JPH07216378A - Lubricating oil composition - Google Patents
Lubricating oil compositionInfo
- Publication number
- JPH07216378A JPH07216378A JP6027477A JP2747794A JPH07216378A JP H07216378 A JPH07216378 A JP H07216378A JP 6027477 A JP6027477 A JP 6027477A JP 2747794 A JP2747794 A JP 2747794A JP H07216378 A JPH07216378 A JP H07216378A
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- atom
- lubricating oil
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 71
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 claims abstract description 11
- 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 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000002199 base oil Substances 0.000 claims description 15
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 230000001050 lubricating effect Effects 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 6
- 239000012990 dithiocarbamate Substances 0.000 abstract description 14
- 239000010705 motor oil Substances 0.000 abstract description 10
- 238000005461 lubrication Methods 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000005069 Extreme pressure additive Substances 0.000 abstract 1
- -1 fatty acid ester Chemical class 0.000 description 38
- 150000002430 hydrocarbons Chemical group 0.000 description 17
- 239000003921 oil Substances 0.000 description 16
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 239000000126 substance Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 8
- 239000003599 detergent Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 150000002902 organometallic compounds Chemical class 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 3
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CCBXBMKHVFTUMN-UHFFFAOYSA-L C(N)([S-])=S.[Mo+2]=S.C(N)([S-])=S Chemical compound C(N)([S-])=S.[Mo+2]=S.C(N)([S-])=S CCBXBMKHVFTUMN-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- ZDXGQHXSMPGQRI-UHFFFAOYSA-N 2,6-ditert-butyl-3-[(2,4-ditert-butyl-3-hydroxyphenyl)methyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC=C1CC1=CC=C(C(C)(C)C)C(O)=C1C(C)(C)C ZDXGQHXSMPGQRI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 150000001638 boron Chemical class 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000005645 linoleyl group Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010937 tungsten 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the 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
- C10M129/68—Esters
- C10M129/76—Esters containing free hydroxy or carboxyl 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/16—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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
-
- 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
- C10M141/08—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 sulfur-, selenium- or tellurium-containing compound
-
- 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
- C10M141/10—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 phosphorus-containing compound
-
- 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
- C10M2207/28—Esters
- C10M2207/287—Partial esters
-
- 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
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/288—Partial esters containing free carboxyl 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
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
-
- 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
- C10M2215/08—Amides
-
- 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
- C10M2215/08—Amides
- C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
-
- 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
- C10M2215/086—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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/12—Partial amides of polycarboxylic acids
-
- 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
- C10M2215/12—Partial amides of polycarboxylic acids
- C10M2215/122—Phtalamic acid
-
- 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
- C10M2215/28—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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
-
- 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
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol-fuelled 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、潤滑油組成物に関し、
さらに詳しくは、良好な耐摩耗性、極圧性、及び低摩擦
係数を有する潤滑油組成物に関する。本発明の潤滑油組
成物は、極低りん化または無りん化を図ることが可能で
あり、内燃機関用潤滑油など広範な分野で使用すること
ができる。FIELD OF THE INVENTION The present invention relates to a lubricating oil composition,
More specifically, it relates to a lubricating oil composition having good wear resistance, extreme pressure resistance, and a low friction coefficient. The lubricating oil composition of the present invention can achieve extremely low phosphorus content or no phosphorus content, and can be used in a wide variety of fields such as lubricating oil for internal combustion engines.
【０００２】[0002]
【従来の技術】内燃機関用潤滑油（エンジン油）は、主
としてピストンリングとシリンダライナ、クランク軸や
連接棒（コネクティングロッド）の軸受、カムとバルブ
リフタを含む動弁機構、オイルポンプやディストリビュ
ータ等の駆動装置など各種摺動部分の潤滑のほか、エン
ジン内の冷却、燃焼生成物の清浄分散、錆や腐食の防止
などの作用を果たす。このようにエンジン油には、多様
な性能が要求され、しかも機関の高性能化、高出力化、
運転条件の過酷化等に伴い、要求性能も変化している。
このため、エンジン油には、多種性能を満たす目的で摩
耗防止剤、金属清浄剤、無灰分散剤、酸化防止剤等の種
々の添加剤が配合されている。2. Description of the Related Art Lubricating oil for internal combustion engine (engine oil) is mainly used for piston rings and cylinder liners, bearings for crankshafts and connecting rods (connecting rods), valve mechanisms including cams and valve lifters, oil pumps and distributors. In addition to lubrication of various sliding parts such as drive devices, it also functions to cool the engine, clean and disperse combustion products, and prevent rust and corrosion. In this way, engine oil is required to have a variety of performances, and in addition, high performance, high output of the engine,
The required performance is changing with the harsh operating conditions.
For this reason, various additives such as antiwear agents, metal detergents, ashless dispersants, and antioxidants are blended with engine oils for the purpose of satisfying various performances.
【０００３】エンジン油の基本的機能として、特に、あ
らゆる条件下で機関を円滑に作用させ、摩耗・焼付き防
止作用を行うことが重要である。エンジン潤滑部は、通
常、流体潤滑状態にあるが、動弁系やピストンの上下死
点などでは境界潤滑状態となり易い。エンジン油の境界
潤滑下における摩耗防止性は、一般に、ジアルキルジチ
オりん酸亜鉛（ＺｎＤＴＰ）の添加によって付与されて
いる。しかし、ＺｎＤＴＰは、これに含まれるりん
（Ｐ）が触媒や酸素センサーを被毒するため、排気ガス
制御システムを劣化するという問題がある。また、Ｚｎ
ＤＴＰは、こはく酸イミドやアルキルアミンなどの他の
添加剤との相互作用によって、耐摩耗性が失われ易い。
そこで、極低りん化または無りん化の潤滑油組成物が望
まれている。As a basic function of engine oil, it is important that the engine operates smoothly under all conditions to prevent wear and seizure. The engine lubrication part is normally in a fluid lubrication state, but it is likely to be in a boundary lubrication state at a valve train, a top dead center of a piston, and the like. Antiwear properties under boundary lubrication of engine oils are generally imparted by the addition of zinc dialkyldithiophosphate (ZnDTP). However, ZnDTP has a problem that the exhaust gas control system is deteriorated because phosphorus (P) contained in the ZnDTP poisons the catalyst and the oxygen sensor. In addition, Zn
DTP easily loses its wear resistance due to the interaction with other additives such as succinimide and alkylamine.
Therefore, an extremely low phosphorus-free or phosphorus-free lubricating oil composition is desired.
【０００４】一方、ガソリン機関では、潤滑油が関与す
る摩擦部分でのエネルギー損失が大きいため、摩擦損失
低減・燃費低減対策として、摩擦低減剤（フリクション
モディファイヤ）が添加されている。摩擦低減剤として
は、硫化ジアルキルジチオカルバミン酸モリブデンなど
の極圧剤や、オクタデシルアミンなどの油性剤に属する
化合物が使用されている。これらの中でも、ジチオカル
バメート型の有機モリブデン化合物である硫化ジアルキ
ルジチオカルバミン酸モリブデンは、特に摩擦低減効果
が大きい。しかしながら、従来用いられてきた硫化ジア
ルキルジチオカルバミン酸モリブデンは、耐摩耗性及び
摩擦特性がいまだ不十分であり、エンジン油に低燃費性
能が益々強く求められる現状では、更なる性能の向上が
求められている。On the other hand, in a gasoline engine, since a large amount of energy is lost in a friction portion where lubricating oil is involved, a friction modifier (friction modifier) is added as a measure for reducing friction loss and fuel consumption. As the friction reducing agent, an extreme pressure agent such as molybdenum sulfide dialkyldithiocarbamate or a compound belonging to an oily agent such as octadecylamine is used. Among these, molybdenum sulfide dialkyldithiocarbamate, which is a dithiocarbamate type organic molybdenum compound, has a particularly large friction reducing effect. However, molybdenum dialkyldithiocarbamate sulfides, which have been conventionally used, are still insufficient in wear resistance and frictional characteristics, and in the current situation where fuel economy performance is required more and more for engine oils, further improvement in performance is required. There is.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、耐摩
耗性と摩擦特性が共に優れた潤滑油組成物を提供するこ
とにある。より具体的に、本発明の目的は、ジチオカル
バメート型の有機金属化合物からなる極圧剤であって、
従来品よりも、摩擦特性及び耐摩耗性が顕著に改善され
た有機金属化合物を含有する潤滑油組成物を提供するこ
とにある。さらに、ジチオホスフェート型の有機金属化
合物等を併用することにより、耐摩耗性及び摩擦特性が
一層改善された潤滑油組成物を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a lubricating oil composition having excellent wear resistance and frictional properties. More specifically, the object of the present invention is an extreme pressure agent comprising a dithiocarbamate type organometallic compound,
It is an object of the present invention to provide a lubricating oil composition containing an organometallic compound having significantly improved friction characteristics and wear resistance as compared with conventional products. Another object of the present invention is to provide a lubricating oil composition having further improved wear resistance and friction characteristics by using a dithiophosphate type organometallic compound in combination.
【０００６】本発明者は、硫化ジアルキルジチオカルバ
ミン酸モリブデンなどの従来のジチオカルバメート型の
有機金属化合物は、アルキル基が、その第一級炭素原子
により窒素原子に結合した構造（即ち、−ＣＨ2−Ｎ
＜）を有していることに着目した。そして、アルキル基
について種々の検討を行った結果、アルキル基の第二級
炭素原子により窒素原子に結合した構造（即ち、＞ＣＨ
−Ｎ＜）を有するジチオカルバメート型の有機金属化合
物であって、金属原子がモリブデンまたはタングステン
であるジチオカルバミン酸金属塩が、潤滑油基油に混合
した場合、対応する従来品を用いた場合と比較して、驚
くべきことに優れた耐摩耗性と摩擦特性を示すことを見
いだした。The present inventor has found that a conventional dithiocarbamate type organometallic compound such as molybdenum dialkyldithiocarbamate has a structure in which an alkyl group is bonded to a nitrogen atom through its primary carbon atom (that is, --CH 2-). N
We paid attention to having <). As a result of various studies on the alkyl group, a structure in which the secondary carbon atom of the alkyl group is bonded to the nitrogen atom (ie,> CH
A dithiocarbamate type organometallic compound having -N <), in which a metal salt of dithiocarbamic acid having a metal atom of molybdenum or tungsten is mixed with a lubricating base oil, and compared with the case where a corresponding conventional product is used. Then, they have surprisingly found to have excellent wear resistance and friction characteristics.
【０００７】本発明の潤滑油組成物は、潤滑油基油に、
前記ジチオカルバミン酸金属塩に加えて、ＺｎＤＴＰ及
び／またはジチオカルバミン酸亜鉛（ＺｎＤＴＣ）を添
加すると、摩擦特性及び耐摩耗性が一層改善される。本
発明のジチオカルバミン酸金属塩は、耐摩耗性及び摩擦
特性に優れているため、ＺｎＤＴＰと組み合わせて用い
る場合であっても、ＺｎＤＴＰの含有量を少なくするこ
とができ、低りん化が可能となる。また、ＺｎＤＴＰを
併用せずに、本発明のジチオカルバミン酸金属塩を単独
で、あるいはＺｎＤＴＣと組み合わせて使用すれば、無
りん化した潤滑油組成物とすることができる。The lubricating oil composition of the present invention comprises a lubricating base oil,
By adding ZnDTP and / or zinc dithiocarbamate (ZnDTC) in addition to the metal salt of dithiocarbamate, friction characteristics and wear resistance are further improved. Since the metal salt of dithiocarbamic acid of the present invention is excellent in wear resistance and frictional characteristics, the content of ZnDTP can be reduced and phosphorus can be reduced even when used in combination with ZnDTP. . In addition, a phosphorus-free lubricating oil composition can be obtained by using the metal salt of dithiocarbamic acid of the present invention alone or in combination with ZnDTC without using ZnDTP together.
【０００８】また、本発明の潤滑油組成物は、脂肪酸エ
ステル及び／または有機アミド化合物を添加すると、摩
擦係数をより一層低減することができる。もちろん、本
発明の潤滑油組成物には、所望に応じて、その他の各種
潤滑油用添加剤を添加することができる。本発明の潤滑
油組成物は、エンジン油をはじめ、優れた耐摩耗性及び
摩擦特性が求められる広範な分野で使用することができ
る。本発明は、これらの知見に基づいて完成するに至っ
たものである。Further, the lubricating oil composition of the present invention can further reduce the coefficient of friction by adding a fatty acid ester and / or an organic amide compound. Of course, various other additives for lubricating oil can be added to the lubricating oil composition of the present invention as desired. The lubricating oil composition of the present invention can be used in a wide range of fields including engine oils, which are required to have excellent wear resistance and friction characteristics. The present invention has been completed based on these findings.
【０００９】[0009]
【課題を解決するための手段】かくして、本発明によれ
ば、 潤滑油基油に、一般式（１）Thus, according to the present invention, the lubricating base oil can be added to the general formula (1)
【００１０】[0010]
【化４】 [Chemical 4]
【００１１】〔式中、Ｍは、モリブデン原子またはタン
グステン原子である。Ｒ1、Ｒ2、Ｒ3及びＲ4は、水素原
子、炭素数１〜２０の飽和または不飽和のアルキル基、
炭素数６〜２６のシクロアルキル基またはアルキル置換
シクロアルキル基、炭素数６〜２６のアリール基、アル
キルアリール基またはアリールアルキル基、あるいはこ
れらの炭化水素基に、エステル結合、エーテル結合、水
酸基またはカルボキシル基が導入された炭化水素基であ
り、互いに同一または異なっていてもよい。ただし、こ
れら４つの内の少なくとも１つは、第二級炭素原子を有
する炭素数５〜２０のアルキル基であって、かつ、その
第二級炭素原子で前記式中の窒素原子（Ｎ）に結合して
いる。Ｘ1及びＸ2は、酸素原子または硫黄原子である。
Ｙ1及びＹ2は、酸素原子または硫黄原子である。〕で表
されるジチオカルバミン酸金属塩（Ａ）を、組成物全量
基準で、０．０１〜１０重量％の割合で含有させてなる
潤滑油組成物が提供される。[In the formula, M is a molybdenum atom or a tungsten atom. R 1 , R 2 , R 3 and R 4 are each a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 6 to 26 carbon atoms or an alkyl-substituted cycloalkyl group, an aryl group having 6 to 26 carbon atoms, an alkylaryl group or an arylalkyl group, or these hydrocarbon groups, an ester bond, an ether bond, a hydroxyl group or a carboxyl group. The groups are introduced hydrocarbon groups and may be the same or different from each other. However, at least one of these four is an alkyl group having a secondary carbon atom and having 5 to 20 carbon atoms, and the secondary carbon atom is a nitrogen atom (N) in the above formula. Are connected. X 1 and X 2 are oxygen atoms or sulfur atoms.
Y 1 and Y 2 are oxygen atoms or sulfur atoms. ] The lubricating oil composition which contains the dithiocarbamic-acid metal salt (A) represented by these in a ratio of 0.01 to 10 weight% on the basis of the total amount of the composition is provided.
【００１２】また、本発明によれば、好ましい実施態様
として、次の〜の潤滑油組成物が提供される。 潤滑油基油に、前記ジチオカルバミン酸金属塩
（Ａ）に加えて、さらに、一般式（２）Further, according to the present invention, as a preferred embodiment, the following lubricating oil compositions are provided. In addition to the above-mentioned metal salt of dithiocarbamic acid (A), a lubricating base oil, and further a compound of the general formula (2)
【００１３】[0013]
【化５】 [Chemical 5]
【００１４】（ただし、式中、Ｒ5、Ｒ6、Ｒ7及びＲ
8は、水素原子、炭素数１〜２０の飽和または不飽和の
アルキル基、炭素数６〜２６のシクロアルキル基または
アルキル置換シクロアルキル基、炭素数６〜２６のアリ
ール基、アルキルアリール基またはアリールアルキル
基、あるいはこれらの炭化水素基に、エステル結合、エ
ーテル結合、水酸基またはカルボキシル基が導入された
炭化水素基であり、互いに同一または異なっていてもよ
い。）で表されるジチオりん酸亜鉛（Ｂ）、及び一般式
（３）(In the formula, R 5 , R 6 , R 7 and R
8 is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 26 carbon atoms or an alkyl-substituted cycloalkyl group, an aryl group having 6 to 26 carbon atoms, an alkylaryl group or aryl An alkyl group or a hydrocarbon group in which an ester bond, an ether bond, a hydroxyl group or a carboxyl group is introduced into these hydrocarbon groups, which may be the same or different from each other. ) Zinc dithiophosphate (B) represented by the formula) and the general formula (3)
【００１５】[0015]
【化６】 [Chemical 6]
【００１６】（ただし、式中、Ｒ9、Ｒ10、Ｒ11及びＲ
12は、水素原子、炭素数１〜２０の飽和または不飽和の
アルキル基、炭素数６〜２６のシクロアルキル基または
アルキル置換シクロアルキル基、炭素数６〜２６のアリ
ール基、アルキルアリール基またはアリールアルキル
基、あるいはこれらの炭化水素基に、エステル結合、エ
ーテル結合、水酸基またはカルボキシル基が導入された
炭化水素基であり、互いに同一または異なっていてもよ
い。）で表されるジチオカルバミン酸亜鉛（Ｃ）からな
る群より選ばれる少なくとも一種の有機亜鉛化合物を、
組成物全量基準で、０．０１〜７重量％の割合で含有さ
せてなる潤滑油組成物。(Wherein R 9 , R 10 , R 11 and R
12 is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 26 carbon atoms or an alkyl-substituted cycloalkyl group, an aryl group having 6 to 26 carbon atoms, an alkylaryl group or aryl An alkyl group or a hydrocarbon group in which an ester bond, an ether bond, a hydroxyl group or a carboxyl group is introduced into these hydrocarbon groups, which may be the same or different from each other. ) At least one organozinc compound selected from the group consisting of zinc dithiocarbamate (C)
A lubricating oil composition containing 0.01 to 7% by weight based on the total weight of the composition.
【００１７】 前記ジチオカルバミン酸金属塩（Ａ）
が、一般式（１）において、Ｒ1、Ｒ2、Ｒ3及びＲ4の内
の少なくとも２つが、第二級炭素原子を有するアルキル
基であって、かつ、その第二級炭素原子で前記式中の窒
素原子（Ｎ）に結合しているものである第項または第
項記載の潤滑油組成物。 前記ジチオカルバミン酸金属塩（Ａ）が、一般式
（１）において、Ｒ1、Ｒ2、Ｒ3及びＲ4の内の少なくと
も３つが、第二級炭素原子を有するアルキル基であっ
て、かつ、その第二級炭素原子で前記式中の窒素原子
（Ｎ）に結合しているものである第項または第項記
載の潤滑油組成物。The metal salt of dithiocarbamic acid (A)
In the general formula (1), at least two of R 1 , R 2 , R 3 and R 4 are alkyl groups having a secondary carbon atom, and at the secondary carbon atom, The lubricating oil composition according to item (1) or (2), which is bonded to a nitrogen atom (N) in the formula. The dithiocarbamic acid metal salt (A) is a compound represented by the general formula (1), wherein at least three of R 1 , R 2 , R 3 and R 4 are alkyl groups having a secondary carbon atom, and The lubricating oil composition according to item 1 or 2, wherein the secondary carbon atom is bonded to the nitrogen atom (N) in the formula.
【００１８】 前記ジチオカルバミン酸金属塩（Ａ）
が、一般式（１）において、Ｒ1、Ｒ2、Ｒ3及びＲ4が炭
素数５〜２０のアルキル基である第〜第項のいずれ
か１項に記載の潤滑油組成物。 潤滑油基油に、前記ジチオカルバミン酸金属塩
（Ａ）に加えて、あるいはジチオカルバミン酸金属塩
（Ａ）とジチオりん酸亜鉛（Ｂ）及び／またはジチオカ
ルバミン酸亜鉛（Ｃ）に加えて、脂肪酸エステル及び／
または有機アミドを含有させてなる第項〜第項のい
ずれか１項に記載の潤滑油組成物。The metal salt of dithiocarbamic acid (A)
In the general formula (1), R 1 , R 2 , R 3 and R 4 are alkyl groups having 5 to 20 carbon atoms. In addition to the metal salt of dithiocarbamic acid (A), or in addition to the metal salt of dithiocarbamic acid (A) and zinc dithiophosphate (B) and / or zinc dithiocarbamate (C), a fatty acid ester and /
Alternatively, the lubricating oil composition according to any one of items 1 to 3, which contains an organic amide.
【００１９】以下、本発明について詳述する。基 油 本発明で用いる基油としては、特に限定されず、従来公
知の各種鉱油や合成油等が使用できる。鉱油としては、
潤滑油原料をフェノール、フルフラール等の芳香族抽出
剤を用いた溶剤精製により得られるラフィネート、シリ
カ−アルミナを担体とするコバルト、モリブデン等の水
素化触媒を用いた水素化処理により得られる水素化処理
油、またはワックスの異性化により得られる潤滑油留分
などの鉱油、具体的には、例えば、６０ニュートラル
油、１００ニュートラル油、１５０ニュートラル油、３
００ニュートラル油、５００ニュートラル油、ブライト
ストックなどが挙げられる。合成油としては、例えば、
ポリ−α−オレフィン、ポリブテン、アルキルベンゼ
ン、ポリアルキレングリコールエステル、ポリオールエ
ステル、二塩基酸エステルなどが挙げられる。これらの
基油は、それぞれ単独で、あるいは２種以上を混合して
使用することができ、鉱油と合成油を混合使用してもよ
い。これらの潤滑油基油の粘度は、エンジン油に使用さ
れる場合、通常、１００℃での動粘度が３〜２０ｃＳｔ
の範囲内にあることが好ましい。The present invention will be described in detail below. Base Oil The base oil used in the present invention is not particularly limited, and various conventionally known mineral oils and synthetic oils can be used. As mineral oil,
Raffinate obtained by solvent refining a lubricating oil raw material using an aromatic extractant such as phenol or furfural, or hydrotreatment obtained by hydrotreatment using a hydrogenation catalyst such as cobalt or molybdenum with silica-alumina as a carrier. Oil or mineral oil such as lubricating oil fraction obtained by isomerization of wax, specifically, for example, 60 neutral oil, 100 neutral oil, 150 neutral oil, 3
Examples include 00 neutral oil, 500 neutral oil, and bright stock. As the synthetic oil, for example,
Examples thereof include poly-α-olefin, polybutene, alkylbenzene, polyalkylene glycol ester, polyol ester, and dibasic acid ester. These base oils may be used alone or in admixture of two or more, and mineral oil and synthetic oil may be mixed and used. When used as an engine oil, the viscosity of these lubricating base oils usually has a kinematic viscosity of 3 to 20 cSt at 100 ° C.
It is preferably within the range.
【００２０】ジチオカルバミン酸金属塩（Ａ） 本発明で使用するジチオカルバミン酸金属塩は、前記一
般式（１）で表される有機金属化合物である。一般式
（１）において、Ｍは、モリブデン原子（Ｍｏ）または
タングステン原子（Ｗ）であり、これらの中でも、特に
モリブデン原子が好ましい。Ｘ1、Ｘ2、Ｙ1及びＹ2は、
各々独立に酸素原子または硫黄原子である。これら４つ
の中で、一般に、酸素原子の合計は、０〜３で、硫黄原
子の合計は、１〜４である。 Metal salt of dithiocarbamic acid (A) The metal salt of dithiocarbamic acid used in the present invention is an organometallic compound represented by the general formula (1). In the general formula (1), M is a molybdenum atom (Mo) or a tungsten atom (W), and among these, a molybdenum atom is particularly preferable. X 1 , X 2 , Y 1 and Y 2 are
Each is independently an oxygen atom or a sulfur atom. Of these four, the sum of oxygen atoms is generally 0-3 and the sum of sulfur atoms is 1-4.
【００２１】Ｒ1、Ｒ2、Ｒ3及びＲ4は、水素原子、炭素
数１〜２０の飽和または不飽和のアルキル基、炭素数６
〜２６のシクロアルキル基またはアルキル置換シクロア
ルキル基、炭素数６〜２６のアリール基、アルキルアリ
ール基またはアリールアルキル基、あるいはこれらの炭
化水素基に、エステル結合、エーテル結合、水酸基また
はカルボキシル基が導入された炭化水素基であり、互い
に同一または異なっていてもよい。Ｒ1〜Ｒ4は、これら
の中でも、炭素数５〜２０のアルキル基であることが好
ましく、炭素数６〜１８のアルキル基であることが、特
に好ましい。R 1 , R 2 , R 3 and R 4 are hydrogen atoms, saturated or unsaturated alkyl groups having 1 to 20 carbon atoms, and 6 carbon atoms.
To a cycloalkyl group or an alkyl-substituted cycloalkyl group having from 26 to 26, an aryl group having 6 to 26 carbon atoms, an alkylaryl group or an arylalkyl group, or these hydrocarbon groups, an ester bond, an ether bond, a hydroxyl group or a carboxyl group is introduced. And the hydrocarbon groups may be the same or different from each other. Among these, R 1 to R 4 are preferably an alkyl group having 5 to 20 carbon atoms, and particularly preferably an alkyl group having 6 to 18 carbon atoms.
【００２２】ただし、Ｒ1、Ｒ2、Ｒ3及びＲ4の内の少な
くとも１つは、第二級炭素原子を有する炭素数５〜２０
のアルキル基であって、かつ、その第二級炭素原子で前
記一般式（１）中の窒素原子（Ｎ）に結合していること
が必要である。好ましくは、これら４つの内の少なくと
も２つ、より好ましくは、少なくとも３つが、第二級炭
素原子で窒素原子に結合している炭素数５〜２０のアル
キル基であることが望ましい。However, at least one of R 1 , R 2 , R 3 and R 4 has 5 to 20 carbon atoms having a secondary carbon atom.
It is necessary that the compound is an alkyl group of and the secondary carbon atom is bonded to the nitrogen atom (N) in the general formula (1). Preferably, at least two, and more preferably at least three of these four groups are alkyl groups having 5 to 20 carbon atoms and bonded to a nitrogen atom at a secondary carbon atom.
【００２３】このような第二級（ｓｅｃｏｎｄａｒｙ）
炭素原子を有するアルキル基としては、例えば、１−メ
チルペンチル、１−エチルブチル、１−メチルヘプチ
ル、１−エチルヘキシル、１−メチルオクチル、１−エ
チルヘプチル、１−メチルノニル、１−エチルオクチ
ル、１−メチルウンデシル、１−エチルデシル、１−メ
チルヘプタデシル、１−エチルヘキサデシル等の基が挙
げられる。これらの第二級炭素原子を有するアルキル基
は、その第二級炭素原子で一般式（１）中の窒素原子
（Ｎ）に結合していることが必要であり、例えば、１−
メチルノニル基の場合、次式で示すように、その第二級
炭素原子で窒素原子に結合している。[0023] Such a secondary
As the alkyl group having a carbon atom, for example, 1-methylpentyl, 1-ethylbutyl, 1-methylheptyl, 1-ethylhexyl, 1-methyloctyl, 1-ethylheptyl, 1-methylnonyl, 1-ethyloctyl, 1- Examples include groups such as methylundecyl, 1-ethyldecyl, 1-methylheptadecyl, 1-ethylhexadecyl. The alkyl group having these secondary carbon atoms needs to be bonded to the nitrogen atom (N) in the general formula (1) at the secondary carbon atom, and for example, 1-
In the case of a methylnonyl group, the secondary carbon atom thereof is bonded to the nitrogen atom as shown in the following formula.
【００２４】[0024]
【化７】 [Chemical 7]
【００２５】したがって、例えば、２−エチルヘキシル
基〔ＣＨ3（ＣＨ2）3ＣＨ（Ｃ2Ｈ5）ＣＨ2−〕は、第二
級炭素原子を有しているけれども、窒素原子とは、第一
級炭素原子で結合しているため、前記で規定する特定の
第二級炭素原子を有するアルキル基には包含されない。Therefore, for example, the 2-ethylhexyl group [CH 3 (CH 2 ) 3 CH (C 2 H 5 ) CH 2- ] has a secondary carbon atom, but the nitrogen atom is Since they are bonded at a primary carbon atom, they are not included in the alkyl group having the specific secondary carbon atom defined above.
【００２６】前記特定の第二級炭素原子を有するアルキ
ル基以外の基としては、炭素数５〜２０の飽和または不
飽和のアルキル基、あるいはアルキルアリール基などの
炭化水素基が好ましい。このような炭化水素基の具体例
としては、例えば、ｎ−ヘキシル、２−エチルヘキシ
ル、ｎ−オクチル、ノニル、デシル、ラウリル、トリデ
シル、オレイル、リノレイルなどの飽和アルキル基また
は不飽和アルキル基（アルケニル基）、ノニルフェニル
などのアルキルアリール基などが挙げられる。これらの
中でも、炭素数６〜１８のアルキル基が特に好ましい。As the group other than the alkyl group having the specific secondary carbon atom, a saturated or unsaturated alkyl group having 5 to 20 carbon atoms, or a hydrocarbon group such as an alkylaryl group is preferable. Specific examples of such a hydrocarbon group include, for example, a saturated alkyl group such as n-hexyl, 2-ethylhexyl, n-octyl, nonyl, decyl, lauryl, tridecyl, oleyl, linoleyl or an unsaturated alkyl group (alkenyl group). ), Alkylaryl groups such as nonylphenyl, and the like. Among these, an alkyl group having 6 to 18 carbon atoms is particularly preferable.
【００２７】これらのジチオカルバミン酸金属塩（Ａ）
は、それぞれ単独で、あるいは２種以上を組み合わせて
使用することができる。ジチオカルバミン酸金属塩
（Ａ）の配合割合は、潤滑油組成物の全量基準で、０．
０１〜１０重量％であり、好ましくは０．０５〜７重量
％、より好ましくは０．１〜５重量％程度である。この
配合割合が小さ過ぎると、十分な摩擦特性及び耐摩耗性
を得ることが困難であり、逆に、多過ぎても、不経済で
あって、耐摩耗性が低下するおそれもある。These metal salts of dithiocarbamic acid (A)
Can be used alone or in combination of two or more. The compounding ratio of the metal salt of dithiocarbamic acid (A) is, based on the total amount of the lubricating oil composition, 0.
It is from 01 to 10% by weight, preferably from 0.05 to 7% by weight, more preferably from 0.1 to 5% by weight. If this blending ratio is too small, it is difficult to obtain sufficient frictional properties and wear resistance, and conversely, if it is too large, it is uneconomical and wear resistance may decrease.
【００２８】ジチオりん酸亜鉛（Ｂ）及びジチオカルバ
ミン酸亜鉛（Ｃ） 本発明では、前記ジチオカルバミン酸金属塩（Ａ）に加
えて、各種潤滑油用添加剤を配合することができるが、
その中でも、特に、前記一般式（２）で表されるジチオ
りん酸亜鉛（Ｂ）及び／または前記一般式（３）で表さ
れるジチオカルバミン酸亜鉛（Ｃ）と併用すると、本発
明の目的である耐摩耗性及び摩擦係数低減効果を更に向
上させることができる。前記一般式（２）において、Ｒ
5〜Ｒ8は、好ましくは炭素数２〜１３の炭化水素基、特
にアルキル基である。前記一般式（３）において、Ｒ9
〜Ｒ12は、好ましくは炭素数２〜１３の炭化水素基、特
にアルキル基である。 Zinc dithiophosphate (B) and dithiocarba
Zinc Minate (C) In the present invention, various lubricating oil additives can be added in addition to the dithiocarbamic acid metal salt (A).
Among them, particularly when used in combination with the zinc dithiophosphate (B) represented by the general formula (2) and / or the zinc dithiocarbamate (C) represented by the general formula (3), for the purpose of the present invention. It is possible to further improve certain wear resistance and the effect of reducing the friction coefficient. In the general formula (2), R
5 to R 8 are preferably hydrocarbon groups having 2 to 13 carbon atoms, particularly alkyl groups. In the general formula (3), R 9
~ R 12 is preferably a hydrocarbon group having 2 to 13 carbon atoms, particularly an alkyl group.
【００２９】ジチオりん酸亜鉛（Ｂ）及び／またはジチ
オカルバミン酸亜鉛（Ｃ）の配合割合は、潤滑油組成物
の全量基準で、０．０１〜７重量％であり、好ましくは
０．０３〜５重量％、より好ましくは０．０５〜２重量
％程度である。この配合割合が少な過ぎると、ジチオカ
ルバミン酸金属塩（Ａ）との併用効果が小さく、十分な
耐摩耗性及び摩擦係数低減向上効果を得ることが困難で
あり、逆に、多過ぎても、不経済であって、摩擦特性が
低下するおそれもある。The compounding ratio of zinc dithiophosphate (B) and / or zinc dithiocarbamate (C) is 0.01 to 7% by weight, preferably 0.03 to 5 based on the total amount of the lubricating oil composition. %, And more preferably about 0.05 to 2% by weight. If this blending ratio is too small, the combined effect with the metal salt of dithiocarbamic acid (A) is small, and it is difficult to obtain sufficient wear resistance and the effect of reducing the friction coefficient. It is economical and there is a risk that the frictional characteristics will deteriorate.
【００３０】その他の添加剤 本発明の潤滑油組成物には、エンジン油等の各用途分野
に応じて、あるいは所望により、各種添加剤を含有させ
ることができる。このような添加剤としては、例えば、
摩擦低減剤、金属清浄剤、無灰清浄分散剤、酸化防止
剤、粘度指数向上剤、防錆剤、消泡剤、腐食防止剤、流
動点降下剤、前記以外の耐摩耗剤などを挙げることがで
きる。 Other Additives The lubricating oil composition of the present invention may contain various additives depending on the field of application such as engine oil or if desired. As such an additive, for example,
Friction reducers, metal detergents, ashless detergent dispersants, antioxidants, viscosity index improvers, rust inhibitors, defoamers, corrosion inhibitors, pour point depressants, anti-wear agents other than the above, etc. You can
【００３１】摩擦低減剤としては、例えば、脂肪酸とグ
リセリンとのモノエステルまたはジエステル、脂肪酸と
ソルビタンのモノエステルまたはジエステル等の脂肪酸
エステル、あるいはオレイン酸アミドやラウリン酸アミ
ドなどの脂肪酸アミドが好ましい。脂肪酸エステルは、
通常０．０１〜１０重量％（組成物全量基準）、好まし
くは０．０５〜５重量％の割合で使用すると、耐摩耗性
と摩擦特性が更に改善される。また、有機アミド化合物
は、通常０．０１〜５重量％（組成物全量基準）、好ま
しくは０．０５〜２重量％の割合で使用すると、銅腐食
性を抑制し、しかも摩擦係数を初期から低減させること
ができる。The friction reducing agent is preferably a fatty acid ester such as a monoester or diester of fatty acid and glycerin, a monoester or diester of fatty acid and sorbitan, or a fatty acid amide such as oleic acid amide or lauric acid amide. Fatty acid ester
When used in an amount of usually 0.01 to 10% by weight (based on the total amount of the composition), preferably 0.05 to 5% by weight, the wear resistance and frictional properties are further improved. When the organic amide compound is used in an amount of usually 0.01 to 5% by weight (based on the total amount of the composition), preferably 0.05 to 2% by weight, it suppresses copper corrosiveness and, moreover, the friction coefficient from the initial stage. Can be reduced.
【００３２】脂肪酸エステル及び有機アミド化合物につ
いて、より具体的に説明すると、次のとおりである。脂
肪酸グリセライドは、例えば、下記一般式（４）及び
（５）で示されるモノエステルまたはジエステルであ
る。The fatty acid ester and organic amide compound will be described more specifically as follows. The fatty acid glyceride is, for example, a monoester or diester represented by the following general formulas (4) and (5).
【００３３】[0033]
【化８】 [Chemical 8]
【００３４】[0034]
【化９】 （これらの式中、Ｒ13、Ｒ14及びＲ15は、炭素数８〜２
２の飽和または不飽和のアルキル基である。）[Chemical 9] (In these formulas, R 13 , R 14 and R 15 have 8 to 2 carbon atoms.
2 is a saturated or unsaturated alkyl group. )
【００３５】脂肪酸エステルは、それぞれ単独で、ある
いは２種以上を組み合わせて使用することができる。前
記ジチオカルバミン酸金属塩（Ａ）と脂肪酸エステルと
を併用すると、それぞれ単独使用の場合と比較して、耐
摩耗性と摩擦特性がさらに向上する。特に、ジチオカル
バミン酸金属塩（Ａ）とジチオりん酸亜鉛（Ｂ）及び／
またはジチオカルバミン酸亜鉛（Ｃ）との併用系に、さ
らに脂肪酸エステルを添加すると、耐摩耗性と摩擦特性
が向上し、摩擦係数が顕著に低減した潤滑油組成物を得
ることができる。有機アミド化合物は、下記一般式
（６）で表される化合物である。The fatty acid ester may be used alone or in combination of two or more kinds. When the metal salt of dithiocarbamic acid (A) is used in combination with the fatty acid ester, the abrasion resistance and the frictional properties are further improved as compared with the case where they are used alone. In particular, metal salts of dithiocarbamic acid (A) and zinc dithiophosphate (B) and /
Alternatively, when a fatty acid ester is further added to the combined use system with zinc dithiocarbamate (C), it is possible to obtain a lubricating oil composition having improved wear resistance and friction characteristics and a significantly reduced friction coefficient. The organic amide compound is a compound represented by the following general formula (6).
【００３６】[0036]
【化１０】 [Chemical 10]
【００３７】（式中、Ｒ16及びＲ17は、水素原子、炭素
数１〜２０のアルキル基、炭素数６〜２６のシクロアル
キル基、炭素数６〜２６のアリール基、アルキルアリー
ル基またはアリールアルキル基、あるいは、炭素数２〜
３０のアルキレンオキシド基であり、互いに同一または
異なっていてもよい。Ｒ18は、水素原子、炭素数１〜２
０のアルキル基、炭素数６〜２６のシクロアルキル基、
炭素数６〜２６のアリール基、アルキルアリール基また
はアリールアルキル基、あるいはエステル結合、エーテ
ル結合、水酸基またはカルボキシル基を含む炭化水素基
である。） 一般式（６）中、アルキレンオキシド基とは、次の一般
式（７）または（８）で表される基である。(In the formula, R 16 and R 17 are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 26 carbon atoms, an aryl group having 6 to 26 carbon atoms, an alkylaryl group or an aryl group. Alkyl group or 2 to 2 carbon atoms
30 alkylene oxide groups, which may be the same or different from each other. R 18 is a hydrogen atom, having 1 to 2 carbon atoms
0 alkyl group, cycloalkyl group having 6 to 26 carbon atoms,
An aryl group having 6 to 26 carbon atoms, an alkylaryl group or an arylalkyl group, or a hydrocarbon group containing an ester bond, an ether bond, a hydroxyl group or a carboxyl group. In the general formula (6), the alkylene oxide group is a group represented by the following general formula (7) or (8).
【００３８】[0038]
【化１１】 [Chemical 11]
【００３９】[0039]
【化１２】 （これらの式中、Ｒ19及びＲ20は、水素原子またはメチ
ル基であり、ｎは、１〜１０の整数である。）[Chemical 12] (In these formulas, R 19 and R 20 are a hydrogen atom or a methyl group, and n is an integer of 1 to 10.)
【００４０】一般式（６）中、Ｒ16及びＲ17は、好まし
くは、水素原子、炭素数２〜８のアルキル基、炭素数８
〜１４のシクロアルキル基、炭素数８〜１４のアルキル
アリール基、ｎ＝１〜５のアルキレンオキシド基であ
る。Ｒ18は、好ましくは、炭素数６〜１８の飽和または
不飽和のアルキル基、炭素数１２〜２４のシクロアルキ
ル基、または炭素数１２〜２４のアルキルアリール基で
ある。In the general formula (6), R 16 and R 17 are preferably a hydrogen atom, an alkyl group having 2 to 8 carbon atoms, or 8 carbon atoms.
To 14 cycloalkyl groups, C 8-14 alkylaryl groups, and n = 1-5 alkylene oxide groups. R 18 is preferably a saturated or unsaturated alkyl group having 6 to 18 carbon atoms, a cycloalkyl group having 12 to 24 carbon atoms, or an alkylaryl group having 12 to 24 carbon atoms.
【００４１】金属清浄剤としては、例えば、バリウム
（Ｂａ）、カルシウム（Ｃａ）、マグネシウム（Ｍｇ）
などのフェネート、スルホネート、ホスホネートなどを
挙げることができるが、これらの中でも、特に、過塩基
性のＣａスルホネート、Ｍｇスルホネート、Ｃａフェネ
ート、または中性のＣａスルホネートが好ましい。金属
清浄剤は、通常、０．１〜１０重量％（組成物全量基
準）の割合で使用する。無灰清浄分散剤としては、例え
ば、ベンジルアミン、ベンジルアミンのホウ素誘導体、
アルケニルこはく酸イミド、アルケニルこはく酸イミド
のホウ素誘導体などを挙げることができる。無灰清浄分
散剤は、通常、０．５〜１５重量％（組成物全量基準）
の割合で使用する。Examples of the metal detergent include barium (Ba), calcium (Ca), magnesium (Mg).
Examples thereof include phenates, sulfonates, phosphonates, and the like. Among these, overbased Ca sulfonate, Mg sulfonate, Ca phenate, or neutral Ca sulfonate is particularly preferable. The metal detergent is usually used in a proportion of 0.1 to 10% by weight (based on the total amount of the composition). As the ashless detergent dispersant, for example, benzylamine, a boron derivative of benzylamine,
Examples thereof include alkenyl succinimide and alkenyl succinimide boron derivatives. The ashless detergent dispersant is usually 0.5 to 15% by weight (based on the total amount of the composition).
Used in proportion.
【００４２】酸化防止剤としては、例えば、アルキル化
ジフェニルアミン、フェニル−α−ナフチルアミン、ア
ルキル化−α−ナフチルアミン等のアミン系酸化防止
剤、２，６−ジ−ｔ−ブチルフェノール、４，４′−メ
チレンビス−（２，６−ジターシャリブチルフェノー
ル）等のフェノール系酸化防止剤などを挙げることがで
きる。酸化防止剤は、通常、０．０５〜２．０重量％
（組成物全量基準）の割合で使用する。Examples of the antioxidant include amine-based antioxidants such as alkylated diphenylamine, phenyl-α-naphthylamine and alkylated-α-naphthylamine, 2,6-di-t-butylphenol, 4,4′- Examples thereof include phenolic antioxidants such as methylenebis- (2,6-ditertiarybutylphenol). The antioxidant is usually 0.05 to 2.0% by weight.
It is used at a ratio of (composition total amount basis).
【００４３】粘度指数向上剤としては、例えば、ポリメ
チルメタクリレート系、ポリイソブチレン系、エチレン
−プロピレン共重合体系、スチレン−ブタジエン水添共
重合体系等が挙げられ、通常、０．５〜３５重量％（組
成物全量基準）の割合で使用する。防錆剤としては、例
えば、アルケニルこはく酸またはその部分エステル等が
挙げられ、適宜添加することができる。消泡剤として
は、例えば、ジメチルポリシロキサン、ポリアクリレー
ト等が挙げられ、適宜添加することができる。Examples of the viscosity index improver include polymethylmethacrylate type, polyisobutylene type, ethylene-propylene copolymer system, styrene-butadiene hydrogenated copolymer system, etc., and usually 0.5 to 35% by weight. It is used at a ratio of (composition total amount basis). Examples of the rust preventive agent include alkenyl succinic acid and its partial ester, and the like, which can be appropriately added. Examples of the defoaming agent include dimethylpolysiloxane and polyacrylate, which can be appropriately added.
【００４４】[0044]
【実施例】以下に、実施例及び比較例を挙げて、本発明
についてさらに具体的に説明するが、本発明は、これら
の実施例のみに限定されるものではない。なお、物性の
測定法は、下記の通りである。 ＜摩擦・摩耗特性＞シェル四球式試験を用いて、試験開
始３０分後の摩耗痕径（ｍｍ）及び摩擦係数を測定し
た。試験条件は、下記の通りである。 荷重：４０ｋｇ 油温：９０℃ 回転数：１８００ｒｐｍ 試験時間：３０分EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The methods for measuring the physical properties are as follows. <Friction / Abrasion Properties> Using a shell four-ball test, the wear scar diameter (mm) and the friction coefficient 30 minutes after the start of the test were measured. The test conditions are as follows. Load: 40 kg Oil temperature: 90 ° C Rotation speed: 1800 rpm Test time: 30 minutes
【００４５】［実施例１］表１に示す潤滑油基油と各成
分を混合して各試験油を調製した。使用した各成分は、
以下のとおりである。 （１）基油 鉱油 ：１５０ニュートラル油；１００℃での動粘度
は、５．１ｃＳｔ（ｍｍ2／ｓ） 合成油：ポリ−α−オレフィン８０重量％とジイソデシ
ルアジペート２０重量％との混合油 （２）ジチオカルバミン酸モリブデン：一般式（１）に
おいて、Ｘ1及びＸ2が酸素原子（Ｏ）で、Ｙ1及びＹ2が
硫黄源子（Ｓ）である硫化ジチオカルバミン酸モリブデ
ンを使用した。 炭化水素基＝ｐ−Ｃ 8〜Ｃ13アルキル：市販の第一級
（ｐｒｉｍａｒｙ）アルキル基（炭素数８〜１３の混合
アルキル基）を有する硫化ジチオカルバミン酸モリブデ
ン 炭化水素基＝ｐ−Ｃ13アルキル：市販の第一級（ｐｒ
ｉｍａｒｙ）アルキル基（炭素数１３）を有する硫化ジ
チオカルバミン酸モリブデン 炭化水素基＝１−メチルヘプチル：Ｒ1〜Ｒ4が１−メ
チルヘプチル基である硫化ジチオカルバミン酸モリブデ
ン 炭化水素基＝１−メチルノニル：Ｒ1〜Ｒ4が１−メチ
ルノニル基である硫化ジチオカルバミン酸モリブデン 炭化水素基＝ｐ−Ｃ13アルキル５０％と１−メチルノ
ニル５０％：Ｒ1〜Ｒ4が第一級アルキル基（炭素数１
３）と１−メチルノニルとの５０対５０の混合アルキル
基である硫化ジチオカルバミン酸モリブデン （３）ジチオりん酸亜鉛：市販のｉ−Ｃ3／ｓ−Ｃ6アル
キルタイプ （４）ジチオカルバミン酸亜鉛：市販のｎ−Ｃ5／ｉ−
Ｃ5アルキルタイプExample 1 Lubricating base oils shown in Table 1 and various compositions
Each test oil was prepared by mixing the minutes. Each component used is
It is as follows. (1) Base oil Mineral oil: 150 neutral oil; Kinematic viscosity at 100 ° C
Is 5.1 cSt (mm2/ S) Synthetic oil: 80% by weight of poly-α-olefin and diisodecyl
Mixed oil with 20% by weight of luadipate (2) Molybdenum dithiocarbamate: In general formula (1)
By the way, X1And X2Is an oxygen atom (O), and Y1And Y2But
Molybde sulfide dithiocarbamate, which is a sulfur source (S)
Used. Hydrocarbon group = p-C 8~ C13Alkyl: Commercially available primary
(Primary) alkyl group (mixture of 8 to 13 carbon atoms
Molybde sulfurized dithiocarbamate having an alkyl group)
Hydrocarbon group = p-C13Alkyl: commercially available primary (pr
imary) disulfide having an alkyl group (having 13 carbon atoms)
Molybdenum thiocarbamate Hydrocarbon group = 1-methylheptyl: R1~ RFourIs 1-me
Molybde sulfide dithiocarbamate, a tylheptyl group
Hydrocarbon group = 1-methylnonyl: R1~ RFourIs 1-meth
Molybdenum sulfurized dithiocarbamate, which is a nononyl group Hydrocarbon group = p-C1350% alkyl and 1-methylno
Nil 50%: R1~ RFourIs a primary alkyl group (having 1 carbon atom
3) 50-50 mixed alkyl of 1-methylnonyl
Molybdenum sulfurized dithiocarbamate (3) Zinc dithiophosphate: commercially available i-C3/ S-C6Al
Kill type (4) Zinc dithiocarbamate: commercially available nCFive/ I-
CFiveAlkyl type
【００４６】表１中の各添加剤成分の配合割合は、組成
物全量基準の重量％であり、残余は基油である（合計１
００重量％）。なお、硫化ジチオカルバミン酸モリブデ
ンの添加量は、モリブデン原子の含量で示した。結果を
表１に示す。The mixing ratio of each additive component in Table 1 is% by weight based on the total amount of the composition, and the balance is base oil (total 1).
00% by weight). The amount of molybdenum sulfide dithiocarbamate added was indicated by the content of molybdenum atoms. The results are shown in Table 1.
【００４７】[0047]
【表１】 （脚注）＊印のついた実験例は、比較例であり、その他
は、本発明例である。[Table 1] (Footnote) Experimental examples marked with * are comparative examples, and others are inventive examples.
【００４８】表１から明らかなように、本発明の特定の
第二級アルキル基を持つ硫化ジチオカルバミン酸モリブ
デンを配合した潤滑油組成物（実験Ｎｏ．４〜６、８及
び１０）は、従来の第一級炭素原子で窒素原子と結合し
ている硫化ジチオカルバミン酸モリブデンを配合した場
合（実験Ｎｏ．２，３，７及び８）と比較して、いずれ
も顕著に優れた耐摩耗性及び摩擦係数低減降下を示して
いる。As is clear from Table 1, the lubricating oil compositions (experiment Nos. 4 to 6, 8 and 10) containing the sulfurized molybdenum dithiocarbamate having a specific secondary alkyl group of the present invention were the conventional ones. Compared with the case of blending molybdenum sulfide dithiocarbamate in which primary carbon atom is bonded to nitrogen atom (Experiment No. 2, 3, 7 and 8), the wear resistance and friction coefficient are remarkably excellent. It shows a reduced descent.
【００４９】［実施例２］表２に示す潤滑油基油と各成
分を混合して各試験油を調製した。使用した各成分は、
以下のとおりである。 （１）基油、硫化ジチオカルバミン酸モリブデン、及び
ジチオりん酸亜鉛は、実施例１で使用したものと同じで
ある。 （２）脂肪酸グリセライド：Example 2 Each test oil was prepared by mixing the lubricating base oil shown in Table 2 with each component. Each component used is
It is as follows. (1) The base oil, molybdenum sulfurized dithiocarbamate, and zinc dithiophosphate are the same as those used in Example 1. (2) Fatty acid glyceride:
【００５０】[0050]
【化１３】 （式中、Ｒは、オレイル基を表す。） （３）有機アミド化合物：オレイン酸アミド 結果を表２に示す。[Chemical 13] (In the formula, R represents an oleyl group.) (3) Organic amide compound: oleic acid amide The results are shown in Table 2.
【００５１】[0051]
【表２】 （脚注）＊印のついた実験例は、比較例であり、その他
は、本発明例である。[Table 2] (Footnote) Experimental examples marked with * are comparative examples, and others are inventive examples.
【００５２】表２の結果から明らかなように、脂肪酸エ
ステルまたは脂肪酸アミドを添加すると、摩擦係数が一
層低減することが分かる。As is clear from the results shown in Table 2, the addition of fatty acid ester or amide further reduces the friction coefficient.
【００５３】[0053]
【発明の効果】本発明によれば、従来の硫化ジチオカル
バミン酸金属塩と比較して、顕著に優れた耐摩耗性と摩
擦特性を有する潤滑油組成物を提供することができる。
本発明の潤滑油組成物は、極低りん化または無りん化す
ることも可能である。したがって、本発明の潤滑油組成
物は、内燃機関用潤滑油をはじめとして広範な分野で使
用することができる。EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a lubricating oil composition having remarkably excellent wear resistance and friction characteristics as compared with the conventional metal salt of sulfurized dithiocarbamic acid.
The lubricating oil composition of the present invention can also be extremely low phosphorus-free or phosphorus-free. Therefore, the lubricating oil composition of the present invention can be used in a wide range of fields including lubricating oils for internal combustion engines.
Claims (2)
である。Ｒ1、Ｒ2、Ｒ3及びＲ4は、水素原子、炭素数１
〜２０の飽和または不飽和のアルキル基、炭素数６〜２
６のシクロアルキル基またはアルキル置換シクロアルキ
ル基、炭素数６〜２６のアリール基、アルキルアリール
基またはアリールアルキル基、あるいはこれらの炭化水
素基に、エステル結合、エーテル結合、水酸基またはカ
ルボキシル基が導入された炭化水素基であり、互いに同
一または異なっていてもよい。ただし、これら４つの内
の少なくとも１つは、第二級炭素原子を有する炭素数５
〜２０のアルキル基であって、かつ、その第二級炭素原
子で前記式中の窒素原子（Ｎ）に結合している。Ｘ1及
びＸ2は、酸素原子または硫黄原子である。Ｙ1及びＹ2
は、酸素原子または硫黄原子である。〕で表されるジチ
オカルバミン酸金属塩（Ａ）を、組成物全量基準で、
０．０１〜１０重量％の割合で含有させてなる潤滑油組
成物。1. A lubricating base oil having the general formula (1): [In the formula, M is a molybdenum atom or a tungsten atom. R 1 , R 2 , R 3 and R 4 are hydrogen atoms and have 1 carbon atom
To saturated or unsaturated alkyl groups having 6 to 20 carbon atoms
An ester bond, an ether bond, a hydroxyl group or a carboxyl group is introduced into a cycloalkyl group of 6 or an alkyl-substituted cycloalkyl group, an aryl group of 6 to 26 carbon atoms, an alkylaryl group or an arylalkyl group, or these hydrocarbon groups. Hydrocarbon groups, which may be the same or different from each other. However, at least one of these four has 5 carbon atoms having a secondary carbon atom.
.About.20 alkyl group, and is bonded to the nitrogen atom (N) in the above formula at its secondary carbon atom. X 1 and X 2 are oxygen atoms or sulfur atoms. Y 1 and Y 2
Is an oxygen atom or a sulfur atom. ] The metal salt of dithiocarbamic acid (A) represented by
A lubricating oil composition containing 0.01 to 10% by weight.
金属塩（Ａ）に加えて、さらに、一般式（２） 【化２】 （ただし、式中、Ｒ5、Ｒ6、Ｒ7及びＲ8は、水素原子、
炭素数１〜２０の飽和または不飽和のアルキル基、炭素
数６〜２６のシクロアルキル基またはアルキル置換シク
ロアルキル基、炭素数６〜２６のアリール基、アルキル
アリール基またはアリールアルキル基、あるいはこれら
の炭化水素基に、エステル結合、エーテル結合、水酸基
またはカルボキシル基が導入された炭化水素基であり、
互いに同一または異なっていてもよい。）で表されるジ
チオりん酸亜鉛（Ｂ）、及び一般式（３） 【化３】 （ただし、式中、Ｒ9、Ｒ10、Ｒ11及びＲ12は、水素原
子、炭素数１〜２０の飽和または不飽和のアルキル基、
炭素数６〜２６のシクロアルキル基またはアルキル置換
シクロアルキル基、炭素数６〜２６のアリール基、アル
キルアリール基またはアリールアルキル基、あるいはこ
れらの炭化水素基に、エステル結合、エーテル結合、水
酸基またはカルボキシル基が導入された炭化水素基であ
り、互いに同一または異なっていてもよい。）で表され
るジチオカルバミン酸亜鉛（Ｃ）からなる群より選ばれ
る少なくとも一種の有機亜鉛化合物を、組成物全量基準
で、０．０１〜７重量％の割合で含有させてなる請求項
１記載の潤滑油組成物。2. A lubricating base oil, in addition to the metal salt of dithiocarbamic acid (A), further having the general formula (2): (In the formula, R 5 , R 6 , R 7 and R 8 are hydrogen atoms,
A saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 26 carbon atoms or an alkyl-substituted cycloalkyl group, an aryl group having 6 to 26 carbon atoms, an alkylaryl group or an arylalkyl group, or these The hydrocarbon group is a hydrocarbon group in which an ester bond, an ether bond, a hydroxyl group or a carboxyl group is introduced,
They may be the same or different from each other. ) Zinc dithiophosphate (B), represented by the general formula (3) (In the formula, R 9 , R 10 , R 11 and R 12 are each a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 6 to 26 carbon atoms or an alkyl-substituted cycloalkyl group, an aryl group having 6 to 26 carbon atoms, an alkylaryl group or an arylalkyl group, or these hydrocarbon groups, an ester bond, an ether bond, a hydroxyl group or a carboxyl group. The groups are introduced hydrocarbon groups and may be the same or different from each other. 2.) At least one organozinc compound selected from the group consisting of zinc dithiocarbamate (C) represented by (4) is contained in a proportion of 0.01 to 7% by weight based on the total amount of the composition. Lubricating oil composition.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6027477A JPH07216378A (en) | 1994-01-31 | 1994-01-31 | Lubricating oil composition |
| PCT/US1995/005144 WO1996037581A1 (en) | 1994-01-31 | 1995-05-24 | Lubricating oil composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6027477A JPH07216378A (en) | 1994-01-31 | 1994-01-31 | Lubricating oil composition |
| PCT/US1995/005144 WO1996037581A1 (en) | 1994-01-31 | 1995-05-24 | Lubricating oil composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07216378A true JPH07216378A (en) | 1995-08-15 |
Family
ID=26365406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6027477A Pending JPH07216378A (en) | 1994-01-31 | 1994-01-31 | Lubricating oil composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH07216378A (en) |
| WO (1) | WO1996037581A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006265493A (en) * | 2005-03-25 | 2006-10-05 | Nippon Oil Corp | Lubricating oil composition |
| JP2008519127A (en) * | 2004-11-04 | 2008-06-05 | ユナイテッド テクノロジーズ コーポレイション | Multi-functional lubricant additive package |
| JP2019189575A (en) * | 2018-04-27 | 2019-10-31 | 株式会社Adeka | Molybdenum dithiocarbamate and method for producing molybdenum dithiocarbamate |
| JP2020524723A (en) * | 2017-06-22 | 2020-08-20 | エクソンモービル リサーチ アンド エンジニアリング カンパニーＥｘｘｏｎ Ｒｅｓｅａｒｃｈ Ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ｃｏｍｐａｎｙ | Lubricating oil for ships and method of manufacturing and using the same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6172013B1 (en) | 1997-09-17 | 2001-01-09 | Exxon Chemical Patents Inc | Lubricating oil composition comprising trinuclear molybdenum compound and diester |
| WO2000005301A1 (en) | 1998-07-22 | 2000-02-03 | Societe De Technologie Michelin | Coupling system (white filler/diene elastomer) based on polysulphide alkoxysilane, zinc dithiophosphate and guanidine derivative |
| US6300291B1 (en) | 1999-05-19 | 2001-10-09 | Infineum Usa L.P. | Lubricating oil composition |
| EP1652908A1 (en) * | 2004-11-01 | 2006-05-03 | Infineum International Limited | Lubricating Compositions |
| JP5203590B2 (en) | 2006-10-27 | 2013-06-05 | 出光興産株式会社 | Lubricating oil composition |
| EP2248878A1 (en) * | 2009-05-01 | 2010-11-10 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2056482A (en) * | 1979-08-13 | 1981-03-18 | Exxon Research Engineering Co | Lubricating oil compositions |
| US4280916A (en) * | 1980-03-31 | 1981-07-28 | Shell Oil Company | Lubricant composition |
| JPS59122597A (en) * | 1982-11-30 | 1984-07-16 | Honda Motor Co Ltd | Lubricating oil composition |
-
1994
- 1994-01-31 JP JP6027477A patent/JPH07216378A/en active Pending
-
1995
- 1995-05-24 WO PCT/US1995/005144 patent/WO1996037581A1/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008519127A (en) * | 2004-11-04 | 2008-06-05 | ユナイテッド テクノロジーズ コーポレイション | Multi-functional lubricant additive package |
| JP2006265493A (en) * | 2005-03-25 | 2006-10-05 | Nippon Oil Corp | Lubricating oil composition |
| JP2020524723A (en) * | 2017-06-22 | 2020-08-20 | エクソンモービル リサーチ アンド エンジニアリング カンパニーＥｘｘｏｎ Ｒｅｓｅａｒｃｈ Ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ｃｏｍｐａｎｙ | Lubricating oil for ships and method of manufacturing and using the same |
| JP2019189575A (en) * | 2018-04-27 | 2019-10-31 | 株式会社Adeka | Molybdenum dithiocarbamate and method for producing molybdenum dithiocarbamate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996037581A1 (en) | 1996-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0700425B1 (en) | Lubricating oil composition | |
| US5672572A (en) | Lubricating oil composition | |
| JP3556355B2 (en) | Lubricating oil composition | |
| EP0725130B1 (en) | Lubricating oil composition for internal combustion engines | |
| JP4201902B2 (en) | Lubricating composition | |
| JPH05279686A (en) | Lubricant oil composition for internal-combustion engine | |
| JP3554757B2 (en) | Engine oil composition | |
| JPH06313183A (en) | Lubricant composition | |
| JPH0931483A (en) | Lubricant composition | |
| JP2000186293A (en) | Diesel engine lubricating oil composition | |
| JP4934844B2 (en) | Lubricating oil composition | |
| JPH08209178A (en) | Lubricant composition | |
| JP3556348B2 (en) | Lubricating oil composition | |
| WO1997004048A1 (en) | Lubricating oil composition | |
| JPH07216378A (en) | Lubricating oil composition | |
| WO1997008280A1 (en) | Lubricating oil composition | |
| JP2005263830A (en) | Lubricating oil composition | |
| WO1994028094A1 (en) | Lubricating oil composition | |
| JP2000290677A (en) | Lubricating oil composition for diesel engine | |
| JPH1046177A (en) | Lubricating oil composition | |
| JP4614022B2 (en) | Lubricating oil composition for internal combustion engines | |
| JP3609526B2 (en) | Lubricating oil composition | |
| JP4095750B2 (en) | Lubricating oil composition for internal combustion engines | |
| JPH07150170A (en) | Lubricating oil composition | |
| JPH07150173A (en) | Lubricating oil composition |