JP5958247B2 - 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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- JP5958247B2 JP5958247B2 JP2012215852A JP2012215852A JP5958247B2 JP 5958247 B2 JP5958247 B2 JP 5958247B2 JP 2012215852 A JP2012215852 A JP 2012215852A JP 2012215852 A JP2012215852 A JP 2012215852A JP 5958247 B2 JP5958247 B2 JP 5958247B2
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- sulfonic acid
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- 229920001971 elastomer Polymers 0.000 title claims description 33
- 239000005060 rubber Substances 0.000 title claims description 33
- 239000000203 mixture Substances 0.000 title claims description 32
- 229920003244 diene elastomer Polymers 0.000 claims description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 244000043261 Hevea brasiliensis Species 0.000 claims description 13
- 229920003052 natural elastomer Polymers 0.000 claims description 13
- 229920001194 natural rubber Polymers 0.000 claims description 13
- -1 organic acid cobalt salt Chemical class 0.000 claims description 12
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 9
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 5
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002184 metal Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- 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
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-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
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- RIOSJKSGNLGONI-UHFFFAOYSA-N 2-phenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C1=CC=CC=C1 RIOSJKSGNLGONI-UHFFFAOYSA-N 0.000 description 1
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-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
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 1
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical compound CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- PTKWYSNDTXDBIZ-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2-disulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C3C(=O)C2=C1 PTKWYSNDTXDBIZ-UHFFFAOYSA-N 0.000 description 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-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
- 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
- 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
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-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
- 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 1
- 238000010521 absorption reaction Methods 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
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 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
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 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
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 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
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 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
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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、熱硬化性樹脂を配合してなるタイヤ用ゴム組成物において、金属コードとの接着性および高温物性に優れる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。 The present invention relates to a tire rubber composition and a pneumatic tire using the same, and more specifically, in a tire rubber composition containing a thermosetting resin, adhesion to a metal cord and high-temperature physical properties. The present invention relates to an excellent rubber composition for tires and a pneumatic tire using the same.
空気入りタイヤのベルト層は、例えばスチールコードのような金属コードと、該金属コードを被覆するゴムとからなる。このような金属コードを被覆するゴムは、耐破壊特性を得るために金属コードとの接着性および高温物性を向上させることが求められている。
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に対し、近年さらなる接着性および高温物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 belt layer of the pneumatic tire is made of, for example, a metal cord such as a steel cord and rubber covering the metal cord. The rubber covering such a metal cord is required to improve adhesion to the metal cord and high-temperature physical properties in order to obtain fracture resistance.
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, in recent years, there has been a demand for further improvement in adhesion and high-temperature physical properties of rubber covering metal cords. For this reason, various technologies have been studied in the industry. I couldn't meet the level enough.
したがって本発明の目的は、熱硬化性樹脂を配合してなるタイヤ用ゴム組成物において、金属コードとの接着性および高温物性を改善し、耐破壊特性に優れる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 tire rubber composition that is improved in adhesion to metal cords and high-temperature physical properties and has excellent fracture resistance in a tire rubber composition containing a thermosetting resin. It is to provide a pneumatic tire.
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、芳香族スルホン酸の特定量および特定の熱硬化性樹脂の特定量を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、芳香族スルホン酸を０．１〜８質量部、ノボラック型フェノール系樹脂を０．１質量部以上５質量部未満配合してなるタイヤ用ゴム組成物。
２．前記芳香族スルホン酸が、ベンゼンスルホン酸、トルエンスルホン酸およびナフタレンスルホン酸から選択された１種以上である前記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、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または２に記載のタイヤ用ゴム組成物。
４．前記１〜３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。
As a result of intensive studies, the present inventors have found that the above problem can be solved by blending a specific amount of aromatic sulfonic acid and a specific amount of specific thermosetting resin with diene rubber including natural rubber. The headline and the present invention could be completed.
That is, the present invention is as follows.
1. A rubber composition for tires comprising 0.1 to 8 parts by mass of aromatic sulfonic acid and 0.1 to 5 parts by mass of novolac type phenolic resin per 100 parts by mass of diene rubber containing natural rubber. object.
2. 2. The rubber composition for tire according to 1, wherein the aromatic sulfonic acid is at least one selected from benzenesulfonic acid, toluenesulfonic acid and naphthalenesulfonic acid.
3. The rubber composition for tires according to 1 or 2 above, wherein 0.1 to 0.5 parts by mass of an organic acid cobalt salt is blended with respect to 100 parts by mass of the diene rubber.
4). A pneumatic tire using the tire rubber composition according to any one of the above items 1 to 3 for covering a tire belt layer.
本発明によれば、天然ゴムを含むジエン系ゴムに、芳香族スルホン酸の特定量および特定の熱硬化性樹脂の特定量を配合したので、金属コードとの接着性および高温物性を改善し、耐破壊特性に優れ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に用いた場合、金属コードとの良好な接着性および高温物性に基づく高い耐破壊特性を提供することができる。
According to the present invention, since a specific amount of aromatic sulfonic acid and a specific amount of a specific thermosetting resin are blended with a diene rubber containing natural rubber, the adhesion with a metal cord and high-temperature physical properties are improved. A rubber composition for a tire excellent in fracture resistance and a pneumatic tire using the same can be provided.
When the tire rubber composition of the present invention is used for coating a tire belt layer, it can provide good fracture resistance based on good adhesion to metal cords and high-temperature physical properties.
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.
（芳香族スルホン酸）
本発明で使用される芳香族スルホン酸は、例えば、ベンゼンスルホン酸、トルエンスルホン酸、キシレンスルホン酸、クメンスルホン酸、ドデシルベンゼンスルホン酸、ヒドロキシベンゼンスルホン酸、ニトロベンゼンスルホン酸、スルホサリチル酸、スルホフタル酸、スルホイソフタル酸、ナフタレンスルホン酸、ナフタレンジスルホン酸、他のアルキルナフタレンスルホン酸、ポリアルキルナフタレンスルホン酸、アントラキノンスルホン酸、アントラキノンジスルホン酸、ビフェニルスルホン酸およびこれらの誘導体等を挙げることができ、中でも本発明の効果が高まるという観点から、ベンゼンスルホン酸、トルエンスルホン酸（例えばｐ−トルエンスルホン酸）、ナフタレンスルホン酸（例えば２−ナフタレンスルホン酸）が好ましい。これら芳香族スルホン酸は２種以上を併用することもできる。
(Aromatic sulfonic acid)
Examples of the aromatic sulfonic acid used in the present invention include benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, hydroxybenzenesulfonic acid, nitrobenzenesulfonic acid, sulfosalicylic acid, sulfophthalic acid, Examples include sulfoisophthalic acid, naphthalene sulfonic acid, naphthalene disulfonic acid, other alkyl naphthalene sulfonic acids, polyalkyl naphthalene sulfonic acid, anthraquinone sulfonic acid, anthraquinone disulfonic acid, biphenyl sulfonic acid, and derivatives thereof. From the viewpoint of enhancing the effect of benzene sulfonic acid, toluene sulfonic acid (for example, p-toluene sulfonic acid), naphthalene sulfonic acid (for example, 2-naphthalene sulfonic acid) is preferable. There. Two or more of these aromatic sulfonic acids can be used in combination.
（ノボラック型フェノール系樹脂）
本発明で使用されるノボラック型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た縮合物であり、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。
ノボラック型フェノール系樹脂は、本発明の効果の観点から、ノボラック型フェノール樹脂が好ましい。
(Novolac type phenolic resin)
The novolak-type phenolic resin used in the present invention is, for example, a condensate obtained by condensing phenol, cresol or resorcin with an aldehyde compound, particularly formaldehyde, and preferably reacts with a curing agent such as a methylene donor, which will be described later. These are originally cross-linked, 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.
From the viewpoint of the effects of the present invention, the novolac type phenol resin is preferably a novolac type phenol resin.
（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。
(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.
（メチレンドナー）
本発明で使用されるメチレンドナーとしては、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。
(Methylene donor)
Examples of the methylene donor 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.
（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、芳香族スルホン酸を０．１〜８質量部、ノボラック型フェノール系樹脂を０．１質量部以上５質量部未満配合してなることを特徴とする。
芳香族スルホン酸の配合量が０．１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。
芳香族スルホン酸の配合量が８質量部を超えると高温物性を満足することができない。
前記ノボラック型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。
前記ノボラック型フェノール系樹脂の配合量が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。
(Combination ratio of tire rubber composition)
In the tire rubber composition of the present invention, 0.1 to 8 parts by mass of an aromatic sulfonic acid and 0.1 to 5 parts by mass of a novolac type phenolic resin with respect to 100 parts by mass of a diene rubber containing natural rubber. It is characterized by comprising less than part.
When the blending amount of the aromatic sulfonic acid is less than 0.1 parts by mass, the addition amount is too small to achieve a desired effect.
If the blending amount of the aromatic sulfonic acid exceeds 8 parts by mass, the high temperature physical properties cannot be satisfied.
When the blending amount of the novolac-type phenolic resin is less than 0.1 parts by mass, the hardness is lowered and the steering stability is deteriorated.
When the blending amount of the novolac type phenolic resin is 5 parts by mass or more, the hardness is excessively increased, and the heat generation and the adhesion to the metal cord are deteriorated.
芳香族スルホン酸のさらに好ましい配合量は、天然ゴムを含むジエン系ゴム１００質量部に対し0.5〜3.0質量部である。
前記ノボラック型フェノール系樹脂のさらに好ましい配合量は、天然ゴムを含むジエン系ゴム１００質量部に対し１〜３質量部である。
A more preferable blending amount of the aromatic sulfonic acid is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the diene rubber containing natural rubber.
A more preferable blending amount of the novolac type phenolic resin is 1 to 3 parts by mass with respect to 100 parts by mass of the diene rubber including natural rubber.
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。
メチレンドナーを使用する場合、その配合量はジエン系ゴム１００質量部に対し、０．５〜５質量部が好ましく、２〜５質量部がさらに好ましい。
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.
When using a methylene donor, the compounding quantity is preferably 0.5 to 5 parts by mass and more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the diene 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、金属コードとの優れた接着性および高温物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。 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. Since the rubber composition for tires of the present invention achieves excellent adhesion to metal cords and high-temperature physical properties, it is particularly suitable for use in coating a tire belt layer.
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、実施例１〜４、比較例１〜３
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, Examples 1-4, Comparative Examples 1-3
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.
高温物性：ＪＩＳ Ｋ６２５１に準拠し、試験温度１００℃で引張試験を行い、１００％モジュラス（Ｍ１００）、引張強さ（ＴＢ）、破断時伸び（ＥＢ）を測定した。結果は、標準例の値を１００として指数で示した。指数が大きいほど高温物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を評価した。結果は、標準例の値を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。
High temperature properties: Based on JIS K6251, a tensile test was conducted at a test temperature of 100 ° C., and 100% modulus (M100), tensile strength (TB), and elongation at break (EB) were measured. The results are shown as an index with the value of the standard example being 100. The larger the index, the better the high temperature physical properties.
Adhesion test: The cord was pulled out according to ASTM-D-2, and the pulling force at the time of pulling was evaluated. The results are shown as an index with the value of the standard example 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.
＊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：亜鉛華（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：ノボラック型クレゾール樹脂（田岡化学工業（株）製スミカノール６１０）
＊７：ＰＭＭＭ（バラケミカル製スミカノール５０７Ａ、ペンタメトキシメチロールメラミン、メラミン誘導体６５％）
＊８：ｐ−トルエンスルホン酸（東京化成工業（株）製）
＊９：２−ナフタレンスルホン酸（東京化成工業（株）製）
＊１０：ベンゼンスルホン酸 （東京化成工業（株）製）
＊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 Hana (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: Novolac-type cresol resin (Sumikanol 610 manufactured by Taoka Chemical Co., Ltd.)
* 7: PMMM (Sumikanol 507A from Bara Chemical, pentamethoxymethylol melamine, 65% melamine derivative)
* 8: p-Toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
* 9: 2-Naphthalenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
* 10: Benzenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
* 11: Sulfur (Muklon OT-20, manufactured by Shikoku Chemicals)
* 12: Vulcanization accelerator (Ouchi Shinsei Chemical Co., Ltd. Noxeller DZ)
上記の表から明らかなように、実施例１〜４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芳香族スルホン酸の特定量および特定の熱硬化性樹脂の特定量を配合したので、従来の代表的な標準例に対し、金属コードとの優れた接着性および優れた高温物性が達成されている。したがって、これらのタイヤ用ゴム組成物を例えばタイヤベルト層の被覆に用いることにより、優れた耐破壊特性が付与される。
これに対し、比較例１は、芳香族スルホン酸の配合量が本発明で規定する下限未満であるので、その効果が全く発現していない。
比較例２は、芳香族スルホン酸の配合量が本発明で規定する上限を超えているので、ＥＢが悪化した。
比較例３は、ノボラック型フェノール系樹脂の配合量が本発明で規定する上限を超えているので、高温物性が悪化し、金属コードに対する接着性も改善が見られなかった。
As is clear from the above table, the tire rubber compositions prepared in Examples 1 to 4 have a specific amount of aromatic sulfonic acid and a specific amount of specific thermosetting resin in the diene rubber containing NR. Since it mix | blended, the outstanding adhesiveness with a metal cord and the outstanding high temperature physical property were achieved with respect to the conventional typical standard example. Therefore, by using these rubber compositions for tires, for example, for coating a tire belt layer, excellent fracture resistance is imparted.
On the other hand, since the compounding quantity of aromatic sulfonic acid is less than the lower limit prescribed | regulated by this invention in the comparative example 1, the effect is not expressed at all.
In Comparative Example 2, since the blending amount of the aromatic sulfonic acid exceeded the upper limit specified in the present invention, the EB deteriorated.
In Comparative Example 3, since the blending amount of the novolac type phenolic resin exceeded the upper limit specified in the present invention, the high temperature physical properties were deteriorated and the adhesiveness to the metal cord was not improved.
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