で、実施例１２〜２１および比較例１１〜１９で得られた組成物を評価した。それぞれの試験結果を表３および４に示す。 The compositions obtained in Examples 12 to 21 and Comparative Examples 11 to 19 were evaluated in the same manner as the test method. The respective test results are shown in Tables 3 and 4.
表３および４の評価結果から、加硫促進剤ＴＢＳＩを使用した場合には、比較例１１のＤＣＢＳと比較して、破断伸びおよびコード接着性に優れていることがわかる。
From the evaluation results of Tables 3 and 4, it can be seen that when the vulcanization accelerator TBSI is used, the elongation at break and the cord adhesion are excellent as compared with the DCBS of Comparative Example 11.
Claims (4)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2008067292A JP4431618B2 (en) | 2007-06-01 | 2008-03-17 | Rubber composition for covering tire cord |
| US12/155,214 US8148452B2 (en) | 2007-06-01 | 2008-05-30 | Rubber composition for coating tire cord |
| CN2008101098482A CN101314652B (en) | 2007-06-01 | 2008-05-30 | Rubber composition for coating tire cord |
| DE102008026113.0A DE102008026113B4 (en) | 2007-06-01 | 2008-05-30 | tire cord |
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| JP2008067292A JP4431618B2 (en) | 2007-06-01 | 2008-03-17 | Rubber composition for covering tire cord |
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| JP2009007549A true JP2009007549A (en) | 2009-01-15 |
| JP4431618B2 JP4431618B2 (en) | 2010-03-17 |
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| JP4431618B2 (en) | 2010-03-17 |
| CN101314652B (en) | 2013-12-11 |
| CN101314652A (en) | 2008-12-03 |
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