JP5462682B2 - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
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- JP5462682B2 JP5462682B2 JP2010073475A JP2010073475A JP5462682B2 JP 5462682 B2 JP5462682 B2 JP 5462682B2 JP 2010073475 A JP2010073475 A JP 2010073475A JP 2010073475 A JP2010073475 A JP 2010073475A JP 5462682 B2 JP5462682 B2 JP 5462682B2
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- mass
- lubricating oil
- metal
- oil composition
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- 239000010687 lubricating oil Substances 0.000 title claims description 69
- 239000000203 mixture Substances 0.000 title claims description 69
- -1 phosphorus compound Chemical class 0.000 claims description 85
- 229910052751 metal Inorganic materials 0.000 claims description 57
- 239000002184 metal Substances 0.000 claims description 56
- 125000000217 alkyl group Chemical group 0.000 claims description 44
- 150000003839 salts Chemical class 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- 229910052698 phosphorus Inorganic materials 0.000 claims description 30
- 239000011574 phosphorus Substances 0.000 claims description 30
- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- 239000002199 base oil Substances 0.000 claims description 27
- 239000011593 sulfur Substances 0.000 claims description 24
- 230000001050 lubricating effect Effects 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 21
- 229910052783 alkali metal Inorganic materials 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 21
- 125000003342 alkenyl group Chemical group 0.000 description 16
- 150000001340 alkali metals Chemical class 0.000 description 15
- 239000003599 detergent Substances 0.000 description 15
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- 150000001342 alkaline earth metals Chemical class 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000004678 hydrides Chemical class 0.000 description 8
- 229960002317 succinimide Drugs 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 230000002265 prevention Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229960001860 salicylate Drugs 0.000 description 5
- 150000003751 zinc Chemical class 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000003981 vehicle Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-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
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000003277 amino group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 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
- 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010725 compressor oil Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical group CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 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
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 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
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000000746 purification Methods 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
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 150000003460 sulfonic acids Chemical class 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
- 239000010723 turbine oil Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RAADJDWNEAXLBL-UHFFFAOYSA-N 1,2-di(nonyl)naphthalene Chemical compound C1=CC=CC2=C(CCCCCCCCC)C(CCCCCCCCC)=CC=C21 RAADJDWNEAXLBL-UHFFFAOYSA-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
- 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
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- 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
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
- QHPKIUDQDCWRKO-UHFFFAOYSA-N 2,6-ditert-butyl-4-[2-(3,5-ditert-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 QHPKIUDQDCWRKO-UHFFFAOYSA-N 0.000 description 1
- VRMHHVOBVLFRFB-UHFFFAOYSA-N 2-(2-cyanoethylsulfanylmethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CSCCC#N VRMHHVOBVLFRFB-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- KSHRPPASRGMRPU-UHFFFAOYSA-N 2-chlorylphenol Chemical compound OC1=CC=CC=C1Cl(=O)=O KSHRPPASRGMRPU-UHFFFAOYSA-N 0.000 description 1
- LLEFDCACDRGBKD-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;nonanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCCC(O)=O LLEFDCACDRGBKD-UHFFFAOYSA-N 0.000 description 1
- CWTQBXKJKDAOSQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;octanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCC(O)=O CWTQBXKJKDAOSQ-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N 2-methylbut-2-enoic acid Chemical compound CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- WDNQRCVBPNOTNV-UHFFFAOYSA-N dinonylnaphthylsulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 WDNQRCVBPNOTNV-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- FVBSDVQDRFRKRF-UHFFFAOYSA-N ditridecyl pentanedioate Chemical compound CCCCCCCCCCCCCOC(=O)CCCC(=O)OCCCCCCCCCCCCC FVBSDVQDRFRKRF-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 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 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 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 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
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- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 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 1
- 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 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 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 1
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- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 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 1
- 239000001384 succinic acid 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
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Lubricants (AREA)
Description
本発明は潤滑油組成物に関する。 The present invention relates to a lubricating oil composition.
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ている。これらの用途における潤滑油のうち特に内燃機関用潤滑油（「エンジン油」ともいう。）には、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ようになってきている。 Conventionally, lubricating oil has been used for internal combustion engines, automatic transmissions, greases, and the like in order to make their operations smooth. Among these lubricating oils, the lubricating oil for internal combustion engines (also referred to as “engine oil”) has high performance due to the high performance, high output, and severe operating conditions of the internal combustion engine. It is becoming required.
従来の内燃機関用潤滑油においては、上述の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。中でもジアルキルジチオリン酸亜鉛（ＺｎＤＴＰ）は、摩耗防止剤又は酸化防止剤としての機能を有するため、内燃機関用潤滑油には不可欠な添加剤として使用されている（例えば、下記特許文献１を参照。）。 In the conventional lubricating oil for internal combustion engines, various additives such as an antiwear agent, a metallic detergent, an ashless dispersant, and an antioxidant are blended in order to satisfy the above-mentioned required performance. Among them, zinc dialkyldithiophosphate (ZnDTP) has a function as an antiwear agent or an antioxidant, and is therefore used as an indispensable additive for lubricating oil for internal combustion engines (for example, see Patent Document 1 below). ).
また、省燃費エンジン油では、摩擦損失を低減させ、燃費を向上させるため、モリブデンジチオカーバメートやモリブデンジチオホスフェートなどの金属及び硫黄を含有する有機モリブデン化合物を添加することが一般的に行われてきた。そして摩擦低減効果を発揮させるためには、ジアルキルジチオリン酸亜鉛（ＺｎＤＴＰ）などの金属及び硫黄を含有する化合物をある程度多量に併用し、摺動面に二硫化モリブデン皮膜を形成させる手法が一般的に行われてきた。このため、従来型の省燃費エンジン油は硫黄分の比較的多い配合となり、性能を維持しつつ低硫黄化するのは困難であるとされてきた。この問題を解決するため、ＺｎＤＴＰに代わってジアルキルリン酸亜鉛（ＺＰ）を配合することにより、優れた摩擦低減性を維持しながら低硫黄化することが提案されたが、摩耗防止性に問題があることが判明した。 Further, in fuel-saving engine oils, in order to reduce friction loss and improve fuel consumption, it has been generally performed to add organic molybdenum compounds containing metals and sulfur such as molybdenum dithiocarbamate and molybdenum dithiophosphate. . In order to exert the friction reducing effect, a method of forming a molybdenum disulfide film on the sliding surface by using a certain amount of a compound containing sulfur and a metal such as zinc dialkyldithiophosphate (ZnDTP) is generally used. Has been done. For this reason, the conventional fuel-saving engine oil has a relatively high sulfur content, and it has been difficult to reduce the sulfur while maintaining the performance. In order to solve this problem, it was proposed that zinc dialkyl phosphate (ZP) is used in place of ZnDTP to reduce sulfur while maintaining excellent friction reduction, but there is a problem with wear prevention. It turned out to be.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、摩耗防止性を維持しながら、低硫黄化と優れた摩擦低減性を両立させることが可能な潤滑油組成物を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and provides a lubricating oil composition capable of achieving both low sulfur and excellent friction reduction while maintaining wear prevention. For the purpose.
本発明者は、上記目的を達成すべく鋭意検討を重ねた結果、ＺｎＤＴＰに代わって、特定のジアルキルモノチオリン酸亜鉛を使用することにより、ＺｎＤＴＰ単独添加油の摩耗防止性を維持しながら、低硫黄化と優れた摩擦低減性を示すことを見出し、以下の本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor uses a specific zinc dialkylmonothiophosphate in place of ZnDTP, thereby maintaining the anti-wear property of the ZnDTP single additive oil while reducing the wear resistance. The inventors have found that it exhibits sulfurization and excellent friction reduction properties, and has completed the following present invention.
第１の本発明は、潤滑油基油、および、下記一般式（１）で表されるリン化合物の金属塩を含有し、該リン化合物の金属塩が、潤滑油組成物全量を基準として、リン元素換算で０．００５〜０．１２質量％含有することを特徴とする潤滑油組成物である。 1st this invention contains lubricating oil base oil and the metal salt of the phosphorus compound represented by following General formula (1), The metal salt of this phosphorus compound is based on lubricating oil composition whole quantity, It is a lubricating oil composition characterized by containing 0.005 to 0.12 mass% in terms of phosphorus element.
第１の本発明において、リン化合物の金属塩における前記直鎖型アルキル基の炭素数は６〜９であることが好ましい。 In 1st this invention, it is preferable that carbon number of the said linear alkyl group in the metal salt of a phosphorus compound is 6-9.
本発明の潤滑油組成物によれば、ＺｎＤＴＰ単独添加油の摩耗防止性を維持しながら、低硫黄化と優れた摩擦低減性を示すことが可能となる。 According to the lubricating oil composition of the present invention, it is possible to exhibit low sulfur and excellent friction reduction properties while maintaining the wear prevention properties of the ZnDTP single additive oil.
以下、本発明の好適な実施形態について詳細に説明する。
＜潤滑油組成物＞
本発明の潤滑油組成物は、潤滑油基油、および、所定のリン化合物金属塩を含有してなる。
Hereinafter, preferred embodiments of the present invention will be described in detail.
<Lubricating oil composition>
The lubricating oil composition of the present invention comprises a lubricating base oil and a predetermined phosphorus compound metal salt.
（潤滑油基油）
本発明の潤滑油組成物に含まれる潤滑油基油としては、特に制限されず、通常の潤滑油に使用されるものが使用できる。具体的には、鉱油系潤滑油基油、合成油系潤滑油基油又はこれらの中から選ばれる２種以上の潤滑油基油を任意の割合で混合した混合物等が使用できる。
(Lubricant base oil)
The lubricating base oil contained in the lubricating oil composition of the present invention is not particularly limited, and those used for ordinary lubricating oils can be used. Specifically, a mineral oil base oil, a synthetic oil base oil, or a mixture of two or more kinds of lubricant base oils selected from these can be used.
鉱油系潤滑油基油としては、具体的には、原油を常圧蒸留して得られる常圧残油を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、溶剤脱ろう、水素化精製等の処理を１つ以上行って精製したもの、あるいはワックス異性化鉱油、ＧＴＬワックス（ガストゥリキッドワックス）を異性化する手法で製造される基油等が例示できる。 Specifically, as the mineral base oil, the lube oil fraction obtained by distilling the atmospheric residue obtained by atmospheric distillation of the crude oil is subjected to solvent removal, solvent extraction, and hydrogenation. Examples include those refined by one or more treatments such as decomposition, solvent dewaxing, hydrorefining, etc., or base oils produced by isomerizing wax isomerized mineral oil, GTL wax (gas-tuly wax) it can.
合成油系潤滑油としては、具体的には、ポリブテン又はその水素化物；１−オクテンオリゴマー、１−デセンオリゴマー等のポリα−オレフィン又はその水素化物；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のジエステル；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のポリオールエステル；アルキルナフタレン、アルキルベンゼン等の芳香族系合成油又はこれらの混合物等が例示できる。 Specific examples of synthetic lubricating oils include polybutene or hydrides thereof; polyα-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; ditridecyl glutarate, di-2-ethylhexyl adipate Diesters such as diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate; Examples thereof include aromatic synthetic oils such as alkylnaphthalene and alkylbenzene, or mixtures thereof.
潤滑油基油の動粘度は特に制限されないが、潤滑油基油の１００℃における動粘度は、好ましくは５０ｍｍ２／ｓ以下、より好ましくは４０ｍｍ２／ｓ以下、更に好ましくは２０ｍｍ２／ｓ以下、特に好ましくは１０ｍｍ２／ｓ以下である。潤滑油基油の１００℃における動粘度が５０ｍｍ２／ｓを超えると、低温粘度特性が不十分となる傾向にある。また、潤滑油基油の１００℃における動粘度は、好ましくは１ｍｍ２／ｓ以上、より好ましくは２ｍｍ２／ｓ以上である。潤滑油基油の１００℃における動粘度が１ｍｍ２／ｓ未満の場合には、潤滑部位における油膜形成が不十分となって潤滑性が低下する傾向にあり、また、潤滑油基油の蒸発損失量が増加する傾向にある。ここでいう１００℃における動粘度とは、ＪＩＳ Ｋ２２８３に規定される１００℃での動粘度を示す。 The kinematic viscosity of the lubricating base oil is not particularly limited, but the kinematic viscosity at 100 ° C. of the lubricating base oil is preferably 50 mm 2 / s or less, more preferably 40 mm 2 / s or less, and even more preferably 20 mm 2 / s or less. Particularly preferably, it is 10 mm 2 / s or less. When the kinematic viscosity at 100 ° C. of the lubricating base oil exceeds 50 mm 2 / s, the low-temperature viscosity characteristics tend to be insufficient. The kinematic viscosity at 100 ° C. of the lubricating base oil is preferably 1 mm 2 / s or more, more preferably 2 mm 2 / s or more. When the kinematic viscosity at 100 ° C. of the lubricating base oil is less than 1 mm 2 / s, oil film formation at the lubrication site tends to be insufficient and the lubricity tends to decrease, and the evaporation loss of the lubricating base oil The amount tends to increase. The kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. defined in JIS K2283.
また、潤滑油基油の粘度指数は特に制限されないが、低温粘度特性の観点から、８０以上であることが好ましい。また、低温から高温までの幅広い温度領域において優れた粘度特性が得られる観点から、潤滑油基油の粘度指数は１００以上であることがより好ましく、１１０以上であることが更に好ましく、特に１２０以上であることが好ましい。 The viscosity index of the lubricating base oil is not particularly limited, but is preferably 80 or more from the viewpoint of low temperature viscosity characteristics. Further, from the viewpoint of obtaining excellent viscosity characteristics in a wide temperature range from low temperature to high temperature, the viscosity index of the lubricating base oil is more preferably 100 or more, further preferably 110 or more, particularly 120 or more. It is preferable that
また、潤滑油基油の硫黄分含有量は特に制限はないが、０．１質量％以下であることが好ましく、０．０１質量％以下であることがさらに好ましく、０．００５質量％以下、特に実質的に含有しない（０．００１質量％以下）ものが好ましい。なお、本発明でいう「硫黄分含有量」とは、ＪＩＳ Ｋ２５４１−４「放射線式励起法」（通常、０．０１〜５質量％の範囲）又はＪＩＳ Ｋ２５４１−５「ボンベ式質量法、附属書（規定）、誘導結合プラズマ発光法」（通常、０．０５質量％以上）に準拠して測定された値を意味する。 The sulfur content of the lubricating base oil is not particularly limited, but is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, 0.005% by mass or less, Particularly preferred are those which do not substantially contain (0.001% by mass or less). The “sulfur content” as used in the present invention is JIS K2541-4 “radiation type excitation method” (usually in the range of 0.01 to 5% by mass) or JIS K2541-5 “bomb type mass method, attached. This is a value measured in accordance with the “Document (normative), inductively coupled plasma emission method” (usually 0.05 mass% or more).
また、潤滑油基油の全芳香族含有量は、特に制限はないが、好ましくは３０質量％以下、より好ましくは１５質量％以下、さらに好ましくは５質量％以下、特に好ましくは２質量％以下である。潤滑油基油の全芳香族含有量が３０質量％を超えると、酸化安定性が不十分となる傾向にある。なお、本発明でいう「全芳香族含有量」とは、ＡＳＴＭ Ｄ２５４９に準拠して測定した芳香族留分（ａｒｏｍａｔｉｃ ｆｒａｃｔｉｏｎ）含有量を意味する。通常この芳香族留分には、アルキルベンゼン、アルキルナフタレンの他、アントラセン、フェナントレン、及びこれらのアルキル化物、ベンゼン環が四環以上縮合した化合物、又はピリジン類、キノリン類、フェノール類、ナフトール類等のヘテロ芳香族を有する化合物等が含まれる。 The total aromatic content of the lubricating base oil is not particularly limited, but is preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 5% by mass or less, and particularly preferably 2% by mass or less. It is. When the total aromatic content of the lubricating base oil exceeds 30% by mass, the oxidation stability tends to be insufficient. The “total aromatic content” as used in the present invention means an aromatic fraction content measured in accordance with ASTM D2549. Usually, this aromatic fraction includes alkylbenzene, alkylnaphthalene, anthracene, phenanthrene, and alkylated products thereof, compounds in which four or more benzene rings are condensed, or pyridines, quinolines, phenols, naphthols, etc. Compounds having heteroaromatics and the like are included.
（リン化合物の金属塩）
本発明の潤滑油組成物は、上記の潤滑油基油に加えて、下記一般式（１）で表されるリン化合物の金属塩を含有する。
(Metal salt of phosphorus compound)
The lubricating oil composition of the present invention contains a metal salt of a phosphorus compound represented by the following general formula (1) in addition to the above lubricating base oil.
上記一般式（１）中、Ｒ１〜Ｒ４は炭素数３〜３０の直鎖型アルキル基であって、Ｒ１〜Ｒ４は互いに同一でも異なっていてもよく、Ｘ１〜Ｘ４は硫黄または酸素原子であって、Ｘ１〜Ｘ４のうちの３個は酸素原子、１個は硫黄原子、Ｙは２価以上の金属原子である。 In the general formula (1), R 1 to R 4 are linear alkyl groups having 3 to 30 carbon atoms, R 1 to R 4 may be the same as or different from each other, and X 1 to X 4 are It is a sulfur or oxygen atom, 3 of X 1 to X 4 are oxygen atoms, 1 is a sulfur atom, and Y is a divalent or higher metal atom.
上記一般式（１）中、Ｒ１〜Ｒ４で表される炭素数３〜３０の直鎖型アルキル基としては、例えば、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−ペンタデシル基、ｎ−ヘキサデシル基、ｎ−ヘプタデシル基、ｎ−オクタデシル基等を挙げることができる。 In the general formula (1), examples of the linear alkyl group having 3 to 30 carbon atoms represented by R 1 to R 4, for example, n- propyl, n- butyl, n- pentyl, n- Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n- A hexadecyl group, n-heptadecyl group, n-octadecyl group, etc. can be mentioned.
Ｒ１〜Ｒ４は、炭素数４〜１４の直鎖型アルキル基であることが好ましく、より好ましくは炭素数５〜１２の直鎖型アルキル基、更に好ましくは炭素数６〜９の直鎖型アルキル基である。 R 1 to R 4 are preferably a linear alkyl group having 4 to 14 carbon atoms, more preferably a linear alkyl group having 5 to 12 carbon atoms, and even more preferably a linear alkyl group having 6 to 9 carbon atoms. Type alkyl group.
Ｘ１〜Ｘ４は硫黄または酸素原子であるが、Ｘ１〜Ｘ４のうちいずれか１個が硫黄原子、残りの３個が酸素原子である限り、Ｘ１〜Ｘ４のうちどれが硫黄原子であっても構わない。 Although X 1 to X 4 is sulfur or oxygen atom, or one sulfur atom in X 1 to X 4, as long as the remaining three are oxygen atoms, which of the X 1 to X 4 Sulfur It may be an atom.
上記金属塩における金属としては、具体的には、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等が挙げられる。これらの中では、カルシウム、マグネシウム等のアルカリ土類金属、モリブデン及び亜鉛が好ましく、亜鉛が特に好ましい。 Specific examples of the metal in the metal salt include alkaline earth metals such as calcium, magnesium and barium, and heavy metals such as zinc, copper, iron, lead, nickel, silver, manganese and molybdenum. Among these, alkaline earth metals such as calcium and magnesium, molybdenum and zinc are preferable, and zinc is particularly preferable.
本発明において、上記一般式（１）で表されるリン化合物の金属塩は、１種を単独で用いてもよく、また、２種以上を組み合わせて用いてもよい。 In the present invention, the metal salt of the phosphorus compound represented by the general formula (1) may be used alone or in combination of two or more.
本発明の潤滑油組成物において、一般式（１）で表されるリン化合物の金属塩の含有量は、潤滑油組成物全量を基準として、リン元素換算で０．００５質量％以上０．１２質量％以下であることが必要であり、好ましくは０．０１質量％以上０．１１５質量％以下、より好ましくは０．０３質量％以上０．１１質量％以下、更に好ましくは０．０５質量％以上０．１０５質量％以下である。なお、一般式（１）で表されるリン化合物の金属塩の含有量が前記下限値未満であると耐摩耗性が不十分となり、また、前記上限値を超えると排気ガス浄化触媒の被毒を起こす可能性があるため好ましくない。 In the lubricating oil composition of the present invention, the content of the metal salt of the phosphorus compound represented by the general formula (1) is 0.005% by mass or more and 0.12 in terms of phosphorus based on the total amount of the lubricating oil composition. It is necessary to be not more than mass%, preferably not less than 0.01 mass% and not more than 0.115 mass%, more preferably not less than 0.03 mass% and not more than 0.11 mass%, still more preferably 0.05 mass% The content is 0.105% by mass or less. In addition, if the content of the metal salt of the phosphorus compound represented by the general formula (1) is less than the lower limit, the wear resistance is insufficient, and if the content exceeds the upper limit, the exhaust gas purification catalyst is poisoned. This is not preferable because it may cause
（各種添加剤）
本発明の潤滑油組成物は、潤滑油基油及び一般式（１）で表されるリン化合物の金属塩に加えて、後述する各種添加剤を含有することができる。
(Various additives)
The lubricating oil composition of the present invention can contain various additives described below in addition to the lubricating base oil and the metal salt of the phosphorus compound represented by the general formula (1).
（その他のリン化合物の金属塩）
本発明の潤滑油組成物は、一般式（１）で表されるリン化合物の金属塩以外に、式（２）および式（３）で示すリン化合物の金属塩を含有することができる。
(Metal salts of other phosphorus compounds)
The lubricating oil composition of the present invention can contain a metal salt of a phosphorus compound represented by the formula (2) and the formula (3) in addition to the metal salt of the phosphorus compound represented by the general formula (1).
上記一般式（２）中、Ｒ５は炭素数１〜３０のアルキル基を示し、Ｒ６及びＲ７は互いに同一でも異なっていてもよく、それぞれ水素原子、炭素数１〜３０のアルキル基を示し、ｍは０又は１を示す。］ In the general formula (2), R 5 represents an alkyl group having 1 to 30 carbon atoms, R 6 and R 7 may be the same as or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. M represents 0 or 1; ]
一般式（３）中、Ｒ８は炭素数１〜３０のアルキル基を示し、Ｒ９及びＲ１０は互いに同一でも異なっていてもよく、水素原子、炭素数１〜３０のアルキル基を示し、ｎは０又は１を示す。 In General Formula (3), R 8 represents an alkyl group having 1 to 30 carbon atoms, R 9 and R 10 may be the same as or different from each other, represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, n represents 0 or 1.
上記一般式（２）および（３）中、Ｒ５〜Ｒ１０は炭素数１〜３０のアルキ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、更に好ましくは炭素数４〜１２のアルキル基である。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。 In the general formulas (2) and (3), R 5 to R 10 are preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 18 carbon atoms, and still more preferably 4 carbon atoms. ˜12 alkyl groups. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl And alkyl groups such as an octadecyl group (these alkyl groups may be linear or branched).
上記金属塩としては、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塩等が挙げられる。これらの中ではカルシウム、マグネシウム等のアルカリ土類金属、モリブデン及び亜鉛が好ましく、亜鉛が特に好ましい。 Specific examples of the metal salt 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, manganese and molybdenum. And heavy metal salts. Among these, alkaline earth metals such as calcium and magnesium, molybdenum and zinc are preferable, and zinc is particularly preferable.
なお、上記一般式（２）および（３）のリン化合物の金属塩は、金属の価数あるいはリン化合物のＯＨ基の数に応じてその構造が異なり、したがって、一般式（２）および（３）のリン化合物の金属塩の構造については何ら限定されない。例えば、酸化亜鉛１ｍｏｌとリン酸ジエステル（ＯＨ基が１つの化合物）２ｍｏｌを反応させた場合、下記式（４）で表わされる構造の化合物が主成分として得られると考えられるが、ポリマー化した分子も存在していると考えられる。 The metal salts of the phosphorus compounds of the general formulas (2) and (3) have different structures depending on the valence of the metal or the number of OH groups of the phosphorus compound, and therefore the general formulas (2) and (3) The structure of the metal salt of the phosphorus compound is not limited at all. For example, when 1 mol of zinc oxide and 2 mol of phosphoric diester (compound having one OH group) are reacted, a compound having a structure represented by the following formula (4) is considered to be obtained as a main component. Is also considered to exist.
上記一般式（４）中、Ｒ１１およびＲ１２は、炭素数１〜３０のアルキル基であり、ｎは０又は１である。 In the general formula (4), R 11 and R 12 are alkyl groups having 1 to 30 carbon atoms, and n is 0 or 1.
また、例えば、酸化亜鉛１ｍｏｌとリン酸モノエステル（ＯＨ基が２つの化合物）１ｍｏｌとを反応させた場合、下記一般式（５）で表わされる構造の化合物が主成分として得られると考えられるが、ポリマー化した分子も存在していると考えられる。 For example, when 1 mol of zinc oxide and 1 mol of phosphoric acid monoester (a compound having two OH groups) are reacted, a compound having a structure represented by the following general formula (5) is considered to be obtained as a main component. It is considered that polymerized molecules exist.
上記一般式（５）中、Ｒ１３は、炭素数１〜３０のアルキル基であり、ｎは０又は１である。 In the general formula (5), R 13 is an alkyl group having 1 to 30 carbon atoms, and n is 0 or 1.
本発明において、上記一般式（２）又は（３）で表されるリン化合物の金属塩は、１種を単独で用いてもよく、また、２種以上を組み合わせて用いてもよい。 In the present invention, the metal salt of the phosphorus compound represented by the general formula (2) or (3) may be used singly or in combination of two or more.
一般式（２）又は（３）で表されるリン化合物の金属塩の含有量は、組成物全量を基準として、リン元素換算で０．０５質量％以下であることが好ましく、０．０４質量％以下であることがより好ましく、０．０３質量％以下であることが更に好ましい。 The content of the metal salt of the phosphorus compound represented by the general formula (2) or (3) is preferably 0.05% by mass or less in terms of phosphorus element based on the total amount of the composition, and 0.04% by mass. % Or less is more preferable, and 0.03% by mass or less is still more preferable.
本発明の潤滑油組成物中の全リン濃度は、潤滑油組成物全量を基準として、リン元素換算で０．００５質量％以上０．１２質量％以下であることが好ましく、０．０３質量％以上０．１１質量％以下であることがより好ましく、０．０５質量％以上０．１０５質量％以下であることがより好ましい。潤滑油組成物中のリン濃度が前記上限値を超えると、排気ガス浄化触媒の被毒を起こすおそれがある。 The total phosphorus concentration in the lubricating oil composition of the present invention is preferably 0.005% by mass or more and 0.12% by mass or less in terms of phosphorus element, based on the total amount of the lubricating oil composition, and 0.03% by mass. The content is more preferably 0.11% by mass or less and more preferably 0.05% by mass or more and 0.105% by mass or less. If the phosphorus concentration in the lubricating oil composition exceeds the upper limit, the exhaust gas purification catalyst may be poisoned.
（金属系清浄剤）
本発明の潤滑油組成物は、その酸中和特性、高温清浄性及び摩耗防止性を更に向上させるために、金属系清浄剤を更に含有することが好ましい。
(Metal-based detergent)
The lubricating oil composition of the present invention preferably further contains a metallic detergent in order to further improve its acid neutralization properties, high temperature cleanability and wear resistance.
金属系清浄剤としては、例えば、アルカリ金属スルホネート又はアルカリ土類金属スルホネート、アルカリ金属フェネート又はアルカリ土類金属フェネート、アルカリ金属サリシレート又はアルカリ土類金属サリシレート、アルカリ金属ホスホネート又はアルカリ土類金属ホスホネート、あるいはこれらの混合物等が挙げられる。 Examples of the metal detergent include alkali metal sulfonate or alkaline earth metal sulfonate, alkali metal phenate or alkaline earth metal phenate, alkali metal salicylate or alkaline earth metal salicylate, alkali metal phosphonate or alkaline earth metal phosphonate, or These mixtures etc. are mentioned.
アルカリ金属又はアルカリ土類金属スルホネートとしては、例えば、分子量１００〜１５００、好ましくは２００〜７００のアルキル芳香族化合物をスルホン化することによって得られるアルキル芳香族スルホン酸のアルカリ金属塩又はアルカリ土類金属塩、特にマグネシウム塩及び／又はカルシウム塩が好ましく用いられ、アルキル芳香族スルホン酸としては、具体的にはいわゆる石油スルホン酸や合成スルホン酸等が挙げられる。 Examples of the alkali metal or alkaline earth metal sulfonate include an alkali metal salt or alkaline earth metal of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 100 to 1500, preferably 200 to 700. Salts, particularly magnesium salts and / or calcium salts are preferably used, and specific examples of alkyl aromatic sulfonic acids include so-called petroleum sulfonic acids and synthetic sulfonic acids.
石油スルホン酸としては、一般に鉱油の潤滑油留分のアルキル芳香族化合物をスルホン化したものやホワイトオイル製造時に副生する、いわゆるマホガニー酸等が用いられる。また合成スルホン酸としては、例えば洗剤の原料となるアルキルベンゼン製造プラントから副生したり、ポリオレフィンをベンゼンにアルキル化することにより得られる、直鎖状や分枝状のアルキル基を有するアルキルベンゼンを原料とし、これをスルホン化したもの、あるいはジノニルナフタレンをスルホン化したもの等が用いられる。またこれらアルキル芳香族化合物をスルホン化する際のスルホン化剤としては特に制限はないが、通常発煙硫酸や硫酸が用いられる。 As the petroleum sulfonic acid, those obtained by sulfonating an alkyl aromatic compound of a lubricating oil fraction of mineral oil or so-called mahoganic acid which is produced as a by-product when white oil is produced is used. As the synthetic sulfonic acid, for example, an alkylbenzene having a linear or branched alkyl group obtained as a by-product from an alkylbenzene production plant that is a raw material for detergents or by alkylating polyolefin with benzene is used as a raw material. , Sulfonated ones thereof, sulfonated ones of dinonylnaphthalene, and the like are used. The sulfonating agent for sulfonating these alkyl aromatic compounds is not particularly limited, but usually fuming sulfuric acid or sulfuric acid is used.
アルカリ金属又はアルカリ土類金属フェネートとしては、より具体的には、炭素数４〜３０、好ましくは６〜１８の直鎖状又は分枝状のアルキル基を少なくとも１個有するアルキルフェノール、このアルキルフェノールと元素硫黄を反応させて得られるアルキルフェノールサルファイド又はこのアルキルフェノールとホルムアルデヒドを反応させて得られるアルキルフェノールのマンニッヒ反応生成物のアルカリ金属塩又はアルカリ土類金属塩、特にマグネシウム塩及び／又はカルシウム塩等が好ましく用いられる。 More specifically, the alkali metal or alkaline earth metal phenate is an alkylphenol having at least one linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, and the alkylphenol and element. Alkyl metal salts or alkaline earth metal salts, especially magnesium salts and / or calcium salts of Mannich reaction products of alkylphenols obtained by reacting sulfur with alkylphenols obtained by reacting this alkylphenol with formaldehyde are preferably used. .
アルカリ金属又はアルカリ土類金属サリシレートとしては、より具体的には、炭素数４〜３０、好ましくは６〜１８の直鎖状又は分枝状のアルキル基を少なくとも１個有するアルキルサリチル酸のアルカリ金属塩又はアルカリ土類金属塩、特にマグネシウム塩及び／又はカルシウム塩等が好ましく用いられる。 More specifically, the alkali metal or alkaline earth metal salicylate is an alkali metal salt of an alkyl salicylic acid having at least one linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms. Alternatively, alkaline earth metal salts, particularly magnesium salts and / or calcium salts are preferably used.
また、アルカリ金属又はアルカリ土類金属スルホネート、アルカリ金属又はアルカリ土類金属フェネート及びアルカリ金属又はアルカリ土類金属サリシレートには、アルキル芳香族スルホン酸、アルキルフェノール、アルキルフェノールサルファイド、アルキルフェノールのマンニッヒ反応生成物、アルキルサリチル酸等を、直接、アルカリ金属又はアルカリ土類金属の酸化物や水酸化物等の金属塩基と反応させたり、又は一度ナトリウム塩やカリウム塩等のアルカリ金属塩としてからアルカリ土類金属塩と置換させること等により得られる中性塩（正塩）だけでなく、さらにこれら中性塩（正塩）と過剰のアルカリ金属又はアルカリ土類金属塩やアルカリ金属又はアルカリ土類金属塩基（アルカリ金属又はアルカリ土類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や、炭酸ガス又はホウ酸若しくはホウ酸塩の存在下で中性塩（正塩）をアルカリ金属又はアルカリ土類金属の水酸化物等の塩基と反応させることにより得られる過塩基性塩（超塩基性塩）も含まれる。 Alkali metal or alkaline earth metal sulfonate, alkali metal or alkaline earth metal phenate and alkali metal or alkaline earth metal salicylate include alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, Mannich reaction product of alkylphenol, alkyl Salicylic acid or the like is directly reacted with a metal base such as an oxide or hydroxide of an alkali metal or alkaline earth metal, or once converted to an alkali metal salt such as a sodium salt or potassium salt and then replaced with an alkaline earth metal salt In addition to the neutral salt (normal salt) obtained by, etc., these neutral salt (normal salt) and excess alkali metal or alkaline earth metal salt or alkali metal or alkaline earth metal base (alkali metal or Alkali earth metal hydroxides and acids Product) heated in the presence of water, or neutral salt (normal salt) of alkali metal or alkaline earth metal in the presence of carbon dioxide, boric acid or borate. An overbased salt (superbasic salt) obtained by reacting with a base such as a product is also included.
また、金属系清浄剤は通常、軽質潤滑油基油等で希釈された状態で市販されており、また、入手可能であるが、一般的に、その金属含有量が１．０〜２０質量％、好ましくは２．０〜１６質量％のものを用いるのが望ましい。また金属系清浄剤の塩基価は、通常０〜５００ｍｇＫＯＨ／ｇ、好ましくは２０〜４５０ｍｇＫＯＨ／ｇである。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。 In addition, metal detergents are usually marketed in a state diluted with a light lubricating base oil or the like, and are available, but generally the metal content is 1.0 to 20% by mass. It is desirable to use 2.0 to 16% by mass. The base number of the metal detergent is usually 0 to 500 mgKOH / g, preferably 20 to 450 mgKOH / g. The base number referred to here is 7. JIS K2501 “Petroleum products and lubricating oils-Neutralization number test method”. This means the base value by the perchloric acid method measured according to
本発明においては、アルカリ金属又はアルカリ土類金属のスルホネート、フェネート、サリシレート等から選ばれる１種を単独で又は２種以上併用して使用することができる。金属系清浄剤としては、アルカリ金属又はアルカリ土類金属サリシレートが低灰化による摩擦低減効果が大きい点、ロングドレイン性により優れる点で特に好ましい。 In the present invention, one selected from sulfonates, phenates, salicylates and the like of alkali metals or alkaline earth metals can be used alone or in combination of two or more. As the metal detergent, alkali metal or alkaline earth metal salicylate is particularly preferable in that it has a large friction reducing effect due to low ashing and is excellent in long drain properties.
金属系清浄剤の金属比は特に制限されず、通常２０以下のものが使用できるが、摩擦低減効果及びロングドレイン性をより向上させることができる点から、好ましくは金属比が１〜１０の金属系清浄剤から選ばれる１種又は２種以上からなることが好ましい。なお、ここでいう金属比とは、金属系清浄剤における金属元素の価数×金属元素含有量（ｍｏｌ％）／せっけん基含有量（ｍｏｌ％）で表され、金属元素とは、カルシウム、マグネシウム等、せっけん基とはスルホン酸基、サリチル酸基等を意味する。 The metal ratio of the metal-based detergent is not particularly limited, and usually 20 or less can be used. However, a metal having a metal ratio of 1 to 10 is preferable because it can further improve the friction reduction effect and the long drain property. It is preferable that it consists of 1 type (s) or 2 or more types chosen from a type | system | group detergent. The metal ratio here is represented by the valence of the metal element in the metal detergent × the metal element content (mol%) / the soap group content (mol%). The metal elements are calcium and magnesium. Etc., a soap group means a sulfonic acid group, a salicylic acid group, and the like.
本発明の潤滑油組成物における金属系清浄剤の含有量の上限値は特に制限はなく、通常、組成物全量を基準として、金属元素換算量で０．５質量％以下であるが、組成物全量を基準として、組成物の硫酸灰分が１．０質量％以下となるようにその他の添加剤と併せて調整することが好ましい。そのような観点から、金属系清浄剤の含有量は、組成物全量を基準として、金属元素換算量で、好ましくは０．３質量％以下、更に好ましくは０．２３質量％以下である。また、金属系清浄剤の含有量は、好ましくは０．０１質量％以上、より好ましくは０．０２質量％以上、更に好ましくは０．１５質量％以上である。金属系清浄剤の含有量が０．０１質量％未満の場合、高温清浄性や酸化安定性、塩基価維持性などのロングドレイン性能が得られにくくなるため好ましくない。 The upper limit of the content of the metallic detergent in the lubricating oil composition of the present invention is not particularly limited, and is usually 0.5% by mass or less in terms of metal element based on the total amount of the composition. It is preferable to adjust it together with other additives so that the sulfated ash content of the composition is 1.0% by mass or less based on the total amount. From such a viewpoint, the content of the metal detergent is preferably 0.3% by mass or less, more preferably 0.23% by mass or less, in terms of metal element, based on the total amount of the composition. Further, the content of the metal detergent is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and further preferably 0.15% by mass or more. When the content of the metal detergent is less than 0.01% by mass, it is difficult to obtain long drain performance such as high temperature cleanability, oxidation stability, and base number maintenance, which is not preferable.
（無灰分散剤）
また、本発明の潤滑油組成物は、無灰分散剤を更に含有することが好ましい。無灰分散剤としては、潤滑油に用いられる任意の無灰分散剤を用いることができるが、例えば、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。
(Ashless dispersant)
The lubricating oil composition of the present invention preferably further contains an ashless dispersant. As the ashless dispersant, any ashless dispersant used in lubricating oils can be used. For example, at least one linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms is included in the molecule. Examples thereof include nitrogen-containing compounds or derivatives thereof, or modified products of alkenyl succinimide. One type or two or more types arbitrarily selected from these can be blended.
このアルキル基又はアルケニル基の炭素数は４０〜４００、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し、一方、アルキル基又はアルケニル基の炭素数が４００を越える場合は、潤滑油組成物の低温流動性が悪化するため、それぞれ好ましくない。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 alkyl group or alkenyl group has 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms. 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 decreases. On the other hand, when the carbon number of the alkyl group or alkenyl group exceeds 400, the low temperature of the lubricating oil composition Since fluidity | liquidity deteriorates, it is unpreferable respectively. 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.
無灰分散剤の具体的としては、例えば、下記の化合物が挙げられる。これらの中から選ばれる１種又は２種以上の化合物を用いることができる。
（Ｉ）炭素数４０〜４００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個有するコハク酸イミド、あるいはその誘導体
（ＩＩ）炭素数４０〜４００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個有するベンジルアミン、あるいはその誘導体
（ＩＩＩ）炭素数４０〜４００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個有するポリアミン、あるいはその誘導体。
Specific examples of the ashless dispersant include the following compounds. One or more compounds selected from these can be used.
(I) Succinimide having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof (II) At least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule A benzylamine having a derivative thereof (III) A polyamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof.
上記（Ｉ）コハク酸イミドとしては、より具体的には、下記一般式（６）又は（７）で示される化合物等が例示できる。 More specifically, examples of the (I) succinimide include compounds represented by the following general formula (6) or (7).
一般式（６）中、Ｒ１４は炭素数４０〜４００、好ましくは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。 In the general formula (6), R 14 represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, and p represents an integer of 1 to 5, preferably 2 to 4.
上記一般式（７）中、Ｒ１５及びＲ１６は、それぞれ個別に炭素数４０〜４００、好ましくは６０〜３５０のアルキル基又はアルケニル基、更に好ましくはポリブテニル基を示し、ｒは０〜４、好ましくは１〜３の整数を示す。 In the general formula (7), R 15 and R 16 individually represent an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, more preferably a polybutenyl group, and r is 0 to 4, Preferably the integer of 1-3 is shown.
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（６）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（７）で表される、いわゆるビスタイプのコハク酸イミドとが包含されるが、本発明の潤滑油組成物においては、それらの一方のみを含んでもよく、あるいはこれらの混合物が含まれていてもよい。 The succinimide includes a so-called monotype succinimide represented by the general formula (6) in which succinic anhydride is added to one end of the polyamine, and a general formula in which succinic anhydride is added to both ends of the polyamine ( 7), which is represented by the so-called bis-type succinimide, but the lubricating oil composition of the present invention may contain only one of them or a mixture thereof. Good.
上記コハク酸イミドの製法は特に制限はないが、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また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 the succinimide is not particularly limited. For example, an alkyl 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. is a polyamine. It can obtain by making it react. Specific examples of the polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
上記（ＩＩ）ベンジルアミンとしては、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。 More specifically, examples of (II) benzylamine include compounds represented by the following general formula (8).
上記一般式（８）中、Ｒ１７は、炭素数４０〜４００、好ましくは６０〜３５０のアルキル基又はアルケニル基を示し、ｙは１〜５、好ましくは２〜４の整数を示す。 In the general formula (8), R 17 represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and y represents an integer of 1 to 5, preferably 2 to 4.
上記（ＩＩＩ）ポリアミンとしては、より具体的には、下記の一般式（９）で表される化合物等が例示できる。
Ｒ１８−ＮＨ−（ＣＨ２ＣＨ２ＮＨ）ｚ−Ｈ （９）
上記一般式（９）中、Ｒ１８は、炭素数４０〜４００、好ましくは６０〜３５０のアルキル基又はアルケニル基を示し、ｚは１〜５、好ましくは２〜４の整数を示す。
More specifically, examples of the (III) polyamine include compounds represented by the following general formula (9).
R 18 -NH- (CH 2 CH 2 NH) z -H (9)
In the general formula (9), R 18 represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and z represents an integer of 1 to 5, preferably 2 to 4.
また、無灰分散剤の一例として挙げた含窒素化合物の誘導体としては、例えば、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、いわゆる酸変性化合物；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したり、アミド化した、いわゆるホウ素変性化合物；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；及び前述の含窒素化合物に酸変性、ホウ素変性、硫黄変性から選ばれた２種以上の変性を組み合わせた変性化合物；等が挙げられる。これらの誘導体の中でもアルケニルコハク酸イミドのホウ素変性化合物は耐熱性、酸化防止性に優れ、本発明の潤滑油組成物においても塩基価維持性及び高温清浄性をより高めるために有効である。 Moreover, as a derivative of the nitrogen-containing compound mentioned as an example of the ashless dispersant, for example, the above-mentioned nitrogen-containing compound is a monocarboxylic acid having 1 to 30 carbon atoms (fatty acid, etc.), oxalic acid, phthalic acid, trimellitic acid, A so-called acid-modified compound obtained by allowing a C2-C30 polycarboxylic acid such as pyromellitic acid to act to neutralize or amidate part or all of the remaining amino group and / or imino group; A so-called boron-modified compound in which boric acid is allowed to act on a nitrogen-containing compound to neutralize or amidate part or all of the remaining amino group and / or imino group; a sulfur compound acts on the nitrogen-containing compound described above And a modified compound in which two or more kinds of modifications selected from acid modification, boron modification, and sulfur modification are combined with the above-mentioned nitrogen-containing compound. Among these derivatives, boron-modified compounds of alkenyl succinimide are excellent in heat resistance and antioxidant properties, and are also effective in the lubricating oil composition of the present invention to further enhance base number maintenance and high temperature cleanability.
本発明の潤滑油組成物に無灰分散剤を含有させる場合、その含有量は、通常、潤滑油組成物全量基準で、０．０１質量％以上２０質量％以下であり、好ましくは０．１質量％以上１０質量％以下である。無灰分散剤の含有量が０．０１質量％未満の場合は、高温下における塩基価維持性に対する効果が少なく、一方、２０質量％を越える場合は、潤滑油組成物の低温流動性が大幅に悪化するため、それぞれ好ましくない。 When the ashless dispersant is contained in the lubricating oil composition of the present invention, the content is usually 0.01% by mass or more and 20% by mass or less, preferably 0.1% by mass based on the total amount of the lubricating oil composition. % To 10% by mass. When the content of the ashless dispersant is less than 0.01% by mass, the effect of maintaining the base number at high temperatures is small. On the other hand, when the content exceeds 20% by mass, the low-temperature fluidity of the lubricating oil composition is greatly increased. Since it deteriorates, it is not preferable respectively.
（連鎖停止型酸化防止剤）
また、本発明の潤滑油組成物は、連鎖停止型酸化防止剤を更に含有することが好ましい。これにより、潤滑油組成物の酸化防止性がより高められるため、本発明における塩基価維持性及び高温清浄性をより高めることができる。
(Chain-stopping antioxidant)
Moreover, it is preferable that the lubricating oil composition of the present invention further contains a chain termination type antioxidant. Thereby, since the antioxidant property of a lubricating oil composition is improved more, the base number maintenance property and high temperature detergency in this invention can be improved more.
連鎖停止型酸化防止剤としては、フェノール系酸化防止剤やアミン系酸化防止剤、金属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。 Any chain-stopping antioxidant can be used as long as it is generally used in lubricating oils such as phenol-based antioxidants, amine-based antioxidants, and metal-based antioxidants.
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１種を単独で用いてもよく、あるいは２種以上を混合して用いてもよい。 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-) Chlorylphenol), 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-hydroxyphenyl) propionate, penta Erythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl- Preferred examples include 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 3-methyl-5-tert-butyl-4-hydroxyphenyl substituted fatty acid esters. These may be used individually by 1 type, or may mix and use 2 or more types.
アミン系酸化防止剤としては、例えば、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１種を単独で用いてもよく、あるいは２種以上を混合して用いてもよい。 Examples of amine-based antioxidants include phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, and dialkyldiphenylamine. These may be used individually by 1 type, or may mix and use 2 or more types.
更に、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せて使用してもよい。 Further, the phenolic antioxidant and the amine antioxidant may be used in combination.
本発明の潤滑油組成物において連鎖停止型酸化防止剤を含有させる場合、その含有量は、通常潤滑油組成物全量基準で５．０質量％以下であり、好ましくは３．０質量％以下であり、さらに好ましくは２．５質量％以下である。その含有量が５．０質量％を超える場合は、含有量に見合った十分な酸化防止性が得られないため好ましくない。一方、その含有量は、潤滑油劣化過程における塩基価維持性及び高温清浄性をより高めるためには、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、好ましくは１質量％以上である。 When the chain-stopping antioxidant is contained in the lubricating oil composition of the present invention, the content is usually 5.0% by mass or less, preferably 3.0% by mass or less, based on the total amount of the lubricating oil composition. Yes, more preferably 2.5% by mass or less. When the content exceeds 5.0% by mass, it is not preferable because sufficient antioxidant properties corresponding to the content cannot be obtained. On the other hand, the content is preferably 0.1% by mass or more, preferably 1% by mass, based on the total amount of the lubricating oil composition, in order to further improve the base number maintenance property and high temperature cleanability in the process of lubricating oil deterioration. That's it.
（一般的な添加剤）
本発明の潤滑油組成物は、その性能をさらに向上させるために、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添加することができる。このような添加剤としては、例えば、摩耗防止剤、摩擦調整剤、粘度指数向上剤、腐食防止剤、防錆剤、抗乳化剤、金属不活性化剤、消泡剤、及び着色剤等の添加剤等を挙げることができる。
(General additives)
In order to further improve the performance of the lubricating oil composition of the present invention, any additive commonly used in lubricating oils can be added depending on the purpose. Examples of such additives include wear inhibitors, friction modifiers, viscosity index improvers, corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, antifoaming agents, and colorants. An agent etc. can be mentioned.
摩耗防止剤としては、例えば、ジスルフィド、硫化オレフィン、硫化油脂、ジチオリン酸金属塩（亜鉛塩、モリブデン塩等）、ジチオカルバミン酸金属塩（亜鉛塩、モリブデン塩等）、ジチオリン酸エステル及びその誘導体（オレフィンシクロペンタジエン、（メチル）メタクリル酸、プロピオン酸等との反応物；プロピオン酸の場合はβ位に付加したものが好ましい。）、トリチオリン酸エステル、ジチオカルバミン酸エステル等の硫黄含有化合物等が挙げられる。これらは通常、組成物全量基準で０．００５質量％以上５質量以下の範囲において本発明の組成物の性能を大幅に損なわない限り含有させることが可能であるが、低硫黄化及びロングドレイン性の点から、その含有量は、組成物全量基準で、硫黄換算値で、０．１質量％以下が好ましく、０．０５質量％以下がより好ましい。 Antiwear agents include, for example, disulfides, sulfurized olefins, sulfurized oils and fats, dithiophosphoric acid metal salts (zinc salts, molybdenum salts, etc.), dithiocarbamic acid metal salts (zinc salts, molybdenum salts, etc.), dithiophosphates and their derivatives (olefins). Reaction products with cyclopentadiene, (methyl) methacrylic acid, propionic acid, etc .; in the case of propionic acid, those added to the β-position are preferred.), Sulfur-containing compounds such as trithiophosphates and dithiocarbamates. These can usually be contained in the range of 0.005% by mass or more and 5% by mass or less based on the total amount of the composition as long as the performance of the composition of the present invention is not significantly impaired. From the above point, the content is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, in terms of sulfur, based on the total amount of the composition.
摩擦調整剤としては、潤滑油用の摩擦調整剤として通常用いられる任意の化合物が使用可能であり、例えば、二硫化モリブデン、モリブデンジチオカーバメート、モリブデンジチオホスフェート等のモリブデン系摩擦調整剤、炭素数６〜３０のアルキル基又はアルケニル基、特に炭素数６〜３０の直鎖アルキル基又は直鎖アルケニル基を分子中に少なくとも１個有する、アミン化合物、脂肪酸エステル、脂肪酸アミド、脂肪酸、脂肪族アルコール、脂肪族エーテル、ヒドラジド（オレイルヒドラジド等）、セミカルバジド、ウレア、ウレイド、ビウレット等の無灰摩擦調整剤等が挙げられる。これら摩擦調整剤の含有量は、通常、組成物全量基準で、０．１質量％以上５質量％以下である。 As the friction modifier, any compound usually used as a friction modifier for lubricating oils can be used. For example, molybdenum-based friction modifier such as molybdenum disulfide, molybdenum dithiocarbamate, molybdenum dithiophosphate, carbon number 6 An amine compound, a fatty acid ester, a fatty acid amide, a fatty acid, a fatty alcohol, a fat having at least one alkyl group or alkenyl group of -30, in particular, a straight-chain alkyl group or straight-chain alkenyl group having 6 to 30 carbon atoms in the molecule. Ashless friction modifiers such as group ethers, hydrazides (eg oleyl hydrazide), semicarbazides, ureas, ureidos, biurets and the like. The content of these friction modifiers is usually 0.1% by mass or more and 5% by mass or less based on the total amount of the composition.
粘度指数向上剤としては、具体的には、各種メタクリル酸エステルから選ばれる１種又は２種以上のモノマーの重合体又は共重合体若しくはその水添物などのいわゆる非分散型粘度指数向上剤、又はさらに窒素化合物を含む各種メタクリル酸エステルを共重合させたいわゆる分散型粘度指数向上剤、非分散型又は分散型エチレン−α−オレフィン共重合体（α−オレフィンとしてはプロピレン、１−ブテン、１−ペンテン等が例示できる）若しくはその水素化物、ポリイソブチレン若しくはその水素化物、スチレン−ジエン共重合体の水素化物、スチレン−無水マレイン酸エステル共重合体及びポリアルキルスチレン等が挙げられる。 As the viscosity index improver, specifically, a so-called non-dispersed viscosity index improver such as a polymer or copolymer of one or more monomers selected from various methacrylates or a hydrogenated product thereof, Or a so-called dispersion-type viscosity index improver obtained by copolymerizing various methacrylic esters containing a nitrogen compound, a non-dispersion type or a dispersion type ethylene-α-olefin copolymer (propylene, 1-butene, 1 -Pentene, etc.) or a hydride thereof, polyisobutylene or a hydride thereof, a hydride of a styrene-diene copolymer, a styrene-maleic anhydride copolymer, and a polyalkylstyrene.
これらの粘度指数向上剤の分子量は、せん断安定性を考慮して選定することが必要である。具体的には、粘度指数向上剤の数平均分子量は、例えば分散型及び非分散型ポリメタクリレートの場合では、通常５，０００〜１，０００，０００、好ましくは１００，０００〜９００，０００のものが、ポリイソブチレン又はその水素化物の場合は通常８００〜５，０００、好ましくは１，０００〜４，０００のものが、エチレン−α−オレフィン共重合体又はその水素化物の場合は通常８００〜５００，０００、好ましくは３，０００〜２００，０００のものが用いられる。 The molecular weight of these viscosity index improvers needs to be selected in consideration of shear stability. Specifically, the number average molecular weight of the viscosity index improver is usually 5,000 to 1,000,000, preferably 100,000 to 900,000 in the case of dispersed and non-dispersed polymethacrylates, for example. In the case of polyisobutylene or a hydride thereof, usually 800 to 5,000, preferably 1,000 to 4,000, and in the case of an ethylene-α-olefin copolymer or a hydride thereof, usually 800 to 500. 3,000, preferably 3,000 to 200,000 are used.
またこれらの粘度指数向上剤の中でもエチレン−α−オレフィン共重合体又はその水素化物を用いた場合には、特にせん断安定性に優れた潤滑油組成物を得ることができる。上記粘度指数向上剤の中から任意に選ばれた１種類あるいは２種類以上の化合物を任意の量で含有させることができる。粘度指数向上剤の含有量は、通常、組成物全量基準で、０．１質量％以上２０質量％以下である。 Further, among these viscosity index improvers, when an ethylene-α-olefin copolymer or a hydride thereof is used, a lubricating oil composition particularly excellent in shear stability can be obtained. One or two or more compounds arbitrarily selected from the above viscosity index improvers can be contained in any amount. The content of the viscosity index improver is usually 0.1% by mass or more and 20% by mass or less based on the total amount of the composition.
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、及び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, and 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、及び多価アルコールエステル等が挙げられる。 Examples of the rust inhibitor 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、及び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, and 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、及び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 include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.
消泡剤としては、例えば、シリコーン、フルオロシリコーン、及びフルオロアルキルエーテル等が挙げられる。 Examples of the antifoaming agent include silicone, fluorosilicone, and fluoroalkyl ether.
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には、その含有量は潤滑油組成物全量基準で、腐食防止剤、防錆剤、抗乳化剤ではそれぞれ０．００５質量％以上５質量％以下、金属不活性化剤では０．００５質量％以上１質量％以下、消泡剤では０．０００５質量％以上１質量％以下の範囲で通常選ばれる。 When these additives are contained in the lubricating oil composition of the present invention, the content thereof is based on the total amount of the lubricating oil composition, and 0.005% by mass or more for each of the corrosion inhibitor, rust inhibitor, and demulsifier. It is usually selected in the range of 0.005% by mass or more and 1% by mass or less for the metal deactivator, and 0.0005% by mass or more and 1% by mass or less for the antifoaming agent.
（本発明の潤滑油組成物の動粘度）
本発明の潤滑油組成物の１００℃における動粘度は、４．１ｍｍ２／ｓ以上２１．９ｍｍ２／ｓ以下であり、好ましくは５．６ｍｍ２／ｓ以上１６．３ｍｍ２／ｓ以下、更に好ましくは５．６ｍｍ２／ｓ以上１２．５ｍｍ２／ｓ以下である。
(Kinematic viscosity of the lubricating oil composition of the present invention)
Kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is less 4.1 mm 2 / s or more 21.9 mm 2 / s, preferably 5.6 mm 2 / s or more 16.3 mm 2 / s or less, further it is preferably at most 5.6 mm 2 / s or more 12.5 mm 2 / s.
（本発明の潤滑油組成物の硫黄含有量）
本発明の潤滑油組成物における硫黄含有量は、潤滑油組成物全量基準で、好ましくは０．３質量％以下、より好ましくは０．２質量％以下、更に好ましくは０．１質量％以下である。硫黄含有量を前記上限値以下とすることによって、ロングドレイン性に優れた低硫黄潤滑油組成物を実現することができる。
(Sulfur content of the lubricating oil composition of the present invention)
The sulfur content in the lubricating oil composition of the present invention is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less, based on the total amount of the lubricating oil composition. is there. By setting the sulfur content to the upper limit or less, a low sulfur lubricating oil composition having excellent long drain properties can be realized.
（本発明の潤滑油組成物の用途）
本発明の潤滑油組成物は、摩耗防止性を維持しながら、低硫黄化と優れた摩擦低減性を両立させることができるため、二輪車、四輪車、発電用、舶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用潤滑油として好ましく使用することができる。また、その他摩耗防止性能及びロングドレイン性能が要求される潤滑油、例えば自動又は手動変速機等の駆動系用潤滑油、湿式ブレーキ、油圧作動油、タービン油、圧縮機油、軸受け油、冷凍機油等の潤滑油としても好適に使用することができる。
(Use of lubricating oil composition of the present invention)
Since the lubricating oil composition of the present invention can achieve both low sulfur and excellent friction reduction while maintaining wear prevention properties, gasoline engines for two-wheeled vehicles, four-wheeled vehicles, power generation, ships, etc., diesel It can be preferably used as a lubricating oil for internal combustion engines such as engines and gas engines. In addition, other lubricating oils that require wear prevention performance and long drain performance, such as lubricating oils for drive systems such as automatic or manual transmissions, wet brakes, hydraulic fluids, turbine oils, compressor oils, bearing oils, refrigerator oils, etc. It can also be suitably used as a lubricating oil.
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。
（１）リン化合物金属塩の摩擦低減効果
（実施例１〜３、比較例１〜４）
実施例１〜３及び比較例１〜４においては、１００℃動粘度２．０ｍｍ２／ｓのポリα−オレフィンを基油として、表１に示すように各種リン化合物金属塩を、リン元素換算で０．１０質量％添加した組成物について摩擦低減効果を評価した。結果を同じく表１に示した。摩擦係数の評価は下記ブロック−オン−リング試験（Ｂｌｏｃｋ ｏｎ ｒｉｎｇ試験）により行った。なお、表１における質量％は、組成物全量基準の値である。
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.
(1) Friction reduction effect of phosphorus compound metal salt (Examples 1 to 3, Comparative Examples 1 to 4)
In Examples 1 to 3 and Comparative Examples 1 to 4, a poly α-olefin having a kinematic viscosity of 100 ° C. of 2.0 mm 2 / s is used as a base oil, and various phosphorus compound metal salts are converted into phosphorus elements as shown in Table 1. The friction reduction effect was evaluated for the composition added at 0.10% by mass. The results are also shown in Table 1. The coefficient of friction was evaluated by the following block-on-ring test (Block on ring test). The mass% in Table 1 is a value based on the total amount of the composition.
（ブロック−オン−リング試験）
ブロック−オン−リング試験は、ＡＳＴＭ Ｄ３７０１、Ｄ２７１４に準拠して行った。試験条件は、荷重：４４５Ｎ、油温：１００℃とし、すべり速度は、表１中に記載した。
(Block-on-ring test)
The block-on-ring test was performed according to ASTM D3701 and D2714. The test conditions were a load: 445 N, an oil temperature: 100 ° C., and the sliding speed is shown in Table 1.
（２）組成物の摩耗防止性評価
（実施例４、比較例５〜６）
鉱油系基油を用い、表２に示すようにリン化合物金属塩およびその他の添加剤を添加した組成物を調製し、摩耗防止性を評価した。結果を同じく表２に示す。摩耗防止性の評価は下記ＫＡ２４Ｅ動弁系摩耗試験により行った。
(2) Evaluation of wear resistance of the composition (Example 4, Comparative Examples 5 to 6)
Using mineral base oil, a composition containing a phosphorus compound metal salt and other additives as shown in Table 2 was prepared, and the antiwear property was evaluated. The results are also shown in Table 2. The evaluation of wear resistance was performed by the following KA24E valve train wear test.
（ＫＡ２４Ｅ動弁系摩耗試験）
ＫＡ２４Ｅ動弁系摩耗試験は、ＪＡＳＯ Ｍ３２８−９５に準拠して行った。
(KA24E valve system wear test)
The KA24E valve train wear test was performed according to JASO M328-95.
表１に示した結果から、直鎖ジアルキルモノチオリン酸亜鉛塩を用いた実施例１〜３の潤滑油組成物は、ジアルキルリン酸亜鉛を用いた比較例１、ジアルキルジチオリン酸亜鉛を用いた比較例２〜３、分枝ジアルキルモノチオリン酸亜鉛塩を用いた比較例４に比べて、いずれの条件においても摩擦係数が低く、省燃費性に優れていることが分かった。 From the results shown in Table 1, the lubricating oil compositions of Examples 1 to 3 using a linear dialkylmonothiophosphate zinc salt were compared with Comparative Example 1 using a dialkylzinc phosphate zinc and using a zinc dialkyldithiophosphate. As compared with Examples 2 to 3 and Comparative Example 4 using a branched dialkylmonothiophosphate zinc salt, it was found that the friction coefficient was low under all conditions and the fuel economy was excellent.
表２に示した結果から、直鎖ジアルキルモノチオリン酸亜鉛塩を用いた実施例４の組成物は、ジアルキルリン酸亜鉛を用いた比較例５、ジアルキルジチオリン酸亜鉛を用いた比較例６に比べて摩耗防止性に優れていることが分かった。 From the results shown in Table 2, the composition of Example 4 using a linear dialkylmonothiophosphate zinc salt was compared with Comparative Example 5 using zinc dialkylphosphate and Comparative Example 6 using zinc dialkyldithiophosphate. It was found that the anti-wear property was excellent.
以上、現時点において、もっとも、実践的であり、かつ、好ましいと思われる実施形態に関連して本発明を説明したが、本発明は、本願明細書中に開示された実施形態に限定されるものではなく、請求の範囲および明細書全体から読み取れる発明の要旨或いは思想に反しない範囲で適宜変更可能であり、そのような変更を伴う潤滑油組成物もまた本発明の技術的範囲に包含されるものとして理解されなければならない。 While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, the present invention can be modified as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and lubricating oil compositions with such changes are also included in the technical scope of the present invention. It must be understood as a thing.
本発明の潤滑油組成物は、摩耗防止性を維持しながら、低硫黄化と優れた摩擦低減性を両立させることができるため、二輪車、四輪車、発電用、舶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用潤滑油として好ましく使用することができる。またその他摩耗防止性能及びロングドレイン性能が要求される潤滑油、例えば自動又は手動変速機等の駆動系用潤滑油、湿式ブレーキ、油圧作動油、タービン油、圧縮機油、軸受け油、冷凍機油等の潤滑油としても好適に使用することができる。 Since the lubricating oil composition of the present invention can achieve both low sulfur and excellent friction reduction while maintaining wear prevention properties, gasoline engines for two-wheeled vehicles, four-wheeled vehicles, power generation, ships, etc., diesel It can be preferably used as a lubricating oil for internal combustion engines such as engines and gas engines. In addition, other lubricants that require wear prevention performance and long drain performance, such as drive system lubricants such as automatic or manual transmissions, wet brakes, hydraulic fluids, turbine oils, compressor oils, bearing oils, refrigerator oils, etc. It can also be suitably used as a lubricating oil.
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| US13/583,702 US8722594B2 (en) | 2010-03-19 | 2011-02-23 | Lubricating oil composition |
| ES11756037.5T ES2502467T3 (en) | 2010-03-19 | 2011-02-23 | Lubricant composition |
| PCT/JP2011/053966 WO2011114848A1 (en) | 2010-03-19 | 2011-02-23 | Lubricant composition |
| EP11756037.5A EP2548939B1 (en) | 2010-03-19 | 2011-02-23 | Lubricant composition |
| CN201180013577.0A CN102812112B (en) | 2010-03-19 | 2011-02-23 | Lubricant composition |
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