CN116964180A - Lubricating oil composition for internal combustion engine - Google Patents
Lubricating oil composition for internal combustion engine Download PDFInfo
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- CN116964180A CN116964180A CN202280019723.9A CN202280019723A CN116964180A CN 116964180 A CN116964180 A CN 116964180A CN 202280019723 A CN202280019723 A CN 202280019723A CN 116964180 A CN116964180 A CN 116964180A
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- composition
- lubricating oil
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- 239000000203 mixture Substances 0.000 title claims abstract description 238
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 164
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 55
- 239000011575 calcium Substances 0.000 claims abstract description 163
- 239000002199 base oil Substances 0.000 claims abstract description 114
- 239000011777 magnesium Substances 0.000 claims abstract description 110
- 239000003599 detergent Substances 0.000 claims abstract description 107
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 102
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 73
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052796 boron Inorganic materials 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 51
- 230000001050 lubricating effect Effects 0.000 claims abstract description 37
- 229920000193 polymethacrylate Polymers 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 26
- -1 calcium salicylate borate Chemical compound 0.000 claims description 18
- 239000012459 cleaning agent Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 description 42
- 239000000446 fuel Substances 0.000 description 32
- 125000004432 carbon atom Chemical group C* 0.000 description 29
- 229910052717 sulfur Inorganic materials 0.000 description 29
- 238000000034 method Methods 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 22
- 239000011593 sulfur Substances 0.000 description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 20
- 229910052750 molybdenum Inorganic materials 0.000 description 20
- 239000011733 molybdenum Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 239000003963 antioxidant agent Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000002585 base Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 15
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 15
- 230000001629 suppression Effects 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 229910052698 phosphorus Inorganic materials 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 230000002401 inhibitory effect Effects 0.000 description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 10
- 229960001860 salicylate Drugs 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000005078 molybdenum compound Substances 0.000 description 9
- 150000002752 molybdenum compounds Chemical class 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 230000000994 depressogenic effect Effects 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000000314 lubricant Substances 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 8
- 235000010446 mineral oil Nutrition 0.000 description 8
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 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 description 6
- 238000004517 catalytic hydrocracking Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 5
- 239000001095 magnesium carbonate Substances 0.000 description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002751 molybdenum Chemical class 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 230000006866 deterioration Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229960002317 succinimide Drugs 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- MQHWFIOJQSCFNM-UHFFFAOYSA-L Magnesium salicylate Chemical compound [Mg+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O MQHWFIOJQSCFNM-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical group 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229940072082 magnesium salicylate Drugs 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
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- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
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- 150000004763 sulfides Chemical class 0.000 description 2
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- LLEFDCACDRGBKD-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;nonanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCCC(O)=O LLEFDCACDRGBKD-UHFFFAOYSA-N 0.000 description 1
- CWTQBXKJKDAOSQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;octanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCC(O)=O CWTQBXKJKDAOSQ-UHFFFAOYSA-N 0.000 description 1
- DMLQDPIAVJTTKJ-UHFFFAOYSA-N 2-nonyl-n-(2-nonylphenyl)aniline Chemical compound CCCCCCCCCC1=CC=CC=C1NC1=CC=CC=C1CCCCCCCCC DMLQDPIAVJTTKJ-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- PXMJCECEFTYEKE-UHFFFAOYSA-N Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, methyl ester Chemical compound COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PXMJCECEFTYEKE-UHFFFAOYSA-N 0.000 description 1
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- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- BRESEFMHKFGSDY-UHFFFAOYSA-N molybdenum;pyrrolidine-2,5-dione Chemical class [Mo].O=C1CCC(=O)N1 BRESEFMHKFGSDY-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical class [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical class SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical class [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
-
- 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
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—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
- C10M145/12—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 monocarboxylic
- C10M145/14—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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
A lubricating oil composition for an internal combustion engine, which comprises (A) a lubricating base oil and (B) a metal-based detergent; the component (B) contains (B1) a calcium-based detergent having a calcium content in a specific range based on the total mass of the composition and (B2) a magnesium-based detergent having a magnesium content in a specific range based on the total mass of the composition; a calcium-based detergent comprising boron and calcium in the component (B1) and (B1-1); the content of boron based on the total mass of the composition is 1000 mass ppm or less; the boron content in the component (B1) based on the total mass of the composition is expressed as B (B1) The content of calcium in the component (B1) based on the total mass of the composition is expressed as Ca (B1) The content of magnesium in the component (B2) based on the total mass of the composition is expressed as Mg (B2) In the case of B (B1) Relative toCa (B1) Ratio (B) (B1) /Ca (B1) ) 0.15 to 0.35, and B (B1) Relative to Ca (B1) With Mg (B2) Is the sum of (Ca) (B1) +Mg (B2) ) Ratio (B) (B1) /[Ca (B1) +Mg (B2) ]) 0.13 to 0.29.
Description
Technical Field
The present invention relates to a lubricating oil composition for an internal combustion engine.
Background
In recent years, with the increase in performance and output of internal combustion engines such as automobile engines, high performance has been demanded for lubricating oils (engine oils) for internal combustion engines, and various lubricating oil compositions in which various additives are blended into a lubricating base oil have been studied.
For example, international publication No. 2019/221295 (patent document 1) discloses a lubricating oil composition for an internal combustion engine, which contains: a lubricating base oil, (A) a metal-based detergent containing calcium borate, and (B) a metal-based detergent containing magnesium, wherein the component (A) is a combination of 1 or more calcium-based detergents highly alkalized with calcium borate or 1 or more calcium-based detergents highly alkalized with calcium borate and 1 or more calcium-based detergents not highly alkalized with calcium borate, and the molar ratio B/Ca of the total boron component B (unit: mol) derived from the metal-based detergent in the lubricating oil composition to the total calcium component Ca (unit: mol) derived from the metal-based detergent in the lubricating oil composition is 0.52 or more.
Further, international publication No. 2018/212340 (patent document 2) discloses a lubricating oil composition for an internal combustion engine, which contains: lubricating base oils, (a) a metal-based detergent containing calcium borate, and (B) a metal-based detergent containing magnesium, disclosed in paragraph [0064] of the document: the molar ratio B/Ca of the total boron component B (unit: mol) from the metal-based detergent in the lubricating oil composition to the total calcium component Ca (unit: mol) from the metal-based detergent in the lubricating oil composition is preferably 0.52 or more.
Further, japanese patent laying-open No. 2017-226793 (patent document 3) discloses a lubricating oil composition for an internal combustion engine, which comprises (a) a lubricating oil base oil and (B) a metal-based detergent, wherein the (B) metal-based detergent contains (B1) a metal-based detergent containing calcium and (B2) a metal-based detergent containing magnesium, in an amount of 500 to 2500 mass ppm in terms of the amount of calcium and 100 to 1000 mass ppm in terms of the amount of magnesium, based on the total amount of the composition.
Prior art literature
Patent literature
Patent document 1: international publication No. 2019/221295
Patent document 2: international publication No. 2018/212340
Patent document 3: japanese patent laid-open No. 2017-226793
Disclosure of Invention
Problems to be solved by the invention
However, the conventional lubricating oil compositions for internal combustion engines described in patent documents 1 to 3 have room for improvement in that they are excellent in performance of suppressing LSPI [ Low Speed Pre-Ignition ] and Low Speed Pre-Ignition ] (LSPI suppressing performance) and in that they have improved friction performance, thereby achieving excellent fuel saving performance.
The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to provide a lubricating oil composition for an internal combustion engine which is excellent in both LSPI-inhibiting performance and fuel-saving performance.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that: a lubricating oil composition for an internal combustion engine comprising (A) a lubricating base oil and (B) a metal-based detergent; the component (B) contains (B1) a calcium-based detergent having a calcium content in the range of 1650 to 2500 mass ppm based on the total mass of the composition, and (B2) a magnesium-based detergent having a magnesium content in the range of 20 to 400 mass ppm based on the total mass of the composition; a calcium-based detergent comprising boron and calcium in the component (B1) and (B1-1); the boron content is set to 1000 mass ppm or less based on the total mass of the composition; further, the content (mass ratio) of boron in the component (B1) based on the total mass of the composition is represented as B (B1) The content (mass ratio) of calcium in the component (B1) based on the total mass of the composition is expressed as Ca (B1) The content (mass ratio) of magnesium in the component (B2) based on the total mass of the composition is expressed as Mg (B2) In the case of (2), let B (B1) Relative to Ca (B1) Ratio (B) (B1) /Ca (B1) ) 0.15 to 0.35, and B is (B1) Relative toCa (B1) With Mg (B2) Is the sum of (Ca) (B1) +Mg (B2) ) Ratio (B) (B1) /[Ca (B1) +Mg (B2) ]) The present invention has been completed by making the LSPI-inhibiting performance of the lubricating oil composition for an internal combustion engine excellent, and by making the friction performance improved and the fuel saving performance excellent, by making the LSPI-inhibiting performance of the lubricating oil composition for an internal combustion engine 0.13 to 0.29.
Specifically, the lubricating oil composition for an internal combustion engine of the present invention comprises (A) a lubricating base oil and (B) a metal-based detergent, wherein the component (B) comprises:
(B1) A calcium-based detergent having a calcium content in the range of 1650 to 2500 mass ppm based on the total mass of the composition; and
(B2) A magnesium-based detergent having a magnesium content in the range of 20 to 400 mass ppm based on the total mass of the composition,
the component (B1) contains (B1-1) a calcium-based detergent containing boron and calcium,
the boron content is 1000 mass ppm or less based on the total mass of the composition,
the boron content in the component (B1) based on the total mass of the composition is expressed as B (B1) The content (mass ratio) of calcium in the component (B1) based on the total mass of the composition is expressed as Ca (B1) The content (mass ratio) of magnesium in the component (B2) based on the total mass of the composition is expressed as Mg (B2) In the case of B (B1) Relative to Ca (B1) Ratio (B) (B1) /Ca (B1) ) 0.15 to 0.35, and B (B1) Relative to Ca (B1) With Mg (B2) Is the sum of (Ca) (B1) +Mg (B2) ) Ratio (B) (B1) /[Ca (B1) +Mg (B2) ]) 0.13 to 0.29. In the description of "the content of boron in the (B1) component based on the total mass of the composition", "the content of calcium in the (B1) component based on the total mass of the composition", and "the content of magnesium in the (B2) component based on the total mass of the composition" in the present specification, the description of "the content" refers to the ratio of the masses (mass ratio: mass) based on the total mass of the composition (total mass of the composition) Content ratio of the amount basis).
In the lubricating oil composition for an internal combustion engine of the present invention, the component (B1) preferably contains calcium salicylate borate as the component (B1-1).
The lubricating oil composition for an internal combustion engine of the present invention preferably further contains (C) a poly (meth) acrylic viscosity index improver. The component (C) preferably contains a comb-type poly (meth) acrylate polymer.
Effects of the invention
According to the present invention, a lubricating oil composition for an internal combustion engine which is excellent in both LSPI suppression performance and fuel saving performance can be provided.
Detailed Description
The present invention will be described in detail below in connection with preferred embodiments thereof. In the present specification, unless otherwise indicated, the expression "X to Y" with respect to the numerical values X and Y means "X or more and Y or less". In such a representation, if only the value Y is marked with a unit, the unit may also be applied to the value X.
The lubricating oil composition for an internal combustion engine of the present invention comprises (A) a lubricating base oil and (B) a metal-based detergent,
the component (B) contains:
(B1) A calcium-based detergent having a calcium content in the range of 1650 to 2500 mass ppm based on the total mass of the composition; and
(B2) A magnesium-based detergent having a magnesium content in the range of 20 to 400 mass ppm based on the total mass of the composition,
the component (B1) contains (B1-1) a calcium-based detergent containing boron and calcium,
the boron content is 1000 mass ppm or less based on the total mass of the composition,
the boron content in the component (B1) based on the total mass of the composition is expressed as B (B1) The content (mass ratio) of calcium in the component (B1) based on the total mass of the composition is expressed as Ca (B1) The content (mass ratio) of magnesium in the component (B2) based on the total mass of the composition) Represented by Mg (B2) In the case of B (B1) Relative to Ca (B1) Ratio (B) (B1) /Ca (B1) ) 0.15 to 0.35, and B (B1) Relative to Ca (B1) With Mg (B2) Is the sum of (Ca) (B1) +Mg (B2) ) Ratio (B) (B1) /[Ca (B1) +Mg (B2) ]) 0.13 to 0.29. First, the components that can be contained in the lubricating oil composition for an internal combustion engine of the present invention will be described.
Component (A): lubricating base oil ]
In the present invention, the lubricating base oil to be used as the component (a) is not particularly limited, and any known base oil usable in the lubricating oil field can be suitably used, and for example, 1 or more mineral base oils, 1 or more synthetic base oils, or a mixed base oil thereof can be used.
As mineral base oils usable as the above-mentioned lubricating base oils, in the classification of base oils based on API (american petroleum institute: american Petroleum Institute), base oils of group II, base oils of group III, base oils of group IV, base oils of group V, or mixtures (mixed base oils) of 2 or more of the above-mentioned base oils may be preferably used (hereinafter, a group classified based on API base oils will be simply referred to as "API group"). The base oil of API group II is a mineral oil base oil having a sulfur content of 0.03 mass% or less, a saturation content of 90 mass% or more, and a viscosity index of 80 or more and less than 120. The base oil of API group III is a mineral oil base oil having a sulfur content of 0.03 mass% or less, a saturation content of 90 mass% or more, and a viscosity index of 120 or more. In addition, the base oil of API set IV is a polyalphaolefin base oil. The base oil of API group V is a base oil other than API groups I to IV, and preferable examples thereof include ester base oils.
As the mineral oil base oil, for example, it is possible to use: the crude oil is subjected to atmospheric distillation and/or vacuum distillation to obtain a lubricating oil fraction, and the lubricating oil fraction is refined by a combination of 1 or more kinds of refining treatments selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, contact dewaxing, hydrofinishing, sulfuric acid washing, clay treatment and the like to obtain a paraffinic mineral oil, an n-paraffinic base oil, an isoparaffinic base oil and mixtures thereof.
Preferable examples of the mineral base oil include base oils (1) to (8) shown below, which are obtained by refining the base oil and/or a lubricating oil fraction recovered from the base oil by a predetermined refining method, and recovering the lubricating oil fraction.
(1) Distillate obtained by atmospheric distillation of crude oil of chain alkyl group and/or crude oil of mixed group
(2) Distillate oil (WVGO) obtained by vacuum distillation of atmospheric residue of crude oil of paraffinic hydrocarbon group and/or crude oil of mixed group
(3) Waxes obtained by dewaxing a lubricating oil (slack waxes, etc.) and/or synthetic waxes obtained by gas-to-liquid (GTL) processes, etc. (Fischer-Tropsch waxes, GTL waxes, etc.)
(4) Mixed oil of 1 or 2 or more kinds selected from base oils (1) to (3) and/or mild hydrocracking treated oil of the mixed oil
(5) Mixed oil of 2 or more kinds selected from base oils (1) to (4)
(6) Deasphalted oil (DAO) of base oil (1), (2), (3), (4) or (5)
(7) Mild hydrocracking oil (MHC) for base oil (6)
(8) And (3) a mixed oil of 2 or more kinds selected from the base oils (1) to (7).
Further, as the above-described predetermined purification method, hydrofining such as hydrocracking and hydrofinishing is preferable; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and contact dewaxing; clay refining with acid clay or activated clay; sulfuric acid washing, caustic soda washing, and other reagent (acid or alkali) washing. One of the above purification methods may be carried out alone, or two or more of the above purification methods may be carried out in combination. In addition, in the case of combining two or more purification methods, the order thereof is not particularly limited, and may be appropriately selected.
The mineral base oil is particularly preferably the following base oil (9) or (10) obtained by subjecting a base oil selected from the above base oils (1) to (8) or a lubricating oil fraction recovered from the base oil to a predetermined treatment.
(9) The hydrocracking base oil is obtained by hydrocracking a base oil selected from the base oils (1) to (8) or a lubricating oil fraction recovered from the base oil, and subjecting the product or the lubricating oil fraction recovered from the product by distillation or the like to dewaxing treatment such as solvent dewaxing or contact dewaxing, or subjecting the product or the lubricating oil fraction to the dewaxing treatment and then distilling the product or fraction.
(10) Hydroisomerization base oils are obtained by hydroisomerizing a base oil selected from the base oils (1) to (8) or a lubricating oil fraction recovered from the base oil, and subjecting the product or a lubricating oil fraction recovered from the product by distillation or the like to dewaxing treatment such as solvent dewaxing or contact dewaxing, or subjecting the product or the lubricating oil fraction to dewaxing treatment and then distilling the product or fraction.
Further, as the lubricant base oils of the above (9) and (10), lubricant base oils produced by contact dewaxing (step) as dewaxing are more preferable, respectively. In addition, when the lubricating base oil of (9) or (10) is obtained, the solvent refining treatment and/or the hydrofinishing treatment step may be further performed at an appropriate stage, if necessary.
% C of mineral base oil P Preferably 70 to 99, more preferably 70 to 95, even more preferably 75 to 95, and particularly preferably 75 to 94. By bringing the% C of the base oil P Above the lower limit, the viscosity-temperature characteristic can be improved, and the fuel saving performance can be further improved. In addition, when an additive is blended with a base oil, the effect of the additive can be fully exerted. In addition, by making% C of base oil P The solubility of the additive can be improved when the upper limit value is not more than the above-mentioned upper limit value.
% C of mineral base oil A Preferably 2 or less, more preferably 1 or less, further preferably 0.8 or less, and particularly preferably 0.5 or less. By bringing the% C of the base oil A Below the upper limit, the viscosity can be increasedBesides the temperature-temperature characteristic, the fuel saving performance can be further improved.
% C of mineral base oil N Preferably 1 to 30, more preferably 4 to 25. By bringing the% C of the base oil N The viscosity-temperature characteristic can be improved and the fuel saving performance can be further improved below the upper limit. In addition, by making% C N Above the lower limit, the solubility of the additive can be improved.
In the present specification,% C P 、％C N And% C A The percentage of the number of paraffin carbon atoms relative to the total number of carbon atoms, the percentage of the number of naphthene carbon atoms relative to the total number of carbon atoms, and the percentage of the number of aromatic carbon atoms relative to the total number of carbon atoms, respectively, are determined by the method according to ASTM D3238-85 (n-D-M ring analysis). Namely, the above% C P 、％C N And% C A The preferable range of (C) is based on the value obtained by the above method, for example,% C obtained by the above method even in the case of a lubricating base oil containing no naphthene component N Values exceeding 0 may also be represented.
The content of the saturated component in the mineral oil base oil is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 99% by mass or more, based on the total amount of the base oil. By setting the saturated component content to the above lower limit value or more, the viscosity-temperature characteristic can be improved. In addition, the saturated component in the present specification means a value measured according to ASTM D2007-93.
In addition, a similar method can be used for separating the saturated component, which can give the same result. For example, in addition to the method described in ASTM D2007-93, a method described in ASTM D2425-93, a method described in ASTM D2549-91, a method using High Performance Liquid Chromatography (HPLC), a method in which these methods are modified, and the like can be mentioned.
The aromatic component in the mineral oil base oil is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, particularly preferably 0 to 1% by mass, and in one embodiment may be 0.1% by mass or more based on the total amount of the base oil. By setting the content of the aromatic component to the above upper limit value or less, the viscosity-temperature characteristic and the low-temperature viscosity characteristic can be improved, the fuel consumption performance can be further improved, and the evaporation loss of the lubricating oil can be reduced to reduce the consumption of the lubricating oil. In addition, the effect of the additive blended in the lubricating oil can be effectively exerted. The lubricant base oil may not contain an aromatic component, but the solubility of the additive may be improved by setting the content of the aromatic component to the above lower limit value or more. In addition, the aromatic component in the present specification means a value measured according to ASTM D2007-93. The aromatic component may contain, in addition to alkylbenzenes and alkylnaphthalenes, anthracene, phenanthrene, and an alkylate thereof, a compound obtained by ring-shrinking four or more benzene rings, and an aromatic compound having a heteroatom such as pyridines, quinolines, phenols, and naphthols.
The synthetic base oil that can be used as the lubricating base oil is not particularly limited, and known synthetic base oils can be suitably used. Examples of the synthetic base oils include poly- α -olefins and their hydrides, isobutylene oligomers and their hydrides, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate), bis-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, bis-2-ethylhexyl sebacate, etc.), polyol esters (trimethylolpropane octanoate, trimethylolpropane nonanoate, pentaerythritol 2-ethylhexanoate, pentaerythritol nonanoate, etc.), polyoxyalkylene glycols, dialkyldiphenyl ethers, polyphenylene ethers, and mixtures thereof, and among these, poly- α -olefin base oils are preferred. Typical examples of the polyalphaolefin base oil include oligomers and co-oligomers of an alpha-olefin having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms (1-octene oligomer, decene oligomer, ethylene-propylene co-oligomer, etc.), and hydrogenated products thereof.
As the lubricating base oil, a dynamic viscosity at 100℃of 2.0 to 5.0mm is preferable 2 /s (more preferably 3.0 to 5.0 mm) 2 And/s, more preferably 4.0 to 4.8mm 2 S, particularly preferably from 4.1 to 4.7mm 2 /s). When the dynamic viscosity of the lubricating base oil at 100 ℃ is equal to or higher than the lower limit, an oil film can be efficiently formed in a lubricating portion, and the evaporation loss of the lubricating oil composition can be reduced, thereby reducing the consumption of the lubricating oil, as compared with the case where the dynamic viscosity is lower than the lower limit. In addition, when the dynamic viscosity of the lubricating base oil at 100 ℃ is equal to or less than the upper limit, the fuel saving performance can be made more excellent than when the dynamic viscosity exceeds the upper limit. In the present specification, "dynamic viscosity at 100℃means dynamic viscosity at 100℃measured in accordance with JIS K2283-2000.
As the lubricating base oil, a dynamic viscosity at 40℃of 9.0 to 36.0mm is preferable 2 /s (more preferably 12.6 to 33.2 mm) 2 And/s, more preferably 15.8 to 25.2mm 2 S, particularly preferably 17.7 to 21.6mm 2 And/s, most preferably 17.5-22.1 mm 2 /s). When the dynamic viscosity of the lubricating base oil at 40 ℃ is equal to or less than the upper limit, the low-temperature viscosity characteristics and fuel economy performance of the lubricating oil composition can be improved as compared with the case where the upper limit is exceeded. In addition, when the dynamic viscosity of the lubricating base oil at 40 ℃ is equal to or higher than the lower limit, the oil film formation property of the lubricating portion can be improved, the lubricating property can be improved, the evaporation loss of the lubricating oil composition can be reduced, and the consumption of the lubricating oil can be reduced, as compared with the case where the dynamic viscosity is lower than the lower limit. In the present specification, "dynamic viscosity at 40℃means dynamic viscosity at 40℃measured in accordance with JIS K2283-2000.
The lubricant base oil preferably has a viscosity index of 100 or more (more preferably 105 or more, still more preferably 110 or more, particularly preferably 115 or more, and most preferably 120 or more). When the viscosity index is equal to or higher than the lower limit, the viscosity-temperature characteristics and wear resistance of the lubricating oil composition can be improved, the fuel consumption performance can be further improved, and the evaporation loss of the lubricating oil can be reduced, thereby reducing the consumption of the lubricating oil, as compared with the case where the viscosity index is lower than the lower limit. In addition, in the present specification, "viscosity index" means a viscosity index measured in accordance with JIS K2283-1993.
The lubricant base oil preferably has a NOACK evaporation amount of 30 mass% or less (more preferably 15 mass% or less) at 250 ℃. The lower limit of the NOACK evaporation amount of the lubricating base oil at 250 ℃ is not particularly limited, and is usually 3 mass% or more. In the present specification, "NOACK evaporation amount at 250 ℃ means an evaporation amount of a lubricating base oil or a lubricating oil composition at 250 ℃ measured according to ASTM D5800.
The lubricant base oil is preferably a lubricant base oil having a pour point of-10 ℃ or lower (more preferably-12.5 ℃ or lower, still more preferably-15 ℃ or lower). When the pour point is equal to or less than the upper limit, the low-temperature fluidity of the entire lubricating oil composition can be improved as compared with the case where the pour point exceeds the upper limit. In addition, in the present specification, the "pour point" means a pour point measured in accordance with JIS K2269-1987.
The sulfur content of the lubricating base oil depends on the sulfur content of its feedstock. For example, when a raw material containing substantially no sulfur, such as a synthetic wax component obtained by the fischer-tropsch reaction, is used, a lubricating base oil containing substantially no sulfur can be obtained. In the present specification, "sulfur component" means a sulfur component measured according to JPI-5S-38. In addition, when a sulfur-containing raw material such as slack wax obtained in the refining process of a lubricating base oil or microcrystalline wax obtained in the refining process of a refined wax is used, the sulfur content in the obtained lubricating base oil is usually 100 mass ppm or more. The sulfur content of the lubricating base oil is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, further preferably 10 mass ppm or less, and particularly preferably 5 mass ppm or less, from the viewpoint of low vulcanization of the lubricating oil composition.
The nitrogen content in the lubricating base oil is preferably 10 mass ppm or less (more preferably 5 mass ppm or less, still more preferably 3 mass ppm or less). In the present specification, the nitrogen component means a nitrogen component measured in accordance with JIS K2609-1990.
The content of the lubricating base oil (total base oil) in the lubricating oil composition is preferably 70 to 95 mass% (more preferably 75 to 85 mass%) based on the total mass of the composition.
Component (B): metal-based cleaning agent >
In the present invention, the metal-based cleaning agent used as the component (B) contains:
(B1) A calcium-based cleaning agent having a calcium content (content of calcium derived from component (B1) based on the total mass of the composition) in the range of 1650 to 2500 mass ppm; and
(B2) A magnesium-based detergent having a magnesium content (content of magnesium derived from component (B2) based on the total mass of the composition) in the range of 20 to 400 mass ppm.
Here, "calcium-based detergent" means a metal-based detergent containing calcium as a metal, and "magnesium-based detergent" means a metal-based detergent containing magnesium as a metal. The metal-based detergent may be appropriately selected from known metal-based detergents (for example, sulfonate detergents, phenate detergents, salicylate detergents, etc. containing calcium or magnesium as a metal) and used so that the amounts of calcium, magnesium, and boron are each at a desired content. Examples of known metal-based cleaners include "sulfonate cleaner", "phenate cleaner" and "salicylate cleaner", and the cleaners described in paragraphs [0038] to [0054] of JP-A2020-76004 and the cleaners described in paragraphs [0043] to [0054] of International publication No. 2018/212340 may be used as appropriate.
< component (B1) >
The "calcium-based detergent" used as the component (B1) is a metal-based detergent containing calcium as a metal, and contains at least boron and calcium as components thereof ((B1-1) component). By including the component (B1-1) in the component (B1), friction can be effectively reduced and LSPI suppressing ability can be improved as compared with the case where the component (B1-1) is not included.
The "calcium-based detergent" used as the component (B1) is required to contain the component (B1-1) containing boron and calcium, but may contain other calcium-based detergents other than the component (B1-1). As the other calcium-based detergent other than the above-mentioned component (B1-1), a known calcium-based detergent containing no boron (a known metal-based detergent containing no boron and calcium as a metal) can be suitably used. As described above, as the component (B1), a component composed only of the component (B1-1) can be suitably used according to the purpose thereof; or a mixture of the component (B1-1) and a boron-free calcium-based detergent.
The type of the calcium-based detergent used as the component (B1) is not particularly limited, and examples thereof include sulfonate detergents, phenate detergents, salicylate detergents, and the like containing calcium as a metal. Among the above-mentioned calcium-based detergents, from the viewpoint of friction-reducing performance, a salicylate detergent containing calcium as a metal is preferable.
The sulfonate detergent (calcium sulfonate detergent) containing calcium as a metal is not particularly limited, and known detergents can be used appropriately. The calcium sulfonate detergent is preferably a calcium salt of an alkylaromatic sulfonic acid obtained by sulfonating an alkylaromatic compound having a molecular weight of 300 to 1500 (more preferably 400 to 1300). Examples of the alkylaromatic sulfonic acid include petroleum sulfonic acid and synthetic sulfonic acid. Further, as the petroleum sulfonic acid or the synthetic sulfonic acid, known ones can be suitably used. As the calcium sulfonate detergent, a known one that can be used in a lubricating oil composition can be suitably used.
The salicylate detergent (calcium salicylate detergent) containing calcium as a metal is not particularly limited, and known detergents can be suitably used. Examples of the salicylate detergent include calcium salts of alkylsalicylic acids having an alkyl group or alkenyl group having 1 to 2 carbon atoms of 4 to 36 (more preferably 14 to 30) as a substituent, and mixtures thereof. As the calcium salicylate detergent, a known detergent that can be used in a lubricating oil composition can be suitably used.
In addition, the component (B1-1) (a calcium-based detergent containing boron and calcium) contained in the component (B1) is preferably a calcium-based detergent containing calcium borate, more preferably a calcium-based detergent highly alkalinized with calcium borate, and particularly preferably a calcium salicylate detergent highly alkalinized with calcium borate (calcium salicylate borate) from the viewpoint of friction reduction performance under particularly severe sliding conditions.
In addition, from the viewpoint of improving fuel economy performance according to applicable conditions, it is preferable to use a mixture of the component (B1-1) and a calcium-based detergent containing (B1-2) calcium carbonate as the component (B1). The component (B1-2) (calcium-based detergent containing calcium carbonate) is not particularly limited, and is more preferably a calcium-based detergent highly alkalized with calcium carbonate, and particularly preferably a calcium salicylate-based detergent highly alkalized with calcium carbonate.
When the component (B1) is a mixture of the component (B1-1) and a calcium-based cleaning agent other than the component (B1-1) (preferably the component (B1-2)), the content of the component (B1-1) in the component (B1) is not particularly limited, but the amount of the component (B1-1) is preferably 30 to 100% by mass (more preferably 45 to 100% by mass, still more preferably 67 to 100% by mass) relative to the total amount of the component (B1). When the content of the component (B1-1) is not less than the lower limit, the friction reduction performance under particularly severe sliding conditions can be further improved as compared with the case where the content is less than the lower limit.
Regarding the component (B1-1) used as the component (B1), the content of boron in the component (B1-1) is preferably 1.0 to 5.0 mass% (more preferably 1.3 to 4.5 mass%, still more preferably 2.0 to 3.0 mass%) with respect to the total amount of the component (B1-1). When the content of B in the component (B1-1) is not less than the lower limit, friction reduction performance and LSPI suppression performance can be further improved as compared with the case where the content is less than the lower limit. On the other hand, when the upper limit is less than or equal to the above, the stability of the lubricating oil composition can be improved as compared with when the upper limit is exceeded.
Among the calcium-based detergents used as the component (B1), the content of calcium (Ca) per each of the calcium-based detergents contained in the component (B1) (1 in the case where the component (B1) is composed of 1 kind of calcium-based detergent) is preferably 2.0 to 11.5% by mass (more preferably 4.0 to 10.0% by mass, still more preferably 5.7 to 7.2% by mass). When the content of calcium (Ca) in each of the calcium-based detergents is equal to or greater than the lower limit, the reduction of friction loss under low-temperature conditions can be improved as compared with the case where the content is lower than the lower limit, while when the content is equal to or less than the upper limit, the stability of the lubricating oil composition can be improved as compared with the case where the content is higher than the upper limit.
The Base Number (TBN) of each of the calcium-based detergents used as the component (B1) is not particularly limited, but each of the calcium-based detergents is 50 to 500mgKOH/g, more preferably 100 to 500mgKOH/g, particularly preferably 150 to 500mgKOH/g. When the base number of each of the calcium-based detergents used as the component (B1) is equal to or greater than the lower limit, the acid neutralization performance can be improved as compared with the case where the base number is lower than the lower limit, and when the base number is equal to or less than the upper limit, the solubility of each of the additives in the lubricating oil composition can be improved as compared with the case where the base number exceeds the upper limit. In the present specification, "base number (TBN)" means a base number measured by the perchloric acid method according to JIS K2501.
(B1) The content of calcium (Ca) in the component (B1) is determined based on the total mass of the composition (B1) ) It is used in such a manner that it is in the range of 1650 to 2500 mass ppm (more preferably 1650 to 2200 mass ppm, still more preferably 1700 to 1900 mass ppm, particularly preferably 1750 to 1900 mass ppm). In terms of the content of calcium (Ca (B1) ) When the lower limit is more than the lower limit, the cleaning performance can be improved as compared with the case where the lower limit is less than the lower limit, and when the lower limit is less than the upper limit, the LSPI suppressing ability and the fuel saving performance can be simultaneously improved as compared with the case where the upper limit is exceeded.
The boron content (B (B1)) derived from the component (B1) is preferably 50 mass ppm based on the total mass of the composition (based on the total amount of the lubricating oil composition)From about 1000 mass ppm (more preferably from about 200 mass ppm to about 700 mass ppm, still more preferably from about 400 mass ppm to about 700 mass ppm, particularly preferably from about 400 mass ppm to about 650 mass ppm). In the boron content (B) (B1)) When the friction coefficient is equal to or higher than the lower limit, friction reduction performance and LSPI suppression performance can be further improved as compared with those when the friction coefficient is lower than the lower limit. On the other hand, when the friction coefficient is equal to or smaller than the upper limit, the friction reduction performance can be further improved as compared with the case where the friction coefficient exceeds the upper limit.
The content of the component (B1) is preferably 1.5 to 3.5 mass% (more preferably 2.0 to 3.2 mass%, still more preferably 2.4 to 2.9 mass%) based on the total amount of the lubricating oil composition. When the content of the component (B1) is not less than the lower limit, the cleaning performance can be improved as compared with the case where the content is less than the lower limit, and when the content is not more than the upper limit, the friction reduction performance can be further improved as compared with the case where the content exceeds the upper limit.
Further, the boron content (B) derived from the component (B1) (B1) ) The total amount of boron contained in the composition is preferably 50% by mass or more, more preferably 60% by mass to 100% by mass, and particularly preferably 70% by mass to 100% by mass. At B (B1) When the ratio of the total amount of boron in the composition is equal to or greater than the lower limit, the LSPI inhibitory ability can be further improved as compared with the case where the ratio is lower than the lower limit.
In addition, the content of calcium (Ca) derived from the component (B1) (B1)) The amount of calcium is preferably 50% by mass or more, more preferably 75% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass, based on the total amount of calcium contained in the composition. At Ca (B1) When the ratio of the total amount of calcium in the composition is equal to or greater than the lower limit, the LSPI inhibitory ability can be further improved as compared with the case where the ratio is lower than the lower limit.
In addition, the content (B) of boron from the component (B1) based on the total mass of the composition (B1) ) And the content of calcium (Ca) derived from the component (B1) based on the total mass of the composition (B1) ) Can be determined by the assay specified in JPI-5S-38.
< concerning component (B2) >
The "magnesium-based detergent" used as the component (B2) is not particularly limited, and a known metal-based detergent containing magnesium as a metal can be suitably used. Examples of the magnesium-based detergent include sulfonate detergents, phenate detergents, salicylate detergents, and the like containing magnesium as a metal. Among the above magnesium-based cleaners, sulfonate cleaners containing magnesium as a metal and salicylate cleaners containing magnesium as a metal are preferable from the viewpoint of friction reducing performance.
The sulfonate detergent (magnesium sulfonate detergent) containing magnesium as a metal is not particularly limited, and known detergents can be used appropriately. The magnesium sulfonate detergent may be, for example, a magnesium salt of an alkylaromatic sulfonic acid obtained by sulfonating an alkylaromatic compound having a molecular weight of 300 to 1500 (more preferably 400 to 1300). Examples of the alkylaromatic sulfonic acid include petroleum sulfonic acid and synthetic sulfonic acid. Further, as the petroleum sulfonic acid or the synthetic sulfonic acid, known ones can be suitably used. As the magnesium sulfonate detergent, known substances usable in lubricating oil compositions can be appropriately used.
The salicylate detergent (magnesium salicylate detergent) containing magnesium as a metal is not particularly limited, and known detergents can be suitably used. Examples of the salicylate detergent include magnesium salts of alkyl salicylic acids having an alkyl group or alkenyl group having 1 to 2 carbon atoms of 4 to 36 (more preferably 14 to 30) as a substituent, and mixtures thereof. As the magnesium salicylate detergent, known substances usable in lubricating oil compositions can be suitably used.
The magnesium-based detergent is preferably a magnesium-based detergent containing magnesium carbonate. The magnesium-based detergent containing magnesium carbonate is not particularly limited, and more preferably a magnesium-based detergent highly alkalized with magnesium carbonate, and among them, a magnesium sulfonate detergent highly alkalized with magnesium carbonate is particularly preferred from the viewpoint of suppressing the disappearance of the base number at the time of moisture mixing (the coarse granulation of the magnesium-based detergent under the condition of adding water, the disappearance of the base number accompanying sedimentation or precipitation).
(B2) The content of magnesium (Mg) in the component (a) is preferably 6.0 to 10.0 mass% (more preferably 7.5 to 9.5 mass%, still more preferably 7.5 to 9.1 mass%) relative to the total amount of the component (B2). When the content of magnesium in the component (B2) is equal to or greater than the lower limit, the viscosity resistance can be reduced as compared with the case where the content is lower than the lower limit, while when the content is equal to or less than the upper limit, the stability of the lubricating oil composition can be improved as compared with the case where the content is higher than the upper limit.
The Base Number (TBN) of each magnesium-based detergent used as the component (B2) is not particularly limited, but is preferably 50 to 500mgKOH/g, more preferably 100 to 500mgKOH/g, particularly preferably 150 to 500mgKOH/g. When the base number of the component (B2) is equal to or greater than the lower limit, the reduction in the viscous resistance can be further improved as compared with the case where the base number is lower than the lower limit. On the other hand, when the upper limit is less than or equal to the above, the stability of the lubricating oil composition can be improved as compared with when the upper limit is exceeded.
(B2) The content of magnesium (Mg) in the component (B2) is determined based on the total mass of the composition (B2) ) The amount is in the range of 20 to 400 mass ppm (more preferably 20 to 300 mass ppm, still more preferably 100 to 300 mass ppm, particularly preferably 100 to 200 mass ppm). In the content of magnesium (Mg (B2) ) When the lower limit is more than the lower limit, the LSPI suppression capability can be improved as compared with the case where the lower limit is less than the lower limit, whereas when the lower limit is less than the upper limit, the fuel saving performance can be improved as compared with the case where the upper limit is exceeded. In addition, the content of magnesium (Mg) from the component (B2) based on the total mass of the composition (B2) ) The measurement can be performed by the measurement method described in JPI-5S-38.
The content of the component (B2) is preferably 0.01 to 0.60 mass% (more preferably 0.01 to 0.40 mass%, still more preferably 0.10 to 0.27 mass%) based on the total amount of the lubricating oil composition. When the content of the component (B2) is not less than the lower limit, the acid neutralization performance can be improved as compared with the case where the content is less than the lower limit, whereas when the content is not more than the upper limit, the friction reduction performance can be further improved as compared with the case where the content exceeds the upper limit.
In addition, the content of magnesium (Mg) derived from the component (B2) (B2)) The amount of magnesium contained in the composition is preferably 50% by mass or more, more preferably 75% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass. At Mg (B2) When the ratio of the magnesium to the total amount of the composition is equal to or more than the lower limit, the fuel saving performance can be further improved as compared with the case of being less than the lower limit.
(B) The component (B1) may contain a metal-based cleaning agent other than the component (B2) as required. The ratio of the total amount of the component (B1) and the component (B2) to the total amount of the component (B) is preferably 50 to 100 mass% (more preferably 75 to 100 mass%, particularly preferably 90 to 100 mass%). When the ratio of the total amount of the component (B1) and the component (B2) is equal to or greater than the lower limit, LSPI-suppressing ability and friction-reducing performance can be further improved as compared with the case where the ratio is lower than the lower limit. The metal-based cleaning agent other than the component (B1) and the component (B2) is not particularly limited, and known metal-based cleaning agents can be suitably used. In addition, from the viewpoint of both LSPI inhibitory ability and friction reducing performance, it is more preferable to use a mixture of the component (B1) and the component (B2).
The content of the component (B) is preferably 1.0 to 4.0 mass% (more preferably 2.2 to 3.0 mass%, still more preferably 2.6 to 3.0 mass%) based on the total amount of the lubricating oil composition. When the content of the component (B) is not less than the lower limit, the acid neutralization performance can be improved as compared with the case where the content is less than the lower limit, whereas when the content is not more than the upper limit, the friction reduction performance can be further improved as compared with the case where the content exceeds the upper limit.
In the lubricating oil composition for an internal combustion engine of the present invention, the total mass of the composition is taken asThe boron content (mass ratio) in the reference (B1) component is expressed as B (B1) The content (mass ratio) of calcium in the component (B1) based on the total mass of the composition is expressed as Ca (B1) In the case of B (B1) Relative to Ca (B1) Ratio (B) (B1) /Ca (B1) ) From 0.15 to 0.35 (more preferably from 0.21 to 0.30, particularly preferably from 0.26 to 0.29). At B (B1) /Ca (B1) When the friction coefficient is equal to or higher than the lower limit, the LSPI suppression ability can be made higher than that when the friction coefficient is lower than that when the friction coefficient is equal to or lower than the upper limit, and therefore, both the excellent LSPI suppression ability and the excellent fuel saving performance can be achieved.
In the lubricating oil composition for an internal combustion engine of the present invention, the content (mass ratio) of boron in the component (B1) based on the total mass of the composition is represented as B (B1) The content (mass ratio) of calcium in the component (B1) based on the total mass of the composition is expressed as Ca (B1) The content (mass ratio) of magnesium in the component (B2) based on the total mass of the composition is expressed as Mg (B2) In the case of B (B1) Relative to Ca (B1) And Mg (magnesium) (B2) Is the sum of (Ca) (B1) +Mg (B2) ) Ratio (B) (B1) /[Ca (B1) +Mg (B2) ]) From 0.13 to 0.29 (more preferably from 0.23 to 0.29, particularly preferably from 0.25 to 0.29). At B (B1) /[Ca (B1) +Mg (B2) ]When the lower limit is more than the lower limit, the LSPI suppression capability can be improved as compared with the case where the lower limit is less than the lower limit, whereas when the lower limit is less than the upper limit, the fuel saving performance can be improved as compared with the case where the upper limit is exceeded.
In the lubricating oil composition for an internal combustion engine of the present invention, the boron content (mass ratio) in the component (B1) based on the total mass of the composition is represented as B (B1) The total amount of calcium in the composition (total calciumThe content of (3): mass ratio) expressed as Ca, B (B1) Ratio relative to Ca (B) (B1) The ratio of Ca to Ca is preferably 0.15 to 0.35 (more preferably 0.21 to 0.31, particularly preferably 0.26 to 0.30). At B (B1) When the ratio of Ca is equal to or greater than the lower limit, the LSPI suppressing ability can be further improved as compared with the case where the ratio is lower than the lower limit, whereas when the ratio is equal to or less than the upper limit, the fuel saving performance can be further improved as compared with the case where the ratio exceeds the upper limit.
In the lubricating oil composition for an internal combustion engine of the present invention, the content (mass ratio) of boron in the component (B1) based on the total mass of the composition is represented as B (B1) When the total amount of calcium in the composition based on the total mass of the composition (total calcium content: mass ratio) is expressed as Ca and the total amount of magnesium in the composition based on the total mass of the composition (total magnesium content: mass ratio) is expressed as Mg, B (B1) Ratio (B) of the total amount (Ca+Mg) of Ca and Mg (B1) /[Ca+Mg]) From 0.13 to 0.29 (more preferably from 0.23 to 0.29, particularly preferably from 0.25 to 0.29). At B (B1) /[Ca+Mg]When the lower limit is higher than the upper limit, the LSPI suppression capability can be further improved as compared with the case where the lower limit is lower than the lower limit, and when the lower limit is lower than the upper limit, the fuel saving performance can be further improved as compared with the case where the upper limit is exceeded.
The method for producing the metal-based detergent used as the component (B) is not particularly limited, and a known method can be suitably used.
In addition to the component (a) and the component (B) (the component including the component (B1) and the component (B2)) in the lubricating oil composition for an internal combustion engine of the present invention, a known additive commonly used in lubricating oil compositions for an internal combustion engine may be appropriately contained in order to further improve the performance thereof. Hereinafter, components that can be suitably used as the above-mentioned additives will be described.
Component (C): poly (meth) acrylate viscosity index improver-
In order to further improve fuel economy performance, the lubricating oil composition for an internal combustion engine of the present invention preferably contains (C) a poly (meth) acrylate-based viscosity index improver. Here, as the "poly (meth) acrylate-based viscosity index improver", a known poly (meth) acrylate-based compound used as a viscosity index improver (for example, "viscosity index improver" described in international publication No. 2019/221295, "poly (meth) acrylate compound" described in japanese patent application laid-open No. 2018-177986, "comb polymer" described in japanese patent application laid-open No. 2017-101211, "viscosity index improver" described in international publication No. 2016/159706, "viscosity index improver" described in international publication No. 2017/099052, "viscosity index improver" described in japanese patent application laid-open No. 2017-110196, "polymer (a)" described in japanese patent application laid-open No. 2017-110196, or the like) can be suitably used.
The poly (meth) acrylate polymer used as the component (C) is not particularly limited in its structure, and may be a so-called linear poly (meth) acrylate polymer or a so-called comb-type poly (meth) acrylate polymer. Among them, the component (C) is more preferably a comb-type poly (meth) acrylate polymer from the viewpoint of improving fuel consumption performance with an improvement in viscosity-temperature characteristics and oil film formation property. The poly (meth) acrylate viscosity index improver is particularly preferably a comb-type poly (meth) acrylate polymer. As such a comb-type poly (meth) acrylate polymer, a known poly (meth) acrylate polymer having a so-called comb structure (for example, "comb-type polymer" described in japanese patent laid-open publication No. 2017-101211, "comb-type poly (meth) acrylate" described in japanese patent laid-open publication No. 2018-177986, "comb-type poly (meth) acrylate" described in international publication No. 2016/159706, "viscosity index improver" described in japanese patent laid-open publication No. 2017-110196, "polymer (a)" described in japanese patent laid-open publication No. 2017-110196, or the like) can be suitably used.
As the above-mentioned comb-type poly (meth) acrylate-based polymer, a copolymer of a (meth) acrylate and a (meth) acrylate-based macromer, that is, a poly (meth) acrylate-based polymer having a comb-type structure can be suitably used. The comb-type poly (meth) acrylate polymer may be a copolymer of a (meth) acrylate and a (meth) acrylate-based macromer and other monomers (for example, ethylene, styrene, or 1-butene). In the present specification, "(meth) acrylate" means acrylate and/or methacrylate.
Among them, copolymers of (meth) acrylic acid esters represented by the following formula (1) (hereinafter, abbreviated as "monomer (M-1)" as the case may be) and (meth) acrylic acid ester-based macromers represented by the following formula (2) (hereinafter, abbreviated as "macromer (M-2) as the case may be) are preferable.
[ in formula (1), R 1 Represents a hydrogen atom or a methyl group, R 2 Represents a linear or branched hydrocarbon group having 2 to 10 carbon atoms.]
[ in formula (2), R 3 Represents a hydrogen atom or a methyl group, R 4 Represents a hydrocarbon group having 12 to 24 carbon atoms. ]
R in formula (1) 2 Is a linear or branched hydrocarbon group having 2 to 10 carbon atoms (more preferably an alkyl group). As R as described above 2 The number of carbon atoms of the selected hydrocarbon group is preferably 4 to 10 (more preferably 4 to 8, particularly preferably 4 to 6).
In addition, R in formula (2) 4 The number of carbon atoms of the selected hydrocarbon group is preferably 12 to 24 (more preferably 12 to 20, particularly preferably 12 to 18). The viscosity index can be increased when the number of carbon atoms is equal to or greater than the lower limit, and the viscosity index can be increased under low-temperature conditions when the number of carbon atoms is equal to or less than the upper limitGood flow. The hydrocarbon group may be linear or branched. In addition, as the macromer (M-2), for example, macromers derived from a hydride of a polyolefin obtained by copolymerizing butadiene and isoprene can be used. As the above-mentioned macromer (M-2), for example, a known macromer (for example, a macromer described in japanese patent application laid-open No. 2018-177986, a "monomer (a)" described in japanese patent application laid-open No. 2017-110196, or the like) can be suitably used.
In addition, in the copolymer of the monomer (M-1) and the macromonomer (M-2), the copolymerization molar ratio of these monomers is not particularly limited, and the monomer (M-1): the monomer (M-2) is preferably 20: 80-90: about 10 (more preferably 30:70 to 80:20, still more preferably 40:60 to 70:30).
The weight average molecular weight (Mw) of the poly (meth) acrylate polymer (preferably, comb-shaped poly (meth) acrylate polymer) contained in the poly (meth) acrylate viscosity index increase is preferably 10 to 100 tens of thousands (more preferably 30 to 100 tens of thousands, still more preferably 60 to 80 tens of thousands). When the weight average molecular weight is equal to or higher than the lower limit, the viscosity index in the case of being dissolved in the lubricating base oil can be increased as compared with the case of being lower than the lower limit, and the fuel economy performance and low-temperature viscosity characteristics can be improved.
In the case where the (C) poly (meth) acrylate viscosity index improver contains a comb-type poly (meth) acrylate polymer, the content of the comb-type poly (meth) acrylate polymer is preferably 30 mass% or more (more preferably 50 to 100 mass%, still more preferably 95 to 100 mass%, particularly preferably 98 to 100 mass%) based on the total amount of the (C) component. When the content of the comb-type poly (meth) acrylate polymer in the component (C) is not less than the lower limit, the fuel economy performance can be further improved by improving the viscosity-temperature characteristics and the oil film formation property as compared with the case of being less than the lower limit. In addition, from the viewpoint of improvement of viscosity-temperature characteristics and oil film formation property, it is more preferable to use a component composed of only a comb-type poly (meth) acrylate polymer as the component (C).
The content of the component (C) is preferably 5 to 15 mass% (more preferably 7 to 11 mass%, still more preferably 9 to 11 mass%) based on the total amount of the lubricating oil composition. When the content of the component (C) is not less than the lower limit, the viscosity-temperature characteristics can be improved as compared with the case where the content is less than the lower limit, and the abrasion resistance can be improved by the formation of an oil film. On the other hand, in the case where the upper limit or less is set, the fuel saving performance can be further improved by suppressing excessive thickening as compared with the case where the upper limit is exceeded.
(C) The method for producing the poly (meth) acrylate polymer used in the component (a) is not particularly limited, and a known method can be suitably used. As the above-mentioned production method, for example, the following method can be employed: the monomer (M-1), the macromer (M-2) and other monomers added as needed are subjected to radical solution polymerization in the presence of a polymerization initiator (e.g., benzoyl peroxide, etc.), thereby obtaining a poly (meth) acrylate polymer.
Component (D): ashless dispersant)
The lubricating oil composition for an internal combustion engine of the present invention preferably further contains (D) an ashless dispersant, from the viewpoint of being capable of highly dispersing metal powder generated by wear during use, improving wear resistance, and improving oxidation stability. The component (D) may be a known compound used as an ashless dispersant in the field of lubricating oil compositions (for example, an ashless dispersant containing nitrogen described in International publication No. 2019/221295, an ashless dispersant described in Japanese patent application laid-open No. 2003-155492, japanese patent application laid-open No. 2020-76004, international publication No. 2013/147162, or the like may be preferably used).
Examples of the ashless dispersant include mono-or bissuccinimide having at least 1 linear or branched alkyl group or alkenyl group in the molecule, benzylamine having at least 1 alkyl group or alkenyl group in the molecule, polyamine having at least 1 alkyl group or alkenyl group in the molecule, and modified products of these compounds based on boron compounds, carboxylic acids, phosphoric acids, and the like. In the component (D), the linear or branched alkyl or alkenyl group is preferably a linear or branched alkyl or alkenyl group having 40 to 400 carbon atoms (more preferably 60 to 350 carbon atoms).
Further, from the viewpoint of imparting more excellent dispersibility to metal powder or the like, the component (D) can be preferably used: (D1) Boronated succinimides (boron modified compounds of the above-mentioned mono-or di-succinimides, etc.), (D2) non-boronated succinimides (mono-or di-succinimides, etc.), and mixtures thereof.
As the component (D1) and the component (D2), a known boronated succinimide compound and a non-boronated succinimide compound used as ashless dispersants may be appropriately used, respectively. The content of the nitrogen atoms in the component (D1) and the component (D2) is preferably 0.5 to 3.0% by mass based on the total amount of the components ((D1) and (D2)). The content of boron in the component (D1) is preferably 0.1 to 5.0 mass% (more preferably 0.1 to 3.0 mass%) based on the total amount of the component (D1). Further, the weight average molecular weight of each of the component (D1) and the component (D2) is preferably 1000 to 20000 (more preferably 2000 to 20000, still more preferably 4000 to 15000). In addition, the component (D) may be used alone in an amount of 1 or in an amount of 2 or more.
In the case where the component (D) is contained in the lubricating oil composition of the present invention, the content of the component (D) is not particularly limited, but is preferably 0.1 to 5.0 mass% (more preferably 1.0 to 2.5 mass%) based on the total amount of the lubricating oil composition. When the content of the component (D) is within the above range, the dispersibility in the formation of insoluble components can be improved.
In addition, when the component (D) contains the component (D1), the boron content (B) derived from the component (D1) (D1) ) The content of boron in the composition is 90% by mass or less (more preferably 7)0 mass% or less, more preferably 27 mass% or less. B (B) (D1) When the ratio of the total amount of boron in the composition is equal to or less than the upper limit, the excessive generation of ash can be suppressed as compared with the case where the upper limit is exceeded.
Component (E): antioxidant >
The lubricating oil composition of the present invention preferably further contains (E) an antioxidant from the viewpoint of improving oxidation stability. The component (E) is not particularly limited, and known substances used as antioxidants in the field of lubricating oil compositions can be suitably used, and examples thereof include: (E1) Phenolic antioxidants, (E2) amine antioxidants, and (E3) metal antioxidants (copper antioxidants, molybdenum antioxidants, etc.), etc.
As the component (E1), known components can be suitably used, and examples thereof include 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate; hindered phenol compounds such as methyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and bisphenol compounds.
As the component (E2), for example, a compound known as an amine antioxidant such as an aromatic amine antioxidant and a hindered amine antioxidant (for example, a compound exemplified in international publication No. 2020/095970, etc.) can be suitably used. Among these, alkylated diphenylamine and alkylated phenyl- α -naphthylamine can be preferably used as the aromatic amine-based antioxidant. As the hindered amine antioxidant, for example, a compound having a 2, 6-tetraalkylpiperidine skeleton (2, 6-tetraalkylpiperidine derivative) or the like can be suitably used. Among these, aromatic amine antioxidants can be more preferably used.
Examples of the component (E3) include molybdenum sulfide or an alkylamine complex of molybdenum oxide, molybdenum sulfide or an alkenylsuccinimide complex of molybdenum oxide, and an organic molybdenum-based antioxidant such as molybdenum sulfide of dithiocarbamate or molybdenum sulfide of dithiophosphoric acid. Among the molybdenum-based antioxidants, molybdenum sulfide or molybdenum oxide-ditridecyl amine complex, molybdenum sulfide or molybdenum oxide-alkenylsuccinimide complex are more preferable from the viewpoint of suppressing an increase in viscosity, facilitating maintenance of fuel-saving performance for a long period of time, and further, from the viewpoint of further excellent high-temperature cleaning property.
In addition, the component (E) may be used alone in an amount of 1 or in an amount of 2 or more. Further, as the component (E), the component (E1), the component (E2) and the component (E3) may be appropriately used in combination, and among them, the component (E2) and the component (E3) are preferably used in combination from the viewpoint of being able to suppress oxidation degradation of the lubricating oil composition for a long period of time.
In the case where the component (E) is contained in the lubricating oil composition for an internal combustion engine of the present invention, the content of the component (E) is preferably 1.5 to 2.5 mass% (more preferably 1.7 to 2.0 mass%) based on the total amount of the lubricating oil composition. By setting the content of the component (E) within the above-described range, the deterioration suppression property of the lubricating oil composition can be improved while maintaining the solubility of the component (E).
In the case where the component (E1) is contained in the lubricating oil composition for an internal combustion engine of the present invention, the content of the component (E1) is preferably 2.0 mass% or less (more preferably 0.5 mass% or less) based on the total amount of the lubricating oil composition. By setting the content of the component (E1) within the above-described range, the deterioration suppression property of the lubricating oil composition can be improved while maintaining the solubility of the component.
In the case where the component (E2) is contained in the lubricating oil composition for an internal combustion engine of the present invention, the content of the component (E2) is preferably 1.3 to 2.3 mass% (more preferably 1.5 to 1.9 mass%) based on the total amount of the lubricating oil composition. By setting the content of the component (E2) within the above-described range, the deterioration suppression property of the lubricating oil composition can be improved while maintaining the solubility of the component.
Further, in the case where the component (E3) is contained in the lubricating oil composition for an internal combustion engine of the present invention, the content of the component (E3) is preferably 0.3 mass% or less (more preferably 0.1 to 0.2 mass%) based on the total amount of the lubricating oil composition. By setting the content of the component (E3) within the above range, the deterioration suppression property of the lubricating oil composition can be improved while maintaining the solubility of the component.
Molybdenum-based friction modifier
The lubricating oil composition for an internal combustion engine of the present invention preferably contains (F) a molybdenum-based friction modifier (oil-soluble organic molybdenum compound). As the molybdenum-based friction modifier, a known one used as a molybdenum-based friction modifier in the field of lubricating oil compositions can be suitably used.
Further, as the component (F), molybdenum dithiocarbamate (molybdenum dithiocarbamate sulfide or molybdenum dithiocarbamate sulfide oxide) is more preferable from the viewpoint of reducing friction under boundary lubrication conditions, and as the molybdenum dithiocarbamate (MoDTC), for example, a compound represented by the following general formula (3) is preferable:
[ in formula (3), R 10 ～R 13 Independently represent an alkyl group having 2 to 24 carbon atoms or an (alkyl) aryl group having 6 to 24 carbon atoms,
Y 1 ～Y 4 Each independently represents a sulfur atom or an oxygen atom, Y 1 ～Y 4 Represents a sulfur atom.]
R in the above general formula (3) 10 ～R 13 And each may be the same or different and represents an alkyl group having 2 to 24 carbon atoms or an (alkyl) aryl group having 6 to 24 carbon atoms (preferably an alkyl group having 4 to 13 carbon atoms or an (alkyl) aryl group having 10 to 15 carbon atoms). Can be used as R 10 ～R 13 The alkyl group may be selected from a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group, and may be a straight chain or a branched chain. In addition, the term "(alkyl) aryl" as used herein means "aryl or alkylaryl". In alkylaryl groups, the substitution position of the alkyl group in the aromatic ring is arbitrary. In addition, Y in the general formula (3) 1 ～Y 4 Each independently is a sulfur atom or an oxygen atom, Y 1 ～Y 4 At least one of which is a sulfur atom.
Examples of the oil-soluble organic molybdenum compounds other than molybdenum dithiocarbamates include molybdenum dithiophosphate; molybdenum compounds (for example, molybdenum oxides such as molybdenum dioxide, molybdenum trioxide, molybdic acid such as orthomolybdic acid, paramolybdic acid, (poly) thiomolybdic acid, molybdenum sulfides such as metal salts and ammonium salts of the above-mentioned molybdic acid, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, molybdenum polysulfide, metal salts and amine salts of thiomolybdic acid, halogenated molybdenum such as molybdenum chloride, and the like), and sulfur-containing organic compounds (for example, alkyl (thio) xanthates, thiadiazoles, mercaptothiadiazoles, thiocarbonates, tetraalkylthiurams disulfide, bis (di (thio) hydrocarbyl dithiophosphonate) disulfide, organic (poly) sulfides, sulfide esters, and the like), or complexes of other organic compounds, and the like; complexes of the sulfur-containing molybdenum compounds such as molybdenum sulfide and molybdic sulfide with alkenylsuccinimides; and organic molybdenum compounds containing sulfur. The organomolybdenum compound may be a mononuclear molybdenum compound, or may be a polynuclear molybdenum compound such as a binuclear molybdenum compound or a trinuclear molybdenum compound.
Further, as the oil-soluble organomolybdenum compound other than molybdenum dithiocarbamate, an organomolybdenum compound containing no sulfur may be used. Examples of the sulfur-free organomolybdenum compound include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, molybdenum salts of alcohols, and the like, and among them, molybdenum-amine complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols are preferable.
The content of the component (F) in the lubricating oil composition is preferably such that the molybdenum content is 100 to 2000 mass ppm (more preferably 300 to 1500 mass ppm, still more preferably 500 to 1200 mass ppm, particularly preferably 700 to 1000 mass ppm) based on the total amount of the lubricating oil composition. By setting the content of the component (F) to the above lower limit value or more, the fuel economy performance and LSPI suppression ability can be further improved. In addition, the storage stability of the lubricating oil composition can be improved by setting the content of the component (F) to the above-mentioned upper limit value or less.
Antiwear agent (G)
The lubricating oil composition for an internal combustion engine of the present invention preferably contains (G) an antiwear agent. The antiwear agent is not particularly limited, and a known compound used as an antiwear agent in a lubricating oil composition can be used. As the antiwear agent, for example, sulfur-based, phosphorus-based, sulfur-phosphorus-based antiwear agents and the like can be used. Specifically, examples of the antiwear agent include phosphites, thiophosphites, dithiophosphites, trithiophosphites, phosphates, thiophosphates, dithiophosphates, trithiophosphates, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamates, zinc dithiocarbamates, disulfides, polysulfides, sulfurized olefins, and sulfurized oils.
Among the above antiwear agents, phosphorus antiwear agents are preferable, and phosphorus antiwear agents containing zinc are more preferable, and among them, zinc dialkyldithiophosphate (ZnDTP) represented by the following formula (4) is particularly preferable:
[ in formula (4), R 14 ～R 17 Each independently represents a linear or branched alkyl group having 1 to 24 carbon atoms.]
R in the above general formula (4) 14 ～R 17 Each independently represents a linear or branched alkyl group having 1 to 24 carbon atoms, or may be a combination of different groups. In addition, R 14 ～R 17 The number of carbon atoms in (a) is preferably 3 or more, more preferably 12 or less, and still more preferably 8 or less. In addition, R 14 ～R 17 May be any of a primary alkyl group, a secondary alkyl group and a tertiary alkyl group, but is preferably a primary alkyl group or a secondary alkyl group or a combination thereof, and further the molar ratio of the primary alkyl group to the secondary alkyl group (primary alkyl: secondary alkyl) is preferably 0: 100-30: 70. the ratio may be a combination ratio of the alkyl chains in the molecule, or may be a mixing ratio of ZnDTP having only a primary alkyl group and ZnDTP having only a secondary alkyl group. By using the secondary alkyl group as the main component, fuel economy performance can be further improved. The method for producing ZnDTP is not particularly limited, and a known method can be suitably used, for exampleThe following synthesis method is adopted: to have a corresponding R 14 ～R 17 The alkyl alcohol of (2) is reacted with phosphorus pentasulfide to synthesize dithiophosphoric acid, which is neutralized with zinc oxide.
The content of the antiwear agent is preferably 0.1 to 5.0 mass% or less (more preferably 0.5 to 3.0 mass% or less) based on the total amount of the lubricating oil composition. If the content of the antiwear agent is within the above-mentioned numerical range, a sufficient antiwear effect can be obtained.
Pour Point depressant (H)
The lubricating oil composition for an internal combustion engine of the present invention preferably contains (H) a pour point depressant. The pour point depressant is not particularly limited, and known pour point depressants used in lubricating oil compositions can be suitably used. Examples of the pour point depressant include poly (meth) acrylate and ethylene-vinyl acetate copolymer, and among them, polymethacrylate is preferable. In addition, as the poly (meth) acrylate (more preferably, polymethacrylate) used as the pour point depressant, a weight average molecular weight of 20000 to 100000 (more preferably 20000 to 80000) is preferable from the viewpoints of pour point depressing effect and shear stability.
The pour point depressant may be used singly or in combination of two or more. When a pour point depressant is used, the content thereof is preferably 0.01 to 1.0 mass% (more preferably 0.03 to 0.6 mass%) based on the total amount of the lubricating oil composition.
Other ingredients (I)
The lubricating oil composition for an internal combustion engine of the present invention may contain other additives useful in the lubricating oil composition in addition to the above-described components. The other components are not particularly limited, and examples thereof include defoamers, rust inhibitors, anti-emulsifying agents, metal deactivators, and the like. The other components mentioned above can be each appropriately used by known substances, and examples of the defoaming agent include a dynamic viscosity of 1000 to 100000mm at 25 DEG C 2 Silicone oil of/s, alkenyl succinic acid derivatives, esters of polyhydroxyaliphatic alcohols with long chain fatty acids, methyl salicylate, o-hydroxybenzyl alcohol and the like. In addition, the aboveThe content of the other components in (a) is not particularly limited as long as the content of each component is appropriately designed to achieve the optimum amount according to the application, but the content of each component is preferably about 0.001 to 5% by mass based on the total amount of the lubricating oil composition. The content of each component used as the component (I) is preferably 0.001 to 0.05 parts by mass based on 100 parts by mass of the total mass of the components in the lubricating oil composition other than the component.
[ concerning lubricating oil compositions ]
In the lubricating oil composition for an internal combustion engine of the present invention, the boron content based on the total mass of the composition (the boron content based on the total mass of the lubricating oil composition) is 1000 mass ppm or less (more preferably 200 mass ppm to 700 mass ppm, still more preferably 400 mass ppm to 650 mass ppm). When the content of boron based on the total amount of the composition is set to the upper limit or less, friction reduction performance can be improved as compared with the case where the content exceeds the upper limit, and when the content is set to the lower limit or more, LSPI inhibition ability can be improved as compared with the case where the content is less than the lower limit.
In the lubricating oil composition for an internal combustion engine of the present invention, the content of calcium based on the total amount of the lubricating oil composition is preferably 1650 to 2500 mass ppm (more preferably 1700 to 1900 mass ppm, still more preferably 1750 to 1900 mass ppm). When the content of calcium based on the total amount of the composition is equal to or less than the upper limit, both LSPI inhibitory ability and friction reducing performance can be achieved as compared with the case where the content exceeds the upper limit, and when the content is equal to or more than the lower limit, the detergency can be improved by improving the acid neutralization property as compared with the case where the content is less than the lower limit.
In the lubricating oil composition for an internal combustion engine of the present invention, the content of magnesium is preferably 20 to 400 mass ppm (more preferably 20 to 300 mass ppm, still more preferably 100 to 200 mass ppm) based on the total amount of the lubricating oil composition. When the content of magnesium based on the total amount of the composition is set to the upper limit or less, the friction reduction performance can be improved as compared with the case where the content exceeds the upper limit, whereas when the content is set to the lower limit or more, the acid neutralization performance can be improved as compared with the case where the content is less than the lower limit.
In the lubricating oil composition for an internal combustion engine of the present invention, when molybdenum is contained in the composition, the content of molybdenum is preferably 100 to 1200 mass ppm (more preferably 700 to 1000 mass ppm) based on the total amount of the lubricating oil composition. By making the content of molybdenum based on the total amount of the composition in the above-described range, the friction reducing performance can be further improved while maintaining the solubility of the additives in the composition.
In the lubricating oil composition for an internal combustion engine of the present invention, when phosphorus is contained in the composition, the content of phosphorus is preferably 600 to 800 mass ppm (more preferably 700 to 800 mass ppm) based on the total amount of the lubricating oil composition. By making the content of phosphorus based on the total amount of the composition fall within the above-described range, friction reducing performance and abrasion preventing performance can be simultaneously achieved while avoiding excessive catalyst poisoning.
In the lubricating oil composition for an internal combustion engine of the present invention, when sulfur is contained in the composition, the sulfur content is preferably 500 to 3000 mass ppm (more preferably 1000 to 2700 mass ppm) based on the total amount of the lubricating oil composition. By setting the sulfur content in the above range based on the total composition, the adhesion resistance (Japanese style) can be improved.
In the lubricating oil composition for an internal combustion engine of the present invention, when zinc is contained in the composition, the zinc content is preferably 500 to 1300 mass ppm (more preferably 700 to 900 mass ppm) based on the total amount of the lubricating oil composition. The abrasion resistance can be improved by setting the content of zinc in the above range based on the total amount of the composition.
In addition, the boron, calcium, magnesium, molybdenum, zinc, sulfur and phosphorus content of the lubricating oil composition can be measured according to JPI-5S-62, respectively.
In the lubricating oil composition for an internal combustion engine of the present invention, the ratio (mass ratio: [ boron ]/[ calcium ]) of the content of boron based on the total amount of the lubricating oil composition to the content of calcium based on the total amount of the lubricating oil composition is preferably 0.15 to 0.35 (more preferably 0.25 to 0.35, still more preferably 0.26 to 0.30). By setting the mass ratio within the above range, the LSPI suppression ability can be improved while maintaining the friction reducing performance.
In the lubricating oil composition for an internal combustion engine of the present invention, the ratio of the boron content based on the total amount of the lubricating oil composition to the total amount (total amount) of calcium based on the total amount of the lubricating oil composition and magnesium based on the total amount of the lubricating oil composition [ mass ratio: [ boron ]/([ calcium ] + [ magnesium ]) ] is preferably 0.13 to 0.29 (more preferably 0.20 to 0.29, still more preferably 0.25 to 0.28). By setting the mass ratio within the above range, the LSPI suppression ability can be improved while maintaining the friction reducing performance.
As the lubricating oil composition for an internal combustion engine of the present invention, a dynamic viscosity at 100℃of 4.0 to 9.3mm is more preferable 2 /s (more preferably 6.5 to 8.0 mm) 2 /s). Further, the dynamic viscosity of the lubricating oil composition of the present invention at 40℃is more preferably 23.0 to 40.0mm 2 /s (more preferably 26.0 to 30.0 mm) 2 /s). When these dynamic viscosities are equal to or less than the upper limit value, fuel efficiency can be further improved as compared with the case where the dynamic viscosities exceed the upper limit value. On the other hand, when these dynamic viscosities are equal to or higher than the lower limit, the abrasion resistance due to the oil film retention can be improved as compared with the case where they are lower than the lower limit.
The lubricating oil composition for an internal combustion engine of the present invention preferably has a viscosity index of 180 or more (more preferably 200 or more, still more preferably 220 or more, particularly preferably 225 or more). When the viscosity index is equal to or higher than the lower limit, the viscosity-temperature characteristics and wear resistance of the lubricating oil composition can be improved, and the fuel economy performance can be further improved, as compared with the case where the viscosity index is lower than the lower limit. In addition, when the viscosity index is equal to or higher than the lower limit, the evaporation loss of the lubricating oil can be reduced, and the consumption of the lubricating oil can be reduced.
The HTHS viscosity at 150℃of the lubricating oil composition for an internal combustion engine of the present invention is preferably 1.7 to 2.9 mPas (more preferably 2.3 to 2.8MPa s, still more preferably 2.6 to 2.8MPa s, particularly preferably 2.6MPa s). When the HTHS viscosity at 150 ℃ is equal to or higher than the lower limit, the abrasion resistance under high shear conditions can be improved as compared with the case where the HTHS viscosity is lower than the lower limit, while when the HTHS viscosity is equal to or lower than the upper limit, the fuel efficiency can be further improved by reducing the viscous resistance as compared with the case where the HTHS viscosity is higher than the upper limit. In addition, in the present specification, "HTHS viscosity at 150℃means high temperature and high shear viscosity at 150℃measured in accordance with ASTM D-4683.
The method for producing the lubricating oil composition for an internal combustion engine of the present invention is not particularly limited, and the lubricating oil composition of the present invention may be prepared by appropriately selecting and mixing the components contained in the composition so as to obtain the lubricating oil composition of the present invention (satisfying the above conditions).
Examples
Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.
(regarding the components used in the examples and the like)
First, lubricating base oils and additives used in the respective examples and the like are shown below.
Component (A): lubricating base oil ]
(A-1)
Base oil of API group II (hydrocracked mineral oil base oil, yubase (registered trademark) 3 made by SK Lubicants Co., ltd.), dynamic viscosity (100 ℃ C.): 3.05mm 2 Dynamic viscosity (40 ℃ C.): 12.3mm 2 S, viscosity index: 105. NOACK evaporation amount (250 ℃, 1 h): 40% by mass of C P ：72.6、％C N ：27.4、％C A :0. saturated components: 99.6 mass% of aromatic components: 0.3 mass%
(A-2)
Base oil of API group III (hydrocracked mineral base oil, yubase 4+ of SK Luica Co., ltd.)Dynamic viscosity (100): 4.2mm 2 Dynamic viscosity (40 ℃ C.): 17.9mm 2 S, viscosity index: 134. NOACK evaporation amount (250 ℃, 1 h): 13.5% by mass,% C P ：87.2、％C N ：12.8、％C A :0. saturated components: 99.8 mass% of aromatic components: 0.1 mass%
(A-3)
Base oils of API group III (hydrocracked mineral oil base oils, yubase (registered trademark) 6+), dynamic viscosity (100 ℃) manufactured by SK Lubricants: 6.4mm 2 Dynamic viscosity (40 ℃ C.): 33.8mm2/s, viscosity index: 145. NOACK evaporation amount (250 ℃, 1 h): 8 mass% C P ：85％、C N ：15％、C A :0% of saturated components: 99.5 mass% of aromatic components: 0.2 mass%
Component (B): metal-based cleaning agent >
Component (B1): calcium-based cleaning agent >
(B1-i)
Calcium borate high alkalization calcium salicylate, calcium content: 6.8 mass percent, boron content: 2.7 mass%, base number (perchloric acid method): 190mgKOH/g
(B1-ii)
Calcium carbonate high alkalization calcium salicylate, calcium content: 8.0 mass%, base number (perchloric acid method): 210mgKOH/g
Component (B2): magnesium-based cleaning agent ]
(B2-i)
Magnesium carbonate magnesium salicide, magnesium content: 7.5 mass%, base number (perchloric acid method): 350mgKOH/g
(B2-ii)
Magnesium carbonate high alkalization magnesium sulfonate, magnesium content: 9.1 mass%, base number (perchloric acid method): 400mgKOH/g.
Component (C): viscosity index improver (Poly (meth) acrylate-based viscosity index improver) >
(C-1)
Comb-type polymethacrylate polymer (trade name: ACLUBE V-7030, mw:52 ten thousand, mn:22 ten thousand, mw/Mn:2.4, manufactured by Sanyo chemical industry Co., ltd.)
(C-2)
Linear polymethacrylate polymers (trade name: ACLUBE V-5090, mw:48 ten thousand, mn:17 ten thousand, mw/Mn:2.8, manufactured by Sanyo chemical industry Co., ltd.).
Component (D): ashless dispersant)
(D-1)
Non-boronated succinimides (nitrogen content: 1.6% by mass, mw: 6000)
(D-2)
Boronated succinimide (nitrogen content: 1.2 mass%, boron content: 0.5 mass%, mw: 7000).
Component (E): antioxidant >
(E-1)
Amine antioxidant (trade name: IRGANOX (registered trademark) L67, bis (nonylphenyl) amine, nitrogen content: 3.6% by mass, manufactured by BASF corporation)
(E-2)
Molybdenum-based antioxidant (dialkylamine molybdate, molybdenum content: 10 mass%, nitrogen content: 3.6 mass%).
Component (F): friction modifier (molybdenum-based friction modifier) >
(F-1)
Molybdenum dithiocarbamate (MoDTC, manufactured by Kyowa Kagaku Co., ltd.: ADEKA SAKURA-LUBE 525, trade name, molybdenum content (theoretical value): 10.0 mass%).
Antiwear agent (G)
(G-1)
Zinc dialkyldithiophosphate (ZnDTP, secondary alkyl type, represented by the formula (4) and R in the formula (4) 14 ～R 17 A compound which is any one of secondary alkyl groups having 4 or 6 carbon atoms, and zinc content: 8.0 mass percent, phosphorus content: 7.0 mass%, sulfur content: 14% by mass)
(G-2)
Zinc dialkyldithiophosphate (ZnDTP, primary alkyl type, represented by the formula (4) and R in the formula (4) 14 ～R 17 Compounds each of which is a primary alkyl group having 8 carbon atoms, zinc content: 8.0 mass percent, phosphorus content: 7.0 mass%, sulfur content:15 mass%)
(G-3)
Zinc dialkylphosphate (ZnP, primary alkyl group type having 8 carbon atoms, zinc content: 5.3 mass%, phosphorus content: 5.2 mass%).
Component (H): pour Point depressant >
(H-1)
Polymethacrylate (trade name: viscoplex1-300, mw:6 ten thousand, mn:3.2 ten thousand, mw/Mn:1.9, manufactured by Evonik INDUSTRIES Co.).
Component (I): other additives-
(I-1)
Defoamer (trade name "KF-96H", believed to be chemical company).
Examples 1 to 5 and comparative examples 1 to 10
Lubricating oil compositions of examples 1 to 5 and comparative examples 1 to 10 were prepared using the above-described components according to the compositions shown in tables 1 to 3. In addition, in the items of "composition" in tables 1 to 3, "-" indicates that the component is not used. In the items of "compositions" in tables 1 to 3, "mass%" in the unit of the content of the component (a) represents the content (mass%) of each base oil component relative to the total amount of the lubricating base oil, and "in mass%" in the unit of the content of the components (B) to (H) represents the content (mass%) of each additive relative to the total amount of the lubricating oil composition, and "parts by mass" represents the proportion (parts by mass) of the component (I-1) when the total mass of the components in the lubricating oil composition from which the component (I-1) is removed is 100 parts by mass. In tables 1 to 3, [ B ] (B1) ]"massppm" of (a) means parts by mass (mass ppm) of boron from the (B1) component based on the total amount of the lubricating oil composition, [ Ca ] (B1) ]"massppm" of (a) means parts by mass (ppm by mass) of calcium derived from the component (B1) [ Mg ] based on the total amount of the lubricating oil composition (B2) ]The "massppm" of the unit (c) means parts by mass (mass ppm) of magnesium from the (B2) component based on the total amount of the lubricating oil composition. In addition, in the item "content of each element in composition" in tables 1 to 3, the content of B, ca, mg, mo, P, S, zn is as followsThe "massppm" of the unit concerned is preferably parts per million by mass (mass ppm) of each element (B, ca, mg, mo, P, S, zn) based on the total amount of the lubricating oil composition. The values of B, ca, mg, mo, P, S and Zn contents in the items of "contents of respective elements in compositions" in tables 1 to 3 are values measured in accordance with JPI-5S-62, respectively.
[ evaluation of Properties of lubricating oil compositions obtained in examples and the like ]
< LSPI Performance evaluation test (LSPI test) >
For each lubricating oil composition, an evaluation test of LSPI inhibition ability according to ASTM D8291 was performed [ test method: one end, a select (seq. Ix ASTM D8291), an engine is used: engine manufactured in 2012 by Ford corporation (2000 CC, 4 cylinder, GDTI engine) ]. The average value of the LSPI generation times of each lubricating oil composition obtained by the above measurement is shown in tables 1 to 3 as LSPI test results. In tables 1 to 3, the condition of "5" or less, which is a reference value of "API SP/ILSAC GF-6" of the engine oil standard, is evaluated as "S" when the reference value is or less (when the reference is satisfied), and as "F" when the reference value is exceeded (when the reference is not satisfied), respectively. Further, when the LSPI test result satisfies the condition of 5 or less, which is the reference value of "API SP/ILSAC GF-6", it can be evaluated that the LSPI inhibitory ability of the lubricating oil composition is excellent.
< SRV test (evaluation test for Fuel consumption saving Performance) >
Each lubricating oil composition was used, and a cylinder-disk-type reciprocating dynamic friction tester (SRV, manufactured by Optimel Co.) was used under load: 100N, disk temperature: 100 ℃, vibration frequency: 50Hz, amplitude: 1mm, test time: the SRV test was performed under test conditions for 15 minutes to determine the coefficient of friction between metals. The results obtained are shown in tables 1 to 3. In addition, it is known that: when the value of the friction coefficient is 0.060 or less, the friction characteristics are excellent, and therefore, the lubricating oil composition can be evaluated as a composition excellent in fuel saving performance.
TABLE 1
TABLE 2
TABLE 3 Table 3
As is clear from the results shown in Table 1, the lubricating oil compositions obtained in examples 1 to 5, which contained (A) a lubricating base oil and (B) a metal-based cleaning liquid, contained (B) a calcium-based cleaning agent ((B1) a magnesium-based cleaning liquid ((B2) a) component, contained (B1-i) a total amount of B) of 1000 ppm by mass or less, and contained (B1-i) a total amount of B in the composition, were confirmed to be excellent in both LSPI inhibitory ability and fuel economy performance (friction characteristics), wherein the content of calcium derived from (B1) was 1650 ppm by mass to 2500 ppm by mass based on the total mass of the composition, and the content of magnesium derived from (B2) was 20 ppm by mass to 400 ppm by mass based on the total mass of the composition (B1) /Ca (B1) 0.15 to 0.35, and B (B1) /[Ca (B1) +Mg (B2) ]0.13 to 0.29. In addition, even B (B1) /[Ca (B1) +Mg (B2) ]0.29 but B (B1) /Ca (B1) The lubricating oil compositions obtained in comparative examples 2 and 9, which were outside the range of 0.15 to 0.35, have a larger value, in particular, friction coefficient, than the lubricating oil compositions obtained in examples 1 to 5.
Industrial applicability
As described above, according to the present invention, it is possible to provide a lubricating oil composition for an internal combustion engine that can be made excellent in both LSPI inhibitory ability and fuel consumption performance. Therefore, the lubricating oil composition for an internal combustion engine of the present invention is particularly useful as a lubricating oil composition for an engine such as a gasoline engine or a diesel engine.
Claims (4)
1. A lubricating oil composition for an internal combustion engine comprising (A) a lubricating base oil and (B) a metal-based detergent,
the component (B) comprises:
(B1) A calcium-based cleaning agent having a calcium content in the range of 1650 to 2500 mass ppm based on the total mass of the composition; and
(B2) A magnesium-based cleaning agent having a magnesium content in the range of 20 to 400 mass ppm based on the total mass of the composition,
the component (B1) contains (B1-1) a calcium-based detergent containing boron and calcium,
the boron content is 1000 mass ppm or less based on the total mass of the composition,
The boron content in the component (B1) based on the total mass of the composition is expressed as B (B1) The content of calcium in the component (B1) based on the total mass of the composition is expressed as Ca (B1) The content of magnesium in the component (B2) based on the total mass of the composition is expressed as Mg (B2) In the case of B (B1) Relative to Ca (B1) Ratio (B) (B1) /Ca (B1) ) 0.15 to 0.35, and B (B1) Relative to Ca (B1) And Mg (magnesium) (B2) Is the sum of (Ca) (B1) +Mg (B2) ) Ratio (B) (B1) /[Ca (B1) +Mg (B2) ]) 0.13 to 0.29.
2. The lubricating oil composition for an internal combustion engine according to claim 1, wherein the component (B1) contains calcium salicylate borate as the component (B1-1).
3. The lubricating oil composition for an internal combustion engine according to claim 1 or 2, further comprising (C) a poly (meth) acrylate-based viscosity index improver.
4. The lubricating oil composition for an internal combustion engine according to claim 3, wherein the component (C) contains a comb-type poly (meth) acrylate polymer.
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| JP2021049156A JP2022147768A (en) | 2021-03-23 | 2021-03-23 | Lubricating oil composition for internal combustion engine |
| JP2021-049156 | 2021-03-23 | ||
| PCT/JP2022/003125 WO2022201845A1 (en) | 2021-03-23 | 2022-01-27 | Lubricant composition for internal combustion engine |
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| CN116964180A true CN116964180A (en) | 2023-10-27 |
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| US20150322367A1 (en) * | 2014-05-09 | 2015-11-12 | Exxonmobil Research And Engineering Company | Method for preventing or reducing low speed pre-ignition |
| CN106459814B (en) * | 2015-03-24 | 2021-04-06 | 出光兴产株式会社 | Lubricating oil composition for gasoline engine and method for producing same |
| JP6716360B2 (en) * | 2016-06-24 | 2020-07-01 | Ｊｘｔｇエネルギー株式会社 | Lubricating oil composition for internal combustion engine |
| EP3369802B1 (en) * | 2017-03-01 | 2019-07-10 | Infineum International Limited | Improvements in and relating to lubricating compositions |
| JP7387593B2 (en) * | 2017-10-20 | 2023-11-28 | シェブロンジャパン株式会社 | Low viscosity lubricating oil composition |
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