CA2799082C - Fuel economical lubricating oil composition for internal combustion engines - Google Patents
Fuel economical lubricating oil composition for internal combustion engines Download PDFInfo
- Publication number
- CA2799082C CA2799082C CA2799082A CA2799082A CA2799082C CA 2799082 C CA2799082 C CA 2799082C CA 2799082 A CA2799082 A CA 2799082A CA 2799082 A CA2799082 A CA 2799082A CA 2799082 C CA2799082 C CA 2799082C
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- CA
- Canada
- Prior art keywords
- carbon atom
- alkyl group
- range
- atom number
- calcium
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 119
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 94
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 11
- 239000000446 fuel Substances 0.000 title abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 159
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 132
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 67
- 239000011575 calcium Substances 0.000 claims abstract description 65
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 56
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 55
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 claims abstract description 47
- 239000003599 detergent Substances 0.000 claims abstract description 39
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 32
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 27
- 239000011733 molybdenum Substances 0.000 claims abstract description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims description 37
- 230000003647 oxidation Effects 0.000 claims description 37
- 238000007254 oxidation reaction Methods 0.000 claims description 37
- 239000003921 oil Substances 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 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 claims description 17
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 17
- -1 borate compound Chemical class 0.000 claims description 16
- 230000001050 lubricating effect Effects 0.000 claims description 12
- 229960002317 succinimide Drugs 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- BRESEFMHKFGSDY-UHFFFAOYSA-N molybdenum;pyrrolidine-2,5-dione Chemical compound [Mo].O=C1CCC(=O)N1 BRESEFMHKFGSDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002199 base oil Substances 0.000 abstract description 18
- 150000001721 carbon Chemical group 0.000 description 73
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000005266 diarylamine group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 229960001860 salicylate Drugs 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- VBIGULIJWJPALH-UHFFFAOYSA-L calcium;2-carboxyphenolate Chemical class [Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O VBIGULIJWJPALH-UHFFFAOYSA-L 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-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
- 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
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 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
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical class C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 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
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229940113162 oleylamide Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 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
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 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
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003580 thiophosphoric acid esters Chemical class 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
- C10M2205/163—Paraffin waxes; Petrolatum, e.g. slack wax used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/09—Complexes with metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/54—Fuel economy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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Abstract
A fuel economical lubricating oil composition for internal combustion engines comprises a base oil and an additive composition comprising an overbased metal- containing detergent and a molybdenum-containing friction modifier, in which the overbased metal- containing detergent comprises calcium salicylate having an alkyl group having an average carbon atom number of 14-18, at least 60 mol. % of the alkyl group having a carbon atom number of 14- 18, and calcium sulfonate having an alkyl group having an average carbon atom number of 20-24, at least 60 mol.% of the alkyl group having a carbon atom number of 20-24, and/or calcium salicylate having an alkyl group having an average carbon atom number of 20-28, at least 60 mol.% of the alkyl group having a carbon atom number of 20-28.
Description
Fuel Economical Lubricating Oil Composition for Internal Combustion Engines This application claims priority to Japanese Patent Application number JP2011-which was filed in Japan on 12-27-2011.
Field of Invention The present invention relates to a lubricating oil composition which is favorably employable for lubricating internal combustion engines such as diesel engines, gasoline engines, and gas engines mounted on land-travelling vehicles, with high fuel economy.
Background of Invention Recently, the requirements for improvement of fuel economy to land-travelling vehicles on which a gasoline engine or a diesel engine is mounted, such as autornotives, have continued with increased severity. It has been known that the improvement of fuel economy is most effec-1 5 tively made by reduction of weight of the vehicle on which an internal combustion engine is mounted. It also has been known that the improvement of fuel economy can be attained by appropriately selecting the lubricating oil composition employed for lubricating the internal combustion engine mounted on the vehicle.
For the reason described above, until now, the companies engaged for developing lubricating oil compositions as well as the companies engaged for developing lubricating oil additives have intensively made studies for providing lubricating oil compositions which show improved fuel economy.
The improvement of fuel economy provided by the lubricating oil composition generally can be attained by reduction of torque of rotation of the engine parts which is caused by the use of a lubricating oil composition providing reduction of friction to the sliding parts of the engine.
The extent of reduction of friction provided by the lubricating oil composition mainly depends on the viscosity of the lubricating oil composition and selection of additives, mainly the selection of the friction modifier. For instance, if the lubricating oil composition is formulated with a base oil of low viscosity, the friction-reducing effect provided by the lubricating oil composition increases. However, the use of the base oil of low viscosity likely results in unfavorable phenomenon such as increase of oil consumption occurring during operation of the engine.
Therefore, the improvement of fuel economy by the use of a lubricating oil composition em-ploying a base oil of low viscosity has its limit. For this reason, intensive studies have been
Field of Invention The present invention relates to a lubricating oil composition which is favorably employable for lubricating internal combustion engines such as diesel engines, gasoline engines, and gas engines mounted on land-travelling vehicles, with high fuel economy.
Background of Invention Recently, the requirements for improvement of fuel economy to land-travelling vehicles on which a gasoline engine or a diesel engine is mounted, such as autornotives, have continued with increased severity. It has been known that the improvement of fuel economy is most effec-1 5 tively made by reduction of weight of the vehicle on which an internal combustion engine is mounted. It also has been known that the improvement of fuel economy can be attained by appropriately selecting the lubricating oil composition employed for lubricating the internal combustion engine mounted on the vehicle.
For the reason described above, until now, the companies engaged for developing lubricating oil compositions as well as the companies engaged for developing lubricating oil additives have intensively made studies for providing lubricating oil compositions which show improved fuel economy.
The improvement of fuel economy provided by the lubricating oil composition generally can be attained by reduction of torque of rotation of the engine parts which is caused by the use of a lubricating oil composition providing reduction of friction to the sliding parts of the engine.
The extent of reduction of friction provided by the lubricating oil composition mainly depends on the viscosity of the lubricating oil composition and selection of additives, mainly the selection of the friction modifier. For instance, if the lubricating oil composition is formulated with a base oil of low viscosity, the friction-reducing effect provided by the lubricating oil composition increases. However, the use of the base oil of low viscosity likely results in unfavorable phenomenon such as increase of oil consumption occurring during operation of the engine.
Therefore, the improvement of fuel economy by the use of a lubricating oil composition em-ploying a base oil of low viscosity has its limit. For this reason, intensive studies have been
-2 -made on employment of appropriate lubricating oil additives, whereby improving the fuel economy provided by the lubricating oil composition. Until now, a variety of inventions made from these studies have been disclosed in a number of patent applications_ Patent publication I (JP 5-163497 A) discloses an engine oil composition showing low friction property, which comprises a base oil and an additive composition comprising a borated alkenylsuccinirnide, an alkaline earth metal salicylate and molybdenum di thiophosphate and/or molybdenum dithiocarbamate.
Patent publication 2 (JP 6-336592 A) describes that a lubricating oil composition comprising zinc dialkyldithiophosphate being mainly composed of a zinc dialkyldithiophosphate having a secondary alkyl group, a metal-containing detergent composition comprising calcium sulfonate (e.g., TBN 200-300) and calcium salicylate (e.g., TBN 10-100), and molybdenum dithiocarbamate having a Cs,23 hydrocarbyl group shows increased low wear-producing property and increased low friction property.
Patent publication 3 (JP 8-302378 A) describes that an engine oil composition comprising a base oil having a specific kinematic viscosity and specific total aromatic content, an alkaline earth metal salicylate, zinc dialkyldithiophosphate, a succinimide ashless dispersant having a polybutenyl group having a molecular weight of 900-3500, a phenol type-ashless oxidation inhibitor, and molybdenum dithiocarbamate shows improved fuel economy.
Summary of Invention Accordingly, it is the object of the invention to provide an improvement of a lubricating oil composition containing a molybdenum-containing friction modifier which is well known to give an excellent friction-reducing property as well as to improve the fuel economy. The improved lubricating oil composition of the invention shows further increased fuel economy.
The inventors of the present invention have studied on the synergistic effects for improvement of fuel economy provided by combinations of the molybdenum-containing friction modifier and various lubricating oil additives_ As a result of the studies, the inventors have found that a lubricating oil composition containing a combination of the molybdenum-containing friction modifier and an overbased metal-containing detergent composition comprising calcium salicylate having an alkyl group having an average carbon atom number of 14-18 (at least 60 mol.% of the alkyl group has a carbon atom number of 14-18), and calcium sulfonate having an alkyl group having an average carbon atom number of 20-24 (at least 60 mol.%
of the alkyl group has a carbon atom number of 20-24), and/or calcium salicylatc having an alkyl group
Patent publication 2 (JP 6-336592 A) describes that a lubricating oil composition comprising zinc dialkyldithiophosphate being mainly composed of a zinc dialkyldithiophosphate having a secondary alkyl group, a metal-containing detergent composition comprising calcium sulfonate (e.g., TBN 200-300) and calcium salicylate (e.g., TBN 10-100), and molybdenum dithiocarbamate having a Cs,23 hydrocarbyl group shows increased low wear-producing property and increased low friction property.
Patent publication 3 (JP 8-302378 A) describes that an engine oil composition comprising a base oil having a specific kinematic viscosity and specific total aromatic content, an alkaline earth metal salicylate, zinc dialkyldithiophosphate, a succinimide ashless dispersant having a polybutenyl group having a molecular weight of 900-3500, a phenol type-ashless oxidation inhibitor, and molybdenum dithiocarbamate shows improved fuel economy.
Summary of Invention Accordingly, it is the object of the invention to provide an improvement of a lubricating oil composition containing a molybdenum-containing friction modifier which is well known to give an excellent friction-reducing property as well as to improve the fuel economy. The improved lubricating oil composition of the invention shows further increased fuel economy.
The inventors of the present invention have studied on the synergistic effects for improvement of fuel economy provided by combinations of the molybdenum-containing friction modifier and various lubricating oil additives_ As a result of the studies, the inventors have found that a lubricating oil composition containing a combination of the molybdenum-containing friction modifier and an overbased metal-containing detergent composition comprising calcium salicylate having an alkyl group having an average carbon atom number of 14-18 (at least 60 mol.% of the alkyl group has a carbon atom number of 14-18), and calcium sulfonate having an alkyl group having an average carbon atom number of 20-24 (at least 60 mol.%
of the alkyl group has a carbon atom number of 20-24), and/or calcium salicylatc having an alkyl group
- 3 -having an average carbon atom number of 20-28 (at least 60 mol.% of the alkyl group has a car-bon atom number of 20-28) shows surprisingly improved fuel economy. The invention described herein has been made on this finding.
Accordingly, the present invention provides a lubricating oil composition for internal combustion engines which comprises a major amount of an oil of lubricating viscosity and a minor amount of an additive composition comprising an overbased metal-containing detergent composition and a molybdenum-containing friction modifier, wherein the overbased metal-containing detergent composition comprises calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% (preferably, at least 70 mol.%) of said alkyl group having a carbon atom number in the range of 14 to 18; and at least one of the following calcium-containing detergents:
calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% (preferably, at least 70 mol.%) of said alkyl group having a carbon atom number in the range of 20 to 24, and calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% (preferably, at least 70 mol.%) of said alkyl group having a carbon atom number in the range of 20 to 28.
The lubricating oil composition of the invention contains the base oil (i.e., oil of lubricat-ing viscosity) generally in the amount of 70 wt.% or more, preferably in the amount of 80 wt.%
2 0 or more, of the lubricating oil composition.
In another aspect, there is provided a lubricating oil composition for internal combustion engines which comprises a major amount of an oil of lubricating viscosity and a minor amount of an additive composition comprising an overbased metal-containing detergent composition and a molybdenum-containing friction modifier;
wherein the overbased metal-containing detergent composition comprises a calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18; and one or more calcium-containing detergents selected from the group consisting of:
a calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24; and -3a-a calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28.
In another aspect, there is provided a method of making the lubricating oil composition comprising adding to an oil of lubricating viscosity the following additive components:
a molybdenum-containing friction modifier; and an overbased metal-containing detergent composition comprising a calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18; and one or more calcium-containing detergents selected from the group consisting of:
a calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24; and a calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28.
Detailed Description of Invention Preferred embodiments of the invention are described below.
(1) The molybdenum-containing friction modifier comprises molybdenum dithiocarbamate.
(2) The calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 has an overbased degree of 1 to 4, and the calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24 and the calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28 have an overbased degree of 6 to 24.
Accordingly, the present invention provides a lubricating oil composition for internal combustion engines which comprises a major amount of an oil of lubricating viscosity and a minor amount of an additive composition comprising an overbased metal-containing detergent composition and a molybdenum-containing friction modifier, wherein the overbased metal-containing detergent composition comprises calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% (preferably, at least 70 mol.%) of said alkyl group having a carbon atom number in the range of 14 to 18; and at least one of the following calcium-containing detergents:
calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% (preferably, at least 70 mol.%) of said alkyl group having a carbon atom number in the range of 20 to 24, and calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% (preferably, at least 70 mol.%) of said alkyl group having a carbon atom number in the range of 20 to 28.
The lubricating oil composition of the invention contains the base oil (i.e., oil of lubricat-ing viscosity) generally in the amount of 70 wt.% or more, preferably in the amount of 80 wt.%
2 0 or more, of the lubricating oil composition.
In another aspect, there is provided a lubricating oil composition for internal combustion engines which comprises a major amount of an oil of lubricating viscosity and a minor amount of an additive composition comprising an overbased metal-containing detergent composition and a molybdenum-containing friction modifier;
wherein the overbased metal-containing detergent composition comprises a calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18; and one or more calcium-containing detergents selected from the group consisting of:
a calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24; and -3a-a calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28.
In another aspect, there is provided a method of making the lubricating oil composition comprising adding to an oil of lubricating viscosity the following additive components:
a molybdenum-containing friction modifier; and an overbased metal-containing detergent composition comprising a calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18; and one or more calcium-containing detergents selected from the group consisting of:
a calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24; and a calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28.
Detailed Description of Invention Preferred embodiments of the invention are described below.
(1) The molybdenum-containing friction modifier comprises molybdenum dithiocarbamate.
(2) The calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 has an overbased degree of 1 to 4, and the calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24 and the calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28 have an overbased degree of 6 to 24.
-4-(3) A ratio of the overbased degree of the calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mot.% of said alkyl group having a carbon atom number in the range of 20 to 24 and the calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28 to the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 is in the range of 2 to 12, (4) The overbased metal-containing detergent composition comprises the calcium salicylatc having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 and the calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24.
(5) The overbased metal-containing detergent composition comprises the calcium alicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 and the calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 2g.
(6) The lubricating oil composition comprises the molybdenum-containing friction modifier in an amount of 0.01 to 0.15 wt.% in terms of molybdenum content in the lubricating oil composition.
(7) The lubricating oil composition comprises each of the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.%
of said alkyl group having a carbon atom number in the range of 14 to 18 and at least one of the following calcium-containing detergents: calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24 and calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 24 to 28 in an amount of 0.01 to 0.4 wt_% in terms of calcium content in the lubricating oil composition.
of said alkyl group having a carbon atom number in the range of 14 to 18 and at least one of the following calcium-containing detergents: calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24 and calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 24 to 28 in an amount of 0.01 to 0.4 wt_% in terms of calcium content in the lubricating oil composition.
(8) The lubricating oil composition further comprises a low overbased calcium sul tb-nate having an alkyl group having an average carbon atom number in the range of 14 to 24, at least 60 mot.% of said alkyl group having a carbon atom number in the range of 14 to 24 and having an overbased degree of 0.1 to 2.
(9) The lubricating oil composition further comprises a lubricating oil additive se-lected from the group consisting of a nitrogen-containing ashless dispersant, a zinc phosphate oxidation inhibitor, a zinc phosphate anti-wear agent, a phenolic oxidation inhibitor, and an amine oxidation inhibitor.
(10) Each of the zinc phosphate oxidation inhibitor and zinc phosphate anti-wear agent comprises a mixture of zinc di(primary alkyl) dithiophosphate and zinc di(secondary alkyl) dithiophosphate in a weight ratio of 1/9 to 9/1.
(11) The nitrogen-containing ashless dispersant is a suceinimide dispersant which may be post-treated with ethylene carbonate or a borate compound.
(12) The lubricating oil composition further comprises a molybdenum complex of succinimide which may contain sulfur.
(13) The oil of lubricating viscosity has a viscosity index of 120 to 160.
(14) The lubricating oil composition satisfies SAE viscosity grade of 0W20.
The lubricating oil composition of the invention provides increased high fuel economy to internal combustion engines such as gasoline engines and diesel engines.
Therefore, vehicles on which these internal combustion engines are mounted show improved fuel economy.
The base oil and additives employable for the preparation of the lubricating oil composition of the invention are described below in more detail.
Base oil The base oil (i.e., oil of lubricating viscosity) generally is a mineral oil or a synthetic oil showing a kinematic viscosity of 2 to 50 n11n2/s at 100 C. There are no specific limitations on JO the natures and other properties of the mineral oil and synthetic oil.
However, the sulfur content of the base oil should be 0.1 wt.% or less. The sulfur content preferably is 0.03 wt.% or less, and more preferably is 0.005 wt.% or less.
The mineral oil preferably is an oil which is obtained by processing a lubricating oil distillate of a mineral oil by solvent refining, hydrogenation, or their combination. Particularly preferred is a highly hydrogenated refined oil (corresponding to a hydrocracked oil, typically has a viscosity index of 120 to 160, an aromatic component content of 5 wt.% or less, a nitrogen con-tent of 50 wt.ppm or less, and a sulfur content of 50 wt ppm or less).
Particularly preferred is a high viscosity index base oil, for instance, a base oil having a viscosity index of 140 to 160 which is obtained by hydroisornerization of slack wax or GTL wax (Gas-To-Liquid).
Examples of the synthetic oils (synthetic lubricating base oils) include poly-D-olefiri such as a polymerized compound of 0-olefin having 3 to 12 carbon atoms; a chalky' ester of a di-basic acid such as sebacic acid, azelaic acid or adipic acid and an alcohol having 4 to 18 carbon atoms, typically dioctyl sebacate; a polyol ester which is an ester of 1,1,1-trimethylolpropane or penta-erythritol and a mono-basic acid having 3 to 18 carbon atoms; and alkylbenzene having an alkyl group of 9 to 40 carbon atoms. The synthetic oil generally contains essentially no sulfur, shows good stability to oxidation and good heat resistance, and gives loss residual carbon and soot when it is burned. Therefore, the synthetic oil is preferably employed for the lubricating oil composi-tion of the invention. Particularly preferred is poly-D-olefin, from the viewpoint of the object of the invention.
Each of the mineral oil and synthetic oil can be employed singly. If desired, however, two or more mineral oils can be employed in combination, and two or more synthetic oils can be employed in combination. The mineral oil and synthetic oil can be employed in combination at an optional ratio.
Molybdenum-containing friction modifier The lubricating oil composition of the invention contains a molybdenum-containing friction modifier. The molybdenum-containing friction modifier can be any one of the known molybdenum-containing friction modifiers or the known molybdenum-containing friction modifier compositions. These friction modifiers and friction modifier compositions are described in the aforementioned Patent publications 1 to 3.
Preferred molybdenum-containing friction modifier is, for example, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, amine-molybde-num complex compound, oxymolybdenum diethylate amid; and oxymolybdenum monoglyceride. Most preferred is a molybdenum dithiocarbamate friction modifier.
The lubricating oil composition of the invention generally contains the molybdenum-containing friction modifier in an amount of 0.01 to 0,15 wt.% in terms of the molybdenum content.
verbose() metal-containing detergent The lubricating oil composition of the invention contains a combination of the following overbased metal-containing detergents:
(a) calcium salicylate (specifically, monoalkylsalicylate) having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group hay-.. ing a carbon atom number in the range of 14 to IS; and (b) calcium sulfonate (specifically, monoalkylsulfonate) having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24, and/or calcium salicylate (specifically, monoalkylsalicylatc) having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group baying a carbon atom number in the range of 20 to 28, Each of the above-mentioned components (b), namely, calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24, and calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.%
of said alkyl group having a carbon atom number in the range of 20 to 28 can be employed singly or in combination.
The above-mentioned component (a), namely, calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 rnol.% of said alkyl group having a carbon atom number in the range of 14 to 18 preferably is a mixture comprising plural calcium salicylates having an alkyl group having an average carbon atom number in the range of 14 to 18 in an amount of 60 mol.% or more, particularly 70 mol.% or more.
One of the above-mentioned component (b), namely, calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol,% of said alkyl group having a carbon atom number in the range of 20 to 24 preferably is a mixture comprising plural calcium sulfonates having an alkyl group having an average carbon atom number in the range of 20 to 24 in an amount of 60 mol.% or more, particularly 70 mol.% or more.
Another of the above-mentioned component (b), namely, calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28 preferably is a mixture comprising plural calcium salicylates having an alkyl group having an average carbon atom number in the range of 20 to 28 in an amount of 60 mol.% or more, particularly 70 mol.% or more.
The lubricating oil composition contains each of the component (a) and component (b) generally in an amount of 0.01 to 0.4 wt.%, in terms of calcium content, based on the total amount of the lubricating oil composition.
It is preferred that the calcium salicylate of the component (a) is calcium salicylate having an overbased degree of 1 to 4, particularly 1.5 to 3. The calcium salicylate can be sulfurized or unsulfurized.
It is preferred that the calcium sulfonate and calcium salicylate of the component (b) are calcium sulfonate and calcium salicylate independently having an overbased degree of 6 to 24.
Preferably, the calcium sulfonate has an overbased degree of 14 to 20, and the calcium salicylate has an overbased degree of 6 to 12.
The ratio of overbased degree for the component (b)/component (a) is preferably in the range of 2 to 12.
It is preferred that the lubricating oil composition of the invention further contains cal-.. cium sulfonate having an alkyl group having an average carbon atom number in the range of 14 to 24, at least 60 mol.% (preferably, at least 70 mol.%) of said alkyl group having a carbon atom number in the range of 14 to 24 and having an overbased degree of 0.1 to 2.
The lubricating oil composition of the invention can further contain relatively small amounts of other overbased or less overbased metal-containing detergents than the above-men-tioned components (a) and (b). These metal-containing detergents may be salicylates, earboxylates, sulfonates and/or phenates.
Other additives The lubricating oil composition of the invention can further contain other lubricating oil additives. Examples of the other lubricating oil additives include nitrogen-containing ashless dispersants, zinc phosphate oxidation inhibitors (or zinc phosphate anti-wear agent) such as zinc dihydrocarbyldithiophosphate, and organic oxidation inhibitors (e.g., phenolic oxidation inhibitors and amine oxidation inhibitors).
¨ 9 ¨
The nitrogen-containing ashless dispersant preferably is an alkenyl- or alkyl-succinimide derived from polyolefin or a derivative thereof. The lubricating oil composition can contain the nitrogen-containing ashless dispersant in an amount of 0.01 to 0.3 wt.%, in terms of the nitrogen content, based on the amount of the lubricating oil composition. A
representative suecinimide can be prepared by the reaction between succinic anhydride substituted with a high molecular weight alkenyl Or alkyl and a polyalkylene polyamine containing average 4 to 10 (preferably 5 to 7) nitrogen atoms in one molecule. The high molecular weight alkenyl or alkyl is preferably derived from polybutene having a number average molecular weight of about 900 to 3,000.
The process for obtaining the polybutexiyl-succinic anhydride by the reaction of polybutcne and maleic anhydride is generally performed by the chlorination process using a chloride compound. Otherwise, a thermal reaction process using no chlorine compound can be employed. It is preferred to employ a polybutenylsuccinirnide which is derived from a polybutenylsuccinic anhydride by the thermal reaction process_ The succinirnide can be a post-treated succinimide which is prepared by the reaction with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate, organic acid or the like. Par-ticularly, a berated alkenyl(or alkyl)-succinimide which is obtained by the reaction with a boron-containing compound such as boric acid or a boron compound is advantageous from the view-points of thermal and oxidation stability.
The lubricating oil composition may contain other ashless dispersants such as an alkenyl-benzylamine ashless dispersant and/or an alkenylsuccinic acid ester ashless dispersant in addition to or in place of the above-mentioned alkenyl(or allcy1)-succinimide ashless dispersant.
The lubricating oil composition may contain a zinc phosphate oxidation inhibitor (or zinc phosphate anti-ware agent). The zinc phosphate oxidation inhibitor (or zinc phosphate anti-ware agent) may be selected from the group consisting of zinc dialkyldithiophosphate, zinc di-alkylmonothiophosphate and zinc dihydmcarbylphosphate). The zinc phosphate oxidation inhibitors/anti-wear agents are well known with respect to their preparation processes and natures. The zinc phosphate oxidation inhibitors/anti-wear agents are generally contained in an amount of 0.01 to 0.12 wt %, in terms of the phosphorus content, based on the amount of the lubricating oil composition. However, the amount preferably is in the range of 0.01 to 0.06 wt.%, in consideration of the preparation of a low-phosphorus, low-sulfur lubricating oil Composition.
The zinc dialkyldithiophosphate preferably contains an alkyl group having 3-18 carbon atoms or an alkylaryl group having C3_ oi alkyl group. Most preferred is a zinc dialkyldithiophosphate containing an alkyl group derived from a secondary alcohol having 3-18 carbon atoms or a zinc diallcyIdithiophosphate containing a mixture of alkyl groups derived from a mixture of a primary alcohol having 3-18 carbon atoms and a secondary alcohol having 3-18 carbon atoms. Both arc particularly effective for reducing wear. A zinc diancyldithiophosphate derived from a primary alcohol shows high thermal resistance. These zinc dialkyldithiophosphates can be employed alone or in combination in the form of a mixture mainly comprising one derived from the secondary alcohol and/or one derived from the primary alcohol.
'the lubricating oil composition of the invention preferably contains an organic oxidation inhibitor in an amount or 0.01-5 wt.%, preferably 0.1-3 wt.%. The oxidation inhibitor can be a hindered phenol oxidation inhibitor or a diarylamine oxidation inhibitor. The diarylamine oxidation inhibitor is advantageous in giving a base number originating from the nitrogen atoms.
The hindered phenol oxidation inhibitor is advantageous in producing no NO
gas.
Examples of the hindered phenol oxidation inhibitors include 2,6-di-t-butyl-p-ercsol, 4,4-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-buty1-o-cresol), 4,4'-isopropy1idenebis(2,6-di-t-butylpheno1), 4,4'-bis(2,6-di-t-butylphenol), 2,2'-rriethylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydoxyphenyl)propionate], octyl 3-(3,5-di-t-buty1-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-t-buty1-4-hydroxypherlyl)propionate, and octyl 3-(3,54-buty1-4-hydroxy-3-methylphenyl)propionate.
Examples of the diarylamine oxidation inhibitors include alkyldiphenylarnine having a mixture of alkyl groups of 4 to 9 carbon atoms, p,p'-dioctyldiphenylamine, phenyl-D-naphthyl amine, phenyl- CI -naphthylamine, alkylated 0-naphthylaminc, and alkylated phenyl-0 -naphthylarnine.
Each of the hindered phenol oxidation inhibitor and diarylamine oxidation inhibitor can be employed alone or in combination. If desired, other oil soluble oxidation inhibitors can be employed in combination with the above-mentioned oxidation inhibitor(s).
The lubricating oil composition of the invention may further contain an oxymolybdenum complex of succinimide, particularly a sulfur-containing oxymolybdenum complex of succinimide. The sulfur-containing oxymolybdenum complex of succinimide can provide increased oxidation inhibition when it is employed in combination with the above-mentioned phenolic or amine oxidation inhibitors.
The lubricating oil composition of the invention may further contain an alkali metal borate hydrate in an amount of 5 wt.% or less, particularly in an amount of 0.01 to 5 wt.%. A
representative alkali metal borate hydrate can be prepared in the manner described in United States Patents 3,929,650 and 4,089,790_ For example, the alkali metal boratc hydrate can be in the form of a dispersion containing micro-particles of an alkali metal borate hydrate which is pro-duced by carbonizing a neutral alkali metal or alkaline earth metal sulfonate in the presence of an alkali metal hydroxide to yield an overbased sulfonate and reacting the overbased sulfonate with boric acid. In the carbonizing procedure, it is desired to incorporate an ashiess dispersant such as succinimidc into the reaction mixture. The alkali metal preferably is potassium or sodium. The alkali metal borate hydrate can be a dispersion of 1(133050H20 particles having a particle size of about 0.3 Din or less which is dispersed in the presence of a neutral calcium sulfonate and succinimide_ The lubricating oil composition of the invention preferably contains a viscosity index improver in an amount of 20 wt.% or less, preferably Ito 20 wt.%. Examples of the viscosity index improvers are polymers such as polyalkyl methacrylate, ethylene-propylene copolymer, styrene-butadiene copolymer, and polyisoprene. A dispersant viscosity index improver and a multi-functional viscosity index improver which are produced by providing dispersing properties to the above-mentioned polymer are preferably employed. The viscosity index improvers can be used alone or in combination.
The lubricating oil composition of the invention may further contain a small amount of various auxiliary additives. Examples of the auxiliary additives are described below_ Oxidation inhibitor or anti-wear agent such as zinc dithiocarbamate, methyIenehis(dibutyldithiocarbarnate), oil soluble copper compounds, sulfur-containing compounds (e.g., sulfurized olefins, sulfurized esters, and polysulfide), phosphoric acid esters, phosphorous acid esters, thiophosphoric acid esters, and organic amide compounds (e.g., oleylamide); benzotriazol compounds and thiadiazol compounds functioning as metal deactivating agent; and nonionic polyoxyalkylene surface active agents such as polyoxyethylene-alkylphenyl ether and copolymers of ethylene oxide and propylene oxide functioning as an anti-rust agent and an anti-emulsifying agent.
Further, various amines, amides, amine salts and their derivatives which can function as friction modifiers can be employed.
Furthermore, various compounds functioning as an anti-foaming agent and a pour point depressant can be incorporated.
Thc above-mentioned auxiliary additives may be incorporated into the lubricating oil composition in an amount of 3 wt.% or less, particularly in an amount of 0.001-3 wt %_ Examples 11-31, and Comparative Examples 11-31 ( 1 ) Preparation of lubricating oil compositions (test oils) Lubricating oil compositions were prepared by adding the below-mentioned additive components to the base oil to give the formulations set forth in Table I. The lubricating oil compositions of Examples 1 to 3 are according to the invention, while the lubricating oil compositions of Comparative Examples to 3 are for comparison. The lubricating oil corn-positions were formulated to show a viscosity grade (SAE viscosity grade) of 0W20 and a kine-matic viscosity of 7.7-7.8 rnm2/s at 100 C, by addition of a viscosity index improver.
(2) Base oil and additives (I)Base oil:
Mineral base oil (kinematic viscosity at 100 C: 4.1 mm2/s, viscosity index:
137) prepared from slack wax via hydrogenation, fractional distillation and dewaxing.
(II) Additives Nitrogen-containing ashless dispersant Ethylene carbonate post-treated suceinimide dispersant (his-type, nitrogen content: 1.0 wt.%) derived from polybutene (number average molecular weight: about 2,300).
Metal-containing detergent Overbased Ca sa.licylate (1)[Ca-sali-11: Calcium monoalkylsalicylate having alkyl .. groups in which approx. 80 mol.% of the whole alkyl groups were C14_18 alkyl groups (Ca: 6.1 wt.%, S: 0.1 wt.%, TBN: 170 mg KOH/g, overbased degree: 2.3) b) Overbased Ca sulfonate [Ca-sulf-1]: Calcium alkyltoluenesulfonate having alkyl groups in which approx. 80 mol.% of the whole alkyl groups were C20-24 alkyl groups (Ca: 16.0 wt.%, S: L6 wt%, TBN: 423 mg KOH/g, overbased degree: 17) Overbased Ca salicylate (2){Ca-sali-2]: Calcium monoalkylsalicylate having alkyl groups in which approx. 80 mot% of the whole alkyl groups were C20-28 alkyl groups (Ca: 11.4 wt_%, S: 0.2 wt.%, TBN: 320 mg KOH/g, overbased degree: 8.2) d) Low overbased Ca sulfonate [Ca-sulf-2]: Calcium alkylbenzenesulfonate having alkyl groups in which approx. 80 mol.% of the whole alkyl groups were C14-24 alkyl groups (Ca: 2_4 wt.%, S: 2.9 wt.%, TBN: 17 mg KOH/g, overbased degree: 0.34) Molybdenum-containing_ friction modifier Sulfurized oxymolybdenum dithiocarbarnate (Mo-DTC, Mo: 10 wt.%, S: 11 wt.%) Zinc phosphate oxidation inhibitor Zinc di(secondary alkyl)dithiophosphate (ZriDTP- , P: 7,8 wt.%, Zn: 7.8 wt.%, S: 14 wt%) Zinc di(primary alkyl)dithiophosphate (ZnDTP-2, P: 73 wt.%, Zn: 8.4 wt.%, S:
14 wt%) Organic oxidation inhibitor(Ox_ Inhi.
Amine oxidation inhibitor: dialkyldiphenylarninc Sulfur-containinsuccinimide-mol bdenurn corn lex Mo com Mo-containing complex (Mo: 5.5 wt_%, Sr 0_2 wt.%, N: 1.6 wt.%, TBN: 10 mg KOH/g) Viscosity index improver Polymethacrylate viscosity index improver (3) Evaluation of lubricating oil compositions a) Test method The crank shaft of a gasoline engine (in-line 4 cylinder engine, engine swept volume: 1.8 L, roller type-valve system) was rotated by means of an electric motor connected via a torque meter, and the running torque was monitored. In advance of starting the test, the ignition plug was removed so as to minimize the effect caused by pumping loss of the pistons, and the test was carried out under open conditions. The oil temperature was kept to 100 C. The test was carried out at respective rotational rates for 150 seconds. The torques were continuously monitored during the period from the time at a lapse o130 sec. from the beginning of the test to 120 sec. An average torque value was calculated from the monitored torque values.
Independently, a reference oil (SAE viscosity grade: 0W20, kinematic viscosity at 100 C:
8_9 mm2/s) was prepared_ From the torque value and the above-mentioned average torque value of the tested oil, a torque reduction ratio (%) was calculated. The torque reduction ratio is set forth in Table I.
b) Test results The test results of the test oils are set forth in Table l below.
Table 1 Additives Ex.1 Ex.2 Ex.3 Corn_lCorn.2 Com.3 ____ Ashless Dispersant 0.03 0.03 0.03 0.03 0.03 0.03 Ca-sali-1 0.12 0.06 0.12 0.13 -Ca-sul-1 0.06 0.12 - 0.18 -Ca-sali-2 0.06 - 0.18 Ca-sul-2 0.02 0.02 0.02 0.02 0_02 0.02 Mo-DTC 0.07 0.07 0.07 0_07 0.07 0.07 ZnDTP-1 0.03 0.03 0.03 0.03 0.03 0.03 ZaDTP-2 0.05 0.05 0.05 0.05 0.05 0.05 Ox.inhi_ 1.2 1.2 1.2 1.2 1.2 1.2 Mo.comp, 0.4 0.4 0.4 0.4 0.4 0.4 In Table 1, Ex. --- Example; Coin. = Comparative Example Test results Torque reduction ratio (%) 550 rpm 6.2 5.9 6.0 5.5 5.3 5_7 950 rpm 4_2 4.2 3.9 3_5 3.7 3.6 1500 rpm 2.0 2.2 2_0 1.6 1.9 1.3 Remarks;
The amounts of the additives are indicated as follows:
Ox.inhi. (i.e., organic oxidation inhibitor) and Mo.cornp. (i.e., sulfur-containing succinimide-molybdenum complex) are set forth in terms of the amount (wt.%) of the additive per se;
Ashless additive, calcium-containing detergents (Ca-sali-1, Ca-sul-I, Ca-sali-2, Ca-sul-2), Mo-DTC, and Zinc-containing compounds (ZnDTP-1, ZnDTP-2) are set forth in terms of N
content (wt.%), Ca content (wt.%), Mo content (wt.%), and P content (wt.%), respectively.
The test results set forth in Table I indicate that the lubricating oil composition according to the invention (Examples I to 3) show extremely high torque reduction as compared with the lubricating oil compositions (Comparison Examples 1 to 3) containing metal-containing deter-gents differing from those contained in the lubrication oil compositions of Examples Ito 3.
The lubricating oil composition of the invention provides increased high fuel economy to internal combustion engines such as gasoline engines and diesel engines.
Therefore, vehicles on which these internal combustion engines are mounted show improved fuel economy.
The base oil and additives employable for the preparation of the lubricating oil composition of the invention are described below in more detail.
Base oil The base oil (i.e., oil of lubricating viscosity) generally is a mineral oil or a synthetic oil showing a kinematic viscosity of 2 to 50 n11n2/s at 100 C. There are no specific limitations on JO the natures and other properties of the mineral oil and synthetic oil.
However, the sulfur content of the base oil should be 0.1 wt.% or less. The sulfur content preferably is 0.03 wt.% or less, and more preferably is 0.005 wt.% or less.
The mineral oil preferably is an oil which is obtained by processing a lubricating oil distillate of a mineral oil by solvent refining, hydrogenation, or their combination. Particularly preferred is a highly hydrogenated refined oil (corresponding to a hydrocracked oil, typically has a viscosity index of 120 to 160, an aromatic component content of 5 wt.% or less, a nitrogen con-tent of 50 wt.ppm or less, and a sulfur content of 50 wt ppm or less).
Particularly preferred is a high viscosity index base oil, for instance, a base oil having a viscosity index of 140 to 160 which is obtained by hydroisornerization of slack wax or GTL wax (Gas-To-Liquid).
Examples of the synthetic oils (synthetic lubricating base oils) include poly-D-olefiri such as a polymerized compound of 0-olefin having 3 to 12 carbon atoms; a chalky' ester of a di-basic acid such as sebacic acid, azelaic acid or adipic acid and an alcohol having 4 to 18 carbon atoms, typically dioctyl sebacate; a polyol ester which is an ester of 1,1,1-trimethylolpropane or penta-erythritol and a mono-basic acid having 3 to 18 carbon atoms; and alkylbenzene having an alkyl group of 9 to 40 carbon atoms. The synthetic oil generally contains essentially no sulfur, shows good stability to oxidation and good heat resistance, and gives loss residual carbon and soot when it is burned. Therefore, the synthetic oil is preferably employed for the lubricating oil composi-tion of the invention. Particularly preferred is poly-D-olefin, from the viewpoint of the object of the invention.
Each of the mineral oil and synthetic oil can be employed singly. If desired, however, two or more mineral oils can be employed in combination, and two or more synthetic oils can be employed in combination. The mineral oil and synthetic oil can be employed in combination at an optional ratio.
Molybdenum-containing friction modifier The lubricating oil composition of the invention contains a molybdenum-containing friction modifier. The molybdenum-containing friction modifier can be any one of the known molybdenum-containing friction modifiers or the known molybdenum-containing friction modifier compositions. These friction modifiers and friction modifier compositions are described in the aforementioned Patent publications 1 to 3.
Preferred molybdenum-containing friction modifier is, for example, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, amine-molybde-num complex compound, oxymolybdenum diethylate amid; and oxymolybdenum monoglyceride. Most preferred is a molybdenum dithiocarbamate friction modifier.
The lubricating oil composition of the invention generally contains the molybdenum-containing friction modifier in an amount of 0.01 to 0,15 wt.% in terms of the molybdenum content.
verbose() metal-containing detergent The lubricating oil composition of the invention contains a combination of the following overbased metal-containing detergents:
(a) calcium salicylate (specifically, monoalkylsalicylate) having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group hay-.. ing a carbon atom number in the range of 14 to IS; and (b) calcium sulfonate (specifically, monoalkylsulfonate) having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24, and/or calcium salicylate (specifically, monoalkylsalicylatc) having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group baying a carbon atom number in the range of 20 to 28, Each of the above-mentioned components (b), namely, calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24, and calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.%
of said alkyl group having a carbon atom number in the range of 20 to 28 can be employed singly or in combination.
The above-mentioned component (a), namely, calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 rnol.% of said alkyl group having a carbon atom number in the range of 14 to 18 preferably is a mixture comprising plural calcium salicylates having an alkyl group having an average carbon atom number in the range of 14 to 18 in an amount of 60 mol.% or more, particularly 70 mol.% or more.
One of the above-mentioned component (b), namely, calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol,% of said alkyl group having a carbon atom number in the range of 20 to 24 preferably is a mixture comprising plural calcium sulfonates having an alkyl group having an average carbon atom number in the range of 20 to 24 in an amount of 60 mol.% or more, particularly 70 mol.% or more.
Another of the above-mentioned component (b), namely, calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28 preferably is a mixture comprising plural calcium salicylates having an alkyl group having an average carbon atom number in the range of 20 to 28 in an amount of 60 mol.% or more, particularly 70 mol.% or more.
The lubricating oil composition contains each of the component (a) and component (b) generally in an amount of 0.01 to 0.4 wt.%, in terms of calcium content, based on the total amount of the lubricating oil composition.
It is preferred that the calcium salicylate of the component (a) is calcium salicylate having an overbased degree of 1 to 4, particularly 1.5 to 3. The calcium salicylate can be sulfurized or unsulfurized.
It is preferred that the calcium sulfonate and calcium salicylate of the component (b) are calcium sulfonate and calcium salicylate independently having an overbased degree of 6 to 24.
Preferably, the calcium sulfonate has an overbased degree of 14 to 20, and the calcium salicylate has an overbased degree of 6 to 12.
The ratio of overbased degree for the component (b)/component (a) is preferably in the range of 2 to 12.
It is preferred that the lubricating oil composition of the invention further contains cal-.. cium sulfonate having an alkyl group having an average carbon atom number in the range of 14 to 24, at least 60 mol.% (preferably, at least 70 mol.%) of said alkyl group having a carbon atom number in the range of 14 to 24 and having an overbased degree of 0.1 to 2.
The lubricating oil composition of the invention can further contain relatively small amounts of other overbased or less overbased metal-containing detergents than the above-men-tioned components (a) and (b). These metal-containing detergents may be salicylates, earboxylates, sulfonates and/or phenates.
Other additives The lubricating oil composition of the invention can further contain other lubricating oil additives. Examples of the other lubricating oil additives include nitrogen-containing ashless dispersants, zinc phosphate oxidation inhibitors (or zinc phosphate anti-wear agent) such as zinc dihydrocarbyldithiophosphate, and organic oxidation inhibitors (e.g., phenolic oxidation inhibitors and amine oxidation inhibitors).
¨ 9 ¨
The nitrogen-containing ashless dispersant preferably is an alkenyl- or alkyl-succinimide derived from polyolefin or a derivative thereof. The lubricating oil composition can contain the nitrogen-containing ashless dispersant in an amount of 0.01 to 0.3 wt.%, in terms of the nitrogen content, based on the amount of the lubricating oil composition. A
representative suecinimide can be prepared by the reaction between succinic anhydride substituted with a high molecular weight alkenyl Or alkyl and a polyalkylene polyamine containing average 4 to 10 (preferably 5 to 7) nitrogen atoms in one molecule. The high molecular weight alkenyl or alkyl is preferably derived from polybutene having a number average molecular weight of about 900 to 3,000.
The process for obtaining the polybutexiyl-succinic anhydride by the reaction of polybutcne and maleic anhydride is generally performed by the chlorination process using a chloride compound. Otherwise, a thermal reaction process using no chlorine compound can be employed. It is preferred to employ a polybutenylsuccinirnide which is derived from a polybutenylsuccinic anhydride by the thermal reaction process_ The succinirnide can be a post-treated succinimide which is prepared by the reaction with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate, organic acid or the like. Par-ticularly, a berated alkenyl(or alkyl)-succinimide which is obtained by the reaction with a boron-containing compound such as boric acid or a boron compound is advantageous from the view-points of thermal and oxidation stability.
The lubricating oil composition may contain other ashless dispersants such as an alkenyl-benzylamine ashless dispersant and/or an alkenylsuccinic acid ester ashless dispersant in addition to or in place of the above-mentioned alkenyl(or allcy1)-succinimide ashless dispersant.
The lubricating oil composition may contain a zinc phosphate oxidation inhibitor (or zinc phosphate anti-ware agent). The zinc phosphate oxidation inhibitor (or zinc phosphate anti-ware agent) may be selected from the group consisting of zinc dialkyldithiophosphate, zinc di-alkylmonothiophosphate and zinc dihydmcarbylphosphate). The zinc phosphate oxidation inhibitors/anti-wear agents are well known with respect to their preparation processes and natures. The zinc phosphate oxidation inhibitors/anti-wear agents are generally contained in an amount of 0.01 to 0.12 wt %, in terms of the phosphorus content, based on the amount of the lubricating oil composition. However, the amount preferably is in the range of 0.01 to 0.06 wt.%, in consideration of the preparation of a low-phosphorus, low-sulfur lubricating oil Composition.
The zinc dialkyldithiophosphate preferably contains an alkyl group having 3-18 carbon atoms or an alkylaryl group having C3_ oi alkyl group. Most preferred is a zinc dialkyldithiophosphate containing an alkyl group derived from a secondary alcohol having 3-18 carbon atoms or a zinc diallcyIdithiophosphate containing a mixture of alkyl groups derived from a mixture of a primary alcohol having 3-18 carbon atoms and a secondary alcohol having 3-18 carbon atoms. Both arc particularly effective for reducing wear. A zinc diancyldithiophosphate derived from a primary alcohol shows high thermal resistance. These zinc dialkyldithiophosphates can be employed alone or in combination in the form of a mixture mainly comprising one derived from the secondary alcohol and/or one derived from the primary alcohol.
'the lubricating oil composition of the invention preferably contains an organic oxidation inhibitor in an amount or 0.01-5 wt.%, preferably 0.1-3 wt.%. The oxidation inhibitor can be a hindered phenol oxidation inhibitor or a diarylamine oxidation inhibitor. The diarylamine oxidation inhibitor is advantageous in giving a base number originating from the nitrogen atoms.
The hindered phenol oxidation inhibitor is advantageous in producing no NO
gas.
Examples of the hindered phenol oxidation inhibitors include 2,6-di-t-butyl-p-ercsol, 4,4-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-buty1-o-cresol), 4,4'-isopropy1idenebis(2,6-di-t-butylpheno1), 4,4'-bis(2,6-di-t-butylphenol), 2,2'-rriethylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydoxyphenyl)propionate], octyl 3-(3,5-di-t-buty1-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-t-buty1-4-hydroxypherlyl)propionate, and octyl 3-(3,54-buty1-4-hydroxy-3-methylphenyl)propionate.
Examples of the diarylamine oxidation inhibitors include alkyldiphenylarnine having a mixture of alkyl groups of 4 to 9 carbon atoms, p,p'-dioctyldiphenylamine, phenyl-D-naphthyl amine, phenyl- CI -naphthylamine, alkylated 0-naphthylaminc, and alkylated phenyl-0 -naphthylarnine.
Each of the hindered phenol oxidation inhibitor and diarylamine oxidation inhibitor can be employed alone or in combination. If desired, other oil soluble oxidation inhibitors can be employed in combination with the above-mentioned oxidation inhibitor(s).
The lubricating oil composition of the invention may further contain an oxymolybdenum complex of succinimide, particularly a sulfur-containing oxymolybdenum complex of succinimide. The sulfur-containing oxymolybdenum complex of succinimide can provide increased oxidation inhibition when it is employed in combination with the above-mentioned phenolic or amine oxidation inhibitors.
The lubricating oil composition of the invention may further contain an alkali metal borate hydrate in an amount of 5 wt.% or less, particularly in an amount of 0.01 to 5 wt.%. A
representative alkali metal borate hydrate can be prepared in the manner described in United States Patents 3,929,650 and 4,089,790_ For example, the alkali metal boratc hydrate can be in the form of a dispersion containing micro-particles of an alkali metal borate hydrate which is pro-duced by carbonizing a neutral alkali metal or alkaline earth metal sulfonate in the presence of an alkali metal hydroxide to yield an overbased sulfonate and reacting the overbased sulfonate with boric acid. In the carbonizing procedure, it is desired to incorporate an ashiess dispersant such as succinimidc into the reaction mixture. The alkali metal preferably is potassium or sodium. The alkali metal borate hydrate can be a dispersion of 1(133050H20 particles having a particle size of about 0.3 Din or less which is dispersed in the presence of a neutral calcium sulfonate and succinimide_ The lubricating oil composition of the invention preferably contains a viscosity index improver in an amount of 20 wt.% or less, preferably Ito 20 wt.%. Examples of the viscosity index improvers are polymers such as polyalkyl methacrylate, ethylene-propylene copolymer, styrene-butadiene copolymer, and polyisoprene. A dispersant viscosity index improver and a multi-functional viscosity index improver which are produced by providing dispersing properties to the above-mentioned polymer are preferably employed. The viscosity index improvers can be used alone or in combination.
The lubricating oil composition of the invention may further contain a small amount of various auxiliary additives. Examples of the auxiliary additives are described below_ Oxidation inhibitor or anti-wear agent such as zinc dithiocarbamate, methyIenehis(dibutyldithiocarbarnate), oil soluble copper compounds, sulfur-containing compounds (e.g., sulfurized olefins, sulfurized esters, and polysulfide), phosphoric acid esters, phosphorous acid esters, thiophosphoric acid esters, and organic amide compounds (e.g., oleylamide); benzotriazol compounds and thiadiazol compounds functioning as metal deactivating agent; and nonionic polyoxyalkylene surface active agents such as polyoxyethylene-alkylphenyl ether and copolymers of ethylene oxide and propylene oxide functioning as an anti-rust agent and an anti-emulsifying agent.
Further, various amines, amides, amine salts and their derivatives which can function as friction modifiers can be employed.
Furthermore, various compounds functioning as an anti-foaming agent and a pour point depressant can be incorporated.
Thc above-mentioned auxiliary additives may be incorporated into the lubricating oil composition in an amount of 3 wt.% or less, particularly in an amount of 0.001-3 wt %_ Examples 11-31, and Comparative Examples 11-31 ( 1 ) Preparation of lubricating oil compositions (test oils) Lubricating oil compositions were prepared by adding the below-mentioned additive components to the base oil to give the formulations set forth in Table I. The lubricating oil compositions of Examples 1 to 3 are according to the invention, while the lubricating oil compositions of Comparative Examples to 3 are for comparison. The lubricating oil corn-positions were formulated to show a viscosity grade (SAE viscosity grade) of 0W20 and a kine-matic viscosity of 7.7-7.8 rnm2/s at 100 C, by addition of a viscosity index improver.
(2) Base oil and additives (I)Base oil:
Mineral base oil (kinematic viscosity at 100 C: 4.1 mm2/s, viscosity index:
137) prepared from slack wax via hydrogenation, fractional distillation and dewaxing.
(II) Additives Nitrogen-containing ashless dispersant Ethylene carbonate post-treated suceinimide dispersant (his-type, nitrogen content: 1.0 wt.%) derived from polybutene (number average molecular weight: about 2,300).
Metal-containing detergent Overbased Ca sa.licylate (1)[Ca-sali-11: Calcium monoalkylsalicylate having alkyl .. groups in which approx. 80 mol.% of the whole alkyl groups were C14_18 alkyl groups (Ca: 6.1 wt.%, S: 0.1 wt.%, TBN: 170 mg KOH/g, overbased degree: 2.3) b) Overbased Ca sulfonate [Ca-sulf-1]: Calcium alkyltoluenesulfonate having alkyl groups in which approx. 80 mol.% of the whole alkyl groups were C20-24 alkyl groups (Ca: 16.0 wt.%, S: L6 wt%, TBN: 423 mg KOH/g, overbased degree: 17) Overbased Ca salicylate (2){Ca-sali-2]: Calcium monoalkylsalicylate having alkyl groups in which approx. 80 mot% of the whole alkyl groups were C20-28 alkyl groups (Ca: 11.4 wt_%, S: 0.2 wt.%, TBN: 320 mg KOH/g, overbased degree: 8.2) d) Low overbased Ca sulfonate [Ca-sulf-2]: Calcium alkylbenzenesulfonate having alkyl groups in which approx. 80 mol.% of the whole alkyl groups were C14-24 alkyl groups (Ca: 2_4 wt.%, S: 2.9 wt.%, TBN: 17 mg KOH/g, overbased degree: 0.34) Molybdenum-containing_ friction modifier Sulfurized oxymolybdenum dithiocarbarnate (Mo-DTC, Mo: 10 wt.%, S: 11 wt.%) Zinc phosphate oxidation inhibitor Zinc di(secondary alkyl)dithiophosphate (ZriDTP- , P: 7,8 wt.%, Zn: 7.8 wt.%, S: 14 wt%) Zinc di(primary alkyl)dithiophosphate (ZnDTP-2, P: 73 wt.%, Zn: 8.4 wt.%, S:
14 wt%) Organic oxidation inhibitor(Ox_ Inhi.
Amine oxidation inhibitor: dialkyldiphenylarninc Sulfur-containinsuccinimide-mol bdenurn corn lex Mo com Mo-containing complex (Mo: 5.5 wt_%, Sr 0_2 wt.%, N: 1.6 wt.%, TBN: 10 mg KOH/g) Viscosity index improver Polymethacrylate viscosity index improver (3) Evaluation of lubricating oil compositions a) Test method The crank shaft of a gasoline engine (in-line 4 cylinder engine, engine swept volume: 1.8 L, roller type-valve system) was rotated by means of an electric motor connected via a torque meter, and the running torque was monitored. In advance of starting the test, the ignition plug was removed so as to minimize the effect caused by pumping loss of the pistons, and the test was carried out under open conditions. The oil temperature was kept to 100 C. The test was carried out at respective rotational rates for 150 seconds. The torques were continuously monitored during the period from the time at a lapse o130 sec. from the beginning of the test to 120 sec. An average torque value was calculated from the monitored torque values.
Independently, a reference oil (SAE viscosity grade: 0W20, kinematic viscosity at 100 C:
8_9 mm2/s) was prepared_ From the torque value and the above-mentioned average torque value of the tested oil, a torque reduction ratio (%) was calculated. The torque reduction ratio is set forth in Table I.
b) Test results The test results of the test oils are set forth in Table l below.
Table 1 Additives Ex.1 Ex.2 Ex.3 Corn_lCorn.2 Com.3 ____ Ashless Dispersant 0.03 0.03 0.03 0.03 0.03 0.03 Ca-sali-1 0.12 0.06 0.12 0.13 -Ca-sul-1 0.06 0.12 - 0.18 -Ca-sali-2 0.06 - 0.18 Ca-sul-2 0.02 0.02 0.02 0.02 0_02 0.02 Mo-DTC 0.07 0.07 0.07 0_07 0.07 0.07 ZnDTP-1 0.03 0.03 0.03 0.03 0.03 0.03 ZaDTP-2 0.05 0.05 0.05 0.05 0.05 0.05 Ox.inhi_ 1.2 1.2 1.2 1.2 1.2 1.2 Mo.comp, 0.4 0.4 0.4 0.4 0.4 0.4 In Table 1, Ex. --- Example; Coin. = Comparative Example Test results Torque reduction ratio (%) 550 rpm 6.2 5.9 6.0 5.5 5.3 5_7 950 rpm 4_2 4.2 3.9 3_5 3.7 3.6 1500 rpm 2.0 2.2 2_0 1.6 1.9 1.3 Remarks;
The amounts of the additives are indicated as follows:
Ox.inhi. (i.e., organic oxidation inhibitor) and Mo.cornp. (i.e., sulfur-containing succinimide-molybdenum complex) are set forth in terms of the amount (wt.%) of the additive per se;
Ashless additive, calcium-containing detergents (Ca-sali-1, Ca-sul-I, Ca-sali-2, Ca-sul-2), Mo-DTC, and Zinc-containing compounds (ZnDTP-1, ZnDTP-2) are set forth in terms of N
content (wt.%), Ca content (wt.%), Mo content (wt.%), and P content (wt.%), respectively.
The test results set forth in Table I indicate that the lubricating oil composition according to the invention (Examples I to 3) show extremely high torque reduction as compared with the lubricating oil compositions (Comparison Examples 1 to 3) containing metal-containing deter-gents differing from those contained in the lubrication oil compositions of Examples Ito 3.
Claims (20)
1. A lubricating oil composition for internal combustion engines which comprises a major amount of an oil of lubricating viscosity and a minor amount of an additive composition comprising an overbased metal-containing detergent composition and a molybdenum-containing friction modifier;
wherein the overbased metal-containing detergent composition comprises a calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18; and one or more calcium-containing detergents selected from the group consisting of:
a calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24; and a calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28.
wherein the overbased metal-containing detergent composition comprises a calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18; and one or more calcium-containing detergents selected from the group consisting of:
a calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24; and a calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28.
2. The lubricating oil composition of claim 1, wherein the molybdenum-containing friction modifier comprises molybdenum dithiocarbamate.
3. The lubricating oil composition of claim 1, wherein the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.%
of said alkyl group having a carbon atom number in the range of 14 to 18 has an overbased degree of 1 to 4, and the calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24 and the calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28 have an overbased degree of 6 to 24.
of said alkyl group having a carbon atom number in the range of 14 to 18 has an overbased degree of 1 to 4, and the calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24 and the calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28 have an overbased degree of 6 to 24.
4. The lubricating oil composition of claim 3, wherein the one or more calcium-containing detergents is the calcium sulfonate and the ratio of the overbased degree of the calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24 to the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 is in the range of 2 to 12.
5, The lubricating oil composition of claim 1, wherein the overbased metal-containing detergent comprises the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 and wherein the one or more calcium-containing detergents is the calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24.
6. The lubricating oil composition of claim 1, wherein the overbased metal-containing detergent composition comprises the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 and wherein the one or more calcium-containing detergents is the calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28.
7. The lubricating oil composition of claim 1, which comprises the molybdenum-containing friction modifier in an amount of 0.01 to 0.15 wt.% in terms of molybdenum content in the lubricating oil composition.
8. The lubricating oil composition of claim 1, wherein the one or more calcium-containing detergents is the calcium sulfonate and the lubricating oil composition comprises each of the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 and the calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24 in an amount of 0.01 to 0.4 wt.% in terms of calcium content in the lubricating oil composition.
9. The lubricating oil composition of claim 1, which further comprises a low overbased calcium sulfonate having an alkyl group having an average carbon atom number in the range of 14 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 24 and having an overbased degree of 0.1 to 2.
10. The lubricating oil composition of claim 1, which further comprises a lubricating oil additive selected from the group consisting of a nitrogen-containing ashless dispersant, a zinc phosphate oxidation inhibitor, a zinc phosphate wear inhibitor, a phenolic oxidation inhibitor, and an amine oxidation inhibitor.
11. The lubricating oil composition of claim 10, wherein each of the zinc phosphate oxidation inhibitor and zinc phosphate wear inhibitor comprises a mixture of zinc di(primary alkyl) dithiophosphate and zinc di(secondary alkyl) dithiophosphate in a weight ratio of 1/9 to 9/1.
12. The lubricating oil composition of claim 10, wherein the nitrogen-containing ashless dispersant is a succinimide dispersant or a succinimide dispersant which is post-treated with ethylene carbonate or a borate compound.
13. The lubricating oil composition of claim 1, which further comprises a molybdenum complex of a succinimide or a sulfur-containing succinimide-molybdenum complex.
14. The lubricating oil composition of claim 1, wherein the oil of lubricating viscosity has a viscosity index of 120 to 160.
15. The lubricating oil composition of claim 1, which satisfies SAE
viscosity grade of 0W20.
viscosity grade of 0W20.
16. The lubricating oil composition of claim 3, wherein the one or more calcium-containing detergents is the calcium salicylate and the ratio of the overbased degree of the calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28 to the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl 2roup having a carbon atom number in the range of 14 to 18 is in the range of 2 to 12.
17. The lubricating oil composition of claim 1, wherein the one or more calcium-containing detergents is the calcium salicylatc and the lubricating oil composition comprises each of the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 and the calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28 in an amount of 0.01 to 0.4 wt.% in terms of calcium content in the lubricating oil composition.
18. A method of making the lubricating oil composition comprising adding to an oil of lubricating viscosity the following additive components:
a molybdenum-containing friction modifier; and an overbased metal-containing detergent composition comprising a calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18; and one or more calcium-containing detergents selected from the group consisting of:
a calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24; and a calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28.
a molybdenum-containing friction modifier; and an overbased metal-containing detergent composition comprising a calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18; and one or more calcium-containing detergents selected from the group consisting of:
a calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24; and a calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28.
19. The method of claim 18, wherein the overbased metal-containing detergent comprises the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 and wherein the one or more calcium-containing detergents is the calcium sulfonate having an alkyl group having an average carbon atom number in the range of 20 to 24, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 24.
20. The method of claim 18, wherein the overbased metal-containing detergent composition comprises the calcium salicylate having an alkyl group having an average carbon atom number in the range of 14 to 18, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 14 to 18 and wherein the one or more calcium-containing detergents is the calcium salicylate having an alkyl group having an average carbon atom number in the range of 20 to 28, at least 60 mol.% of said alkyl group having a carbon atom number in the range of 20 to 28.
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| JP2011286254A JP5773365B2 (en) | 2011-12-27 | 2011-12-27 | Fuel-saving lubricating oil composition for internal combustion engines |
| JP2011-286254 | 2011-12-27 |
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| JP6023675B2 (en) | 2013-08-16 | 2016-11-09 | Ｊｘエネルギー株式会社 | Lubricating oil additive and lubricating oil composition |
| EP2851413A1 (en) * | 2013-09-23 | 2015-03-25 | Chevron Japan Ltd. | Fuel economy engine oil composition |
| WO2015067724A1 (en) * | 2013-11-06 | 2015-05-14 | Chevron Oronite Technology B.V. | Marine diesel cylinder lubricant oil compositions |
| JP6375117B2 (en) * | 2014-01-27 | 2018-08-15 | 出光興産株式会社 | Lubricating oil composition for internal combustion engines |
| JP2015189944A (en) * | 2014-03-28 | 2015-11-02 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricant composition for trunk piston diesel engine |
| WO2015164682A1 (en) * | 2014-04-25 | 2015-10-29 | The Lubrizol Corporation | Multigrade lubricating compositions |
| CN107109286B (en) * | 2014-10-31 | 2021-03-19 | 路博润公司 | Marine diesel lubricating composition |
| EP3215591B1 (en) * | 2014-11-06 | 2021-06-30 | Chevron Oronite Technology B.V. | Marine diesel cylinder lubricant oil compositions |
| US20180044610A1 (en) * | 2015-03-09 | 2018-02-15 | The Lubrizol Corporation | Method Of Lubricating An Internal Combustion Engine |
| JP6235549B2 (en) * | 2015-12-07 | 2017-11-22 | Ｅｍｇルブリカンツ合同会社 | Lubricating oil composition |
| US11155764B2 (en) * | 2016-05-05 | 2021-10-26 | Afton Chemical Corporation | Lubricants for use in boosted engines |
| EP3480284A4 (en) | 2016-06-29 | 2020-03-04 | Adeka Corporation | Lubricating oil composition for internal combustion engine |
| JP6730123B2 (en) * | 2016-07-29 | 2020-07-29 | Ｅｍｇルブリカンツ合同会社 | Lubricating oil composition |
| US20180148663A1 (en) * | 2016-11-30 | 2018-05-31 | Chevron Japan Ltd. | Lubricating oil compositions for motorcycles |
| CA3050417A1 (en) | 2017-01-24 | 2018-08-02 | Adeka Corporation | Engine oil composition |
| JP7021908B2 (en) * | 2017-11-07 | 2022-02-17 | Ｅｍｇルブリカンツ合同会社 | Lubricating oil composition |
| CN108085091B (en) * | 2017-12-08 | 2021-06-11 | 锦州新兴石油添加剂有限责任公司 | High-performance CI-4, CH-4 and CF-4 economical stepped universal internal combustion engine oil complexing agent and application thereof |
| JP2019206644A (en) * | 2018-05-29 | 2019-12-05 | 出光興産株式会社 | Lubricant composition and method for producing the same |
| JP6913704B2 (en) | 2019-03-29 | 2021-08-04 | 出光興産株式会社 | Lubricating oil composition |
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| US3929650A (en) | 1974-03-22 | 1975-12-30 | Chevron Res | Extreme pressure agent and its preparation |
| US4089790A (en) | 1975-11-28 | 1978-05-16 | Chevron Research Company | Synergistic combinations of hydrated potassium borate, antiwear agents, and organic sulfide antioxidants |
| JP2911668B2 (en) | 1991-12-12 | 1999-06-23 | 出光興産株式会社 | Engine oil composition |
| JP3613530B2 (en) | 1993-05-27 | 2005-01-26 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
| JP3615267B2 (en) | 1995-04-28 | 2005-02-02 | 新日本石油株式会社 | Engine oil composition |
| CN1242034C (en) * | 2000-12-08 | 2006-02-15 | 申保安 | Railway locomotive IC engine lube oil |
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| US7867957B2 (en) * | 2007-03-30 | 2011-01-11 | Nippon Oil Corporation | Lubricating oil composition |
| US8703673B2 (en) * | 2007-04-24 | 2014-04-22 | Infineum International Limited | Method of improving the compatibility of an overbased detergent with other additives in a lubricating oil composition |
| EP2280057B2 (en) * | 2008-02-20 | 2016-11-23 | Idemitsu Kosan Co., Ltd. | Lubricating oil composition for internal combustion engine |
| JP5225786B2 (en) * | 2008-08-20 | 2013-07-03 | シェブロンジャパン株式会社 | Lubricating oil composition for internal combustion engine lubrication |
| CN101838575A (en) * | 2009-03-20 | 2010-09-22 | 中国石油天然气股份有限公司 | Energy-saving engine oil additive composition |
| JP2011132404A (en) * | 2009-12-25 | 2011-07-07 | Chevron Japan Ltd | Lubricating oil composition for internal combustion engine |
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