EP1310548A1 - Composition lubrifiantes contenant du bore - Google Patents
Composition lubrifiantes contenant du bore Download PDFInfo
- Publication number
- EP1310548A1 EP1310548A1 EP01309510A EP01309510A EP1310548A1 EP 1310548 A1 EP1310548 A1 EP 1310548A1 EP 01309510 A EP01309510 A EP 01309510A EP 01309510 A EP01309510 A EP 01309510A EP 1310548 A1 EP1310548 A1 EP 1310548A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mass
- ppm
- composition
- boron
- oil composition
- 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.)
- Withdrawn
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- 239000000203 mixture Substances 0.000 title claims abstract description 164
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 65
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 49
- 239000000654 additive Substances 0.000 claims abstract description 90
- 239000003921 oil Substances 0.000 claims abstract description 63
- 230000000996 additive effect Effects 0.000 claims abstract description 57
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011593 sulfur Substances 0.000 claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011574 phosphorus Substances 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 38
- 230000001050 lubricating effect Effects 0.000 claims abstract description 14
- 239000003599 detergent Substances 0.000 claims description 68
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 239000002199 base oil Substances 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 7
- 229960001860 salicylate Drugs 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 4
- -1 dithiocarbamate compound Chemical class 0.000 description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 150000007524 organic acids Chemical class 0.000 description 9
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 150000001639 boron compounds Chemical class 0.000 description 7
- 150000002118 epoxides Chemical class 0.000 description 7
- 235000005985 organic acids Nutrition 0.000 description 7
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- MQHWFIOJQSCFNM-UHFFFAOYSA-L Magnesium salicylate Chemical compound [Mg+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O MQHWFIOJQSCFNM-UHFFFAOYSA-L 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005461 lubrication Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000010705 motor oil Substances 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229940072082 magnesium salicylate Drugs 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 229960002317 succinimide Drugs 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003870 salicylic acids Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- PICWHVQPMXIVDC-UHFFFAOYSA-J C(N)([S-])=S.O(S(=O)(=O)O)[Mo+3].C(N)([S-])=S.C(N)([S-])=S Chemical compound C(N)([S-])=S.O(S(=O)(=O)O)[Mo+3].C(N)([S-])=S.C(N)([S-])=S PICWHVQPMXIVDC-UHFFFAOYSA-J 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JPYPZXAFEOFGSM-UHFFFAOYSA-N O.[B]=O Chemical compound O.[B]=O JPYPZXAFEOFGSM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940051879 analgesics and antipyretics salicylic acid and derivative Drugs 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000003819 basic metal compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- C10M2215/28—Amides; Imides
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron
Definitions
- This invention relates to lubricating oil compositions, more especially to compositions suitable for use in piston engine, especially gasoline (spark-ignited) and diesel (compression-ignited), crankcase lubrication.
- Such compositions may be referred to as crankcase lubricants.
- ZDDP's zinc dialkyldithiophosphates
- phosphorus derivatives deriving from the ZDDP's can poison the components of exhaust gas catalytic converters.
- Calatytic converters are used to reduce pollution and to meet governmental regulations requiring reduction in the levels of undesirable gases, such as hydrocarbons, carbon monoxide, and oxides of nitrogen, from internal engine combustion exhaust emissions.
- Such converters use catalysts which are installed in the exhaust streams, e.g. the exhausts of automobiles, to treat the undesirable gases.
- Phosphorus derivatives, such as decomposition products of ZDDP's can be carried into the exhaust, where they are believed to poison the catalyst.
- engine oils containing phosphorus additives may substantially reduce the life and effectiveness of catalytic converters. Therefore, it would be desirable to reduce, or eliminate, the phosphorus-content of engine oils so as to maintain the activity and extend the life of catalytic converters. Also, it is possible that sulfur-containing components may poison the catalysts, for example those used to reduce the levels of oxides of nitrogen.
- the invention provides a crankcase lubricating oil composition
- a crankcase lubricating oil composition comprising, or made by admixing, an oil of lubricating viscosity in a major amount, and, in respective minor amounts, a boron-containing additive and one or more co-additives, wherein the lubricating oil composition has greater than 200 ppm by mass of boron, less than 600 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, ppm by mass of sulfur, based on the mass of the oil composition.
- the invention provides a crankcase lubricating oil composition
- a crankcase lubricating oil composition comprising, or made by admixing, an oil of lubricating viscosity in a major amount, and, in respective minor amounts, a boron-containing additive and one or more co-additives, wherein the lubricating oil composition has greater than 300 ppm by mass of boron, less than 900 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, ppm by mass of sulfur, based on the mass of the oil composition.
- the invention provides a crankcase lubricating oil composition
- a crankcase lubricating oil composition comprising, or made by admixing, an oil of lubricating viscosity in a major amount, and, in respective minor amounts, a boron-containing additive, a detergent additive composition and one or more co-additives, wherein the lubricating oil composition has greater than 50 ppm by mass of boron, less than 800 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, ppm by mass of sulfur, based on the mass of the oil composition, provided that the detergent additive composition comprises at least two detergents of at least two metals.
- the invention provides an additive composition comprising, or made by admixing, a diluent or carrier oil, a boron-containing additive and one or more co-additives in such proportions so to provide a crankcase lubricating oil composition having greater than 200 ppm or boron, less than 600 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, by mass ppm by mass of sulfur, based on the mass of the oil composition, when the oil composition contains 4 to 10 mass % of the additives.
- the invention provides an additive composition comprising, or made by admixing, a diluent or carrier oil, a boron-containing additive and one or more co-additives in such proportions so to provide a crankcase lubricating oil composition having greater than 300 ppm or boron, less than 900 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, by mass ppm by mass of sulfur, based on the mass of the oil composition, when the oil composition contains 4 to 10 mass % of the additives.
- the invention provides an additive composition comprising, or made by admixing, a diluent or carrier oil, a boron-containing additive, a detergent additive composition comprising at least two detergents of at least two metals and one or more co-additives in such proportions so to provide a crankcase lubricating oil composition having greater than 50 ppm by mass of boron, less than 800 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, ppm by mass of sulfur, based on the mass of the oil composition, when the oil composition contains 4 to 10 mass % of the additives.
- the invention provides a method for conferring wear resistance to a crankcase lubricating oil composition that contains less than 900 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, ppm by mass of sulfur, based on the mass of the oil composition, by provision in the oil composition of a boron-containing additive to provide greater than 50 ppm by mass of boron based on the mass of the oil composition.
- the invention provides a method of lubricating the crankcase of a spark-ignited or a compression-ignited internal combustion engine which comprises supplying to the engine a lubricating oil composition according to the first, second or third aspect of the invention.
- the invention provides the use of an effective amount of a boron-containing additive in a crankcase lubricating oil composition that contains less than 900 ppm by mass of phosphorus and less than 6000 ppm by mass of sulfur, based on the mass of the oil composition, to provide wear resistance, in particular in the Peugeot TU3M Scuffing Test and Sequence IVA Test.
- An effective amount is preferably an amount sufficient to provide at least 50 ppm by mass of boron based on mass of the oil composition.
- the lubricating oil compositions of this invention comprise defined individual, i.e., separate, components that may or may not remain the same chemically before and after mixing.
- various components of the composition essential as well as optional and customary, may react under the conditions of formulation, storage or use, and that the invention also provides the product obtainable or obtained as a result of any such reaction.
- the amount of phosphorus, sulfur or boron in the lubricating oil composition is measured according to ASTM D5185.
- the amount of phosphorus in the lubricating oil composition, independent of the amount of sulfur or boron, with respect to the first or fourth aspect of the invention is preferably less than 550, more preferably less than 500, such as less than 400, especially less than 300 or 200, advantageously less than 100, ppm based on the mass of the oil composition. More preferably, it is zero.
- the amount of phosphorus in the lubricating oil composition is preferably less than 800 or 700, more preferably less than 600 or 550, such as less than 500 or 400, especially less than 300 or 200, advantageously less than 100, ppm based on the mass of the oil composition. More preferably, it is zero.
- the amount of phosphorus in the lubricating oil composition, independent of the amount of sulfur or boron, with respect to the third or sixth aspect of the invention is preferably less than 700, more preferably less than 600 or 550, such as less than 500 or 400, especially less than 300 or 200, advantageously less than 100, ppm based on the mass of the oil composition. More preferably, it is zero.
- the amount of sulfur in the lubricating oil composition is preferably at most 5000 or 4000, or at most 3000 or 2500, ppm by mass, based on the mass of the oil composition; especially it is at most 2000, or at most 1500, ppm by mass; advantageously it is less than 1000, or less than 700, ppm. More preferably, it is zero.
- the phosphorus in the oil composition is derived from a phosphorus-containing additive, such as a ZDDP that may be present.
- the sulfur can be derived from the oil of lubricating viscosity, such as Group 1, II or III basestock; the diluent oil or carrier oil, which is used as a carrier fluid for the additive components and additive compositions; and any sulfur-containing additives, for example, ZDDPs and sulfonate detergents.
- the defined amount of phosphorus is in respect of the amount of phosphorus derived from ZDDP that is present.
- the amount of boron, independent of the amount of sulfur or phosphorus, with respect to the first or fourth aspect is preferably greater than 250, for example, greater than 300, ppm based on the mass of the oil composition; more preferably the amount of boron is greater than any one of 400, 500, 600, 700, 800 or 900, ppm; especially the amount of boron is greater than any one of 1000, 1100, 1200 or 1500, ppm.
- the amount of boron does not exceed 2000 ppm, based on the mass of the oil composition.
- the amount of boron, independent of the amount of sulfur or phosphorus, with respect to the second or fifth aspect is preferably greater than 350, for example, greater than 400, ppm based on the mass of the oil composition; more preferably the amount of boron is greater than any one of 500, 600, 700, 800 or 900, ppm; especially the amount of boron is greater than any one of 1000, 1100, 1200 or 1500, ppm.
- the amount of boron does not exceed 2000 ppm, based on the mass of the oil composition.
- the amount of boron, independent of the amount of sulfur or phosphorus, with respect to the third, sixth, seventh or ninth aspect is preferably greater than 100, for example, greater than 200, ppm based on the mass of the oil composition; more preferably the amount of boron is greater than any one of 300, 400, 500, 600, 700, 800 or 900, ppm; especially the amount of boron is greater than any one of 1000, 1100, 1200 or 1500, ppm.
- the amount of boron does not exceed 2000 ppm, based on the mass of the oil composition.
- the boron in the oil composition is derived from a boron-containing additive.
- one or more of a zinc dithiocarbamate and a copper-containing compound are substantially absent.
- a molybdenum-containing additive for example a molybdenum dithiocarbamate is present in the oil composition, then the amount of molybdenum in the oil composition is at most 400, preferably 300, such as 200, especially 100, ppm by mass based on the mass of the oil composition.
- the lubricating oil composition has less than 1.5, especially less than 1.3, such as in the range from 0.01 to 0.5, mass % of sulfated ash, according to the method ASTM D874.
- the lubricating oil composition is a multigrade identified by the descriptor SAE 5W-20 or SAE 5W-30, whose properties are defined in the Society of Automotive Engineers document SAE J300.
- the oil of lubricating viscosity or lubricating oil can be a synthetic or mineral oil of lubricating viscosity selected from the group consisting of Group I, II, III, IV and V basestocks, and a mixture containing any two or more thereof.
- Basestocks may be made using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining.
- API 1509 "Engine Oil Licensing and Certification System” Fourteenth Edition, December 1996 states that all basestocks are divided into five general categories:
- Group IV basestocks i.e., polyalphaolefins (PAO)
- PAO polyalphaolefins
- Group IV basestocks include hydrogenated oligomers of an alpha-olefin, the most important methods of oligomerization being free radical processes, Ziegler catalysis, cationic and Friedel-Crafts catalysis.
- the lubricating oil is selected from any one of Group I to V basestocks and mixtures thereof.
- test methods used in defining the above groups are ASTM D2007 for saturates; ASTM D2270 for viscosity index; and one of ASTM D2622, 4294, 4927 and 3120 for sulfur.
- Boron-containing additives may be prepared by reacting a boron compound with an oil-soluble or oil-dispersible additive or compound.
- Boron compounds include boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boron acid such as boronic acid, boric acid, tetraboric acid and metaboric acid, boron hydrides, boron amides and various esters of boron acids.
- boron-containing additives include a borated dispersant; a borated dispersant VI improver; an alkali metal or a mixed alkali metal or an alkaline earth metal borate; a borated overbased metal detergent; a borated epoxide; a borate ester; and a borate amide.
- Borated dispersants may be prepared by boration of succinimide, succinic ester, benzylamine and their derivatives, each of which has an alkyl or alkenyl group of molecular weight of 700 to 3000. Processes for manufacture of these additives are known to those skilled in the art. A preferred amount of boron contained in these dispersants is 0.1 to 5 mass % (especially 0.2 to 2 mass %). A particularly preferable borated dispersant is a succinimide derivative of boron, for example borated polyisobutenyl succinimide.
- Alkali metal and alkaline earth metal borates are generally hydrated particulate metal borates, which are known in the art.
- Alkali metal borates include mixed alkali and alkaline earth metal borates. These metal borates are available commercially.
- Representative patents describing suitable alkali metal and alkaline earth metal borates and their methods of manufacture include U.S. 3,997,454; 3,819,521; 3,853.772; 3,907,601; 3,997,454; and 4,089,790.
- Boron-containing additives include borated fatty amines.
- the borated amines maybe prepared by reacting one or more of the above boron compounds with one or more of fatty amines, e.g., an amine having from four to eighteen carbon atoms. They may be prepared by reacting the amine with the boron compound from 50 to 300, preferably from 100 to 250 at a temperature in the range of °C and at a ratio from 3:1 to 1:3 equivalents of amine to equivalents of boron compound.
- Borated fatty epoxides are generally the reaction product of one or more of the above boron compounds with at least one epoxide.
- the epoxide is generally an aliphatic epoxide having from 8 to 30, preferably from 10 to 24, more preferably from 12 to 20, carbon atoms.
- Examples of useful aliphatic epoxides include heptyl epoxide and octyl epoxide. Mixtures of epoxides may also be used, for instance commercial mixtures of epoxides having from 14 to 16 carbon atoms and from 14 to 18 carbon atoms.
- the borated fatty epoxides are generally known and are described in U.S. Patent 4,584,115.
- Borate esters may be prepared by reacting one or more of the above boron compounds with one or more alcohols of suitable oleophilicity. Typically, the alcohols contain from 6 to 30, or from 8 to 24, carbon atoms. The methods of making such borate esters are known in the art.
- the borate esters can be borated phospholipids. Such compounds, and processes for making such compounds, are described in EP-A-0 684 298.
- Borated overbased metal detergents are known in the art where the borate substitutes the carbonate in the core either in part or in full.
- a preferred boron-containing additive is a borated polyisobutenyl succinimide wherein the average number molecular weight ( M n) of the polybutenyl backbone is in the range from 700 to 1250.
- a detergent additive composition which comprises one or more detergents, may be provided in the lubricating oil composition.
- a detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is usually based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
- Organic acids useful in present invention typically have one or more functional groups, such as OH or COOH or SO 3 H, and a hydrocarbyl substituent. Examples of organic acids include sulfonic acids, phenols and sulfurised derivatives thereof, and carboxylic acids.
- the metal detergent may be neutral or overbased, which terms are known in the art.
- the detergent additive composition may comprise one or more neutral detergents or one or more overbased detergents or a mixture thereof.
- the metals are preferably selected from Group 1 and Group 2 metals, e.g., sodium, potassium, lithium, calcium, and magnesium.
- the detergent additive composition in respect of each aspect of the invention, comprises a metal salt of an aromatic carboxylic acid, for example a salicylate-based detergent, such as calcium salicylate.
- the detergent additive composition comprises more than 50 mole % of a metal salt of an aromatic carboxylic acid, based on the moles of the metal salts of organic acids in the detergent composition. More preferably the proportion of the metal salt of an aromatic carboxylic acid is at least 60 or at least 70 mole %; more preferably at least 80 or at least 90 mole %, based on the moles of the metal salts of organic acids in the detergent additive composition.
- the detergent additive composition comprises 100 mole % of a metal salt of an aromatic carboxylic acid, based on the moles of the metal salts of organic acids in the detergent composition, that is the detergent additive composition comprises only aromatic carboxylic acids as the organic acids.
- aromatic carboxylic acids are salicylic acids and sulphurised derivatives thereof, such as hydrocarbyl substituted salicylic acid and derivatives thereof. Especially preferred are salicylic acids.
- the detergent additive composition comprises one or more detergents of the same metal, for example calcium or magnesium, preferably calcium; more preferably the detergents are of different surfactant types, such as calcium salicylate and calcium sulfonate.
- the detergent additive composition comprises at least two detergents of at least different two metals, for example a neutral or overbased magnesium detergent and at least one other metal detergent, or a neutral or overbased calcium detergent and/or neutral or overbased sodium detergent.
- Preferred detergent additive compositions in respect of each aspect of the invention comprise a mixture of calcium and magnesium detergents.
- Detergent additive compositions comprising only salicylate detergents, whether neutral or overbased, are particularly advantageous.
- Surfactants that may also be used include aliphatic carboxylates; sulfonates; phenates, non-sulfurised or sulfurised; thiophosphonates; and naphthenates.
- a detergent in the form of a hybrid complex detergent wherein the basic material is stabilised by more than one type of surfactant.
- a single type of organic acid may contain a mixture of organic acids of the same type.
- a sulphonic acid may contain a mixture of sulphonic acids of varying molecular weights.
- Such an organic acid composition is considered as one type.
- complex detergents are distinguished from mixtures of two or more separate overbased detergents, an example of such a mixture being one of an overbased calcium salicylate detergent with an overbased calcium phenate detergent.
- EP-A-0 750 659 describes a calcium salicylate phenate complex made by carboxylating a calcium phenate and then sulfurising and overbasing the mixture of calcium salicylate and calcium phenate. Such complexes may be referred to as "phenalates"
- the proportion of one surfactant to another in a complex detergent is not critical.
- Preferred complex detergents are salicylate-based detergents, for example, "phenalates”.
- the detergents can have a Total Base Number (TBN) in the range of 15 or 60 to 600, preferably 100 to 450, more preferably 160 to 400.
- TBN Total Base Number
- the detergent additive composition consists of metal salicylate detergents
- the salicylate is either calcium salicylate or a mixture of calcium and magnesium salicylates. More preferably, at least one or each metal salicylate detergent is overbased.
- both calcium and magnesium salicylates are present, more calcium salicylate than magnesium salicylate can be present, based on the mass of the respective metals.
- the detergent additive composition comprises two or more metal detergents of different surfactant types, it is preferred that the detergents have the same metal, for example, calcium.
- the total amount of metal derived from the metal detergents in the lubricating oil composition is at most 2700 ppm, based on the mass of the oil composition.
- co-additives may be present to meet particular requirements.
- examples of such include viscosity index improvers, corrosion inhibitors, detergents other than those mentioned, metal rust inhibitors, pour point depressants, anti-foaming agents, dispersants other than those mentioned, anti-wear agents, oxidation inhibitors or anitoxidants, and friction modifiers.
- the preparation of an additive composition is a convenient method of adding the additives to a lubricating oil in order to yield a lubricating oil composition.
- the amount of additives in the oil composition is preferably in the range from 5 to 9, especially from 6 to 8, mass % based on the mass of the oil composition.
- the sulfated ash content of each composition is on or about 1 mass %.
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Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01309510A EP1310548A1 (fr) | 2001-11-09 | 2001-11-09 | Composition lubrifiantes contenant du bore |
| US10/277,440 US7026273B2 (en) | 2001-11-09 | 2002-10-22 | Lubricating oil compositions |
| DE60211835T DE60211835T2 (de) | 2001-11-09 | 2002-10-30 | Borenthaltende Schmierölzusammensetzung mit niedrigem Schwefel- und Phosphor-Gehalt |
| AT02257525T ATE328056T1 (de) | 2001-11-09 | 2002-10-30 | Borenthaltende schmierölzusammensetzung mit niedrigem schwefel- und phosphor-gehalt |
| EP02257525A EP1310549B1 (fr) | 2001-11-09 | 2002-10-30 | Composition d'huile lubrifiante contenant du bore et une faible concentration de soufre et de phosphore |
| CNB021499349A CN100497558C (zh) | 2001-11-09 | 2002-11-08 | 润滑油组合物 |
| SG200206754-4A SG148008A1 (en) | 2001-11-09 | 2002-11-08 | Lubricating oil compositions |
| JP2002324640A JP5048196B2 (ja) | 2001-11-09 | 2002-11-08 | 潤滑油組成物 |
| CA002411463A CA2411463C (fr) | 2001-11-09 | 2002-11-08 | Compositions d'huile lubrifiante |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01309510A EP1310548A1 (fr) | 2001-11-09 | 2001-11-09 | Composition lubrifiantes contenant du bore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1310548A1 true EP1310548A1 (fr) | 2003-05-14 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01309510A Withdrawn EP1310548A1 (fr) | 2001-11-09 | 2001-11-09 | Composition lubrifiantes contenant du bore |
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| Country | Link |
|---|---|
| EP (1) | EP1310548A1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004020558A1 (fr) * | 2002-08-27 | 2004-03-11 | Nippon Oil Corporation | Composition d'huile lubrifiante pour moteur a combustion interne |
| EP1712606A4 (fr) * | 2004-02-04 | 2010-09-01 | Nippon Oil Corp | Composition d huile lubrifiante |
-
2001
- 2001-11-09 EP EP01309510A patent/EP1310548A1/fr not_active Withdrawn
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004020558A1 (fr) * | 2002-08-27 | 2004-03-11 | Nippon Oil Corporation | Composition d'huile lubrifiante pour moteur a combustion interne |
| US7648947B2 (en) | 2002-08-27 | 2010-01-19 | Nippon Oil Corporation | Lubricating oil composition for internal combustion engine |
| EP1712606A4 (fr) * | 2004-02-04 | 2010-09-01 | Nippon Oil Corp | Composition d huile lubrifiante |
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