JP6065575B2 - Rubber composition for tire and pneumatic tire using the same - Google Patents
Rubber composition for tire and pneumatic tire using the same Download PDFInfo
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- JP6065575B2 JP6065575B2 JP2012279565A JP2012279565A JP6065575B2 JP 6065575 B2 JP6065575 B2 JP 6065575B2 JP 2012279565 A JP2012279565 A JP 2012279565A JP 2012279565 A JP2012279565 A JP 2012279565A JP 6065575 B2 JP6065575 B2 JP 6065575B2
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- 239000000203 mixture Substances 0.000 title claims description 44
- 229920001971 elastomer Polymers 0.000 title claims description 43
- 239000005060 rubber Substances 0.000 title claims description 43
- 229920003244 diene elastomer Polymers 0.000 claims description 21
- 244000043261 Hevea brasiliensis Species 0.000 claims description 14
- 229920003052 natural elastomer Polymers 0.000 claims description 14
- 229920001194 natural rubber Polymers 0.000 claims description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 14
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- -1 organic acid cobalt salt Chemical class 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- 229960004889 salicylic acid Drugs 0.000 claims description 7
- 150000001491 aromatic compounds Chemical class 0.000 description 56
- 239000002184 metal Substances 0.000 description 24
- 229910052751 metal Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- BOGPQKRGMIVEMJ-UHFFFAOYSA-N [[4,6-bis(dimethoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CON(CO)C1=NC(N(OC)OC)=NC(N(OC)OC)=N1 BOGPQKRGMIVEMJ-UHFFFAOYSA-N 0.000 description 2
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VBSTXRUAXCTZBQ-UHFFFAOYSA-N 1-hexyl-4-phenylpiperazine Chemical compound C1CN(CCCCCC)CCN1C1=CC=CC=C1 VBSTXRUAXCTZBQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- KFVIYKFKUYBKTP-UHFFFAOYSA-N 2-n-(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCNC1=NC(N)=NC(N)=N1 KFVIYKFKUYBKTP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- YJEUJARPQSLENW-UHFFFAOYSA-M B([O-])([O-])[O-].C(CCCCCC(C)(C)C)(=O)[O-].[Co+4] Chemical compound B([O-])([O-])[O-].C(CCCCCC(C)(C)C)(=O)[O-].[Co+4] YJEUJARPQSLENW-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 235000019492 Cashew oil Nutrition 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- JACRWUWPXAESPB-QMMMGPOBSA-N Tropic acid Natural products OC[C@H](C(O)=O)C1=CC=CC=C1 JACRWUWPXAESPB-QMMMGPOBSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-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
- WCBKUQQCKNNACH-UHFFFAOYSA-N [[4,6-bis[butyl(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-butylamino]methanol Chemical compound CCCCN(CO)C1=NC(N(CO)CCCC)=NC(N(CO)CCCC)=N1 WCBKUQQCKNNACH-UHFFFAOYSA-N 0.000 description 1
- MHVFYGIQJNFWGQ-UHFFFAOYSA-N [[4,6-bis[hydroxymethyl(methyl)amino]-1,3,5-triazin-2-yl]-methylamino]methanol Chemical compound OCN(C)C1=NC(N(C)CO)=NC(N(C)CO)=N1 MHVFYGIQJNFWGQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010467 cashew oil Substances 0.000 description 1
- 229940059459 cashew oil Drugs 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
- WEZJBAOYGIDDLB-UHFFFAOYSA-N cobalt(3+);borate Chemical compound [Co+3].[O-]B([O-])[O-] WEZJBAOYGIDDLB-UHFFFAOYSA-N 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 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
- MZYHMUONCNKCHE-UHFFFAOYSA-N naphthalene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 MZYHMUONCNKCHE-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、タイヤ用ゴム組成物およびそれを用いた空気入りタイヤに関するものであり、詳しくは、金属コードとの接着性を改善し、さらに硬度および引張特性を高めたタイヤ用ゴム組成物およびそれを用いた空気入りタイヤに関するものである。 TECHNICAL FIELD The present invention relates to a tire rubber composition and a pneumatic tire using the same, and more particularly, to improve the adhesion to a metal cord and further improve the hardness and tensile properties, and the tire rubber composition The present invention relates to a pneumatic tire using a tire.
一般に、空気入りタイヤは、スチールコードのような金属コードを被覆したゴム組成物が使用されている。近年、タイヤの使用期間が長期化する中、金属コードによる補強効果を高め、耐久性を長期にわたり維持することが重要視されている。耐久性を向上させるには、金属コードとこれを被覆するゴム組成物との接着性を改善する必要があるが、その達成には困難性を伴う。一方当業界において、金属コードを被覆するゴム組成物に対し硬度および引張特性を向上させ、操縦安定性や耐破壊特性を改善することも強く求められている。 Generally, a rubber composition coated with a metal cord such as a steel cord is used for a pneumatic tire. 2. Description of the Related Art In recent years, as tires have been used for a long period of time, it has become important to enhance the reinforcement effect of metal cords and maintain durability over a long period of time. In order to improve the durability, it is necessary to improve the adhesion between the metal cord and the rubber composition covering the metal cord, but this is accompanied by difficulty. On the other hand, there is a strong demand in the industry to improve the hardness and tensile properties of rubber compositions covering metal cords, and to improve handling stability and fracture resistance.
下記特許文献１には、ワイヤとゴムとの接着性を改善することを目的として、ジエン系ゴムにアミノ安息香酸エステルを配合する技術が開示されている。
しかしながら、金属コードを被覆するゴム組成物、例えばタイヤベルト層の被覆またはカーカス層の被覆に用いられるゴム組成物に対し、上記のように近年さらなる接着性、硬度および引張特性の良化の要求があり、そのため当業界では種々の技術が検討されているが、提案されているゴム組成物ではその要求レベルに十分に応えることができなかった。
The following Patent Document 1 discloses a technique of blending an aminobenzoic acid ester with a diene rubber for the purpose of improving the adhesion between the wire and the rubber.
However, as described above, in recent years, there has been a demand for further improvement in adhesion, hardness and tensile properties for rubber compositions covering metal cords, for example, rubber compositions used for coating a tire belt layer or a carcass layer. For this reason, various techniques have been studied in the industry, but the proposed rubber composition has not been able to sufficiently meet the required level.
したがって本発明の目的は、金属コードとの接着性を改善し、さらに硬度および引張特性を高めたタイヤ用ゴム組成物およびそれを用いた空気入りタイヤを提供することにある。 Accordingly, an object of the present invention is to provide a rubber composition for a tire that has improved adhesion to a metal cord and further has increased hardness and tensile properties, and a pneumatic tire using the same.
本発明者らは鋭意研究を重ねた結果、天然ゴムを含むジエン系ゴムに、特定の複数種類の芳香族化合物を併用し、これを特定量で配合することにより、上記課題を解決できることを見出し、本発明を完成することができた。
すなわち本発明は以下のとおりである。
１．天然ゴムを含むジエン系ゴム１００質量部に対し、分子中に１個以上のカルボキシル基および水酸基を有する芳香族化合物（１）と分子中に３個以上のカルボキシル基を有する芳香族化合物（２）とを合計で０．２〜１０質量部配合してなるタイヤ用ゴム組成物。
２．前記芳香族化合物（１）がサリチル酸であり、かつ前記芳香族化合物（２）がトリメリト酸である前記１に記載のタイヤ用ゴム組成物。
３．前記ジエン系ゴム１００質量部に対し、さらにフェノール系樹脂を０．１質量部以上５質量部未満および硬化剤を０．１〜１０質量部配合してなる前記１または２に記載のタイヤ用ゴム組成物。
４．前記ジエン系ゴム１００質量部に対し、さらにコバルト量として０．１〜０．５質量部の有機酸コバルト塩を配合した前記１〜３のいずれかに記載のタイヤ用ゴム組成物。
５．前記１〜４のいずれかに記載のタイヤ用ゴム組成物をタイヤベルト層の被覆に用いた空気入りタイヤ。
６．前記１〜４のいずれかに記載のタイヤ用ゴム組成物をカーカス層の被覆に用いた空気入りタイヤ。
As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a specific plurality of aromatic compounds in combination with a diene rubber containing natural rubber and blending them in a specific amount. The present invention has been completed.
That is, the present invention is as follows.
1. Aromatic compound (1) having one or more carboxyl groups and hydroxyl groups in the molecule and aromatic compound (2) having three or more carboxyl groups in the molecule with respect to 100 parts by mass of diene rubber including natural rubber A rubber composition for tires comprising 0.2 to 10 parts by mass in total.
2. 2. The tire rubber composition according to 1 above, wherein the aromatic compound (1) is salicylic acid and the aromatic compound (2) is trimellitic acid.
3. The tire rubber according to 1 or 2 above, further comprising 0.1 to 5 parts by mass of a phenolic resin and 0.1 to 10 parts by mass of a curing agent with respect to 100 parts by mass of the diene rubber. Composition.
4). 4. The tire rubber composition according to any one of 1 to 3, wherein 0.1 to 0.5 parts by mass of an organic acid cobalt salt is further blended as a cobalt amount with respect to 100 parts by mass of the diene rubber.
5. A pneumatic tire using the tire rubber composition according to any one of the above 1 to 4 for covering a tire belt layer.
6). A pneumatic tire using the tire rubber composition according to any one of 1 to 4 for coating a carcass layer.
本発明によれば、天然ゴムを含むジエン系ゴムに、特定の複数種類の芳香族化合物を併用し、これを特定量で配合したので、金属コードとの接着層の形成が促進され、接着性を改善し、さらに引張特性および硬度を高めたタイヤ用ゴム組成物およびそれを用いた空気入りタイヤを提供することができる。
本発明のタイヤ用ゴム組成物をタイヤベルト層の被覆またはカーカス層の被覆に用いた場合、金属コードとの良好な接着性に基づく高い耐久性と、高い硬度および引張特性に基づく優れた操縦安定性や耐破壊特性を提供することができる。
According to the present invention, since a plurality of specific types of aromatic compounds are used in combination with a diene rubber containing natural rubber and blended in a specific amount, formation of an adhesive layer with a metal cord is promoted and adhesion is improved. It is possible to provide a rubber composition for a tire having improved tensile properties and hardness and a pneumatic tire using the same.
When the tire rubber composition of the present invention is used for coating a tire belt layer or a carcass layer, it has high durability based on good adhesion to a metal cord, and excellent handling stability based on high hardness and tensile properties. Property and fracture resistance can be provided.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明で使用されるジエン系ゴムは、天然ゴム（ＮＲ）の使用を必須とする。また、ＮＲ以外にも、タイヤ用ゴム組成物に配合することができる任意のジエン系ゴムを用いることができ、例えば、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）等が挙げられる。これらは、単独で用いてもよく、２種以上を併用してもよい。また、ジエン系ゴムはその分子量やミクロ構造はとくに制限されず、アミン、アミド、シリル基等で末端変性されていてもよい。
本発明において、ジエン系ゴム全体を１００質量部としたとき、ＮＲは、５０質量部以上であることが好ましく、１００質量部であることがさらに好ましい。
The diene rubber used in the present invention requires the use of natural rubber (NR). In addition to NR, any diene rubber that can be blended in the tire rubber composition can be used, for example, isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber. (SBR), acrylonitrile-butadiene copolymer rubber (NBR), and the like. These may be used alone or in combination of two or more. The molecular weight and microstructure of the diene rubber are not particularly limited, and may be terminal-modified with an amine, amide, silyl group or the like.
In the present invention, when the entire diene rubber is 100 parts by mass, the NR is preferably 50 parts by mass or more, and more preferably 100 parts by mass.
（分子中に１個以上のカルボキシル基および水酸基を有する芳香族化合物（１））
本発明で使用される芳香族化合物（１）は、分子中に１個以上のカルボキシル基および水酸基を有する芳香族化合物であり、例えば、サリチル酸、ｍ−オキシ安息香酸、ｐ−オキシ安息香酸、没食子酸、マンデル酸及びトロパ酸等が挙げられる。
また、本発明で使用される芳香族化合物（２）は、分子中に３個以上のカルボキシル基を有する芳香族化合物であり、例えば、トリメリト酸、トリメシン酸、ピロメリト酸、ナフタレンテトラカルボン酸等が挙げられる。
中でも本発明の効果が高まるという観点から、芳香族化合物（１）はサリチル酸が、芳香族化合物（２）はトリメリト酸がそれぞれ好ましい。
なお、芳香族化合物（１）および芳香族化合物（２）の使用割合は、芳香族化合物（１）１モルに対し、芳香族化合物（２）は0.1〜1.5モルが好ましく、0.4〜0.8モルがさらに好ましい。
(Aromatic compound having one or more carboxyl groups and hydroxyl groups in the molecule (1))
The aromatic compound (1) used in the present invention is an aromatic compound having one or more carboxyl groups and hydroxyl groups in the molecule, such as salicylic acid, m-oxybenzoic acid, p-oxybenzoic acid, gallic acid. Examples include acids, mandelic acid, and tropic acid.
The aromatic compound (2) used in the present invention is an aromatic compound having three or more carboxyl groups in the molecule. For example, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, etc. Can be mentioned.
Among them, from the viewpoint of enhancing the effect of the present invention, the aromatic compound (1) is preferably salicylic acid, and the aromatic compound (2) is preferably trimellitic acid.
In addition, the usage-amount of an aromatic compound (1) and an aromatic compound (2) has 0.1-1.5 mol of aromatic compound (2) with respect to 1 mol of aromatic compounds (1), 0.4-0.8 mol is preferable. Further preferred.
（フェノール系樹脂）
本発明で使用されるフェノール系樹脂は、例えばフェノール、クレゾールまたはレゾルシンをアルデヒド化合物、特にホルムアルデヒドを用いて縮合して得られるノボラック型フェノール系樹脂が挙げられ、好ましくは後述するメチレンドナーなどの硬化剤と反応して三次元架橋化したものであり、これらはいずれも公知の樹脂である。ノボラック型フェノール系樹脂は、オイルまたは脂肪酸で変性していてもよく、例えば、ロジン油、トール油、カシュー油、リノール酸、オレイン酸、リノレイン酸などのオイルで変性した樹脂を挙げることができる。
(Phenolic resin)
Examples of the phenolic resin used in the present invention include novolak type phenolic resins obtained by condensing phenol, cresol or resorcin with an aldehyde compound, particularly formaldehyde, and preferably a curing agent such as a methylene donor described later. These are three-dimensionally crosslinked by reacting with each other, and these are all known resins. The novolac-type phenolic resin may be modified with oil or fatty acid, and examples thereof include resins modified with oils such as rosin oil, tall oil, cashew oil, linoleic acid, oleic acid, and linolenic acid.
（硬化剤）
本発明で使用される硬化剤としては、ヘキサメチレンテトラミンやメラミン誘導体等が挙げられる。メラミン誘導体は、例えば、ヘキサメチロールメラミン、ヘキサメトキシメチルメラミン、ペンタメトキシメチロールメラミン、ヘキサエトキシメチルメラミン、ヘキサキス−（メトキシメチル）メラミン、Ｎ，Ｎ’，Ｎ’’−トリメチル−Ｎ，Ｎ’，Ｎ’’−トリメチロールメラミン、Ｎ，Ｎ’，Ｎ’’−トリメチロールメラミン、Ｎ−メチロールメラミン、Ｎ，Ｎ’−（メトキシメチル）メラミン、Ｎ，Ｎ’，Ｎ’’−トリブチル−Ｎ，Ｎ’，Ｎ’’−トリメチロールメラミンが挙げられる。特にヘキサメトキシメチロールメラミン若しくはペンタメトキシメチロールメラミンが好ましい。
(Curing agent)
Examples of the curing agent used in the present invention include hexamethylenetetramine and melamine derivatives. Melamine derivatives include, for example, hexamethylol melamine, hexamethoxymethyl melamine, pentamethoxymethylol melamine, hexaethoxymethyl melamine, hexakis- (methoxymethyl) melamine, N, N ′, N ″ -trimethyl-N, N ′, N '' -Trimethylol melamine, N, N ', N''-trimethylol melamine, N-methylol melamine, N, N'-(methoxymethyl) melamine, N, N ', N''-tributyl-N, N ', N ″ -trimethylolmelamine is mentioned. In particular, hexamethoxymethylol melamine or pentamethoxymethylol melamine is preferable.
フェノール系樹脂および硬化剤の配合量は、ジエン系ゴム１００質量部に対し、フェノール系樹脂が例えば０．１質量部以上５質量部未満、好ましくは１〜３質量部、硬化剤が例えば０．１〜１０質量部、好ましくは０．５〜５質量部である。フェノール系樹脂および硬化剤を配合する場合、フェノール系樹脂の配合量が０．１質量部未満であると、硬度が低下し、操縦安定性が悪化する。また５質量部以上であると、硬度が過度に上昇し、発熱性と金属コードに対する接着性が悪化する。 The blending amount of the phenolic resin and the curing agent is, for example, 0.1 to less than 5 parts by mass, preferably 1 to 3 parts by mass, and 0.1 to 3 parts by mass of the curing agent with respect to 100 parts by mass of the diene rubber. 1 to 10 parts by mass, preferably 0.5 to 5 parts by mass. When the phenolic resin and the curing agent are blended, if the blending amount of the phenolic resin is less than 0.1 parts by mass, the hardness is lowered and the steering stability is deteriorated. On the other hand, if it is 5 parts by mass or more, the hardness is excessively increased, and the heat build-up and the adhesion to the metal cord are deteriorated.
（有機酸コバルト塩）
本発明では、その効果の観点、とくに金属コードに対する接着性の観点から、有機酸コバルト塩を配合するのが好ましい。
本発明で使用する有機酸コバルト塩としては、例えばナフテン酸コバルト、ネオデカン酸コバルト、ステアリン酸コバルト、ロジン酸コバルト、バーサチック酸コバルト、トール油酸コバルト、ホウ酸ネオデカン酸コバルト、アセチルアセトナートコバルト等を例示することができる。また、ホウ素を含む有機酸コバルト塩、例えばオルトホウ酸コバルト等も使用できる。
有機酸コバルト塩を使用する場合、その配合量はジエン系ゴム１００質量部に対し、コバルト量として０．１〜０．５質量部が好ましく、０．１５〜０．２５質量部がさらに好ましい。
(Organic acid cobalt salt)
In this invention, it is preferable to mix | blend organic acid cobalt salt from the viewpoint of the effect, especially an adhesive viewpoint with respect to a metal cord.
Examples of the organic acid cobalt salt used in the present invention include cobalt naphthenate, cobalt neodecanoate, cobalt stearate, cobalt rosinate, cobalt versatate, cobalt tall oil, cobalt borate neodecanoate, cobalt acetylacetonate and the like. It can be illustrated. Also, organic acid cobalt salts containing boron, such as cobalt orthoborate, can be used.
When using an organic acid cobalt salt, the compounding amount is preferably 0.1 to 0.5 parts by mass, more preferably 0.15 to 0.25 parts by mass with respect to 100 parts by mass of the diene rubber.
（タイヤ用ゴム組成物の配合割合）
本発明のタイヤ用ゴム組成物は、天然ゴムを含むジエン系ゴム１００質量部に対し、分子中に１個以上のカルボキシル基および水酸基を有する芳香族化合物（１）と分子中に３個以上のカルボキシル基を有する芳香族化合物（２）とを合計で０．２〜１０質量部配合してなることを特徴とする。
芳香族化合物（１）および芳香族化合物（２）の合計の配合量が０．２質量部未満であると、添加量が少な過ぎて所望の効果が奏されない。逆に１０質量部を超えると金属コードとの接着性が悪化する。
(Combination ratio of tire rubber composition)
The rubber composition for tires of the present invention comprises an aromatic compound (1) having one or more carboxyl groups and hydroxyl groups in a molecule and three or more molecules in a molecule with respect to 100 parts by mass of a diene rubber containing natural rubber. A total of 0.2 to 10 parts by mass of the aromatic compound (2) having a carboxyl group is characterized.
When the total blending amount of the aromatic compound (1) and the aromatic compound (2) is less than 0.2 parts by mass, the addition amount is too small to achieve the desired effect. Conversely, when it exceeds 10 mass parts, adhesiveness with a metal cord will deteriorate.
さらに好ましい芳香族化合物（１）および芳香族化合物（２）の合計の配合量は、天然ゴムを含むジエン系ゴム１００質量部に対し２〜６質量部である。 Further, the total amount of the aromatic compound (1) and the aromatic compound (2) is 2 to 6 parts by mass with respect to 100 parts by mass of the diene rubber containing natural rubber.
本発明のタイヤ用ゴム組成物には、前記した成分に加えて、シリカ、カーボンブラックなどの補強剤、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑剤などのタイヤ用ゴム組成物に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In the tire rubber composition of the present invention, in addition to the above-described components, reinforcing agents such as silica and carbon black, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, plasticizers, and the like Various additives that are generally blended in the tire rubber composition can be blended, and these additives are kneaded by a general method into a composition and used for vulcanization or crosslinking. Can do. The blending amounts of these additives can be set to conventional general blending amounts as long as the object of the present invention is not violated.
本発明のタイヤ用ゴム組成物は従来の空気入りタイヤの製造方法に従って空気入りタイヤを製造するのに使用することができる。本発明のタイヤ用ゴム組成物は、金属コードとの良好な接着性に基づく高い耐久性と、高い硬度および引張特性に基づく優れた操縦安定性や耐破壊特性を達成していることから、とくにタイヤベルト層の被覆に用いるのが好適である。
これとは別に、本発明のタイヤ用ゴム組成物は、上記のような金属コードとの良好な接着性に基づく高い耐久性と、高い硬度および引張特性に基づく優れた操縦安定性や耐破壊特性を達成していることから、カーカス層の被覆にも好適に用いられる。
前者のタイヤベルト層の被覆に用いる場合において、加硫剤としての硫黄は、ジエン系ゴム１００質量部に対し、５〜１０質量部配合するのが好ましく、後者のカーカス層の被覆に用いる場合において、加硫剤としての硫黄は、ジエン系ゴム１００質量部に対し、２〜５質量部配合するのが好ましい。
The rubber composition for tires of the present invention can be used for producing a pneumatic tire according to a conventional method for producing a pneumatic tire. The rubber composition for tires of the present invention has achieved high durability based on good adhesion to metal cords, and excellent handling stability and fracture resistance based on high hardness and tensile properties. It is suitable for use in covering the tire belt layer.
Apart from this, the rubber composition for tires of the present invention has high durability based on good adhesion to the metal cord as described above, and excellent handling stability and fracture resistance based on high hardness and tensile properties. Therefore, it is also suitably used for coating the carcass layer.
When used for coating the former tire belt layer, sulfur as a vulcanizing agent is preferably blended in an amount of 5 to 10 parts by mass with respect to 100 parts by mass of the diene rubber, and when used for coating the latter carcass layer. The sulfur as a vulcanizing agent is preferably blended in an amount of 2 to 5 parts by mass with respect to 100 parts by mass of the diene rubber.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example.
標準例１、実施例１〜３、比較例１〜５
サンプルの調製
表１に示す配合（質量部）において、加硫促進剤と硫黄を除く成分を１．５リットルの密閉式バンバリーミキサーで５分間混練した後、ミキサー外に放出させて室温冷却した。続いて、該組成物を同バンバリーミキサーに再度入れ、加硫促進剤および硫黄を加えて混練し、タイヤ用ゴム組成物を得た。次に得られたタイヤ用ゴム組成物を所定の金型中で１７０℃で１５分間プレス加硫して加硫ゴム試験片を調製した。得られた加硫ゴム試験片について以下に示す試験法で物性を測定した。
Standard Example 1, Examples 1-3, Comparative Examples 1-5
Preparation of Sample In the formulation (parts by mass) shown in Table 1, components other than the vulcanization accelerator and sulfur were kneaded for 5 minutes with a 1.5 liter closed Banbury mixer, then discharged outside the mixer and cooled at room temperature. Subsequently, the composition was put into the Banbury mixer again, and a vulcanization accelerator and sulfur were added and kneaded to obtain a tire rubber composition. Next, the obtained rubber composition for tire was press vulcanized at 170 ° C. for 15 minutes in a predetermined mold to prepare a vulcanized rubber test piece. The physical properties of the obtained vulcanized rubber specimens were measured by the following test methods.
硬度：ＪＩＳ ６２５３に準拠して、２０℃で測定した。結果は、標準例１の値を１００として指数表示した。指数が大きいほど硬度が高いことを示す。
引張特性：ＪＩＳ Ｋ６２５１に準拠し、引張試験を行い、引張強さ（ＴＢ）、破断時伸び（ＥＢ）を測定した。結果は、標準例１の値を１００として指数で示した。指数が大きいほど引張特性に優れることを示す。
接着試験：ASTM-D-2に準拠してコードを引き抜き、その引き抜き時の引抜力とゴム付着量を評価した。結果は、標準例１の値を１００として指数で示した。指数が大きいほどスチールワイヤとの初期接着力に優れることを示す。
結果を表１に併せて示す。
Hardness: Measured at 20 ° C. according to JIS 6253. The results are shown as an index with the value of standard example 1 being 100. The larger the index, the higher the hardness.
Tensile properties: Tensile tests were performed in accordance with JIS K6251, and tensile strength (TB) and elongation at break (EB) were measured. The results are shown as an index with the value of Standard Example 1 being 100. A larger index indicates better tensile properties.
Adhesion test: The cord was pulled out in accordance with ASTM-D-2, and the pulling force and the rubber adhesion amount at the time of pulling were evaluated. The results are shown as an index with the value of Standard Example 1 being 100. It shows that it is excellent in the initial stage adhesive force with a steel wire, so that an index | exponent is large.
The results are also shown in Table 1.
＊１：ＮＲ（ＴＳＲ２０）
＊２：カーボンブラック（東海カーボン（株）製シースト３００、ＣＴＡＢ比表面積＝８４ｍ２／ｇ、Ｎ２ＳＡ＝７６ｍ２／ｇ、ＤＢＰ吸油量＝７４ｃｍ３／１００ｇ）
＊３：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊４：老化防止剤（フレキシス社製サントフレックス６ＰＰＤ）
＊５：ステアリン酸コバルト（ＤＩＣ（株）製）
＊６：レゾルシン樹脂（田岡化学工業（株）製スミカノール６２０）
＊７：ＨＭＭＭ（ＣＹＴＥＣ ＩＮＤＵＳＴＲＩＥＳ製ＣＹＲＥＺ ９６４ＲＰＣ、ヘキサメトキシメチロールメラミン）
＊８：サリチル酸（吉富製薬（株）製）
＊９：トリメリト酸（ＤＩＣ（株）製モノサイザーＷ−７００）
＊１０：プロピオン酸（東京化成株式会社）
＊１１：硫黄（四国化成工業製ミュークロンＯＴ−２０）
＊１２：加硫促進剤（大内新興化学工業（株）製ノクセラーＤＺ）
* 1: NR (TSR20)
* 2: Carbon black (manufactured by Tokai Carbon Co., Ltd. Seast 300, CTAB specific surface = 84m 2 / g, N 2 SA = 76m 2 / g, DBP oil absorption = 74cm 3/100 g)
* 3: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 4: Anti-aging agent (Santflex 6PPD manufactured by Flexis)
* 5: Cobalt stearate (manufactured by DIC Corporation)
* 6: Resorcin resin (Sumikanol 620 manufactured by Taoka Chemical Industry Co., Ltd.)
* 7: HMMM (CYREZ 964RPC, hexamethoxymethylol melamine manufactured by CYTEC INDUSTRIES)
* 8: Salicylic acid (manufactured by Yoshitomi Pharmaceutical Co., Ltd.)
* 9: Trimellitic acid (DIC Corporation Monosizer W-700)
* 10: Propionic acid (Tokyo Chemical Industry Co., Ltd.)
* 11: Sulfur (Muklon OT-20, manufactured by Shikoku Chemicals)
* 12: Vulcanization accelerator (Ouchi Shinsei Chemical Co., Ltd. Noxeller DZ)
上記の表１から明らかなように、実施例１〜３で調製されたタイヤ用ゴム組成物は、ＮＲを含むジエン系ゴムに、特定の複数種類の芳香族化合物を併用し、これを特定量で配合しているので、従来の代表的な標準例１に対し、金属コードとの優れた接着性および高い硬度および引張特性が達成されている。
これに対し、比較例１は、分子中に１個以上のカルボキシル基および水酸基を有する芳香族化合物（１）のみを配合した例であるので、実施例１と比較すると、金属コードとの接着性および引張特性がいずれも劣る結果となった。
比較例２は、分子中に３個以上のカルボキシル基を有する芳香族化合物（２）のみを配合した例であるので、実施例１と比較すると、金属コードとの接着性および引張特性がいずれも劣る結果となった。
比較例３は、芳香族化合物（１）および（２）の合計の配合量が本発明で規定する下限未満であるので、金属コードとの接着性、硬度および引張特性がいずれも改善されなかった。
比較例４は、芳香族化合物（１）および（２）の合計の配合量が本発明で規定する上限を超えているので、金属コードとの接着性および引張特性が共に改善されなかった。
比較例５は、トリメリト酸の替わりにプロピオン酸を使用した例であるので、金属コードとの接着性および引張特性が共に改善されなかった。
As is clear from Table 1 above, the rubber compositions for tires prepared in Examples 1 to 3 were used in combination with a diene rubber containing NR and a plurality of specific aromatic compounds in combination. Therefore, superior adhesion to a metal cord and high hardness and tensile properties are achieved with respect to the conventional representative standard example 1.
On the other hand, since Comparative Example 1 is an example in which only an aromatic compound (1) having one or more carboxyl groups and hydroxyl groups is blended in the molecule, compared with Example 1, the adhesion to the metal cord Both the tensile properties and the tensile properties were inferior.
Since Comparative Example 2 is an example in which only the aromatic compound (2) having three or more carboxyl groups in the molecule is blended, compared with Example 1, both the adhesiveness to metal cords and tensile properties are both The result was inferior.
In Comparative Example 3, since the total amount of the aromatic compounds (1) and (2) was less than the lower limit specified in the present invention, none of the adhesion to the metal cord, hardness and tensile properties were improved. .
In Comparative Example 4, since the total blending amount of the aromatic compounds (1) and (2) exceeded the upper limit specified in the present invention, both the adhesion to the metal cord and the tensile properties were not improved.
Since Comparative Example 5 is an example in which propionic acid is used instead of trimellitic acid, neither the adhesion to the metal cord nor the tensile properties were improved.
標準例２、実施例４〜８、比較例６〜９
サンプルの調製
表１に示す配合（質量部）において、加硫促進剤と硫黄を除く成分を１．５リットルの密閉式バンバリーミキサーで５分間混練した後、ミキサー外に放出させて室温冷却した。続いて、該組成物を同バンバリーミキサーに再度入れ、加硫促進剤および硫黄を加えて混練し、タイヤ用ゴム組成物を得た。次に得られたタイヤ用ゴム組成物を所定の金型中で１７０℃で１５分間プレス加硫して加硫ゴム試験片を調製した。得られた加硫ゴム試験片について以下に示す試験法で物性を測定した。
Standard Example 2, Examples 4-8, Comparative Examples 6-9
Preparation of Sample In the formulation (parts by mass) shown in Table 1, components other than the vulcanization accelerator and sulfur were kneaded for 5 minutes with a 1.5 liter closed Banbury mixer, then discharged outside the mixer and cooled at room temperature. Subsequently, the composition was put into the Banbury mixer again, and a vulcanization accelerator and sulfur were added and kneaded to obtain a tire rubber composition. Next, the obtained rubber composition for tire was press vulcanized at 170 ° C. for 15 minutes in a predetermined mold to prepare a vulcanized rubber test piece. The physical properties of the obtained vulcanized rubber specimens were measured by the following test methods.
硬度：ＪＩＳ ６２５３に準拠して、２０℃で測定した。結果は、標準例２の値を１００として指数表示した。指数が大きいほど硬度が高いことを示す。
引張試験（１００％モジュラス（Ｍ１００）、３００％モジュラス（Ｍ３００）：ＪＩＳ Ｋ６２５１に準拠して測定した。結果は、標準例２の値を１００として指数表示した。指数が大きいほど引張強度が高いことを示す。
発熱性：（株）東洋精機製作所製の粘弾性スペクトロメーターを用いて、初期歪＝１０％、振幅＝±２％、周波数＝２０Ｈｚの条件下でｔａｎδ（６０℃）を測定し、この値をもって発熱性を評価した。結果は標準例２の値を１００として指数表示した。指数が大きいほど、低発熱性であることを示す。
接着力：ＪＩＳ Ｌ１０１７に準拠し、未加硫ゴム組成物に処理コードを埋設し、１７０℃×1０分加硫した後に、ゴムからコードを引き抜く接着力を測定した。結果は、標準例２の値を１００として指数で示した。指数が大きいほどスチールワイヤとの接着力に優れることを示す。
結果を表２に併せて示す。
Hardness: Measured at 20 ° C. according to JIS 6253. The results are shown as an index with the value of standard example 2 as 100. The larger the index, the higher the hardness.
Tensile test (100% modulus (M100), 300% modulus (M300): Measured in accordance with JIS K6251. The result is expressed as an index with the value of standard example 2 being 100. The larger the index, the higher the tensile strength. Indicates.
Exothermic property: Using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd., tan δ (60 ° C.) was measured under the conditions of initial strain = 10%, amplitude = ± 2%, frequency = 20 Hz. Exotherm was evaluated. The result was expressed as an index with the value of Standard Example 2 being 100. A larger index indicates a lower exothermic property.
Adhesive strength: In accordance with JIS L1017, a treatment cord was embedded in an unvulcanized rubber composition, vulcanized at 170 ° C. for 10 minutes, and then the adhesive strength for pulling the cord from the rubber was measured. The results are shown as an index with the value of Standard Example 2 being 100. It shows that it is excellent in the adhesive force with a steel wire, so that an index | exponent is large.
The results are also shown in Table 2.
＊１：ＮＲ（ＴＳＲ２０）
＊２：ＳＢＲ（日本ゼオン（株）製ＮＩＰＯＬ １５０２）
＊３：ＢＲ（日本ゼオン（株）製ＮＩＰＯＬ ＢＲ １２２０）
＊４：カーボンブラック（ＴＨＡＩＢＬＡＣＫ Ｎ６６０）
＊５：ステアリン酸コバルト（ＤＩＣ（株）製）
＊６：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊７：老化防止剤（フレキシス社製サントフレックス６ＰＰＤ）
＊８：プロピオン酸（東京化成株式会社）
＊９：サリチル酸（吉富製薬（株）製）
＊１０：トリメリト酸（ＤＩＣ（株）製モノサイザーＷ−７００）
＊１１：硫黄（四国化成工業製ミュークロンＯＴ−２０）
＊１２：加硫促進剤（大内新興化学工業（株）製ノクセラーＤＺ）
* 1: NR (TSR20)
* 2: SBR (NIPOL 1502 manufactured by Zeon Corporation)
* 3: BR (NIPOL BR 1220 manufactured by Nippon Zeon Co., Ltd.)
* 4: Carbon black (THAIBLACK N660)
* 5: Cobalt stearate (manufactured by DIC Corporation)
* 6: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 7: Anti-aging agent (Santflex 6PPD manufactured by Flexis)
* 8: Propionic acid (Tokyo Chemical Industry Co., Ltd.)
* 9: Salicylic acid (manufactured by Yoshitomi Pharmaceutical Co., Ltd.)
* 10: Trimellitic acid (DIC Corporation Monosizer W-700)
* 11: Sulfur (Muklon OT-20, manufactured by Shikoku Chemicals)
* 12: Vulcanization accelerator (Ouchi Shinsei Chemical Co., Ltd. Noxeller DZ)
上記の表２から明らかなように、実施例４〜８で調製されたタイヤ用ゴム組成物は、ＮＲを含むジエン系ゴムに、特定の複数種類の芳香族化合物を併用し、これを特定量で配合しているので、従来の代表的な標準例２に対し、金属コードとの優れた接着性および高い硬度および引張特性が達成されている。また、発熱性を損なうこともない。
これに対し、比較例６は、芳香族化合物（１）および（２）の合計の配合量が本発明で規定する下限未満であるので、金属コードとの接着性、硬度および引張特性がいずれも改善されなかった。
比較例７は、芳香族化合物（１）および（２）の合計の配合量が本発明で規定する上限を超えているので、引張特性が改善されなかった。
比較例８は、サリチル酸の替わりにプロピオン酸を使用した例であるので、金属コードとの接着性および引張特性が共に改善されなかった。
比較例９は、分子中に１個以上のカルボキシル基および水酸基を有する芳香族化合物（１）のみを配合した例であるので、実施例４と比較すると、硬度および引張特性がいずれも劣る結果となった。
As is clear from Table 2 above, the tire rubber compositions prepared in Examples 4 to 8 were obtained by using a specific amount of a plurality of specific aromatic compounds in combination with diene rubber containing NR. Therefore, superior adhesion to a metal cord and high hardness and tensile properties are achieved with respect to the conventional representative standard example 2. Moreover, exothermic property is not impaired.
On the other hand, since the total compounding amount of the aromatic compounds (1) and (2) is less than the lower limit specified in the present invention, Comparative Example 6 has all the adhesion, hardness and tensile properties with the metal cord. It was not improved.
In Comparative Example 7, the total blending amount of the aromatic compounds (1) and (2) exceeded the upper limit defined in the present invention, so the tensile properties were not improved.
Since Comparative Example 8 is an example in which propionic acid was used instead of salicylic acid, neither the adhesion to the metal cord nor the tensile properties were improved.
Since Comparative Example 9 is an example in which only the aromatic compound (1) having one or more carboxyl groups and hydroxyl groups in the molecule is blended, the results are inferior in hardness and tensile properties as compared with Example 4. became.
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