JP5756353B2 - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
- Publication number
- JP5756353B2 JP5756353B2 JP2011137140A JP2011137140A JP5756353B2 JP 5756353 B2 JP5756353 B2 JP 5756353B2 JP 2011137140 A JP2011137140 A JP 2011137140A JP 2011137140 A JP2011137140 A JP 2011137140A JP 5756353 B2 JP5756353 B2 JP 5756353B2
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- JP
- Japan
- Prior art keywords
- group
- mass
- lubricating oil
- less
- carbon atoms
- 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
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- 239000010687 lubricating oil Substances 0.000 title claims description 54
- 239000000203 mixture Substances 0.000 title claims description 48
- -1 phosphorus compound Chemical class 0.000 claims description 83
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 239000002199 base oil Substances 0.000 claims description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 43
- 229910052698 phosphorus Inorganic materials 0.000 claims description 29
- 239000011574 phosphorus Substances 0.000 claims description 29
- 125000003342 alkenyl group Chemical group 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 230000001050 lubricating effect Effects 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 150000004982 aromatic amines Chemical group 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 26
- 229910052796 boron Inorganic materials 0.000 description 26
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 24
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 23
- 239000002270 dispersing agent Substances 0.000 description 20
- 150000002430 hydrocarbons Chemical group 0.000 description 19
- 150000003839 salts Chemical class 0.000 description 18
- 239000003599 detergent Substances 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- 229960001860 salicylate Drugs 0.000 description 13
- 229960002317 succinimide Drugs 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 11
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 11
- 229960004889 salicylic acid Drugs 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002480 mineral oil Substances 0.000 description 9
- 235000010446 mineral oil Nutrition 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 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
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000010705 motor oil Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 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 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 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 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000002156 mixing Methods 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
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-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
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 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 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 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 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001841 imino group Chemical group [H]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
- 239000011133 lead Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 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 2
- 239000006078 metal deactivator Substances 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
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 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 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 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 2
- 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 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-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
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- 238000000638 solvent extraction Methods 0.000 description 2
- 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 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 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 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
- 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 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
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- MBIZXFATKUQOOA-UHFFFAOYSA-N 1,3,4-thiadiazole Chemical compound C1=NN=CS1 MBIZXFATKUQOOA-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
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- GSOYMOAPJZYXTB-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 GSOYMOAPJZYXTB-UHFFFAOYSA-N 0.000 description 1
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 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
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000004711 α-olefin Substances 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
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
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- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/06—Metal salts
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- 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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- 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
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- 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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- 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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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- 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
- 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
- C10M2223/042—Metal salts thereof
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- 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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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- 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
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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
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
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- 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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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
本発明は新規な潤滑油組成物に関し、詳しくは特定構造のチオリン酸エステルの金属塩を基油に配合することにより製造される、優れた酸化安定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 more particularly to a lubricating oil composition having excellent oxidation stability, which is produced by blending a metal salt of a thiophosphate ester having a specific structure with a base oil. 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などには、その作用を円滑にするために潤滑油やグリースが用いられる。特に内燃機関用潤滑油(エンジン油)はエンジンの高性能化、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。こうした要求性能を満たすため、従来のエンジン油には摩耗防止剤、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。)。特にエンジン油はピストン-シリンダ域で常に酸化劣化の活性種である過酸化物と接触するため、優れた耐酸化性が求められる。そのため、エンジン油には過酸化物分解剤として機能するジアルキルジチオリン酸亜鉛(ZDTP)が使用されてきた。また、他の過酸化物分解剤としてモリブデン系化合物の使用も知られている。またZDTPは優れた摩耗防止剤であり、モリブデン化合物は摩擦を低減する優れた摩擦調整剤としても知られており、多くのエンジン油で使用されている。 Conventionally, lubricating oil and grease are used for an internal combustion engine, an automatic transmission, 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 engine increases, the output increases, and the operating conditions become severe. In order to satisfy these required performances, various additives such as antiwear agents, metallic detergents, ashless dispersants, and antioxidants are blended in conventional engine oils (see, for example, Patent Documents 1 to 3). .) In particular, engine oil is always in contact with peroxide, which is an active species for oxidative degradation, in the piston-cylinder region, and therefore requires excellent oxidation resistance. Therefore, zinc dialkyldithiophosphate (ZDTP) that functions as a peroxide decomposer has been used for engine oil. The use of molybdenum compounds as other peroxide decomposing agents is also known. ZDTP is also an excellent anti-wear agent, and molybdenum compounds are also known as excellent friction modifiers that reduce friction and are used in many engine oils.
前述したようにZDTPは酸化防止剤あるいは摩耗防止剤として作用するが、これが分解した後はむしろ潤滑油の塩基価を低下させ、またデポジットの原因となる。このため長寿命を求められる潤滑油において、ZDTPはきわめて扱いの難しい添加剤である。
このためアルキル基の異なる様々なZDTPが製造され、またこれを添加した潤滑油組成は、金属系清浄剤や他の酸化防止剤との組合せに様々な工夫がなされているが、いまだ解決には至っていない。
As described above, ZDTP acts as an antioxidant or an anti-wear agent. However, after it decomposes, ZDTP rather lowers the base number of the lubricating oil and causes deposits. For this reason, ZDTP is an extremely difficult additive in lubricating oils that require a long life.
For this reason, various ZDTPs with different alkyl groups have been produced, and the lubricating oil composition to which these are added has been devised in various combinations with metallic detergents and other antioxidants. Not reached.
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)成分として一般式(1)で示されるリン化合物を1種以上含有し、油中のリンと一般式(1)の化合物に基づく硫黄の元素比率(S/Pモル比)が0.05〜0.7であり、かつ(A)成分に基づく油中リン量が0.01〜0.5質量%であることを特徴する潤滑油組成物である。
That is, the present invention contains at least one phosphorus compound represented by the general formula (1) as the component (A) in the lubricating base oil, and is a sulfur element based on phosphorus in the oil and the compound of the general formula (1). Lubricating oil composition characterized in that the ratio (S / P molar ratio) is 0.05 to 0.7 and the amount of phosphorus in oil based on component (A) is 0.01 to 0.5% by mass. It is.
本発明によれば、従来のジアルキルジチオリン酸亜鉛(ZDTP)を配合した潤滑油では不可能であった優れた酸化安定性が得られる内燃機関、自動変速機などの潤滑油、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が可能となる。 According to the present invention, lubricating oil for internal combustion engines, automatic transmissions, and the like, particularly lubricating for internal combustion engines, can be obtained with excellent oxidation stability that was not possible with conventional lubricating oils containing zinc dialkyldithiophosphate (ZDTP). It becomes possible to provide a lubricating oil composition suitably used as an oil.
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。 Mineral oil base oils include, for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation, and solvent removal, solvent extraction, hydrocracking, hydroisomerization, solvent dewaxing, catalytic dewaxing. Examples include paraffinic mineral oil, normal paraffinic base oil, and isoparaffinic base oil that are refined by combining one or more kinds of refining treatments such as wax, hydrorefining, sulfuric acid washing, and clay treatment. It is done.
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20mm2/s以下であることが好ましく、より好ましくは10mm2/s以下、さらに好ましくは6mm2/s以下、特に好ましくは5mm2/s以下である。一方、当該100℃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20mm2/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 20 mm 2 / s or less, more preferably 10 mm 2 / s or less, still more preferably 6 mm 2 / s or less, particularly preferably 5 mm 2 / s. s or less. On the other hand, the 100 ° C. 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 or more, 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 20 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20mm2/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1〜20mm2/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 20 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. In addition, examples of the synthetic base oil include synthetic base oils having a kinematic viscosity at 100 ° C. outside the range of 1 to 20 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を持つアルキルチオエチル基であり、それぞれ同一でも異なっていてもよい。また、X1〜X4は硫黄または酸素を示し、それぞれ同一でも異なっていてもよい。Yは金属元素を示す。 Here, R 1 to R 4 in the general formula (1) are each a hydrocarbon group having 1 to 30 carbon atoms, or an alkylthioethyl group having an alkyl group or alkenyl group having 1 to 30 carbon atoms, which are the same or different. May be. X 1 to X 4 represent sulfur or oxygen, and may be the same or different. 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、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, 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(炭素数1〜30のアルキル基またはアルケニル基を持つアルキルチオエチル基のアルキル基を含む)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 (including an alkyl group having 1 to 30 carbon atoms or an alkylthioethyl group having an alkenyl group) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and other alkyl groups (these alkyl groups are linear or branched) May be).
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(炭素数1〜30のアルキル基またはアルケニル基を持つアルキルチオエチル基のアルケニル基を含む)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 (including an alkyl group having 1 to 30 carbon atoms or an alkenyl group having an alkenyl group having an alkenyl group) include a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group. Group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, etc. (these alkenyl groups may be linear or branched, and the position of the double bond) Are 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、より好ましくは炭素数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。 The hydrocarbon group having 1 to 30 carbon atoms represented by R 1 to R 4 is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 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。特に亜鉛若しくはモリブデンまたは亜鉛とモリブデンの組み合わせが好ましい。
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. In particular, zinc or molybdenum or a combination of zinc and molybdenum is 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は、油中のリンと一般式(1)の化合物に基づく硫黄の元素の比率(S/Pモル比)が0.05以上であることが必要である。好ましくは0.07以上であり、さらに好ましくは0.1以上である。一方、好ましくは0.7以下であり、さらに好ましくは0.5以下、特に好ましくは0.3以下である。
S/Pモル比が0.05未満の場合硫黄分が不足するため、十分な酸化防止効果が得られず、0.7を超える場合は、硫黄量が多すぎ、逆に酸化安定性が悪化するため好ましくない。
なお上記(A)成分のうち、硫黄を含有する化合物を使用する場合、一般式(1)においてX1からX4がすべて酸素である化合物または(A)成分以外の硫黄を含まないリン化合物を併せて使用する必要がある。
In the lubricating oil composition of the present invention, the ratio of sulfur element (S / P molar ratio) based on phosphorus in the oil and the compound of the general formula (1) needs to be 0.05 or more. Preferably it is 0.07 or more, More preferably, it is 0.1 or more. On the other hand, good Mashiku is 0.7 or less, more preferably 0.5 or less, particularly preferably 0.3 or less.
When the S / P molar ratio is less than 0.05, the sulfur content is insufficient, so that a sufficient antioxidant effect cannot be obtained. When the S / P molar ratio exceeds 0.7 , the amount of sulfur is too large and the oxidation stability deteriorates. Therefore, it is not preferable.
Note Of the component (A), when using a compound containing sulfur, the formula (1) X 4 are all from X 1 is oxygen in the compound or (A) a phosphorus compound containing no sulfur other than the component It is necessary to use together.
本発明における(A)成分以外の硫黄を含まないリン化合物としては、一般式(2)で表されるリン化合物、一般式(3)で表されるリン化合物、それらのアミン塩、及びこれらの誘導体からなる群より選ばれる少なくとも1種の化合物が挙げられる。 As the phosphorus compound containing no sulfur other than the component (A) in the present invention, a phosphorus compound represented by the general formula (2), a phosphorus compound represented by the general formula (3), amine salts thereof, and these Examples thereof include at least one compound selected from the group consisting of derivatives.
一般式(2)において、R1、R2及びR3は、それぞれ個別に水素原子又は炭素数1〜30の炭化水素基を示す。 In the general formula (2), R 1, R 2 and R 3 are each independently hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
一般式(3)において、R4、R5及びR6は、それぞれ個別に水素原子又は炭素数1〜30の炭化水素基を示す。 In General formula (3), R < 4 >, R < 5 > and R < 6 > show a hydrogen atom or a C1-C30 hydrocarbon group each separately.
上記式(2)および(3)におけるR1〜R6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、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。
かかる炭素数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、さらに好ましくは炭素数3〜18、さらに好ましくは炭素数4〜12のアルキル基である。
Specific examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 1 to R 6 in the above formulas (2) and (3) include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkyl-substituted cycloalkyl. Groups, aryl groups, alkyl-substituted aryl groups, and arylalkyl groups.
The hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 4 carbon atoms. ˜12 alkyl groups.
一般式(2)で表されるリン化合物としては、例えば、亜リン酸;上記炭素数1〜30の炭化水素基を1つ有する亜リン酸モノエステル、;上記炭素数1〜30の炭化水素基を2つ有する亜リン酸ジエステル;上記炭素数1〜30の炭化水素基を3つ有する亜リン酸トリエステル;及びこれらの混合物を挙げることができる。
なお亜リン酸物エステルならびに亜リン酸時エステルの互変異性体であるホスホン酸エステルもこの化合物に含まれる。
Examples of the phosphorus compound represented by the general formula (2) include phosphorous acid; phosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms; and hydrocarbon having 1 to 30 carbon atoms. Mention may be made of phosphorous acid diesters having two groups; phosphorous acid triesters having three hydrocarbon groups having 1 to 30 carbon atoms; and mixtures thereof.
In addition, phosphonic acid esters which are tautomers of phosphorous acid esters and phosphorous acid esters are also included in this compound.
一般式(3)で表されるリン化合物としては、例えば、リン酸;上記炭素数1〜30の炭化水素基を1つ有するリン酸モノエステル;上記炭素数1〜30の炭化水素基を2つ有するリン酸ジエステル;上記炭素数1〜30の炭化水素基を3つ有するリン酸トリエステル;及びこれらの混合物を挙げることができる。 Examples of the phosphorus compound represented by the general formula (3) include phosphoric acid; phosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms; and 2 hydrocarbon groups having 1 to 30 carbon atoms. And phosphoric acid triesters having three hydrocarbon groups having 1 to 30 carbon atoms; and mixtures thereof.
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%以上である。一方、その含有量は、0.5質量%以下であり、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 0.005% by mass or more, preferably 0.02% by mass or more, particularly preferably 0.8% by mass in terms of phosphorus element based on the total amount of the composition. It is 05 mass% or more. On the other hand, the content is 0.5% by mass or less, preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less. 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(A)成分以外の硫黄を含まないリン化合物を併用する場合、リンの含有量は、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%以上である。一方、その含有量は、0.5質量%以下であり、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。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 addition, when using together the phosphorus compound which does not contain sulfur other than (A) component, content of phosphorus is 0.005 mass% or more as phosphorus element conversion amount on the basis of a composition whole quantity, Preferably it is 0.02 mass%. Above, especially preferably 0.05% by mass or more. On the other hand, the content is 0.5% by mass or less, preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less. When the amount of phosphorus is less than 0.005% by mass, there is no effect on the wear resistance, and when it exceeds 0.5% by mass, there is a concern about the adverse effect of phosphorus on the exhaust gas aftertreatment device. Absent.
本発明で用いる(A)成分の1種の金属がモリブデンである場合、その配合量はMo量で0.03質量%以下である。好ましくは0.02質量%以下、さらに好ましくは0.01質量%以下である。0.03質量%を超えると酸化防止効果がむしろ低下するため好ましくない。 When one kind of metal of the component (A) used in the present invention is molybdenum, the blending amount is 0.03% by mass or less in terms of Mo amount. Preferably it is 0.02 mass% or less, More preferably, it is 0.01 mass% or less. If it exceeds 0.03% by mass, the antioxidant effect is rather lowered, which is not preferable.
(A)成分の金属がモリブデンである場合、例えば、次の一般式(4)で表されるモリブデンジチオホスフェートを用いることができる。
上記(4)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 (4), 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.
アルキル基の好ましい例としては、例えば、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, for example, 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. Group, hexadecyl group, heptadecyl group, octadecyl group and the like, which 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.
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。 Specific examples of molybdenum dithiophosphate include molybdenum diethyldithiophosphate, molybdenum dipropyldithiophosphate, molybdenum dibutyldithiophosphate, molybdenum dipentyldithiophosphate, molybdenum dihexyldithiophosphate, molybdenum dioctyldithiophosphate, molybdenum didecyl sulfide. Dithiophosphate, molybdenum sulfide didodecyl dithiophosphate, molybdenum sulfide di (butylphenyl) dithiophosphate, molybdenum di (nonylphenyl) dithiophosphate, sulfurized oxymolybdenum diethyldithiophosphate, sulfurized oxymolybdenum dipropyldithiophosphate, sulfurized oxymolybdenum dibutyldithiophosphate, sulfurized oxymolyb Dipentyldithiophosphate, sulfurized oxymolybdenum dihexyldithiophosphate, sulfurized oxymolybdenum dioctyldithiophosphate, sulfurized oxymolybdenum didecyldithiophosphate, sulfurized oxymolybdenum didodecyldithiophosphate, sulfurized oxymolybdenum di (butylphenyl) dithiophosphate, sulfurized oxymolybdenum di (nonylphenyl) Examples include 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 dithiophosphates, compounds having hydrocarbon groups having different carbon numbers and / or structures in one molecule can be preferably used.
本発明の潤滑油組成物では、(B)成分として無灰系酸化防止剤を含有することが好ましい。酸化防止剤は、フェノール系酸化防止剤やアミン系酸化防止剤等の無灰系酸化防止剤等の潤滑油に一般的に使用されているものであれば使用可能である。無灰系酸化防止剤の添加により、本発明による潤滑油組成物の酸化防止性をより高められ、本発明の潤滑油組成物の、デポジットの生成の抑制性、鉛含有金属の腐食又は腐食摩耗防止性能や、塩基価維持性等をより高めることができる。 The lubricating oil composition of the present invention preferably contains an ashless antioxidant as the component (B). The antioxidant can be used as long as it is generally used for lubricating oils such as ashless antioxidants such as phenolic antioxidants and amine antioxidants. By adding an ashless antioxidant, the antioxidant properties of the lubricating oil composition according to the present invention can be further enhanced, and the lubricating oil composition of the present invention can suppress deposit formation, corrosion or corrosive wear of lead-containing metals. Prevention performance, base number maintenance property, etc. can be improved more.
フェノール系酸化防止剤としては、例えば、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)、4,4’−ビス(2−メチル−6−tert−ブチルフェノール)、2,2’−メチレンビス(4−エチル−6−tert−ブチルフェノール)、2,2’−メチレンビス(4−メチル−6−tert−ブチルフェノール)、4,4’−ブチリデンビス(3−メチル−6−tert−ブチルフェノール)、4,4’−イソプロピリデンビス(2,6−ジ−tert−ブチルフェノール)、2,2’−メチレンビス(4−メチル−6−ノニルフェノール)、2,2’−イソブチリデンビス(4,6−ジメチルフェノール)、2,2’−メチレンビス(4−メチル−6−シクロヘキシルフェノール)、2,6−ジ−tert−ブチル−4−メチルフェノール、2,6−ジ−tert−ブチル−4−エチルフェノール、2,4−ジメチル−6−tert−ブチルフェノール、2,6−ジ−tert−α−ジメチルアミノ−p−クレゾール、2,6−ジ−tert−ブチル−4(N,N’−ジメチルアミノメチルフェノール)、4,4’−チオビス(2−メチル−6−tert−ブチルフェノール)、4,4’−チオビス(3−メチル−6−tert−ブチルフェノール)、2,2’−チオビス(4−メチル−6−tert−ブチルフェノール)、ビス(3−メチル−4−ヒドロキシ−5−tert−ブチルベンジル)スルフィド、ビス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)スルフィド、2,2’−チオ−ジエチレンビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]、トリデシル−3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート、ペンタエリスリチル−テトラキス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]、オクチル−3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート、オクタデシル−3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート、3−メチル−5−tert−ブチル−4−ヒドロキシフェニル置換脂肪酸エステル類等を好ましい例として挙げることができる。これらは二種以上を混合して使用してもよい。 Examples of phenolic antioxidants include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4 ′. -Bis (2-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6) -Nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-methylenebis (4-methyl) 6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2, 6-di-tert-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-4 (N, N′-dimethylaminomethylphenol), 4,4′-thiobis (2-methyl-6) -Tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4- Hydroxy-5-tert-butylbenzyl) sulfide, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide 2,2′-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tridecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3-methyl-5-tert-butyl-4-hydroxyphenyl substituted fatty acid esters and the like are preferable examples. Can do. You may use these in mixture of 2 or more types.
アミン系酸化防止剤としては、例えば、芳香族系アミン系酸化防止剤であるフェニル−α−ナフチルアミン、アルキルフェニル−α−ナフチルアミン、及びジアルキルジフェニルアミンを挙げることができる。これらは二種以上を混合して使用してもよい。 Examples of the amine antioxidant include phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, and dialkyldiphenylamine which are aromatic amine antioxidants. You may use these in mixture of 2 or more types.
上記フェノール系酸化防止剤とアミン系酸化防止剤は組み合わせて配合してもよいが、特に芳香族系アミン系酸化防止剤を単独で用いることが好ましい。 Although the said phenolic antioxidant and amine antioxidant may be mix | blended in combination, it is preferable to use especially an aromatic amine antioxidant especially.
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、粘度指数向上剤や金属系清浄剤、無灰分散剤、摩耗防止剤(又は極圧剤)、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. Such additives include, for example, viscosity index improvers, metal detergents, ashless dispersants, antiwear agents (or extreme pressure agents), corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators. And additives such as antifoaming agents.
金属系清浄剤としては、アルカリ金属/アルカリ土類金属サリシレート、アルカリ金属/アルカリ土類金属スルホネート、アルカリ金属/アルカリ土類金属フェネート、及びアルカリ金属/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、特にカルシウムがより好ましい。
なかでも金属サリシレート系清浄剤が酸化防止性、摩擦低減の面から好ましい。
As metal-based detergents, alkali salts / basic salts such as alkali metal / alkaline earth metal salicylate, alkali metal / alkaline earth metal sulfonate, alkali metal / alkaline earth metal phenate, and alkali metal / alkaline earth metal salicylate 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 more preferable.
Of these, metal salicylate detergents are preferred from the standpoint of antioxidant properties and friction reduction.
金属サリシレート系清浄剤は、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。 The metal salicylate detergent is a neutral salicylic acid metal salt obtained by allowing an equivalent metal salt or metal base to act on salicylic acid having one hydrocarbon group having 8 to 30 carbon atoms, and further, the neutral salicylic acid metal. A basic salt obtained by heating an excess metal salt or metal base (metal hydroxide or oxide) in the presence of water, carbon dioxide gas or boron in the presence of the neutral salicylic acid metal salt. Examples include overbased salts (superbasic salts) obtained by reacting an acid or borate with a base such as a metal hydroxide.
前記サリシレートの金属塩又は金属塩基における金属(すなわち金属サリシレート系清浄剤に含まれる金属)としては、ナトリウム、カリ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等が挙げられ、アルカリ土類金属であることが好ましく、特にカルシウムであることが望ましい。 Examples of the metal in the metal salt or metal base of salicylate (that is, the metal contained in the metal salicylate detergent) include alkali metals such as sodium and potassium, alkaline earth metals such as calcium, magnesium and barium, and the like. It is preferably an earth metal, particularly calcium.
本発明においては、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 a combination of both. 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おいてサリシレート系清浄剤を含有する場合の含有量は、潤滑油組成物全量基準で、下限値として、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、上限値として、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6質量%以下、特に好ましくは4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。 When the salicylate detergent is contained in the lubricating oil composition of the present invention, the lower limit is preferably 0.1% by mass or more, more preferably 0.5%, based on the total amount of the lubricating oil composition. It is at least 1% by mass, more preferably at least 1% by mass. Moreover, as an upper limit, Preferably it is 15 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 6 mass% or less, Most preferably, it is 4 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.
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。 Further, the lower limit of the amount of metal 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. is there. Moreover, as an upper limit, Preferably it is 1.5 mass% or less, More preferably, it is 1.0 mass% or less, More preferably, it is 0.5 mass% or less, Most preferably, it is 0.3 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.
本発明の潤滑油組成物は、無灰分散剤を含有することが好ましい。
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。
The lubricating oil composition of the present invention preferably contains an ashless dispersant.
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、アルキル基又はアルケニル基の炭素数が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、具体的には、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 carbon number of the alkyl group or alkenyl group is less than 40, the solubility of the compound in the lubricating base oil tends to be reduced. On the other hand, when the carbon number of the alkyl group or alkenyl group exceeds 400, the lubricating oil composition The low-temperature fluidity of the product tends to deteriorate. This alkyl group or alkenyl group may be linear or branched, but specifically, preferred are derived from olefin oligomers such as propylene, 1-butene and isobutylene, and co-oligomers of ethylene and propylene. And a branched 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、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、いわゆるビスタイプのコハク酸イミドとが含まれる。
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 succinimide includes a so-called mono-type succinimide in which succinic anhydride is added to one end of the polyamine and a so-called bis-type succinimide in which succinic anhydride is added to both ends of the polyamine. .
The lubricating oil composition of the present invention may contain either monotype or bistype succinimide, or may contain both.
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(5)で表される化合物等が例示できる。
一般式(5)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 (5), 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.
無灰分散剤としてのポリアミンとしては、具体的には、下記の一般式(6)で表される化合物等が例示できる。
R13‐NH−(CH2CH2NH)s−H (6)
一般式(6)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。
Specific examples of the polyamine as the ashless dispersant include compounds represented by the following general formula (6).
R 13 -NH- (CH 2 CH 2 NH) s -H (6)
In the general formula (6), R 13 represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and s is an integer of 1 to 5, preferably 2 to 4. Indicates.
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、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. Oxygen compounds such as 2 to 30 polycarboxylic acids and hydroxy (poly) alkylene carbonates are allowed to act to neutralize part or all of the remaining amino groups and / or imino groups, or amidated organic acids, etc. And a sulfur-modified compound obtained by allowing a sulfur compound to act on the aforementioned nitrogen-containing compound. Moreover, the thing modified | denatured with the boron compound is also mentioned.
ホウ素化無灰分散剤とは、潤滑油に用いられる任意の無灰分散剤をホウ素化したものである。
ホウ素化は、一般に、前述の含窒素化合物にホウ酸を作用させて、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することにより行われる。
The boronated ashless dispersant is a borated ashless dispersant used in lubricating oils.
Boronation is generally performed by allowing boric acid to act on the aforementioned nitrogen-containing compound to neutralize part or all of the remaining amino group and / or imino group.
例えば、ホウ酸変性コハク酸イミドの製造方法としては、特公昭42-8013号公報及び同42-8014号公報、特開昭51-52381号公報、及び特開昭51-130408号公報等に開示されている方法等が挙げられる。具体的には例えば、アルコール類やヘキサン、キシレン等の有機溶媒、軽質潤滑油基油等にポリアミンとポリアルケニルコハク酸(無水物)にホウ酸、ホウ酸エステル、又はホウ酸塩等のホウ素化合物を混合し、適当な条件で加熱処理することにより得ることができる。なお、この様にして得られるホウ酸性コハク酸イミドのホウ酸含有量は通常0.1〜4.0質量%とすることができる。
アルケニルコハク酸イミドのホウ酸変性化合物(ホウ素含有コハク酸イミド)は耐熱性、酸化防止性及び摩耗防止性に優れる。
For example, methods for producing boric acid-modified succinimide are disclosed in JP-B-42-8013 and JP-A-42-8014, JP-A-51-52381, JP-A-51-130408, and the like. The method currently used is mentioned. Specifically, for example, organic compounds such as alcohols, hexane, xylene, etc., light lubricating oil base oil, polyamine and polyalkenyl succinic acid (anhydride), boric acid, boric acid ester, or boron compounds such as borate Can be obtained by mixing and heat-treating under appropriate conditions. In addition, boric acid content of the boric acid succinimide obtained in this way can be normally 0.1-4.0 mass%.
A boric acid-modified compound (boron-containing succinimide) of alkenyl succinimide is excellent in heat resistance, oxidation resistance and wear resistance.
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.
また、上記ホウ素含有コハク酸イミド等のホウ素含有無灰分散剤を用いる場合、そのホウ素含有量は特に制限はなく、通常0.1〜3質量%であるが、本発明の1つの態様としては、好ましくは0.2質量%以上、より好ましくは0.4質量%以上、また、好ましくは2質量%以下、より好ましくは1.5質量%以下、さらに好ましくは1.0質量%以下、特に好ましくは0.6質量%以下のホウ素含有量のホウ素含有無灰分散剤、好ましくはホウ素含有コハク酸イミド、特に、ホウ素含有ビスコハク酸イミドを使用することが望ましい。上記のようなホウ素含有無灰分散剤を使用する場合、そのホウ素含有量は、組成物全量基準で、0.01質量%以上、好ましくは0.02質量%以上、より好ましくは0.025質量%以上であり、また、0.15質量%以下、好ましくは0.1質量%以下、特に好ましくは0.05質量%以下である。 In addition, when using a boron-containing ashless dispersant such as the boron-containing succinimide, the boron content is not particularly limited and is usually 0.1 to 3% by mass, but as one aspect of the present invention, Preferably 0.2% by weight or more, more preferably 0.4% by weight or more, preferably 2% by weight or less, more preferably 1.5% by weight or less, still more preferably 1.0% by weight or less, particularly preferably It is desirable to use a boron-containing ashless dispersant having a boron content of 0.6% by mass or less, preferably a boron-containing succinimide, particularly a boron-containing bissuccinimide. When using the boron-containing ashless dispersant as described above, the boron content is 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.025% by mass, based on the total amount of the composition. Further, it is 0.15% by mass or less, preferably 0.1% by mass or less, particularly preferably 0.05% by mass or less.
また、上記ホウ素含有コハク酸イミド等のホウ素含有無灰分散剤を用いる場合、そのホウ素/窒素質量比(B/N比)は特に制限はなく、通常0.05〜5であるが、本発明の1つの態様としては、B/N比が好ましくは0.1以上、より好ましくは0.2以上であり、また好ましくは1以下、より好ましくは0.7以下、さらに好ましくは0.5以下のホウ素含有無灰分散剤、好ましくはホウ素含有コハク酸イミド、特に、ホウ素含有ビスコハク酸イミドを使用することが望ましい。上記のようなホウ素含有無灰分散剤を使用する場合、そのホウ素含有量は、組成物全量基準で、0.01質量%以上、好ましくは0.02質量%以上、より好ましくは0.025質量%以上であり、また、0.15質量%以下、好ましくは0.1質量%以下、特に好ましくは0.05質量%以下である。 In addition, when using a boron-containing ashless dispersant such as the above-mentioned boron-containing succinimide, the boron / nitrogen mass ratio (B / N ratio) is not particularly limited and is usually 0.05 to 5, but it is As one aspect, the B / N ratio is preferably 0.1 or more, more preferably 0.2 or more, and preferably 1 or less, more preferably 0.7 or less, and further preferably 0.5 or less. It is desirable to use boron-containing ashless dispersants, preferably boron-containing succinimides, especially boron-containing bissuccinimides. When using the boron-containing ashless dispersant as described above, the boron content is 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.025% by mass, based on the total amount of the composition. Further, it is 0.15% by mass or less, preferably 0.1% by mass or less, particularly preferably 0.05% by mass or less.
また、ホウ素含有コハク酸イミド等のホウ素含有無灰分散剤のホウ素/窒素質量比(B/N比)に関し、もう1つの態様としては、B/N比が0.1以上、好ましくは0.2以上、好ましくは0.5未満、より好ましくは0.4以下のホウ素含有無灰分散剤、好ましくはホウ素含有コハク酸イミド、特にホウ素含有ビスコハク酸イミドを使用することが望ましい。 Further, regarding the boron / nitrogen mass ratio (B / N ratio) of the boron-containing ashless dispersant such as boron-containing succinimide, as another aspect, the B / N ratio is 0.1 or more, preferably 0.2. As described above, it is desirable to use a boron-containing ashless dispersant, preferably less than 0.5, more preferably 0.4 or less, preferably boron-containing succinimide, particularly boron-containing bissuccinimide.
なお、B/N比が1を超える場合、安定性に懸念があるだけでなく、組成物中のホウ素量が多くなりすぎ、硫酸灰分の増加とともに、排ガス後処理装置への影響が懸念されるため好ましくない。また、B/N比が0.1未満の場合、摩擦低減性能向上効果が小さく、別のホウ素化合物を併用することが望ましい。 In addition, when B / N ratio exceeds 1, not only there is a concern about stability, but the amount of boron in the composition becomes too large, and there is a concern about the influence on the exhaust gas aftertreatment device as the sulfated ash content increases. Therefore, it is not preferable. When the B / N ratio is less than 0.1, the effect of improving the friction reduction performance is small, and it is desirable to use another boron compound in combination.
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。 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.
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。 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る。ただし、その使用は、前述したように油中リン含有量は0.01〜0.5質量%であり、またリンと(A)成分に起因する硫黄のモル比が0.05〜0.8を満足する範囲内で許容される。 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-based extreme pressure agents and the like can be used. However, as described above, the use is such that the phosphorus content in the oil is 0.01 to 0.5% by mass, and the molar ratio of phosphorus and sulfur resulting from the component (A) is 0.05 to 0.8. Is allowed within a range that satisfies the above.
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の潤滑油組成物に含有させる場合の含有量は、潤滑油組成物全量基準で、消泡剤は0.0001〜0.01質量%、他の添加剤は0.01〜10質量%であることが好ましい。 When these additives are contained in the lubricating oil composition of the present invention, the content of the antifoaming agent is 0.0001 to 0.01% by mass and the other additives are 0.00% based on the total amount of the lubricating oil composition. It is preferable that it is 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、比較例1〜5]
本発明の潤滑油組成物(実施例1〜4)、比較用の潤滑油組成物(比較例1〜5)をそれぞれ調製し、JASO M333−93に基づくエンジン試験(高温酸化安定性試験)にて評価した。その結果を表1に示す。
[Examples 1 to 4, Comparative Examples 1 to 5]
Lubricating oil compositions of the present invention (Examples 1 to 4) and comparative lubricating oil compositions (Comparative Examples 1 to 5) were respectively prepared and subjected to an engine test (high temperature oxidation stability test) based on JASO M333-93. And evaluated. The results are shown in Table 1.
表1に示す結果から明らかなように、実施例1〜4の本発明の潤滑油組成物は、比較例1〜5に比べ、粘度増加、酸化増加が少なく、塩基価の維持性にも優れていることがわかる。 As is clear from the results shown in Table 1, the lubricating oil compositions of the present invention of Examples 1 to 4 have less increase in viscosity and increase in oxidation than Comparative Examples 1 to 5, and excellent base number maintenance. You can see that
本発明の潤滑油組成物は、内燃機関、自動変速機などの潤滑油として好適に用いられる。 The lubricating oil composition of the present invention is suitably used as a lubricating oil for internal combustion engines, automatic transmissions and the like.
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JP2011137140A JP5756353B2 (en) | 2011-06-21 | 2011-06-21 | Lubricating oil composition |
US14/124,333 US20140113845A1 (en) | 2011-06-21 | 2012-01-20 | Lubricating oil composition |
CN201280030596.9A CN103620006B (en) | 2011-06-21 | 2012-01-20 | Lubricating oil composition |
PCT/JP2012/051220 WO2012176484A1 (en) | 2011-06-21 | 2012-01-20 | Lubricating oil composition |
EP12802100.3A EP2725088A4 (en) | 2011-06-21 | 2012-01-20 | Lubricating oil composition |
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IT1054641B (en) | 1974-08-05 | 1981-11-30 | Mobil Oil Corp | REACTION PRODUCTS CONSTITUTED BY AMINO-ALCOHOLS AND COMPOSITIONS CONTAINING THEM |
JPS51130408A (en) | 1975-05-10 | 1976-11-12 | Karonaito Kagaku Kk | Oil-soluble lubricant additives |
JP3615267B2 (en) | 1995-04-28 | 2005-02-02 | 新日本石油株式会社 | Engine oil composition |
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 |
EP1227145B1 (en) * | 2001-01-24 | 2013-03-13 | Nippon Mitsubishi Oil Corporation | Lubricating oil compositions |
US6764982B2 (en) * | 2001-02-07 | 2004-07-20 | The Lubrizol Corporation | Lubricating oil composition |
US7790659B2 (en) * | 2002-06-28 | 2010-09-07 | Nippon Oil Corporation | Lubricating oil compositions |
JP2004059604A (en) * | 2002-07-24 | 2004-02-26 | Nippon Oil Corp | Grease composition |
US7563752B2 (en) * | 2002-08-05 | 2009-07-21 | Nippon Oil Corporation | Lubricating oil compositions |
CN100500817C (en) * | 2002-08-27 | 2009-06-17 | 新日本石油株式会社 | Lubricating oil compositions |
JP4578115B2 (en) * | 2004-02-04 | 2010-11-10 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition |
WO2008011338A2 (en) * | 2006-07-17 | 2008-01-24 | The Lubrizol Corporation | Lubricating oil composition and method of improving efficiency of emissions control system |
US7772171B2 (en) * | 2006-07-17 | 2010-08-10 | The Lubrizol Corporation | Method of lubricating an internal combustion engine and improving the efficiency of the emissions control system of the engine |
US20080039348A1 (en) * | 2006-08-09 | 2008-02-14 | Chevron Oronite Company Llc | Low phosphorus lubricating oil composition having lead corrosion control |
US20080103072A1 (en) * | 2006-11-01 | 2008-05-01 | The Lubrizol Corporation | Antiwear Containing Lubricating Composition |
JP5565999B2 (en) * | 2007-01-31 | 2014-08-06 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition |
ES2380424T3 (en) * | 2008-09-05 | 2012-05-11 | Infineum International Limited | A lubricating oil composition |
US8211840B2 (en) * | 2008-12-09 | 2012-07-03 | Afton Chemical Corporation | Additives and lubricant formulations for improved antiwear properties |
CA2772226A1 (en) * | 2009-08-18 | 2011-02-24 | The Lubrizol Corporation | Lubricating composition containing an antiwear agent |
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