JP7434897B2 - トレッドゴム組成物及び空気入りタイヤ - Google Patents
トレッドゴム組成物及び空気入りタイヤ Download PDFInfo
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- JP7434897B2 JP7434897B2 JP2019556294A JP2019556294A JP7434897B2 JP 7434897 B2 JP7434897 B2 JP 7434897B2 JP 2019556294 A JP2019556294 A JP 2019556294A JP 2019556294 A JP2019556294 A JP 2019556294A JP 7434897 B2 JP7434897 B2 JP 7434897B2
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- 239000005060 rubber Substances 0.000 title claims description 123
- 239000000203 mixture Substances 0.000 title claims description 92
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- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 41
- 239000005062 Polybutadiene Substances 0.000 claims description 35
- 229920002857 polybutadiene Polymers 0.000 claims description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 34
- 239000003431 cross linking reagent Substances 0.000 claims description 34
- 229910052717 sulfur Inorganic materials 0.000 claims description 34
- 239000011593 sulfur Substances 0.000 claims description 33
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- 230000008859 change Effects 0.000 claims description 27
- 238000012360 testing method Methods 0.000 claims description 25
- 239000006229 carbon black Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229920003049 isoprene rubber Polymers 0.000 claims description 15
- 238000004132 cross linking Methods 0.000 claims description 14
- 238000005259 measurement Methods 0.000 claims description 14
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 241000872198 Serjania polyphylla Species 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 39
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- 125000004432 carbon atom Chemical group C* 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
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- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 10
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 4
- ZEUAKOUTLQUQDN-UHFFFAOYSA-N 6-(dibenzylcarbamothioyldisulfanyl)hexylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSCCCCCCSSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 ZEUAKOUTLQUQDN-UHFFFAOYSA-N 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000005370 alkoxysilyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- VTEKOFXDMRILGB-UHFFFAOYSA-N bis(2-ethylhexyl)carbamothioylsulfanyl n,n-bis(2-ethylhexyl)carbamodithioate Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=S)SSC(=S)N(CC(CC)CCCC)CC(CC)CCCC VTEKOFXDMRILGB-UHFFFAOYSA-N 0.000 description 2
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- 125000000753 cycloalkyl group Chemical group 0.000 description 2
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- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
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- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical class O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
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- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 description 1
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- XDDVRYDDMGRFAZ-UHFFFAOYSA-N thiobenzophenone Chemical class C=1C=CC=CC=1C(=S)C1=CC=CC=C1 XDDVRYDDMGRFAZ-UHFFFAOYSA-N 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- ZZUIPNXRUAGCJF-UHFFFAOYSA-N tributoxy(3-trimethylsilylsulfanylpropyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)CCCS[Si](C)(C)C ZZUIPNXRUAGCJF-UHFFFAOYSA-N 0.000 description 1
- FPBXRRDHCADTAL-UHFFFAOYSA-N triethoxy(3-nitropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC[N+]([O-])=O FPBXRRDHCADTAL-UHFFFAOYSA-N 0.000 description 1
- IWJOAWOCUCJBII-UHFFFAOYSA-N triethoxy(3-trimethylsilylsulfanylpropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCS[Si](C)(C)C IWJOAWOCUCJBII-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FJXRKYLOOJTENP-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyldisulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSCC[Si](OCC)(OCC)OCC FJXRKYLOOJTENP-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- URIYERBJSDIUTC-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltrisulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSCC[Si](OCC)(OCC)OCC URIYERBJSDIUTC-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- PTRSAJDNBVXVMV-UHFFFAOYSA-N triethoxy-[4-(4-triethoxysilylbutyldisulfanyl)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCSSCCCC[Si](OCC)(OCC)OCC PTRSAJDNBVXVMV-UHFFFAOYSA-N 0.000 description 1
- NOPBHRUFGGDSAD-UHFFFAOYSA-N triethoxy-[4-(4-triethoxysilylbutyltetrasulfanyl)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCSSSSCCCC[Si](OCC)(OCC)OCC NOPBHRUFGGDSAD-UHFFFAOYSA-N 0.000 description 1
- QPPXVBLDIDEHBA-UHFFFAOYSA-N trimethoxy(3-nitropropyl)silane Chemical compound CO[Si](OC)(OC)CCC[N+]([O-])=O QPPXVBLDIDEHBA-UHFFFAOYSA-N 0.000 description 1
- PMXKHNVLACXGAZ-UHFFFAOYSA-N trimethoxy(3-trimethylsilylsulfanylpropyl)silane Chemical compound CO[Si](OC)(OC)CCCS[Si](C)(C)C PMXKHNVLACXGAZ-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- NQRACKNXKKOCJY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSCCC[Si](OC)(OC)OC NQRACKNXKKOCJY-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- BNBXBRPOAJZBNB-UHFFFAOYSA-N trimethoxy-[4-(4-trimethoxysilylbutyldisulfanyl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCSSCCCC[Si](OC)(OC)OC BNBXBRPOAJZBNB-UHFFFAOYSA-N 0.000 description 1
- GSZUEPNJCPXEGU-UHFFFAOYSA-N trimethoxy-[4-(4-trimethoxysilylbutyltrisulfanyl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCSSSCCCC[Si](OC)(OC)OC GSZUEPNJCPXEGU-UHFFFAOYSA-N 0.000 description 1
- LQBHRPIAMBRGHZ-UHFFFAOYSA-N trimethyl(3-tripropoxysilylpropylsulfanyl)silane Chemical compound CCCO[Si](OCCC)(OCCC)CCCS[Si](C)(C)C LQBHRPIAMBRGHZ-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Description
|ΔHs|≦3.0 (1)
|ΔSwell|≦20% (2)
前記ゴム組成物は、硫黄以外の架橋剤のみを含むことが好ましい。
これにより、必要なグリップ性能等を発揮するだけでなく、優れた耐摩耗性を得ることができる。
熱老化(熱劣化)が大きく現れる物性として、ゴムの硬さや架橋度が考えられ、先ず、ポリマーの架橋を-S-S-よりも強い結合を持つ材料で行うことで、硬さや架橋度の変化を抑制できると考えた。そして、所定量のスチレンブタジエンゴム(SBR)、ブタジエンゴム(BR)を含む配合ゴムにおいて、ゴムの硬さHs、架橋度の指標としてSwellを用い、熱老化前後の硬度変化絶対値|ΔHs|が式(1)、熱老化前後のSwell変化絶対値|ΔSwell|が式(2)を満たすように調整することで、タイヤの新品時と劣化時の性能差を抑制できるという知見を見出した。従って、所定量のSBRとBRを含み、かつ式(1)、(2)を満たす場合、長期間に渡って、優れた耐摩耗性が得られるものと推察される。
|ΔHs|≦3.0 (1)
好ましくは|ΔHs|≦2.5、より好ましくは|ΔHs|≦2.0、更に好ましくは|ΔHs|≦1.5、特に好ましくは|ΔHs|≦1.0、最も好ましくは|ΔHs|≦0.5である。上記範囲内の場合、熱老化前後における硬さHsの変化が少なく、優れた耐摩耗性が長期間に渡って得られる傾向がある。
40≦Hs≦80 (1-1)
好ましくは50≦Hs≦75、より好ましくは55≦Hs≦70、更に好ましくは60≦Hs≦68である。上記範囲内の場合、優れたトレッドゴムとしての実用性や耐摩耗性が得られる傾向がある。また、Hsの下限又は上限は、50.0、55.0、60.0、64.0、64.5、65.0、65.5、66.0、66.5、67.0、67.5、68.0、68.5、69.0、69.5、70.0、71.0、72.0、73.0、74.0、75.0、76.0でもよい。
|ΔSwell|≦20% (2)
好ましくは|ΔSwell|≦15%、より好ましくは|ΔSwell|≦10%、更に好ましくは|ΔSwell|≦5%である。上記範囲内の場合、熱老化前後における架橋度(Swell)の変化が少なく、優れた耐摩耗性が長期間に渡って得られる傾向がある。また、|ΔSwell|は、19%以下、18%以下、17%以下、16%以下、14%以下、13%以下、11%以下、8%以下、4%以下でもよい。
150%≦Swell≦450% (2-1)
好ましくは200%≦Swell≦400%、より好ましくは230%≦Swell≦350%、更に好ましくは250%≦Swell≦300%である。上記範囲内の場合、優れた耐摩耗性が得られる傾向がある。また、Swellの下限又は上限は、245、262、264、268、271、279、280、283、286、288、292、296、302、304、310、311、312、316、319、320、322、327、331、335、336、339、341でもよい。
なお、スチレン含有量は、1H-NMR測定により算出される。
なお、上記化合物(変性剤)による変性は公知の方法で実施可能である。
なお、BRのシス含量は、赤外吸収スペクトル分析法によって測定できる。
なお、微粒子カーボンブラックのN2SAは、JIS K 6217-2:2001に準拠して測定できる。
なお、シリカの窒素吸着比表面積は、ASTM D3037-81に準じてBET法で測定される値である。
液状ジエン系重合体は、ゲルパーミエーションクロマトグラフィー(GPC)で測定したポリスチレン換算の重量平均分子量(Mw)が、1.0×103~2.0×105であることが好ましく、3.0×103~1.5×104であることがより好ましい。
なお、本明細書において、液状ジエン系重合体のMwは、ゲルパーミエーションクロマトグラフィー(GPC)で測定したポリスチレン換算値である。
架橋剤としては、硫黄(硫黄加硫剤)、硫黄以外の架橋剤(ポリマー間にS-C結合を含む結合を形成できる架橋剤、直接ポリマー同士によるC-C結合を形成できる架橋剤、ジチオリン酸亜鉛等)が挙げられる。なかでも、架橋剤として、硫黄及び硫黄以外の架橋剤の併用、硫黄以外の架橋剤のみの使用が好ましく、硫黄及びポリマー間にS-C結合を含む結合を形成できる架橋剤の併用、直接ポリマー同士によるC-C結合を形成できる架橋剤のみの使用、硫黄及びジチオリン酸亜鉛の併用が特に好ましい。
ワックスとしては、特に限定されず、パラフィンワックス、マイクロクリスタリンワックス等の石油系ワックス;植物系ワックス、動物系ワックス等の天然系ワックス;エチレン、プロピレン等の重合物等の合成ワックス等が挙げられる。市販品として、大内新興化学工業(株)、日本精蝋(株)、精工化学(株)等の製品を使用できる。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。なかでも、石油系ワックスが好ましく、パラフィンワックスがより好ましい。
老化防止剤としては特に限定されず、例えば、フェニル-α-ナフチルアミン等のナフチルアミン系老化防止剤;オクチル化ジフェニルアミン、4,4’-ビス(α,α’-ジメチルベンジル)ジフェニルアミン等のジフェニルアミン系老化防止剤;N-イソプロピル-N’-フェニル-p-フェニレンジアミン、N-(1,3-ジメチルブチル)-N’-フェニル-p-フェニレンジアミン、N,N’-ジ-2-ナフチル-p-フェニレンジアミン等のp-フェニレンジアミン系老化防止剤;2,2,4-トリメチル-1,2-ジヒドロキノリンの重合物等のキノリン系老化防止剤;2,6-ジ-t-ブチル-4-メチルフェノール、スチレン化フェノール等のモノフェノール系老化防止剤;テトラキス-[メチレン-3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオネート]メタン等のビス、トリス、ポリフェノール系老化防止剤などが挙げられる。市販品としては、精工化学(株)、住友化学(株)、大内新興化学工業(株)、フレクシス社等の製品を使用できる。これらは単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。なかでも、p-フェニレンジアミン系老化防止剤(より好ましくは、N-(1,3-ジメチルブチル)-N’-フェニル-p-フェニレンジアミン)が好ましい。
ステアリン酸としては、従来公知のものを使用でき、例えば、日油(株)、NOF社、花王(株)、富士フイルム和光純薬(株)、千葉脂肪酸(株)等の製品を使用できる。
酸化亜鉛としては、従来公知のものを使用でき、例えば、三井金属鉱業(株)、東邦亜鉛(株)、ハクスイテック(株)、正同化学工業(株)、堺化学工業(株)等の製品を使用できる。
NR:TSR20
SBR:JSR(株)製のJSR1502(スチレン含有量23.5質量%)
BR:宇部興産(株)製のBR150B(シス含量98質量%)
微粒子カーボンブラック:試作用カーボンブラック(N2SA181m2/g)
シリカ:デグッサ社製のULTRASIL VN3(N2SA175m2/g)
シランカップリング剤:エボニックデグッサ社製のSi266(ビス(3-トリエトキシシリルプロピル)ジスルフィド)
オイル:出光興産(株)製のダイアナプロセスNH-70S(アロマ系プロセスオイル)
ワックス:日本精蝋(株)製のオゾエース0355
老化防止剤6C:大内新興化学工業(株)製のノクラック6C(N-(1,3-ジメチルブチル)-N’-フェニル-p-フェニレンジアミン)
老化防止剤FR:住友化学(株)製のアンチゲンFR(アミンとケトンの反応品を精製したものでアミンの残留がないもの、キノリン系老化防止剤)
有機樹脂:ストラクトール社製のストラクトール40MS(エチレンプロピレンスチレン共重合体、軟化点78℃、EP含有量82質量%)
脂肪酸亜鉛:ストラクトール社製のEF44
ステアリン酸:日油(株)製のつばき
酸化亜鉛:三井金属鉱業(株)製の酸化亜鉛
硫黄:細井化学(株)製のHK-200-5(5%オイル硫黄)
架橋剤1:ランクセス社製のVulcuren VP KA9188(1,6-ビス(N,N’-ジベンジルチオカルバモイルジチオ)ヘキサン)
架橋剤2:ジクミルパーオキサイド
架橋剤3:ラインケミー社製のTP-50(ジチオリン酸亜鉛及びポリマーの混合物、前記一般式において、R1~R4がn-ブチル基、有効成分50質量%)
加硫促進剤NS:三新化学工業(株)製のサンセラーNS-G
表1~4に示す配合処方にしたがい、(株)神戸製鋼所製の1.7Lバンバリーミキサーを用いて、硫黄及び加硫促進剤以外の薬品を150℃の条件下で5分間混練りし、混練り物を得た。次に、得られた混練り物に硫黄及び加硫促進剤を添加し、オープンロールを用いて、80℃の条件下で5分間練り込み、未加硫ゴム組成物を得た。得られた未加硫ゴム組成物を170℃で20分間プレス加硫し、加硫ゴム組成物を得た。
尚、実施例1-4、2-4、3-4、4-4に関しては、プレス加硫後、加硫ゴム組成物、試験用タイヤとも、オーブン等を用いて120℃で2時間二次加硫を行った。
新品(熱老化前)の加硫ゴム組成物について、JIS K6257:2010に準じて熱老化(100℃、96時間)を実施し、熱老化後の加硫ゴム組成物を得た。
熱老化前、熱老化後の各加硫ゴムシート(加硫ゴム組成物)からなる各試験片について、JIS K6253の「加硫ゴム及び熱可塑性ゴムの硬さ試験方法」に従ってタイプAデュロメーターにより、新品、熱老化後の試験片のHs(硬度)をそれぞれ測定した(測定温度23℃±2℃)。
熱老化前、熱老化後の各加硫ゴムシート(加硫ゴム組成物)の試験片(20mm×20mm×2mm)について、トルエンに25℃で24時間浸漬し、浸漬前後の体積変化(Swell(%))をそれぞれ測定した。
各試験用タイヤを国産FF車に装着し、走行距離8000km後のタイヤトレッド部の溝深さを測定し、タイヤ溝深さが1mm減るときの走行距離を算出し、基準比較例を100とした時の指数で表示した(耐摩耗性指数)。指数が大きいほど、タイヤ溝深さが1mm減るときの走行距離が長く、耐摩耗性に優れることを示す。
Claims (7)
- ゴム成分100質量%中のスチレンブタジエンゴムの含有量が10質量%以上、ブタジエンゴムの含有量が10質量%以上であり、
チッ素吸着比表面積が120m2/g以上のカーボンブラックの含有量が、ゴム成分100質量部に対して、45質量部以上であり、かつ
以下の熱老化試験の熱老化前、熱老化後の加硫ゴム組成物について、以下のゴムの硬さ(Hs)の測定、架橋度(Swell)の測定を用いて測定する熱老化前後の硬度変化絶対値|ΔHs|が下記式(1)、熱老化前後のSwell変化絶対値|ΔSwell|が下記式(2)を満たすトレッド用ゴム組成物。
|ΔHs|≦3.0 (1)
|ΔSwell|≦20% (2)
<熱老化試験>
熱老化前の加硫ゴム組成物について、JIS K6257:2010に準じて熱老化(100℃、96時間)を実施し、熱老化後の加硫ゴム組成物を得る。
(ゴムの硬さ(Hs)の測定)
熱老化前、熱老化後の加硫ゴム組成物からなる各試験片について、JIS K6253の「加硫ゴム及び熱可塑性ゴムの硬さ試験方法」に従ってタイプAデュロメーターにより、熱老化前、熱老化後の試験片のHs(硬度)を測定する(測定温度23℃±2℃)。
(架橋度(Swell)の測定)
熱老化前、熱老化後の加硫ゴム組成物の各試験片(20mm×20mm×2mm)について、トルエンに25℃で24時間浸漬し、浸漬前後の体積変化(Swell(%))を測定する。 - ゴム成分100質量%中のスチレンブタジエンゴムの含有量が10質量%以上、ブタジエンゴムの含有量が10質量%以上であり、
イソプレン系ゴムを含み、かつ
以下の熱老化試験の熱老化前、熱老化後の加硫ゴム組成物について、以下のゴムの硬さ(Hs)の測定、架橋度(Swell)の測定を用いて測定する熱老化前後の硬度変化絶対値|ΔHs|が下記式(3)、熱老化前後のSwell変化絶対値|ΔSwell|が下記式(4)を満たすトレッド用ゴム組成物。
|ΔHs|≦2.5 (3)
|ΔSwell|≦19% (4)
<熱老化試験>
熱老化前の加硫ゴム組成物について、JIS K6257:2010に準じて熱老化(100℃、96時間)を実施し、熱老化後の加硫ゴム組成物を得る。
(ゴムの硬さ(Hs)の測定)
熱老化前、熱老化後の加硫ゴム組成物からなる各試験片について、JIS K6253の「加硫ゴム及び熱可塑性ゴムの硬さ試験方法」に従ってタイプAデュロメーターにより、熱老化前、熱老化後の試験片のHs(硬度)を測定する(測定温度23℃±2℃)。
(架橋度(Swell)の測定)
熱老化前、熱老化後の加硫ゴム組成物の各試験片(20mm×20mm×2mm)について、トルエンに25℃で24時間浸漬し、浸漬前後の体積変化(Swell(%))を測定する。 - ゴム成分100質量%中のスチレンブタジエンゴムの含有量が10質量%以上、ブタジエンゴムの含有量が10質量%以上であり、
芳香族炭化水素と脂肪族炭化水素との共重合体を含み、かつ
以下の熱老化試験の熱老化前、熱老化後の加硫ゴム組成物について、以下のゴムの硬さ(Hs)の測定、架橋度(Swell)の測定を用いて測定する熱老化前後の硬度変化絶対値|ΔHs|が下記式(1)、熱老化前後のSwell変化絶対値|ΔSwell|が下記式(2)を満たすトレッド用ゴム組成物。
|ΔHs|≦3.0 (1)
|ΔSwell|≦20% (2)
<熱老化試験>
熱老化前の加硫ゴム組成物について、JIS K6257:2010に準じて熱老化(100℃、96時間)を実施し、熱老化後の加硫ゴム組成物を得る。
(ゴムの硬さ(Hs)の測定)
熱老化前、熱老化後の加硫ゴム組成物からなる各試験片について、JIS K6253の「加硫ゴム及び熱可塑性ゴムの硬さ試験方法」に従ってタイプAデュロメーターにより、熱老化前、熱老化後の試験片のHs(硬度)を測定する(測定温度23℃±2℃)。
(架橋度(Swell)の測定)
熱老化前、熱老化後の加硫ゴム組成物の各試験片(20mm×20mm×2mm)について、トルエンに25℃で24時間浸漬し、浸漬前後の体積変化(Swell(%))を測定する。 - 硫黄と、硫黄以外の架橋剤とを含む請求項1~3のいずれかに記載のトレッド用ゴム組成物。
- 硫黄以外の架橋剤のみを含む請求項1~3のいずれかに記載のトレッド用ゴム組成物。
- ゴム成分100質量%中のイソプレン系ゴムの含有量が25質量%以上である請求項1~5のいずれかに記載のトレッド用ゴム組成物。
- 請求項1~6のいずれかに記載のゴム組成物で構成されたトレッドを有する空気入りタイヤ。
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