JP5767215B2 - Fuel-saving engine oil composition - Google Patents
Fuel-saving engine oil composition Download PDFInfo
- Publication number
- JP5767215B2 JP5767215B2 JP2012521342A JP2012521342A JP5767215B2 JP 5767215 B2 JP5767215 B2 JP 5767215B2 JP 2012521342 A JP2012521342 A JP 2012521342A JP 2012521342 A JP2012521342 A JP 2012521342A JP 5767215 B2 JP5767215 B2 JP 5767215B2
- Authority
- JP
- Japan
- Prior art keywords
- fuel
- engine oil
- oil
- compound
- oil composition
- 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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- 239000010705 motor oil Substances 0.000 title claims description 35
- 239000000203 mixture Substances 0.000 title claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000004593 Epoxy Substances 0.000 claims description 18
- 125000002723 alicyclic group Chemical group 0.000 claims description 17
- 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 claims description 17
- 239000002199 base oil Substances 0.000 claims description 16
- 230000001050 lubricating effect Effects 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 150000001924 cycloalkanes Chemical class 0.000 claims description 7
- 239000005078 molybdenum compound Substances 0.000 claims description 7
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 7
- -1 acid amide compound Chemical class 0.000 description 25
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 16
- 239000000446 fuel Substances 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 10
- 239000010687 lubricating oil Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000001565 benzotriazoles Chemical class 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 229960002317 succinimide Drugs 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-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
- 150000001639 boron compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- DHTAIMJOUCYGOL-UHFFFAOYSA-N 2-ethyl-n-(2-ethylhexyl)-n-[(4-methylbenzotriazol-1-yl)methyl]hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1C DHTAIMJOUCYGOL-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZZGHZLUTIKGEDL-UHFFFAOYSA-M C(CC(C)C)SP(=S)(OCCC(C)C)[O-].[Zn+] Chemical compound C(CC(C)C)SP(=S)(OCCC(C)C)[O-].[Zn+] ZZGHZLUTIKGEDL-UHFFFAOYSA-M 0.000 description 1
- NIGWBUOGUODAAT-UHFFFAOYSA-N CCCCCC(CC)(CC)[S+]=P([O-])([O-])[S-].CCCCCC(CC)(CC)[S+]=P([O-])([O-])[S-].[Zn+2].[Zn+2].[Zn+2] Chemical compound CCCCCC(CC)(CC)[S+]=P([O-])([O-])[S-].CCCCCC(CC)(CC)[S+]=P([O-])([O-])[S-].[Zn+2].[Zn+2].[Zn+2] NIGWBUOGUODAAT-UHFFFAOYSA-N 0.000 description 1
- ZDMLGWPLXFTSNJ-UHFFFAOYSA-N CCCCCCCCCCCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCCCCCCCCCCC.CCCCCCCCCCCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCCCCCCCCCCC.[Zn+2].[Zn+2].[Zn+2] Chemical compound CCCCCCCCCCCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCCCCCCCCCCC.CCCCCCCCCCCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCCCCCCCCCCC.[Zn+2].[Zn+2].[Zn+2] ZDMLGWPLXFTSNJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- QVNAMABWPANHBT-UHFFFAOYSA-N P(=S)(S)(O)O.C(CCCCCCCC)[Zn]CCCCCCCCC Chemical compound P(=S)(S)(O)O.C(CCCCCCCC)[Zn]CCCCCCCCC QVNAMABWPANHBT-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- QGLKNQRTHJUNFJ-UHFFFAOYSA-N n-(benzotriazol-1-ylmethyl)-2-ethylhexan-1-amine Chemical compound C1=CC=C2N(CNCC(CC)CCCC)N=NC2=C1 QGLKNQRTHJUNFJ-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229960001860 salicylate Drugs 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
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- WAILXPVSJYWOEV-UHFFFAOYSA-L zinc;(2,3-didodecylphenyl)sulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCCCCC1=CC=CC(SP([O-])([O-])=S)=C1CCCCCCCCCCCC WAILXPVSJYWOEV-UHFFFAOYSA-L 0.000 description 1
- OBPRGCGYBYCAIB-UHFFFAOYSA-L zinc;(2,3-dipentylphenyl)sulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCC1=CC=CC(SP([O-])([O-])=S)=C1CCCCC OBPRGCGYBYCAIB-UHFFFAOYSA-L 0.000 description 1
- NDMGGNOLFUKCSA-UHFFFAOYSA-L zinc;(2,3-dipropylphenyl)sulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCC1=CC=CC(SP([O-])([O-])=S)=C1CCC NDMGGNOLFUKCSA-UHFFFAOYSA-L 0.000 description 1
- DAIDCNOEIKGXQG-UHFFFAOYSA-L zinc;(2-methyl-3,4-dipropylphenyl)sulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCC1=CC=C(SP([O-])([O-])=S)C(C)=C1CCC DAIDCNOEIKGXQG-UHFFFAOYSA-L 0.000 description 1
- PXJZGBFRKRTOPA-UHFFFAOYSA-L zinc;[2,3-di(nonyl)phenyl]sulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCC1=CC=CC(SP([O-])([O-])=S)=C1CCCCCCCCC PXJZGBFRKRTOPA-UHFFFAOYSA-L 0.000 description 1
- ZNCAMSISVWKWHL-UHFFFAOYSA-L zinc;butoxy-butylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCOP([O-])(=S)SCCCC.CCCCOP([O-])(=S)SCCCC ZNCAMSISVWKWHL-UHFFFAOYSA-L 0.000 description 1
- BCLLIVNRSGTXBX-UHFFFAOYSA-L zinc;decoxy-decylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCCOP([O-])(=S)SCCCCCCCCCC.CCCCCCCCCCOP([O-])(=S)SCCCCCCCCCC BCLLIVNRSGTXBX-UHFFFAOYSA-L 0.000 description 1
- ZBDJNBFTEIUHPK-UHFFFAOYSA-L zinc;dihexoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCOP([S-])(=S)OCCCCCC.CCCCCCOP([S-])(=S)OCCCCCC ZBDJNBFTEIUHPK-UHFFFAOYSA-L 0.000 description 1
- VYEHCXHIPZIYIJ-UHFFFAOYSA-L zinc;dodecoxy-dodecylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCCCCOP([O-])(=S)SCCCCCCCCCCCC.CCCCCCCCCCCCOP([O-])(=S)SCCCCCCCCCCCC VYEHCXHIPZIYIJ-UHFFFAOYSA-L 0.000 description 1
- GBEDXBRGRSPHRI-UHFFFAOYSA-L zinc;octoxy-octylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCOP([O-])(=S)SCCCCCCCC.CCCCCCCCOP([O-])(=S)SCCCCCCCC GBEDXBRGRSPHRI-UHFFFAOYSA-L 0.000 description 1
- HHMFJIHYTYQNJP-UHFFFAOYSA-L zinc;oxido-pentoxy-pentylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCOP([O-])(=S)SCCCCC.CCCCCOP([O-])(=S)SCCCCC HHMFJIHYTYQNJP-UHFFFAOYSA-L 0.000 description 1
- LZVDFWITYZHIEU-UHFFFAOYSA-L zinc;oxido-propoxy-propylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCOP([O-])(=S)SCCC.CCCOP([O-])(=S)SCCC LZVDFWITYZHIEU-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
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Description
本発明は、腐食、摩耗防止性能に優れた省燃費型エンジン油に関する。 The present invention relates to a fuel-saving engine oil excellent in corrosion and wear prevention performance.
近年、地球温暖化防止のために自動車の燃費を向上させ、CO2の排出を抑制する要求が非常に高まっている。自動車の燃費を向上させるにはエンジンの効率化が重要である一方、エンジンの摩擦を低減することも燃費向上に貢献できることから、摺動部品への低摩擦材料の使用や省燃費型エンジン油の採用が図られている。In recent years, there has been a great demand for improving the fuel efficiency of automobiles and suppressing CO 2 emissions to prevent global warming. While improving engine efficiency is important for improving automobile fuel efficiency, reducing engine friction can also contribute to improving fuel efficiency. Therefore, the use of low-friction materials for sliding parts and fuel-saving engine oil Adopted.
省燃費型エンジン油としては、SAE(米国自動車技術会)J300に規定されている粘度分類で5W−30や0W−30という低粘度化や、摩擦を低下させる添加剤(摩擦調整剤、以下FMと称することもある)としてモリブデンジチオカーバメイト(MoDTC)などの有機モリブデン系FMを配合することが有効であることが知られている。 Fuel-saving engine oils include low viscosity of 5W-30 and 0W-30 in the viscosity classification stipulated by SAE (American Automotive Engineers) J300, and additives that reduce friction (friction modifiers, hereinafter FM It is known that it is effective to mix organic molybdenum FM such as molybdenum dithiocarbamate (MoDTC).
しかしながら、燃料やエンジ油中の硫黄分から硫酸が生成され、生成した硫酸の一部分がエンジン油に含まれることとなり、エンジン部材を腐食し、摩耗させることが知られている。したがって、MoDTCなどを配合しても腐食防止性に優れたエンジン油が強く求められている。 However, it is known that sulfuric acid is generated from the sulfur content in fuel and engine oil, and a part of the generated sulfuric acid is contained in the engine oil, which corrodes and wears engine members. Therefore, there is a strong demand for engine oils that are excellent in corrosion resistance even when blended with MoDTC.
この腐食防止、摩耗低減を向上させた内燃機関用潤滑油組成物として、潤滑油基油に、硫化オキシモリブデンジチオカーバメート、酸アミド化合物、脂肪酸部分エステル化合物及び/または脂肪族アミン化合物、及びベンゾトリアゾール誘導体を含むものが提案されている(特許文献1)。しかしながら、この潤滑油組成物では、腐食防止効果や摩耗低減効果が、いまだ十分ではない。
また、鉛及び銅に対する耐食性を改善した特定のエポキシ化エステル化合物を含む潤滑油が提案され(特許文献2)、この特許文献2にはシクロアルキル基を含む各種のエポキシ化エステル化合物が列記されているが、具体的な化合物としては、エポキシ化トロール油脂肪酸2‐エチルヘキシルのみしか開示されておらず、また摩擦調整剤として有機モリブデン化合物を添加できるという通り一遍の記載はあるものの、その効果、特にエポキシ化合物と有機モリブデン化合物との相乗効果については何ら開示されていない。As a lubricating oil composition for internal combustion engines with improved corrosion prevention and wear reduction, lubricating base oil, sulfurized oxymolybdenum dithiocarbamate, acid amide compound, fatty acid partial ester compound and / or aliphatic amine compound, and benzotriazole The thing containing a derivative | guide_body is proposed (patent document 1). However, this lubricating oil composition is not yet sufficient for preventing corrosion and reducing wear.
Further, a lubricating oil containing a specific epoxidized ester compound with improved corrosion resistance to lead and copper has been proposed (Patent Document 2), and in Patent Document 2, various epoxidized ester compounds containing a cycloalkyl group are listed. However, as a specific compound, only epoxidized troll oil fatty acid 2-ethylhexyl is disclosed, and although there is a general description that an organic molybdenum compound can be added as a friction modifier, its effect, particularly There is no disclosure of a synergistic effect between the epoxy compound and the organomolybdenum compound.
本発明が解決しようとする課題は、腐食、摩耗防止性能、さらに省燃費性に優れたエンジン油を提供することである。 The problem to be solved by the present invention is to provide an engine oil that is excellent in corrosion, wear prevention performance and fuel efficiency.
本発明者は、上記課題を解決すべく、エンジン油を構成するさまざまな潤滑油基材、潤滑油添加剤に関して鋭意研究を進めた結果、潤滑油添加剤として脂環式エポキシ化合物と、有機モリブデン化合物の特定量を組み合わせて配合したエンジン油が省燃費性に優れつつ、優れた腐食、摩耗防止性能を示すことを見出し、本発明に想到した。 In order to solve the above-mentioned problems, the present inventor has conducted extensive research on various lubricating oil base materials and lubricating oil additives constituting the engine oil, and as a result, alicyclic epoxy compounds and organic molybdenum as lubricating oil additives. The present inventors have found that an engine oil formulated by combining a specific amount of a compound has excellent fuel economy and exhibits excellent corrosion and wear prevention performance, and has come to the present invention.
すなわち、上記課題を解決するための本発明の省燃費型エンジン油組成物は、潤滑油基油に、有機モリブデン化合物をモリブデン(Mo)量として0.02質量%以上と脂環式エポキシ化合物を含有するものである。
また、本発明において、好ましくは、上記有機モリブデン化合物として、モリブデンジチオカーバメイト(MoDTC)を用い、上記脂環式エポキシ化合物として、エステル結合及び2個のエポキシ化シクロアルカンを有するものを用い、さらに上記潤滑油基油として、100℃における動粘度が4.5mm2/s以下のものを用いるものである。That is, the fuel-saving engine oil composition of the present invention for solving the above-mentioned problems comprises a lubricating base oil containing 0.02% by mass or more of an organic molybdenum compound as a molybdenum (Mo) amount and an alicyclic epoxy compound. It contains.
In the present invention, preferably, the organic molybdenum compound is molybdenum dithiocarbamate (MoDTC), and the alicyclic epoxy compound is an ester having an ester bond and two epoxidized cycloalkanes. As the lubricating base oil, one having a kinematic viscosity at 100 ° C. of 4.5 mm 2 / s or less is used.
本発明の省燃費型エンジン油組成物は、長い期間使用してもエンジン部材の腐食、摩耗が少なく、さらに、低摩擦特性に優れているため、特に高温領域での省燃費性に優れている。 The fuel-saving engine oil composition of the present invention is excellent in fuel efficiency especially in a high temperature region because it has little corrosion and wear of engine members even after long-term use and is excellent in low friction characteristics. .
本発明の省燃費型エンジン油組成物に用いる潤滑油基油としては、鉱油、合成油、及びその混合物のいずれも使用できる。鉱油では粘度指数が120以上の高粘度指数潤滑油基油が好ましい。粘度指数が120以上の高粘度指数潤滑油基油は、ワックスの水素異性化或いは重質油の水素化分解で得られた生成油を溶剤脱ロウ又は水素化脱ロウすることにより得ることができる。 As the lubricating base oil used in the fuel-saving engine oil composition of the present invention, any of mineral oil, synthetic oil, and mixtures thereof can be used. As mineral oil, a high viscosity index lubricating base oil having a viscosity index of 120 or more is preferable. A high viscosity index lubricating base oil having a viscosity index of 120 or more can be obtained by solvent dewaxing or hydrodewaxing a product oil obtained by hydroisomerization of wax or hydrocracking of heavy oil. .
ワックスの水素異性化は、沸点範囲が300〜600℃、炭素数として20〜70の範囲にあるワックス、例えば、鉱油系潤滑油の溶剤脱ロウ工程で得られるスラックワックスや、炭化水素ガス等を一酸化炭素と水素に転化して液体燃料を合成するフィッシャー・トロプシュ合成で得られたワックス等を原料として、水素異性化触媒、例えばアルミナ、或いはシリカ−アルミナ担体上にニッケル、コバルト等の8族金属、及びモリブデン、タングステン等の6A族金属の1種以上を担持した触媒や、ゼオライト触媒、もしくはゼオライト含有担体に白金等を担持した触媒と、水素分圧5〜14MPaの水素存在下、300〜450℃の温度、0.1〜2h−1のLHSV(液空間速度)で接触させることによって行うことができる。このとき、直鎖状のパラフィンの転化率が80%以上、軽質留分への転化率が40%以下となるようにすることが好ましい。In the hydroisomerization of wax, wax having a boiling range of 300 to 600 ° C. and a carbon number of 20 to 70, such as slack wax obtained in a solvent dewaxing step of mineral oil-based lubricating oil, hydrocarbon gas, etc. Using a wax obtained by Fischer-Tropsch synthesis, which converts liquid monoxide and hydrogen to synthesize a liquid fuel, as a raw material, a hydroisomerization catalyst, for example, alumina, or a group 8 of nickel, cobalt, etc. on a silica-alumina carrier A catalyst in which one or more of metals and a group 6A metal such as molybdenum and tungsten are supported, a zeolite catalyst, or a catalyst in which platinum or the like is supported on a zeolite-containing support; and in the presence of hydrogen at a hydrogen partial pressure of 5 to 14 MPa, It can be carried out by contacting at a temperature of 450 ° C. and an LHSV (liquid space velocity) of 0.1 to 2 h −1 . At this time, it is preferable that the conversion rate of the linear paraffin is 80% or more and the conversion rate to the light fraction is 40% or less.
一方、重質油の水素化分解を用いる高粘度指数の潤滑油基油は、次のようにして得ることができる。必要により水素化脱硫及び脱窒素を行った沸点が300〜600℃の範囲の常圧留出油、減圧留出油又はブライトストックを、水素化分解触媒、例えばシリカ−アルミナ担体上にニッケル、コバルト等の8族金属の1種以上、及びモリブデン、タングステン等の6A族金属の1種以上を担持した触媒と、水素分圧7〜14MPaの水素存在下、350〜450℃の温度、0.1〜2h−1のLHSV(液空間速度)で接触させて行うことができ、分解率(生成物に占める360℃以上の留分の減少した質量%)が40〜90%となるようにすることが好ましい。On the other hand, a lubricating base oil having a high viscosity index using hydrocracking of heavy oil can be obtained as follows. If necessary, hydrodesulfurization and denitrogenation, normal pressure distillate, vacuum distillate or bright stock having a boiling point in the range of 300 to 600 ° C., nickel, cobalt on hydrocracking catalyst such as silica-alumina support A catalyst supporting one or more group 8 metals such as molybdenum and tungsten, and a catalyst having a hydrogen partial pressure of 7 to 14 MPa in the presence of hydrogen at a temperature of 350 to 450 ° C., 0.1 It can be carried out by contact at LHSV (liquid space velocity) of ˜2h −1 , and the decomposition rate (the reduced mass% of the fraction of 360 ° C. or more in the product) is 40 to 90%. Is preferred.
上記方法で得られる水素異性化生成油又は水素化分解生成油から軽質留分を留去して潤滑油留分を得ることができるが、この留分は、このままでは一般に流動点や粘度が高く、また粘度指数が十分に高くないため、脱ロウ処理を行い、ワックス分を除去して、n‐d‐M環分析による%CPが80以上、流動点が−10℃以下で粘度指数が120以上の潤滑油基油を得ることができる。Lubricating oil fraction can be obtained by distilling off the light fraction from the hydroisomerized product oil or hydrocracked product oil obtained by the above method, but this fraction generally has a high pour point and viscosity. and the viscosity index is not high enough, perform dewaxing treatment, to remove the wax fraction, n-d-M ring analysis% C P is 80 or more, a pour point viscosity index at -10 ° C. or less More than 120 lubricating base oils can be obtained.
このワックス分の除去を溶剤脱ロウ処理で行う場合、上記の軽質留分の留去に際して精密蒸留装置を用いて蒸留分離し、あらかじめガスクロマトグラフィー蒸留法による沸点371℃以上491℃未満の留分が70質量%以上になるようにカットすることが、溶剤脱ロウ処理をより効率的に行うために好ましい。この溶剤脱ロウ処理は、脱ロウ溶剤として例えばメチルエチルケトン/トルエン(容量比1/1)を用い、溶剤/油比2/1〜4/1の範囲で、−15〜−40℃の温度下に行うとよい。 When removing the wax by solvent dewaxing, the light fraction is distilled off using a precision distillation apparatus, and the fraction having a boiling point of 371 ° C. or higher and lower than 491 ° C. by gas chromatography distillation is previously used. Is preferably 70% by mass or more in order to perform the solvent dewaxing process more efficiently. In this solvent dewaxing treatment, for example, methyl ethyl ketone / toluene (volume ratio 1/1) is used as a dewaxing solvent, and the solvent / oil ratio is in the range of 2/1 to 4/1. It is good to do.
一方、ワックス分の除去を水素化脱ロウ法で行う場合は、軽質留分の留去は水素化脱ロウに支障とならない程度とし、水素化脱ロウ後に、精密蒸留装置を用いて蒸留分離してガスクロマトグラフィー蒸留法による沸点371℃以上491℃未満の留分が70質量%以上になるようにカットすることが、効率的で好ましい。この水素化脱ロウは、ゼオライト触媒と、水素分圧3〜15MPaの水素存在下、320〜430℃の温度、0.2〜4h−1のLHSV(液空間速度)で接触させ、最終的な潤滑油基油における流動点が−10℃以下となるようにするとよい。On the other hand, when the wax content is removed by hydrodewaxing, distilling the light fractions should not hinder hydrodewaxing, and after hydrodewaxing, they are separated by distillation using a precision distillation apparatus. It is efficient and preferable that the fraction having a boiling point of 371 ° C. or higher and lower than 491 ° C. is 70% by mass or higher by gas chromatography distillation. This hydrodewaxing is performed by contacting the zeolite catalyst with a hydrogen partial pressure of 3 to 15 MPa in the presence of hydrogen at a temperature of 320 to 430 ° C. and a LHSV (liquid space velocity) of 0.2 to 4 h −1. The pour point in the lubricating base oil should be −10 ° C. or lower.
以上のような方法で、粘度指数120以上の潤滑油基油を得ることができるが、所望により、さらに溶剤精製或いは水素化精製を行うことができる。 A lubricating base oil having a viscosity index of 120 or more can be obtained by the method as described above, but solvent purification or hydrorefining can be further performed as desired.
また、合成油としては、α‐オレフィンのオリゴマー、アジピン酸等の二塩基酸と一価アルコールから合成されるジエステルやネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール等の多価アルコールと一塩基酸とから合成されるポリオールエステル、及びこれらの混合物等が挙げられる。 Synthetic oils include α-olefin oligomers, diesters synthesized from dibasic acids such as adipic acid and monohydric alcohols, polyhydric alcohols such as neopentyl glycol, trimethylolpropane, pentaerythritol, and monobasic acids. Polyol esters synthesized from the above, and mixtures thereof.
さらに、適宜の鉱油と合成油を組み合わせた混合油も、本エンジン油の基油として用いることができる。
鉱油、合成油又はこれらの混合油にしても、本発明の省燃費型エンジン油組成物に用いる場合、JIS K2283に規定する方法による100℃における動粘度が4.5mm2/s以下でかつ粘度指数が120以上のものが好ましいが、さらには、100℃における動粘度が1.0mm2/s以上、ASTM D2140に規定する方法のn‐d‐M環分析による%CPが80以上、JIS K2269に規定する方法による流動点が−10℃以下のものが、より好ましい。Furthermore, a mixed oil combining an appropriate mineral oil and a synthetic oil can also be used as the base oil of the engine oil.
Even if it is a mineral oil, a synthetic oil or a mixed oil thereof, when used in the fuel-saving engine oil composition of the present invention, the kinematic viscosity at 100 ° C. by the method specified in JIS K2283 is 4.5 mm 2 / s or less and the viscosity is Although indices are preferred those 120 or more, further, the kinematic viscosity at 100 ° C. is 1.0 mm 2 / s or more, n-d-M ring analysis% C P of the method prescribed in ASTM d 2140 is 80 or more, JIS A pour point determined by the method defined in K2269 is more preferably −10 ° C. or lower.
本発明の省燃費型エンジン油組成物は、エンジン油組成物全量基準で、有機モリブデン化合物をモリブデン(Mo)量として0.02質量%以上含有する。0.02質量%未満では、十分な省燃費持続性を得ることができない。この有機モリブデン化合物は、モリブデン(Mo)量として、0.03〜0.20質量%含有させることが好ましい。
有機モリブデン化合物として、具体的には、モリブデンジチオカーバメイト(MoDTC)、モリブデンジチオホスフェート(MoDTP)、Moアミンコンプレックスなどが挙げられる。この中で、MoDTCが最も好ましく、MoDTPはリンが排ガス浄化の三元触媒を被毒するため、あまり好ましくない。
本発明において、MoDTCとしては、下記一般式(1)で表されるものを好ましく使用できる。The fuel-saving engine oil composition of the present invention contains 0.02% by mass or more of an organomolybdenum compound as the amount of molybdenum (Mo) based on the total amount of the engine oil composition. If the amount is less than 0.02% by mass, sufficient fuel saving cannot be obtained. This organic molybdenum compound is preferably contained in an amount of 0.03 to 0.20% by mass as the amount of molybdenum (Mo).
Specific examples of the organic molybdenum compound include molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), and Mo amine complex. Of these, MoDTC is most preferred, and MoDTP is less preferred because phosphorus poisons the exhaust gas purification three-way catalyst.
In the present invention, as MoDTC, those represented by the following general formula (1) can be preferably used.
式中、R1〜R4は、炭素数4〜18個を有する直鎖及び/又は分岐のアルキル基及び/又はアルケニル基を表し、Xは酸素原子又は硫黄原子を表し、その酸素原子と硫黄原子との比は1/3〜3/1である。R1〜R4は、好ましくはアルキル基であり、特に好ましくは炭素数8〜14の分岐のアルキル基であり、具体的にはブチル基、2‐エチルヘキシル基、イソトリデシル基、ステアリル基等が挙げられる。1分子中に存在する4個のR1〜R4は、同一であってもよく、異なっていてもよい。また、R1〜R4の異なるMoDTCを2種以上混合して用いることもできる。In the formula, R 1 to R 4 represent a linear and / or branched alkyl group and / or alkenyl group having 4 to 18 carbon atoms, X represents an oxygen atom or a sulfur atom, and the oxygen atom and sulfur The ratio with the atoms is 1/3 to 3/1. R 1 to R 4 are preferably alkyl groups, particularly preferably branched alkyl groups having 8 to 14 carbon atoms, and specific examples thereof include a butyl group, a 2-ethylhexyl group, an isotridecyl group, and a stearyl group. It is done. Four R < 1 > -R < 4 > which exists in 1 molecule may be the same, and may differ. Further, two or more kinds of MoDTCs having different R 1 to R 4 can be mixed and used.
本発明において、脂環式エポキシ化合物としては、エポキシ化シクロアルカン及びその誘導体が挙げられる。エポキシ化シクロアルカンとしては、炭素数3〜12が好ましい。エポキシ化シクロアルカンの具体例としては、エポキシ化シクロプロパン、エポキシ化シクロブタン、エポキシ化シクロペンタン、エポキシ化ジシクロペンタン、エポキシ化シクロヘキサン、エポキシ化シクロヘプタン、エポキシ化シクロオクタン、エポキシ化シクロノナン、エポキシ化シクロデカン、エポキシ化シクロドデカン、エポキシ化ノルボルナン等が挙げられる。 In the present invention, the alicyclic epoxy compound includes epoxidized cycloalkane and derivatives thereof. As an epoxidized cycloalkane, C3-C12 is preferable. Specific examples of epoxidized cycloalkanes include epoxidized cyclopropane, epoxidized cyclobutane, epoxidized cyclopentane, epoxidized dicyclopentane, epoxidized cyclohexane, epoxidized cycloheptane, epoxidized cyclooctane, epoxidized cyclononane, and epoxidized. Examples include cyclodecane, epoxidized cyclododecane, and epoxidized norbornane.
エポキシ化シクロアルカン誘導体としては、脂環部分にアルキル基又はアルケニル基が1個以上導入されたアルキル化又はアルケニル化エポキシシクロアルカン、脂環部分に脂肪族若しくは芳香族のアルコキシ基が1個以上導入されたエーテル化合物、脂環部分にイミド基が1個以上導入されたイミド化合物及びビスイミド化合物、脂環部分にアミド基が1個以上導入されたアミド化合物等が挙げられ、より好ましくは脂環部分にカルボキシル基が1個以上導入されたエステル化合物が挙げられる。さらに好ましくは、エポキシ化シクロアルカンを2個有するものが好ましく、特には3,4‐エポキシシクロアルキル‐3,4‐エポキシシクロアルキルカルボキシレート(各アルキル基の炭素数は3〜12)が好ましく、具体的な化合物として、3,4‐エポキシシクロヘキシルメチル‐3,4‐エポキシシクロヘキサンカルボキシレートがもっとも好ましい。これら脂環式エポキシ化合物は、一種単独で用いてもよいし、二種以上を組み合わせて用いてもよい。
この脂環式エポキシ化合物の含有量は有効量含有させればよく、エンジン油組成物全量基準で0.05〜2質量%の範囲で適宜選定すればよい。Epoxidized cycloalkane derivatives include alkylated or alkenylated epoxycycloalkanes in which one or more alkyl groups or alkenyl groups are introduced into the alicyclic moiety, and one or more aliphatic or aromatic alkoxy groups introduced in the alicyclic moiety. Ether compounds, imide compounds and bisimide compounds in which one or more imide groups are introduced into the alicyclic portion, amide compounds in which one or more amide groups are introduced into the alicyclic portion, and the like, more preferably alicyclic portions And an ester compound in which one or more carboxyl groups are introduced. More preferably, those having two epoxidized cycloalkanes are preferable, and particularly, 3,4-epoxycycloalkyl-3,4-epoxycycloalkylcarboxylate (wherein each alkyl group has 3 to 12 carbon atoms) is preferable. As a specific compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is most preferable. These alicyclic epoxy compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
What is necessary is just to make content of this alicyclic epoxy compound contain effective amount, and what is necessary is just to select suitably in the range of 0.05-2 mass% on the basis of engine oil composition whole quantity.
本発明の省燃費型エンジン油組成物は、潤滑油としての性能をバランスよく確保するために上記以外の各種の添加剤を配合することができる。特には優れた清浄性及びスラッジ分散性、摩耗防止性能を確保するために、金属系清浄剤や無灰分散剤、摩耗防止剤を含有することが好ましい。 The fuel-saving engine oil composition of the present invention can be blended with various additives other than those described above in order to ensure a good balance of performance as a lubricating oil. In particular, in order to ensure excellent cleanliness, sludge dispersibility, and antiwear performance, it is preferable to contain a metallic detergent, an ashless dispersant, and an antiwear agent.
金属系清浄剤としては、アルカリ土類金属スルホネート、アルカリ土類金属フェネート及びアルカリ土類金属サリシレートから選ばれる少なくとも1種のアルカリ土類金属清浄剤を用いることが好ましい。
アルカリ土類金属スルホネートとしては、分子量300〜1,500、特に好ましくは400〜700のアルキル芳香族スルホン酸のアルカリ土類金属塩、特にマグネシウム塩及び/又はカルシウム塩であり、カルシウム塩が好ましく用いられる。As the metal detergent, it is preferable to use at least one alkaline earth metal detergent selected from alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate.
The alkaline earth metal sulfonate is an alkaline earth metal salt of an alkyl aromatic sulfonic acid having a molecular weight of 300 to 1,500, particularly preferably 400 to 700, particularly a magnesium salt and / or a calcium salt, and a calcium salt is preferably used. It is done.
アルカリ土類金属フェネートとしては、炭素数4〜30、好ましくは6〜18の直鎖又は分枝のアルキル基を有する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物の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る。
アルカリ土類金属サリシレートとしては、炭素数1〜30、好ましくは6〜18の直鎖又は分枝のアルキル基を有するアルキルサリチル酸のアルカリ土類金属塩、特に好ましくは、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る。
上記金属系清浄剤の含有量は任意であるが、省燃費型エンジン油組成物全質量に対して、金属量で0.05〜0.22質量%、好ましくは0.1〜0.2質量%含有させることが望ましい。Alkaline earth metal phenates include alkylphenols having a linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, alkylphenol sulfides, alkaline earth metal salts of Mannich reactants of alkylphenols, especially magnesium salts And / or calcium salts are preferably used.
Alkaline earth metal salicylates are preferably alkaline earth metal salts of alkylsalicylic acid having 1 to 30 carbon atoms, preferably 6 to 18 linear or branched alkyl groups, particularly preferably magnesium salts and / or calcium salts. Is preferably used.
The content of the metallic detergent is arbitrary, but is 0.05 to 0.22% by mass, preferably 0.1 to 0.2% by mass, based on the total mass of the fuel-saving engine oil composition. % Content is desirable.
また、無灰分散剤としては、ポリオレフィンから誘導されるアルケニルコハク酸イミド、アルキルコハク酸イミド及びそれらの誘導体が挙げられる。代表的なコハク酸イミドは、高分子量のアルケニル基もしくはアルキル基で置換されたコハク酸無水物と、1分子当たり平均4〜10個、より好ましくは5〜7個の窒素原子を含むポリアルキレンポリアミンとの反応により得ることができる。特には、高分子量のアルケニル基もしくはアルキル基として、数平均分子量が700〜5000のポリイソブテン、特に数平均分子量が900〜3000のポリイソブテンを有するポリブテニルコハク酸イミドがより好ましい。 Examples of the ashless dispersant include alkenyl succinimides, alkyl succinimides and derivatives thereof derived from polyolefins. Typical succinimides are polyalkylene polyamines containing succinic anhydride substituted with high molecular weight alkenyl or alkyl groups and an average of 4 to 10, more preferably 5 to 7 nitrogen atoms per molecule. It can obtain by reaction with. In particular, a polybutenyl succinimide having a polyisobutene having a number average molecular weight of 700 to 5000, particularly a polyisobutene having a number average molecular weight of 900 to 3000 is more preferable as a high molecular weight alkenyl group or alkyl group.
このポリブテニルコハク酸イミドは、高純度イソブテンあるいは1‐ブテンとイソブテンの混合物をフッ化ホウ素系触媒あるいは塩化アルミニウム系触媒で重合させて得られるポリブテンから得られるものであり、ポリブテン末端にビニリデン構造を有するものが通常5〜100mol%含有される。なお、ポリアルキレンポリアミン鎖には優れたスラッジ抑制効果を得る観点から2〜5個、特には3〜4個の窒素原子を含むものが好ましい。
また、ポリブテニルコハク酸イミドの誘導体としては、上記ポリブテニルコハク酸イミドに、ホウ酸等のホウ素化合物や、アルコール、アルデヒド、ケトン、アルキルフェノール、環状カーボネート、有機酸等の含酸素有機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又はアミド化した、いわゆる変性コハク酸イミドとして用いることができる。特に、ホウ酸等のホウ素化合物との反応で得られるホウ素含有アルケニル(もしくはアルキル)コハク酸イミドは、熱・酸化安定性の面で優れている。
この無灰分散剤の含有量は任意であるが、省燃費型エンジン油組成物全質量に対して、0.5〜15質量%含有することが好ましい。This polybutenyl succinimide is obtained from polybutene obtained by polymerizing a high-purity isobutene or a mixture of 1-butene and isobutene with a boron fluoride catalyst or an aluminum chloride catalyst, and has a vinylidene structure at the polybutene end. In general, 5 to 100 mol% is contained. The polyalkylene polyamine chain preferably contains 2 to 5, particularly 3 to 4 nitrogen atoms from the viewpoint of obtaining an excellent sludge inhibiting effect.
In addition, as derivatives of polybutenyl succinimide, boron compounds such as boric acid and oxygen-containing organic compounds such as alcohols, aldehydes, ketones, alkylphenols, cyclic carbonates, and organic acids are added to the polybutenyl succinimides. It can be used as a so-called modified succinimide in which a part or all of the remaining amino group and / or imino group is neutralized or amidated by acting. In particular, a boron-containing alkenyl (or alkyl) succinimide obtained by a reaction with a boron compound such as boric acid is excellent in terms of thermal and oxidation stability.
The content of the ashless dispersant is arbitrary, but is preferably 0.5 to 15% by mass with respect to the total mass of the fuel-saving engine oil composition.
本発明の省燃費型エンジン油組成物は、摩耗防止剤としてジチオリン酸亜鉛(ZnDTP)を、エンジン油組成物全質量基準で、リン(P)量として0.01〜0.10質量%含有させることが好ましく、0.05〜0.08質量%がより好ましい。エンジン油全質量に対するZnDTPに含まれるリン金属元素質量が0.01質量%未満では十分な摩耗防止性能を得ることができず、0.10質量%より大きい場合では自動車の排ガス浄化触媒に与える被毒の影響が大きくなる。
ZnDTPとしては、炭素数1〜24の直鎖状又は分枝状のアルキル基、炭素数3〜24の直鎖状又は分枝状のアルケニル基又は直鎖状若しくは分枝状のアルキルシクロアルキル基、炭素数6〜18のアリール基又は直鎖状若しくは分枝状のアルキルアリール基を有する化合物が好ましい。なお、このアルキル基やアルケニル基は、第1級、第2級及び第3級のいずれであってもよい。The fuel-saving engine oil composition of the present invention contains zinc dithiophosphate (ZnDTP) as an antiwear agent in an amount of 0.01 to 0.10 mass% as phosphorus (P) based on the total mass of the engine oil composition. It is preferably 0.05 to 0.08% by mass. When the phosphorus metal element mass contained in ZnDTP with respect to the total mass of the engine oil is less than 0.01% by mass, sufficient anti-wear performance cannot be obtained, and when it is greater than 0.10% by mass, it is applied to the exhaust gas purification catalyst of the automobile. The effect of poison is increased.
As ZnDTP, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 3 to 24 carbon atoms, or a linear or branched alkylcycloalkyl group And a compound having an aryl group having 6 to 18 carbon atoms or a linear or branched alkylaryl group is preferable. The alkyl group or alkenyl group may be any of primary, secondary, and tertiary.
ジチオリン酸亜鉛の具体例としては、ジプロピルジチオリン酸亜鉛、ジブチルジチオリン酸亜鉛、ジペンチルジチオリン酸亜鉛、ジヘキシルジチオリン酸亜鉛、ジイソペンチルジチオリン酸亜鉛、ジエチルヘキシルジチオリン酸亜鉛、ジオクチルジチオリン酸亜鉛、ジノニルジチオリン酸亜鉛、ジデシルジチオリン酸亜鉛、ジドデシルジチオリン酸亜鉛、ジプロピルフェニルジチオリン酸亜鉛、ジペンチルフェニルジチオリン酸亜鉛、ジプロピルメチルフェニルジチオリン酸亜鉛、ジノニルフェニルジチオリン酸亜鉛、ジドデシルフェニルジチオリン酸亜鉛、ジドデシルフェニルジチオリン酸亜鉛等が挙げられる。
ZnDTPの含有量は、エンジン油全重量に対して、ZnDTPに含まれるリン(P)金属元素重量で0.01〜0.10質量%が好ましく、0.03〜0.08質量%がより好ましい。Specific examples of zinc dithiophosphate include zinc dipropyldithiophosphate, zinc dibutyldithiophosphate, zinc dipentyldithiophosphate, zinc dihexyldithiophosphate, zinc diisopentyldithiophosphate, zinc diethylhexyldithiophosphate, zinc dioctyldithiophosphate, dinonyl Zinc dithiophosphate, zinc didecyl dithiophosphate, zinc didodecyl dithiophosphate, zinc dipropylphenyl dithiophosphate, zinc dipentylphenyl dithiophosphate, zinc dipropylmethylphenyl dithiophosphate, zinc dinonylphenyl dithiophosphate, zinc didodecylphenyl dithiophosphate And zinc didodecylphenyldithiophosphate.
The content of ZnDTP is preferably 0.01 to 0.10% by mass and more preferably 0.03 to 0.08% by mass with respect to the total weight of the engine oil in terms of the phosphorus (P) metal element content contained in ZnDTP. .
本発明のエンジン油には、所望により、さらに無灰系の酸化防止剤、粘度指数向上剤、流動点降下剤、金属不活性化剤、防錆剤や消泡剤等の添加剤を添加することができる。 If desired, additives such as ashless antioxidants, viscosity index improvers, pour point depressants, metal deactivators, rust inhibitors and antifoaming agents are added to the engine oil of the present invention. be able to.
次に、実施例により本発明を具体的に説明する。
基油としては、重質油の水素化分解で得られた生成油を水素化脱ロウすることで得られた鉱油系基油(動粘度:17.7mm2/s(40℃)、4.1mm2/s(100℃)、粘度指数:134、%CP:85、流動点:−20℃)を用いた。Next, the present invention will be described specifically by way of examples.
As the base oil, a mineral oil base oil (kinematic viscosity: 17.7 mm 2 / s (40 ° C.)) obtained by hydrodewaxing the product oil obtained by hydrocracking of heavy oil, 4. 1 mm 2 / s (100 ° C.), viscosity index: 134,% C P : 85, pour point: −20 ° C.).
上記基油に、添加剤として下記に説明するMoDTC、防食剤として潤滑油に対して広く添加されているベンゾトリアゾール誘導体(BTA)、エポキシ化合物、粘度指数向上剤(VI)及びその他添加剤を表1に示す割合で配合して実施例1〜2及び比較例1〜6のエンジン油を調製した。なお、その他の添加剤は、アルキルジチオリン酸亜鉛(ZnDTP)、Caスルホネート、アルケニルコハク酸イミド、流動点降下剤及び消泡剤からなる添加剤混合物であり、実施例及び比較例全部に共通して同じ添加量で添加した。粘度指数向上剤は、実施例及び比較例全部について組成物の100℃における動粘度が9.3〜9.5mm2/s(SAEエンジン油粘度分類の30に相当)になるよう添加した。In the above base oil, MoDTC described below as an additive, benzotriazole derivative (BTA), epoxy compound, viscosity index improver (VI) and other additives widely added to lubricating oil as anticorrosives are shown. The engine oils of Examples 1-2 and Comparative Examples 1-6 were prepared by blending at a ratio shown in FIG. The other additive is an additive mixture consisting of zinc alkyldithiophosphate (ZnDTP), Ca sulfonate, alkenyl succinimide, pour point depressant and antifoaming agent, and is common to all examples and comparative examples. Added in the same amount. The viscosity index improver was added so that the kinematic viscosity at 100 ° C. of the composition was 9.3 to 9.5 mm 2 / s (corresponding to 30 in the SAE engine oil viscosity classification) for all of the examples and comparative examples.
MoDTCとしては、一般式(1)で表される化合物で、R1〜R4が2‐エチルヘキシル基とイソトリデシル基との混合物で、酸素原子と硫黄原子との比が1/1のものを使用した。
ベンゾトリアゾール誘導体としては、N,N-ビス[(2‐エチルヘキシル)アミノメチル]‐1H‐ベンゾトリアゾール(チバスペシャリティ社製、Irgamet39)を使用した。
エポキシ化合物としては、脂環式エポキシ化合物である3,4‐エポキシシクロヘキシルメチル‐3,4‐エポキシシクロヘキサンカルボキシレートを、また比較のために、非脂環式エポキシ化合物である2‐エチルヘキシルグリシジルエーテル(エポキシ化合物1)及びネオデカン酸グリシジルエステル(エポキシ化合物2)を使用した。
粘度指数向上剤としては、ポリメタクリレート系化合物を用いた。As MoDTC, a compound represented by the general formula (1), in which R 1 to R 4 are a mixture of 2-ethylhexyl group and isotridecyl group and the ratio of oxygen atom to sulfur atom is 1/1 is used. did.
As the benzotriazole derivative, N, N-bis [(2-ethylhexyl) aminomethyl] -1H-benzotriazole (manufactured by Ciba Specialty, Irgamet 39) was used.
As the epoxy compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, which is an alicyclic epoxy compound, and 2-ethylhexyl glycidyl ether, which is a non-alicyclic epoxy compound (for comparison) ( Epoxy compound 1) and neodecanoic acid glycidyl ester (epoxy compound 2) were used.
As a viscosity index improver, a polymethacrylate compound was used.
表1の実施例及び比較例のエンジン油それぞれについて、腐食酸化安定性試験を実施して、試験後のオイルを誘導結合プラズマ‐原子発光分光法(ICP‐AES)で元素分析を行った。腐食酸化安定性試験はJISK2503に準拠して行ったが、試験条件は試験温度を135℃、試験片を銅(Cu)、鉛(Pb)、錫(Sn)に変更した。
また、供試エンジン油の省燃費性をSRV摩擦試験(試験条件:荷重400N、振幅1.5mm、 振動数50Hz、温度100℃)で評価し、良好な場合を○とし、不良な場合を×とした。
これらの結果を表2に示す。Each of the engine oils of the examples and comparative examples in Table 1 was subjected to a corrosion oxidation stability test, and the oil after the test was subjected to elemental analysis by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The corrosion oxidation stability test was conducted in accordance with JISK2503, but the test conditions were changed to 135 ° C. and the test piece was changed to copper (Cu), lead (Pb), and tin (Sn).
In addition, the fuel economy of the engine oil under test is evaluated by SRV friction test (test conditions: load 400N, amplitude 1.5mm, frequency 50Hz, temperature 100 ° C). It was.
These results are shown in Table 2.
表2に示すとおり、実施例1〜2のエンジン油組成物は、良好な省燃費性を示すと共に、腐食酸化安定性試験でのCuやPb、Snの溶出が少ないことが分かる。したがって、腐食摩耗防止性に優れつつ、高い省燃費性を発揮できる。
一方、MoDTCも脂環式エポキシも用いない比較例1では、腐食酸化安定性試験でのCuやPbの溶出は少ないものの、省燃費性が劣る。MoDTCを配合し、脂環式エポキシ化合物を配合しなかった比較例2では、省燃費性に優れるものの、腐食酸化安定性試験でのCuの著しい腐食が生じた。
また、MoDTCと共にベンゾトリアゾール誘導体を用いた比較例3、4ではベンゾトリアゾール誘導体の配合量が少ないとCuの溶出が多く、又はベンゾトリアゾール誘導体の配合量が多いとPbの溶出が多く、省燃費性に優れるものの腐食酸化安定性に劣ることが分かる。また、MoDTCと共に非脂環式エポキシ化合物を用いた比較例5、6ではCuの溶出が多く、特に脂肪酸とエポキシのエステルは、防食性が極めて低いことが分かる。As shown in Table 2, it can be seen that the engine oil compositions of Examples 1 and 2 show good fuel economy and less elution of Cu, Pb, and Sn in the corrosion oxidation stability test. Therefore, high fuel efficiency can be exhibited while being excellent in corrosion wear prevention.
On the other hand, in Comparative Example 1 in which neither MoDTC nor alicyclic epoxy is used, the elution of Cu and Pb in the corrosion oxidation stability test is small, but the fuel efficiency is inferior. In Comparative Example 2 in which MoDTC was blended and no alicyclic epoxy compound was blended, although Cu was excellent in fuel economy, significant corrosion of Cu occurred in the corrosion oxidation stability test.
In Comparative Examples 3 and 4 using a benzotriazole derivative together with MoDTC, the dissolution of Cu is large when the blending amount of the benzotriazole derivative is small, or the dissolution of Pb is large when the blending amount of the benzotriazole derivative is large. It can be seen that the corrosion oxidation stability is inferior although it is excellent. Further, in Comparative Examples 5 and 6 using a non-alicyclic epoxy compound together with MoDTC, it can be seen that there is much elution of Cu, and in particular, esters of fatty acid and epoxy have extremely low anticorrosion properties.
本発明は、腐食、摩耗防止性能、さらは省燃費性に優れており、ガソリンエンジン、ディーゼルエンジン、ガスエンジンなどの内燃機関用のエンジン油として利用することができる。 The present invention is excellent in corrosion, wear prevention performance, and fuel efficiency, and can be used as an engine oil for internal combustion engines such as gasoline engines, diesel engines, and gas engines.
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