EP0622444A1 - Lubricating oil composition for wet clutch or wet brake - Google Patents
Lubricating oil composition for wet clutch or wet brake Download PDFInfo
- Publication number
- EP0622444A1 EP0622444A1 EP94908130A EP94908130A EP0622444A1 EP 0622444 A1 EP0622444 A1 EP 0622444A1 EP 94908130 A EP94908130 A EP 94908130A EP 94908130 A EP94908130 A EP 94908130A EP 0622444 A1 EP0622444 A1 EP 0622444A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wet
- friction
- oil
- lubricant
- clutch
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000010687 lubricating oil Substances 0.000 title abstract 2
- -1 phosphorus compound Chemical class 0.000 claims abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- 239000002199 base oil Substances 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 239000000470 constituent Substances 0.000 claims abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims description 59
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000003921 oil Substances 0.000 abstract description 15
- 230000003068 static effect Effects 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000035939 shock Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000001629 suppression Effects 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 230000002688 persistence Effects 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000003607 modifier Substances 0.000 description 19
- 230000005540 biological transmission Effects 0.000 description 18
- 235000019198 oils Nutrition 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000002480 mineral oil Substances 0.000 description 10
- 235000010446 mineral oil Nutrition 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000002265 prevention Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000005456 glyceride group Chemical group 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- TXGJTWACJNYNOJ-UHFFFAOYSA-N hexane-2,4-diol Chemical compound CCC(O)CC(C)O TXGJTWACJNYNOJ-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- HOWLAKMIIWUJEJ-UHFFFAOYSA-N octane-2,4-diol Chemical compound CCCCC(O)CC(C)O HOWLAKMIIWUJEJ-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- HKGKYUVCADNOOC-UHFFFAOYSA-N 1-aminotetradecan-2-ol Chemical compound CCCCCCCCCCCCC(O)CN HKGKYUVCADNOOC-UHFFFAOYSA-N 0.000 description 1
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 description 1
- BITAPBDLHJQAID-KTKRTIGZSA-N 2-[2-hydroxyethyl-[(z)-octadec-9-enyl]amino]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCCN(CCO)CCO BITAPBDLHJQAID-KTKRTIGZSA-N 0.000 description 1
- NKFNBVMJTSYZDV-UHFFFAOYSA-N 2-[dodecyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCCCN(CCO)CCO NKFNBVMJTSYZDV-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 101100208720 Homo sapiens USP5 gene Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 102100021017 Ubiquitin carboxyl-terminal hydrolase 5 Human genes 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910000438 diphosphorus tetroxide Inorganic materials 0.000 description 1
- GVEPAEOOBURRFW-UHFFFAOYSA-N dodecane-1,3-diol Chemical compound CCCCCCCCCC(O)CCO GVEPAEOOBURRFW-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- IOKYPACLTOWHCM-UHFFFAOYSA-N n,n-diethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(CC)CC IOKYPACLTOWHCM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N phosphorus trioxide Inorganic materials O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- COTPAMORPWZHKE-UHFFFAOYSA-H trizinc;thiophosphate;thiophosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=O.[O-]P([O-])([O-])=S COTPAMORPWZHKE-UHFFFAOYSA-H 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- JGSUMMPGKPITGK-UHFFFAOYSA-L zinc;n,n-dipentylcarbamodithioate Chemical compound [Zn+2].CCCCCN(C([S-])=S)CCCCC.CCCCCN(C([S-])=S)CCCCC JGSUMMPGKPITGK-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/24—Compounds containing phosphorus, arsenic or antimony
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/08—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least 2 hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
- C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
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Definitions
- the present invention relates to a lubricant composition for use in a wet clutch or a wet brake of a power transmission device for an automobile, an agricultural machine, a construction machine, or other industrial machines.
- a wet clutch or a wet brake of a power transmission device such as an automatic transmission for an automobile, an agricultural machine, a construction machine, or other industrial machines transmits a driving force by regulating the frictional properties of a plate on the driving side and a plate on the driven side, wherein the frictional properties of a lubricant employed for lubrication have a very important bearing.
- a wet clutch is taken up for explanation as a representative in the following description. Since inappropriate frictional properties cause a power transmission loss in the clutch and greatly affect the comfort on operating the machine, it is important for the lubricant to have appropriate frictional properties.
- the friction control of a wet clutch of this type involves three friction coefficients, i.e. dynamic friction coefficient, break-away friction coefficient, and static friction coefficient, and it is conventionally required for the regulation of the friction in a wet clutch of this type to raise the power transmission torque (called as dynamic friction coefficient in view of the friction coefficient and usually expressed as ⁇ d; hereinafter referred to as ⁇ d), and at the same time, to lower the friction transmission torque at the engaging point of the wet clutch (called as break-away friction coefficient in view of the friction coefficient and usually expressed as ⁇ 0; hereinafter referred to as ⁇ 0). If the ratio of ⁇ 0/ ⁇ d exceeds 1, a transmission shock is produced to arouse discomfort at the change of speed (when the clutch is operated). If the ratio is 1 or less, no such a transmission shock is produced and the transmission properties which do not impair the comfort are obtained.
- the power transmitting capacity of the wet clutch is also of importance, and in this connection, it is usually important to increase the static friction torque (called as static friction coefficient and expressed as ⁇ s to be distinguished from the break-away friction coefficient; hereinafter referred to as ⁇ s).
- the lubricant is required to show good durability in a long-time use while undergoing little aging change in the friction coefficient and to suppress the transmission shock over a long period of time, however, the addition of a large amount of a friction modifier, etc. to obtain this effect is associated with a problem of lowering in ⁇ s.
- the ⁇ 0/ ⁇ d ratio and the ⁇ s are in a trade-off relation with each other as described heretofore, and accordingly, a variety of designs and inventions have hitherto been made as will be described below.
- a lock-up clutch has recently come to be used in an automatic transmission for an automobile to reduce the fuel consumption and to reduce the power loss in a torque converter and thus, the lubricant has been imposed with a still more complicated factor.
- the problem in the lock-up clutch case is a vibration called shudder.
- the frictional properties at different rotations have an important bearing on the suppression of the vibration and the lubricant composition need be designed to have a ratio of the change in friction coefficient ( ⁇ ) to the change in slipping velocity (v) at the time when the speed of rotation is changed, i.e., d ⁇ /dv ⁇ 0.
- a lubricant composition comprising (A) a phosphoric ester having from 4 to 30 carbon atoms or an amine salt thereof, and (B) one compound selected from the group consisting of a sorbitan fatty acid ester, a glycerol fatty acid ester, a palm kernel oil fatty acid, a coconut oil fatty acid, a compound represented by the general formula (RCOO)2Zn, a mixture of a fat and oil and a fatty acid, and a reaction product of a polyalkylenepolyamine and a fatty acid.
- a series of Japanese Patent Application (Laid-Open) Nos. 39395/1991, 39396/1991, 39397/1992, 39398/1991 and 39399/1991 propose the use of a combination of (A) one compound selected from a phosphoric ester, a phosphorous ester, and an amine salt thereof each having from 4 to 30 carbon atoms, and (B) a tertiary amine, an aliphatic dicarboxylic acid, a primary zinc thiophosphate, a succinimide, an overbased magnesium, calcium sulfonate, or the like to improve frictional properties.
- A one compound selected from a phosphoric ester, a phosphorous ester, and an amine salt thereof each having from 4 to 30 carbon atoms
- B a tertiary amine, an aliphatic dicarboxylic acid, a primary zinc thiophosphate, a succinimide, an overbased magnesium, calcium sulfonate, or the like
- the present invention accordingly, provides, as a lubricant composition suitable for such a wet clutch, a lubricant composition satisfying such conditions that (1) the ⁇ 0/ ⁇ d ratio is reduced to eliminate any shock arising from a speed change, (2) the ⁇ s is increased as high as possible to enhance a torque transmitting property, and (3) the vibration of a lock-up clutch is prevented, while all friction coefficients are free from the temperature dependence.
- the present invention also provides a lubricant composition which is excellent in not only initial properties but also durability in view of the prevention of vibration of a lock-up clutch.
- the present invention relates to a lubricant composition for a wet clutch or a wet brake comprising a base oil having added thereto an inorganic phosphorus compound which may contain a sulfur atom and/or an oxygen atom as its constituent elements, or an amine salt thereof.
- a lubricant composition for a wet clutch or a wet brake comprising a base oil having added thereto an inorganic phosphorus compound which may contain sulfur atoms and/or oxygen atoms as its constituent elements, or an amine salt thereof, and an organic polyol compound having at least two hydroxyl groups in one molecule.
- the above-described lubricant composition for a wet clutch or a wet brake may further comprise an ashless dispersing agent containing a nitrogen atom.
- the base oil used as a principal component of the lubricant composition is not particularly restricted as far as it is a base oil usually employed for a lubricant, and may be a synthetic oil, a mineral oil, or a mixture thereof.
- the base oil preferably has a kinematic viscosity of 1 to 80 cSt (centisokes), more preferably 2 to 50 cSt, at 100°C.
- Examples of the mineral oil include a paraffin-based mineral oil, a naphthene-based mineral oil, and a paraffin-naphthene-based mineral oil, and further, a mineral oil dewaxed by a usual method or a mineral oil modified to have a high viscosity index may be used.
- Examples of the synthetic lubricant oil include various synthetic oils such as poly- ⁇ -olefin, a low-molecular ethylene- ⁇ -olefin copolymer, polybutene, a dibasic acid ester, polyglycol, a hindered ester, alkylbenzene, and polyether.
- a mixed oil of the above-described mineral oil and synthetic oil may also be used.
- the inorganic phosphorus compound which may contain an oxygen atom and/or a sulfur atom as its constituent elements includes the followings.
- Examples are phosphorous acid, phosphoric acid, hypophosphoric acid, phosphorus trioxide, phosphorus tetroxide, phosphorous pentoxide, phosphorotetrathionic acid (H3PS4), phosphoromonothionic acid (H3PO3S), phosphorodithionic acid (H3PO2S2), phosphorotrithionic acid (H3PO2S3), and P2S5.
- phosphorous acid and phosphoric acid are preferred.
- An amine salt of an inorganic phosphorus compound can also be preferably used.
- Examples of the amine for use in the amine salt include primary, secondary and tertiary amines, and, in particular, amines containing a tertiary alkyl group, for example, those containing tertiary carbon atoms as carbon atoms adjacent to nitrogen atoms, more specifically, those represented by R-C(CH3)2-NH2 (wherein R is an alkyl group having from 16 to 22 carbon atoms), are preferred. It is also possible to use a plurality of inorganic phosphorus compounds of these together.
- the inorganic phosphorus compound is preferably contained in an amount of from 0.005 wt% to 0.1 wt%, preferably from 0.01 wt% to 0.05 wt%, in terms of the molar amount of phosphorus, based on the total lubricant oil composition, and within this range, the effect of the present invention can be achieved.
- Examples of the organic polyol compound having at least two hydroxyl groups in one molecule include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-hexanediol, 2,4-hexanediol, 2,4-octanediol, and 1,3-dodecanediol.
- a triol, tetraol, or higher alcohol can be used as a simple substance, or as a partially esterified compound of the alcohol, such as a monoester, diester, or triester compound.
- a monoester, diester, or triester compound such as a monoester, diester, or triester compound.
- an ester with a carboxylic acid having from 1 to 40 carbon atoms, preferably with a fatty acid having from 1 to 24 carbon atoms is used.
- the ester is usually a mixture of mono-, di- and triesters, and it is preferred to distill and refine it by molecular distillation, etc. to convert it into a mixture of diester and monoester, or preferably a monoester of higher purity.
- An ester of a polyhydric alcohol such as tetraol can also be used, and a mixture of di-, tri-, and tetraesters formed with the above-described acids can also be used to leave at least two hydroxyl groups in one molecule.
- an alkylaryl group may be used or a carboxylic ester having an alkylarly group may be formed to increase solubility in the base oil.
- a polyhydric alcohol having an ester group may be in the form of a thioester.
- one of the hydroxyl groups is preferably in the ⁇ , ⁇ , or ⁇ -position relative to the other hydroxyl group. Two or more of various compounds containing these hydroxyl groups may also be used.
- the polyol compound containing at least two hydroxyl groups in one molecule is preferably contained in an amount of from 0.01 wt% to 4 wt%, preferably from 0.1 wt% to 1 wt% based on the total lubricant composition, and within this range, the effects of the present invention can be achieved.
- the lubricant composition of the present invention may contain, for the purpose of improving performance as a lubricant, additives usually employed, if desire, such as an antioxidant, a detergent-dispersant, an extreme-pressure agent, a friction modifier, an oiliness improver, an anti-wear agent, a corrosion inhibitor, a rust preventing agent, a rubber swelling agent, a defoaming agent, a pour-point depressant, and a viscosity index improver.
- additives usually employed, if desire such as an antioxidant, a detergent-dispersant, an extreme-pressure agent, a friction modifier, an oiliness improver, an anti-wear agent, a corrosion inhibitor, a rust preventing agent, a rubber swelling agent, a defoaming agent, a pour-point depressant, and a viscosity index improver.
- a phenol-based antioxidant As the antioxidant, a phenol-based antioxidant, an aromatic amine-based antioxidant, a zinc dithiophosphate, etc., is used, and specific examples thereof include 2,6-di-t-butyl-4-methylphenol, 4,4'-methylenebis(2,6-di-t-butylphenol), phenyl- ⁇ -naphthylamine, dialkyldiphenylamine, zinc di-2-ethylhexyldithiophosphate, zinc diamyldithiocarbamate, and pinene pentasulfide.
- the antioxidant is added in an amount of from 0.01 wt% to 2 wt%, preferably from 0.05 wt% to 1 wt%, based on the lubricant composition.
- the detergent-dispersant may be an ashless dispersant, a metallic detergent, or an ashless dispersant containing boron. Specific examples thereof include alkenyl succinimide- and benzylamine-type ashless dispersants, boronized polyisobutenyl succinimide- and boronized benzylamine-type ashless dispersants, metal sulfonate, metal phenate and metal salicylate.
- the metallic detergent indicates those containing a metal such as magnesium, calcium, or barium.
- the detergent-dispersant is added in an amount of from 0.01 wt% to 10 wt%, preferably from 0.5 wt% to 5 wt%, based on the lubricant composition.
- the friction modifier examples include an amine compound such as oleyldiethanolamine, dodecyldiethanolamine, dodecyldipropanolamine, oleylamine, hexadecylamine, dodecyldiethylamine, dodecylethanolamine, and a mixture thereof, an amide such as oleic amide, dodecylcarboxylic acid diethanolamide, dodecylcarboxylic acid propanolamide, oleic acid diethanolamide, oleic acid propanolamide, hexadecylcarboxylic acid diethanolamide, hexadecylcarboxylic acid propanolamide, and a mixture thereof, and N-hydroxyethyl oleylimidazoline.
- an amine compound such as oleyldiethanolamine, dodecyldiethanolamine, dodecyldipropanolamine, oleylamine, hex
- additives other than the antioxidant, the detergent-dispersant and the friction modifier are added in such an amount as in the addition for modifying a lubricant for a wet clutch or a wet brake.
- the ⁇ d was likewise adopted as for ⁇ d.
- Disk Paper disk for automatic transmission (1 disk)
- Plate Steel plate for automatic transmission (1 plate)
- Surface pressure 10 kg/cm2
- Lubricant temp. 40°C, 100°C
- Motor rotating speed 40°C, 100°C
- the rotating speed was intermittently varied in a range of from 1 to 100 rpm.
- the rotating speed was varied to determine the friction coefficient ( ⁇ ) versus the slip velocity (v), and when d ⁇ /dv ⁇ 0, the vibration was prevented and judgement was good.
- the friction coefficient at the rotation speed of 1 rpm was defined as ⁇ 1 and the friction coefficient at 50 rpm was defined as ⁇ 50.
- the ⁇ 1/ ⁇ 50 ratio was employed as the index.
- the lubricant satisfying ⁇ l/ ⁇ 50 ⁇ 1 was concluded as having a preferred ability of preventing vibration.
- ⁇ l/ ⁇ 50 ⁇ 1 is easily achieved in the vicinity of a practical working temperature range of from 80°C to 120°C, the reduction in the absolute value of ⁇ 1 disadvantageously causes the slipping of the clutch.
- the value of ⁇ generally shows the temperature dependence and becomes smaller as the temperature is elevated, and a lubricant free of the temperature dependence is demanded.
- the test was conducted at 165.5°C for 120 hours in accordance with the oxidation stability test of a lubricant for an internal combustion engine (JIS K-2514).
- the amount of copper eluted after the processing at 150°C for 16 hours in accordance with JIS K-2513 was measured and the evaluation was made for judging the corrosion thereafter.
- Samples each having the following composition were prepared by further adding thereto, in addition to the additives set forth below and additives described in respective tables, a paraffin-based mineral oil having a kinematic viscosity of 4.2 cSt at 100°C as the rest to make up 100 wt% in total, in which the phosphorus was added so that the molar amounts of the phosphorus in the compositions became equal, and the above-described evaluation was conducted.
- the evaluation results are shown in Table 1 and Table 2.
- Tables the overall characteristics as a lubricant composition are expressed by O as excellent, ⁇ as good, ⁇ as acceptable, and X as unacceptable.
- Lubricant Composition wt%) Polybutenyl succinimide (HiTEC 644: produced by Ethyl Petroleum Additives Inc.) 4.0 Phenol-based antioxidant (HiTEC 4728: produced by Ethyl Petroleum Additives Inc.) 0.5 N-Hydroxyethyl oleylimidazoline 0.02 Hydroxyethyl long-chained amine (Ethomeen T-12: produced by Akzo Chem.
- orthophosphorous acid was used as an inorganic phosphorus compound and monolauryl glyceride as a polyol.
- Example 1 As is apparent from comparison of Example 1 with Comparative Examples 1, 3 and 5, the samples containing the inorganic phosphorus compound show high ⁇ d and ⁇ s, the lowest ⁇ 0/ ⁇ 1200 ratio, and low ⁇ s and ⁇ d indicating the aging change of the friction coefficient, revealing to be best. Other samples show high ⁇ 0/ ⁇ d ratio and also high ⁇ s and ⁇ d, revealing to be bad.
- Lubricant compositions were prepared in the same manner as the lubricant compositions in Examples 1 and 2 and Comparative Examples 1 to 6, except for adding 0.1 wt% of boric acid.
- Example 3 As is apparent from comparison between Examples 3 and 4 and Comparative Examples 7 to 10, when the inorganic phosphorus compound and monolauryl glyceride are present together as in Example 3, the samples satisfying both the frictional properties in SAE No. 2 test and the durability and temperature dependence in LVFA test are obtained.
- Lubricant compositions were prepared in the same manner as the lubricant compositions in Examples 3 and 4 and Comparative Examples 7 to 10 above, except for changing the friction modifier to an amine-type friction modifier and the polyol compound variously.
- the composition of each lubricant composition is shown in Table 5, and the results are shown in Tables 5 and 6.
- the samples containing an inorganic phosphorus compound of the present invention and 2,4-hexanediol, 2,4-octanediol, monobutyl glyceride, monolauryl glyceride, or dioleylpentaerythritol ester show a low ⁇ 0/ ⁇ d ratio, while maintaining a high ⁇ s.
- the ⁇ l/ ⁇ 50 ratio in LVFA of the lubricant used in the SAE NO. 2 friction test is low and no temperature dependence appears.
- the lubricant composition of the present invention exhibits excellent frictional properties in a wet clutch and a wet brake, in particular, provides a high ⁇ d (dynamic friction coefficient) and a high ⁇ s (static friction coefficient), shows good prevention of vibration in a lock-up clutch used for an automatic transmission, is imparted with good durability for preventing the vibration, thus showing excellent properties as a lubricant composition for a wet clutch or a wet brake, further, has friction coefficients free from the temperature dependence, and works sufficiently effectively as a shock absorber oil, a power steering oil, a hydraulic suspension oil, etc.
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Abstract
Description
- The present invention relates to a lubricant composition for use in a wet clutch or a wet brake of a power transmission device for an automobile, an agricultural machine, a construction machine, or other industrial machines.
- A wet clutch or a wet brake of a power transmission device such as an automatic transmission for an automobile, an agricultural machine, a construction machine, or other industrial machines transmits a driving force by regulating the frictional properties of a plate on the driving side and a plate on the driven side, wherein the frictional properties of a lubricant employed for lubrication have a very important bearing. A wet clutch is taken up for explanation as a representative in the following description. Since inappropriate frictional properties cause a power transmission loss in the clutch and greatly affect the comfort on operating the machine, it is important for the lubricant to have appropriate frictional properties.
- The friction control of a wet clutch of this type involves three friction coefficients, i.e. dynamic friction coefficient, break-away friction coefficient, and static friction coefficient, and it is conventionally required for the regulation of the friction in a wet clutch of this type to raise the power transmission torque (called as dynamic friction coefficient in view of the friction coefficient and usually expressed as µd; hereinafter referred to as µd), and at the same time, to lower the friction transmission torque at the engaging point of the wet clutch (called as break-away friction coefficient in view of the friction coefficient and usually expressed as µ0; hereinafter referred to as µ0). If the ratio of µ0/µd exceeds 1, a transmission shock is produced to arouse discomfort at the change of speed (when the clutch is operated). If the ratio is 1 or less, no such a transmission shock is produced and the transmission properties which do not impair the comfort are obtained.
- The power transmitting capacity of the wet clutch is also of importance, and in this connection, it is usually important to increase the static friction torque (called as static friction coefficient and expressed as µs to be distinguished from the break-away friction coefficient; hereinafter referred to as µs).
- Since these friction coefficients depend largely upon the lubricant employed, for improving the transmission shock, the use of a friction modifier, etc. has usually been practiced to reduce the ratio of µ0/µd to 1 or less, however, the addition of the friction modifier, etc. causes at the same time a problem of lowering in µs. It is, therefore, important in lubricating machines under consideration to obtain a lubricant capable of reducing the µ0/µd ratio to 1 or less and increasing µs as much as possible, thereby eliminating the transmission shock and attaining a high transmitting capacity.
- The lubricant is required to show good durability in a long-time use while undergoing little aging change in the friction coefficient and to suppress the transmission shock over a long period of time, however, the addition of a large amount of a friction modifier, etc. to obtain this effect is associated with a problem of lowering in µs. The µ0/µd ratio and the µs are in a trade-off relation with each other as described heretofore, and accordingly, a variety of designs and inventions have hitherto been made as will be described below.
- A lock-up clutch has recently come to be used in an automatic transmission for an automobile to reduce the fuel consumption and to reduce the power loss in a torque converter and thus, the lubricant has been imposed with a still more complicated factor. Specifically, the problem in the lock-up clutch case is a vibration called shudder. The frictional properties at different rotations have an important bearing on the suppression of the vibration and the lubricant composition need be designed to have a ratio of the change in friction coefficient (µ) to the change in slipping velocity (v) at the time when the speed of rotation is changed, i.e., dµ/dv ≧ 0.
- The addition of the friction modifier, etc. for achieving dµ/dv ≧ 0, however, usually results in the reduction of static friction coefficient (µs). Moreover, the vibration is more likely to occur at a relatively low temperature, and therefore, the above-described dµ/dv ≧ 0 need be achieved at a low temperature, however, the friction coefficient is usually so dependent on temperature as to drop along with an elevation in lubricant temperature. Even though the prevention of vibration at a low temperature, for example, 40°C, is achieved by blending a large amount of friction modifier, etc., or by blending a very effective friction modifier with too much care to the prevention of vibration, the friction coefficient in a working temperature range of 80°C to 120°C lowers excessively and thereby the torque transmitting capacity in the lock-up clutch decreases, leading to a problem of easy slipping. The friction coefficient is, therefore, desired to be free from the temperature dependence. And also, the durability is required for the suppression of vibration in the lock-up clutch. Accordingly, blending of a large amount of friction modifier, etc. is required in the prior art, which gives rise to the reduction in static friction coefficient (µs).
- The frictional properties are mutually contradictory as stated above, and therefore, a variety of friction modifiers, detergents, phosphoric esters, etc. have hitherto been used. Japanese Patent Application (Laid-Open) No. 173097/1985 (corresponding to Japanese Patent Publication No. 46635/1990), for example, proposes a lubricant composition comprising (A) a phosphoric ester having from 4 to 30 carbon atoms or an amine salt thereof, and (B) one compound selected from the group consisting of a sorbitan fatty acid ester, a glycerol fatty acid ester, a palm kernel oil fatty acid, a coconut oil fatty acid, a compound represented by the general formula (RCOO)₂Zn, a mixture of a fat and oil and a fatty acid, and a reaction product of a polyalkylenepolyamine and a fatty acid.
- A series of Japanese Patent Application (Laid-Open) Nos. 39395/1991, 39396/1991, 39397/1992, 39398/1991 and 39399/1991 propose the use of a combination of (A) one compound selected from a phosphoric ester, a phosphorous ester, and an amine salt thereof each having from 4 to 30 carbon atoms, and (B) a tertiary amine, an aliphatic dicarboxylic acid, a primary zinc thiophosphate, a succinimide, an overbased magnesium, calcium sulfonate, or the like to improve frictional properties.
- All of these techniques employ an amine salt of an organic phosphoric acid having from 4 to 30 carbon atoms to improve the friction behavior.
- These conventional lubricant compositions are, however, still unsatisfactory not only in the friction behavior but also in durability and need be more improved. More specifically, in the prior techniques, a very effective compound is used as a friction modifier or a large amount of friction modifier is used to prevent the vibration of a lock-up clutch. The use of such a friction modifier, however, impairs a static friction coefficient (µs), or the friction control power cannot be maintained by the deterioration or consumption of friction modifier, resulting in the failure to provide satisfactory durability. Moreover, satisfactory performance is not provided with respect to oxidation stability and corrosiveness to copper.
- The present invention, accordingly, provides, as a lubricant composition suitable for such a wet clutch, a lubricant composition satisfying such conditions that (1) the µ0/µd ratio is reduced to eliminate any shock arising from a speed change, (2) the µs is increased as high as possible to enhance a torque transmitting property, and (3) the vibration of a lock-up clutch is prevented, while all friction coefficients are free from the temperature dependence.
- The present invention also provides a lubricant composition which is excellent in not only initial properties but also durability in view of the prevention of vibration of a lock-up clutch.
- The present invention relates to a lubricant composition for a wet clutch or a wet brake comprising a base oil having added thereto an inorganic phosphorus compound which may contain a sulfur atom and/or an oxygen atom as its constituent elements, or an amine salt thereof.
- It also relates to a lubricant composition for a wet clutch or a wet brake comprising a base oil having added thereto an inorganic phosphorus compound which may contain sulfur atoms and/or oxygen atoms as its constituent elements, or an amine salt thereof, and an organic polyol compound having at least two hydroxyl groups in one molecule.
- The above-described lubricant composition for a wet clutch or a wet brake may further comprise an ashless dispersing agent containing a nitrogen atom.
- In the lubricant composition for a wet clutch or a wet brake according to the present invention, the base oil used as a principal component of the lubricant composition is not particularly restricted as far as it is a base oil usually employed for a lubricant, and may be a synthetic oil, a mineral oil, or a mixture thereof. The base oil preferably has a kinematic viscosity of 1 to 80 cSt (centisokes), more preferably 2 to 50 cSt, at 100°C. Examples of the mineral oil include a paraffin-based mineral oil, a naphthene-based mineral oil, and a paraffin-naphthene-based mineral oil, and further, a mineral oil dewaxed by a usual method or a mineral oil modified to have a high viscosity index may be used.
- Examples of the synthetic lubricant oil include various synthetic oils such as poly-α-olefin, a low-molecular ethylene-α-olefin copolymer, polybutene, a dibasic acid ester, polyglycol, a hindered ester, alkylbenzene, and polyether. A mixed oil of the above-described mineral oil and synthetic oil may also be used.
- The inorganic phosphorus compound which may contain an oxygen atom and/or a sulfur atom as its constituent elements includes the followings.
- Examples are phosphorous acid, phosphoric acid, hypophosphoric acid, phosphorus trioxide, phosphorus tetroxide, phosphorous pentoxide, phosphorotetrathionic acid (H₃PS₄), phosphoromonothionic acid (H₃PO₃S), phosphorodithionic acid (H₃PO₂S₂), phosphorotrithionic acid (H₃PO₂S₃), and P₂S₅. Among these, phosphorous acid and phosphoric acid are preferred. An amine salt of an inorganic phosphorus compound can also be preferably used. Examples of the amine for use in the amine salt include primary, secondary and tertiary amines, and, in particular, amines containing a tertiary alkyl group, for example, those containing tertiary carbon atoms as carbon atoms adjacent to nitrogen atoms, more specifically, those represented by R-C(CH₃)₂-NH₂ (wherein R is an alkyl group having from 16 to 22 carbon atoms), are preferred. It is also possible to use a plurality of inorganic phosphorus compounds of these together.
- The inorganic phosphorus compound is preferably contained in an amount of from 0.005 wt% to 0.1 wt%, preferably from 0.01 wt% to 0.05 wt%, in terms of the molar amount of phosphorus, based on the total lubricant oil composition, and within this range, the effect of the present invention can be achieved.
- Examples of the organic polyol compound having at least two hydroxyl groups in one molecule include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-hexanediol, 2,4-hexanediol, 2,4-octanediol, and 1,3-dodecanediol.
- A triol, tetraol, or higher alcohol can be used as a simple substance, or as a partially esterified compound of the alcohol, such as a monoester, diester, or triester compound. Specifically, when glycerol or trimethylolpropane formed from triol is used, an ester with a carboxylic acid having from 1 to 40 carbon atoms, preferably with a fatty acid having from 1 to 24 carbon atoms is used. Industrially, the ester is usually a mixture of mono-, di- and triesters, and it is preferred to distill and refine it by molecular distillation, etc. to convert it into a mixture of diester and monoester, or preferably a monoester of higher purity. An ester of a polyhydric alcohol such as tetraol can also be used, and a mixture of di-, tri-, and tetraesters formed with the above-described acids can also be used to leave at least two hydroxyl groups in one molecule. When using a polyhydric alcohol, an alkylaryl group may be used or a carboxylic ester having an alkylarly group may be formed to increase solubility in the base oil. A polyhydric alcohol having an ester group may be in the form of a thioester. In the polyol containing hydroxyl groups, one of the hydroxyl groups is preferably in the α, β, or γ-position relative to the other hydroxyl group. Two or more of various compounds containing these hydroxyl groups may also be used.
- The polyol compound containing at least two hydroxyl groups in one molecule is preferably contained in an amount of from 0.01 wt% to 4 wt%, preferably from 0.1 wt% to 1 wt% based on the total lubricant composition, and within this range, the effects of the present invention can be achieved.
- In addition to the above-described essential components, the lubricant composition of the present invention may contain, for the purpose of improving performance as a lubricant, additives usually employed, if desire, such as an antioxidant, a detergent-dispersant, an extreme-pressure agent, a friction modifier, an oiliness improver, an anti-wear agent, a corrosion inhibitor, a rust preventing agent, a rubber swelling agent, a defoaming agent, a pour-point depressant, and a viscosity index improver.
- As the antioxidant, a phenol-based antioxidant, an aromatic amine-based antioxidant, a zinc dithiophosphate, etc., is used, and specific examples thereof include 2,6-di-t-butyl-4-methylphenol, 4,4'-methylenebis(2,6-di-t-butylphenol), phenyl-α-naphthylamine, dialkyldiphenylamine, zinc di-2-ethylhexyldithiophosphate, zinc diamyldithiocarbamate, and pinene pentasulfide. The antioxidant is added in an amount of from 0.01 wt% to 2 wt%, preferably from 0.05 wt% to 1 wt%, based on the lubricant composition.
- The detergent-dispersant may be an ashless dispersant, a metallic detergent, or an ashless dispersant containing boron. Specific examples thereof include alkenyl succinimide- and benzylamine-type ashless dispersants, boronized polyisobutenyl succinimide- and boronized benzylamine-type ashless dispersants, metal sulfonate, metal phenate and metal salicylate. The metallic detergent indicates those containing a metal such as magnesium, calcium, or barium. The detergent-dispersant is added in an amount of from 0.01 wt% to 10 wt%, preferably from 0.5 wt% to 5 wt%, based on the lubricant composition.
- Examples of the friction modifier include an amine compound such as oleyldiethanolamine, dodecyldiethanolamine, dodecyldipropanolamine, oleylamine, hexadecylamine, dodecyldiethylamine, dodecylethanolamine, and a mixture thereof, an amide such as oleic amide, dodecylcarboxylic acid diethanolamide, dodecylcarboxylic acid propanolamide, oleic acid diethanolamide, oleic acid propanolamide, hexadecylcarboxylic acid diethanolamide, hexadecylcarboxylic acid propanolamide, and a mixture thereof, and N-hydroxyethyl oleylimidazoline.
- The above-described additives other than the antioxidant, the detergent-dispersant and the friction modifier are added in such an amount as in the addition for modifying a lubricant for a wet clutch or a wet brake.
- The present invention will now be described with reference to Examples. The addition amount in Examples are in wt%.
- The evaluation on performance of the lubricant composition described below is conducted in accordance with the following test method.
- Evaluation was conducted by using this tester under the following conditions:
- Disk:
- Paper disk for automatic transmission
- Plate:
- Steel plate for automatic transmission
- Motor rotating speed:
- 3000 rpm
- The higher values of µd and µs were judged the better, and those satisfying µ0/µd≦1.1 were concluded preferable. Those satisfying µ0/µd≦1.0 were more preferred.
-
- The lower Δµs and Δµd were accordingly judged the better.
- The evaluation was conducted on the prevention of vibration of a lock-up clutch by using a single-plate low-velocity friction tester. The relation of the friction coefficient-the slip velocity (hereinafter referred to as µ-v characteristics) at a fixed temperature was obtained.
Disk: Paper disk for automatic transmission (1 disk)
Plate: Steel plate for automatic transmission (1 plate)Surface pressure: 10 kg/cm² Lubricant temp.: 40°C, 100°C
Motor rotating speed: - The rotating speed was intermittently varied in a range of from 1 to 100 rpm.
- The rotating speed was varied to determine the friction coefficient (µ) versus the slip velocity (v), and when dµ/dv≧0, the vibration was prevented and judgement was good.
- For the sake of convenience, the friction coefficient at the rotation speed of 1 rpm was defined as µ1 and the friction coefficient at 50 rpm was defined as µ50. The µ1/µ50 ratio was employed as the index. The lubricant satisfying µl/µ50≦1 was concluded as having a preferred ability of preventing vibration.
- In LVFA, the lower the lubricant temperature, the more difficult the prevention of vibration, and the µl/µ50 ratio as an index of frictional properties is likely to become µ1/µ50≧1. On the other hand, although µl/µ50≦1 is easily achieved in the vicinity of a practical working temperature range of from 80°C to 120°C, the reduction in the absolute value of µ1 disadvantageously causes the slipping of the clutch. The value of µ generally shows the temperature dependence and becomes smaller as the temperature is elevated, and a lubricant free of the temperature dependence is demanded. Therefore, the ratio of µl(40°C)/µl(100°C)=µ1(T) was employed as the index showing the temperature dependence, by taking the friction coefficient at 1 rpm and 40°C as µl(40°C), and the friction coefficient at 1 rpm and 100°C as µl(100°C), with the value of µl(T) close to 1 being concluded as good.
- For evaluating the durability on the prevention of vibration, the evaluation of µ-v characteristics was conducted in LVFA for the tested lubricant after 10,000 cycles in the SAE No. 2 friction test using a new disk and a new plate. The µl/µ50 ratio of the new lubricant and the µl/µ50 ratio of the used lubricant were compared and the lubricant which showed little difference in the ratio value was concluded as having good durability.
- The test was conducted at 165.5°C for 120 hours in accordance with the oxidation stability test of a lubricant for an internal combustion engine (JIS K-2514).
- The amount of copper eluted after the processing at 150°C for 16 hours in accordance with JIS K-2513 was measured and the evaluation was made for judging the corrosion thereafter.
- Samples each having the following composition were prepared by further adding thereto, in addition to the additives set forth below and additives described in respective tables, a paraffin-based mineral oil having a kinematic viscosity of 4.2 cSt at 100°C as the rest to make up 100 wt% in total, in which the phosphorus was added so that the molar amounts of the phosphorus in the compositions became equal, and the above-described evaluation was conducted. The evaluation results are shown in Table 1 and Table 2. In Tables, the overall characteristics as a lubricant composition are expressed by Ⓞ as excellent, ○ as good, △ as acceptable, and X as unacceptable.
Formulation of Lubricant Composition (wt%) Polybutenyl succinimide (HiTEC 644: produced by Ethyl Petroleum Additives Inc.) 4.0 Phenol-based antioxidant (HiTEC 4728: produced by Ethyl Petroleum Additives Inc.) 0.5 N-Hydroxyethyl oleylimidazoline 0.02 Hydroxyethyl long-chained amine (Ethomeen T-12: produced by Akzo Chem. Inc.) 0.1 Sulfurized fats and oils (Sulperm 10S: produced by Keil Products Division of Ferro Corporation) 0.5 Tolyltriazole 0.04 Caprylic acid 0.05 Calcium phenate (Oloa 216: produced by Chevron Chemical Co.) 0.05 Silicone-based defoaming agent (added to account for 8 ppm in the test oil in terms of silicon element) Acrylate copolymer (PC-1244: produced by Monsanto Co.) 0.02 Dispersion-type polymethacrylate 6.0 Compounds shown in each Table amounts shown in each Table Paraffin-based mineral oil (kinematic viscosity at 100°C: 4.2 cSt) the rest (100 in total) -
- As is apparent from comparison of Example 1 with Comparative Examples 1, 3 and 5, the samples containing the inorganic phosphorus compound show high µd and µs, the lowest µ0/µ1200 ratio, and low Δµs and Δµd indicating the aging change of the friction coefficient, revealing to be best. Other samples show high µ0/µd ratio and also high Δµs and Δµd, revealing to be bad.
- The effect of monolauryl glyceride as a polyol is confirmed by the evaluation in LVFA of the lubricants used in the SAE No. 2 friction test, that is, without monolauryl glyceride, the µl/µ50 ratio exceeds 1, and the temperature dependence appears as seen from µl(T).
- In conclusion, it is found that, when the inorganic phosphorus compound and monolauryl glyceride are present together, ideal frictional properties are obtained such as high µd and µs and a low µ0/µd ratio in the SAE NO. 2 frictional properties, and µl/µ50 below 1 and µl(T) closest to 1 in the µ-v characteristics by LVFA for the used oil.
- Lubricant compositions were prepared in the same manner as the lubricant compositions in Examples 1 and 2 and Comparative Examples 1 to 6, except for adding 0.1 wt% of boric acid.
-
- As is apparent from comparison between Examples 3 and 4 and Comparative Examples 7 to 10, when the inorganic phosphorus compound and monolauryl glyceride are present together as in Example 3, the samples satisfying both the frictional properties in SAE No. 2 test and the durability and temperature dependence in LVFA test are obtained.
- Lubricant compositions were prepared in the same manner as the lubricant compositions in Examples 3 and 4 and Comparative Examples 7 to 10 above, except for changing the friction modifier to an amine-type friction modifier and the polyol compound variously. The composition of each lubricant composition is shown in Table 5, and the results are shown in Tables 5 and 6.
- As is apprent from Comparative Examples 11 to 13, although the µ0/µd ratio is improved by increasing the addition amount of the amine-type friction modifier, the µs lowers as the addition amount increases, which is disadvantageous. Also, in the µ-v characteristics by LVFA, the µ1/µ50 ratio is improved as the addition amount increases, but the absolute value of µl decreases and the value of µl(T) becomes larger, which is disadvantageous. In other words, when the amount of ordinary friction modifier is increased to prevent vibration in the lock-up clutch, the prevention of vibration can be achieved but the µs indicating a torque transmitting capacity lowers and also the value of µ1 in a high lubricant temperature range decreases in the case of a lock-up clutch due to the temperature dependence, accompanied with the slipping of the clutch, which is disadvantageous.
- On the other hand, as is apparent from Examples 5 to 10, the samples containing an inorganic phosphorus compound of the present invention and 2,4-hexanediol, 2,4-octanediol, monobutyl glyceride, monolauryl glyceride, or dioleylpentaerythritol ester show a low µ0/µd ratio, while maintaining a high µs. Moreover, the µl/µ50 ratio in LVFA of the lubricant used in the SAE NO. 2 friction test is low and no temperature dependence appears.
-
- As is apparent from the Table, when the inorganic phosphorus compound is added, the oxidation stability is good with a small increase in kinematic viscosity and total acid number. The less the eluted copper amount, the better, and samples containing the phosphorus compound showed good results.
- The same lubricant compositions as in Examples 11 and 12 and Comparative Examples 14 to 17 were subjected to a corrosion test of copper plates.
-
- Also in the corrosion test of copper plate, the eluted amount of copper is small when added the inorganic phosphorus compound, revealing the superiority of the addition.
- The lubricant composition of the present invention exhibits excellent frictional properties in a wet clutch and a wet brake, in particular, provides a high µd (dynamic friction coefficient) and a high µs (static friction coefficient), shows good prevention of vibration in a lock-up clutch used for an automatic transmission, is imparted with good durability for preventing the vibration, thus showing excellent properties as a lubricant composition for a wet clutch or a wet brake, further, has friction coefficients free from the temperature dependence, and works sufficiently effectively as a shock absorber oil, a power steering oil, a hydraulic suspension oil, etc.
Piston pressure: | 40 psi |
Lubricant temperature: | 120°C |
The maximum friction coefficient at the engaging point at 0.7 rpm was measured as the static friction coefficient (µs).
Claims (3)
- A lubricant composition for a wet clutch or a wet brake comprising a base oil having added thereto an inorganic phosphorus compound which may contain sulfur atoms and/or oxygen atoms as its constituent elements, or an amine salt thereof.
- A lubricant composition for a wet clutch or a wet brake comprising a base oil having added thereto an inorganic phosphorus compound which may contain sulfur atoms and/or oxygen atoms as its constituent elements, or an amine salt thereof, and an organic polyol compound having at least two hydroxyl groups in one molecule.
- A lubricant composition for a wet clutch or a wet brake according to Claim 1 or Claim 2, which contains an ashless dispersant containing nitrogen atoms.
Applications Claiming Priority (4)
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JP21920092 | 1992-08-18 | ||
JP21920092 | 1992-08-18 | ||
JP219200/92 | 1992-08-18 | ||
PCT/JP1993/001155 WO1994004637A1 (en) | 1992-08-18 | 1993-08-18 | Lubricating oil composition for wet clutch or wet brake |
Publications (4)
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EP0622444A1 true EP0622444A1 (en) | 1994-11-02 |
EP0622444A4 EP0622444A4 (en) | 1995-02-15 |
EP0622444B1 EP0622444B1 (en) | 1999-12-29 |
EP0622444B2 EP0622444B2 (en) | 2003-10-22 |
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EP94908130A Expired - Lifetime EP0622444B2 (en) | 1992-08-18 | 1993-08-18 | Use of inorganic phosphorus compounds as friction improvers in wet clutch or wet brake lubricant compositions |
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Country | Link |
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EP (1) | EP0622444B2 (en) |
DE (1) | DE69327453T3 (en) |
WO (1) | WO1994004637A1 (en) |
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- 1993-08-18 WO PCT/JP1993/001155 patent/WO1994004637A1/en active IP Right Grant
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- 1993-08-18 EP EP94908130A patent/EP0622444B2/en not_active Expired - Lifetime
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Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100239817B1 (en) * | 1994-12-09 | 2000-01-15 | 만셀 케이쓰 로드니 | Synergistic antioxidant system |
WO1996017914A1 (en) * | 1994-12-09 | 1996-06-13 | Exxon Chemical Patents Inc. | Oil soluble complexes of phosphorus-containing acids useful as lubricating oil additives |
WO1996017912A1 (en) * | 1994-12-09 | 1996-06-13 | Exxon Chemical Patents Inc. | Synergistic antioxidant systems |
US6121209A (en) * | 1994-12-09 | 2000-09-19 | Exxon Chemical Patents Inc | Synergistic antioxidant systems |
US5773392A (en) * | 1994-12-09 | 1998-06-30 | Exxon Chemical Patents Inc. | Oil soluble complexes of phosphorus-containing acids useful as lubricating oil additives |
AU693624B2 (en) * | 1994-12-09 | 1998-07-02 | Exxon Chemical Patents Inc. | Oil soluble complexes of phosphorus-containing acids useful as lubricating oil additives |
AU697033B2 (en) * | 1994-12-09 | 1998-09-24 | Exxon Chemical Patents Inc. | Synergistic antioxidant systems |
EP0747464A1 (en) * | 1995-06-09 | 1996-12-11 | The Lubrizol Corporation | A composition for providing anti-shudder friction durability performance for automatic transmissions |
AU711001C (en) * | 1995-06-09 | 2002-10-17 | Lubrizol Corporation, The | A composition for providing anti-shudder friction durability performance for automatic transmissions |
US5858929A (en) * | 1995-06-09 | 1999-01-12 | The Lubrizol Corporation | Composition for providing anti-shudder friction durability performance for automatic transmissions |
AU711001B2 (en) * | 1995-06-09 | 1999-10-07 | Lubrizol Corporation, The | A composition for providing anti-shudder friction durability performance for automatic transmissions |
US6251840B1 (en) | 1995-09-12 | 2001-06-26 | The Lubrizol Corporation | Lubrication fluids for reduced air entrainment and improved gear protection |
EP0761805A3 (en) * | 1995-09-12 | 1997-06-11 | Lubrizol Corp | Lubrication fluids for reduced air entrainment and improved gear protection |
EP0761805A2 (en) * | 1995-09-12 | 1997-03-12 | The Lubrizol Corporation | Lubrication fluids for reduced air entrainment and improved gear protection |
EP0769546A3 (en) * | 1995-10-18 | 1998-06-17 | The Lubrizol Corporation | Antiwear enhancing composition for lubricants and functional fluids |
US5972851A (en) * | 1997-11-26 | 1999-10-26 | Ethyl Corporation | Automatic transmission fluids having enhanced performance capabilities |
WO2000073406A1 (en) * | 1999-05-28 | 2000-12-07 | Infineum International Limited | Zinc-free continuously variable transmission fluid |
US6528458B1 (en) | 2002-04-19 | 2003-03-04 | The Lubrizol Corporation | Lubricant for dual clutch transmission |
EP1518919A1 (en) * | 2003-09-25 | 2005-03-30 | Afton Chemical Corporation | Boron free automotive gear oil |
EP1739321A3 (en) * | 2005-06-30 | 2007-01-10 | Afton Chemical Corporation | Methods for improved power transmission performance |
DE102008043231A1 (en) | 2008-10-28 | 2010-04-29 | Volkswagen Ag | Synthetic lubricant composition and its use |
DE102010028168A1 (en) | 2010-04-23 | 2011-10-27 | Volkswagen Ag | Synthetic lubricant composition and its use in active differentials |
WO2011131614A1 (en) | 2010-04-23 | 2011-10-27 | Volkswagen Ag | Synthetic lubricant composition and use thereof in active differentials |
Also Published As
Publication number | Publication date |
---|---|
DE69327453D1 (en) | 2000-02-03 |
EP0622444A4 (en) | 1995-02-15 |
EP0622444B2 (en) | 2003-10-22 |
WO1994004637A1 (en) | 1994-03-03 |
DE69327453T3 (en) | 2004-07-01 |
EP0622444B1 (en) | 1999-12-29 |
DE69327453T2 (en) | 2000-05-11 |
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