EP3625288A1 - Schwefelvernetzte kautschukmischung für fahrzeugreifen enthaltend carbon nanotubes (cnt), fahrzeugreifen, der die schwefelvernetzte kautschukmischung aufweist, sowie verfahren zur herstellung der schwefelvernetzten kautschukmischung enthaltend cnt - Google Patents
Schwefelvernetzte kautschukmischung für fahrzeugreifen enthaltend carbon nanotubes (cnt), fahrzeugreifen, der die schwefelvernetzte kautschukmischung aufweist, sowie verfahren zur herstellung der schwefelvernetzten kautschukmischung enthaltend cntInfo
- Publication number
- EP3625288A1 EP3625288A1 EP18713170.1A EP18713170A EP3625288A1 EP 3625288 A1 EP3625288 A1 EP 3625288A1 EP 18713170 A EP18713170 A EP 18713170A EP 3625288 A1 EP3625288 A1 EP 3625288A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cnt
- sulfur
- rubber mixture
- rubber
- phr
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 141
- 239000005060 rubber Substances 0.000 title claims abstract description 141
- 239000000203 mixture Substances 0.000 title claims abstract description 130
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 93
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 34
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 54
- 229920001194 natural rubber Polymers 0.000 claims description 49
- 239000004014 plasticizer Substances 0.000 claims description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 239000012763 reinforcing filler Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000004073 vulcanization Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000010059 sulfur vulcanization Methods 0.000 claims description 6
- 230000003712 anti-aging effect Effects 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 41
- 229920003052 natural elastomer Polymers 0.000 description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 17
- 239000005062 Polybutadiene Substances 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 14
- 229920003048 styrene butadiene rubber Polymers 0.000 description 14
- 102100023116 Sodium/nucleoside cotransporter 1 Human genes 0.000 description 12
- 101710123675 Sodium/nucleoside cotransporter 1 Proteins 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 12
- 235000019241 carbon black Nutrition 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 10
- 229920002857 polybutadiene Polymers 0.000 description 10
- 239000000945 filler Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- -1 aminosiloxane Chemical class 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920003051 synthetic elastomer Polymers 0.000 description 6
- 229920003244 diene elastomer Polymers 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 4
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 229960002447 thiram Drugs 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000002019 disulfides Chemical class 0.000 description 3
- 229920005555 halobutyl Polymers 0.000 description 3
- 125000004968 halobutyl group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000008117 stearic acid Substances 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
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 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
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000013032 Hydrocarbon resin Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 229920003211 cis-1,4-polyisoprene Polymers 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920006270 hydrocarbon resin Polymers 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WGACMNAUEGCUHG-VYBOCCTBSA-N (2s)-2-[[(2s)-2-[[(2s)-2-acetamidopropanoyl]amino]propanoyl]amino]-n-[(2s)-6-amino-1-[[(2s)-1-[(2s)-2-[[(2s)-1-[[(2s)-5-amino-1-[[(2s)-1-[[(2s)-1-[[(2s)-6-amino-1-[[(2s)-1-amino-3-(4-hydroxyphenyl)-1-oxopropan-2-yl]amino]-1-oxohexan-2-yl]amino]-3-hydroxy- Chemical compound CC(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCCCN)C(=O)N[C@H](C(N)=O)CC1=CC=C(O)C=C1 WGACMNAUEGCUHG-VYBOCCTBSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- PIBIAJQNHWMGTD-UHFFFAOYSA-N 1-n,3-n-bis(4-methylphenyl)benzene-1,3-diamine Chemical compound C1=CC(C)=CC=C1NC1=CC=CC(NC=2C=CC(C)=CC=2)=C1 PIBIAJQNHWMGTD-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- XODFSNXVWMJCOU-UHFFFAOYSA-N 3-trimethoxysilylpropyl thiocyanate Chemical compound CO[Si](OC)(OC)CCCSC#N XODFSNXVWMJCOU-UHFFFAOYSA-N 0.000 description 1
- HPGLJHGYYVLNTR-UHFFFAOYSA-N 4-n-(2-methylphenyl)-1-n-(4-methylphenyl)benzene-1,4-diamine Chemical compound C1=CC(C)=CC=C1NC(C=C1)=CC=C1NC1=CC=CC=C1C HPGLJHGYYVLNTR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- TXLINXBIWJYFNR-UHFFFAOYSA-N 4-phenylpyridine-2-carbonitrile Chemical compound C1=NC(C#N)=CC(C=2C=CC=CC=2)=C1 TXLINXBIWJYFNR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- RBMRMPXCJOZCRH-UHFFFAOYSA-O NCCC[S+]=S(O)(O)=O Chemical compound NCCC[S+]=S(O)(O)=O RBMRMPXCJOZCRH-UHFFFAOYSA-O 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- IKFVTPMSIBDKGU-UHFFFAOYSA-L P(=S)(SCl)(OCl)[O-].[Zn+2].ClSP(=S)(OCl)[O-] Chemical compound P(=S)(SCl)(OCl)[O-].[Zn+2].ClSP(=S)(OCl)[O-] IKFVTPMSIBDKGU-UHFFFAOYSA-L 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229920000026 Si 363 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical group NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- QQBWQAURZPGDOG-UHFFFAOYSA-N ethyl hexanoate;zinc Chemical compound [Zn].CCCCCC(=O)OCC QQBWQAURZPGDOG-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 108010074544 myelin peptide amide-12 Proteins 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000012721 stereospecific polymerization Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- GWIKYPMLNBTJHR-UHFFFAOYSA-M thiosulfonate group Chemical group S(=S)(=O)[O-] GWIKYPMLNBTJHR-UHFFFAOYSA-M 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical group 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
- 239000012991 xanthate Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing 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
-
- 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
- B60C1/0025—Compositions of the sidewalls
-
- 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
- B60C19/00—Tyre parts or constructions not otherwise provided for
- B60C19/08—Electric-charge-dissipating arrangements
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- 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
- C08L2310/00—Masterbatches
Definitions
- Sulfur-crosslinked rubber mixture for vehicle tires comprising carbon nanotubes (CNT), vehicle tires having the sulfur-crosslinked rubber mixture, and processes for producing the sulfur-crosslinked rubbers
- the invention relates to a sulfur-crosslinked rubber mixture for vehicle tires comprising carbon nanotubes (CNT), a vehicle tire having the sulfur-crosslinked rubber mixture, and a process for preparing the sulfur-crosslinked rubber mixture containing CNT.
- CNT carbon nanotubes
- the rubber compositions of the individual components of vehicle tires, in particular the composition of the tread, to a large extent determine their driving characteristics.
- WO 2012/080160 A1 discloses a rubber compound for treads of vehicle tires, which comprises a masterbatch of carbon nanotubes (CNT;
- Carbon nanotube) in ESBR emulsion-polymerized styrene-butadiene rubber
- ESBR emulsion-polymerized styrene-butadiene rubber
- the invention is based on the prior art based on the object to provide a sulfur-crosslinked rubber mixture containing carbon nanotubes (CNT), which is characterized by optimized electrical conductivity properties, the other properties, in particular the abrasion behavior remain at the same level or even improved become.
- This object is achieved in that the CNT are predispersed in at least one polyisoprene in the sulfur-crosslinked rubber mixture.
- Rubber composition thereby has an unexpectedly good electrical conductivity. This effect is particularly evident when compared with rubber blends containing polymer blends of styrene-butadiene rubbers and polyisoprene; in the case where the CNTs are predispersed in at least one polyisoprene (polyisoprene-CNT masterbatch), the surprisingly high electrical conductivity occurs.
- Another object underlying the present invention is to provide a vehicle tire having an improvement over the prior art in terms of conductivity.
- the vehicle tire has at least one component in a component at least one sulfur-crosslinked rubber mixture with the above-mentioned or below detailed features.
- the abrasion behavior remains at least at the same level or is also improved.
- the rubber mixture according to the invention can be used both for the cap and for the base.
- at least the cap has at least one
- sulfur-crosslinked rubber mixture is to be understood as meaning a rubber mixture which consists of a rubber final mixture (or rubber raw mixture)
- a sulfur-crosslinked rubber compound is thus a vulcanizate.
- a conductivity track is any type of rubber compound known to the person skilled in the art which is suitable for conducting the conductivity between at least two tire components and / or at least one inner tire component and the road surface or other external surfaces with which the tire in FIG Touch comes, make sure.
- the conductive sheet may be a so-called "carbon center beam” or else a strip which is in the
- vehicle tires are understood to mean pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction vehicles, truck, passenger car and two-wheeled tires.
- the rubber mixture according to the invention is also suitable for other components of
- Vehicle tires suitable such. B. in particular the, horn profile, and inner
- the rubber mixture according to the invention is also for others technical rubber articles, such as bellows, conveyor belts, air springs, straps, belts or hoses, as well as shoe soles.
- phr parts per hundred parts of rubber by weight
- the dosage of the parts by weight of the individual substances in this document is based on 100 parts by weight of the total mass of all rubbers present in the mixture, ie the at least one polyisoprene plus optionally further sulfur-vulcanizable rubbers which are added to the rubber mixture according to the invention.
- the subject of the invention is a sulfur-crosslinked one
- Carbon nanotubes Rubber mixture containing carbon nanotubes (CNT), which is also known as
- Carbon nanotubes or tubes Carbon nanotubes or tubes.
- CNT discrete carbon nanotubes
- the form factor is the quotient of the average length of the CNT divided by the
- the CNT have a
- the dimensions of the CNT are known to those skilled in the art
- the CNT have a length of 0.2 ⁇ to 1.4 ⁇ , preferably 0.5 ⁇ to 1 ⁇ , ie 200 nm to 1400 nm, preferably 500 nm to 1000 nm, on.
- the CNTs are predispersed in at least one polyisoprene. Surprisingly, only the predispersion of CNT in at least one polyisoprene results in a surprisingly high electrical conductivity.
- the CNT preferably only in at least one
- Polyisoprene are predispersed and not additionally masterbatches in the
- Rubber mixture are included, in which CNTs are predispersed in a different rubber matrix than polyisoprene.
- inventive rubber mixture are included, in which CNTs are predispersed in a different rubber matrix than polyisoprene.
- Rubber mixture does not prefer a masterbatch in which CNT are predispersed in ESBR.
- a polyisoprene-CNT masterbatch may contain other substances, such as plasticizers, s. below.
- the at least one polyisoprene may be a natural polyisoprene (NR, natural rubber) and / or a synthetic polyisoprene (IR).
- All embodiments may be both cis-1,4-polyisoprene and 3,4-polyisoprene. However, preference is given to the use of cis-1,4-polyisoprenes having an iron content of> 90% by weight. For one, such a
- NR natural rubber
- NR is such an iron-1,4-polyisoprene
- the cis-1,4-content in natural rubber is greater than 99% by weight.
- the at least one polyisoprene is at least one natural polyisoprene. This results in particularly good properties with regard to the requirements of the rubber mixture for use in at least one tire component with an excellent electrical
- Essential to the invention is that the CNT in the at least one polyisoprene
- the CNT are predispersed, i.
- the CNT are therefore present as a single, separate CNT in the at least one polyisoprene, but it can not be ruled out that even so
- the CNT can be present as a single CNT and possibly also as agglomerates. Both of the separate CNTs as well as the agglomerates can be measured by REM length and
- Diameter are determined, which reference is made at this point for details to the statements in WO 2012/080160 AI.
- an effective form factor "English, effective aspect ratio" as a quotient of the average length (arithmetic mean) and the
- Bundle diameter determined.
- the dispersion of the CNT in the at least one polyisoprene is carried out by methods known to the person skilled in the art, for example in accordance with the following
- the dispersion of CNT can be carried out by shear forces, namely z.
- CNTs may be incorporated into a rubber matrix via a prior wetting with ethanol followed by evaporation of the ethanol, such as
- the CNT and the at least one polyisoprene in which they are predispersed form a masterbatch which may contain other ingredients.
- the viscosity of the masterbatch (Mooney ML 1 + 4 at 100 ° C.) is preferably 80 to 120 MU.
- the content by weight of the CNT in the masterbatch is preferably from 0.1 to 20% by weight, based on the total amount of the masterbatch.
- the proportion of CNT in the masterbatch is 13 to 20 wt .-%, particularly preferably 14 to 18 wt .-%, in particular and for example 15 to 17 wt .-%.
- the masterbatch may, as a further constituent, in particular at least one
- the weight fraction of the plasticizer based on the total amount of the masterbatch is in this case preferably 0.1 to 20 wt .-%. According to an advantageous embodiment of the invention, it is 6 to 16 wt .-%, particularly preferably 8 to 14 wt .-%, in particular and for example 9 to 10 wt .-%.
- the proportion by weight of the CNT in the masterbatch here is also preferably 0.1 to 20% by weight, based on the total amount of the masterbatch, and according to a particularly advantageous embodiment of the invention 13 to 20% by weight, particularly preferably 14 to 18% by weight. %, in particular and for example 15 to 17 wt .-%.
- the sulfur-crosslinked rubber mixture contains, in addition to the polyisoprene in which the CNTs are predispersed, at least one further sulfur vulcanizable prior to vulcanization and thus at least one further diene rubber.
- the at least one further diene rubber is preferably selected from the group consisting of natural polyisoprene and / or synthetic polyisoprene and / or epoxidized polyisoprene and / or butadiene rubber and / or butadiene-isoprene rubber and / or solution-polymerized styrene-butadiene rubber and or emulsion-polymerized styrene-butadiene rubber and / or styrene-isoprene rubber and / or liquid rubbers having a molecular weight M w greater than 20,000 g / mol and / or halobutyl rubber and / or polynorbornene and / or isoprene-isobutylene copolymer and / or ethylene-propylene-diene rubber and / or nitrile rubber and / or chloroprene rubber and / or acrylate rubber and / or fluorinated
- nitrile rubber hydrogenated acrylonitrile-butadiene rubber
- Chloroprene rubber, butyl rubber, halobutyl rubber or ethylene-propylene-diene rubber are used in the manufacture of technical rubber articles such as straps, belts and hoses, and / or shoe soles.
- the rubber compound is particularly suitable for vehicle tires, and it can be used in principle in any component, such as in particular the tread, the
- the diene rubber is preferably selected from the group consisting of synthetic polyisoprene (IR) and natural polyisoprene (NR) and styrene-butadiene rubber (SBR) and polybutadiene (BR) and butyl rubber (HR) and
- the diene rubber is particularly preferably selected from the group consisting of synthetic polyisoprene (IR) and natural polyisoprene (NR) and styrene-butadiene rubber (SBR) and polybutadiene (BR),
- Polybutadiene may be any of the types known to those skilled in the art. These include u.a. the so-called high-cis and low-cis types, wherein polybutadiene with an eis content greater than or equal to 90 wt .-% as high-cis type and polybutadiene with an eis content less than 90 wt .-% as low cis type is called.
- a low-cis polybutadiene is e.g. Li-BR (lithium-catalyzed butadiene rubber) with a cis content of 20 to 50 wt .-%. With a high-cis BR will be particularly good
- the employed polybutadiene (s) can be modified with and
- the modification may be those having hydroxy groups and / or ethoxy groups and / or epoxy groups and / or siloxane groups and / or amino groups and / or aminosiloxane and / or carboxy groups and / or
- Phthalocyanine groups and / or silane-sulfide groups are also known to the expert person, modifications, as well
- Functionalizations referred to, in question. Part of such functionalizations may be metal atoms.
- styrene-butadiene rubber styrene-butadiene copolymer
- SSBR solution-polymerized styrene-butadiene rubber
- ESBR emulsion-polymerized styrene-butadiene rubber
- SSBR styrene-butadiene rubber
- ESBR emulsion-polymerized styrene-butadiene rubber
- the styrene-butadiene copolymer used can be end-group-modified with the modifications and functionalizations mentioned above for the polybutadiene and / or be functionalized along the polymer chains.
- the rubber mixture contains at least one further reinforcing filler, wherein the ratio of further reinforcing fillers to CNT 1000 is from 1 to 2 to 1.
- the ratio is 200 to 1 to 2 to 1, most preferably 80 to 1 to 2 to 1.
- the amount of the at least one further reinforcing filler is preferably from 0.1 to 250 phr, more preferably from 20 to 250 phr, most preferably from 20 to 150 phr.
- the further reinforcing filler is preferably at least one carbon black and / or at least one silica.
- the rubber mixture contains 0.1 to 250 phr, preferably 2 to 200 phr, more preferably 10 to 100 phr, again preferably 20 to 80 phr of at least one carbon black.
- carbon black which has an iodine adsorption number according to ASTM D 1510 of 20 to 180 g / kg, more preferably 30 to 140 g / kg, and a DBP number according to ASTM D 2414 of 30 to 200 ml / 100 g 90 to 180 ml / 100g, more preferably 110 to 180 ml / 100g.
- a particularly suitable carbon black in the context of the present invention is, for example, a carbon black of the
- ASTM type N339 with an iodine adsorption number of 90 g / kg and a DBP number of 120 ml / 100g. This is for use in vehicle tires, especially in
- the rubber mixture contains 0.1 to 30 phr at least one silicic acid, preferably 5 to 30 phr of at least one silica. It can therefore also be a so-called partial silica mixture.
- silica and silica "are used synonymously in the context of the present invention.
- the silicas may be the silicas known to those skilled in the art which are suitable as a filler for tire rubber mixtures. However, it is particularly preferred if a finely divided, precipitated silica is used which has a nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) of 35 to 350 m 2 / g, preferably from 35 to 260 m 2 / g, more preferably from 70 to 235 m 2 / g and most preferably from 70 to 205 m 2 / g, and a CTAB surface (according to ASTM D 3765) from 30 to 400 m 2 / g, preferably from 30 to 255 m 2 / g, particularly preferably from 65 to 230 m 2 / g and very particularly preferably from 65 to 200 m 2 / g.
- BET surface area nitrogen surface area
- CTAB surface accordinging to ASTM D 3765
- Such silicas lead z. B. in rubber blends for inner tire components to particularly good physical properties of the vulcanizates.
- silicas can thus z. B. both those of the type Ultrasil® VN3
- the rubber mixture according to the invention may contain, preferably very small amounts, ie preferably 0 to 3 phr, further non-reinforcing fillers non-reinforcing fillers are within the scope of the present invention
- Zinc oxide does not belong to the fillers in the context of the present invention.
- the optional silica may be in the form of tethered or not
- the rubber mixture preferably contains at least one silane coupling agent.
- Silane coupling agents are also referred to in the context of the present invention as "silane”.
- the rubber mixture may thus contain a mixture of different silanes.
- silane coupling agents react with the superficial silanol groups of the silica or other polar groups during the mixing of the rubber or the rubber mixture (in situ) or even before the addition of the filler to the
- Rubber blends known silane coupling agents can be used.
- Such known from the prior art coupling agents are bifunctional organosilanes having on the silicon atom at least one alkoxy, cycloalkoxy or phenoxy group as a leaving group and have as other functionality a group which may optionally undergo a chemical reaction with the double bonds of the polymer after cleavage , In the latter group may be z.
- they may be the following chemical groups:
- silane coupling agents z. 3-mercaptopropyltriethoxysilane
- TESPT Sulfur atoms with different contents of the different sulfides.
- TESPT can also be used as a mixture with carbon black
- silane mixture which comprises 40 to 100% by weight of disulfides, particularly preferably 55 to 85% by weight of disulfides and very particularly preferably 60 to 80% by weight of disulfides.
- a silane mixture is e.g. available under the trade name Si 266® Evonik, which is e.g. is described in DE 102006004062 AI.
- blocked mercaptosilanes, as z. B. from WO 99/09036 are known, can be used as a silane coupling agent.
- Silanes as described in WO 2008/083241 Al, WO 2008/083242 Al, WO 2008/083243 Al and WO 2008/083244 Al, can also be used. Suitable for.
- silanes sold under the name NXT eg 3- (octanoylthio) -l-propyl-triethoxysilane
- NXT eg 3- (octanoylthio) -l-propyl-triethoxysilane
- VP Si 363® e.g 3- (octanoylthio) -l-propyl-triethoxysilane
- 3-mercaptopropyltriethoxysilane in combination with processing aids (which are listed below), in particular PEG carboxylic acid ester, can be used.
- the rubber mixture contains a combination of 3-mercaptopropyltriethoxysilane and PEG carboxylic acid ester, which gives particularly good properties, in particular with regard to the technical problem to be solved and overall a good level of properties in terms of other properties.
- the rubber mixture may contain further activators and / or agents for the binding of fillers, in particular carbon black. This can happen
- the rubber mixture according to the invention contains a maximum of 35 phr of at least one plasticizer, wherein the
- Rubber mixture in particular the extrudates before crosslinking, while good properties in view of the problem to be solved.
- plasticizer s
- the heat buildup properties hysteresis
- the conflict of objectives is made up of reinforcing properties
- the plasticizer can also be completely or partly pass through the above-described masterbatch comprising CNT and polyisoprene into the rubber base mixture in the appropriate amounts.
- plasticizers used in the present invention include all known in the art plasticizers such as aromatic, naphthenic or
- paraffinic mineral oil softening agents such as e.g. MES (mild extraction solvate) or RAE (Residual Aromatic Extract) or TDAE (treated distillate aromatic extract), or rubber-to-liquid oils (RTL) or biomass-to-liquid oils (BTL) are preferred with a content of polycyclic Aromatics of less than 3 wt .-% according to method IP 346 or rapeseed oil or resin acids in particular or fact or liquid polymers whose average molecular weight (determined by GPC gel permeation chromatography, based on BS ISO 11344: 2004) between 500 and 20,000 g / mol is located. Be in the
- rubber mixture used additional liquid polymers as plasticizers, they do not go as a rubber in the calculation of the composition of the polymer matrix.
- the plasticizer is preferably selected from the group consisting of the above-mentioned plasticizers. According to a particularly preferred embodiment of the invention contains the
- Masterbatch already at least one plasticizer (see above), preferably in this case at least one resin acid, in particular disproportionated resin soap (eg.
- Rubber mixture additionally - added to any existing plasticizer in the masterbatch - at least one plasticizer.
- Mineral oils are particularly preferred as plasticizers.
- mineral oil this is preferably selected from the group consisting of DAE (Distilled Aromatic Extracts) and / or RAE (Residual Aromatic Extract) and / or TDAE (Treated Distilled Aromatic Extracts) and / or MES (Mild Extracted Solvents) and / or naphthenic oils.
- the rubber mixture contains at least one mineral oil plasticizer, preferably at least TDAE and / or RAE as plasticizer. This results in particularly good processability, in particular a good miscibility of the rubber mixture.
- the plasticizer (s) which are not already contained in the masterbatch are preferably added in at least one basic mixing stage during the preparation of the rubber mixture according to the invention. Furthermore, the rubber mixture customary additives in conventional
- anti-aging agents such as. N-phenyl-N '- (1,3-dimethylbutyl) -p-phenylenediamine (6PPD), N, N'-diphenyl-p-phenylenediamine (DPPD), N, N'-ditolyl-p-phenylenediamine (DTPD ), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), b) activators, such. As zinc oxide and fatty acids (eg., Stearic acid) and / or other activators, such as zinc complexes such as zinc ethylhexanoate,
- Mastikationswhismittel such. 2,2'-dibenzamidodiphenyl disulphide (DBD); and f) process aids such as, in particular, fatty acid esters and metal soaps, e.g.
- Zinc soaps and / or calcium soaps Zinc soaps and / or calcium soaps.
- the proportion of the total amount of further additives is 3 to 150 phr, preferably 3 to 100 phr and more preferably 5 to 80 phr.
- the total amount of other additives zinc oxide (ZnO) may be included in the above amounts.
- zinc oxides may be any type of zinc oxide known to those skilled in the art, such as ZnO granules or powder.
- the conventionally used zinc oxide usually has a BET surface area of less than 10 m 2 / g. However, it is also possible to use a zinc oxide having a BET surface area of from 10 to 100 m 2 / g, for example so-called "nano-zinc oxides".
- the rubber mixture according to the invention is sulfur-crosslinked, which means that the vulcanization of the underlying crude mixture in the presence of sulfur and / or sulfur donors is carried out with the aid of vulcanization accelerators.
- Some vulcanization accelerators can also act as sulfur donors.
- the accelerator is preferably selected from the group consisting of
- Thiourea accelerators and / or xanthate accelerators and / or guanidine accelerators Thiourea accelerators and / or xanthate accelerators and / or guanidine accelerators.
- a sulfenamide Beschleumgers which is selected from the group consisting of N-cyclohexyl-2-benzothiazolesufenamid (CBS) and / or N, N Dicyclohexylbenzothiazole-2-sulfenamide (DCBS) and / or benzothiazyl-2-sulfenmorpholide (MBS) and / or N-tert-butyl-2-benzothiazyl sulfenamide (TBBS).
- CBS N-cyclohexyl-2-benzothiazolesufenamid
- DCBS N Dicyclohexylbenzothiazole-2-sulfenamide
- MBS benzothiazyl-2-sulfenmorpholide
- TBBS N-tert-butyl-2-benzothiazyl sulfenamide
- Sulfur donating substances are used. If the rubber mixture contains a sulfur-donating substance, it is preferably selected from the group comprising e.g. Thiuram disulfides, e.g. Tetrabenzylthiuram disulfide (TBzTD) and / or
- TMTD Tetramethylthiuram disulfide
- TETD tetraethylthiuram disulfide
- thiuramate tetrasulfides e.g. Dipentamethylene thiuram tetrasulfide (DPTT), and / or dithiophosphates, e.g.
- DipDis bis (diisopropyl) thiophosphoryl disulfide) and / or bis (0,0-2-ethylhexyl thiophosphoryl) polysulfide (eg Rhenocure SDT 50®, Rheinchemie GmbH) and / or zinc dichloro dithiophosphate (eg Rhenocure ZDT / S®, Rheinchemie GmbH) and / or zinc alkyl dithiophosphate, and / or 1, 6-bis (N, N-dibenzylthiocarbamoyldithio) hexane and / or diaryl polysulfides and / or dialkyl polysulfides.
- the vulcanizing agent which has a functionality of greater than four crosslinked, for example, the general formula D):
- G is a polyvalent cyclic hydrocarbon group and / or a polyvalent heterohydrocarbon group and / or a polyvalent siloxane group containing 1 to 100 atoms; wherein each Y independently selected from a rubber active group contains sulfur-containing functionalities; and wherein a, b and c are integers for which independently: a is 0 to 6; b is 0 to 8; and c is 3 to 5.
- the rubber-active group is preferably selected from a thiosulfonate group, a dithiocarbamate group, a thiocarbonyl group, a mercapto group, a
- vulcanization retarders may be present in the rubber compound.
- Another object of the present invention is a vehicle tire, the at least one sulfur-crosslinked in at least one component according to the invention
- Rubber mixture has.
- the vehicle tire according to the invention can in
- the at least one component is particularly preferably at least one tread and / or one side wall and / or one conductivity track.
- a further subject of the present invention is a process for preparing a sulfur-crosslinked rubber mixture containing CNT comprising at least the following process steps: a) preparation of a masterbatch of at least one polyisoprene and CNT, the CNTs being intensively mixed into the polyisoprene; and
- step b) optionally providing further ingredients comprising at least one reinforcing filler and / or at least one sulfur crosslinkable rubber and / or antiaging agent and / or at least one silane coupling agent; and c) optionally mixing the further constituents from step b) with the polyisoprene CNT masterbatch; and
- step f) vulcanization of the mixture from step e) to a sulfur-crosslinked
- a masterbatch comprising at least one polyisoprene and CNT is prepared, which is subsequently optionally mixed with further constituents to form a rubber base mixture.
- the masterbatch itself constitutes a rubber masterbatch to which, according to step e), a sulfur vulcanization system may also be added, thereby providing a final rubber compound.
- step a) The preparation of the polyisoprene NR masterbatch according to step a) is carried out by methods known to the person skilled in the art, as described above.
- the ready mix is e.g. further processed by an extrusion process or calendering and brought into the appropriate form. Subsequently, the further processing by vulcanization according to step f), wherein due to the vulcanization system added in the context of the present invention, a sulfur crosslinking takes place.
- the mixture is preferably pre-vulcanized in the form of a tread and / or sidewall and / or a conductivity track and deposited as known in the manufacture of the vehicle tire blank.
- Mixtures here are mixtures according to the invention, while the mixtures marked with “V” are comparative mixtures
- the preparation of the mixture was carried out under customary conditions in three stages in a laboratory tangential mixer.
- test specimens were prepared by vulcanization and determined with these specimens typical for the rubber industry material properties.
- test procedures were used:
- Mooney viscosity according to ASTM D1646; e.g. ML1 + 4 at 100 ° C (Mooney units M.E.
- Dispersion by means of a dispergrader microwave disperGRADER
- FIG. 1 is a diagrammatic representation of FIG. 1:
- NR-CNT masterbatch CNT predispersed in NR: 67.3 wt% NR, 18.7 wt% CNT, 14 wt% resin acids; Density 1.03 g / cm 3
- Other additives Process auxiliaries: PEG carboxylic acid ester;
- Hydrocarbon resin Anti-aging agents; Antiozonant wax, zinc oxide;
- ESBR1500_CNT_1 ESBR as the sole rubber matrix, partly from an ESBR-CNT masterbatch and partially added separately:
- NR_CNT_1 NR as sole rubber matrix, partly from an NR-CNT masterbatch and partially added separately:
- CNT 60 phr of an NR-CNT masterbatch containing 82.8% by weight of NR and 17% by weight of CNT and the remainder of plasticizer and 50.32 phr of NR.
- E4 6.5 vol% CNT: 90 phr of the NR-CNT masterbatch (as described under 4.5 vol% CNT) and 25.48 phr NR.
- NR CNT MB The rubber matrix consists of 50% by weight of ESBR and 50% by weight of NR; the CNTs are predispersed exclusively in the NR (NR-CNT masterbatch):
- CNT 24.91 phr of the same NR-CNT masterbatch and 29.37 phr of NR and 50 phr of ESBR;
- CNT 37.75 phr of the same NR-CNT masterbatch and 18.74 phr of NR and 50 phr of ESBR;
- CNT 60.39 phr of the same NR-CNT masterbatch and no additional NR, i. 0 phr NR and 50 phr ESBR;
- ESBR CNT MB The rubber matrix consists of 50% by weight ESBR and 50% by weight NR; the CNT are predispersed exclusively in the ESBR (ESBR-CNT masterbatch):
- ESBR1500 CNT 1 ESBR1500 CNT 1
- no additional ESBR i. 0 phr ESBR and 50 phr NR
- NR / 50 ESBR (1/2 NR CNT MB, 1/2 ESBR CNT_MB): The rubber matrix consists of 50% by weight of ESBR and 50% by weight of NR; the CNT are both in
- ESBR-CNT-MB ESBR predispersed (ESBR-CNT-MB) as well as in the NR (NR-CNT masterbatch):
- V7 1.5% by volume
- CNT 9.29 phr of the NR-CNT masterbatch (as described under 4.5% by volume of CNT) and 42.3 phr of NR and 9.91 phr of the ESBR-CNT masterbatch ( as under
- V8 2% by volume
- CNT 12.46 phr of the NR-CNT masterbatch (as described under 4.5% by volume of CNT) and 39.69 phr of NR and 13.27 phr of the ESBR-CNT masterbatch (as described in US Pat
- V9 5% by volume CNT: 32.12 phr of the NR-CNT masterbatch (as described under 4.5% by volume of CNT) and 23.4 phr of NR and 34.24 phr of the ESBR-CNT masterbatch (as described in US Pat ESBR1500 CNT 1 described) and 21.61 phr ESBR;
- V10 8.7% by volume CNT: 60.39 phr of the NR-CNT masterbatch (as described under 4.5% by volume of CNT) and no additional ie 0 phr NR and 60.31 phr of the ESBR-CNT Masterbatches (as described under ESBR1500 CNT 1) and no additional ie 0 phr ESBR;
- Polyisoprene here NR
- NR Polyisoprene
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102017208137.6A DE102017208137A1 (de) | 2017-05-15 | 2017-05-15 | Schwefelvernetzte Kautschukmischung für Fahrzeugreifen enthaltend carbon nanotubes (CNT), Fahrzeugreifen, der die schwefelvernetzte Kautschukmischung aufweist, sowie Verfahren zur Herstellung der schwefelvernetzten Kautschukmischung enthaltend CNT |
PCT/EP2018/056808 WO2018210471A1 (de) | 2017-05-15 | 2018-03-19 | Schwefelvernetzte kautschukmischung für fahrzeugreifen enthaltend carbon nanotubes (cnt), fahrzeugreifen, der die schwefelvernetzte kautschukmischung aufweist, sowie verfahren zur herstellung der schwefelvernetzten kautschukmischung enthaltend cnt |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3625288A1 true EP3625288A1 (de) | 2020-03-25 |
Family
ID=61768277
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18713170.1A Pending EP3625288A1 (de) | 2017-05-15 | 2018-03-19 | Schwefelvernetzte kautschukmischung für fahrzeugreifen enthaltend carbon nanotubes (cnt), fahrzeugreifen, der die schwefelvernetzte kautschukmischung aufweist, sowie verfahren zur herstellung der schwefelvernetzten kautschukmischung enthaltend cnt |
Country Status (5)
Country | Link |
---|---|
US (1) | US11326028B2 (zh) |
EP (1) | EP3625288A1 (zh) |
CN (1) | CN110678508A (zh) |
DE (1) | DE102017208137A1 (zh) |
WO (1) | WO2018210471A1 (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4223474A3 (de) | 2018-12-18 | 2023-09-06 | Continental Reifen Deutschland GmbH | Verfahren zur herstellung einer kautschukfertigmischung und vorrichtung zur durchführung des verfahrens sowie verfahren zur herstellung eines vulkanisats |
CN110591177A (zh) * | 2019-09-21 | 2019-12-20 | 赛轮集团股份有限公司 | 一种高耐磨长里程的全钢胎面配方及其制备工艺 |
CN113337018B (zh) * | 2021-06-04 | 2023-06-02 | 徐工集团工程机械股份有限公司 | 一种高速履带用橡胶 |
CN113652011A (zh) * | 2021-07-05 | 2021-11-16 | 中策橡胶集团有限公司 | 一种低生热高导热的胎面橡胶组合物及其混炼方法和轮胎 |
DE112022000091T5 (de) * | 2021-08-24 | 2023-09-14 | Xuzhou Industrial Vocational And Technical College | Schützende gummikettenschuhe für bagger |
US11692084B2 (en) * | 2021-08-24 | 2023-07-04 | Xuzhou College of industrial Technology | Protective rubber track shoes for excavator |
WO2023152765A1 (en) * | 2022-02-09 | 2023-08-17 | Tvs Srichakra Limited | A rubber composition for off highway tyre treads using pineapple leaf fibre and method thereof |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE239737T1 (de) | 1997-08-21 | 2003-05-15 | Crompton Corp | Blockierte merkaptosilane als kupplungsmittel für gefüllte kautschukzusammensetzung |
JP4005048B2 (ja) | 2003-04-09 | 2007-11-07 | 日信工業株式会社 | 炭素繊維複合材料およびその製造方法 |
DE102006004062A1 (de) | 2006-01-28 | 2007-08-09 | Degussa Gmbh | Kautschukmischungen |
US7968633B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US7968634B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated core polysulfides |
US7968636B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
US8182626B2 (en) | 2008-10-30 | 2012-05-22 | Continental Ag | Tire composition with improved vulcanizing agent |
JP2012012456A (ja) | 2010-06-30 | 2012-01-19 | Sumitomo Chemical Co Ltd | S−(3−アミノプロピル)チオ硫酸および/またはその金属塩の使用方法 |
CN103313934A (zh) * | 2010-12-14 | 2013-09-18 | 思迪隆欧洲有限公司 | 改进的弹性体配制物 |
CN104513410B (zh) | 2013-09-30 | 2017-02-01 | 山东大展纳米材料有限公司 | 预分散碳纳米管橡胶母粒的制备方法 |
DE102014209255A1 (de) * | 2014-05-15 | 2015-11-19 | Continental Reifen Deutschland Gmbh | Schwefelvernetzbare Kautschukmischung und Fahrzeugreifen |
CN105459284B (zh) * | 2014-08-25 | 2019-04-05 | 山东大展纳米材料有限公司 | 高分散碳纳米管母炼胶的液相连续混炼工艺及其橡胶制品 |
CN105037830A (zh) * | 2015-09-08 | 2015-11-11 | 中北大学 | 一种高强度低生热复合材料及其制备方法 |
DE102015220492A1 (de) * | 2015-10-21 | 2017-04-27 | Continental Reifen Deutschland Gmbh | Fahrzeugluftreifen |
CN105482175A (zh) * | 2016-01-21 | 2016-04-13 | 中国民航大学 | 多壁碳纳米管改性航空轮胎橡胶材料的制备方法 |
CN105670055A (zh) * | 2016-04-01 | 2016-06-15 | 山东容奈材料设计有限公司 | 橡胶复合散热剂和其制备方法及其应用 |
CN105924705A (zh) * | 2016-05-13 | 2016-09-07 | 赛轮金宇集团股份有限公司 | 一种充气轮胎用具有良好导电和导热性高填充白炭黑胎面胶 |
CN105860133B (zh) * | 2016-06-23 | 2018-10-09 | 上海绿韧新材料有限公司 | 碳管母料及其在轮胎胎面的应用 |
CN106146932A (zh) * | 2016-09-27 | 2016-11-23 | 钟光 | 一种碳纳米环保橡胶复合材料及其制备方法 |
-
2017
- 2017-05-15 DE DE102017208137.6A patent/DE102017208137A1/de active Pending
-
2018
- 2018-03-19 EP EP18713170.1A patent/EP3625288A1/de active Pending
- 2018-03-19 WO PCT/EP2018/056808 patent/WO2018210471A1/de unknown
- 2018-03-19 CN CN201880032287.2A patent/CN110678508A/zh active Pending
- 2018-03-19 US US16/610,213 patent/US11326028B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
US20210163696A1 (en) | 2021-06-03 |
CN110678508A (zh) | 2020-01-10 |
DE102017208137A1 (de) | 2018-11-15 |
WO2018210471A1 (de) | 2018-11-22 |
US11326028B2 (en) | 2022-05-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3150401B1 (de) | Kautschukmischung und fahrzeugreifen | |
WO2018210471A1 (de) | Schwefelvernetzte kautschukmischung für fahrzeugreifen enthaltend carbon nanotubes (cnt), fahrzeugreifen, der die schwefelvernetzte kautschukmischung aufweist, sowie verfahren zur herstellung der schwefelvernetzten kautschukmischung enthaltend cnt | |
EP3500440B1 (de) | Schwefelvernetzbare kautschukmischung und fahrzeugreifen | |
DE102015218746A1 (de) | Kautschukmischung und Fahrzeugreifen | |
EP2977227B1 (de) | Schwefelvernetzbare kautschukmischung und fahrzeugreifen | |
EP3500441B1 (de) | Schwefelvernetzbare kautschukmischung und fahrzeugreifen | |
WO2018033315A1 (de) | Kautschukblend, schwefelvernetzbare kautschukmischung und fahrzeugreifen | |
WO2015043901A1 (de) | Schwefelvernetzbare kautschukmischung | |
EP3156443A1 (de) | Kautschukmischung und fahrzeugluftreifen | |
DE102019212916A1 (de) | Vernetzbare Kautschukmischung, Vulkanisat und Fahrzeugreifen | |
EP2987813B1 (de) | Schwefelvernetzbare kautschukmischung und fahrzeugreifen | |
EP3785929B1 (de) | Kautschukmischung und fahrzeugluftreifen | |
WO2018033505A1 (de) | Schwefelvernetzbare kautschukmischung und fahrzeugreifen | |
EP3418072B1 (de) | Kautschukmischung und fahrzeugluftreifen | |
EP3500600B1 (de) | Schwefelvernetzbare kautschukmischung und fahrzeugreifen | |
EP3500626B1 (de) | Kautschukblend, schwefelvernetzbare kautschukmischung und fahrzeugreifen | |
EP3720905A1 (de) | Schwefelvernetzbare kautschukmischung, vulkanisat der kautschukmischung und fahrzeugreifen | |
DE102016225584B4 (de) | Schwefelvernetzbare Kautschukmischung, Vulkanisat der Kautschukmischung und deren Verwendung in Fahrzeugreifen | |
EP3500598B1 (de) | Kautschukblend, schwefelvernetzbare kautschukmischung und fahrzeugreifen | |
EP4105277B1 (de) | Kautschukmischung und reifen | |
DE102019207526B4 (de) | Schwefelvernetzbare Kautschukmischung, Vulkanisat und Verwendung in einem Fahrzeugreifen | |
WO2022262913A1 (de) | Kautschukmischung und reifen | |
DE102021206273A1 (de) | Kautschukmischung und Reifen | |
WO2023072348A1 (de) | Schwefelvernetzbare kautschukmischung, vulkanisat der kautschukmischung und fahrzeugreifen | |
DE102016201195A1 (de) | Kautschukmischung und Fahrzeugreifen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20191216 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: RECKER, CARLA Inventor name: HOJDIS, NILS WALTER |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: CONTINENTAL REIFEN DEUTSCHLAND GMBH |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20230706 |
|
RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: CONTINENTAL REIFEN DEUTSCHLAND GMBH |