US20020000280A1 - Rubber mixtures for producing highly reinforced vulcanisates with low damping behaviour - Google Patents
Rubber mixtures for producing highly reinforced vulcanisates with low damping behaviour Download PDFInfo
- Publication number
- US20020000280A1 US20020000280A1 US09/862,149 US86214901A US2002000280A1 US 20020000280 A1 US20020000280 A1 US 20020000280A1 US 86214901 A US86214901 A US 86214901A US 2002000280 A1 US2002000280 A1 US 2002000280A1
- Authority
- US
- United States
- Prior art keywords
- rubber
- rubber mixtures
- mineral oil
- tires
- vulcanisates
- 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.)
- Abandoned
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 60
- 239000005060 rubber Substances 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000013016 damping Methods 0.000 title description 11
- 239000002480 mineral oil Substances 0.000 claims abstract description 37
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 15
- 238000005096 rolling process Methods 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 239000005864 Sulphur Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 235000019241 carbon black Nutrition 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- -1 silicon halides Chemical class 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XDLNRRRJZOJTRW-UHFFFAOYSA-N thiohypochlorous acid Chemical compound ClS XDLNRRRJZOJTRW-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000011814 protection agent Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004608 Heat Stabiliser Substances 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 239000006233 lamp black Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- 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
- B60C17/00—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor
- B60C17/0009—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor comprising sidewall rubber inserts, e.g. crescent shaped inserts
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
-
- 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
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present patent application relates to rubber mixtures consisting of rubber, filler and a specific sulphurised mineral oil.
- Vulcanisates with surprisingly good reinforcement- and temperature-dependent dynamic damping behaviour which are particularly suitable for producing tires with low-damping treads with a high resistance to wet skidding and for producing tires with low-damping highly reinforced lateral walls can be produced from the rubber mixtures according to the invention.
- a further object of the present invention was to provide mineral oil-containing rubber mixtures and vulcanisates with improved reinforcement behaviour.
- JP-B 47 008 135 describes reaction products of aromatic mineral oils with sulphur monochloride for improving the processing behaviour of rubber mixtures.
- the modified mineral oils are produced by a method which predominantly leads to mono- and disulphide bridges due to the chemical nature of sulphur monochloride.
- the sulphur monochloride used leads to an undesirable residue of bound chlorine in the end product.
- the present invention therefore relates to rubber mixtures consisting of a rubber, a fillet and optionally further rubber auxiliaries and cross-linking agents and 0.1 to 75 parts by weight, based on 100 parts by weight of rubber, of a specific sulphurised mineral oil, the sulphurised mineral oil having been obtained by reacting an aromatic-containing mineral oil with sulphur.
- the sulphurised mineral oil used was produced according to the invention in that an aromatic-containing mineral oil with an aromatic content according to ASTM D 2140 of 5 to 50 wt. % and a viscosity-density constant VDK of 0.82 to 1.05 was reacted with 2.5 to 40 parts by weight of sulphur per 100 parts by weight of mineral oil at temperatures of 130 to 250° C., optionally in the presence of catalysts.
- the sulphurised mineral oils according to the invention have a bound sulphur content of 2.5 to 12.5 wt. %, preferably 4 to 10 wt. %, and a glass transition temperature (determined by DSC) of ⁇ 25 to ⁇ 65° C., preferably ⁇ 35 to ⁇ 55° C., and a density of 0.85 to 1.1 g/cm 3 , preferably 0.92 to 1.03 g/cm 3 (at 20° C.).
- the viscosities are 0.3 to 100 Pa.sec, particularly preferably 0.8 to 20 Pa.sec at 20° C. (plate and cone viscometer, 20 rpm).
- the starting products for producing the sulphurised mineral oils used according to the invention are aromatic-containing mineral oils with an aromatic content (according to ASTM D 2140) of 5 to 50%, preferably 15 to 40%, a viscosity-density constant VDK (according to ASTM D 2501) of 0.82 to 1.05, preferably 0.84 to 1.0.
- Preferred aromatic-containing mineral oils moreover have a density of 0.85 to 1.03 g/cm 3 (at 15° C.), preferably 0.9 to 1.0 g/cm 3 and a pour point (according to ASTM D 97) between ⁇ 20° C. and +30° C., particularly preferably between ⁇ 15° C. and +20° C., and contain less than 0.1 wt.
- Mineral oil products of this type are commercially available; suitable products are, for example, Enerthene® 1849-1 (BP) and Catenex Oil SNR® (Shell). In this regard see Kautschuk, Kunststoffe, 45 (1992), pages 24-29.
- the reaction of aromatic-containing mineral oils with sulphur is preferably carried out with 5 to 20 parts by weight of sulphur per 100 parts by weight of aromatic-containing mineral oils at temperatures of preferably 160 to 220° C., particularly preferably 180 to 210° C., for a time period of a few minutes (5 min) up to several hours (10 hours), optionally in the presence of catalysts.
- Suitable catalysts are acidic or basic catalysts, such as zinc chloride, aluminium chloride, tin chloride, hydrogen sulphide and/or alkyl amines, such as dodecylamine or octadecylamine.
- Suitable quantities of catalysts are 0.01 to 3 parts by weight based on aromatic-containing mineral oil.
- the reaction is preferably carried out without a catalyst.
- residues of hydrogen sulphide and volatile mercaptans can be removed, for example, by applying a vacuum or blowing out with nitrogen or by chemical methods, such as oxidising agents (for example atmospheric oxygen or peroxides). Unreacted sulphur can be removed by filtering off, for example.
- oxidising agents for example atmospheric oxygen or peroxides
- synthetic rubbers are also suitable for producing the rubber mixtures and vulcanisates according to the invention.
- Preferred synthetic rubbers are described, for example, in W. Hofmann, Kautschuktechnologie, Gentner Verlag, Stuttgart 1980 and I. Franta, Elastomers and Rubber Coumpounding Materials, Elsevier, Amsterdam 1989. They include inter alia
- SBR styrene/butadiene copolymers with styrene contents of 1-60, preferably 20-50 wt. %
- NBR butadiene acrylonitrile copolymers with acrylonitrile contents of 5-60, preferably 10-40 wt. %
- HNBR partially or completely hydrogenated NBR rubber
- EPDM ethylene propylene diene copolymers
- the rubber mixtures according to the invention contain the fillers known and used in the rubber industry; these include both the active and the inactive fillers, notably:
- fine-particled silicas produced, for example, by precipitation of solutions of silicates or flame hydrolysis of silicon halides with specific surface areas of 5 -1000, preferably 20-400 m 2 /g (BET surface area) and with primary particle sizes of 10-400 nm.
- the silicas can optionally be present as mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti oxides;
- synthetic silicates such as aluminium silicate, alkaline-earth silicate such as magnesium silicate or calcium silicate, with BET surface areas of 20-400 m 2 /g and primary particle diameters of 10-400 nm;
- glass-fibres and glass-fibre products (mats, strands) or glass microbeads;
- metal oxides such as zinc oxide, calcium oxide, magnesium oxide, aluminium oxide
- metal carbonates such as magnesium carbonate, calcium carbonate, zinc carbonate
- metal hydroxides such as for example, aluminium hydroxide, magnesium hydroxide
- carbon blacks are produced by the lamp black, furnace or gas black process and have BET surface areas of 20-200 m 2 /g, for example, SAF, ISAF, HAF, FEF or GPF carbon blacks;
- rubber powder obtained, for example, by size-reduction of rubber vulcanisates. Preferred particle sizes are between 0.001 to 0.5 mm.
- Fine-particle silicas and carbon blacks, optionally together with rubber powder, are preferably used as fillers.
- the fillers mentioned can be used alone or in a mix, specifically in quantities of 1 to 300 parts by weight, preferably 10 to 150 parts by weight based on 100 parts by weight of rubber.
- the rubber mixtures contain as fillers, a mixture of light fillers, such as fine-particled silicas, and carbon blacks, the mixing ratio of light filler to carbon blacks being 1:0.05 to 20, preferably 1:0.1 to 10.
- the rubber mixtures according to the invention can obviously also contain other rubber auxiliaries and cross-linking agents.
- Sulphur or sulphur-supplying compounds or peroxides are used as cross-linking agents.
- Particularly preferred are sulphur or sulphur-supplying compounds in quantities of 0.01 to 3 parts by weight based on rubber.
- the rubber mixtures according to the invention can contain further auxiliary agents, such as the known reaction accelerators, anti-ageing agents, heat stabilisers, light protection agents, ozone protection agents, process aids, reinforcing resins, for example phenolic resins, steel cord bonding agents, such as, for example, silica/resorcinol/hexamethylenetetramine or cobalt-naphthenate, plasticisers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarding agents, metal oxides and activators.
- auxiliary agents such as the known reaction accelerators, anti-ageing agents, heat stabilisers, light protection agents, ozone protection agents, process aids, reinforcing resins, for example phenolic resins, steel cord bonding agents, such as, for example, silica/resorcinol/hexamethylenetetramine or cobalt-naphthenate, plasticisers, tackifiers, blow
- the rubber auxiliaries are used in the usual, known quantities, the quantity used depending on the subsequent intended purpose of the rubber mixtures.
- normal quantities of rubber auxiliaries are in the range of 2 to 70 parts by weight, based on 100 parts by weight of rubber.
- filler activators are sulphur-containing silyl ethers, in particular bis-(trialkoxysilyl-alkyl)-polysulphides as described in DE-A 2 141 159 and DE-A 2 255 577. Further possibilities are oligomeric and/or polymeric sulphur-containing silyl ethers according to the description in DE-A 4 435 311 and EP-A 670 347.
- Mercapto-alkyltrialkoxysilanes in particular mercaptopropyltriethoxysilane and thiocyanatoalkylsilylethers (see DE-A 19 544 469), amino group-containing silyl ethers, such as for example 3-amino-propyltriethoxysilane and N-oleyl-N-propyl-trimethoxysilane and trimethylolpropane.
- the filler activators are used in the usual quantities, i.e. in quantities of 0.1 to 15 parts by weight, based on 100 parts by weight of rubber.
- the rubber mixtures according to the invention can be produced, for example, by mixing the rubbers with the fillers, rubber auxiliaries and the sulphurised mineral oils in suitable mixing apparatuses, such as kneaders, rollers or extruders, or by mixing the rubber solutions with fillers and the sulphurised mineral oils and removing the solvent, for example by steam distillation.
- the present invention also relates to the use of the rubber mixtures according to the invention for producing vulcanisates which, in turn, are used for the production of highly reinforced rubber shaped articles, in particular for the production of tires.
- 1,045 g of a black oil were obtained with a sulphur content of 5.3 wt.%, viscosity 5 Pa.sec (plate and cone, 20 rpm, 20° C.), glass transition temperature of ⁇ 50° C. (according to DSC) and density 0.97g/cm 3 .
Abstract
The rubber mixtures according to the invention consisting of a rubber, a filler and a specific sulphurized mineral oil are suitable for producing shaped vulcanizates, in particular for producing tires with reduced rolling resistance and high resistance to wet skidding, and tires with particularly reinforced side walls (“run flat tires”).
Description
- The present patent application relates to rubber mixtures consisting of rubber, filler and a specific sulphurised mineral oil. Vulcanisates with surprisingly good reinforcement- and temperature-dependent dynamic damping behaviour which are particularly suitable for producing tires with low-damping treads with a high resistance to wet skidding and for producing tires with low-damping highly reinforced lateral walls can be produced from the rubber mixtures according to the invention.
- Mineral oils are often added to rubbers and rubber mixtures to improve the processing properties. The differing content of paraffinic, naphthenic and aromatic contents in the mineral oils is known to have a corresponding effect on the damping properties of the rubber vulcanisates produced, wherein, disadvantageously, it is not possible to improve both the rolling resistance and the resistance to wet skidding together in tires by altering the mineral oil composition, but only one of the two properties at the cost of the other. In this regard, see Kautschuk, Gummi, Kunststoffe 44, 1991, page 528 to 536.
- Therefore, it was an object of the present invention to provide rubber mixtures containing a specific mineral oil which do not have these disadvantages in the damping behaviour of the vulcanisates.
- Many methods of producing vehicle tires with low-damping tire treads and low-damping highly reinforced lateral walls have been investigated. U.S. Pat. No. 5,227,425 thus describes the production of tire treads with low rolling resistance and with high resistance to wet skidding made of solution SBR rubber, silica, conventional aromatic mineral oil and a polysulphide-containing silyl ether. The mineral oil certainly improves the flowability and processibility of the rubber mixtures, but simultaneously reduces the reinforcement level. To obtain acceptable reinforcement properties, large quantities of an expensive polysulphide-containing silyl ether are therefore required.
- Therefore, a further object of the present invention was to provide mineral oil-containing rubber mixtures and vulcanisates with improved reinforcement behaviour.
- JP-B 47 008 135 describes reaction products of aromatic mineral oils with sulphur monochloride for improving the processing behaviour of rubber mixtures. The modified mineral oils are produced by a method which predominantly leads to mono- and disulphide bridges due to the chemical nature of sulphur monochloride. Moreover, the sulphur monochloride used leads to an undesirable residue of bound chlorine in the end product.
- It has now been found that rubber vulcanisates with exceptionally favourable dynamic damping behaviour and an exceptionally high reinforcement level can be obtained from rubber mixtures containing certain sulphurised mineral oils and that rubber mixtures of this type are suitable, in particular, for producing tires which are resistant to wet skidding with particularly low rolling resistance and for producing tires with low damping with highly reinforced lateral walls (“run flat tires”).
- The present invention therefore relates to rubber mixtures consisting of a rubber, a fillet and optionally further rubber auxiliaries and cross-linking agents and 0.1 to 75 parts by weight, based on 100 parts by weight of rubber, of a specific sulphurised mineral oil, the sulphurised mineral oil having been obtained by reacting an aromatic-containing mineral oil with sulphur.
- The sulphurised mineral oil used was produced according to the invention in that an aromatic-containing mineral oil with an aromatic content according to ASTM D 2140 of 5 to 50 wt. % and a viscosity-density constant VDK of 0.82 to 1.05 was reacted with 2.5 to 40 parts by weight of sulphur per 100 parts by weight of mineral oil at temperatures of 130 to 250° C., optionally in the presence of catalysts.
- The sulphurised mineral oils according to the invention have a bound sulphur content of 2.5 to 12.5 wt. %, preferably 4 to 10 wt. %, and a glass transition temperature (determined by DSC) of −25 to −65° C., preferably −35 to −55° C., and a density of 0.85 to 1.1 g/cm3, preferably 0.92 to 1.03 g/cm3 (at 20° C.).
- The viscosities are 0.3 to 100 Pa.sec, particularly preferably 0.8 to 20 Pa.sec at 20° C. (plate and cone viscometer, 20 rpm).
- The starting products for producing the sulphurised mineral oils used according to the invention are aromatic-containing mineral oils with an aromatic content (according to ASTM D 2140) of 5 to 50%, preferably 15 to 40%, a viscosity-density constant VDK (according to ASTM D 2501) of 0.82 to 1.05, preferably 0.84 to 1.0. Preferred aromatic-containing mineral oils moreover have a density of 0.85 to 1.03 g/cm3 (at 15° C.), preferably 0.9 to 1.0 g/cm3 and a pour point (according to ASTM D 97) between −20° C. and +30° C., particularly preferably between −15° C. and +20° C., and contain less than 0.1 wt. %, preferably less than 0.005 wt. %, of polycyclic aromatic hydrocarbons and/or a DMSO-extract according to IP 346<3 wt. %. Mineral oil products of this type are commercially available; suitable products are, for example, Enerthene® 1849-1 (BP) and Catenex Oil SNR® (Shell). In this regard see Kautschuk, Gummi, Kunststoffe, 45 (1992), pages 24-29.
- The reaction of aromatic-containing mineral oils with sulphur is preferably carried out with 5 to 20 parts by weight of sulphur per 100 parts by weight of aromatic-containing mineral oils at temperatures of preferably 160 to 220° C., particularly preferably 180 to 210° C., for a time period of a few minutes (5 min) up to several hours (10 hours), optionally in the presence of catalysts. Suitable catalysts are acidic or basic catalysts, such as zinc chloride, aluminium chloride, tin chloride, hydrogen sulphide and/or alkyl amines, such as dodecylamine or octadecylamine. Suitable quantities of catalysts are 0.01 to 3 parts by weight based on aromatic-containing mineral oil. However, the reaction is preferably carried out without a catalyst.
- Following the reaction, residues of hydrogen sulphide and volatile mercaptans can be removed, for example, by applying a vacuum or blowing out with nitrogen or by chemical methods, such as oxidising agents (for example atmospheric oxygen or peroxides). Unreacted sulphur can be removed by filtering off, for example.
- In addition to natural rubbers, synthetic rubbers are also suitable for producing the rubber mixtures and vulcanisates according to the invention. Preferred synthetic rubbers are described, for example, in W. Hofmann, Kautschuktechnologie, Gentner Verlag, Stuttgart 1980 and I. Franta, Elastomers and Rubber Coumpounding Materials, Elsevier, Amsterdam 1989. They include inter alia
- BR—polybutadiene
- ABR—butadiene acrylic acid-C1-4-alkyl ester copolymers
- CR—polychloroprene
- IR—polyisoprene
- SBR—styrene/butadiene copolymers with styrene contents of 1-60, preferably 20-50 wt. %
- IIR—isobutylene isoprene copolymers
- NBR—butadiene acrylonitrile copolymers with acrylonitrile contents of 5-60, preferably 10-40 wt. %
- HNBR—partially or completely hydrogenated NBR rubber
- EPDM—ethylene propylene diene copolymers
- and mixtures of these rubbers. Of interest for the production of car tires, are, in particular, natural rubber, emulsion SBR and solution SBR rubbers with a glass transition temperature above −50° C. which can optionally be modified with silyl ethers or other functional groups according to EP-A 447 066, polybutadiene rubber with a high 1.4-cis-content (>90%) produced by catalysts based on Ni, Co, Ti or Nd, and polybutadiene rubber with a vinyl content of up to 75% and mixtures thereof. Most particularly preferred are the so-called solution SBR and polybutadiene rubbers.
- The rubber mixtures according to the invention contain the fillers known and used in the rubber industry; these include both the active and the inactive fillers, notably:
- fine-particled silicas, produced, for example, by precipitation of solutions of silicates or flame hydrolysis of silicon halides with specific surface areas of 5 -1000, preferably 20-400 m2/g (BET surface area) and with primary particle sizes of 10-400 nm. The silicas can optionally be present as mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti oxides;
- synthetic silicates, such as aluminium silicate, alkaline-earth silicate such as magnesium silicate or calcium silicate, with BET surface areas of 20-400 m2/g and primary particle diameters of 10-400 nm;
- natural silicates such as kaolin and other naturally occurring silicas;
- glass-fibres and glass-fibre products (mats, strands) or glass microbeads;
- metal oxides, such as zinc oxide, calcium oxide, magnesium oxide, aluminium oxide;
- metal carbonates, such as magnesium carbonate, calcium carbonate, zinc carbonate;
- metal hydroxides, such as for example, aluminium hydroxide, magnesium hydroxide;
- carbon blacks. The carbon blacks to be used in this process are produced by the lamp black, furnace or gas black process and have BET surface areas of 20-200 m2/g, for example, SAF, ISAF, HAF, FEF or GPF carbon blacks;
- rubber gels
- rubber powder, obtained, for example, by size-reduction of rubber vulcanisates. Preferred particle sizes are between 0.001 to 0.5 mm.
- Fine-particle silicas and carbon blacks, optionally together with rubber powder, are preferably used as fillers.
- The fillers mentioned can be used alone or in a mix, specifically in quantities of 1 to 300 parts by weight, preferably 10 to 150 parts by weight based on 100 parts by weight of rubber. In a particularly preferred embodiment, the rubber mixtures contain as fillers, a mixture of light fillers, such as fine-particled silicas, and carbon blacks, the mixing ratio of light filler to carbon blacks being 1:0.05 to 20, preferably 1:0.1 to 10.
- The rubber mixtures according to the invention can obviously also contain other rubber auxiliaries and cross-linking agents. Sulphur or sulphur-supplying compounds or peroxides are used as cross-linking agents. Particularly preferred are sulphur or sulphur-supplying compounds in quantities of 0.01 to 3 parts by weight based on rubber.
- Furthermore, as mentioned, the rubber mixtures according to the invention can contain further auxiliary agents, such as the known reaction accelerators, anti-ageing agents, heat stabilisers, light protection agents, ozone protection agents, process aids, reinforcing resins, for example phenolic resins, steel cord bonding agents, such as, for example, silica/resorcinol/hexamethylenetetramine or cobalt-naphthenate, plasticisers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarding agents, metal oxides and activators.
- The rubber auxiliaries are used in the usual, known quantities, the quantity used depending on the subsequent intended purpose of the rubber mixtures. For example, normal quantities of rubber auxiliaries are in the range of 2 to 70 parts by weight, based on 100 parts by weight of rubber.
- The use of additional filler activators is particularly advantageous for the rubber mixtures according to the invention which are filled with highly active silicas. Preferred filler activators are sulphur-containing silyl ethers, in particular bis-(trialkoxysilyl-alkyl)-polysulphides as described in DE-A 2 141 159 and DE-A 2 255 577. Further possibilities are oligomeric and/or polymeric sulphur-containing silyl ethers according to the description in DE-A 4 435 311 and EP-A 670 347. Mercapto-alkyltrialkoxysilanes, in particular mercaptopropyltriethoxysilane and thiocyanatoalkylsilylethers (see DE-A 19 544 469), amino group-containing silyl ethers, such as for example 3-amino-propyltriethoxysilane and N-oleyl-N-propyl-trimethoxysilane and trimethylolpropane. The filler activators are used in the usual quantities, i.e. in quantities of 0.1 to 15 parts by weight, based on 100 parts by weight of rubber.
- The rubber mixtures according to the invention can be produced, for example, by mixing the rubbers with the fillers, rubber auxiliaries and the sulphurised mineral oils in suitable mixing apparatuses, such as kneaders, rollers or extruders, or by mixing the rubber solutions with fillers and the sulphurised mineral oils and removing the solvent, for example by steam distillation.
- The present invention also relates to the use of the rubber mixtures according to the invention for producing vulcanisates which, in turn, are used for the production of highly reinforced rubber shaped articles, in particular for the production of tires.
- Particularly preferred is the use of the rubber mixtures for producing tire treads with low rolling resistance and resistance to wet skidding and for producing particularly reinforced lateral walls for tires with emergency running properties (“run flat tires”), as described, for example, in U.S. Pat. No. 5,368,082, EP-A 475 258, U.S. Pat. No. 5,427,166, U.S. Pat. No. 5,511,599 and EP-A 943 466.
- 100 g sulphur were added to 1,000 g Enerthene 1849-1 (solvent-refined mineral oil from BP, aromatics content according to ASTM D 2140: 24%, density 0.945 g/cm3, S content 0.9%, pour point 0° C., VDK 0.884, polycyclic aromatic compound content <50 ppm), DMSO-extract (according to IP 346): 2.2 wt.%) and heated for 2 hours to 200° C., hydrogen sulphide being released. A vacuum was then applied for 10 minutes at 110° C. to remove the released hydrogen sulphide. 1,045 g of a black oil were obtained with a sulphur content of 5.3 wt.%, viscosity 5 Pa.sec (plate and cone, 20 rpm, 20° C.), glass transition temperature of −50° C. (according to DSC) and density 0.97g/cm3.
- The following rubber mixtures were produced in a 1.51 kneader. (Mixing time: 5 minutes, speed 60 rpm). The sulphur and accelerators were finally added on a roller at 50° C.:
Comparison Example Example 2.1 2.A 2.B Mixed in the kneader: L-SBR Buna VSL 5025-0 (Bayer AG) 70 70 70 Polybutadiene Buna CB 25 30 30 30 (Bayer AG) Silica Vulkasil 5 70 70 70 (Bayer AG) Aromatic mineral oil Enerthene 1849-1 (BP) 37.5 17.5 0 Sulphurised mineral oil, 0 20 37.5 Example 1 Zinc oxide 2.5 2.5 2.5 Stearic acid 1 1 1 Antioxidant Vulkanox 4020 (Bayer AG) 1 1 1 Silane Si 69 (Degussa Hüls) 5.6 5.6 5.6 Mixed on the roller: Sulphur 1.5 1.5 1.5 Accelerator Vulkacit CZ 1.8 1.8 1.8 (Bayer AG) Accelerator Vulkacit D 2 2 2 (Bayer AG) Mooney-Viscosity ML 1 + 4 41 43 45 (100° C.) - The mixtures were then vulcanised for 15 minutes at 170° C. The following vulcanisate properties were found:
Comparison Example Example 2.1 2.A 2.B Tensile modulus 100% 2.2 2.8 3.3 elongation (MPa) Tensile modulus 300% 8.4 10.8 12.5 elongation (MPa) Tensile strength (MPa) 15.7 16.1 17 Rebound at 23° C. (%) 34 33 32 Rebound at 70° C. (%) 53 59 60 Shore A hardness (23° C.) 60 63 66 Abrasion DIN 53.516 (mm3) 109 92 93 - The test results show that vulcanisates with improved dynamic damping properties (low rebound at 23° C. correlated with high resistance to wet skidding in tires, high rebound at 70° C. correlated with low rolling resistance in tires) and low abrasion at a significantly higher reinforcement level can be produced from the rubber mixtures with the content according to the invention of sulphurised mineral oils (I).
Claims (3)
1. Rubber mixtures consisting of a rubber, a filler and 0.1 to 75 parts by weight, based on 100 parts by weight of rubber, of a sulphurised mineral oil, wherein the sulphurised mineral oil is obtained by reacting an aromatic-containing mineral oil with sulphur.
2. Rubber mixtures according to claim 1 , characterised in that the sulphurised mineral oil has a bound sulphur content of 2.5 to 12.5 wt. %, a glass transition temperature of −25 to −65° C. and a density of 0.85 to 1.1 g/cm3.
3. Use of the rubber mixtures according to the invention and according to claim 1 for producing shaped vulcanisates, in particular for producing tires with reduced rolling resistance and high resistance to wet skidding and tires with particularly reinforced lateral walls (“run flat tires”).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10025625A DE10025625A1 (en) | 2000-05-24 | 2000-05-24 | A rubber mixture containing filler and sulfurized mineral oil useful for the manufacture of shaped vulcanisates, especially tires gives tires of decreased rolling resistance and high wet slip stability |
DE10025625.2 | 2000-05-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
US20020000280A1 true US20020000280A1 (en) | 2002-01-03 |
Family
ID=7643323
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/862,149 Abandoned US20020000280A1 (en) | 2000-05-24 | 2001-05-22 | Rubber mixtures for producing highly reinforced vulcanisates with low damping behaviour |
Country Status (4)
Country | Link |
---|---|
US (1) | US20020000280A1 (en) |
JP (1) | JP2002020552A (en) |
CA (1) | CA2348177A1 (en) |
DE (1) | DE10025625A1 (en) |
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2000
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2001
- 2001-05-18 CA CA002348177A patent/CA2348177A1/en not_active Abandoned
- 2001-05-22 US US09/862,149 patent/US20020000280A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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DE10025625A1 (en) | 2001-11-29 |
CA2348177A1 (en) | 2001-11-24 |
JP2002020552A (en) | 2002-01-23 |
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