JP7392711B2 - タイヤ用ゴム組成物及び空気入りタイヤ - Google Patents
タイヤ用ゴム組成物及び空気入りタイヤ Download PDFInfo
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- JP7392711B2 JP7392711B2 JP2021504001A JP2021504001A JP7392711B2 JP 7392711 B2 JP7392711 B2 JP 7392711B2 JP 2021504001 A JP2021504001 A JP 2021504001A JP 2021504001 A JP2021504001 A JP 2021504001A JP 7392711 B2 JP7392711 B2 JP 7392711B2
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- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- CXENHBSYCFFKJS-UHFFFAOYSA-N (3E,6E)-3,7,11-Trimethyl-1,3,6,10-dodecatetraene Natural products CC(C)=CCCC(C)=CCC=C(C)C=C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 claims description 32
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 32
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- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- 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
- 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 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
- 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
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread 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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0041—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers
- B60C11/005—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers with cap and base layers
-
- 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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/03—Tread patterns
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
- C08L45/02—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers of coumarone-indene polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
- B60C2011/0016—Physical properties or dimensions
- B60C2011/0025—Modulus or tan delta
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- 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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
- B60C2011/0016—Physical properties or dimensions
- B60C2011/0033—Thickness of the tread
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- 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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/03—Tread patterns
- B60C2011/0337—Tread patterns characterised by particular design features of the pattern
- B60C2011/0339—Grooves
- B60C2011/0341—Circumferential grooves
- B60C2011/0353—Circumferential grooves characterised by width
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- 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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/03—Tread patterns
- B60C2011/0337—Tread patterns characterised by particular design features of the pattern
- B60C2011/0339—Grooves
- B60C2011/0341—Circumferential grooves
- B60C2011/0355—Circumferential grooves characterised by depth
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
ピーク位置のtanδ/半値幅≧0.025 (1)
0.025≦ピーク位置のtanδ/半値幅≦0.100
0.027≦ピーク位置のtanδ/半値幅≦0.080
ファルネセン系ポリマーを含むことが好ましい。
クマロンインデン樹脂を含むことが好ましい。
前記タイヤは、トレッドの総厚みの最大値が5mm以上であることが好ましい。
前記タイヤは、トレッドの主溝深さが8.0~13.0mmであることが好ましい。
前記タイヤは、主溝底部におけるサブトレッド総厚みの最大値が0.5~2.0mmであることが好ましい。
ピーク位置のtanδ/半値幅≧0.025 (1)
「ピーク位置のtanδ(tanδの温度分布曲線における最大tanδ値)」/「半値幅(該最大tanδ値の1/2のtanδ値になる高温側の温度-該最大tanδ値の1/2のtanδ値になる低温側の温度(FWHM))」(単位:1/℃)が下限以上であると、良好なウェットグリップ性能、低燃費性の総合性能が得られる傾向がある。ピーク位置のtanδ/半値幅≧0.027が好ましく、tanδ/半値幅≧0.029がより好ましく、tanδ/半値幅≧0.030が更に好ましい。上限は特に限定されないが、ピーク位置のtanδ/半値幅≦0.100が好ましく、ピーク位置のtanδ/半値幅≦0.080がより好ましく、ピーク位置のtanδ/半値幅≦0.060が更に好ましい。
tanδの温度分布曲線のピーク位置のtanδ/tanδの温度分布曲線の半値幅が式(1)を満たす場合、ピーク位置のtanδが比較的高い、tanδの温度分布曲線の波形が比較的シャープになる、等の物性を有しているため、高いtanピークによりウェットグリップ性能が向上する、シャープな波形によりウェットグリップ性能、低燃費性が改善される、等の作用効果が得られると推察される。従って、前記ゴム組成物では、ウェットグリップ性能、低燃費性の総合性能が顕著に改善されるものと推察される。
ピーク位置のtanδ≧0.80 (2)
ピーク位置のtanδが下限以上であると、良好なウェットグリップ性能が得られる傾向がある。ピーク位置のtanδ≧1.00がより好ましく、ピーク位置のtanδ≧1.05が更に好ましく、ピーク位置のtanδ≧1.10が特に好ましい。上限は特に限定されず、tanδは大きいほど望ましい。
半値幅≦50℃ (3)
半値幅が上限以下であると、良好な低燃費性が得られる傾向がある。半値幅≦48℃がより好ましく、半値幅≦46℃が更に好ましく、半値幅≦44℃が特に好ましい。下限は特に限定されず、半値幅は小さいほど望ましい。
-30℃≦tanδのピーク温度≦10℃ (4)
上記範囲内であると、良好なウェットグリップ性能、低燃費性の総合性能が得られる傾向がある。-25℃≦tanδのピーク温度≦5℃がより好ましく、-20℃≦tanδのピーク温度≦0℃が更に好ましい。
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、カーボンブラックの窒素吸着比表面積は、ASTM D4820-93に従って測定され、DBP吸収量は、ASTM D2414-93に従って測定される。
なお、シリカのN2SAは、ASTM D3037-93に準じてBET法で測定される値である。
シランカップリング剤としては、特に限定されず、例えば、ビス(3-トリエトキシシリルプロピル)テトラスルフィド、ビス(2-トリエトキシシリルエチル)テトラスルフィド、ビス(4-トリエトキシシリルブチル)テトラスルフィド、ビス(3-トリメトキシシリルプロピル)テトラスルフィド、ビス(2-トリメトキシシリルエチル)テトラスルフィド、ビス(2-トリエトキシシリルエチル)トリスルフィド、ビス(4-トリメトキシシリルブチル)トリスルフィド、ビス(3-トリエトキシシリルプロピル)ジスルフィド、ビス(2-トリエトキシシリルエチル)ジスルフィド、ビス(4-トリエトキシシリルブチル)ジスルフィド、ビス(3-トリメトキシシリルプロピル)ジスルフィド、ビス(2-トリメトキシシリルエチル)ジスルフィド、ビス(4-トリメトキシシリルブチル)ジスルフィド、3-トリメトキシシリルプロピル-N,N-ジメチルチオカルバモイルテトラスルフィド、2-トリエトキシシリルエチル-N,N-ジメチルチオカルバモイルテトラスルフィド、3-トリエトキシシリルプロピルメタクリレートモノスルフィド、などのスルフィド系、3-メルカプトプロピルトリメトキシシラン、2-メルカプトエチルトリエトキシシラン、Momentive社製のNXT、NXT-Zなどのメルカプト系、ビニルトリエトキシシラン、ビニルトリメトキシシランなどのビニル系、3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシランなどのアミノ系、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、などのグリシドキシ系、3-ニトロプロピルトリメトキシシラン、3-ニトロプロピルトリエトキシシランなどのニトロ系、3-クロロプロピルトリメトキシシラン、3-クロロプロピルトリエトキシシランなどのクロロ系などがあげられる。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。なかでも、本発明の効果がより良好に得られるという理由から、スルフィド系、メルカプト系が好ましい。
なお、Tgは、JIS-K7121:1987に従い、ティー・エイ・インスツルメント・ジャパン社製の示差走査熱量計(Q200)を用いて、昇温速度10℃/分の条件で測定した値である。
なお、溶融粘度は、ブルックフィールド型粘度計(BROOKFIELD ENGINEERING LABS.INC.製)を用いて、38℃で測定した値である。
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。
なお、OH価とは、樹脂1gをアセチル化するとき、水酸基と結合した酢酸を中和するのに要する水酸化カリウムの量をミリグラム数で表したものであり、電位差滴定法(JIS K 0070:1992)により測定した値である。
なお、軟化点は、JIS K 6220-1:2001に規定される軟化点を環球式軟化点測定装置で測定し、球が降下した温度である。
ポリテルペンは、テルペン化合物を重合して得られる樹脂及びそれらの水素添加物である。テルペン化合物は、(C5H8)nの組成で表される炭化水素及びその含酸素誘導体で、モノテルペン(C10H16)、セスキテルペン(C15H24)、ジテルペン(C20H32)などに分類されるテルペンを基本骨格とする化合物であり、例えば、α-ピネン、β-ピネン、ジペンテン、リモネン、ミルセン、アロオシメン、オシメン、α-フェランドレン、α-テルピネン、γ-テルピネン、テルピノレン、1,8-シネオール、1,4-シネオール、α-テルピネオール、β-テルピネオール、γ-テルピネオールなどが挙げられる。
テルペンフェノールとしては、上記テルペン化合物とフェノール系化合物とを共重合した樹脂、及び該樹脂に水素添加処理した樹脂が挙げられ、具体的には、上記テルペン化合物、フェノール系化合物及びホルマリンを縮合させた樹脂が挙げられる。なお、フェノール系化合物としては、例えば、フェノール、ビスフェノールA、クレゾール、キシレノールなどが挙げられる。
芳香族変性テルペン樹脂としては、テルペン樹脂を芳香族化合物で変性して得られる樹脂、及び該樹脂に水素添加処理した樹脂が挙げられる。なお、芳香族化合物としては、芳香環を有する化合物であれば特に限定されないが、例えば、フェノール、アルキルフェノール、アルコキシフェノール、不飽和炭化水素基含有フェノールなどのフェノール化合物;ナフトール、アルキルナフトール、アルコキシナフトール、不飽和炭化水素基含有ナフトールなどのナフトール化合物;スチレン、アルキルスチレン、アルコキシスチレン、不飽和炭化水素基含有スチレンなどのスチレン誘導体;クマロン、インデンなどが挙げられる。
また、上記アクリル系樹脂は、水酸基、カルボキシル基、シラノール基等を有していてよい。
オイルの含有量は、ゴム成分100質量部に対して、ウェットグリップ性能等の観点から、好ましくは1.0質量部以上、より好ましくは2.0質量部以上、更に好ましくは2.5質量部以上である。低燃費性の観点から、上限は、好ましくは10.0質量部以下、より好ましくは7.0質量部以下、更に好ましくは5.0質量部以下である。
なお、オイルの含有量には、ゴム(油展ゴム)に含まれるオイルの量も含まれる。
ゴム成分100質量部に対するアミド化合物の含有量は、好ましくは0.1質量部以上、より好ましくは1.0質量部以上であり、また、好ましくは10.0質量部以下、より好ましくは7.0質量部以下、更に好ましくは5.0質量部以下である。上記範囲内にすることで、ウェットグリップ性能、低燃費性の総合性能が顕著に改善される傾向がある。なお、本明細書において、アミド化合物として、アミド化合物以外に脂肪酸金属塩を含む混合物を用いる場合、アミド化合物の含有量は、該脂肪酸金属塩も含む量を意味する。
脂肪酸金属塩を構成する金属としては、カリウム、ナトリウム、マグネシウム、カルシウム、バリウム、亜鉛、ニッケル、モリブデンなどが挙げられる。なかでも、カルシウム、亜鉛などのアルカリ土類金属が好ましく、カルシウムがより好ましい。
ワックスの含有量は、氷上制動性能、破壊強度の総合性能の観点から、ゴム成分100質量部に対して、好ましくは0.5~20質量部、より好ましくは1.0~10質量部である。
老化防止剤の含有量は、氷上制動性能、破壊強度の総合性能の観点から、ゴム成分100質量部に対して、好ましくは1~10質量部以上、より好ましくは2~7質量部以上である。
硫黄の含有量は、ウェットグリップ性能、低燃費性の総合性能の観点から、ゴム成分100質量部に対して、好ましくは0.1~10.0質量部、より好ましくは0.5~5.0質量部、更に好ましく0.7~3.0質量部である。
加硫促進剤の含有量は、ウェットグリップ性能、低燃費性の総合性能の観点から、ゴム成分100質量部に対して、好ましくは0.3~7.0質量部、より好ましくは1.0~5.0、更に好ましくは1.5~4.5質量部である。
ベース練り工程の混練条件は、混練機の種類、回転数等に応じて適宜選択すればよいが、混練温度は、通常50~200℃、好ましくは80~190℃であり、混練時間は、通常30秒~30分、好ましくは1~30分である。
すなわち、前記成分を配合したゴム組成物を、未加硫の段階でトレッドなどの各タイヤ部材の形状にあわせて押出し加工し、他のタイヤ部材とともに、タイヤ成型機上にて通常の方法で成形することにより、未加硫タイヤを形成する。この未加硫タイヤを加硫機中で加熱加圧することによりタイヤを得る。
予め、0.18ミリモルのバーサチック酸ネオジムを含有するシクロヘキサン溶液、3.6ミリモルのメチルアルモキサンを含有するトルエン溶液、6.7ミリモルの水素化ジイソブチルアルミニウムを含有するトルエン溶液、及び、0.36ミリモルのトリメチルシリルアイオダイドを含有するトルエン溶液と1,3-ブタジエン0.90ミリモルを30℃で60分間反応熟成させて得られる触媒組成物(ヨウ素原子/ランタノイド含有化合物(モル比)=2.0)を得た。続いて、シクロヘキサン2.4kg、1,3-ブタジエン300gを窒素置換された5Lオートクレーブに投入した。そして、上記触媒組成物を上記オートクレーブに投入し、30℃で2時間、重合反応させて、重合体溶液を得た。なお、投入した1,3-ブタジエンの反応転化率は、ほぼ100%であった。
変性共役ジエン系重合体(以下、「変性重合体」とも称する。)を得るために、合成例1の共役ジエン系重合体の重合体溶液に次の処理を行った。温度30℃に保持した重合体溶液に、1.71ミリモルの3-グリシドキシプロピルトリメトキシシランを含有するトルエン溶液を添加し、30分間反応させて反応溶液を得た。それから、この反応溶液に1.71ミリモルの3-アミノプロピルトリエトキシシランを含有するトルエン溶液を添加し、30分間撹拌した。続いて、この反応溶液に1.28ミリモルのテトライソプロピルチタネートを含有するトルエン溶液を添加し、30分間撹拌した。その後、重合反応を停止させるため、2,4-ジ-tert-ブチル-p-クレゾールを1.5g含むメタノール溶液を添加して、この溶液を変性重合体溶液とした。収量は2.5kgであった。続いて、この変性重合体溶液に、水酸化ナトリウムによりpH10に調整した水溶液20Lを添加し、110℃で2時間、脱溶媒とともに縮合反応させた。その後、110℃のロールで乾燥して、得られた乾燥物を変性重合体(変性BR)とした。
[シス-1,4-結合量、1,2-ビニル結合量]
シス-1,4-結合の含量、及び1,2-ビニル結合の含量は、1H-NMR分析及び13C-NMR分析により測定を行った。NMR分析には、日本電子社製の商品名「EX-270」を使用した。具体的には、1H-NMR分析としては、5.30~5.50ppm(1,4-結合)、及び4.80-5.01ppm(1,2-結合)におけるシグナル強度から、重合体中の1,4-結合と1,2-結合の比を算出した。更に、13C-NMR分析としては、27.5ppm(シス-1,4-結合)、及び32.8ppm(トランス-1,4-結合)におけるシグナル強度から、重合体中のシス-1,4-結合とトランス-1,4-結合の比を算出した。これらの算出した値の比率を算出し、シス-1,4-結合量(質量%)及び1,2-ビニル結合量(質量%)とした。
JIS K 6300に準じて、Lローターを使用して、予熱1分、ローター作動時間4分、温度125℃の条件で測定した。
ゲルパーミエーションクロマトグラフ(商品名;HLC-8120GPC、東ソー社製)を使用し、検知器として、示差屈折計を用いて、以下の条件で測定し、標準ポリスチレン換算値として算出した。
カラム ;商品名「GMHHXL」、(東ソー社製)2本
カラム温度 ;40℃
移動相 ;テトラヒドロフラン、流速 ;1.0ml/分
サンプル濃度;10mg/20ml
圧力3.5lb/in2、温度50℃で重合体を1/4インチオリフィスに通して押し出すことにより測定した。定常状態にするため、10分間放置後、押し出し速度を測定し、その測定値を毎分のミリグラム数(mg/分)で表示した。
90℃の恒温槽で2日間保存した後のムーニー粘度(ML1+4,125℃)を測定し、下記式により算出した値である。なお、値が小さいほど経時安定性が良好である。
式:[90℃の恒温槽で2日間保存した後のムーニー粘度(ML1+4,125℃)]-[合成直後に測定したムーニー粘度(ML1+4,125℃)]
ガラス転移温度は、JIS K 7121に準じて、ティー・エイ・インスツルメント・ジャパン社製の示差走査熱量計(Q200)を用いて昇温速度10℃/分で昇温しながら測定することにより、ガラス転移開始温度として求めた。
NR:TSR20(SP値8.1)
SBR:日本ゼオン(株)製のNipol NS612(S-SBR、SP値8.5)
変性BR:製造例1で合成したNd系変性BR
カーボンブラック:三菱化学(株)製のシーストN220(N2SA:111m2/g、DBP吸収量:115ml/100g)
シリカ:エボニックデグッサ社製のウラトシルVN3(N2SA172m2/g)
シランカップリング剤:エボニックデグッサ社製のSi266
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)
クマロンインデン樹脂:日塗化学(株)製のニットレジン クマロン V-120(軟化点120℃、水酸基価30mgKOH/g、SP値9.1)
ファルネセン系ポリマー:クラレ製のL-FBR-742(液状ファルネセンブタジエン共重合体、SP値8.1)
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-フェニル-N’-(1,3-ジメチルブチル)-p-フェニレンジアミン)(6PPD)
老化防止剤RD:川口化学工業(株)製のアンテージRD(2,2,4-トリメチル-1,2-ジヒドロキノリンの重合体)
ステアリン酸:日油(株)製の桐
アミド化合物:ストラクトール社製のWB16(脂肪酸カルシウム、脂肪酸アミド及び脂肪酸アミドエステルの混合物、灰分割合4.5%)
酸化亜鉛:三井金属鉱業(株)製の酸化亜鉛2種
硫黄:細井化学工業(株)製のHK200-5(5%オイル含有粉末硫黄)
加硫促進剤CZ:大内新興化学工業(株)製のノクセラーCZ(N-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド)
加硫促進剤DPG:大内新興化学工業(株)製のノクセラーD(ジフェニルグアニジン)
(混合物の製造)
各表の混合物に示す配合内容に従い、(株)神戸製鋼所製の1.7Lバンバリーミキサーを用いて、ゴム成分(NR、SBR)、ポリマー成分(クマロンインデン樹脂、ファルネセン系ポリマー)を約150℃の条件下で5分間混練りし、各混合物を得た。
各試験用タイヤから切り出したトレッドゴム(加硫後)について、(株)岩本製作所製の粘弾性スペクトロメータを用い、周波数10Hz、初期歪10%、振幅±0.25%及び昇温速度2℃/minの条件下で、-120℃から70℃までの温度範囲で、tanδの温度分布曲線を測定した。そして、得られたtanδの温度分布曲線を基に、ピーク位置のtanδ、半値幅、ピーク位置のtanδ/半値幅を測定した。なお、図3に、代表例として、実施例1-1、比較例1-1~1-4のtanδの温度分布曲線を示し、実施例1-1のピーク位置のtanδ、半値幅を記載した。
試験用タイヤを車両(国産FF2000cc)の全輪に装着して、湿潤アスファルト路面にて初速度100km/hからの制動距離を求め、基準比較例を100としたときの指数で表示した(ウェットグリップ性能指数)。指数が大きいほど、制動距離が短く、ウェットグリップ性能に優れることを示す。
転がり抵抗試験機を用い、試験タイヤを、リム(15×6JJ)、内圧(230kPa)、荷重(3.43kN)、速度(80km/h)で走行させたときの転がり抵抗を測定し、基準比較例を100とした時の指数で表示した。指数は大きい方が良好(低燃費性)である。
4 トレッド
14 カーカス
16 ベルト
18 バンド
20 インナーライナー
24 トレッド面
26 溝
28 ベース層
30 キャップ層
42 主溝
42a 溝底面
P トレッド面24上の点
T トレッド4の厚み
Ps 溝底面42a上の点
Ts 主溝底部におけるサブトレッド総厚み
D 主溝深さ
Claims (14)
- 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、スチレンブタジエンゴムの含有量が35質量%以上であり、
シリカを含み、
tanδの温度分布曲線におけるピーク位置のtanδ及び半値幅が下記式(1)を満たすタイヤ用ゴム組成物。
0.025≦ピーク位置のtanδ/半値幅≦0.080 (1) - 下記式を満たす請求項1記載のタイヤ用ゴム組成物。
0.025≦ピーク位置のtanδ/半値幅≦0.060 - 下記式を満たす請求項1記載のタイヤ用ゴム組成物。
0.027≦ピーク位置のtanδ/半値幅≦0.060 - ゴム成分100質量部に対するシリカの含有量が60質量部以上である請求項1~3のいずれかに記載のタイヤ用ゴム組成物。
- ファルネセン系ポリマーを含む請求項1~4のいずれかに記載のタイヤ用ゴム組成物。
- クマロンインデン樹脂を含む請求項1~5のいずれかに記載のタイヤ用ゴム組成物。
- ファルネセン系ポリマー及びクマロンインデン樹脂を含む請求項1~6のいずれかに記載のタイヤ用ゴム組成物。
- ゴム成分100質量部に対するカーボンブラックの含有量が10~30質量部である請求項1~7のいずれかに記載のタイヤ用ゴム組成物。
- イソプレン系ゴム、スチレンブタジエンゴム、ポリマー成分1、及びポリマー成分2を含み、
前記イソプレン系ゴムと前記ポリマー成分1との溶解度パラメーターの差が1.5以下であり、
前記スチレンブタジエンゴムと前記ポリマー成分2との溶解度パラメーターの差が1.5以下である請求項1~8のいずれかに記載のタイヤ用ゴム組成物。 - 請求項1~9のいずれかに記載のゴム組成物を用いた空気入りタイヤ。
- トレッドの総厚みの最大値が5mm以上である請求項10記載の空気入りタイヤ。
- トレッドの主溝深さが8.0~13.0mmである請求項10又は11記載の空気入りタイヤ。
- トレッドの主溝幅が6~16mmである請求項10~12のいずれかに記載の空気入りタイヤ。
- 主溝底部におけるサブトレッド総厚みの最大値が0.5~2.0mmである請求項10~13のいずれかに記載の空気入りタイヤ。
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EP3812174B1 (en) | 2023-11-01 |
JPWO2020179582A1 (ja) | 2021-12-23 |
WO2020179582A1 (ja) | 2020-09-10 |
EP3812174A1 (en) | 2021-04-28 |
US20230202235A1 (en) | 2023-06-29 |
CN112638666B (zh) | 2023-01-10 |
EP3812174A4 (en) | 2021-09-22 |
CN112638666A (zh) | 2021-04-09 |
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