WO1997008280A1 - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
- Publication number
- WO1997008280A1 WO1997008280A1 PCT/JP1996/002436 JP9602436W WO9708280A1 WO 1997008280 A1 WO1997008280 A1 WO 1997008280A1 JP 9602436 W JP9602436 W JP 9602436W WO 9708280 A1 WO9708280 A1 WO 9708280A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- carbon atoms
- weight
- lubricating oil
- boron
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 56
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052796 boron Inorganic materials 0.000 claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 16
- 239000003599 detergent Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 239000002199 base oil Substances 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- -1 olefin sulfide Chemical class 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 17
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 235000021323 fish oil Nutrition 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 239000010698 whale oil Substances 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229960005069 calcium Drugs 0.000 claims 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 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 230000001050 lubricating effect Effects 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229940072082 magnesium salicylate Drugs 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000004867 thiadiazoles Chemical class 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 39
- 239000007789 gas Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000006866 deterioration Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000001639 boron compounds Chemical class 0.000 abstract 2
- BCBHLWYLGWJAJF-UHFFFAOYSA-J molybdenum(4+) sulfur monoxide tetracarbamodithioate Chemical compound [Mo+4].S=O.NC([S-])=S.NC([S-])=S.NC([S-])=S.NC([S-])=S BCBHLWYLGWJAJF-UHFFFAOYSA-J 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 15
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 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 8
- 239000001384 succinic acid Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 125000002347 octyl 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])[H] 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 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 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 125000001421 myristyl 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])C([H])([H])[H] 0.000 description 5
- 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 5
- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 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 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 125000002960 margaryl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001634822 Biston Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002270 dispersing agent Substances 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
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003900 succinic acid esters Chemical class 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- UWKRVGVDUSXMDU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[2-(3,5-ditert-butyl-4-hydroxyphenyl)propyl]phenol Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1C(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 UWKRVGVDUSXMDU-UHFFFAOYSA-N 0.000 description 1
- DBFZTOFZNSPIPC-UHFFFAOYSA-N 4,5-bis(octylsulfanyl)thiadiazole Chemical compound CCCCCCCCSC=1N=NSC=1SCCCCCCCC DBFZTOFZNSPIPC-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N anhydrous n-heptane Natural products CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 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
- WYLGULQOXHDWBD-UHFFFAOYSA-N barium;phenol Chemical compound [Ba].OC1=CC=CC=C1 WYLGULQOXHDWBD-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical group C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 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
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulphide Natural products C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 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
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229940021019 disal Drugs 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- JDVPQXZIJDEHAN-UHFFFAOYSA-N succinamic acid Chemical compound NC(=O)CCC(O)=O JDVPQXZIJDEHAN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
- C10M2227/062—Cyclic esters
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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/063—Complexes of boron halides
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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
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- 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
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
Definitions
- the present invention relates to a novel lubricating oil composition. More specifically, the present invention provides an internal combustion engine that has excellent low wear and low friction properties, does not deteriorate even in an air atmosphere containing nitrogen oxide gas, and has long-lasting low friction properties.
- the present invention relates to a lubricating oil composition that can be suitably used as a lubricating oil for automatic transmissions, shock absorbers, power steering, and the like, particularly a lubricating oil for internal combustion engines.
- Lubricating oil is used in internal combustion engines, drive systems such as automatic transmissions, shock absorbers, and power steering, and gears to facilitate their operation.
- lubricating oil for internal combustion engines mainly lubricates various sliding parts, such as piston rings and cylinder liners, bearings for crankshafts and connecting rods, and valve trains including cams and valve lifters. It acts to cleanly disperse the combustion products and prevent corrosion.
- lubricating oil for internal combustion engines satisfies the above required performance and does not deteriorate even in an atmosphere containing nitrogen oxide gas.
- anti-wear agents metal-based detergents, and ashless
- additives such as powders and antioxidants are blended.
- a friction modifier is added to lubricating oil as a measure to reduce friction loss and fuel consumption because the energy loss in the friction part involving lubricating oil is large.
- the friction modifier for example, an organic molybdenum compound, a fatty acid ester, an alkylamine and the like are generally used.
- the present inventors have conducted intensive studies and found that the friction modifier has an effect of being added at the beginning of use, but loses its effect when subjected to oxidative deterioration due to oxygen in the air.
- the effect was significantly reduced in the presence of nitrogen oxide gas, and a lubricating oil composition that could maintain the effect of reducing engine friction over a long period of time without being affected by nitrogen oxide gas. It was made for the purpose of providing.
- a lubricating oil base oil has a specific alkyl group-containing oxymolybdenum dithiocarbamate.
- a lubricating oil composition containing a specific ratio of zinc dialkyldithiophosphate having a specific alkyl group, a specific sulfur compound, a specific metal-based detergent and a boron-containing compound in a specific ratio may be suitable for the purpose.
- the present inventors have completed the present invention based on this finding.
- (1) a lubricating base oil (A) oxymolybdenum dithiocarbamate having an alkyl group having 8 to 18 carbon atoms, (B) a primary class having 1 to 18 carbon atoms Zinc dialkyldithiophosphate having an alkyl group; (C) zinc dialkyldithiophosphate having an alkyl group having 2 to 18 carbon atoms; copper or dialkyldithiocarbamate or nickel dialkyldithiocarbamate; Tetraalkylthiuram disulfide having 2 to 18 carbon atoms, disulfide having an alkyl group having 2 to 18 carbon atoms, aryl group having 6 to 18 carbon atoms, alkylaryl group or aryl Disulfide having a reel alkyl group, thiadiazole compound having 3 to 24 carbon atoms and having a substituent containing sulfur, olefin sulfide, sulfide fish oil and One or more sulfur compounds selected from the group consist
- the amount of molybdenum derived from oxymolybdenum dithiocarbamate is 300 to 80 ppm (weight ratio), and the amount of phosphorus derived from zinc dialkyldithiophosphate is 0.04 to 12 ppm.
- the amount of boron derived from the boron-containing compound is 0.01 to 0.04% by weight.
- the lubricating base oil used in the lubricating oil composition of the present invention is not particularly limited, and those conventionally used as base oils for lubricating oils, for example, mineral oils and synthetic oils can be used.
- Mineral oil includes hydroprocessing using lubricating oil raw materials such as raffinate obtained by solvent refining using an aromatic extraction solvent such as fenol or furfural, and silica-alumina using a hydroprocessing catalyst such as cobalt or molybdenum.
- lubricating oil raw materials such as raffinate obtained by solvent refining using an aromatic extraction solvent such as fenol or furfural, and silica-alumina using a hydroprocessing catalyst such as cobalt or molybdenum.
- hydrotreated oil obtained by Any mineral oil, for example, 60 neutral oils, 100 neutral oils, 150 neutral oils, 300 neutral oils, 500 neutral oils, bright stocks, etc. can be mentioned.
- the synthetic oil N includes, for example, poly- ⁇ -olefin oligomer, polybutene, alkylbenzene, CsMM polyol ester, polyglycol ester, dibasic acid ester, phosphate ester, and silicone oil. It can.
- Each of these base oils may be used alone, or two or more may be used in combination, or a mixture of a mineral oil and a synthetic oil may be used.
- the base oil used in the lubricating oil composition of the present invention those having a viscosity at 100 ° C. in the range of 3 to 20 nnn 2 / s are preferable. % Or less, a sulfur content of 5 Oppm or less and a nitrogen content of 5 Oppm or less are particularly preferred.
- RR 2 , R 3, and R 4 are each an alkyl group having 8 to 18 carbon atoms, which may be the same or different, and X is sulfur or oxygen.) Is used.
- the alkyl group having 8 to 18 carbon atoms represented by RR 2 , R 5 and R ′ 1 in the general formula (1) may be linear or branched.
- the number of carbon atoms of the alkyl group represented by R ⁇ R 2, R s and R 1 is 8-1 3 is preferably especially.
- alkyl group represented by R ⁇ R 2 , R 3 and R ′ include an octyl group, a nonyl group, a decyl group, an decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pendecyl group, Hexadecyl, heptane decyl and octadecyl groups You can have children.
- one type of oxymolybdenum dithiocarbamate may be used, or two or more types may be used in combination.
- the oxymolybdenum dithiocarbamate is preferably used so that the amount of molybdenum derived from oxymolybdenum dithiocarbamate is 200 to 2,000 Opm (weight ratio) based on the total weight of the composition. It is blended to be 300 to 80 Oppm (weight ratio).
- the amount of oxymolybdenum dithiocarbamate is less than 20 Opm (weight ratio) based on the total weight of the composition, based on the total weight of the composition.
- the amount is too small, the effect of improving the friction characteristics (low friction property) will not be sufficiently exhibited, and the amount of oxymolybdenum dithiocarbamate will be reduced based on the total weight of the composition. If the amount of molybdenum derived from carbamate is more than 2000 ppm (weight ratio), the effect is not improved for the amount, and sludge is likely to be caused.
- the primary alkyl group represented by RR b , R 7 and R s in the general formula (2) may be linear or branched, for example, a methyl group, an ethyl group, a propyl group , Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, pendecyl, dodecyl, tridecyl, tetradecyl, pendecyl, hexadecyl, heptadecyl,
- the lubricating oil composition of the present invention is a dialkyldithiol group having a primary alkyl group having 3 to 12 carbon atoms. It is particularly preferred to use zinc phosphate.
- the zinc dialkyldithiophosphate is such that the amount of phosphorus derived from the zinc dialkyldithiophosphate is 0.02 to 0.15% by weight, preferably 0.04 to 0.12% by weight based on the total weight of the composition. Mix. If the content of zinc dialkyldithiophosphate is such that the amount of phosphorus derived from zinc dialkyldithiophosphate based on the total weight of the composition is less than 0.02% by weight, the abrasion resistance becomes insufficient and the oil temperature becomes high.
- dialkyldithiolbaminates to be distributed in the lubricating oil composition of the present invention include the following general formula (3): sSR 11
- R 11 and R 1: 2 is an alkyl group having 2 to 18 carbon atoms, even they be the same or different from each other Good.
- the alkyl group having 2 to 18 carbon atoms represented by R q , R H) , R 11 and R 12 in the general formula (3) may be linear or branched. Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pencil decyl, hexadecyl And heptadecyl and octadecyl groups.
- the tetraalkylthiuram disulphide to be added to the lubricating oil composition of the present invention is represented by the general formula (4): R 13 RI s
- the alkyl group may be linear or branched, for example, ethyl group, propyl
- the disulphide to be added to the lubricating oil composition of the present invention is represented by the general formula (5), R 17 -S-S-R 18 (5)
- the alkyl group having 2 to 18 carbon atoms represented by R 17 and R 18 in the general formula (5) may be linear or branched, for example, ethyl, propyl, butyl Group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, pendecyl group, dodecyl group, tridecyl group, tetradecyl group, pendudecyl group, hexadecyl group, hepnodecyl group , it can either be given Okutadeshiru group, also ⁇ Li Ichiru group R 17 ⁇ beauty R 1 carbon atoms represented by S.
- the alkyl ⁇ aryl group or ⁇ Li one Ruarukiru group is, for example, Fuweniru Group, benzyl group, phenyl group, methylbenzyl group, diphenylmethyl group and the like.
- R 19 and R 2 ⁇ are monovalent groups having 3 to 24 carbon atoms and containing at least one sulfur atom, and they may be the same or different from each other in NCH.
- Examples of the monovalent group having 3 to 24 carbon atoms represented by R 19 and R 2 ° represented by R 19 and R 2 ° in the general formula (6) and containing at least one sulfur atom include, for example, a 5-thianonyl group, 5-dithihexyl, 3,4-dithiahexyl, 4,5—dithiahexyl, 3,4,5—trithiaheptyl, 3,4,5,6-tetrathiao Octyl, 5-thio-2-heptenyl, 4-thiacyclohexyl, 1,4-dithianaphthyl, 5- (methylthio) octyl, 4- (ethylthio) 1-2-pentenyl, 4- (methylthio) Examples thereof include a cyclohexyl group, a 4-mercaptophenyl group, a 4- (methylthio) phenyl group, and a 4- (hexylthio) benzyl group.
- a 3,4-dithiahexyl group represented by the formula (7), a 4,5-dithiahexyl group represented by the formula (8), and a 3,4 represented by the formula (9) , 5—trithiaheptyl group, 3,4,5,6-tetrathiaoctyl group of formula (10) Attached groups are particularly preferred.
- the sulfur sulfide incorporated in the lubricating oil composition of the present invention has a sulfur content obtained by sulfidizing a polymer such as isoptylene. It is 25 to 40% by weight of sulfurized olefin (polysulfide). Sulfurized fish oil and whale oil are obtained by similarly sulfurizing fish oil and whale oil.
- a dialkyldithiocarbamate represented by the general formula (3) a tetraalkylthiuram disulfide represented by the general formula (4)
- the disulfide, the thiadiazole compound represented by the general formula (6), the sulfided olefin, the sulfided fish oil and the sulfided whale oil can be used alone or in combination of two or more.
- These sulfur compounds are blended so that the amount of sulfur derived from these sulfur compounds is from 0.02 to 0.30% by weight based on the total weight of the composition.
- the amount of these sulfur compounds is such that the amount of sulfur derived from these sulfur compounds based on the total weight of the composition is less than 0.02% by weight, friction reduction is maintained over a long period of time. The effect is insufficient. If the amount of these sulfur compounds is more than 0.3% by weight based on the total weight of the composition, the effect will be improved. unacceptable.
- the lubricating oil composition of the present invention contains one or more metal detergents selected from the group consisting of calcium salicylate, magnesium salicylate, calcium sulfonate, magnesium sulfonate and calcium phenate. These metallic detergents are blended in an amount of 1 to 10% by weight based on the total weight of the composition. If the amount of these metallic detergents is less than 1% by weight based on the total weight of the composition, the cleaning effect is insufficient, and the amount of these metallic detergents is based on the total weight of the composition. If it exceeds 10% by weight, the effect is not improved for the amount, but the ash increases.
- the total base number of the composition is preferably from 3 to 10, and more preferably from 4 to 7.
- the total base number can be measured according to J1SK2501. Adjustment of the total base number can be suitably performed by selecting a metal-based detergent having an appropriate base number.
- boron-containing compound examples include boron-containing succinic acid imido and boron-containing succinic acid ester.
- boron-containing succinic acid imides include those represented by the following general formulas (11) and (12). 0
- R 21 is a hydrocarbon group having 1 to 50 carbon atoms
- R 22 is an alkylene group having 2 to 5 carbon atoms
- n is 1 to 10
- R 21 may be the same as or different from each
- n + 1 pieces of R 22 in the general formula (12) may be the same or different
- Z is a boron-containing substituent der For Z, for example,
- ECA 525 manufactured by Exxon Chemical Co., Ltd.
- LUBR I ZOL 935 manufactured by Lubrizol Co., Ltd.
- boron-containing succinate examples include those represented by the following general formula (13).
- Y and ⁇ are boron-containing substituents, at least one of which is coordinated to the succinate ester by a coordination bond.
- LUBR1ZOL9336 manufactured by Lubrisol
- boron-containing succinic acid imid is boron-containing succinic acid imid. It is also an effective means to combine a boron-containing succinic acid ester with a succinic acid imide described later.
- the boron-containing compound is preferably present in an amount of from 0.05 to 0.06% by weight, preferably from 0.01 to 0.04% by weight, based on the total weight of the composition. It is blended so that If the amount of the boron-containing compound is such that the amount of boron derived from the boron-containing compound based on the total weight of the composition is less than 0.05% by weight, sufficient friction characteristics (low friction) can be obtained. If no improvement can be obtained and the amount of the boron-containing compound is more than 0.06% by weight, the amount of boron derived from the boron-containing compound based on the total weight of the composition is too large. No improvement in the effect is observed.
- various additives conventionally used in lubricating oils for example, other friction modifiers, other metal-based detergents, as long as the autonomy of the present invention is not impaired,
- An antifoaming agent, an antioxidant, a corrosion inhibitor and the like can be appropriately compounded.
- Examples of other friction modifiers include polyhydric alcohol partial esters, amides, amides, sulfide esters, and the like.
- metal-based detergents include, for example, barium sulfonate, barium phenol and the like, which are usually used in a proportion of 0.1 to 5% by weight.
- antiwear agents include, for example, metal thiophosphates, sulfur compounds, phosphoric esters, phosphites, etc., which are usually used at a rate of 0.05 to 5.0% by weight. You.
- Examples of other ashless dispersants include succinic acid imid type, succinic acid amide type, benzylamine type, ester type and the like, and these are usually 0.5 to 7% by weight. Used in percentages.
- antioxidants examples include amide-based antioxidants such as alkylated diphenylamine, fuunyl- ⁇ -naphthylamine, and alkylated mono- ⁇ -naphthylamine, and 2,6-di-t-butyl-4-methylthiophene.
- phenolic antioxidants such as 4,4′-methylethylenebis (2,6-di-t-butylphenol), and the like. Used in proportions of 4% by weight.
- examples of the viscosity index improver include polymethacrylates, polybutylenes, ethylene-propylene copolymers, styrene-butadiene hydrogenated copolymers, etc., and these are usually 0.5 to 35. Used in percentages by weight.
- examples of the pour point depressant include polyalkyl methacrylate, chlorinated balafinaphthalene condensate, and alkylated polystyrene.
- examples of the antifoaming agent include dimethylpolysiloxane and polyacrylic acid.
- Examples of the protective agent include fatty acids, alkenyl succinic acid partial esters, fatty acid segen, alkyl sulfonates, fatty acid polyhydric alcohol esters, fatty acid amines, oxidized paraffins, and alkyl polyoxyethylene ethers.
- Corrosion inhibitors include, for example, benzotriazole and benzoimidazole Can be mentioned.
- the friction coefficient of the lubricating oil composition was determined using a reciprocating sliding friction tester [SRV friction tester] at a vibration frequency of 50 Hz, amplitude of 3 h, load of 25 N, temperature of 80 ° C, and test time. Measured at 25 minutes.
- SRV friction tester reciprocating sliding friction tester
- the oxidation test using air containing nitrogen oxide gas was performed on 150 ml of test oil at a temperature of 130 ° C, a nitrogen oxide (NO,) concentration of 1% by volume, a flow rate of 2 liters, and a test time of 8 hours.
- NO nitrogen oxide
- Examples 1 to 10 were (A) oxymolybdenum budindithiol phosphate, (B) zinc dialkyldithiophosphate, (C) zinc diamyldithiol phosphate, dibutyldithiol phosphate, and tetrabutylthiuramda disal.
- Comparative Examples 1 and 2 are lubricating oil compositions that contain component (A), component (B), component (D) and component (E) but do not contain component (C).
- C-MoDTC Oxymolybdenum sulfide - ⁇ , ⁇ -ditridecyldithirubbamate C, -ZnDTP ( ⁇ ⁇ ⁇ ): di-2-ethylhexyldithio flWMiifti
- the lubricating oil compositions of the present invention of Examples 1 to 10 all have a low coefficient of friction and good friction characteristics, and are heated at 1,30 ° C for 8 hours in the presence of nitrogen oxide gas. Even after oxidation, the coefficient of friction hardly changes, indicating that these lubricating oil compositions have good oxidation resistance.
- the lubricating oil compositions of Comparative Examples 1 and 2 which do not contain the sulfur compound (C) component, have a low coefficient of friction immediately after preparation, but have a low friction coefficient of 130 ° C. in the presence of nitrogen oxide gas. After heating and oxidizing at C for 8 hours, the coefficient of friction increases, indicating that the oxidation resistance is poor.
- the lubricating oil composition of the present invention has excellent properties by blending a specific structure of oxymolybdenum dithiocarbamate, zinc dialkyldithiophosphate, a sulfur compound, a metal-based detergent, and a boron-containing compound with a base oil. It has low abrasion resistance, and exhibits excellent oxidation resistance even at high temperatures and in the presence of nitrogen oxide gas, maintaining good friction characteristics (low friction).
- Internal combustion engine, automatic transmission, shock absorber, power It can be suitably used as a lubricating oil such as a steering oil, particularly a lubricating oil for an internal combustion engine.
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Abstract
A lubricating oil composition prepared by blending a lube base oil with a molybdenum oxysulfide dithiocarbamate with a specified structure, zinc dialkyl dithiophosphate, sulfur compounds, metallic detergents, and boron compounds. The content of molybdenum originating in the dithiocarbamate, that of phosphorus originating in the dithiophosphate, that of the sulfur originating in the sulfur compounds, that of the detergent, and that of the boron originating in the boron compounds are 200-2,000 ppm, 0.02-0.15 wt.%, 0.02-0.30 wt.%, 1-10 wt.%, and 0.005-0.06 wt.%, respectively, based on the whole composition. The composition is excellent in oxidation resistance, does not undergo deterioration caused by nitrogen oxide gases, and can retain the effect of lowering the friction of engines for long.
Description
明 細 書 Specification
潤 滑 油 組 成 物 Lubricating oil composition
発明の技術分野 TECHNICAL FIELD OF THE INVENTION
本発明は、 新規な潤滑油組成物に関する。 さらに詳しくは、 本発明は、 優れた 低摩耗性及び低摩擦性を有し、 かつ、 窒素酸化物ガスを含む空気雰囲気中でも劣 化せず、 長期にわたる低摩擦性の持続性を有する、 内燃機関、 自動変速機、 緩衝 器、 パワーステアリ ングなどの潤滑油、 特に内燃機関用潤滑油として好適に用い ることができる潤滑油組成物に関するものである。 The present invention relates to a novel lubricating oil composition. More specifically, the present invention provides an internal combustion engine that has excellent low wear and low friction properties, does not deteriorate even in an air atmosphere containing nitrogen oxide gas, and has long-lasting low friction properties. The present invention relates to a lubricating oil composition that can be suitably used as a lubricating oil for automatic transmissions, shock absorbers, power steering, and the like, particularly a lubricating oil for internal combustion engines.
背景技術 Background art
内燃機関や、 自動変速機、 緩衝器、 パワーステアリ ングなどの駆動系機器、 ギ ャなどには、 その作動を円滑にするために潤滑油が用いられている。 特に内燃機 関用潤滑油は、 主としてビス トンリ ングとシリンダライナ、 クランク軸やコネク 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など、 各種摺動部分 の潤滑のほか、 エンジン内の冷却や燃焼生成物の清浄分散、 さらには锖ゃ腐食を 防止するなどの作用を果たす。 Lubricating oil is used in internal combustion engines, drive systems such as automatic transmissions, shock absorbers, and power steering, and gears to facilitate their operation. In particular, lubricating oil for internal combustion engines mainly lubricates various sliding parts, such as piston rings and cylinder liners, bearings for crankshafts and connecting rods, and valve trains including cams and valve lifters. It acts to cleanly disperse the combustion products and prevent corrosion.
このように、 内燃機関用潤滑油には多様な性能が要求され、 しかも近年の内燃 機関の低燃費化、 高出力化、 運転条件の過酷化などの高性能化に伴い、 高度な潤 滑油性能が要求されてきている。 一方、 内燃機関における燃焼ガスは、 その一部 がビス トンとシリンダの間からブローバイガスとしてクランクケース内に漏洩す る。 この燃焼ガス中には窒素酸化物ガスがかなり高濃度で含まれており、 これが ブローバイガス中の酸素と共に内燃機関用潤滑油を劣化させる。 近年における内 燃機関の高性能化により、 クランクケース内に漏洩する窒素酸化物ガスの濃度が 増加する傾向にある。 したがって、 内燃機関用潤滑油には、 上記の要求性能を満 たし、 窒素酸化物ガス含有空気雰囲気下においても劣化を生じないために、 例え ば、 摩耗防止剤、 金属系清浄剤、 無灰分散剤、 酸化防止剤などの種々の添加剤が 配合されている。 As described above, various performances are required for lubricating oils for internal combustion engines, and in addition to the recent high performance of internal combustion engines such as lower fuel consumption, higher output, and severe operating conditions, advanced lubricating oils have been developed. Performance is being demanded. On the other hand, part of the combustion gas in the internal combustion engine leaks into the crankcase as blow-by gas from between the biston and the cylinder. This combustion gas contains a considerably high concentration of nitrogen oxide gas, which together with the oxygen in the blow-by gas degrades the lubricating oil for internal combustion engines. In recent years, the concentration of nitrogen oxide gas leaking into the crankcase tends to increase due to the high performance of internal combustion engines. Therefore, lubricating oil for internal combustion engines satisfies the above required performance and does not deteriorate even in an atmosphere containing nitrogen oxide gas. For example, anti-wear agents, metal-based detergents, and ashless Various additives such as powders and antioxidants are blended.
内燃機関用潤滑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、 焼付き防止を行うことが重要である。 エンジン潤滑部は、 大部 分が流体潤滑状態にあるが、 動弁系やビス トンの上下死点などでは境界潤滑状態
となりやすく、 このような境界潤滑状態における摩耗防止性は、 一般にジチォ燐 酸亜鉛の添加によつて付与されている。 As a basic function of lubricating oil for internal combustion engines, it is especially important to ensure that the engine works smoothly under all conditions to prevent wear and seizure. Most of the engine lubrication part is in a fluid lubrication state, but it is in a boundary lubrication state in the valve train and the vertical dead center of the biston. Wear resistance in such a boundary lubrication state is generally imparted by the addition of zinc dithiophosphate.
内燃機関では、 潤滑油が関与する摩擦部分でのエネルギー損 が大きいために、 摩擦損失低減や燃費低減対策として、 摩擦調整剤が潤滑油に添加されている。 こ の摩擦調整剤としては、 例えば、 有機モリブデン化合物、 脂肪酸エステル、 アル キルアミ ンなどが一般に用いられている。 In an internal combustion engine, a friction modifier is added to lubricating oil as a measure to reduce friction loss and fuel consumption because the energy loss in the friction part involving lubricating oil is large. As the friction modifier, for example, an organic molybdenum compound, a fatty acid ester, an alkylamine and the like are generally used.
発明の概要 Summary of the Invention
本発明は、 このような事情のもとで、 鋭意研究の結果、 摩擦調整剤は使用開始 初期には添加効果が認められるが、 空気中の酸素による酸化劣化を受けるとその 効果を喪失し、 特に窒素酸化物ガスの存在下ではその効果の低減が著しいという 点を見いだし、 窒素酸化物ガスの影響を受けることなく、 エンジンの摩擦低減効 果を長期にわたって維持することができる潤滑油組成物を提供することを目的と してなされたものである。 Under such circumstances, the present inventors have conducted intensive studies and found that the friction modifier has an effect of being added at the beginning of use, but loses its effect when subjected to oxidative deterioration due to oxygen in the air. In particular, they found that the effect was significantly reduced in the presence of nitrogen oxide gas, and a lubricating oil composition that could maintain the effect of reducing engine friction over a long period of time without being affected by nitrogen oxide gas. It was made for the purpose of providing.
本発明者らは、 前記の好ましい性質を有する潤滑油組成物を開発すべく鋭意研 究を重ねた結果、 潤滑油基油に対して、 特定のアルキル基を有する硫化ォキシモ リブデンジチォカルバメ一卜、 特定のアルキル基を有するジアルキルジチォ燐酸 亜鉛及び特定の硫黄化合物、 特定の金属系清浄剤及びホウ素含有化合物を、 それ ぞれ特定の割合で配合した潤滑油組成物が、 その目的に適合しうることを見いだ し、 この知見に基づいて本発明を完成するに至った。 The present inventors have made intensive studies to develop a lubricating oil composition having the above-mentioned preferable properties, and as a result, have found that a lubricating oil base oil has a specific alkyl group-containing oxymolybdenum dithiocarbamate. A lubricating oil composition containing a specific ratio of zinc dialkyldithiophosphate having a specific alkyl group, a specific sulfur compound, a specific metal-based detergent and a boron-containing compound in a specific ratio may be suitable for the purpose. The present inventors have completed the present invention based on this finding.
すなわち、 本発明は、 That is, the present invention
( 1 ) 潤滑油基油に対して、 （A ) 炭素数が 8〜1 8のアルキル基を有する硫化 ォキシモリプデンジチォカルバメー ト、 （B ) 炭素数 1〜1 8の第一級アルキル 基を有するジアルキルジチォ燐酸亜鉛、 （C ) 炭素数が 2〜1 8のアルキル基を 有するジアルキルジチォ力ルバミ ン酸亜鉛、 ジアルキルジチォ力ルバミ ン酸銅又 はジアルキルジチォカルバミ ン酸ニッケル、 アルキル基の炭素数が 2〜 1 8であ るテトラアルキルチウラムダイサルフアイ ド、 炭素数が 2〜1 8のアルキル基を 有するダイサルファィ ド、 炭素数が 6〜 1 8のァリール基、 アルキルァリール基 又はァリールアルキル基を有するダイサルファィ ド、 炭素数が 3〜2 4でかつ硫 黄を含む置換基を有するチアジアゾール化合物、 硫化ォレフィ ン、 硫化魚油及び
硫化鯨油よりなる群より選ばれた 1種以上の硫黄化合物、 （D) カルシウムサリ チレート、 マグネシウムサリチレート、 カルシウムスルホネート、 マグネシウム スルホネー卜及びカルシウムフヱネートよりなる群より選ばれた 1種以上の金属 系清浄剤及び （E) ホウ素含有化合物を配合した潤滑油組成物であって、 組成物 全重量に基づき、 硫化ォキシモリプデンジチォカルバメ一トに由来するモリブデ ンの量が 200〜2， 00 Oppm (重量比） であり、 ジアルキルジチォ燐酸亜鉛に 由来する燐の量が 0.02〜0.15重量％であり、 硫黄化合物に由来する硫黄の 量が 0.02〜0.30重量％であり、 金属系清浄剤の含有量が 1〜 10重量％で あり、 ホウ素含有化合物に由来するホウ素の量が 0.005〜0.06重量％であ ることを特徵とする潤滑油組成物を提供するものである。 (1) a lubricating base oil, (A) oxymolybdenum dithiocarbamate having an alkyl group having 8 to 18 carbon atoms, (B) a primary class having 1 to 18 carbon atoms Zinc dialkyldithiophosphate having an alkyl group; (C) zinc dialkyldithiophosphate having an alkyl group having 2 to 18 carbon atoms; copper or dialkyldithiocarbamate or nickel dialkyldithiocarbamate; Tetraalkylthiuram disulfide having 2 to 18 carbon atoms, disulfide having an alkyl group having 2 to 18 carbon atoms, aryl group having 6 to 18 carbon atoms, alkylaryl group or aryl Disulfide having a reel alkyl group, thiadiazole compound having 3 to 24 carbon atoms and having a substituent containing sulfur, olefin sulfide, sulfide fish oil and One or more sulfur compounds selected from the group consisting of sulfurized whale oil; (D) one or more sulfur compounds selected from the group consisting of calcium salicylate, magnesium salicylate, calcium sulfonate, magnesium sulfonate and calcium phenate; A lubricating oil composition containing a metal-based detergent and a boron-containing compound (E), wherein the amount of molybdenum derived from oxymolybdenum dithiocarbamate is from 200 to 200, based on the total weight of the composition. 2,000 ppm by weight, the amount of phosphorus derived from zinc dialkyldithiophosphate is 0.02 to 0.15% by weight, and the amount of sulfur derived from sulfur compounds is 0.02 to 0.30% by weight. A lubricating oil composition characterized in that the amount of boron is 1 to 10% by weight and the amount of boron derived from the boron-containing compound is 0.005 to 0.06% by weight. is there.
さらに、 本発明の好ましい態様として、 Further, as a preferred embodiment of the present invention,
(2) (A) 硫化ォキシモリプデンジチォ力ルバメートのアルキル基の炭素数が 8〜13であり、 （B) ジアルキルジチォ燐酸亜鉛の第一級アルキル基の炭素数 が 3〜12であり、 （E) ホウ素含有化合物がホウ素含有コハク酸イ ミ ドである 前記の潤滑油組成物、 及び、 (2) (A) the number of carbon atoms of the alkyl group of the oxymolybdenum dithiophosphate is 8 to 13 carbon atoms, and (B) the number of carbon atoms of the primary alkyl group of the zinc dialkyldithiophosphate is 3 to 12; (E) the above lubricating oil composition wherein the boron-containing compound is boron-containing succinic acid imid; and
(3) 組成物全重量に基づき、 硫化ォキシモリブデンジチォカルバメ一卜に由来 するモリブデンの量が 300〜80 Oppm (重量比） であり、 ジアルキルジチォ 燐酸亜鉛に由来する燐の量が 0.04〜 12重量％であり、 ホウ素含有化合物 に由来するホウ素の量が 0.01〜0.04重量％である前記の潤滑油組成物を挙 げることができる。 (3) Based on the total weight of the composition, the amount of molybdenum derived from oxymolybdenum dithiocarbamate is 300 to 80 ppm (weight ratio), and the amount of phosphorus derived from zinc dialkyldithiophosphate is 0.04 to 12 ppm. And the amount of boron derived from the boron-containing compound is 0.01 to 0.04% by weight.
実施態様の詳細な説明 Detailed description of the embodiments
以下、 本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の潤滑油組成物において用いられる潤滑油基油については特に制限はな く、 従来、 潤滑油の基油として慣用されているもの、 例えば、 鉱油や合成油を使 用することができる。 The lubricating base oil used in the lubricating oil composition of the present invention is not particularly limited, and those conventionally used as base oils for lubricating oils, for example, mineral oils and synthetic oils can be used.
鉱油としては、 潤滑油原料をフュノール若しくはフルフラールなどの芳香族抽 出溶剤を用いた溶剤精製により得られるラフィネート、 シリカ一アルミナを担体 とするコバルト若しくはモリブデンなどの水素化処理触媒を用いた水素化処理に より得られる水素化処理油、 又はヮックスの異性化により得られる潤滑油留分な
どの鉱油、 例えば、 6 0ニュー トラル油、 1 0 0ニュー トラル油、 1 5 0ニュー トラル油、 3 0 0ニュー トラル油、 5 0 0ニュー トラル油、 ブライ トス トックな どを挙げることができる。 Mineral oil includes hydroprocessing using lubricating oil raw materials such as raffinate obtained by solvent refining using an aromatic extraction solvent such as fenol or furfural, and silica-alumina using a hydroprocessing catalyst such as cobalt or molybdenum. Such as hydrotreated oil obtained by Any mineral oil, for example, 60 neutral oils, 100 neutral oils, 150 neutral oils, 300 neutral oils, 500 neutral oils, bright stocks, etc. can be mentioned.
—方、 合成油 Nとしては、 例えば、 ポリ α—才レフイ ンオリゴマー、 ポリブテン、 アルキルベンゼン、C s MMポリオールエステル、 ポリグリ コールエステル、 二塩基酸ェ ステル、 燐酸エステル、 シリ コーン油などを挙げることができる。 これらの基油 はそれぞれ単独で用いてもよいし、 2種以上を組み合わせて用いてもよく、 また 鉱油と合成油とを混合使用してもよい。 On the other hand, the synthetic oil N includes, for example, poly-α-olefin oligomer, polybutene, alkylbenzene, CsMM polyol ester, polyglycol ester, dibasic acid ester, phosphate ester, and silicone oil. it can. Each of these base oils may be used alone, or two or more may be used in combination, or a mixture of a mineral oil and a synthetic oil may be used.
本発明の潤滑油組成物において用いられる基油としては、 1 0 0°Cにおける粘 度が 3〜2 0nnn2/sの範囲にあるものが好適であり、 なかでも、 芳香族成分 3重 量％以下、 硫黄分 5 Oppm以下及び窒素分 5 Oppm以下の水素化分解油及びヮック ス異性化油が特に好適である。 As the base oil used in the lubricating oil composition of the present invention, those having a viscosity at 100 ° C. in the range of 3 to 20 nnn 2 / s are preferable. % Or less, a sulfur content of 5 Oppm or less and a nitrogen content of 5 Oppm or less are particularly preferred.
本発明の潤滑油組成物に配合する硫化ォキシモリブデンジチォ力ルバメー トと しては、 一般式（1)、 As the oxymolybdenum dithiol compound to be added to the lubricating oil composition of the present invention, general formula (1):
X X X S X X X S
\ II / \ II II / \ II / \ II II /
S- o M 0 - S - C - / \ / \ (1) S- o M 0-S-C-/ \ / \ (1)
R X R' R X R '
(式中、 R R2、 R3及び R4はそれぞれ炭素数 8〜18のアルキル基であり、 それらは互いに同一でも異なっていてもよく、 Xは硫黄又は酸素である。 ） で表される化合物を用いる。 (Wherein, RR 2 , R 3, and R 4 are each an alkyl group having 8 to 18 carbon atoms, which may be the same or different, and X is sulfur or oxygen.) Is used.
—般式（1)における R R2、 R5及び R'1で表される炭素数 8〜 1 8のアルキ ル基は、 直鎖状でも分枝鎖状であってもよい。 本発明の潤滑油組成物においては、 R \ R2、 Rs及び R 1で表されるアルキル基の炭素数が 8〜 1 3であることが特 に好ましい。 —The alkyl group having 8 to 18 carbon atoms represented by RR 2 , R 5 and R ′ 1 in the general formula (1) may be linear or branched. In the lubricating oil composition of the present invention, the number of carbon atoms of the alkyl group represented by R \ R 2, R s and R 1 is 8-1 3 is preferably especially.
R \ R2、 R3及び R 'で表されるアルキル基の具体例としては、 ォクチル基、 ノニル基、 デシル基、 ゥンデシル基、 ドデシル基、 ト リデシル基、 テ トラデシル 基、 ペン夕デシル基、 へキサデシル基、 ヘプ夕デシル基、 ォクタデシル基を挙げ
るこどができる。 Specific examples of the alkyl group represented by R \ R 2 , R 3 and R ′ include an octyl group, a nonyl group, a decyl group, an decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pendecyl group, Hexadecyl, heptane decyl and octadecyl groups You can have children.
本発明の潤滑油組成物においては、 硫化ォキシモリブデンジチォカルバメ一ト は 1種用いてもよいし、 2種以上を組み合わせて用いてもよい。 また硫化ォキシ モリプデンジチォカルバメ一トは、 組成物全重量に基づき硫化ォキシモリブデン ジチォカルバメ一トに由来するモリブテンの量が 200〜2， 00 O pm (重量比） となるよう、 好ましくは 3 0 0〜8 0 Oppm (重量比） となるよう配合する。 硫 化ォキシモリブデンジチォカルバメ一卜の配合量が、 組成物全重量に基づき硫化 ォキシモ リ ブデン ジチォ力ルバメ ー ト に由来する モ リ ブテ ンの量が 2 0 O pm (重量比） 未満となる量であると、 摩擦特性 （低摩擦性） の向上効果 が十分に発揮されず、 硫化ォキシモリブデンジチォカルバメ一卜の配合量が、 組 成物全重量に基づき硫化ォキシモリブデンジチォカルバメー 卜に由来するモリブ テンの量が 2， 0 0 Oppm (重量比） を超える量であると、 その量の割には効果の 向上が認められず、 またスラッジなどの原因となりやすい。 In the lubricating oil composition of the present invention, one type of oxymolybdenum dithiocarbamate may be used, or two or more types may be used in combination. The oxymolybdenum dithiocarbamate is preferably used so that the amount of molybdenum derived from oxymolybdenum dithiocarbamate is 200 to 2,000 Opm (weight ratio) based on the total weight of the composition. It is blended to be 300 to 80 Oppm (weight ratio). The amount of oxymolybdenum dithiocarbamate is less than 20 Opm (weight ratio) based on the total weight of the composition, based on the total weight of the composition. If the amount is too small, the effect of improving the friction characteristics (low friction property) will not be sufficiently exhibited, and the amount of oxymolybdenum dithiocarbamate will be reduced based on the total weight of the composition. If the amount of molybdenum derived from carbamate is more than 2000 ppm (weight ratio), the effect is not improved for the amount, and sludge is likely to be caused.
本発明の潤滑油組成物に配合するジアルキルジチォ燐酸亜鉛としては、 一般式 (2)、 As the zinc dialkyldithiophosphate to be added to the lubricating oil composition of the present invention, general formula (2):
R5 - 0 S S 0 - R7 R 5 - 0 SS 0 - R 7
\ II I！ / \ II I! /
P-S-Zn-S-P , ヽ P-S-Zn-S-P, ヽ
/ \ (2) / \ (2)
Rし 0 〇一 R8 R and 0 〇 one R 8
(式中、 R=、 R\ R7及び Rsは炭素数 1〜1 8の第一級アルキル基であり、 それらは互いに同一でも異なっていてもよい。 ） (Wherein, R =, R \ R 7 and Rs are primary alkyl groups having 1 to 1 8 carbon atoms, which may be the same or different from each other.)
で表される化合物を用いる。 Is used.
—般式（2)における R Rb、 R7及び Rsで表される第一級アルキル基は、 直 鎖状でも分枝鎖状であってもよく、 例えば、 メチル基、 ェチル基、 プロピル基、 ブチル基、 ペンチル基、 へキシル基、 ヘプチル基、 ォクチル基、 ノニル基、 デシ ル基、 ゥンデシル基、 ドデシル基、 ト リデシル基、 テトラデシル基、 ペン夕デシ ル基、 へキサデシル基、 ヘプタデシル基、 ォクタデシル基であるが、 本発明の潤 滑油組成物には、 炭素数 3〜 1 2の第一級アルキル基を有するジアルキルジチォ
燐酸亜鉛を用いることが特に好ましい。 —The primary alkyl group represented by RR b , R 7 and R s in the general formula (2) may be linear or branched, for example, a methyl group, an ethyl group, a propyl group , Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, pendecyl, dodecyl, tridecyl, tetradecyl, pendecyl, hexadecyl, heptadecyl, The lubricating oil composition of the present invention is a dialkyldithiol group having a primary alkyl group having 3 to 12 carbon atoms. It is particularly preferred to use zinc phosphate.
本発明の潤滑油組成物において、 ジアルキルジチォ燐酸亜鉛は、 組成物全重量 に基づきジアルキルジチォ燐酸亜鉛に由来する燐の量が 0.02〜0.1 5重量 %となるよう、 好ましくは 0.04〜 0.12重量％となるよう配合する。 ジアル キルジチォ燐酸亜鉛の配合量が、 組成物全重量に基づく ジアルキルジチォ燐酸亜 鉛に由来する燐の量が 0.02重量％未満となる量であると、 耐摩耗性が不十分 となる上、 高油温かつ低速回転の運転条件下で満足しうる低摩擦係数が得られず、 ジアルキルジチォ燐酸亜鉛の配合量が、 組成物全重量に基づく ジアルキルジチォ 燐酸亜鉛に由来する燐の量が 0.15重量％を超えると、 その量の割には効果の 向上が認められない。 In the lubricating oil composition of the present invention, the zinc dialkyldithiophosphate is such that the amount of phosphorus derived from the zinc dialkyldithiophosphate is 0.02 to 0.15% by weight, preferably 0.04 to 0.12% by weight based on the total weight of the composition. Mix. If the content of zinc dialkyldithiophosphate is such that the amount of phosphorus derived from zinc dialkyldithiophosphate based on the total weight of the composition is less than 0.02% by weight, the abrasion resistance becomes insufficient and the oil temperature becomes high. When a satisfactory low coefficient of friction is not obtained under low-speed operation conditions and the amount of zinc derived from the zinc dialkyldithiophosphate based on the total weight of the composition exceeds 0.15% by weight, There is no improvement in the effect for that amount.
本発明の潤滑油組成物に配台するジアルキルジチォ力ルバミ ン酸塩としては、 —般式（3)、 s S R 11 The dialkyldithiolbaminates to be distributed in the lubricating oil composition of the present invention include the following general formula (3): sSR 11
\ II II / \ II II /
N-C-S-M-S-C-N N-C-S-M-S-C-N
/ \ (3) / \ (3)
R 10 R 10
R1 R 1
(式中、 Mは亜鉛、 銅又はニッケルであり、 Rq、 R1:)、 R11及び R1 :2は炭素 数 2〜18のアルキル基であり、 それらは互いに同一でも異なっていてもよ い。 ) (Wherein, M is zinc, copper or nickel, R q, R 1:) , R 11 and R 1: 2 is an alkyl group having 2 to 18 carbon atoms, even they be the same or different from each other Good. )
で表される化合物を用いる。 Is used.
—般式（3)における Rq、 RH)、 R11及び R12で表される炭素数 2〜18のアル キル基は、 直鎖状でも分枝鎖状であってもよく、 例えば、 ェチル基、 プロピル基、 ブチル基、 ペンチル基、 へキシル基、 ヘプチル基、 ォクチル基、 ノニル基、 デシ ル基、 ゥンデシル基、 ドデシル基、 ト リデシル基、 テトラデシル基、 ペン夕デシ ル基、 へキサデシル基、 ヘプ夕デシル基、 ォクタデシル基を挙げることができる。 本発明の潤滑油組成物に配合するテトラアルキルチウラムダイサルフアイ ドと しては、 一般式（4)、
R 13 R I s —The alkyl group having 2 to 18 carbon atoms represented by R q , R H) , R 11 and R 12 in the general formula (3) may be linear or branched. Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pencil decyl, hexadecyl And heptadecyl and octadecyl groups. The tetraalkylthiuram disulphide to be added to the lubricating oil composition of the present invention is represented by the general formula (4): R 13 RI s
(4) (Four)
R1 R 16 R 1 R 16
(式中、 R13、 R1 N4、 R15及び R16は炭素数 2〜18のアルキル基であり、 そ れらは互いに同一でc sも =異なっていてもよい。 ） (In the formula, R 13 , R 1 N 4 , R 15 and R 16 are alkyl groups having 2 to 18 carbon atoms, which may be the same and may have different cs and =.)
s s
で表される化合物を用いる。 Is used.
s s
—般式（4)における R13、 R14、 R15及び Rlbで表される炭素数 2〜 1 8のァ —The C 2-18 atom represented by R 13 , R 14 , R 15 and R lb in the general formula (4)
c s = c s =
ルキル基は、 直鎖状でも分枝鎖状であってもよく、 例えば、 ェチル基、 プロピル The alkyl group may be linear or branched, for example, ethyl group, propyl
N N
基、 プチル基、 ペンチル基、 へキシル基、 ヘプチル基、 ォクチル基、 ノニル基、 デシル基、 ゥンデシル基、 ドデシル基、 ト リデシル基、 テトラデシル基、 ペン夕 デシル基、 へキサデシル基、 ヘプタデシル基、 ォクタデシル基を挙げることがで きる。 Group, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, pendecyl, dodecyl, tridecyl, tetradecyl, pencil decyl, hexadecyl, heptadecyl, octadecyl Groups.
本発明の潤滑油組成物に配合するダイサルフアイ ドと しては、 一般式（5)、 R17 - S - S - R18 (5) The disulphide to be added to the lubricating oil composition of the present invention is represented by the general formula (5), R 17 -S-S-R 18 (5)
(式中、 17及び1 1!3は炭素数2〜18のアルキル基又は炭素数 6〜18のァ リール基、 アルキルァリール基、 ァリールアルキル基であり、 それらは互い に同一でも異なっていてもよい。 ） (Wherein, 17 and 11 ! 3 are an alkyl group having 2 to 18 carbon atoms or an aryl group, an alkyl aryl group or an aryl alkyl group having 6 to 18 carbon atoms, which are the same or different from each other. May be.)
で表される化合物を用いる。 Is used.
—般式（5)における R 17及び R 18で表される炭素数 2〜 1 8のアルキル基は、 直鎖状でも分枝鎖状であってもよく、 例えば、 ェチル基、 プロピル基、 ブチル基、 ペンチル基、 へキシル基、 ヘプチル基、 ォクチル基、 ノニル基、 デシル基、 ゥン デシル基、 ドデシル基、 ト リデシル基、 テトラデシル基、 ペン夕デシル基、 へキ サデシル基、 ヘプ夕デシル基、 ォクタデシル基を挙げることかでき、 又、 R17及 び R 1 Sで表される炭素数 6〜 18のァリ一ル基、 アルキルァリール基又はァリ一 ルアルキル基としては、 例えば、 フヱニル基、 ベンジル基、 フヱネチル基、 メチ ルベンジル基、 ジフヱニルメチル基などを挙げることかできる。 —The alkyl group having 2 to 18 carbon atoms represented by R 17 and R 18 in the general formula (5) may be linear or branched, for example, ethyl, propyl, butyl Group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, pendecyl group, dodecyl group, tridecyl group, tetradecyl group, pendudecyl group, hexadecyl group, hepnodecyl group , it can either be given Okutadeshiru group, also § Li Ichiru group R 17及beauty R 1 carbon atoms represented by S. 6 to 18, the alkyl § aryl group or § Li one Ruarukiru group is, for example, Fuweniru Group, benzyl group, phenyl group, methylbenzyl group, diphenylmethyl group and the like.
本発明の潤滑油組成物に配合する硫黄を含む置換基を有するチアジアゾール化
合物としては、 一般式（6)、 Thiadiazole having a sulfur-containing substituent to be incorporated into the lubricating oil composition of the present invention As the compound, general formula (6),
(6) (6)
R R
(式中、 R 19及び R 2ϋは炭素数 3〜 24でかつ硫黄原子を 1個以上含む 1価の 基であり、 それらは互い NCHに\同一でも異なっていてもよい。 ） (In the formula, R 19 and R 2ϋ are monovalent groups having 3 to 24 carbon atoms and containing at least one sulfur atom, and they may be the same or different from each other in NCH.)
一 S One S
で表される化合物を用いる。 Is used.
—般式（6)における R 19及び R2°で表 Rされる炭素数が 3〜 24でかつ硫黄原子 を 1個以上を含む 1価の基としては、 例えば、 5—チアノニル基、 2, 5—ジチ ァへキシル基、 3 , 4— ジチアへキシル基、 4 , 5 — ジチアへキ シル基、 3, 4, 5— ト リチアへプチル基、 3， 4 , 5, 6—テトラチアォクチル基、 5—チ ァー 2—ヘプテニル基、 4—チアシクロへキシル基、 1 , 4—ジチアナフチル基、 5 - (メチルチオ） ォクチル基、 4— (ェチルチオ） 一2—ペンテニル基、 4一 (メチルチオ） シクロへキシル基、 4一メルカプトフエニル基、 4一 （メチルチ ォ） フヱニル基、 4一 （へキシルチオ） ベンジル基などを挙げることができる。 これらの中で、 式（7)で表される 3 , 4—ジチアへキシル基、 式（8)で表される 4, 5-ジチアへキシル基、 式（9)で表される 3， 4, 5— ト リチアへプチル基、 式 (10)で表される 3, 4， 5, 6—テトラチアォクチル基などのように、 鎖中におい て 2〜 4個の硫黄原子が連続して結合した基が特に好ましい。 —Examples of the monovalent group having 3 to 24 carbon atoms represented by R 19 and R 2 ° represented by R 19 and R 2 ° in the general formula (6) and containing at least one sulfur atom include, for example, a 5-thianonyl group, 5-dithihexyl, 3,4-dithiahexyl, 4,5—dithiahexyl, 3,4,5—trithiaheptyl, 3,4,5,6-tetrathiao Octyl, 5-thio-2-heptenyl, 4-thiacyclohexyl, 1,4-dithianaphthyl, 5- (methylthio) octyl, 4- (ethylthio) 1-2-pentenyl, 4- (methylthio) Examples thereof include a cyclohexyl group, a 4-mercaptophenyl group, a 4- (methylthio) phenyl group, and a 4- (hexylthio) benzyl group. Among these, a 3,4-dithiahexyl group represented by the formula (7), a 4,5-dithiahexyl group represented by the formula (8), and a 3,4 represented by the formula (9) , 5—trithiaheptyl group, 3,4,5,6-tetrathiaoctyl group of formula (10) Attached groups are particularly preferred.
CH3CH2-S-S-CH2CH2- (7) CH 3 CH 2 -SS-CH 2 CH 2- (7)
CH3-S- S -CH2CH2CH2- (8) CH 3 -S- S -CH 2 CH 2 CH 2- (8)
CH3CH2— S— S— S— CH2CH2 - （9) CH 3 CH 2 — S— S— S— CH 2 CH 2- (9)
CH3CH2- S - S -S-S -CH2CH2- (1Q) 本発明の潤滑油組成物に配合する硫化ォレフィ ンは、 ィソプチレンなどの重合 物を硫化処理して得られる硫黄含有量が 25〜40重量％の硫化ォレフィ ン （多 硫化物） であり、 硫化魚油及び硫化鯨油は、 魚油及び鯨油を同様に硫化処理して 得られるものである。
本発明の潤滑油組成物において、 一般式（3)で表されるジアルキルジチォカル バミ ン酸塩、 一般式（4)で表されるテトラアルキルチウラムダイサルファィ ド、 —般式（5)表されるダイサルフアイ ド、 一般式（6)で表されるチアジアゾール化合 物、 硫化ォレフィ ン、 硫化魚油及び硫化鯨油は、 1種又は、 2種以上を組み合わ せて、 用いることができる。 これらの硫黄化合物は、 組成物全重量に基づき、 こ れらの硫黄化合物に由来する硫黄の量が 0 . 0 2〜 0 . 3 0重量％になるよう配合 される。 これらの硫黄化合物の配合量が、 組成物全重量に基づく これらの硫黄化 合物に由来する硫黄の量が 0 . 0 2重量％未満となる量であると、 摩擦低減を長 期にわたって持続する効果が不十分となる。 これらの硫黄化合物の配合量が、 組 成物全重量に基づく これらの硫黄化合物に由来する硫黄の量が 0 . 3 0重量％を 超える量であると、 その量の割には効果の向上が認められない。 CH 3 CH 2 -S -S -SS -CH 2 CH 2- (1Q) The sulfur sulfide incorporated in the lubricating oil composition of the present invention has a sulfur content obtained by sulfidizing a polymer such as isoptylene. It is 25 to 40% by weight of sulfurized olefin (polysulfide). Sulfurized fish oil and whale oil are obtained by similarly sulfurizing fish oil and whale oil. In the lubricating oil composition of the present invention, a dialkyldithiocarbamate represented by the general formula (3), a tetraalkylthiuram disulfide represented by the general formula (4), The disulfide, the thiadiazole compound represented by the general formula (6), the sulfided olefin, the sulfided fish oil and the sulfided whale oil can be used alone or in combination of two or more. These sulfur compounds are blended so that the amount of sulfur derived from these sulfur compounds is from 0.02 to 0.30% by weight based on the total weight of the composition. If the amount of these sulfur compounds is such that the amount of sulfur derived from these sulfur compounds based on the total weight of the composition is less than 0.02% by weight, friction reduction is maintained over a long period of time. The effect is insufficient. If the amount of these sulfur compounds is more than 0.3% by weight based on the total weight of the composition, the effect will be improved. unacceptable.
本発明の潤滑油組成物においては、 カルシウムサリチレート、 マグネシウムサ リチレート、 カルシウムスルホネート、 マグネシウムスルホネート及びカルシゥ ムフエネートよりなる群より選ばれた 1種又は 2種以上の金属系清浄剤を配合す る。 これらの金属系清浄剤は、 組成物全重量に対して 1〜1 0重量％配合される。 これらの金属系清浄剤の配合量が、 組成物全重量に基づき 1重量％未満であると、 清浄効果が不十分であり、 これらの金属系清浄剤の配合量が、 組成物全重量に基 づき 1 0重量％を超えると、 その量の割には効果の向上が認められず、 むしろ灰 分が増加する。 The lubricating oil composition of the present invention contains one or more metal detergents selected from the group consisting of calcium salicylate, magnesium salicylate, calcium sulfonate, magnesium sulfonate and calcium phenate. These metallic detergents are blended in an amount of 1 to 10% by weight based on the total weight of the composition. If the amount of these metallic detergents is less than 1% by weight based on the total weight of the composition, the cleaning effect is insufficient, and the amount of these metallic detergents is based on the total weight of the composition. If it exceeds 10% by weight, the effect is not improved for the amount, but the ash increases.
本発明の潤滑油組成物においては、 組成物の全塩基価を 3〜 1 0とすることが 好ましく、 全塩基価を 4〜 7とすることがより好ましい。 全塩基価は J 1 S K 2 5 0 1にしたがって測定することができる。 全塩基価の調整は、 適当な塩基価 をもつ金属系清浄剤を選定することにより好適に行うことができる。 In the lubricating oil composition of the present invention, the total base number of the composition is preferably from 3 to 10, and more preferably from 4 to 7. The total base number can be measured according to J1SK2501. Adjustment of the total base number can be suitably performed by selecting a metal-based detergent having an appropriate base number.
本発明の潤滑油組成物において、 ホウ素含有化合物としては具体的に、 ホウ素 含有コハク酸イ ミ ド、 ホウ素含有コハク酸エステルなどが挙げられる。 ホウ素含 有コハク酸イ ミ ドとしては、 例えば、 下記一般式（11)、 （12)などで表されるもの が挙げられる。
0 In the lubricating oil composition of the present invention, specific examples of the boron-containing compound include boron-containing succinic acid imido and boron-containing succinic acid ester. Examples of boron-containing succinic acid imides include those represented by the following general formulas (11) and (12). 0
R21—
R 21 —
(式中、 R21は炭素数 1〜50の炭化水素基、 R22は炭素数 2〜5のアルキレ ン基、 nは 1〜1 0であり、 一般式（12)の化合物において 2個の R21は同一 でも異なっていてもよく、 一般式（11)において n個、 一般式（12)において n + 1個の R 22は同一でも異なっていてもよく、 Zはホウ素含有置換基であ り、 Zとしては、 例えば、 (In the formula, R 21 is a hydrocarbon group having 1 to 50 carbon atoms, R 22 is an alkylene group having 2 to 5 carbon atoms, n is 1 to 10, and in the compound of the general formula (12), R 21 may be the same as or different from each, n pieces in the general formula (11), n + 1 pieces of R 22 in the general formula (12) may be the same or different, Z is a boron-containing substituent der For Z, for example,
OH
OH
などを挙げることができる。 ） And the like. )
具体的には、 例えば、 E C A 5 0 2 5 (ェク ソ ンケ ミ カル社製） LUBR I ZOL 935 (ルブリゾル社製） などが挙げられる。
また、 ホウ素含有コハク酸エステルとしては、 例えば、 下記一般式（13)で表さ れるものが挙げられる。 Specifically, for example, ECA 525 (manufactured by Exxon Chemical Co., Ltd.) and LUBR I ZOL 935 (manufactured by Lubrizol Co., Ltd.) are exemplified. Examples of the boron-containing succinate include those represented by the following general formula (13).
CH3-
CH 3-
〇 〇
z z
(式中、 nは 1〜2 0、 R23は炭素数 2〜1 8の直鎖状又は分枝状の炭化水素 基であり、 鎖中に芳香族基及び Z又は二重結合を含んでいてもよい。 Y、 Ζはホウ素含有置換基であり少なく とも一方は配位結合によってコハク酸ェ ステルに配位している。 ） (In the formula, n is 1 to 20; R 23 is a linear or branched hydrocarbon group having 2 to 18 carbon atoms, including an aromatic group and Z or a double bond in the chain. Y and Ζ are boron-containing substituents, at least one of which is coordinated to the succinate ester by a coordination bond.)
具体的には、 例えば、 L U B R 1 Z O L 9 3 6 (ルブリ ゾル社製） などが挙 げられる。 Specifically, for example, LUBR1ZOL9336 (manufactured by Lubrisol) can be mentioned.
ホウ素含有化合物の中で好ましいものは、 ホウ素含有コハク酸イ ミ ドてある。 また、 ホウ素含有コハク酸エステルに、 後述するコハク酸イ ミ ドを組み合わせ配 合することも有効な手段である。 ホウ素含有化合物は、 組成物全重量に基づき、 ホウ素含有化合物に由来するホウ素の量が 0. 0 05〜0. 0 6重量％となるよう、 好ましくは 0. 0 1〜0. 0 4重量％となるよう配合する。 ホウ素含有化合物の配 合量が、 組成物全重量に基づく ホウ素含有化合物に由来するホウ素の量が 0. 0 0 5重量％未満となる量であると、 十分な摩擦特性 （低摩擦性） の向上が 得られず、 ホウ素含有化合物の配合量が、 組成物全重量に基づくホウ素含有化台 物に由来するホウ素の量が 0. 0 6重量％を超える量であると、 その量の割には 効果の向上が認められない。 Preferred among the boron-containing compounds is boron-containing succinic acid imid. It is also an effective means to combine a boron-containing succinic acid ester with a succinic acid imide described later. The boron-containing compound is preferably present in an amount of from 0.05 to 0.06% by weight, preferably from 0.01 to 0.04% by weight, based on the total weight of the composition. It is blended so that If the amount of the boron-containing compound is such that the amount of boron derived from the boron-containing compound based on the total weight of the composition is less than 0.05% by weight, sufficient friction characteristics (low friction) can be obtained. If no improvement can be obtained and the amount of the boron-containing compound is more than 0.06% by weight, the amount of boron derived from the boron-containing compound based on the total weight of the composition is too large. No improvement in the effect is observed.
本発明の潤滑油組成物には、 本発明の自的が損なわれない範囲で、 従来、 潤滑 油に慣用されている各種添加剤、 例えば、 他の摩擦調整剤、 他の金属系清浄剤、 他の摩耗防止剤、 他の無灰分散剤、 酸化防止剤、 粘度指数向上剤、 流動点降下剤、
消泡剤、 防锖剤、 腐食防止剤などを適宜配合することができる。 In the lubricating oil composition of the present invention, various additives conventionally used in lubricating oils, for example, other friction modifiers, other metal-based detergents, as long as the autonomy of the present invention is not impaired, Other antiwear agents, other ashless dispersants, antioxidants, viscosity index improvers, pour point depressants, An antifoaming agent, an antioxidant, a corrosion inhibitor and the like can be appropriately compounded.
他の摩擦調整剤としては、 例えば、 多価アルコール部分エステル、 ァミ ン、 ァ ミ ド、 硫化エステルなどを挙げることができる。 Examples of other friction modifiers include polyhydric alcohol partial esters, amides, amides, sulfide esters, and the like.
他の金属系清浄剤としては、 例えば、 バリウムスルホネート、 バリウムフヱネ 一トなどを挙げることができ、 これらは通常 0 . 1〜 5重量％の割合で使用され る o Other metal-based detergents include, for example, barium sulfonate, barium phenol and the like, which are usually used in a proportion of 0.1 to 5% by weight.
他の摩耗防止剤としては、 例えば、 チォ燐酸金属塩、 硫黄化合物、 燐酸エステ ル、 亜燐酸エステルなどを挙げることができ、 これらは通常 0 . 0 5〜5 . 0重量 %の割合で使用される。 Other antiwear agents include, for example, metal thiophosphates, sulfur compounds, phosphoric esters, phosphites, etc., which are usually used at a rate of 0.05 to 5.0% by weight. You.
他の無灰分散剤としては、 例えば、. コハク酸イ ミ ド系、 コハク酸アミ ド系、 ベ ンジルァ ミ ン系、 エステル系のものなどを挙げることができ、 これらは通常 0 . 5〜 7重量％の割合で使用される。 Examples of other ashless dispersants include succinic acid imid type, succinic acid amide type, benzylamine type, ester type and the like, and these are usually 0.5 to 7% by weight. Used in percentages.
酸化防止剤としては、 例えば、 アルキル化ジフヱニルァミ ン、 フユニル— α— ナフチルァミ ン、 アルキル化一 α—ナフチルァミ ンなどのァミ ン系酸化防止剤、 2 , 6—ジ一 t —プチルー 4 —メ チルフエ ノ ール、 4 , 4 ' ーメ チ レ ン ビス ( 2 , 6—ジ一 t —ブチルフエノール） などのフエノール系酸化防止剤などを挙 げることができ、 これらは通常 0 . 0 5〜 4重量％の割合で使用される。 Examples of the antioxidant include amide-based antioxidants such as alkylated diphenylamine, fuunyl-α-naphthylamine, and alkylated mono-α-naphthylamine, and 2,6-di-t-butyl-4-methylthiophene. And phenolic antioxidants such as 4,4′-methylethylenebis (2,6-di-t-butylphenol), and the like. Used in proportions of 4% by weight.
粘度指数向上剤としては、 例えば、 ポリメタク リ レー ト系、 ポリィソプチレン 系、 エチレン—プロピレン共重合体系、 スチレン一ブタジエン水添共重合体系な どを挙げることができ、 これらは通常 0 . 5〜3 5重量％の割合で使用される。 流動点降下剤としては、 例えば、 ポリアルキルメタク リ レー ト、 塩素化バラフ ィ ンーナフタレン縮合物、 ァルキル化ポリスチレンなどを挙げることができる。 消泡剤としては、 例えば、 ジメチルポリ シロキサンやポリアク リル酸などを挙 げることができる。 Examples of the viscosity index improver include polymethacrylates, polybutylenes, ethylene-propylene copolymers, styrene-butadiene hydrogenated copolymers, etc., and these are usually 0.5 to 35. Used in percentages by weight. Examples of the pour point depressant include polyalkyl methacrylate, chlorinated balafinaphthalene condensate, and alkylated polystyrene. Examples of the antifoaming agent include dimethylpolysiloxane and polyacrylic acid.
防锖剤としては、 例えば、 脂肪酸、 アルケニルコハク酸部分エステル、 脂肪酸 セッゲン、 アルキルスルホン酸塩、 脂肪酸多価アルコールエステル、 脂肪酸アミ ン、 酸化パラフィ ン、 アルキルポリオキシエチレンエーテルなどを挙げることが できる。 Examples of the protective agent include fatty acids, alkenyl succinic acid partial esters, fatty acid segen, alkyl sulfonates, fatty acid polyhydric alcohol esters, fatty acid amines, oxidized paraffins, and alkyl polyoxyethylene ethers.
腐食防止剤としては、 例えば、 ベンゾト リアゾールやベンゾィ ミダゾールなど
を挙げることができる。 Corrosion inhibitors include, for example, benzotriazole and benzoimidazole Can be mentioned.
実施例 Example
以下に実施例を挙げて本発明をさらに詳細に説明するが、 本発明はこれらの実 施例によってなんら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
なお、 潤滑油組成物の摩擦係数は、 往復動すベり摩擦試験機 [SRV摩擦試験 機] を用い、 振動数 5 0Hz、 振幅 3隱、 荷重 2 5 N、 温度 8 0°C、 試験時間 25分において測定した。 The friction coefficient of the lubricating oil composition was determined using a reciprocating sliding friction tester [SRV friction tester] at a vibration frequency of 50 Hz, amplitude of 3 h, load of 25 N, temperature of 80 ° C, and test time. Measured at 25 minutes.
また、 窒素酸化物ガス含有空気による酸化試験は、 試験油 150mlについて、 温度 130°C、 窒素酸化物 （NO、） 濃度 1容量％、 流速 2 リ ッ トル 時、 試験 時間 8時間で行った。 The oxidation test using air containing nitrogen oxide gas was performed on 150 ml of test oil at a temperature of 130 ° C, a nitrogen oxide (NO,) concentration of 1% by volume, a flow rate of 2 liters, and a test time of 8 hours.
実施例 1〜 10及び比較例 1〜 2 Examples 1 to 10 and Comparative Examples 1 to 2
実施例 1〜 1 0は、 （A) 硫化ォキシモリ ブデンジチォ力ルバメ ー ト、 (B) ジアルキルジチォ燐酸亜鉛、 （C) ジァミルジチォ力ルバミ ン酸亜鉛、 ジ ブチルジチォ力ルバミ ン酸鋦、 テトラブチルチウラムダィサルファイ ド、 ジベン ジルダイサルファイ ド又はジ （チアノニル） チアジアゾール、 （D) カルシウム サリチレート及び （E) ホウ素含有コハク酸ィ ミ ドを配合した潤滑油組成物であ な Examples 1 to 10 were (A) oxymolybdenum budindithiol phosphate, (B) zinc dialkyldithiophosphate, (C) zinc diamyldithiol phosphate, dibutyldithiol phosphate, and tetrabutylthiuramda disal. A lubricating oil composition containing sulfide, dibenzyl disulfide or di (thianonyl) thiadiazole, (D) calcium salicylate, and (E) boron-containing succinic acid imid.
また、 比較例 1〜2は、 （A) 成分、 （B) 成分、 （D) 成分及び （E) 成分 は含有するが、 （C) 成分を含有しない潤滑油組成物である。 Comparative Examples 1 and 2 are lubricating oil compositions that contain component (A), component (B), component (D) and component (E) but do not contain component (C).
基油 （100ニュートラル油、 100°Cにおける粘度 4.4隱 2Zs) に対し、 表 1に示す種類と量の各配合成分を含有する潤滑油組成物を調製し、 調製直後の 摩擦係数、 及び、 窒素酸化物ガスの存在下、 130°Cで 8時間保持して酸化した のちの摩擦係数を測定した。 結果を表 1に示す。
« 1 For a base oil (100 neutral oil, viscosity at 100 ° C 4.4 Hidden 2 Zs), a lubricating oil composition containing the components and types shown in Table 1 was prepared, and the friction coefficient immediately after the preparation, and The friction coefficient was measured after the sample was oxidized at 130 ° C for 8 hours in the presence of nitrogen oxide gas. Table 1 shows the results. «1
C-MoDTC： 硫化ォキシモリブデン -Ν, Ν-ジトリデシルジチ才力ルバメート C, - ZnDTP (笫一极）： ジ -2-ェチルへキシルジチォ flWMiifti C-MoDTC: Oxymolybdenum sulfide -Ν, Ν-ditridecyldithirubbamate C, -ZnDTP (笫 一 极): di-2-ethylhexyldithio flWMiifti
： ジァミルジチ才力ルバミン (½il|i.ft» : Jiamiljichi Talented Lebamin (½il | i.ft »
C4-CuDTC： ジブチルジチ才力ルバミン 焖
C 4 -CuDTC: dibutyldithi talented rubamine 焖
実施例 1〜 1 0の本発明の潤滑油組成物は、 いずれも摩擦係数が低く良好な摩 擦特性を示し、 かつ、 窒素酸化物ガスの存在下、 1, 3 0 °Cで 8時間加熱して酸化 した後も、 摩擦係数はほとんど変化なく、 これらの潤滑油組成物は良好な耐酸化 性を有していることがわかる。 これに対して、 （C ) 成分である硫黄化合物を含 有しない比較例 1〜2の潤滑油組成物は、 調製直後の摩擦係数は低いが、 窒素酸 化物ガスの存在下、 1 3 0 °Cで 8時間加熱して酸化した後には摩擦係数が高くな り、 耐酸化性に劣っていることが分かる。 The lubricating oil compositions of the present invention of Examples 1 to 10 all have a low coefficient of friction and good friction characteristics, and are heated at 1,30 ° C for 8 hours in the presence of nitrogen oxide gas. Even after oxidation, the coefficient of friction hardly changes, indicating that these lubricating oil compositions have good oxidation resistance. On the other hand, the lubricating oil compositions of Comparative Examples 1 and 2, which do not contain the sulfur compound (C) component, have a low coefficient of friction immediately after preparation, but have a low friction coefficient of 130 ° C. in the presence of nitrogen oxide gas. After heating and oxidizing at C for 8 hours, the coefficient of friction increases, indicating that the oxidation resistance is poor.
本発明の潤滑油組成物は、 基油に対して、 特定構造の硫化ォキシモリブデンジ チォカルバメート、 ジアルキルジチォ燐酸亜鉛、 硫黄化合物、 金属系清浄剤、 ホ ゥ素含有化合物を配合することによって、 優れた低摩耗性を有するとともに、 高 温かつ窒素酸化物ガスの存在下においても耐酸化性を発揮して良好な摩擦特性 (低摩擦性） を持続し、 内燃機関、 自動変速機、 緩衝器、 パワーステアリ ングな どの潤滑油、 特に、 内燃機関用潤滑油として好適に用いることができる。
The lubricating oil composition of the present invention has excellent properties by blending a specific structure of oxymolybdenum dithiocarbamate, zinc dialkyldithiophosphate, a sulfur compound, a metal-based detergent, and a boron-containing compound with a base oil. It has low abrasion resistance, and exhibits excellent oxidation resistance even at high temperatures and in the presence of nitrogen oxide gas, maintaining good friction characteristics (low friction). Internal combustion engine, automatic transmission, shock absorber, power It can be suitably used as a lubricating oil such as a steering oil, particularly a lubricating oil for an internal combustion engine.
Claims
1 . 潤滑油基油に対して、 （A ) 炭素数が 8〜 1 8のアルキル基を有する硫化ォ キシモリブデンジチォ力ルバメート、 ( B ) 炭素数 1〜 1 8の第一級アルキル基 を有するジアルキルジチォ燐酸亜鉛、 （C ) 炭素数が 2〜1 8のアルキル基を有 するジアルキルジチォカルバミ ン酸亜鉛、 ジアルキルジチォカルバミ ン酸銅又は ジアルキルジチォカルバミ ン酸ニッケル、 アルキル基の炭素数が 2〜 1 8である テトラアルキルチウラムダイサルフアイ ド、 炭素数が 2〜1 8のアルキル基を有 するダイサルフアイ ド、 炭素数が 6〜1 8のァリール基、 アルキルァリール基又 はァリールアルキル基を有するダイサルフアイ ド、 炭素数が 3〜2 4でかつ硫黄 を含む置換基を有するチアジアゾール化合物、 硫化ォレフィ ン、 硫化魚油及び硫 化鯨油よりなる群より選ばれた 1種以上の硫黄化合物、 （D ) カルシウムサリチ レー ト、 マグネシウムサリチレート、 カルシウムスルホネー ト、 マグネシウムス ルホネート及びカルシウムフエネートよりなる群より選ばれた 1種以上の金属系 清浄剤及び （E ) ホウ素含有化合物を配合した潤滑油組成物であって、 組成物全 重量に基づき、 硫化ォキシモリブデンジチォカルバメ一卜に由来するモリプデン の量が 2 0 0〜2 , 0 0 O ppm (重量比） であり、 ジアルキルジチォ燐酸亜鉛に由 来する燐の量が 0 . 0 2〜0 . 1 5重量％であり、 硫黄化合物に由来する硫黄の量 が 0 . 0 2〜0 . 3 0重量％であり、 金属系清浄剤の含有量が 1〜1 0重量％であ り、 ホウ素含有化合物に由来するホウ素の量が 0 . 0 0 5〜0 . 0 6重量％である ことを特徵とする潤滑油組成物。
1. With respect to the lubricating base oil, (A) an oxymolybdenum dithiolbamate having an alkyl group having 8 to 18 carbon atoms, and (B) a primary alkyl group having 1 to 18 carbon atoms. Zinc dialkyldithiophosphate, (C) zinc dialkyldithiocarbamate having an alkyl group having 2 to 18 carbon atoms, copper dialkyldithiocarbamate or nickel dialkyldithiocarbamate, Tetraalkylthiuram disulfide having 2 to 18 carbon atoms, disulfide having an alkyl group having 2 to 18 carbon atoms, aryl group having 6 to 18 carbon atoms, alkylaryl group or Selected from the group consisting of dialkyl sulfide having an arylalkyl group, thiadiazole compounds having 3 to 24 carbon atoms and having a substituent containing sulfur, olefin sulfide, sulfide fish oil and sulphated whale oil. One or more sulfur compounds, (D) one or more metallic detergents selected from the group consisting of calcium salicylate, magnesium salicylate, calcium sulfonate, magnesium sulfonate and calcium phenate And (E) a lubricating oil composition containing a boron-containing compound, wherein the amount of molybdenum derived from oxymolybdenum dithiocarbamate is 200 to 200,000 O, based on the total weight of the composition. ppm (weight ratio), the amount of phosphorus derived from the zinc dialkyldithiophosphate is 0.02 to 0.15% by weight, and the amount of sulfur derived from the sulfur compound is 0.02 to 0.3. 0% by weight, the content of the metallic detergent is 1 to 10% by weight, and the amount of boron derived from the boron-containing compound is 0.05 to 0.06% by weight. Featured lubricating oil compositions.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU68380/96A AU6838096A (en) | 1995-08-30 | 1996-08-30 | Lubricating oil composition |
| EP96928703A EP0855437A4 (en) | 1995-08-30 | 1996-08-30 | Lubricating oil composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24550595A JP3556348B2 (en) | 1994-09-01 | 1995-08-30 | Lubricating oil composition |
| JP7/245505 | 1995-08-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997008280A1 true WO1997008280A1 (en) | 1997-03-06 |
Family
ID=17134677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1996/002436 WO1997008280A1 (en) | 1995-08-30 | 1996-08-30 | Lubricating oil composition |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0855437A4 (en) |
| AU (1) | AU6838096A (en) |
| CA (1) | CA2223256A1 (en) |
| WO (1) | WO1997008280A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7148186B2 (en) | 1999-04-08 | 2006-12-12 | Tonengeneral Sekiyu K.K. | Lubricant oil composition for diesel engines (LAW964) |
| JP2000319682A (en) | 1999-05-10 | 2000-11-21 | Tonen Corp | Lubricating oil composition for internal combustion engine |
| ATE466921T1 (en) | 1999-12-22 | 2010-05-15 | Lubrizol Corp | LUBRICANT WITH A MIXTURE OF A MOLYBDENUM COMPONENT, PHOSPHORUS COMPONENT AND DISPERSANT |
| US20020151443A1 (en) * | 2001-02-09 | 2002-10-17 | Sanjay Srinivasan | Automatic transmission fluids with improved anti-wear properties |
| EP1262538B1 (en) * | 2001-05-11 | 2014-11-26 | Infineum International Limited | Anti-wear and Anti-oxidant Additives for Lubricating Oil Compositions |
| US6784143B2 (en) * | 2001-05-11 | 2004-08-31 | Infineum International Ltd. | Lubricating oil composition |
| EP1256619A1 (en) * | 2001-05-11 | 2002-11-13 | Infineum International Limited | Lubricating oil composition |
| US6500786B1 (en) | 2001-11-26 | 2002-12-31 | Infineum International Ltd. | Lubricating oil composition |
| US6723685B2 (en) * | 2002-04-05 | 2004-04-20 | Infineum International Ltd. | Lubricating oil composition |
| JP5027426B2 (en) * | 2006-02-17 | 2012-09-19 | 昭和シェル石油株式会社 | Lubricant composition |
| US20080171677A1 (en) * | 2006-04-13 | 2008-07-17 | Buck William H | Low SAP engine lubricant additive and composition containing non-corrosive sulfur and organic borates |
| FR2961823B1 (en) * | 2010-06-25 | 2013-06-14 | Total Raffinage Marketing | LUBRICATING COMPOSITIONS FOR AUTOMOTIVE TRANSMISSIONS |
| EP3263676B1 (en) | 2016-06-30 | 2023-07-19 | Infineum International Limited | Lubricating oil compositions |
| CN113046159A (en) * | 2021-03-24 | 2021-06-29 | 雅士盾(天津)石油科技有限公司 | Engine lubricating oil and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742797A (en) * | 1980-08-26 | 1982-03-10 | Masaaki Takahashi | Lubricant for screw roll threading |
| JPS62181397A (en) * | 1985-12-02 | 1987-08-08 | エチル コーポレイション | Metal-containing lubricant composition |
| JPH01503545A (en) * | 1987-04-10 | 1989-11-30 | マックス グリル ゲゼルシャフト ミット ベシュレンクテル | Lubricants or lubricant concentrates |
| JPH05311188A (en) * | 1992-05-08 | 1993-11-22 | Toyota Motor Corp | Aluminum plate excellent in forming processability |
| JPH06184578A (en) * | 1992-12-21 | 1994-07-05 | Oronaito Japan Kk | Engine oil composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0778876A1 (en) * | 1994-09-01 | 1997-06-18 | Tonen Corporation | Lubricants with sustained fuel economy performance |
-
1996
- 1996-08-30 EP EP96928703A patent/EP0855437A4/en not_active Withdrawn
- 1996-08-30 AU AU68380/96A patent/AU6838096A/en not_active Abandoned
- 1996-08-30 CA CA002223256A patent/CA2223256A1/en not_active Abandoned
- 1996-08-30 WO PCT/JP1996/002436 patent/WO1997008280A1/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742797A (en) * | 1980-08-26 | 1982-03-10 | Masaaki Takahashi | Lubricant for screw roll threading |
| JPS62181397A (en) * | 1985-12-02 | 1987-08-08 | エチル コーポレイション | Metal-containing lubricant composition |
| JPH01503545A (en) * | 1987-04-10 | 1989-11-30 | マックス グリル ゲゼルシャフト ミット ベシュレンクテル | Lubricants or lubricant concentrates |
| JPH05311188A (en) * | 1992-05-08 | 1993-11-22 | Toyota Motor Corp | Aluminum plate excellent in forming processability |
| JPH06184578A (en) * | 1992-12-21 | 1994-07-05 | Oronaito Japan Kk | Engine oil composition |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP0855437A4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0855437A1 (en) | 1998-07-29 |
| CA2223256A1 (en) | 1997-03-06 |
| AU6838096A (en) | 1997-03-19 |
| EP0855437A4 (en) | 1999-06-23 |
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