JP5756342B2 - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
- Publication number
- JP5756342B2 JP5756342B2 JP2011117733A JP2011117733A JP5756342B2 JP 5756342 B2 JP5756342 B2 JP 5756342B2 JP 2011117733 A JP2011117733 A JP 2011117733A JP 2011117733 A JP2011117733 A JP 2011117733A JP 5756342 B2 JP5756342 B2 JP 5756342B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- molybdenum
- mass
- carbon atoms
- lubricating oil
- 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.)
- Expired - Fee Related
Links
- 239000010687 lubricating oil Substances 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 title claims description 40
- -1 phosphate ester Chemical class 0.000 claims description 80
- 125000000217 alkyl group Chemical group 0.000 claims description 59
- 239000002199 base oil Substances 0.000 claims description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 46
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 230000001050 lubricating effect Effects 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 239000005078 molybdenum compound Substances 0.000 claims description 11
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 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 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 29
- 125000003342 alkenyl group Chemical group 0.000 description 19
- 239000003599 detergent Substances 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 14
- 229960001860 salicylate Drugs 0.000 description 14
- 229960004889 salicylic acid Drugs 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 13
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 12
- 229910052750 molybdenum Inorganic materials 0.000 description 12
- 239000011733 molybdenum Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000002480 mineral oil Substances 0.000 description 9
- 235000010446 mineral oil Nutrition 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- 230000001603 reducing effect Effects 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- LYYTXMXELKUIRO-UHFFFAOYSA-K P(=S)([S-])([O-])[O-].[Mo+3]=S Chemical compound P(=S)([S-])([O-])[O-].[Mo+3]=S LYYTXMXELKUIRO-UHFFFAOYSA-K 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 229960002317 succinimide Drugs 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000004517 catalytic hydrocracking Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000012990 dithiocarbamate Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 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 3
- 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 3
- 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 3
- 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 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000004519 manufacturing process Methods 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
- 239000003607 modifier Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 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 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 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 3
- 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 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 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 3
- 125000002958 pentadecyl 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])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000007670 refining Methods 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
- 238000003860 storage Methods 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 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 3
- 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 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- HZTZZGSVCLBQMX-UHFFFAOYSA-J N,N-dipentylcarbamodithioate molybdenum(4+) Chemical compound C(CCCC)N(C([S-])=S)CCCCC.[Mo+4].C(CCCC)N(C([S-])=S)CCCCC.C(CCCC)N(C([S-])=S)CCCCC.C(CCCC)N(C([S-])=S)CCCCC HZTZZGSVCLBQMX-UHFFFAOYSA-J 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- BXLYEXBWCGDPPL-UHFFFAOYSA-N (2-butylphenoxy)-(2-butylphenyl)sulfanyl-hydroxy-sulfanylidene-lambda5-phosphane Chemical compound CCCCC1=CC=CC=C1OP(O)(=S)SC1=CC=CC=C1CCCC BXLYEXBWCGDPPL-UHFFFAOYSA-N 0.000 description 1
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- MUUTTYVDNWSSMK-UHFFFAOYSA-N (2-butylphenyl)sulfanylcarbothioyl-sulfidoazanium Chemical compound CCCCC1=CC=CC=C1SC(=S)[NH2+][S-] MUUTTYVDNWSSMK-UHFFFAOYSA-N 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003580 thiophosphoric acid esters Chemical class 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
- C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
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- 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
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- 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
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- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- 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
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- 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
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- 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
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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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/44—Boron free or low content boron compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
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- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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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
- C10N2040/25—Internal-combustion engines
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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
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- 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
Description
本発明は新規な潤滑油組成物に関し、詳しくはリン酸エステルの金属塩と特定構造のモリブデン系摩擦調整剤を基油に配合することにより製造される、優れた摩擦低減性を有する潤滑油組成物に関する。特に内燃機関用潤滑油として好適に用いられる潤滑油組成物に関する。 The present invention relates to a novel lubricating oil composition, and in particular, a lubricating oil composition having excellent friction reducing properties, which is produced by blending a metal salt of a phosphate ester and a molybdenum friction modifier having a specific structure into a base oil. Related to things. In particular, the present invention relates to a lubricating oil composition suitably used as a lubricating oil for an internal combustion engine.
従来、内燃機関や自動変速機、グリースなどには、その作用を円滑にするために潤滑油が用いられる。特に内燃機関用潤滑油（エンジン油）は内燃機関の高性能化、高出力化、運転条件の苛酷化などに伴い、高度な性能が要求される。したがって、従来のエンジン油にはこうした要求性能を満たすため、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（例えば、特許文献１〜３を参照。）。また、省燃費エンジン油では、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、摩擦損失低減や燃費低減対策として、摩擦調整剤（ＦＭ：フリクションモディファイヤ）を初め、各種添加剤を組み合わせた潤滑油も使用されている（例えば、特許文献４を参照。）。中でもジアルキルジチオリン酸亜鉛（ＺＤＴＰ）とモリブデン系化合物との併用した摩擦低減技術が最も一般的であるが、この場合、モリブデン系化合物を比較的に多量に配合しないと優れた摩擦低減性能が得られない。
さらに、モリブデン化合物もＺＤＴＰも内燃機関用潤滑油に使用された場合、金属系であるがゆえに、排気ガスの後処理システムを汚染し、その浄化効率を低下させるという不具合がある。またモリブデン化合物を大量に使用すると、劣化によるデポジット増大や、シール材へ悪影響を及ぼす可能性もあり、その使用はできるだけ少ない量で十分な摩擦低減効果が発揮されることが望まれる。
Conventionally, lubricating oil is used for an internal combustion engine, an automatic transmission, grease, and the like in order to make the operation smooth. In particular, lubricating oil (engine oil) for internal combustion engines is required to have high performance as the performance of the internal combustion engine increases, the output increases, and the operating conditions become severe. Therefore, in order to satisfy such required performance, conventional engine oils are blended with various additives such as antiwear agents, metallic detergents, ashless dispersants, antioxidants (for example, Patent Documents 1 to 3). See). In addition, fuel-saving engine oils have a large energy loss in the frictional part where the lubricating oil is involved. Therefore, friction modifiers (FM: friction modifier) and other additives are combined to reduce friction loss and fuel consumption. Lubricating oil is also used (see, for example, Patent Document 4). Of these, friction reduction technology using zinc dialkyldithiophosphate (ZDTP) and a molybdenum compound is the most common, but in this case, excellent friction reduction performance can be obtained unless a relatively large amount of molybdenum compound is added. Absent.
Furthermore, when both molybdenum compounds and ZDTP are used in lubricating oils for internal combustion engines, there is a problem that the exhaust gas aftertreatment system is contaminated and its purification efficiency is lowered because it is metallic. Further, when a large amount of molybdenum compound is used, there is a possibility that deposits increase due to deterioration and the sealing material may be adversely affected. It is desired that the use of the molybdenum compound exhibits a sufficient friction reducing effect with as little amount as possible.
本発明は、低濃度モリブデン量でも優れた摩擦低減性が得られる内燃機関、自動変速機、グリースなどの潤滑油、特に内燃機関用潤滑油として好適に用いられる潤滑油組成物を提供することを目的とする。 The present invention provides a lubricating oil composition suitably used as a lubricating oil for internal combustion engines, automatic transmissions, greases, etc., particularly as a lubricating oil for an internal combustion engine, which can provide excellent friction reduction even at a low concentration of molybdenum. Objective.
本発明者は、上記課題について鋭意研究した結果、本発明を完成するに至ったものである。
すなわち、本発明は、潤滑油基油に、（Ａ）一般式（１）で示されるリン酸エステルの金属塩および（Ｂ）モリブデン元素と硫黄元素の比が１：４以上である硫化モリブデンジチオカーバメートおよび硫化モリブデンジチオホスフェートから選ばれる有機モリブデン化合物をモリブデン元素量換算で１０質量ｐｐｍ以上３００質量ｐｐｍ以下含有させて成る潤滑油組成物に関する。
That is, the present invention provides a lubricant base oil containing (A) a metal salt of a phosphate ester represented by the general formula (1) and (B) a molybdenum sulfide dithio having a ratio of molybdenum element to sulfur element of 1: 4 or more. The present invention relates to a lubricating oil composition comprising an organic molybdenum compound selected from carbamate and sulfurized molybdenum dithiophosphate in an amount of 10 to 300 ppm by mass in terms of molybdenum element .
本発明によれば、少ないモリブデン量で、潤滑油の性能低下抑制や、排気ガスの後処理装置への悪影響の低減、さらには低コストで、混合潤滑条件下での摩擦を十分に低減することができ、摩擦損失低減や燃費低減性に優れる潤滑油組成物を提供することが可能となる。 According to the present invention, with a small amount of molybdenum, it is possible to suppress the deterioration of the performance of the lubricating oil, reduce the adverse effect on the exhaust gas after-treatment device, and sufficiently reduce the friction under mixed lubrication conditions at low cost. It is possible to provide a lubricating oil composition that is excellent in reducing friction loss and reducing fuel consumption.
以下、本発明について説明する。 The present invention will be described below.
本発明の潤滑油組成物において用いられる潤滑油基油（以下、「本発明に係る潤滑油基油」という。）としては、鉱油系基油および／または合成油系基油が挙げられる。 Examples of the lubricating base oil used in the lubricating oil composition of the present invention (hereinafter referred to as “the lubricating base oil according to the present invention”) include mineral base oils and / or synthetic base oils.
鉱油系基油としては、例えば、原油を常圧蒸留及び／又は減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、水素化異性化、溶剤脱ろう、接触脱ろう、水素化精製、硫酸洗浄、白土処理等の精製処理のうちの１種を単独で又は２種以上を組み合わせて精製したパラフィン系鉱油、あるいはノルマルパラフィン系基油、イソパラフィン系基油などが挙げられる。 As the mineral oil base oil, for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, hydroisomerization, solvent dewaxing, Paraffinic mineral oil, or normal paraffinic base oil, isoparaffinic base oil, etc., refined by combining one or more of purification processes such as catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment alone Is mentioned.
鉱油系基油の好ましい例としては、以下に示す基油（１）〜（７）及び／又はこの基油（１）〜（７）から回収された潤滑油留分を、所定の精製方法によって精製し、潤滑油留分を回収することによって得られる基油を挙げることができる。 As a preferable example of the mineral base oil, the following base oils (1) to (7) and / or lubricating oil fractions recovered from the base oils (1) to (7) are obtained by a predetermined refining method. The base oil obtained by refine | purifying and collect | recovering lubricating oil fractions can be mentioned.
（１）パラフィン基系原油及び／又は混合基系原油の常圧蒸留残渣油の減圧蒸留による留出油（ＷＶＧＯ）
（２）潤滑油脱ろう工程により得られるワックス（スラックワックス等）及び／又はガストゥリキッド（ＧＴＬ）プロセス等により得られる合成ワックス（フィッシャートロプシュワックス、ＧＴＬワックス等）
（３）基油（１）〜（２）から選ばれる１種又は２種以上の混合油及び／又は当該混合油のマイルドハイドロクラッキング処理油
（４）基油（１）〜（３）から選ばれる２種以上の混合油
（５）パラフィン基系原油及び／又は混合基系原油の常圧蒸留残渣油の減圧蒸残渣油の脱れき油（ＤＡＯ）
（６）基油（５）のマイルドハイドロクラッキング処理油（ＭＨＣ）
（７）基油（１）〜（６）から選ばれる２種以上の混合油。
(1) Distilled oil (WVGO) by distillation under reduced pressure of paraffin base crude oil and / or mixed base crude oil at atmospheric distillation residue
(2) Wax (slack wax, etc.) obtained by the lubricant dewaxing process and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by the gas-to-liquid (GTL) process, etc.
(3) One or two or more mixed oils selected from base oils (1) to (2) and / or mild hydrocracking treatment oils of the mixed oils (4) selected from base oils (1) to (3) Two or more kinds of mixed oils (5) Paraffinic crude oil and / or degassed oil (DAO) of vacuum distillation residual oil of atmospheric distillation residue of mixed base crude oil
(6) Mild hydrocracking treatment oil (MHC) of base oil (5)
(7) Two or more mixed oils selected from base oils (1) to (6).
なお、上記所定の精製方法としては、水素化分解、水素化仕上げなどの水素化精製；フルフラール溶剤抽出などの溶剤精製；溶剤脱ろうや接触脱ろうなどの脱ろう；酸性白土や活性白土などによる白土精製；硫酸洗浄、苛性ソーダ洗浄などの薬品（酸又はアルカリ）洗浄などが好ましい。本発明では、これらの精製方法のうちの１種を単独で行ってもよく、２種以上を組み合わせて行ってもよい。また、２種以上の精製方法を組み合わせる場合、その順序は特に制限されず、適宜選定することができる。 The above-mentioned predetermined purification methods include hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; acid clay and activated clay White clay purification; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning is preferable. In the present invention, one of these purification methods may be performed alone, or two or more may be combined. Moreover, when combining 2 or more types of purification methods, the order in particular is not restrict | limited, It can select suitably.
鉱油系基油としては、下記で示される基油（８）が特に好ましい。
（８）上記基油（１）〜（７）から選ばれる基油又は当該基油から回収された潤滑油留分を水素化分解し、その生成物又はその生成物から蒸留等により回収される潤滑油留分について溶剤脱ろうや接触脱ろうなどの脱ろう処理を行い、又は当該脱ろう処理をした後に蒸留することによって得られる水素化分解鉱油。
なお、上記（８）の潤滑油基油を得るに際して、好都合なステップで、必要に応じて溶剤精製処理及び／又は水素化仕上げ処理工程を更に設けてもよい。
As the mineral base oil, the base oil (8) shown below is particularly preferable.
(8) Hydrocracking a base oil selected from the base oils (1) to (7) or a lubricating oil fraction recovered from the base oil, and recovering the product or the product by distillation or the like Hydrocracked mineral oil obtained by performing dewaxing treatment such as solvent dewaxing or catalytic dewaxing on the lubricating oil fraction, or by performing distillation after the dewaxing treatment.
In addition, when obtaining the lubricating base oil of (8) above, a solvent refining treatment and / or a hydrofinishing treatment step may be further provided as necessary at a convenient step.
また、鉱油系基油における硫黄分の含有量については特に制限はないが、熱・酸化安定性の更なる向上および低硫黄化の点から、硫黄分の含有量が１００質量ｐｐｍ以下であることが好ましく、５０質量ｐｐｍ以下であることがより好ましく、１０質量ｐｐｍ以下であることが更に好ましく、５質量ｐｐｍ以下であることが特に好ましい。 In addition, the sulfur content in the mineral oil base oil is not particularly limited, but from the viewpoint of further improving thermal and oxidation stability and reducing sulfur content, the sulfur content should be 100 mass ppm or less. Is preferably 50 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 5 ppm by mass or less.
また、鉱油系基油の％ＣＡは２以下であることが好ましく、より好ましくは１以下、更に好ましくは０．８以下、特に好ましくは０．５以下であり、最も好ましくは０である。％ＣＡが２を超えると、粘度−温度特性、熱・酸化安定性および省燃費性が低下する傾向にある。 Further, it is preferred that the% C A of the mineral base oil is 2 or less, more preferably 1 or less, more preferably 0.8 or less, particularly preferably 0.5 or less, and most preferably 0. % If C A is more than 2, the viscosity - temperature characteristic, thermal and oxidation stability and fuel efficiency tends to decrease.
本発明に係る潤滑油基油として合成系基油を用いても良い。合成系基油としては、ポリα−オレフィン又はその水素化物、イソブテンオリゴマー又はその水素化物、イソパラフィン、アルキルベンゼン、アルキルナフタレン、ジエステル（ジトリデシルグルタレート、ジ−２−エチルヘキシルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、ジ−２−エチルヘキシルセバケート等）、ポリオールエステル（トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール２−エチルヘキサノエート、ペンタエリスリトールペラルゴネート等）、ポリオキシアルキレングリコール、ジアルキルジフェニルエーテル、ポリフェニルエーテル等が挙げられ、中でも、ポリα−オレフィンが好ましい。ポリα−オレフィンとしては、典型的には、炭素数２〜３２、好ましくは６〜１６のα−オレフィンのオリゴマー又はコオリゴマー（１−オクテンオリゴマー、デセンオリゴマー、エチレン−プロピレンコオリゴマー等）及びそれらの水素化物が挙げられる。 A synthetic base oil may be used as the lubricating base oil according to the present invention. Synthetic base oils include poly α-olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate , Di-2-ethylhexyl sebacate, etc.), polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, dialkyldiphenyl ether, Examples thereof include polyphenyl ether, and among them, poly α-olefin is preferable. As the poly α-olefin, typically, an oligomer or co-oligomer (1-octene oligomer, decene oligomer, ethylene-propylene co-oligomer, etc.) having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms, and those. Of the hydrides.
本発明に係る潤滑油基油の粘度指数は、１１０以上であることが好ましい。より好ましくは１２０以上、さらに好ましくは１２５以上である。また１６０以下であることが好ましい。粘度指数が１１０未満であると、粘度−温度特性及び熱・酸化安定性、揮発防止性が悪化するだけでなく、摩擦係数が上昇する傾向にあり、また、摩耗防止性が低下する傾向にある。また、粘度指数が１６０を超えると、低温粘度特性が低下する傾向にある。
なお、本発明でいう粘度指数とは、ＪＩＳ Ｋ ２２８３−１９９３に準拠して測定された粘度指数を意味する。
The viscosity index of the lubricating base oil according to the present invention is preferably 110 or more. More preferably, it is 120 or more, More preferably, it is 125 or more. Moreover, it is preferable that it is 160 or less. When the viscosity index is less than 110, not only the viscosity-temperature characteristics, thermal / oxidative stability, and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase, and the wear prevention properties tend to decrease. . On the other hand, when the viscosity index exceeds 160, the low-temperature viscosity characteristics tend to deteriorate.
In addition, the viscosity index as used in the field of this invention means the viscosity index measured based on JISK2283-1993.
本発明に係る潤滑油基油の１００℃における動粘度は１０ｍｍ２／ｓ以下であることが好ましく、より好ましくは６ｍｍ２／ｓ以下、さらに好ましく５．０ｍｍ２／ｓ以下、特に好ましくは４．５ｍｍ２／ｓ以下、最も好ましくは４．２ｍｍ２／ｓ以下である。一方、当該動粘度は、１ｍｍ２／ｓ以上であることが好ましく、１．５ｍｍ２／ｓ以上であることがより好ましく、さらに好ましくは２ｍｍ２／ｓ以上、特に好ましくは２．５ｍｍ２／ｓ以上、最も好ましくは３ｍｍ２／ｓ以上である。ここでいう１００℃における動粘度とは、ＡＳＴＭ Ｄ−４４５に規定される１００℃での動粘度を示す。潤滑油基油成分の１００℃動粘度が６ｍｍ２／ｓを超える場合には、低温粘度特性が悪化し、また十分な省燃費性が得られないおそれがあり、１ｍｍ２／ｓ未満の場合は潤滑箇所での油膜形成が不十分であるため潤滑性に劣り、また潤滑油組成物の蒸発損失が大きくなるおそれがあるため好ましくない。 The kinematic viscosity at 100 ° C. of the lubricating base oil according to the present invention is preferably 10 mm 2 / s or less, more preferably 6 mm 2 / s or less, still more preferably 5.0 mm 2 / s or less, particularly preferably 4. 5 mm 2 / s or less, and most preferably not more than 4.2 mm 2 / s. On the other hand, the kinematic viscosity is preferably 1 mm 2 / s or more, more preferably 1.5 mm 2 / s or more, further preferably 2 mm 2 / s or more, and particularly preferably 2.5 mm 2 / s. As described above, it is most preferably 3 mm 2 / s or more. The kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445. If the 100 ° C. kinematic viscosity of the lubricating base oil component exceeds 6 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel economy, in the case of less than 1 mm 2 / s Since the formation of an oil film at the lubrication site is insufficient, the lubricity is inferior, and the evaporation loss of the lubricating oil composition may increase.
本発明の潤滑油組成物においては、上記本発明に係る潤滑油基油を単独で用いてもよく、また、本発明に係る潤滑油基油を他の基油の１種又は２種以上と併用してもよい。なお、本発明に係る潤滑油基油と他の基油とを併用する場合、それらの混合基油中に占める本発明に係る潤滑油基油の割合は、３０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、７０質量％以上であることが更に好ましい。 In the lubricating oil composition of the present invention, the lubricating base oil according to the present invention may be used alone, and the lubricating base oil according to the present invention may be one or more of other base oils. You may use together. When the lubricating base oil according to the present invention is used in combination with another base oil, the ratio of the lubricating base oil according to the present invention in the mixed base oil is preferably 30% by mass or more. 50% by mass or more is more preferable, and 70% by mass or more is still more preferable.
本発明に係る潤滑油基油と併用される他の基油については特に制限されるものではないが、鉱油系基油としては、例えば１００℃における動粘度が１０ｍｍ２／ｓを超え２００ｍｍ２／ｓ以下の、溶剤精製鉱油、水素化分解鉱油、水素化精製鉱油、溶剤脱ろう鉱油などが挙げられる。また、合成系基油としては、１００℃における動粘度が１〜１０ｍｍ２／ｓの範囲外となる合成系基油が挙げられる。 Although it does not restrict | limit in particular about the other base oil used together with the lubricating base oil which concerns on this invention, As a mineral oil type | system | group base oil, kinematic viscosity in 100 degreeC exceeds 10 mm < 2 > / s, for example, 200 mm < 2 > / s or less solvent refined mineral oil, hydrocracked mineral oil, hydrorefined mineral oil, solvent dewaxed mineral oil and the like. Examples of the synthetic base oil include synthetic base oils having a kinematic viscosity at 100 ° C. outside the range of 1 to 10 mm 2 / s.
本発明の潤滑油組成物における（Ａ）成分は、一般式（１）で表されるリン酸エステルの金属塩である。 The component (A) in the lubricating oil composition of the present invention is a metal salt of a phosphate represented by the general formula (1).
ここで、一般式（１）中のＲ１〜Ｒ４は炭素数１〜３０の炭化水素基または炭素数１〜３０のアルキル基あるいはアルケニル基、または炭素数１〜３０のアルキル基からなるアルキルチオエチル基であり、同一でも異なっていてもよい。Ｘ１、Ｘ２、Ｘ３およびＸ４は、それぞれ硫黄または酸素を示し、Ｘ１およびＸ２はどちらか一方が酸素、または全て酸素、Ｘ３およびＸ４はどちらか一方が酸素、または全て酸素であり、Ｙは金属元素を示す。 Here, R 1 to R 4 in the general formula (1) are alkylthios composed of a hydrocarbon group having 1 to 30 carbon atoms, an alkyl group or alkenyl group having 1 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms. An ethyl group, which may be the same or different. X 1 , X 2 , X 3 and X 4 each represent sulfur or oxygen, X 1 and X 2 are either oxygen or all oxygen, X 3 and X 4 are either oxygen or all Oxygen and Y represents a metal element.
上記Ｒ１〜Ｒ４で表される炭素数１〜３０の炭化水素基としては、具体的には、アルキル基、シクロアルキル基またはアルケニル基、アルキル置換シクロアルキル基、アリール基、アルキル置換アリール基、及びアリールアルキル基を挙げることができる。 Specific examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 1 to R 4 include an alkyl group, a cycloalkyl group or an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, and an alkyl-substituted aryl group. And arylalkyl groups.
上記アルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等のアルキル基（これらアルキル基は直鎖状でも分枝状でもよい）を挙げることができる。 Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and the like. Group, hexadecyl group, heptadecyl group, octadecyl group and other alkyl groups (these alkyl groups may be linear or branched).
上記シクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の炭素数５〜７のシクロアルキル基を挙げることができる。
また上記アルキルシクロアルキル基としては、例えば、メチルシクロペンチル基、ジメチルシクロペンチル基、メチルエチルシクロペンチル基、ジエチルシクロペンチル基、メチルシクロヘキシル基、ジメチルシクロヘキシル基、メチルエチルシクロヘキシル基、ジエチルシクロヘキシル基、メチルシクロヘプチル基、ジメチルシクロヘプチル基、メチルエチルシクロヘプチル基、ジエチルシクロヘプチル基等の炭素数６〜１１のアルキルシクロアルキル基（アルキル基のシクロアルキル基への置換位置も任意である）を挙げることができる。
As said cycloalkyl group, C5-C7 cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, can be mentioned, for example.
Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, a diethylcyclohexyl group, a methylcycloheptyl group, Examples thereof include an alkylcycloalkyl group having 6 to 11 carbon atoms such as a dimethylcycloheptyl group, a methylethylcycloheptyl group, and a diethylcycloheptyl group (the substitution position of the alkyl group with the cycloalkyl group is also arbitrary).
上記アルケニル基としては、例えば、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基等のアルケニル基（これらアルケニル基は直鎖状でも分枝状でもよく、また二重結合の位置も任意である）を挙げることができる。 Examples of the alkenyl group include butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, An alkenyl group such as an octadecenyl group (these alkenyl groups may be linear or branched, and the position of the double bond is also optional).
上記アリール基としては、例えば、フェニル基、ナフチル基等のアリール基を挙げることができる。
上記アルキルアリール基としては、例えば、トリル基、キシリル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ペンチルフェニル基、ヘキシルフェニル基、ヘプチルフェニル基、オクチルフェニル基、ノニルフェニル基、デシルフェニル基、ウンデシルフェニル基、ドデシルフェニル基等の炭素数７〜１８のアルキルアリール基（アルキル基は直鎖状でも分枝状でもよく、またアリール基への置換位置も任意である）を挙げることができる。
上記アリールアルキル基としては、例えばベンジル基、フェニルエチル基、フェニルプロピル基、フェニルブチル基、フェニルペンチル基、フェニルヘキシル基等の炭素数７〜１２のアリールアルキル基（これらのアルキル基は直鎖状でも分枝状でもよい）を挙げることができる。
As said aryl group, aryl groups, such as a phenyl group and a naphthyl group, can be mentioned, for example.
Examples of the alkylaryl group include tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, and decylphenyl group. And an alkylaryl group having 7 to 18 carbon atoms such as undecylphenyl group and dodecylphenyl group (the alkyl group may be linear or branched, and the substitution position on the aryl group is arbitrary). it can.
Examples of the arylalkyl group include arylalkyl groups having 7 to 12 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, and phenylhexyl group (these alkyl groups are linear). Or may be branched).
上記Ｒ１〜Ｒ４で表される炭素数１〜３０の炭化水素基は、炭素数１〜３０のアルキル基又は炭素数６〜２４のアリール基であることが好ましく、更に好ましくは炭素数３〜１８のアルキル基であり、最も好ましくは炭素数が４〜８の直鎖型のアルキル基である。 R 1 above hydrocarbon group having 1 to 30 carbon atoms represented by the to R 4, preferably an alkyl group or an aryl group having 6 to 24 carbon atoms having 1 to 30 carbon atoms, more preferably 3 carbon atoms -18 alkyl group, most preferably a linear alkyl group having 4-8 carbon atoms.
上記Ｙで示される金属としては、具体的には、リチウム、ナトリウム、カリウム、セシウム等のアルカリ金属、カルシウム、マグネシウム、バリウム等のアルカリ土類金属、亜鉛、銅、鉄、鉛、ニッケル、銀、マンガン、モリブデン等の重金属が挙げられる。これらの中では亜鉛、モリブデン、カルシウム等のアルカリ土類金属が好ましい。特に亜鉛が好ましい。
なお、上記リン化合物の金属塩としては、金属の価数に応じリン化合物の配位数が異なり、例えば、２価の亜鉛、カルシウムでは、１つの金属原子に対しリン化合物が２つ配位する錯体を形成すると考えられる。
Specific examples of the metal represented by Y include alkali metals such as lithium, sodium, potassium and cesium, alkaline earth metals such as calcium, magnesium and barium, zinc, copper, iron, lead, nickel, silver, Examples include heavy metals such as manganese and molybdenum. Of these, alkaline earth metals such as zinc, molybdenum and calcium are preferred. Zinc is particularly preferable.
In addition, as the metal salt of the phosphorus compound, the coordination number of the phosphorus compound varies depending on the valence of the metal. For example, in divalent zinc and calcium, two phosphorus compounds coordinate to one metal atom. It is thought to form a complex.
本発明の潤滑油組成物において（Ａ）成分の含有量は、組成物全量基準でリン元素換算量として０．００５質量％以上であることが好ましく、より好ましくは０．０２質量％以上、特に好ましくは０．０５質量％以上であり、一方、その含有量は、０．５質量％以下であることが好ましく、より好ましくは０．２質量％以下であり、特に好ましくは０．１質量％以下である。（Ａ）成分の含有量が、リン元素として０．００５質量％未満の場合は、耐摩耗性に対して効果がなく、０．５質量％を超える場合は、リンによる排ガス後処理装置への悪影響が懸念されるため、それぞれ好ましくない。 In the lubricating oil composition of the present invention, the content of the component (A) is preferably 0.005% by mass or more, more preferably 0.02% by mass or more, and particularly preferably 0.02% by mass or more, based on the total amount of the composition. Preferably, the content is 0.05% by mass or more, while the content thereof is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass. It is as follows. When the content of the component (A) is less than 0.005% by mass as the phosphorus element, there is no effect on the wear resistance, and when it exceeds 0.5% by mass, the exhaust gas aftertreatment device with phosphorus Since there are concerns about adverse effects, they are not preferable.
なお、本発明における上記（Ａ）成分のうち、硫黄を含有する化合物についても、上記リン元素量の範囲内で含有させることができるが、好ましくは、その含有量は、硫黄元素換算量で、０．１質量％以下であることが好ましく、より好ましくは０．０８質量％以下である。
ＮＯｘ雰囲気下における塩基価維持性を極めて向上させるために、また本発明の摩擦低減効果を発揮させるためにも硫黄を含有する化合物を含有しないことが最も好ましい。
Of the component (A) in the present invention, the sulfur-containing compound can also be contained within the range of the phosphorus element amount, but preferably the content is in terms of elemental sulfur, The content is preferably 0.1% by mass or less, more preferably 0.08% by mass or less.
It is most preferable not to contain a sulfur-containing compound in order to greatly improve the base number maintenance property under the NOx atmosphere and to exhibit the friction reducing effect of the present invention.
本発明の潤滑油組成物における（Ｂ）成分は、モリブデン元素と硫黄元素の比が１：４以上である有機モリブデン化合物である。
かかる（Ｂ）成分として用いられる有機モリブデン化合物としては、（Ｂ１）硫化モリブデンジチオカーバメートおよび（Ｂ２）硫化モリブデンジチオホスフェートを挙げることができる。
Component (B) in the lubricating oil composition of the present invention is an organic molybdenum compound in which the ratio of molybdenum element to sulfur element is 1: 4 or more.
Examples of the organic molybdenum compound used as the component (B) include (B1) molybdenum sulfide dithiocarbamate and (B2) molybdenum sulfide dithiophosphate.
本発明における（Ｂ１）硫化モリブデンジチオカーバメートは、次の一般式（２）で表される有機モリブデン化合物であって、化合物中のモリブデン元素に対する硫黄元素の比率が４以上の化合物である。 (B1) Molybdenum dithiocarbamate in the present invention is an organic molybdenum compound represented by the following general formula (2), and is a compound having a ratio of sulfur element to molybdenum element in the compound of 4 or more.
上記（２）式中、Ｒ１、Ｒ２、Ｒ３及びＲ４は同一でも異なっていてもよく、それぞれ炭素数２〜２４、好ましくは炭素数４〜１３のアルキル基又は炭素数６〜２４、好ましくは炭素数８〜１５のアリール基（アルキルアリール基を含む）等の炭化水素基を示す。また、Ｘ１、Ｘ２、Ｘ３及びＸ４は同一でも異なっていてもよく、それぞれ硫黄原子又は酸素原子を示す。 (2) wherein, R 1, R 2, R 3 and R 4 may be the same or different, carbon atoms respectively 2 to 24, preferably an alkyl group carbon atoms or 4 to 13 having 6 to 24 carbon atoms , Preferably a hydrocarbon group such as an aryl group having 8 to 15 carbon atoms (including an alkylaryl group). X 1 , X 2 , X 3 and X 4 may be the same or different and each represents a sulfur atom or an oxygen atom.
アルキル基の好ましい例としては、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等が挙げられ、これらは１級アルキル基、２級アルキル基又は３級アルキル基でも良く、また直鎖状でも分枝状でもよい。（アルキル）アリール基の好ましい例としては、フェニル基、トリル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ペンチルフェニル基、ヘキシルフェニル基、オクチルフェニル基、ノニルフェニル基、デシルフェニル基、ウンデシルフェニル基、ドデシルフェニル基等が挙げられ、そのアルキル基は１級アルキル基、２級アルキル基又は３級アルキル基でも良く、また直鎖状でも分枝状でもよい。さらにこれら（アルキル）アリール基には、アリール基へのアルキル基の置換位置が異なる、全ての置換異性体が含まれる。 Preferred examples of the alkyl group include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, A hexadecyl group, a heptadecyl group, an octadecyl group, etc. are mentioned, These may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, and may be linear or branched. Preferred examples of (alkyl) aryl groups include phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, octylphenyl, nonylphenyl, decylphenyl, Examples thereof include a decylphenyl group and a dodecylphenyl group, and the alkyl group may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, and may be linear or branched. Further, these (alkyl) aryl groups include all substituted isomers in which the substitution position of the alkyl group to the aryl group is different.
（Ｂ１）硫化モリブデンジチオカーバメートとしては、具体的には、硫化モリブデンジエチルジチオカーバメート、硫化モリブデンジプロピルジチオカーバメート、硫化モリブデンジブチルジチオカーバメート、硫化モリブデンジペンチルジチオカーバメート、硫化モリブデンジヘキシルジチオカーバメート、硫化モリブデンジオクチルジチオカーバメート、硫化モリブデンジデシルジチオカーバメート、硫化モリブデンジドデシルジチオカーバメート、硫化モリブデンジ（ブチルフェニル）ジチオカーバメート、硫化モリブデンジ（ノニルフェニル）ジチオカーバメート、硫化オキシモリブデンジエチルジチオカーバメート、硫化オキシモリブデンジプロピルジチオカーバメート、硫化オキシモリブデンジブチルジチオカーバメート、硫化オキシモリブデンジペンチルジチオカーバメート、硫化オキシモリブデンジヘキシルジチオカーバメート、硫化オキシモリブデンジオクチルジチオカーバメート、硫化オキシモリブデンジデシルジチオカーバメート、硫化オキシモリブデンジドデシルジチオカーバメート、硫化オキシモリブデンジ（ブチルフェニル）ジチオカーバメート、硫化オキシモリブデンジ（ノニルフェニル）ジチオカーバメート（アルキル基は直鎖状でも分枝状でも良く、また、アルキルフェニル基のアルキル基の結合位置は任意である）、及びこれらの混合物等が例示できる。なお、これら硫化モリブデンジチオカーバメートとしては、１分子中に異なる炭素数及び／又は構造の炭化水素基を有する化合物も、好ましく用いることができる。 (B1) Specific examples of molybdenum dithiocarbamate sulfide include molybdenum diethyldithiocarbamate, molybdenum dipropyldithiocarbamate, molybdenum dibutyldithiocarbamate, molybdenum dipentyldithiocarbamate, molybdenum dipentyldithiocarbamate, molybdenum dihexyldithiocarbamate, and molybdenum dioctyldithiocarbamate. , Molybdenum didecyl dithiocarbamate sulfide, molybdenum didodecyl dithiocarbamate sulfide, molybdenum di (butylphenyl) dithiocarbamate sulfide, molybdenum di (nonylphenyl) dithiocarbamate sulfide, sulfurized oxymolybdenum diethyldithiocarbamate, sulfurized oxymolybdenum dipropyldithiocarbamate, sulfurized oxymolybdenum dibutyldithio Carbamate, sulfide Xylmolybdenum dipentyldithiocarbamate, sulfurized oxymolybdenum dihexyldithiocarbamate, sulfurized oxymolybdenum dioctyldithiocarbamate, sulfurized oxymolybdenum didecyldithiocarbamate, sulfurized oxymolybdenum didodecyldithiocarbamate, sulfurized oxymolybdenum di (butylphenyl) dithiocarbamate, sulfurized oxymolybdenum di (nonylphenyl) ) Dithiocarbamate (the alkyl group may be linear or branched, and the bonding position of the alkyl group of the alkylphenyl group is arbitrary), and mixtures thereof. As these molybdenum sulfide dithiocarbamates, compounds having hydrocarbon groups having different carbon numbers and / or structures in one molecule can also be preferably used.
本発明における（Ｂ２）硫化モリブデンジチオホスフェートは、次の一般式（３）で表される有機モリブデン化合物であって、化合物中のモリブデン元素に対する硫黄元素の比率が４以上の化合物である。 The (B2) molybdenum sulfide dithiophosphate in the present invention is an organic molybdenum compound represented by the following general formula (3), wherein the ratio of the sulfur element to the molybdenum element in the compound is 4 or more.
上記（３）式中、Ｒ５、Ｒ６、Ｒ７及びＲ８は同一でも異なっていてもよく、それぞれ炭素数２〜３０、好ましくは炭素数５〜１８、より好ましくは炭素数５〜１２のアルキル基又は炭素数６〜１８のアリール基（アルキルアリール基を含む）等の炭化水素基を示す。また、Ｙ１、Ｙ２、Ｙ３及びＹ４は同一でも異なっていてもよく、それぞれ硫黄原子又は酸素原子を示す。 In the above formula (3), R 5 , R 6 , R 7 and R 8 may be the same or different and each have 2 to 30 carbon atoms, preferably 5 to 18 carbon atoms, more preferably 5 to 12 carbon atoms. Or a hydrocarbon group such as an aryl group having 6 to 18 carbon atoms (including an alkylaryl group). Y 1 , Y 2 , Y 3 and Y 4 may be the same or different and each represents a sulfur atom or an oxygen atom.
アルキル基として好ましい例としては、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等が挙げられ、これらは１級アルキル基、２級アルキル基又は３級アルキル基でも良く、また直鎖状でも分枝状でもよい。（アルキル）アリール基の好ましい例としては、フェニル基、トリル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ペンチルフェニル基、ヘキシルフェニル基、オクチルフェニル基、ノニルフェニル基、デシルフェニル基、ウンデシルフェニル基、ドデシルフェニル基等が挙げられ、そのアルキル基は１級アルキル基、２級アルキル基又は３級アルキル基でも良く、また直鎖状でも分枝状でもよい。さらにこれら（アルキル）アリール基には、アリール基へのアルキル基の置換位置が異なる全ての置換異性体が含まれる。 Preferred examples of the alkyl group include ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, A hexadecyl group, a heptadecyl group, an octadecyl group, etc. are mentioned, These may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, and may be linear or branched. Preferred examples of (alkyl) aryl groups include phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, octylphenyl, nonylphenyl, decylphenyl, Examples thereof include a decylphenyl group and a dodecylphenyl group, and the alkyl group may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, and may be linear or branched. Furthermore, these (alkyl) aryl groups include all substituted isomers having different substitution positions of alkyl groups on aryl groups.
（Ｂ２）硫化モリブデンジチオホスフェートとしては、具体的には、硫化モリブデンジエチルジチオホスフェート、硫化モリブデンジプロピルジチオホスフェート、硫化モリブデンジブチルジチオホスフェート、硫化モリブデンジペンチルジチオホスフェート、硫化モリブデンジヘキシルジチオホスフェート、硫化モリブデンジオクチルジチオホスフェート、硫化モリブデンジデシルジチオホスフェート、硫化モリブデンジドデシルジチオホスフェート、硫化モリブデンジ（ブチルフェニル）ジチオホスフェート、硫化モリブデンジ（ノニルフェニル）ジチオホスフェート、硫化オキシモリブデンジエチルジチオホスフェート、硫化オキシモリブデンジプロピルジチオホスフェート、硫化オキシモリブデンジブチルジチオホスフェート、硫化オキシモリブデンジペンチルジチオホスフェート、硫化オキシモリブデンジヘキシルジチオホスフェート、硫化オキシモリブデンジオクチルジチオホスフェート、硫化オキシモリブデンジデシルジチオホスフェート、硫化オキシモリブデンジドデシルジチオホスフェート、硫化オキシモリブデンジ（ブチルフェニル）ジチオホスフェート、硫化オキシモリブデンジ（ノニルフェニル）ジチオホスフェート（アルキル基は直鎖状でも分枝状でも良く、また、アルキルフェニル基のアルキル基の結合位置は任意である）、及びこれらの混合物等が例示できる。なお、これら硫化モリブデンジチオホスフェートとしては、１分子中に異なる炭素数及び／又は構造の炭化水素基を有する化合物も、好ましく用いることができる。 (B2) Specific examples of the molybdenum sulfide dithiophosphate include molybdenum sulfide diethyldithiophosphate, molybdenum dipropyldithiophosphate, molybdenum dibutyldithiophosphate, molybdenum dipentyldithiophosphate, molybdenum dihexyldithiophosphate, molybdenum dioctyldithiophosphate. , Molybdenum didecyl dithiophosphate, Molybdenum didodecyl dithiophosphate, Molybdenum di (butylphenyl) dithiophosphate, Molybdenum di (nonylphenyl) dithiophosphate, Oxymolybdenum diethyldithiophosphate, Oxymolybdenum dipropyldithiophosphate, Oxymolybdenum dibutyldithio Phosphate, sulfide Xylmolybdenum dipentyldithiophosphate, sulfurized oxymolybdenum dihexyldithiophosphate, sulfurized oxymolybdenum dioctyldithiophosphate, sulfurized oxymolybdenum didecyldithiophosphate, sulfurized oxymolybdenum didodecyldithiophosphate, sulfurized oxymolybdenum di (butylphenyl) dithiophosphate, sulfurized oxymolybdenum di (nonylphenyl) ) Dithiophosphate (the alkyl group may be linear or branched, and the bonding position of the alkyl group of the alkylphenyl group is arbitrary), and mixtures thereof. As these molybdenum sulfide dithiophosphates, compounds having hydrocarbon groups having different carbon numbers and / or structures in one molecule can be preferably used.
（Ｂ）成分としては、硫化モリブデンジチオカーバメートや硫化モリブデンジチオホスフェートをそれぞれ単独で使用できるが、硫化モリブデンジチオカーバメートがその効果やリンを含まない点でより好ましい。
しかし性能の面から（Ｂ１）硫化モリブデンジチオカーバメートに（Ｂ２）硫化モリブデンジチオホスフェートを混合使用することも有効である。この場合、（Ｂ１）成分と（Ｂ２）成分の含有量の合計に対する（Ｂ１）成分の含有量の比率は、モリブデン元素量換算で、好ましくは５０〜９５質量％、より好ましくは６０〜９５質量％、更に好ましくは７０〜９５質量％である。
As the component (B), can be used alone molybdenum sulfide dithiocarbamate and molybdenum sulfide dithiophosphate respectively, more preferred in that the molybdenum dithiocarbamate sulfide does not contain the effect and phosphorus.
However, in view of performance, it is also effective to use (B2) molybdenum sulfide dithiocarbamate in combination with (B2) molybdenum sulfide dithiophosphate. In this case, the ratio of the content of the component (B1) to the total content of the components (B1) and (B2) is preferably 50 to 95% by mass, more preferably 60 to 95% by mass in terms of molybdenum element. %, More preferably 70 to 95% by mass.
本発明の潤滑油組成物においては、（Ｂ）成分中のモリブデン元素と硫黄元素の比率は、モリブデン元素１に対して硫黄元素４以上であることが必要であり、好ましく５以上である。モリブデン元素に対する硫黄元素の比率が４未満の場合は、低摩擦性が低下する。 In the lubricating oil composition of the present invention, the ratio of elemental molybdenum and sulfur elements in component (B), it is necessary that the relative elemental molybdenum 1 is elemental sulfur 4 or more, is favorable Mashiku 5 or more . When the ratio of the sulfur element to the molybdenum element is less than 4 , the low friction property is lowered.
本発明の潤滑油組成物における（Ｂ）成分の含有量は、摩擦低減効果の観点から、潤滑油組成物全量を基準として、モリブデン元素量換算で、好ましくは１０質量ｐｐｍ以上、より好ましくは５０質量ｐｐｍ以上、さらに好ましくは１００質量ｐｐｍ以上、特に好ましくは２００質量ｐｐｍ以上である。一方、潤滑油基油への溶解性、貯蔵安定性および酸化安定性、さらには経済性の観点から、好ましくは６００質量ｐｐｍ以下、より好ましくは５００質量ｐｐｍ以下、特に好ましくは３００質量ｐｐｍ以下である。なお、（Ｂ）成分の含有量が６００質量ｐｐｍを超えると、特に、潤滑油基油としてポリα−オレフィン又はその水素化物を用いる場合に、十分な溶解性が得られず、長期貯蔵に際し沈殿する恐れがある。さらには経済性の面からも好ましくない。 The content of the component (B) in the lubricating oil composition of the present invention is preferably 10 ppm by mass or more, more preferably 50 ppm in terms of the amount of molybdenum element, based on the total amount of the lubricating oil composition, from the viewpoint of a friction reducing effect. The mass ppm or more, more preferably 100 mass ppm or more, and particularly preferably 200 mass ppm or more. On the other hand, from the viewpoints of solubility in lubricating base oil, storage stability and oxidative stability, and economic efficiency, it is preferably 600 ppm by mass or less, more preferably 500 ppm by mass or less, and particularly preferably 300 ppm by mass or less. is there. In addition, when the content of the component (B) exceeds 600 ppm by mass, particularly when a poly α-olefin or a hydride thereof is used as a lubricating base oil, sufficient solubility cannot be obtained, and precipitation occurs during long-term storage. There is a fear. Furthermore, it is not preferable from the aspect of economy.
本発明の潤滑油組成物には、さらにその性能を向上させるために、その目的に応じて潤滑油に一般的に使用されている任意の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、金属系清浄剤、無灰分散剤、粘度指数向上剤、摩耗防止剤（又は極圧剤）、酸化防止剤、腐食防止剤、防錆剤、抗乳化剤、金属不活性化剤、消泡剤等の添加剤等を挙げることができる。 In order to further improve the performance, the lubricating oil composition of the present invention may contain any additive generally used in lubricating oils depending on the purpose. Examples of such additives include metal detergents, ashless dispersants, viscosity index improvers, antiwear agents (or extreme pressure agents), antioxidants, corrosion inhibitors, rust inhibitors, demulsifiers, metals Examples thereof include additives such as an inactivating agent and an antifoaming agent.
金属系清浄剤としては、アルカリ金属またはアルカリ土類金属サリシレート、アルカリ金属またはアルカリ土類金属スルホネート、アルカリ金属またはアルカリ土類金属フェネート、及びアルカリ金属またはアルカリ土類金属サリシレート等の正塩又は塩基性塩を挙げることができる。アルカリ金属としてはナトリウム、カリウム等、アルカリ土類金属としてはマグネシウム、カルシウム、バリウム等が挙げられるが、マグネシウム又はカルシウムが好ましく、カルシウムが特に好ましい。 As metal-based detergents, normal salts or basics such as alkali metals or alkaline earth metal salicylates, alkali metals or alkaline earth metal sulfonates, alkali metals or alkaline earth metal phenates, and alkali metals or alkaline earth metal salicylates Mention may be made of salts. Examples of the alkali metal include sodium and potassium, and examples of the alkaline earth metal include magnesium, calcium and barium. Magnesium or calcium is preferable, and calcium is particularly preferable.
なかでもアルカリ金属またはアルカリ土類金属サリシレート系清浄剤（以下、金属サリシレート系清浄剤という。）が摩擦低減の面から好ましい。
金属サリシレート系清浄剤は、サリチル酸に等モルの炭化水素基（例えば炭素数８〜３０のオレフィン）を付加させたサリチル酸、又は、フェノールに等モル炭化水素基（例えば炭素数８〜３０のオレフィン）を付加させ、次いで炭酸ガス等によりカルボキシル化させた、炭素数８〜３０の炭化水素基を１つ有するサリチル酸に、当量の金属塩や金属塩基等を作用させて得られる中性サリチル酸金属塩、さらには当該中性サリチル酸金属塩に過剰の金属塩又は金属塩基（金属の水酸化物や酸化物）を水の存在下で加熱することにより得られる塩基性塩、前記中性のサリチル酸金属塩の存在下において炭酸ガス又はホウ酸若しくはホウ酸塩と金属の水酸化物等の塩基とを反応させることにより得られる過塩基性塩（超塩基性塩）などが挙げられる。なお、これらの（過）塩基化の反応は、通常、溶媒（ヘキサン等の脂肪族炭化水素溶剤、キシレン等の芳香族炭化水素溶剤、軽質潤滑油基油等）中で行われる。
Of these, alkali metal or alkaline earth metal salicylate detergents (hereinafter referred to as metal salicylate detergents) are preferred from the viewpoint of friction reduction.
Metallic salicylate detergents are salicylic acid obtained by adding equimolar hydrocarbon groups (for example, olefins having 8 to 30 carbon atoms) to salicylic acid, or equimolar hydrocarbon groups (for example, olefins having 8 to 30 carbon atoms) to phenol. A neutral salicylic acid metal salt obtained by allowing an equivalent metal salt or metal base or the like to act on salicylic acid having one hydrocarbon group having 8 to 30 carbon atoms, which is then carboxylated with carbon dioxide or the like, Furthermore, a basic salt obtained by heating an excess metal salt or metal base (metal hydroxide or oxide) in the presence of water to the neutral salicylic acid metal salt, the neutral salicylic acid metal salt Examples include overbased salts (superbasic salts) obtained by reacting carbon dioxide or boric acid or borates with bases such as metal hydroxides in the presence. . In addition, these (over) basification reactions are usually performed in a solvent (an aliphatic hydrocarbon solvent such as hexane, an aromatic hydrocarbon solvent such as xylene, a light lubricating oil base oil, or the like).
サリシレートを合成する際に用いられる炭素数８〜３０のオレフィンは、通常、炭素数８〜１９のオレフィンのグループと炭素数２０〜３０のオレフィンのグループとに大別され、それぞれの炭化水素基が付加したサリチル酸が合成される。
炭化水素基は、エチレン、プロピレン、ブチレン等の重合体又は共重合体等から誘導されるアルキル基、特にエチレン重合体等の直鎖α−オレフィンから誘導されるアルキル基であることが好ましい。
The olefins having 8 to 30 carbon atoms used for synthesizing salicylate are generally roughly divided into a group of olefins having 8 to 19 carbon atoms and a group of olefins having 20 to 30 carbon atoms, and each hydrocarbon group has Added salicylic acid is synthesized.
The hydrocarbon group is preferably an alkyl group derived from a polymer or copolymer such as ethylene, propylene and butylene, particularly an alkyl group derived from a linear α-olefin such as an ethylene polymer.
本発明では、金属サリシレート系清浄剤として、炭素数８〜１９の炭化水素基（例えば炭素数８〜１９のアルキル基）を有するサリチル酸金属塩（以下、場合により「サリチル酸金属塩Ｃ−ａ」ともいう）又は炭素数２０〜３０の炭化水素基（例えば炭素数２０〜３０のアルキル基）を有するサリチル酸金属塩（以下、場合により「サリチル酸金属塩Ｃ−ｂ」ともいう）の一方を単独で、又は双方を組み合わせて使用することができる。摩擦低減の観点からはサリチル酸金属塩Ｃ−ｂが好ましい。一方、貯蔵安定性、低温流動性を相乗的に改善できる観点から、サリチル酸金属塩Ｃ−ａとサリチル酸金属塩Ｃ−ｂとを併用することももちろん可能である。 In the present invention, as a metal salicylate detergent, a salicylic acid metal salt having a hydrocarbon group having 8 to 19 carbon atoms (for example, an alkyl group having 8 to 19 carbon atoms) (hereinafter sometimes referred to as “salicylic acid metal salt C-a”). Or a salicylic acid metal salt having a hydrocarbon group having 20 to 30 carbon atoms (for example, an alkyl group having 20 to 30 carbon atoms) (hereinafter also referred to as “salicylic acid metal salt Cb” in some cases) alone, Or both can be used in combination. The salicylic acid metal salt Cb is preferable from the viewpoint of friction reduction. On the other hand, from the viewpoint of synergistically improving storage stability and low-temperature fluidity, it is of course possible to use salicylic acid metal salt Ca and salicylic acid metal salt Cb in combination.
金属サリシレート系清浄剤は、通常、溶剤や潤滑油基油等の希釈剤中で反応させて得られるが、そのようにして得られた金属サリシレート系清浄剤の金属含有量は、金属サリシレート系清浄剤全量を基準として、下限値は、好ましくは１．０質量％以上、より好ましくは２．０質量％以上、さらに好ましくは５．０質量％以上、特に好ましくは７．０質量％以上である。また、上限値は、好ましくは２０質量％以下、より好ましくは１５質量％以下、さらに好ましくは１２質量％以下、特に好ましくは１０％以下である。 Metal salicylate detergents are usually obtained by reaction in diluents such as solvents and lubricating base oils. The metal content of the metal salicylate detergent thus obtained is the metal salicylate detergent. Based on the total amount of the agent, the lower limit is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, further preferably 5.0% by mass or more, and particularly preferably 7.0% by mass or more. . The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, and particularly preferably 10% or less.
金属サリシレート系清浄剤の塩基価は、下限値として、好ましくは５０ｍｇＫＯＨ／ｇ以上、より好ましくは１００ｍｇＫＯＨ／ｇ以上、さらに好ましくは１５０ｍｇＫＯＨ／ｇ以上、特に好ましくは２００ｍｇＫＯＨ／ｇ以上に調整されてなる過塩基性サリシレート系清浄剤を主成分として用いることが望ましい。また、上限値は、好ましくは４００ｍｇＫＯＨ／ｇ以下、より好ましくは３００ｍｇＫＯＨ／ｇ以下、さらに好ましくは２５０ｍｇＫＯＨ／ｇ以下に調整されてなる過塩基性サリシレート系清浄剤を主成分として用いることがより好ましい。なお、ここでいう塩基価とは、ＪＩＳ Ｋ２５０１「石油製品及び潤滑油−中和価試験法」の７．に準拠して測定される過塩素酸法による塩基価を意味する。 The base number of the metal salicylate detergent is preferably adjusted to a lower limit of preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more, still more preferably 150 mgKOH / g or more, particularly preferably 200 mgKOH / g or more. It is desirable to use a basic salicylate detergent as the main component. The upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, and more preferably an overbased salicylate-based detergent used as a main component. The base number referred to here is 7. JIS K2501 “Petroleum products and lubricating oils-Neutralization number test method”. Means the base number measured by the perchloric acid method according to the above.
また、金属サリシレート系清浄剤の金属比は特に制限されず、通常２０以下のものを１種又は２種以上混合して使用できる。当該金属比は、好ましくは金属比が４．５未満、より好ましくは３以下である。なお、ここでいう金属比とは、（サリシレート系清浄剤における金属元素の価数）×（金属元素含有量（モル％））／（せっけん基含有量（モル％））で表され、金属元素とは、カルシウム、マグネシウム等、せっけん基とはサリチル酸基を意味する。 In addition, the metal ratio of the metal salicylate detergent is not particularly limited, and usually 20 or less can be used alone or in combination. The metal ratio is preferably less than 4.5, more preferably 3 or less. The metal ratio referred to here is expressed by (valence of metal element in salicylate detergent) × (metal element content (mol%)) / (soap group content (mol%)). The term “soap group” means a salicylic acid group such as calcium and magnesium.
本発明の潤滑油組成物に金属サリシレート系清浄剤を含有させる場合、その含有量は、潤滑油組成物全量基準で、好ましくは、０．１質量％以上であり、より好ましくは０．５質量％以上、さらに好ましくは１質量％以上である。また、好ましくは１５質量％以下であり、より好ましくは１０質量％以下、さらに好ましくは５質量％以下、特に好ましくは３質量％以下である。含有量が０．１質量％に満たない場合には、摩擦低減効果が短期間しか持続しないおそれがあり、また１５質量％を超える場合には、含有量に見合った効果が得られないおそれがある。また、金属量の下限値として好ましくは０．０１質量％以上であり、より好ましくは０．０５質量％以上、さらに好ましくは０．１質量％以上、特に好ましくは０．１５質量％以上である。また、上限値として好ましくは１．５質量％以下であり、より好ましくは１.０質量％以下、さらに好ましくは０．５質量％以下、特に好ましくは０．３質量％以下である。金属量が０．０１質量％に満たない場合には、摩擦低減効果が短期間しか持続しないおそれがあり、また１．５質量％を超える場合には、含有量に見合った効果が得られないおそれがある。 When the lubricating oil composition of the present invention contains a metal salicylate detergent, the content is preferably 0.1% by mass or more, more preferably 0.5% by mass based on the total amount of the lubricating oil composition. % Or more, more preferably 1% by mass or more. Moreover, it is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less. If the content is less than 0.1% by mass, the friction reduction effect may last only for a short period, and if it exceeds 15% by mass, the effect commensurate with the content may not be obtained. is there. Further, the lower limit of the metal amount is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more. . The upper limit is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. If the amount of metal is less than 0.01% by mass, the friction reduction effect may last only for a short period of time, and if it exceeds 1.5% by mass, an effect commensurate with the content cannot be obtained. There is a fear.
無灰分散剤としては、炭素数４０〜４００の直鎖若しくは分枝状のアルキル基又はアルケニル基を分子中に少なくとも１個有する含窒素化合物又はその誘導体、あるいはアルケニルコハク酸イミドの変性品等が挙げられる。これらの中から任意に選ばれる１種類あるいは２種類以上を配合することができる。 Examples of the ashless dispersant include nitrogen-containing compounds having at least one linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms or derivatives thereof, or modified products of alkenyl succinimide. It is done. One type or two or more types arbitrarily selected from these can be blended.
無灰分散剤が有するアルキル基又はアルケニル基の炭素数は、好ましくは４０〜４００、より好ましくは６０〜３５０である。アルキル基又はアルケニル基の炭素数が４０未満の場合は化合物の潤滑油基油に対する溶解性が低下する傾向にあり、一方、４００を超える場合は、潤滑油組成物の低温流動性が悪化する傾向にある。このアルキル基又はアルケニル基は、直鎖状でも分枝状でもよいが、好ましいものとしては、プロピレン、１−ブテン、イソブチレン等のオレフィンのオリゴマーやエチレンとプロピレンのコオリゴマーから誘導される分枝状アルキル基や分枝状アルケニル基等が挙げられる。 The carbon number of the alkyl group or alkenyl group of the ashless dispersant is preferably 40 to 400, more preferably 60 to 350. When the number of carbon atoms of the alkyl group or alkenyl group is less than 40, the solubility of the compound in the lubricating base oil tends to decrease. On the other hand, when it exceeds 400, the low-temperature fluidity of the lubricating oil composition tends to deteriorate. It is in. The alkyl group or alkenyl group may be linear or branched, but is preferably branched from an olefin oligomer such as propylene, 1-butene, isobutylene, or a co-oligomer of ethylene and propylene. Examples thereof include an alkyl group and a branched alkenyl group.
なお、コハク酸イミドには、ポリアミンの一端に無水コハク酸が付加した一般式（５）で表される、いわゆるモノタイプのコハク酸イミドと、ポリアミンの両端に無水コハク酸が付加した一般式（６）で表される、いわゆるビスタイプのコハク酸イミドとが含まれる。
一般式（５）において、Ｒ９は炭素数４０〜４００のアルキル基又はアルケニル基、好ましくは炭素数６０〜３５０のアルキル基又はアルケニル基を示し、ｐは１〜５、好ましくは２〜４の整数を示す。
一般式（６）において、Ｒ１０及びＲ１１は同一でも異なっていてもよく、それぞれ炭素数４０〜４００のアルキル基又はアルケニル基、好ましくは炭素数６０〜３５０のアルキル基又はアルケニル基を示し、ポリブテニル基であることが好ましい。ｑは０〜４、好ましくは１〜３の整数を示す。
In the general formula (5), R 9 represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably an alkyl group or alkenyl group having 60 to 350 carbon atoms, and p is 1 to 5, preferably 2 to 4. Indicates an integer.
In the general formula (6), R 10 and R 11 may be the same or different and each represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably an alkyl group or alkenyl group having 60 to 350 carbon atoms, A polybutenyl group is preferred. q represents an integer of 0 to 4, preferably 1 to 3.
本発明の潤滑油組成物は、モノタイプ又はビスタイプのコハク酸イミドのいずれか一方を含有してもよく、あるいは双方を含有してもよい。 The lubricating oil composition of the present invention may contain either monotype or bistype succinimide, or may contain both.
コハク酸イミドの製造方法は特に制限されないが、例えば炭素数４０〜４００のアルキル基又はアルケニル基を有する化合物を無水マレイン酸と１００〜２００℃で反応させて得たアルキルコハク酸又はアルケニルコハク酸をポリアミンと反応させることにより得ることができる。ポリアミンとしては、具体的には、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、及びペンタエチレンヘキサミン等が例示できる。 The method for producing succinimide is not particularly limited. For example, an alkyl succinic acid or alkenyl succinic acid obtained by reacting a compound having an alkyl group or alkenyl group having 40 to 400 carbon atoms with maleic anhydride at 100 to 200 ° C. It can be obtained by reacting with a polyamine. Specific examples of the polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
本発明においては、上記コハク酸イミド及び／又はその誘導体の中から選ばれる任意のものが使用可能であるが、その重量平均分子量は、６，５００以上が好ましく、より好ましくは７，０００以上、さらに好ましくは８，０００以上、特に好ましくは９，０００以上である。重量平均分子量が６，５００未満では、非極性基のポリブテニル基の分子量が小さくスラッジの分散性に劣り、また、酸化劣化の活性点となる恐れのある極性基のアミン部分が相対的に多くなって酸化安定性に劣るため、長寿命化効果は得られないと考えられる。一方、上限値は特に制限はないが、低温粘度特性の悪化を防止する観点から、２０，０００以下であることが好ましく、１５，０００以下であることがより好ましい。
なお、ここでいう重量平均分子量とは、ウォーターズ製の１５０−Ｃ ＡＬＣ／ＧＰＣ装置に東ソー製のＧＭＨＨＲ−Ｍ（７．８ｍｍＩＤ×３０ｃｍ）のカラムを２本直列に使用し、溶媒としてはテトラヒドロフラン、温度２３℃、流速１ｍＬ／分、試料濃度１質量％、試料注入量７５μＬ、検出器示差屈折率計（ＲＩ）で測定したポリスチレン換算の重量平均分子量のことである。
In the present invention, any one selected from the succinimides and / or derivatives thereof can be used, but the weight average molecular weight is preferably 6,500 or more, more preferably 7,000 or more, More preferably, it is 8,000 or more, Especially preferably, it is 9,000 or more. When the weight average molecular weight is less than 6,500, the molecular weight of the non-polar polybutenyl group is small and the sludge dispersibility is poor, and the polar group amine portion that may become an active site for oxidative degradation is relatively large. Therefore, it is considered that the effect of prolonging the life cannot be obtained because of poor oxidation stability. On the other hand, the upper limit is not particularly limited, but is preferably 20,000 or less, and more preferably 15,000 or less, from the viewpoint of preventing deterioration of the low-temperature viscosity characteristics.
In addition, the weight average molecular weight as used herein means that two columns of Tosoh GMHHR-M (7.8 mm ID × 30 cm) are used in series on a Waters 150-C ALC / GPC apparatus, and the solvent is tetrahydrofuran, It is a weight-average molecular weight in terms of polystyrene measured by a temperature of 23 ° C., a flow rate of 1 mL / min, a sample concentration of 1 mass%, a sample injection amount of 75 μL, and a detector differential refractometer (RI).
また、無灰分散剤として、ベンジルアミンを用いることもできる。好ましいベンジルアミンとしては、具体的には、下記の一般式（７）で表される化合物等が例示できる。
一般式（７）において、Ｒ１２は、炭素数４０〜４００のアルキル基又はアルケニル基、好ましくは炭素数６０〜３５０のアルキル基又はアルケニル基を示し、ｒは１〜５、好ましくは２〜４の整数を示す。 In the general formula (7), R 12 represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably an alkyl group or alkenyl group having 60 to 350 carbon atoms, and r is 1 to 5, preferably 2 to 4. Indicates an integer.
ベンジルアミンの製造方法は何ら限定されるものではないが、例えば、プロピレンオリゴマー、ポリブテン、及びエチレン−α−オレフィン共重合体等のポリオレフィンをフェノールと反応させてアルキルフェノールとした後、これにホルムアルデヒドとジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、及びペンタエチレンヘキサミン等のポリアミンをマンニッヒ反応により反応させることにより得ることができる。 The method for producing benzylamine is not limited in any way. For example, after reacting polyolefin such as propylene oligomer, polybutene, and ethylene-α-olefin copolymer with phenol to form alkylphenol, formaldehyde and diethylenetriamine are added thereto. , Triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and other polyamines can be obtained by reacting by a Mannich reaction.
上記ポリアミンとしては、より具体的には、下記の一般式（８）で表される化合物等が例示できる。
Ｒ１３−ＮＨ−（ＣＨ2ＣＨ2ＮＨ）ｓ−Ｈ （８）
一般式（８）において、Ｒ１３は、炭素数４０〜４００のアルキル基又はアルケニル基、好ましくは６０〜３５０のアルキル基又はアルケニル基を示し、ｓは１〜５、好ましくは２〜４の整数を示す。
More specifically, examples of the polyamine include compounds represented by the following general formula (8).
R 13 -NH- (CH 2 CH 2 NH) s -H (8)
In the general formula (8), R 13 represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably an alkyl group or alkenyl group having 60 to 350, and s is an integer of 1 to 5, preferably 2 to 4. Indicates.
ポリアミンの製造方法は何ら限定されるものではないが、例えば、プロピレンオリゴマー、ポリブテン、及びエチレン−α−オレフィン共重合体等のポリオレフィンを塩素化した後、これにアンモニアやエチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、及びペンタエチレンヘキサミン等のポリアミンを反応させることにより得ることができる。 The production method of polyamine is not limited in any way. For example, after chlorinating polyolefin such as propylene oligomer, polybutene, and ethylene-α-olefin copolymer, ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine It can be obtained by reacting polyamines such as tetraethylenepentamine and pentaethylenehexamine.
また、その他の誘導体としては、具体的には、前述の含窒素化合物に炭素数１〜３０のモノカルボン酸（脂肪酸等）やシュウ酸、フタル酸、トリメリット酸、ピロメリット酸等の炭素数２〜３０のポリカルボン酸、アルコール、アルデヒド、ケトン、アルキルフェノール、環状カーボネート（例、炭酸エチレン）、ヒドロキシ（ポリ）アルキレンカーボネート等の含酸素化合物を作用させて、残存するアミノ基及び／又はイミノ基の一部又は全部を中和したり、アミド化した有機酸等による変性化合物、前述の含窒素化合物に硫黄化合物を作用させた、硫黄変性化合物等が挙げられる。またホウ素化合物で変性したものも挙げられる。 In addition, as other derivatives, specifically, the above-mentioned nitrogen-containing compounds may have 1 to 30 carbon atoms such as monocarboxylic acids (fatty acids, etc.), oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc. 2 to 30 polycarboxylic acids, alcohols, aldehydes, ketones, alkylphenols, cyclic carbonates (for example, ethylene carbonate), hydroxy (poly) alkylene carbonates and the like are allowed to act on the remaining amino groups and / or imino groups Examples thereof include a modified compound obtained by neutralizing a part or all of the above or an amidated organic acid, a sulfur-modified compound obtained by allowing a sulfur compound to act on the above-described nitrogen-containing compound, and the like. Moreover, the thing modified | denatured with the boron compound is also mentioned.
しかし、本発明の潤滑油組成物において、無灰分散剤としてはホウ素化されていない上述の窒素系化合物が好ましい。 However, in the lubricating oil composition of the present invention, the above-described nitrogen-based compound that is not boronated is preferred as the ashless dispersant.
本発明の潤滑油組成物が無灰分散剤を含有する場合、無灰分散剤の含有量は、潤滑油組成物全量基準で、好ましくは０．０１〜２０質量％であり、より好ましくは０．１〜１０質量％である。無灰分散剤の含有量が０．０１質量％未満の場合は、摩擦低減性向上効果が不十分となるおそれがあり、一方、２０質量％を超える場合は、潤滑油組成物の低温流動性が大幅に悪化するおそれがある。 When the lubricating oil composition of the present invention contains an ashless dispersant, the content of the ashless dispersant is preferably 0.01 to 20% by mass, more preferably 0.1%, based on the total amount of the lubricating oil composition. -10 mass%. When the content of the ashless dispersant is less than 0.01% by mass, the effect of improving the friction reduction property may be insufficient. On the other hand, when the content exceeds 20% by mass, the low-temperature fluidity of the lubricating oil composition is low. There is a risk of significant deterioration.
粘度指数向上剤は、具体的には非分散型又は分散型エステル基含有粘度指数向上剤であり、例として非分散型又は分散型ポリ（メタ）アクリレート系粘度指数向上剤、非分散型又は分散型オレフィン−（メタ）アクリレート共重合体系粘度指数向上剤、スチレン−無水マレイン酸エステル共重合体系粘度指数向上剤及びこれらの混合物等が挙げられ、これらの中でも非分散型又は分散型ポリ（メタ）アクリレート系粘度指数向上剤であることが好ましい。特に非分散型又は分散型ポリメタクリレート系粘度指数向上剤であることが好ましい。
粘度指数向上剤としては、その他に、非分散型又は分散型エチレン−α−オレフィン共重合体又はその水素化物、ポリイソブチレン又はその水素化物、スチレン−ジエン水素化共重合体及びポリアルキルスチレン等を挙げることができる。
The viscosity index improver is specifically a non-dispersed or dispersed ester group-containing viscosity index improver, for example, a non-dispersed or dispersed poly (meth) acrylate viscosity index improver, non-dispersed or dispersed Type olefin- (meth) acrylate copolymer-based viscosity index improver, styrene-maleic anhydride copolymer-based viscosity index improver, and mixtures thereof. Among these, non-dispersed or dispersed poly (meth) An acrylate viscosity index improver is preferable. A non-dispersed or dispersed polymethacrylate viscosity index improver is particularly preferable.
Other examples of the viscosity index improver include non-dispersed or dispersed ethylene-α-olefin copolymers or hydrogenated products thereof, polyisobutylene or hydrogenated products thereof, styrene-diene hydrogenated copolymers, and polyalkylstyrenes. Can be mentioned.
摩耗防止剤（又は極圧剤）としては、潤滑油に用いられる任意の摩耗防止剤・極圧剤が使用できる。例えば、硫黄系、リン系、硫黄−リン系の極圧剤等が使用でき、具体的には、ジアルキルジチオリン酸亜鉛（ＺｎＤＴＰ）、亜リン酸エステル類、チオ亜リン酸エステル類、ジチオ亜リン酸エステル類、トリチオ亜リン酸エステル類、リン酸エステル類、チオリン酸エステル類、ジチオリン酸エステル類、トリチオリン酸エステル類、これらのアミン塩、これらの金属塩、これらの誘導体、ジチオカーバメート、亜鉛ジチオカーバメート、ＭｏＤＴＣ、ジサルファイド類、ポリサルファイド類、硫化オレフィン類、硫化油脂類等が挙げられる。これらの中では硫黄系極圧剤の添加が好ましく、特に硫化油脂が好ましい。 As the antiwear agent (or extreme pressure agent), any antiwear agent / extreme pressure agent used for lubricating oil can be used. For example, sulfur-based, phosphorus-based, sulfur-phosphorus extreme pressure agents and the like can be used. Specifically, zinc dialkyldithiophosphate (ZnDTP), phosphites, thiophosphites, dithiophosphites Acid esters, trithiophosphites, phosphate esters, thiophosphate esters, dithiophosphate esters, trithiophosphate esters, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamate, zinc dithio Carbamate, MoDTC, disulfides, polysulfides, sulfurized olefins, sulfurized fats and oils, and the like can be given. Among these, addition of a sulfur-based extreme pressure agent is preferable, and sulfurized fats and oils are particularly preferable.
酸化防止剤としては、フェノール系、アミン系等の無灰酸化防止剤、銅系、モリブデン系等の金属系酸化防止剤が挙げられる。具体的には、例えば、フェノール系無灰酸化防止剤としては、４，４’−メチレンビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、４，４’−ビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）等が、アミン系無灰酸化防止剤としては、フェニル−α−ナフチルアミン、アルキルフェニル−α−ナフチルアミン、ジアルキルジフェニルアミン等が挙げられる。 Examples of the antioxidant include ashless antioxidants such as phenols and amines, and metal antioxidants such as copper and molybdenum. Specifically, for example, as a phenol-based ashless antioxidant, 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert- Butylphenol) and the like are amine-based ashless antioxidants such as phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, and dialkyldiphenylamine.
腐食防止剤としては、例えば、ベンゾトリアゾール系、トリルトリアゾール系、チアジアゾール系、又はイミダゾール系化合物等が挙げられる。 Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, or imidazole compounds.
防錆剤としては、例えば、石油スルホネート、アルキルベンゼンスルホネート、ジノニルナフタレンスルホネート、アルケニルコハク酸エステル、又は多価アルコールエステル等が挙げられる。 Examples of the rust preventive include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
抗乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、又はポリオキシエチレンアルキルナフチルエーテル等のポリアルキレングリコール系非イオン系界面活性剤等が挙げられる。 Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, or polyoxyethylene alkyl naphthyl ether.
金属不活性化剤としては、例えば、イミダゾリン、ピリミジン誘導体、アルキルチアジアゾール、メルカプトベンゾチアゾール、ベンゾトリアゾール又はその誘導体、１，３，４−チアジアゾールポリスルフィド、１，３，４−チアジアゾリル−２，５−ビスジアルキルジチオカーバメート、２−（アルキルジチオ）ベンゾイミダゾール、又はβ−（ｏ−カルボキシベンジルチオ）プロピオンニトリル等が挙げられる。 Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples thereof include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.
消泡剤としては、例えば、２５℃における動粘度が１０００〜１０万ｍｍ２／ｓのシリコーンオイル、アルケニルコハク酸誘導体、ポリヒドロキシ脂肪族アルコールと長鎖脂肪酸のエステル、メチルサリチレートとｏ−ヒドロキシベンジルアルコール等が挙げられる。 Examples of the antifoaming agent include silicone oil having a kinematic viscosity at 25 ° C. of 1000 to 100,000 mm 2 / s, alkenyl succinic acid derivative, ester of polyhydroxy aliphatic alcohol and long chain fatty acid, methyl salicylate and o- Examples thereof include hydroxybenzyl alcohol.
これらの添加剤を本発明に係る潤滑油組成物に含有させる場合には、それぞれの含有量は、潤滑油組成物全量基準で、消泡剤については０．０００５〜１質量％、その他の添加剤については通常０．０１〜１０質量％の範囲から選ばれる。 When these additives are contained in the lubricating oil composition according to the present invention, the respective contents are based on the total amount of the lubricating oil composition, 0.0005 to 1% by mass for the antifoaming agent, and other additions. About an agent, it is normally chosen from the range of 0.01-10 mass%.
以下、実施例及び比較例に基づき本発明を更に具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
（実施例１〜４、参考例１〜４、比較例１〜５）
本発明に係る潤滑油組成物（実施例１〜４）および比較のための潤滑油組成物（比較例１〜５）を調製した。これらの組成物につき、往復動摩擦試験機（ＳＲＶ，油温：１１０℃、荷重：４００Ｎ、時間：３０ｍｉｎ）を用いて摩擦試験を行い、その結果を表１に示した。
表１に示す結果から明らかなように、実施例１〜４の潤滑油組成物は、基準油対比の摩擦係数改善率に優れ、（Ａ）成分もしくは（Ｂ）成分を含有していない比較例１〜５の組成物に対し、摩擦低減性に大幅に優れることがわかる。
( Examples 1-4 , Reference Examples 1-4 , Comparative Examples 1-5)
Lubricating oil compositions according to the present invention (Examples 1 to 4 ) and comparative lubricating oil compositions (Comparative Examples 1 to 5) were prepared. These compositions were subjected to a friction test using a reciprocating friction tester (SRV, oil temperature: 110 ° C., load: 400 N, time: 30 min), and the results are shown in Table 1.
As is apparent from the results shown in Table 1, the lubricating oil compositions of Examples 1 to 4 are excellent in the coefficient of friction improvement ratio relative to the reference oil and are comparative examples not containing the component (A) or (B). It turns out that it is excellent in friction reduction property with respect to the composition of 1-5.
本発明の潤滑油組成物は、摩擦低減効果が求められる潤滑油一般に使用できる、自動車用の変速機や終減速機用ギヤ油、さらには二輪車用、四輪車用、発電用、コジェネレーション用等のガソリンエンジン、ディーゼルエンジン、ガスエンジン等の内燃機関に特に好適に使用でき、船舶用、船外機用の各種エンジンに対しても有用である。 The lubricating oil composition of the present invention can be used in general for lubricating oils that are required to have a friction reducing effect, gear oil for automobile transmissions and final reduction gears, and also for motorcycles, automobiles, power generation, and cogeneration. It can be particularly suitably used for internal combustion engines such as gasoline engines, diesel engines, gas engines, etc., and is also useful for various engines for ships and outboard motors.
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| JP2011117733A JP5756342B2 (en) | 2011-05-26 | 2011-05-26 | Lubricating oil composition |
| CN201280037071.8A CN103717718B (en) | 2011-05-26 | 2012-01-20 | Lubricating oil composition |
| EP12790030.6A EP2716743A4 (en) | 2011-05-26 | 2012-01-20 | Lubricating oil composition |
| PCT/JP2012/051219 WO2012160840A1 (en) | 2011-05-26 | 2012-01-20 | Lubricating oil composition |
| US14/122,074 US20140100148A1 (en) | 2011-05-26 | 2012-01-20 | Lubricating oil composition |
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| JP2011117733A JP5756342B2 (en) | 2011-05-26 | 2011-05-26 | Lubricating oil composition |
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| US (1) | US20140100148A1 (en) |
| EP (1) | EP2716743A4 (en) |
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| CA3146968A1 (en) | 2019-07-29 | 2021-02-04 | Ecolab Usa Inc. | Oil soluble molybdenum complexes for inhibiting high temperature corrosion and related applications in petroleum refineries |
| WO2021021888A1 (en) * | 2019-07-29 | 2021-02-04 | Ecolab USA, Inc. | Oil soluble molybdenum complexes as high temperature fouling inhibitors |
| CN111187649B (en) * | 2020-02-05 | 2022-01-28 | 新疆工程学院 | Trimellitate lubricating oil base oil based on block polyester chemical modification and preparation method thereof |
| WO2022026434A1 (en) * | 2020-07-29 | 2022-02-03 | Ecolab Usa Inc. | Phophorous-free oil soluble molybdenum complexes for high temperature naphthenic acid corrosion inhibition |
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| JP2693698B2 (en) | 1993-04-22 | 1997-12-24 | 株式会社ジャパンエナジー | Fuel-efficient lubricating oil |
| AU680553B2 (en) * | 1993-09-13 | 1997-07-31 | Exxon Chemical Patents Inc. | Mixed antioxidant composition |
| EP0718395B1 (en) * | 1994-07-05 | 2002-03-06 | Asahi Denka Kogyo Kabushiki Kaisha | Engine oil composition |
| JP3615267B2 (en) | 1995-04-28 | 2005-02-02 | 新日本石油株式会社 | Engine oil composition |
| US5858931A (en) * | 1995-08-09 | 1999-01-12 | Asahi Denka Kogyo K.K | Lubricating composition |
| CA2213075C (en) * | 1995-12-22 | 2001-10-09 | Japan Energy Corporation | Lubricating oil for internal combustion engines |
| DE69824886T2 (en) * | 1997-12-12 | 2005-06-30 | Infineum Usa L.P. | METHOD FOR THE PRODUCTION OF 3-DIFFERENT MOLYBDENUM SULFUR COMPOUNDS AND THEIR USE AS LUBRICATING ADDITIVES |
| ATE309315T1 (en) * | 2000-03-29 | 2005-11-15 | Infineum Int Ltd | METHOD FOR PRODUCING LUBRICANT ADDITIVES |
| JP4416261B2 (en) | 2000-03-29 | 2010-02-17 | 新日本石油株式会社 | Engine oil composition |
| JP4856305B2 (en) | 2000-10-30 | 2012-01-18 | Ｊｘ日鉱日石エネルギー株式会社 | Engine oil composition |
| JP4327519B2 (en) * | 2002-06-28 | 2009-09-09 | 新日本石油株式会社 | Lubricating oil composition |
| US7790659B2 (en) * | 2002-06-28 | 2010-09-07 | Nippon Oil Corporation | Lubricating oil compositions |
| WO2004003117A1 (en) * | 2002-06-28 | 2004-01-08 | Nippon Oil Corporation | Lubricating oil composition |
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| EP2716743A4 (en) | 2014-11-19 |
| CN103717718A (en) | 2014-04-09 |
| JP2012246362A (en) | 2012-12-13 |
| EP2716743A1 (en) | 2014-04-09 |
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