JP4768965B2 - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
- Publication number
- JP4768965B2 JP4768965B2 JP2004074883A JP2004074883A JP4768965B2 JP 4768965 B2 JP4768965 B2 JP 4768965B2 JP 2004074883 A JP2004074883 A JP 2004074883A JP 2004074883 A JP2004074883 A JP 2004074883A JP 4768965 B2 JP4768965 B2 JP 4768965B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- group
- component
- less
- salicylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 59
- 239000010687 lubricating oil Substances 0.000 title claims description 49
- -1 Alkali metal salicylate Chemical class 0.000 claims description 67
- 239000002199 base oil Substances 0.000 claims description 50
- 229960001860 salicylate Drugs 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 239000003599 detergent Substances 0.000 claims description 27
- 239000002585 base Substances 0.000 claims description 23
- 230000001050 lubricating effect Effects 0.000 claims description 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims description 21
- 238000002485 combustion reaction Methods 0.000 claims description 19
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 16
- 150000001447 alkali salts Chemical class 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000010248 power generation Methods 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000009472 formulation Methods 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 description 19
- 150000002430 hydrocarbons Chemical group 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 12
- 239000004071 soot Substances 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 230000003749 cleanliness Effects 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229960002317 succinimide Drugs 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 230000002862 amidating effect Effects 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001083 polybutene Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- RAADJDWNEAXLBL-UHFFFAOYSA-N 1,2-di(nonyl)naphthalene Chemical compound C1=CC=CC2=C(CCCCCCCCC)C(CCCCCCCCC)=CC=C21 RAADJDWNEAXLBL-UHFFFAOYSA-N 0.000 description 1
- MBIZXFATKUQOOA-UHFFFAOYSA-N 1,3,4-thiadiazole Chemical compound C1=NN=CS1 MBIZXFATKUQOOA-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- VRMHHVOBVLFRFB-UHFFFAOYSA-N 2-(2-cyanoethylsulfanylmethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CSCCC#N VRMHHVOBVLFRFB-UHFFFAOYSA-N 0.000 description 1
- LLEFDCACDRGBKD-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;nonanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCCC(O)=O LLEFDCACDRGBKD-UHFFFAOYSA-N 0.000 description 1
- CWTQBXKJKDAOSQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;octanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCC(O)=O CWTQBXKJKDAOSQ-UHFFFAOYSA-N 0.000 description 1
- 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
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DJBVDAUKGXUPLO-QEMDMZNVSA-N C(C)C(C(=O)O)CCCC.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O Chemical compound C(C)C(C(=O)O)CCCC.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O DJBVDAUKGXUPLO-QEMDMZNVSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- URGQBRTWLCYCMR-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] nonanoate Chemical compound CCCCCCCCC(=O)OCC(CO)(CO)CO URGQBRTWLCYCMR-UHFFFAOYSA-N 0.000 description 1
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 125000003901 ceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- WDNQRCVBPNOTNV-UHFFFAOYSA-N dinonylnaphthylsulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 WDNQRCVBPNOTNV-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- LZJUZSYHFSVIGJ-UHFFFAOYSA-N ditridecyl hexanedioate Chemical compound CCCCCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCCCC LZJUZSYHFSVIGJ-UHFFFAOYSA-N 0.000 description 1
- FVBSDVQDRFRKRF-UHFFFAOYSA-N ditridecyl pentanedioate Chemical compound CCCCCCCCCCCCCOC(=O)CCCC(=O)OCCCCCCCCCCCCC FVBSDVQDRFRKRF-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002818 heptacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000002819 montanyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002465 nonacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003209 petroleum derivative 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
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003580 thiophosphoric acid esters Chemical class 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Lubricants (AREA)
Description
本発明は、潤滑油組成物に関し、詳しくは高温清浄性及びすす分散性に優れ、かつ長期間の使用においてもストレージタンク内での貯蔵安定性に優れる潤滑油組成物に関し、特に船舶、発電あるいは鉄道に使用される内燃機関用、内燃機関減速機用、又は内燃機関油圧作動機器用の潤滑油として好適な潤滑油組成物に関するものである。 The present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition having excellent high-temperature cleanliness and soot dispersibility, and excellent storage stability in a storage tank even when used for a long period of time. The present invention relates to a lubricating oil composition suitable as a lubricating oil for an internal combustion engine, an internal combustion engine speed reducer, or an internal combustion engine hydraulic operating device used in railways.
船舶、発電、鉄道等に使用される内燃機関は、経済性の観点からアスファルテン成分を含む重質燃料（Ａ重油、Ｃ重油等）を使用することが多い。このような内燃機関には、重質燃料からのアスファルテン成分で機関が汚損されるため、潤滑油にサリシレート系清浄剤を多量に配合して清浄性の向上が図られてきた。
しかしながら、一般的に使用されている炭素数２０未満のアルキル基を有する過塩基性のモノアルキルサリシレート系清浄剤は高温清浄性が不十分であり、また、高粘度基油あるいは無灰分散剤や他の金属系清浄剤等の潤滑油成分との相互作用や重質燃料の燃焼残渣として混入するすすにより不溶解分を析出し易い問題があった。
さらに、４ストロークトランクピストン機関においては、近年、アンチポリッシングリングの装着によりオイル消費量の低減が進みつつあるが、これにより燃焼残渣分であるすすの潤滑油への混入量が増加し、上記サリシレート系清浄剤に起因する不溶分析出に加え、粘度増加やすすに起因する不溶分による機関軸受けの損傷などの不具合の発生が懸念され始めた。
Internal combustion engines used for ships, power generation, railways, and the like often use heavy fuels (A heavy oil, C heavy oil, etc.) containing asphaltene components from the viewpoint of economy. In such an internal combustion engine, the asphaltene component from the heavy fuel pollutes the engine, and therefore, a large amount of salicylate detergent has been blended into the lubricating oil to improve the cleanliness.
However, generally used overbased monoalkyl salicylate detergents having an alkyl group with less than 20 carbon atoms are insufficient in high-temperature cleanability, and high viscosity base oils or ashless dispersants and other There is a problem that insoluble components are likely to precipitate due to the interaction with the lubricating oil components such as metal detergents and soot mixed as a combustion residue of heavy fuel.
Furthermore, in the 4-stroke trunk piston engine, the oil consumption has been reduced in recent years due to the installation of the anti-polishing ring, but this has increased the amount of soot as a combustion residue mixed into the lubricating oil. In addition to insoluble analysis due to system detergents, there are concerns about the occurrence of problems such as damage to engine bearings due to insolubles due to increased viscosity and soot.
本発明はこのような実状に鑑みなされたものであり、その目的は長期間の使用においてもストレージタンクにおける貯蔵安定性を改善し、かつ、高温清浄性に優れ、すす混入下においても粘度増加が少ない新規な潤滑油組成物を提供することにある。 The present invention has been made in view of such a situation, and the purpose thereof is to improve the storage stability in the storage tank even during long-term use, and it is excellent in high-temperature cleanliness and increases viscosity even under soot mixing. The object is to provide a small number of new lubricating oil compositions.
本発明者らは、上記課題を解決するために鋭意検討した結果、特定のサリシレート系清浄剤と特定の金属系清浄剤を含有する潤滑油組成物が、貯蔵安定性、高温清浄性に優れ、すす混入下においても粘度増加が少ないことを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a lubricating oil composition containing a specific salicylate detergent and a specific metal detergent is excellent in storage stability and high-temperature cleanability, The present inventors have found that the increase in viscosity is small even when soot is mixed, and the present invention has been completed.
すなわち、本発明は、基油全量基準で、１００℃における動粘度が４〜１７ｍｍ ２ ／ｓ未満の潤滑油基油５０質量％以上及び１００℃における動粘度が３０〜５０ｍｍ ２ ／ｓのブライトストックを１０質量％以上配合してなる潤滑油基油に、
（Ａ）塩基価が２４０ｍｇＫＯＨ／ｇ未満及び／又は金属比が４．５未満であり、炭素数２０〜３０のαオレフィン（１００ｍｏｌ％）から誘導されるアルキル基からなる炭化水素基を１つ有するアルカリ金属サリシレート又はアルカリ土類金属サリシレート及び／又はその（過）塩基性塩、および
（Ｂ）塩基価が２４０ｍｇＫＯＨ／ｇ以上及び／又は金属比が４．５以上であり、炭素数１４〜１８のαオレフィン（１００ｍｏｌ％）から誘導されるアルキル基からなる炭化水素基を１つ有するアルカリ金属サリシレート又はアルカリ土類金属サリシレート及び／又はその（過）塩基性塩である（Ａ）成分以外のサリシレート系金属系清浄剤、とからなる金属系清浄剤を含有して成る、アスファルテン分や残留炭素分を含む重質燃料を使用する船舶、発電もしくは鉄道に使用される内燃機関用、内燃機関減速機用、又は内燃機関油圧作動器機用の潤滑油組成物にある。
That is, the present invention is a base oil based on a total amount, 100 kinematic viscosity at ° C. kinematic viscosity at 4~17mm 2 / s less than the lubricating base oil 50 mass% or more and 100 ° C. is 30 to 50 mm 2 / s bright stock In a lubricating base oil containing 10% by mass or more of
(A) The base number is less than 240 mgKOH / g and / or the metal ratio is less than 4.5, and it has one hydrocarbon group composed of an alkyl group derived from an α-olefin (100 mol%) having 20 to 30 carbon atoms. Alkali metal salicylate or alkaline earth metal salicylate and / or (over) basic salt thereof, and (B) a base number of 240 mgKOH / g or more and / or a metal ratio of 4.5 or more, and having 14 to 18 carbon atoms Salicylate system other than (A) component which is an alkali metal salicylate or alkaline earth metal salicylate having one hydrocarbon group derived from an α-olefin (100 mol%) and / or an (over) basic salt thereof metallic detergents, comprising a metallic detergent consisting city, to use heavy fuel containing asphaltene component and carbon residue Ships, internal combustion engines used power or the railway, for an internal combustion engine speed reducer, or the lubricating oil compositions for internal combustion engines hydraulic equipment is.
また、本発明は、組成物全量基準で、前記（Ａ）成分の含有量が１〜３０質量％、前記（Ｂ）成分の含有量が１〜１０質量％であることを特徴とする前記記載の潤滑油組成物にある。
また、本発明は、さらに無灰分散剤を０．１〜２０質量％含有することを特徴とする前記記載の潤滑油組成物にある。
In the present invention, the content of the component (A) is 1 to 30% by mass and the content of the component (B) is 1 to 10% by mass based on the total amount of the composition. In the lubricating oil composition.
Further, the present invention is Ru lubricating oil composition near the wherein further contain an ashless dispersant from 0.1 to 20 mass%.
以下、本発明について詳述する。
本発明の潤滑油組成物における潤滑油基油は、特に制限はなく、通常の潤滑油に使用される鉱油系基油及び／又は合成系基油が使用できる。
鉱油系基油としては、具体的には、原油を常圧蒸留して得られる常圧残油を減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、水素化精製等の処理を１つ以上行って精製したもの、あるいはワックス異性化鉱油、フィッシャートロプシュプロセス等により製造されるＧＴＬ ＷＡＸ（ガストゥリキッドワックス）を異性化する手法で製造される潤滑油基油等が例示できる。
Hereinafter, the present invention will be described in detail.
The lubricating base oil in the lubricating oil composition of the present invention is not particularly limited, and a mineral base oil and / or a synthetic base oil used for ordinary lubricating oils can be used.
Specifically, as the mineral base oil, the lubricating oil fraction obtained by subjecting the crude oil to atmospheric distillation obtained under reduced pressure is subjected to solvent removal, solvent extraction, hydrocracking, Produced by one or more processes such as solvent dewaxing, hydrorefining, etc., or by a method of isomerizing GTL WAX (Gas Liquid Wax) produced by wax isomerized mineral oil, Fischer-Tropsch process, etc. Lubricating oil base oil and the like.
鉱油系基油の全芳香族分は、特に制限はないが、好ましくは４０質量％以下であり、より好ましくは３０質量％以下である。全芳香族分は０質量％でも良いが、添加剤の溶解性の点で１質量％以上であることが好ましく、５質量％以上であることがさらに好ましく、１０質量％以上であることがさらに好ましく、２０質量％以上であることが特に好ましい。基油の全芳香族分が４０質量％を越える場合は、酸化安定性が劣るため好ましくない。
なお、上記全芳香族分とは、ＡＳＴＭ Ｄ２５４９に準拠して測定した芳香族留分（ａｒｏｍａｔｉｃ ｆｒａｃｔｉｏｎ）含有量を意味する。通常この芳香族留分には、アルキルベンゼン、アルキルナフタレンの他、アントラセン、フェナントレン、これらのアルキル化物、ベンゼン環が四環以上縮合した化合物、及びピリジン類、キノリン類、フェノール類、ナフトール類等のヘテロ芳香族を有する化合物等が含まれる。
The total aromatic content of the mineral oil base oil is not particularly limited, but is preferably 40% by mass or less, and more preferably 30% by mass or less. Although the total aromatic content may be 0% by mass, it is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more in terms of the solubility of the additive. It is preferably 20% by mass or more. When the total aromatic content of the base oil exceeds 40% by mass, oxidation stability is inferior, which is not preferable.
In addition, the said total aromatic content means the aromatic fraction (aromatic fraction) content measured based on ASTMD2549. Usually, this aromatic fraction includes alkylbenzene, alkylnaphthalene, anthracene, phenanthrene, alkylated products thereof, compounds in which four or more benzene rings are condensed, and heterogeneous compounds such as pyridines, quinolines, phenols, and naphthols. Compounds having aromatics are included.
また、鉱油系基油中の硫黄分は、特に制限はないが、１質量％以下であることが好ましく、０．５質量％以下であることがさらに好ましく、硫黄分は０質量％でも良いが、好ましくは０．１質量％以上、より好ましくは０．２質量％以上である。鉱油系基油の硫黄分をある程度含むことにより、添加剤の溶解性を十分に高めることができる。 Further, the sulfur content in the mineral oil base oil is not particularly limited, but is preferably 1% by mass or less, more preferably 0.5% by mass or less, and the sulfur content may be 0% by mass. , Preferably 0.1% by mass or more, more preferably 0.2% by mass or more. By including the sulfur content of the mineral oil base oil to some extent, the solubility of the additive can be sufficiently increased.
合成系基油としては、具体的には、ポリブテン又はその水素化物；１−オクテンオリゴマー、１−デセンオリゴマー等のポリα−オレフィン又はその水素化物；ジトリデシルグルタレート、ジ−２−エチルヘキシルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、ジ−２−エチルヘキシルセバケート等のジエステル；トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール−２−エチルヘキサノエート、ペンタエリスリトールペラルゴネート等のポリオールエステル；マレイン酸ジブチル等のジカルボン酸類と炭素数２〜３０のα−オレフィンとの共重合体、アルキルナフタレン、アルキルベンゼン、芳香族エステル等の芳香族系合成油又はこれらの混合物等が例示できる。 Specific examples of synthetic base oils include polybutene or hydrides thereof; poly α-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; ditridecyl glutarate, di-2-ethylhexyl adipate, Diesters such as diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate; Examples thereof include a copolymer of a dicarboxylic acid such as dibutyl acid and an α-olefin having 2 to 30 carbon atoms, an aromatic synthetic oil such as alkylnaphthalene, alkylbenzene and aromatic ester, or a mixture thereof.
本発明では、潤滑油基油として、鉱油系基油、合成系基油又はこれらの中から選ばれる２種以上の潤滑油の任意混合物等が使用できる。例えば、１種以上の鉱油系基油、１種以上の合成系基油、１種以上の鉱油系基油と１種以上の合成系基油との混合油等を挙げることができる。 In the present invention, a mineral base oil, a synthetic base oil, or an arbitrary mixture of two or more kinds of lubricating oils selected from these can be used as the lubricating base oil. Examples thereof include one or more mineral base oils, one or more synthetic base oils, a mixed oil of one or more mineral base oils and one or more synthetic base oils, and the like.
潤滑油基油の動粘度は特に制限はないが、その１００℃での動粘度は、４〜５０ｍｍ2／ｓであることが好ましく、より好ましくは、６〜４０ｍｍ2／ｓ、特に好ましくは８〜３５ｍｍ2／ｓである。潤滑油基油の１００℃での動粘度が５０ｍｍ2／ｓを越える場合は、低温粘度特性が悪化し、一方、その動粘度が４ｍｍ2／ｓ未満の場合は、潤滑箇所での油膜形成が不十分であるため潤滑性に劣り、また潤滑油基油の蒸発損失が大きくなるため、それぞれ好ましくない。 The kinematic viscosity of the lubricating base oil is not particularly limited, but the kinematic viscosity at 100 ° C. is preferably 4 to 50 mm 2 / s, more preferably 6 to 40 mm 2 / s, and particularly preferably 8 ˜35 mm 2 / s. When the kinematic viscosity at 100 ° C. of the lubricating base oil exceeds 50 mm 2 / s, the low-temperature viscosity characteristics deteriorate, whereas when the kinematic viscosity is less than 4 mm 2 / s, an oil film is formed at the lubricating location. Insufficient lubrication results in poor lubricity and increases the evaporation loss of the lubricating base oil, which is not preferable.
本発明の潤滑油組成物において、潤滑油基油としては、１００℃での動粘度が４〜１７ｍｍ2／ｓ未満及び／又は１００℃での動粘度が１７〜５０ｍｍ2／ｓの潤滑油基油を含有することが好ましい。１００℃における動粘度が４〜１６ｍｍ2／ｓの潤滑油基油としては、例えば、ＳＡＥ１０〜４０等の鉱油系基油や合成系基油が挙げられ、その動粘度は、５．６ｍｍ2／ｓ以上、より好ましくは９．３ｍｍ2／ｓ以上であり、好ましくは１４ｍｍ2／ｓ以下、より好ましくは１２．５ｍｍ2／ｓ以下である。また、１００℃における動粘度が１７〜５０ｍｍ2／ｓの潤滑油基油としては、例えば、ＳＡＥ５０、ブライトストック等の鉱油系基油や合成系基油が挙げられ、その動粘度は、好ましくは２０ｍｍ2／ｓ以上、より好ましくは２５ｍｍ2／ｓであり、好ましくは４０ｍｍ2／ｓ以下、より好ましくは３５ｍｍ2／ｓ以下である。
本発明においては、１００℃での動粘度が４〜１７ｍｍ2／ｓ未満の潤滑油基油を主成分、例えば、基油全量基準で５０質量％以上、より好ましくは７０質量％以上含有させ、必要に応じて１００℃での動粘度が１７〜５０ｍｍ2／ｓの潤滑油基油を配合することができる。なお、１００℃での動粘度が１７〜５０ｍｍ2／ｓの潤滑油基油、特に３０ｍｍ2／ｓ以上のブライトストック等の基油を１０質量％以上、例えば２０質量％程度以上配合する場合、従来の炭素数２０未満の炭化水素基を１つ有するサリシレート系清浄剤を単独で多量に使用した場合には不溶分を析出させやすかったため、本願発明における（Ａ）成分は極めて有用である。
In the lubricating oil composition of the present invention, the lubricating base oil may have a kinematic viscosity at 100 ° C. of 4 to less than 17 mm 2 / s and / or a kinematic viscosity at 100 ° C. of 17 to 50 mm 2 / s. It is preferable to contain oil. Examples of the lubricating base oil having a kinematic viscosity at 100 ° C. of 4 to 16 mm 2 / s include mineral base oils and synthetic base oils such as SAE 10 to 40, and the kinematic viscosity is 5.6 mm 2 / s or more, more preferably 9.3 mm 2 / s or more, preferably 14 mm 2 / s or less, more preferably 12.5 mm 2 / s. Examples of the lubricating base oil having a kinematic viscosity at 100 ° C. of 17 to 50 mm 2 / s include mineral base oils and synthetic base oils such as SAE50 and bright stock, and the kinematic viscosity is preferably It is 20 mm 2 / s or more, more preferably 25 mm 2 / s, preferably 40 mm 2 / s or less, more preferably 35 mm 2 / s or less.
In the present invention, a lubricating base oil having a kinematic viscosity at 100 ° C. of less than 4 to 17 mm 2 / s as a main component, for example, 50% by mass or more based on the total amount of the base oil, more preferably 70% by mass or more, If necessary, a lubricating base oil having a kinematic viscosity at 100 ° C. of 17 to 50 mm 2 / s can be blended. In the case where the kinematic viscosity at 100 ℃ 17~50mm 2 / s lubricating base oils, in particular 30 mm 2 / s or more base oil, bright stock and the like 10% by weight or more, blended or more, for example about 20 wt%, When a conventional salicylate detergent having one hydrocarbon group having less than 20 carbon atoms is used alone in a large amount, the insoluble matter was easily precipitated, so the component (A) in the present invention is extremely useful.
潤滑油基油の蒸発損失量としては、ＮＯＡＣＫ蒸発量で、２０質量％以下であることが好ましく、１６質量％以下であることがさらに好ましく、１０質量％以下であることが特に好ましい。潤滑油基油のＮＯＡＣＫ蒸発量が２０質量％を超える場合、潤滑油の蒸発損失が大きく、粘度増加等の原因となるため好ましくない。なお、ここでいうＮＯＡＣＫ蒸発量とは、ＡＳＴＭ Ｄ ５８００に準拠して測定される潤滑油の蒸発量を測定したものである。 The amount of evaporation loss of the lubricating base oil is preferably 20% by mass or less, more preferably 16% by mass or less, and particularly preferably 10% by mass or less in terms of NOACK evaporation. When the NOACK evaporation amount of the lubricating base oil exceeds 20% by mass, the evaporation loss of the lubricating oil is large, which causes an increase in viscosity and the like, which is not preferable. Here, the NOACK evaporation amount is a value obtained by measuring the evaporation amount of the lubricating oil measured in accordance with ASTM D 5800.
潤滑油基油の粘度指数は特に制限はないが、低温から高温まで優れた粘度特性が得られるようにその値は好ましくは８０以上であり、より好ましくは９０以上であり、更に好ましくは１００以上であり、粘度指数の上限については特に制限はなく、ノルマルパラフィン、スラックワックスやＧＴＬワックス等、あるいはこれらを異性化したイソパラフィン系鉱油のような１３５〜１８０程度のものや、コンプレックスエステル系基油やＨＶＩ−ＰＡＯ系基油のような１５０〜２５０程度のものも使用することができるが、添加剤の溶解性や貯蔵安定性の点で１２０以下であることが好ましく、１１０以下であることが望ましい。 The viscosity index of the lubricating base oil is not particularly limited, but the value is preferably 80 or more, more preferably 90 or more, and still more preferably 100 or more so that excellent viscosity characteristics can be obtained from low temperature to high temperature. The upper limit of the viscosity index is not particularly limited, and those of about 135 to 180 such as normal paraffin, slack wax, GTL wax, etc., or isoparaffin mineral oil obtained by isomerizing these, complex ester base oil, Although about 150 to 250 like HVI-PAO base oil can be used, it is preferably 120 or less, and preferably 110 or less in terms of the solubility and storage stability of the additive. .
本発明の潤滑油組成物における（Ａ）成分は、塩基価が２４０ｍｇＫＯＨ／ｇ未満であるか、及び／又は金属比が４．５未満であり、炭素数２０〜４０の炭化水素基を１つ有するアルカリ金属サリシレート又はアルカリ土類金属サリシレート、及び／又はその（過）塩基性塩である。
（Ａ）成分の製造法としては、特に制限はないが、炭素数２０〜４０、好ましくは炭素数２０〜３２の炭化水素基を等モルのサリチル酸に付加し、又は、炭素数２０〜４０、好ましくは炭素数２０〜３２の炭化水素基を等モルのフェノールに付加した後にカルボキシル化し、次いで当量のアルカリ金属及び／又はアルカリ土類金属の酸化物や水酸化物等の金属塩基と反応させ、又は当量のアルカリ金属塩としてからアルカリ土類金属塩と置換させる方法や、上記により得られた中性のアルカリ金属サリシレート及び／又はアルカリ土類金属サリシレートに、さらに過剰のアルカリ金属塩又はアルカリ土類金属塩やアルカリ金属塩基又はアルカリ土類金属塩基（アルカリ金属又はアルカリ土類金属の水酸化物や酸化物）等を反応させる方法、さらには、当該中性のアルカリ金属サリシレート又はアルカリ土類金属サリシレート存在下において炭酸ガス又はホウ酸若しくはホウ酸塩とアルカリ金属又はアルカリ土類金属の水酸化物等の塩基とを反応させる方法等が挙げられる。
なお、これらの（過）塩基化の反応は、通常、溶媒（ヘキサン等の脂肪族炭化水素溶剤、キシレン等の芳香族炭化水素溶剤、軽質潤滑油基油等）中で行われる。
The component (A) in the lubricating oil composition of the present invention has a base number of less than 240 mgKOH / g and / or a metal ratio of less than 4.5 and one hydrocarbon group having 20 to 40 carbon atoms. And / or alkaline earth metal salicylates and / or (over) basic salts thereof.
Although there is no restriction | limiting in particular as a manufacturing method of (A) component, C20-C40, Preferably a C20-C32 hydrocarbon group is added to equimolar salicylic acid, or C20-C40, Preferably, a hydrocarbon group having 20 to 32 carbon atoms is added to an equimolar phenol and then carboxylated, and then reacted with an equivalent metal base such as an alkali metal and / or alkaline earth metal oxide or hydroxide, Alternatively, an equivalent alkali metal salt is then replaced with an alkaline earth metal salt, or the neutral alkali metal salicylate and / or alkaline earth metal salicylate obtained as described above is further added with an excess of alkali metal salt or alkaline earth metal salt. A method of reacting a metal salt, an alkali metal base or an alkaline earth metal base (an alkali metal or alkaline earth metal hydroxide or oxide), etc. Include a method of reacting carbon dioxide gas or boric acid or borate with a base such as an alkali metal or alkaline earth metal hydroxide in the presence of the neutral alkali metal salicylate or alkaline earth metal salicylate. Can be mentioned.
In addition, these (over) basification reactions are usually performed in a solvent (an aliphatic hydrocarbon solvent such as hexane, an aromatic hydrocarbon solvent such as xylene, a light lubricating oil base oil, or the like).
ここで、上記炭素数２０〜４０の炭化水素基としては、炭素数２０〜４０のアルキル基、シクロアルキル基、アルケニル基、アルキル置換シクロアルキル基、アリール基、アルキル置換アリール基、及びアリールアルキル基アルキル基、アルケニル基、シクロアルキル基等が挙げられ、アルキル基、アルケニル基であることが好ましく、アルキル基であることがより好ましい。 Here, examples of the hydrocarbon group having 20 to 40 carbon atoms include an alkyl group having 20 to 40 carbon atoms, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, an alkyl-substituted aryl group, and an arylalkyl group. An alkyl group, an alkenyl group, a cycloalkyl group, etc. are mentioned, It is preferable that it is an alkyl group and an alkenyl group, and it is more preferable that it is an alkyl group.
炭素数２０〜４０の炭化水素基としては、具体的には、イコシル基、ヘンイコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基、ヘキサコシル基、ヘプタコシル基、オクタコシル基、ノナコシル基、及びトリアコンチル基等の炭素数２０〜４０のアルキル基（これらは直鎖状であっても分枝状であっても良い）、イコセニル基、ヘンイコセニル基、ドコセニル基、トリコセニル基、テトラコセニル基、ペンタコセニル基、ヘキサコセニル基、ヘプタコセニル基、オクタコセニル基、ノナコセニル基、及びトリアコンテニル基等の炭素数２０〜４０のアルケニル基（これらアルケニル基は直鎖状でも分枝状でもよく、また二重結合の位置も任意である）等を挙げることができる。
本発明においては、炭素数２０〜３２のアルキル基又はアルケニル基がより好ましく、またエチレン、プロピレン、ブチレン等の重合体又は共重合体等から誘導されるアルキル基、特にエチレン重合体等の直鎖αオレフィンから誘導されるアルキル基であることが好ましい。
Specific examples of the hydrocarbon group having 20 to 40 carbon atoms include icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, and triacontyl group. An alkyl group having 20 to 40 carbon atoms such as these (which may be linear or branched), icocenyl group, henecocenyl group, dococenyl group, tricocenyl group, tetracocenyl group, pentacocenyl group, hexacocenyl group , An alkenyl group having 20 to 40 carbon atoms such as a heptacosenyl group, an octacocenyl group, a nonacosenyl group, and a triacontenyl group (these alkenyl groups may be linear or branched, and the position of the double bond is also arbitrary. And the like.
In the present invention, an alkyl group or alkenyl group having 20 to 32 carbon atoms is more preferable, and an alkyl group derived from a polymer or copolymer such as ethylene, propylene, or butylene, particularly a linear chain such as an ethylene polymer. An alkyl group derived from an α-olefin is preferred.
また、アルカリ金属又はアルカリ土類金属としては、ナトリウム、カリウム、マグネシウム、バリウム、カルシウム等が挙げられ、特にマグネシウム及び／又はカルシウムが好ましく用いられる。 Examples of the alkali metal or alkaline earth metal include sodium, potassium, magnesium, barium, calcium and the like, and magnesium and / or calcium are particularly preferably used.
なお、上記のようにして得られた（Ａ）成分を構成するアルカリ金属サリシレート又はアルカリ土類金属サリシレートは、炭化水素基が１つ付加したモノ置換サリシレート（例えばモノアルキルサリシレート）が主成分であり、不純物として炭化水素基を２つ以上有するサリシレート（例えばジアルキルサリシレート）を含んでいてもよいが、通常、モノ置換サリシレートの構成比は、８５モル％以上、好ましくは９０モル％以上である。また、前記モノ置換サリシレートにおける炭化水素基の置換位置に何ら制限はないが、潤滑油基油への溶解性、摩耗防止剤の効果を阻害しにくい点で、炭化水素基を３位に置換基として有するサリシレートの構成比が４０モル％以上であることが好ましく、５０モル％以上であることがより好ましく、６０モル％以上であることが特に好ましい。 The alkali metal salicylate or alkaline earth metal salicylate constituting the component (A) obtained as described above is mainly composed of a mono-substituted salicylate (for example, monoalkyl salicylate) to which one hydrocarbon group is added. In addition, a salicylate having two or more hydrocarbon groups (for example, dialkyl salicylate) may be contained as an impurity, but the composition ratio of the mono-substituted salicylate is usually 85 mol% or more, preferably 90 mol% or more. Further, there is no limitation on the position of substitution of the hydrocarbon group in the mono-substituted salicylate, but the hydrocarbon group is substituted at the 3-position in that it is difficult to inhibit the solubility in the lubricating base oil and the effect of the antiwear agent. The constituent ratio of the salicylate is preferably 40 mol% or more, more preferably 50 mol% or more, and particularly preferably 60 mol% or more.
本発明において、上記のようにして得られたサリシレート系清浄剤の金属含有量は、通常１．０〜２０質量％、好ましくは２．０〜１６質量％のものを用いるのが望ましい。 In the present invention, the metal content of the salicylate detergent obtained as described above is usually 1.0 to 20% by mass, preferably 2.0 to 16% by mass.
本発明において、（Ａ）成分のアルカリ金属サリシレート又はアルカリ土類金属サリシレート、及び／又はその（過）塩基性塩は、塩基価が２４０ｍｇＫＯＨ／ｇ未満であるか、及び／又は金属比が４．５未満であることが必須である。 In the present invention, the alkali metal salicylate or alkaline earth metal salicylate of component (A) and / or its (over) basic salt has a base number of less than 240 mgKOH / g and / or a metal ratio of 4. It is essential that it is less than 5.
すなわち、塩基価としては２４０ｍｇＫＯＨ／ｇ未満、好ましくは２００ｍｇＫＯＨ／ｇ未満、好ましくは６０ｍｇＫＯＨ／ｇ以上、より好ましくは１００ｍｇＫＯＨ／ｇ以上、さらに好ましくは１５０ｍｇＫＯＨ／ｇ以上である。なお、ここでいう塩基価とは、ＪＩＳ Ｋ２５０１「石油製品及び潤滑油−中和価試験法」の７．に準拠して測定される過塩素酸法による塩基価を意味する。 That is, the base number is less than 240 mgKOH / g, preferably less than 200 mgKOH / g, preferably 60 mgKOH / g or more, more preferably 100 mgKOH / g or more, and further preferably 150 mgKOH / g or more. The base number referred to here is 7. JIS K2501 “Petroleum products and lubricating oils-Neutralization number test method”. Means the base number measured by the perchloric acid method according to the above.
金属比としては４．５未満、好ましくは３．５未満、より好ましくは３未満、好ましくは１以上、より好ましくは２以上、特に好ましくは２．３以上である。
なお、本発明において金属比とは、金属系清浄剤における金属元素の価数×金属元素含有量（モル％）／せっけん基含有量（モル％）で表され、金属元素とは、カルシウム、マグネシウム等、せっけん基とは、サリチル酸基、フェノール基、スルホン酸基等を意味する。（Ａ）成分のせっけん基はサリチル酸基である。
The metal ratio is less than 4.5, preferably less than 3.5, more preferably less than 3, preferably 1 or more, more preferably 2 or more, and particularly preferably 2.3 or more.
In the present invention, the metal ratio is represented by the valence of the metal element in the metal detergent × the metal element content (mol%) / the soap group content (mol%), and the metal elements are calcium and magnesium. Etc., a soap group means a salicylic acid group, a phenol group, a sulfonic acid group, and the like. The soap group of the component (A) is a salicylic acid group.
なお、通常、（Ａ）成分は溶剤、潤滑油基油等により希釈された添加剤として供されるが、塩基価は、その希釈率により大きく異なり、塩基価による（Ａ）成分の規定は極めて不明確である。そのため、本発明の（Ａ）成分の規定を、せっけん基と金属量の関係が明確に規定された金属比で表すことで、希釈率にかかわらず（Ａ）成分を明確に規定することができる。 Normally, the component (A) is provided as an additive diluted with a solvent, a lubricating base oil, etc., but the base number varies greatly depending on the dilution rate, and the definition of the component (A) by the base number is extremely It is unclear. Therefore, the (A) component of the present invention can be clearly defined regardless of the dilution ratio by expressing the definition of the (A) component with a metal ratio in which the relationship between the soap group and the amount of metal is clearly defined. .
本発明の潤滑油組成物における（Ａ）成分の配合量は、通常、希釈油混合ベースで、組成物全量基準で０．１〜３０質量％であり、好ましくは１質量％以上、より好ましくは５質量％以上、さらに好ましくは８質量％以上、さらに好ましくは１０質量％以上であり、好ましくは２５質量％以下、より好ましくは２０質量％である。また、（Ａ）成分の配合量は、組成物全量基準で、金属量として好ましくは０．０１質量％以上、より好ましくは０．１質量％以上、さらに好ましくは０．３質量％以上、特に好ましくは０．５質量％以上であり、また好ましくは２質量％以下、特に、低温流動性を良好に維持する点で、望ましくは１質量％以下である。なお、上述のように、（Ａ）成分の希釈率により、その含有量は大きく異なり不明確であるので、金属量としてその配合量を規定することでより明確な規定となる。（Ａ）成分の金属量としての配合量が２質量％を超える場合、低温流動性が極めて悪化するため好ましくなく、０．０１質量％未満では、高温清浄性を十分に高めることができない。 The blending amount of the component (A) in the lubricating oil composition of the present invention is usually 0.1 to 30% by mass, preferably 1% by mass or more, more preferably, based on the total amount of the composition on a diluted oil mixture basis. It is 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, preferably 25% by mass or less, more preferably 20% by mass. In addition, the amount of component (A) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.3% by mass or more, particularly as a metal amount, based on the total amount of the composition. The amount is preferably 0.5% by mass or more, more preferably 2% by mass or less, and particularly preferably 1% by mass or less in view of maintaining good low temperature fluidity. As described above, the content varies greatly depending on the dilution ratio of the component (A) and is unclear. Therefore, by defining the blending amount as the metal amount, the content becomes clearer. When the blending amount of the component (A) as the metal amount exceeds 2% by mass, the low temperature fluidity is extremely deteriorated, which is not preferable. When the amount is less than 0.01% by mass, the high temperature cleanability cannot be sufficiently improved.
本発明の潤滑油組成物における（Ｂ）成分は、塩基価が２４０ｍｇＫＯＨ／ｇ以上であるか、及び／又は金属比が４．５以上である金属系清浄剤である。
本発明における金属系清浄剤（Ｂ）としては、前記（Ａ）成分以外のサリシレート系清浄剤（Ｂ−１）、スルホネート系清浄剤（Ｂ−２）及びフェネート系清浄剤（Ｂ−３）から選ばれる少なくとも１種の金属系清浄剤を使用することが好ましく、貯蔵安定性の点で、前記（Ａ）成分以外のサリシレート系清浄剤（Ｂ−１）及び／又はフェネート系清浄剤（Ｂ−３）を使用することが特に好ましい。
The component (B) in the lubricating oil composition of the present invention is a metallic detergent having a base number of 240 mgKOH / g or more and / or a metal ratio of 4.5 or more.
As the metal detergent (B) in the present invention, from salicylate detergent (B-1), sulfonate detergent (B-2) and phenate detergent (B-3) other than the component (A). It is preferable to use at least one metal-based detergent selected, and in terms of storage stability, salicylate-based detergent (B-1) and / or phenate-type detergent (B-) other than the component (A). Particular preference is given to using 3).
（Ａ）成分以外のサリシレート系清浄剤（Ｂ−１）としては、塩基価が２４０ｍｇＫＯＨ／ｇ以上であるか、及び／又は金属比が４．５以上であって、炭素数１〜１９の炭化水素基を１つ有するアルカリ金属サリシレート又はアルカリ土類金属サリシレート、及び／又はその（過）塩基性塩、炭素数２０〜４０の炭化水素基を１つ有するアルカリ金属サリシレート又はアルカリ土類金属サリシレート、及び／又はその（過）塩基性塩、炭素数１〜４０の炭化水素基を２つ又はそれ以上有するアルカリ金属サリシレート又はアルカリ土類金属サリシレート及び／又はその（過）塩基性塩（これら炭化水素基は同一でも異なっていても良い）等が挙げられる。これらの中では、低温流動性に優れる点で、炭素数８〜１９の炭化水素基を１つ有するアルカリ金属サリシレート又はアルカリ土類金属サリシレート、及び／又はその（過）塩基性塩を用いることが望ましい。また、アルカリ金属又はアルカリ土類金属としては、ナトリウム、カリウム、マグネシウム、バリウム、カルシウム等が挙げられ、マグネシウム及び／又はカルシウムが好ましく、カルシウムが特に好ましく用いられる。 The salicylate detergent (B-1) other than the component (A) has a base number of 240 mgKOH / g or more and / or a metal ratio of 4.5 or more, and carbonization of 1 to 19 carbon atoms. An alkali metal salicylate or alkaline earth metal salicylate having one hydrogen group, and / or its (over) basic salt, an alkali metal salicylate or alkaline earth metal salicylate having one hydrocarbon group having 20 to 40 carbon atoms, And / or (over) basic salts thereof, alkali metal salicylates or alkaline earth metal salicylates having two or more hydrocarbon groups having 1 to 40 carbon atoms and / or (over) basic salts thereof (these hydrocarbons) Group may be the same or different). Among these, use of an alkali metal salicylate or alkaline earth metal salicylate having one hydrocarbon group having 8 to 19 carbon atoms and / or a (over) basic salt thereof is excellent in low temperature fluidity. desirable. Examples of the alkali metal or alkaline earth metal include sodium, potassium, magnesium, barium, and calcium. Magnesium and / or calcium are preferable, and calcium is particularly preferably used.
スルホネート系清浄剤（Ｂ−２）としては、塩基価が２４０ｍｇＫＯＨ／ｇ以上であるか、及び／又は金属比が４．５以上であって、分子量１３００〜１５００、好ましくは４００〜７００のアルキル芳香族化合物をスルフォン化することによって得られるアルキル芳香族スルフォン酸のアルカリ金属塩又はアルカリ土類金属塩、及び／又はその（過）塩基性塩を用いることができる。また、アルカリ金属又はアルカリ土類金属としては、ナトリウム、カリウム、マグネシウム、バリウム、カルシウム等が挙げられ、マグネシウム及び／又はカルシウムが好ましく、カルシウムが特に好ましく用いられる。 The sulfonate detergent (B-2) is an alkyl fragrance having a base number of 240 mgKOH / g or more and / or a metal ratio of 4.5 or more and a molecular weight of 1300 to 1500, preferably 400 to 700. Alkali metal salts or alkaline earth metal salts of alkyl aromatic sulfonic acids obtained by sulfonating group compounds and / or (over) basic salts thereof can be used. Examples of the alkali metal or alkaline earth metal include sodium, potassium, magnesium, barium, and calcium. Magnesium and / or calcium are preferable, and calcium is particularly preferably used.
上記アルキル芳香族スルフォン酸としては、具体的にはいわゆる石油スルフォン酸や合成スルフォン酸等が挙げられる。
ここでいう石油スルフォン酸としては、一般に鉱油の潤滑油留分のアルキル芳香族化合物をスルフォン化したものやホワイトオイル製造時に副生する、いわゆるマホガニー酸等が用いられる。また合成スルフォン酸としては、例えば洗剤の原料となるアルキルベンゼン製造プラントから副生したり、ポリオレフィンをベンゼンにアルキル化することにより得られる、直鎖状や分枝状のアルキル基を有するアルキルベンゼンをスルフォン化したもの、あるいはジノニルナフタレン等のアルキルナフタレンをスルフォン化したもの等が用いられる。またこれらアルキル芳香族化合物をスルフォン化する際のスルフォン化剤としては特に制限はないが、通常、発煙硫酸や無水硫酸が用いられる。
Specific examples of the alkyl aromatic sulfonic acid include so-called petroleum sulfonic acid and synthetic sulfonic acid.
As the petroleum sulfonic acid here, generally used is a product obtained by sulfonating an alkyl aromatic compound of a lubricating oil fraction of mineral oil, or so-called mahoganic acid produced as a by-product when white oil is produced. In addition, as the synthetic sulfonic acid, for example, a sulfonated alkylbenzene having a linear or branched alkyl group, which is obtained as a by-product from an alkylbenzene production plant that is a raw material of a detergent or is obtained by alkylating polyolefin with benzene, is obtained. Or those obtained by sulfonating alkylnaphthalene such as dinonylnaphthalene. The sulfonating agent for sulfonating these alkyl aromatic compounds is not particularly limited, but usually fuming sulfuric acid or anhydrous sulfuric acid is used.
フェネート系清浄剤（Ｂ−３）としては、アルキルフェノール、アルキルフェノールサルファイド、アルキルフェノールのマンニッヒ反応物のアルカリ金属塩又はアルカリ土類金属塩、及び／又はその（過）塩基性塩を用いることができる。また、アルカリ金属又はアルカリ土類金属としては、ナトリウム、カリウム、マグネシウム、バリウム、カルシウム等が挙げられ、マグネシウム及び／又はカルシウムが好ましく、カルシウムが特に好ましく用いられる。 As the phenate detergent (B-3), alkylphenol, alkylphenol sulfide, alkali metal salt or alkaline earth metal salt of an alkylphenol Mannich reaction product, and / or (over) basic salt thereof can be used. Examples of the alkali metal or alkaline earth metal include sodium, potassium, magnesium, barium, and calcium. Magnesium and / or calcium are preferable, and calcium is particularly preferably used.
本発明において、（Ｂ）成分の金属系清浄剤は、塩基価が２４０ｍｇＫＯＨ／ｇ以上であるか、及び／又は金属比が４．５以上であることが必須である。
すなわち、塩基価としては２４０ｍｇＫＯＨ／ｇ以上、好ましくは２４０〜５００ｍｇＫＯＨ／ｇ、より好ましくは２４０〜４５０ｍｇＫＯＨ／ｇであり、金属比としては４．５以上、好ましくは５以上、特に好ましくは８以上、好ましくは４０以下、より好ましくは２０以下、特に好ましくは１５以下である。
In the present invention, it is essential that the metal detergent of the component (B) has a base number of 240 mgKOH / g or more and / or a metal ratio of 4.5 or more.
That is, the base number is 240 mgKOH / g or more, preferably 240 to 500 mgKOH / g, more preferably 240 to 450 mgKOH / g, and the metal ratio is 4.5 or more, preferably 5 or more, particularly preferably 8 or more. Preferably it is 40 or less, more preferably 20 or less, particularly preferably 15 or less.
本発明の組成物において、（Ｂ）成分の含有量は、組成物全量基準で、０．１〜１０質量％、好ましくは１〜８質量％、特に好ましくは２〜５質量％である。また、（Ｂ）成分の配合量は、組成物全量基準で、金属量として好ましくは０．０１質量％以上、より好ましくは０．１質量％以上、さらに好ましくは０．２質量％以上、特に好ましくは０．３質量％以上であり、また、好ましくは、１質量％以下、より好ましくは０．８質量％以下、特に好ましくは０．５質量％以下である。（Ｂ）成分の含有量が０．１質量％未満の場合は、高温清浄性をさらに高めることができず、一方、１０質量％を越える場合は、添加量に見合う効果が得られないので好ましくない。 In the composition of the present invention, the content of the component (B) is 0.1 to 10% by mass, preferably 1 to 8% by mass, particularly preferably 2 to 5% by mass, based on the total amount of the composition. Further, the blending amount of the component (B) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, particularly as a metal amount based on the total amount of the composition. Preferably it is 0.3 mass% or more, Preferably it is 1 mass% or less, More preferably, it is 0.8 mass% or less, Most preferably, it is 0.5 mass% or less. When the content of the component (B) is less than 0.1% by mass, the high-temperature cleanability cannot be further increased. On the other hand, when the content exceeds 10% by mass, an effect commensurate with the addition amount cannot be obtained. Absent.
本発明の潤滑油組成物は、潤滑油基油に、上記（Ａ）成分および（Ｂ）成分に加え、さらに無灰分散剤（Ｃ）及び／又は摩耗防止剤（Ｄ）の添加剤を含有させることができる。 The lubricating oil composition of the present invention contains, in addition to the above components (A) and (B), the ashless dispersant (C) and / or the antiwear agent (D) in the lubricating base oil. be able to.
本発明の組成物に用いる無灰分散剤（Ｃ）としては、潤滑油に用いられる任意の無灰分散剤が使用でき、例えば、炭素数４０〜４００、好ましくは６０〜３５０の直鎖若しくは分枝状のアルキル基又はアルケニル基を分子中に少なくとも１個有する含窒素化合物又はその誘導体、マンニッヒ系分散剤、あるいはアルケニルコハク酸イミドの変性品等が挙げられる。使用に際してはこれらの中から任意に選ばれる１種類あるいは２種類以上を配合することができる。
前記含窒素化合物又はその誘導体のアルキル基又はアルケニル基の炭素数が４０未満の場合は、潤滑油基油に対する溶解性が低下し、一方、アルキル基又はアルケニル基の炭素数が４００を越える場合は、潤滑油組成物の低温流動性が悪化するためそれぞれ好ましくない。このアルキル基又はアルケニル基は、直鎖状でも分枝状でもよいが、好ましいものとしては、例えば、プロピレン、１−ブテン、イソブチレン等のオレフィンのオリゴマーやエチレンとプロピレンとのコオリゴマーから誘導される分枝状アルキル基や分枝状アルケニル基等が挙げられる。
As the ashless dispersant (C) used in the composition of the present invention, any ashless dispersant used in lubricating oils can be used, for example, a straight or branched chain having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms. A nitrogen-containing compound having at least one alkyl group or alkenyl group in the molecule or a derivative thereof, a Mannich dispersant, or a modified product of alkenyl succinimide. In use, one kind or two or more kinds arbitrarily selected from these can be blended.
In the case where the carbon number of the alkyl group or alkenyl group of the nitrogen-containing compound or derivative thereof is less than 40, the solubility in the lubricating oil base oil is reduced, whereas in the case where the carbon number of the alkyl group or alkenyl group exceeds 400, The low-temperature fluidity of the lubricating oil composition is deteriorated, which is not preferable. The alkyl group or alkenyl group may be linear or branched, but is preferably derived from, for example, an olefin oligomer such as propylene, 1-butene, isobutylene, or a co-oligomer of ethylene and propylene. Examples include branched alkyl groups and branched alkenyl groups.
（Ｃ）成分としては、例えば、以下の（Ｃ−１）成分〜（Ｃ−３）成分から選択される１種又は２種以上の化合物を用いることができる。
（Ｃ−１）炭素数４０〜４００のアルキル基又はアルケニル基を分子中に少なくとも１個有するコハク酸イミド、あるいはその誘導体、
（Ｃ−２）炭素数４０〜４００のアルキル基又はアルケニル基を分子中に少なくとも１個有するベンジルアミン、あるいはその誘導体、
（Ｃ−３）炭素数４０〜４００のアルキル基又はアルケニル基を分子中に少なくとも１個有するポリアミン、あるいはその誘導体。
As the component (C), for example, one or more compounds selected from the following components (C-1) to (C-3) can be used.
(C-1) Succinimide having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof,
(C-2) benzylamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof,
(C-3) A polyamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof.
（Ｃ−１）成分としては、式（１）又は（２）で示される化合物等が例示できる。
式（１）中、Ｒ20は炭素数４０〜４００、好ましくは６０〜３５０のアルキル基又はアルケニル基を示し、ｈは１〜５、好ましくは２〜４の整数を示す。一方、式（２）中、Ｒ21及びＲ22は、それぞれ個別に炭素数４０〜４００、好ましくは６０〜３５０のアルキル基又はアルケニル基を示し、特に好ましくはポリブテニル基である。またｉは０〜４、好ましくは１〜３の整数を示す。 In the formula (1), R 20 represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and h represents an integer of 1 to 5, preferably 2 to 4. On the other hand, in the formula (2), R 21 and R 22 each independently represents an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, and particularly preferably a polybutenyl group. I represents an integer of 0 to 4, preferably 1 to 3.
（Ｃ−１）成分には、ポリアミンの一端に無水コハク酸が付加した式（１）で表される、いわゆるモノタイプのコハク酸イミドと、ポリアミンの両端に無水コハク酸が付加した式（２）で表される、いわゆるビスタイプのコハク酸イミドとが含まれるが、本発明の組成物には、それらのいずれも、あるいはこれらの混合物が含まれていても良い。
これら（Ｃ−１）成分であるコハク酸イミドの製法は特に制限はなく、例えば、炭素数４０〜４００のアルキル基又はアルケニル基を有する化合物を、無水マレイン酸と１００〜２００℃で反応させて得たアルキルコハク酸又はアルケニルコハク酸をポリアミンと反応させることにより得られる。
ポリアミンとしては、具体的には、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等が例示できる。
The component (C-1) includes a so-called monotype succinimide represented by the formula (1) in which succinic anhydride is added to one end of the polyamine, and a formula (2 in which succinic anhydride is added to both ends of the polyamine. The so-called bis-type succinimide represented by formula (1)) is included, and the composition of the present invention may contain any of them or a mixture thereof.
There is no restriction | limiting in particular in the manufacturing method of succinimide which is these (C-1) components, For example, the compound which has a C40-C400 alkyl group or an alkenyl group is made to react with maleic anhydride at 100-200 degreeC. It is obtained by reacting the obtained alkyl succinic acid or alkenyl succinic acid with a polyamine.
Specific examples of the polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
（Ｃ−２）成分としては、具体的には式（３）で表される化合物等が例示できる。
式（３）中、Ｒ23は炭素数４０〜４００、好ましくは６０〜３５０のアルキル基又はアルケニル基を示し、ｊは１〜５、好ましくは２〜４の整数を示す。
この（Ｃ−２）成分であるベンジルアミンの製法は特に制限はなく、例えば、プロピレンオリゴマー、ポリブテン、又はエチレン−α−オレフィン共重合体等のポリオレフィンを、フェノールと反応させてアルキルフェノールとした後、これにホルムアルデヒドと、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、又はペンタエチレンヘキサミン等のポリアミンとをマンニッヒ反応により反応させることにより得られる。
In the formula (3), R 23 represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and j represents an integer of 1 to 5, preferably 2 to 4.
There is no restriction | limiting in particular in the manufacturing method of this (C-2) component benzylamine, For example, after making polyolefin, such as a propylene oligomer, a polybutene, or an ethylene-alpha-olefin copolymer, react with phenol to make alkylphenol, This is obtained by reacting formaldehyde with a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or pentaethylenehexamine by a Mannich reaction.
（Ｃ−３）成分としては、具体的には、式（４）で表される化合物等が例示できる。
Ｒ24‐ＮＨ−（ＣＨ2ＣＨ2ＮＨ）k−Ｈ （４）
式（４）中、Ｒ24は炭素数４０〜４００、好ましくは６０〜３５０のアルキル基又はアルケニル基を示し、ｋは１〜５、好ましくは２〜４の整数を示す。
この（Ｃ−３）成分であるポリアミンの製法は特に制限はなく、例えば、プロピレンオリゴマー、ポリブテン、及びエチレン−α−オレフィン共重合体等のポリオレフィンを塩素化した後、これにアンモニアやエチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、又はペンタエチレンヘキサミン等のポリアミンを反応させることにより得られる。
Specific examples of the component (C-3) include a compound represented by the formula (4).
R 24 -NH- (CH 2 CH 2 NH) k -H (4)
In the formula (4), R 24 represents an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and k represents an integer of 1 to 5, preferably 2 to 4.
The production method of the polyamine which is the component (C-3) is not particularly limited. For example, after chlorinating a polyolefin such as a propylene oligomer, polybutene and an ethylene-α-olefin copolymer, ammonia, ethylenediamine, diethylenetriamine is added thereto. , Triethylenetetramine, tetraethylenepentamine, or a polyamine such as pentaethylenehexamine.
前記（Ｃ）成分の１例として挙げた含窒素化合物の誘導体としては、例えば、前述の含窒素化合物に炭素数１〜３０のモノカルボン酸（脂肪酸等）やシュウ酸、フタル酸、トリメリット酸、ピロメリット酸等の炭素数２〜３０のポリカルボン酸若しくはこれらの無水物、又はエステル化合物、炭素数２〜６のアルキレンオキサイド、ヒドロキシ（ポリ）オキシアルキレンカーボネート等を作用させて、残存するアミノ基及び／又はイミノ基の一部又は全部を中和したり、アミド化した、いわゆる含酸素有機化合物による変性化合物；前述の含窒素化合物にホウ酸を作用させて、残存するアミノ基及び／又はイミノ基の一部又は全部を中和したり、アミド化した、いわゆるホウ素変性化合物；前述の含窒素化合物にリン酸を作用させて、残存するアミノ基及び／又はイミノ基の一部又は全部を中和したり、アミド化した、いわゆるリン酸変性化合物；前述の含窒素化合物に硫黄化合物を作用させた硫黄変性化合物；及び前述の含窒素化合物に含酸素有機化合物による変性、ホウ素変性、リン酸変性、硫黄変性から選ばれた２種以上の変性を組み合わせた変性化合物等が挙げられる。これらの誘導体の中でもアルケニルコハク酸イミドのホウ酸変性化合物は耐熱性、酸化防止性に優れ、本発明の潤滑油組成物においても高温清浄性をより高めるために有効である。 Examples of the derivative of the nitrogen-containing compound cited as an example of the component (C) include, for example, the above-mentioned nitrogen-containing compounds, monocarboxylic acids having 1 to 30 carbon atoms (fatty acids, etc.), oxalic acid, phthalic acid, trimellitic acid Remaining amino by reacting polycarboxylic acids having 2 to 30 carbon atoms such as pyromellitic acid or their anhydrides or ester compounds, alkylene oxides having 2 to 6 carbon atoms, hydroxy (poly) oxyalkylene carbonate, etc. A modified compound by a so-called oxygen-containing organic compound obtained by neutralizing or amidating some or all of the group and / or imino group; boric acid is allowed to act on the above-mentioned nitrogen-containing compound, and the remaining amino group and / or A so-called boron-modified compound obtained by neutralizing or amidating part or all of the imino group; remaining by reacting the above-mentioned nitrogen-containing compound with phosphoric acid A so-called phosphoric acid-modified compound obtained by neutralizing or amidating part or all of an amino group and / or imino group; a sulfur-modified compound obtained by allowing a sulfur compound to act on the above-mentioned nitrogen-containing compound; and the above-mentioned nitrogen-containing compound And modified compounds in which two or more kinds of modifications selected from modification with oxygen-containing organic compounds, boron modification, phosphoric acid modification, and sulfur modification are combined. Among these derivatives, boric acid-modified compounds of alkenyl succinimides are excellent in heat resistance and antioxidant properties, and are effective for further enhancing the high temperature cleanliness in the lubricating oil composition of the present invention.
本発明の組成物において、（Ｃ）成分の含有量は、組成物全量基準で、０．１〜２０質量％、好ましくは０．１〜５質量％、さらに好ましくは０．１〜２質量％、特に好ましくは０．５〜１．５質量％である。（Ｃ）成分の含有量が０．１質量％未満の場合は、すす分散性に対する効果が少なく、一方、２０質量％を越える場合は、組成物の低温流動性が大幅に悪化する。本発明においては、１質量％程度の配合で十分な効果を確認している。 In the composition of the present invention, the content of the component (C) is 0.1 to 20% by mass, preferably 0.1 to 5% by mass, more preferably 0.1 to 2% by mass, based on the total amount of the composition. Especially preferably, it is 0.5-1.5 mass%. When the content of the component (C) is less than 0.1% by mass, the effect on the soot dispersibility is small. On the other hand, when the content exceeds 20% by mass, the low-temperature fluidity of the composition is greatly deteriorated. In the present invention, a sufficient effect is confirmed with about 1% by mass.
本発明の組成物に用いる摩耗防止剤（Ｄ）としては、潤滑油に用いられる任意の摩耗防止剤が使用できる。例えば、硫黄系、リン系、硫黄−リン系の摩耗防止剤等が使用でき、具体的には、亜リン酸エステル類、チオ亜リン酸エステル類、ジチオ亜リン酸エステル類、トリチオ亜リン酸エステル類、リン酸エステル類、チオリン酸エステル類、ジチオリン酸エステル類、トリチオリン酸エステル類、これらのアミン塩、これらの金属塩、これらの誘導体、ジチオカーバメート、亜鉛ジチオカーバメート、モリブデンジチオカーバメート、ジスルフィド類、硫化オレフィン類、硫化油脂類等が挙げられる。
本発明においては、ジチオリン酸亜鉛を使用することが好ましい。
本発明の組成物において、（Ｄ）成分の含有量は、特に制限はないが、組成物全量基準で、０．１〜５質量％、好ましくは０．１〜２質量％、特に好ましくは０．１〜１質量％である。（Ｄ）成分の含有量が０．１質量％未満の場合は、摩耗防止性に対する効果が少なく、一方、５質量％を越える場合は、組成物の高温清浄性が大幅に悪化するためそれぞれ好ましくない。
As the antiwear agent (D) used in the composition of the present invention, any antiwear agent used in lubricating oils can be used. For example, sulfur-based, phosphorus-based, sulfur-phosphorous antiwear agents, etc. can be used. Specifically, phosphites, thiophosphites, dithiophosphites, trithiophosphites Esters, phosphate esters, thiophosphate esters, dithiophosphate esters, trithiophosphate esters, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamate, zinc dithiocarbamate, molybdenum dithiocarbamate, disulfides , Sulfurized olefins, sulfurized fats and oils, and the like.
In the present invention, it is preferable to use zinc dithiophosphate.
In the composition of the present invention, the content of the component (D) is not particularly limited, but is 0.1 to 5% by mass, preferably 0.1 to 2% by mass, particularly preferably 0, based on the total amount of the composition. 0.1 to 1% by mass. When the content of the component (D) is less than 0.1% by mass, the effect on the anti-wear property is small. On the other hand, when it exceeds 5% by mass, the high temperature cleanliness of the composition is greatly deteriorated. Absent.
本発明の潤滑油組成物は、上記構成に加え、その性能を更に向上させるため又は他に要求される性能を付加するために、その目的に応じて潤滑油に一般的に使用されている任意の添加剤をさらに添加することができる。このような添加剤としては、例えば、酸化防止剤、摩擦調整剤、粘度指数向上剤、腐食防止剤、防錆剤、抗乳化剤、金属不活性化剤、消泡剤、及び着色剤等の添加剤を挙げることができる。 The lubricating oil composition of the present invention is an optional component commonly used in lubricating oils depending on its purpose in order to further improve its performance or to add other required performance in addition to the above configuration. Further additives can be added. Examples of such additives include addition of antioxidants, friction modifiers, viscosity index improvers, corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, antifoaming agents, and colorants. An agent can be mentioned.
酸化防止剤としては、フェノール系、アミン系等の無灰酸化防止剤、銅系、モリブデン系等の金属系酸化防止剤が挙げられる。これらの含有量は、組成物全量基準で、通常０．１〜５質量％である。
摩擦調整剤としては、脂肪酸エステル系、脂肪族アミン系、脂肪酸アミド系等の無灰摩擦調整剤、モリブデンジチオカーバメート、モリブデンジチオホスフェート等の金属系摩擦調整剤等が挙げられる。これらの含有量は、組成物全量基準で、通常０．１〜５質量％である。
Examples of the antioxidant include ashless antioxidants such as phenols and amines, and metal antioxidants such as copper and molybdenum. These contents are usually 0.1 to 5% by mass based on the total amount of the composition.
Examples of the friction modifier include ashless friction modifiers such as fatty acid esters, aliphatic amines, and fatty acid amides, and metal friction modifiers such as molybdenum dithiocarbamate and molybdenum dithiophosphate. These contents are usually 0.1 to 5% by mass based on the total amount of the composition.
粘度指数向上剤としては、ポリメタクリレート系粘度指数向上剤、オレフィン共重合体系粘度指数向上剤、スチレン−ジエン共重合体系粘度指数向上剤、スチレン−無水マレイン酸エステル共重合体系粘度指数向上剤又はポリアルキルスチレン系粘度指数向上剤等が挙げられる。これら粘度指数向上剤の重量平均分子量は、通常８００〜１，０００，０００、好ましくは１００，０００〜９００，０００である。また、粘度指数向上剤の含有量は、組成物全量基準で通常０．１〜２０質量％である。
腐食防止剤としては、例えば、ベンゾトリアゾール系、トリルトリアゾール系、チアジアゾール系、又はイミダゾール系化合物等が挙げられる。
As the viscosity index improver, polymethacrylate viscosity index improver, olefin copolymer viscosity index improver, styrene-diene copolymer viscosity index improver, styrene-maleic anhydride copolymer viscosity index improver or poly Examples thereof include alkylstyrene viscosity index improvers. The weight average molecular weight of these viscosity index improvers is usually 800 to 1,000,000, preferably 100,000 to 900,000. Moreover, content of a viscosity index improver is 0.1-20 mass% normally on the composition whole quantity basis.
Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, or imidazole compounds.
防錆剤としては、例えば、石油スルホネート、アルキルベンゼンスルホネート、ジノニルナフタレンスルホネート、アルケニルコハク酸エステル、又は多価アルコールエステル等が挙げられる。
抗乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、又はポリオキシエチレンアルキルナフチルエーテル等のポリアルキレングリコール系非イオン系界面活性剤等が挙げられる。
金属不活性化剤としては、例えば、イミダゾリン、ピリミジン誘導体、アルキルチアジアゾール、メルカプトベンゾチアゾール、ベンゾトリアゾール又はその誘導体、１，３，４−チアジアゾールポリスルフィド、１，３，４−チアジアゾリル−２，５−ビスジアルキルジチオカーバメート、２−（アルキルジチオ）ベンゾイミダゾール、又はβ−（ｏ−カルボキシベンジルチオ）プロピオンニトリル等が挙げられる。
消泡剤としては、例えば、シリコーン、フルオロシリコール、又はフルオロアルキルエーテル等が挙げられる。
Examples of the rust preventive include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, or polyoxyethylene alkyl naphthyl ether.
Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples thereof include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.
Examples of the antifoaming agent include silicone, fluorosilicol, or fluoroalkyl ether.
これらの添加剤を本発明の潤滑油組成物に含有させる場合には、その含有量は組成物全量基準で、腐食防止剤、防錆剤、抗乳化剤ではそれぞれ通常０．００５〜５質量％、金属不活性化剤では通常０．００５〜１質量％、消泡剤では通常０．０００５〜１質量％の範囲から選ばれる。 When these additives are contained in the lubricating oil composition of the present invention, the content is based on the total amount of the composition, and is usually 0.005 to 5% by mass for the corrosion inhibitor, the rust inhibitor, and the demulsifier, The metal deactivator is usually selected from the range of 0.005 to 1% by mass, and the antifoaming agent is usually selected from the range of 0.0005 to 1% by mass.
なお、本発明の潤滑油組成物の１００℃における動粘度は、特に制限はないが、好ましくは６〜５０ｍｍ2／ｓ、より好ましくは９．３〜３０ｍｍ2／ｓ、特に好ましくは１２．５〜２１．９ｍｍ2／ｓである。ここでいう１００℃における動粘度とは、ＡＳＴＭ Ｄ−４４５に規定される１００℃での動粘度を示す。 The kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is not particularly limited, but is preferably 6 to 50 mm 2 / s, more preferably 9.3 to 30 mm 2 / s, and particularly preferably 12.5. ˜21.9 mm 2 / s. The kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445.
また、本発明の潤滑油組成物の塩基価は、特に制限はないが、アスファルテンを含有する高硫黄燃料を使用する場合に対しても優れた高温清浄性と酸中和性能を付加するためには、好ましくは５〜１００ｍｇＫＯＨ／ｇ、より好ましくは１０ｍｇＫＯＨ／ｇ以上、さらに好ましくは２０ｍｇＫＯＨ／ｇ以上、より好ましくは８０ｍｇＫＯＨ／ｇ以下、さらに好ましくは５０ｍｇＫＯＨ／ｇ以下である。ここで塩基価とは、ＡＳＴＭ Ｄ−２８９６により測定される塩基価を示す。 In addition, the base number of the lubricating oil composition of the present invention is not particularly limited, but in order to add excellent high temperature cleanliness and acid neutralization performance even when using a high sulfur fuel containing asphaltenes. Is preferably 5 to 100 mgKOH / g, more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, more preferably 80 mgKOH / g or less, and further preferably 50 mgKOH / g or less. Here, the base number refers to a base number measured by ASTM D-2896.
また、本発明の潤滑油組成物の硫酸灰分量は、特に制限はないが、好ましくは１．２質量％以上、より好ましくは２質量％以上、特に好ましくは３質量％以上、好ましくは２０質量％以下、より好ましくは１０質量％以下である。なお、ここでいう硫酸灰分とは、ＪＩＳ Ｋ２２７２の５．「硫酸灰分の試験方法」に規定される方法により測定される値を示し、主として金属含有添加剤に起因するものである。 The amount of sulfated ash in the lubricating oil composition of the present invention is not particularly limited, but is preferably 1.2% by mass or more, more preferably 2% by mass or more, particularly preferably 3% by mass or more, preferably 20% by mass. % Or less, more preferably 10% by mass or less. The sulfated ash here refers to 5. of JIS K2272. The value measured by the method specified in “Testing method for sulfated ash” is mainly attributable to the metal-containing additive.
本発明の潤滑油組成物は、貯蔵安定性、高温清浄性及びすす分散性に優れるものであり、内燃機関用潤滑油、特にディーゼル燃料を使用する内燃機関用潤滑油としても好適であるが、長期にわたりストレージタンクに貯蔵される潤滑油、アスファルテン成分や残留炭素分を含む重質燃料（例えばＡ重油、Ｃ重油等）を使用する内燃機関等、特に、船舶、発電、鉄道等に使用される内燃機関用、内燃機関減速機用、又は内燃機関油圧作動器機用の潤滑油として好適に使用することができる。 The lubricating oil composition of the present invention is excellent in storage stability, high-temperature cleanability and soot dispersibility, and is also suitable as a lubricating oil for internal combustion engines, particularly a lubricating oil for internal combustion engines using diesel fuel. Used in long-term storage tanks, internal combustion engines that use heavy fuels (eg, heavy oil A, heavy oil C, etc.) that contain asphaltene components and residual carbon, especially for ships, power generation, railways, etc. It can be suitably used as a lubricating oil for an internal combustion engine, an internal combustion engine speed reducer, or an internal combustion engine hydraulic actuator.
以下、本発明の内容を実施例及び比較例によってさらに具体的に説明するが、本発明はこれらに何ら限定されるものではない。 Hereinafter, the content of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.
（実施例１〜２、比較例１〜４）
表１に示す組成の本発明の潤滑油組成物（実施例１〜２）、比較用の潤滑油組成物（比較例１〜４）をそれぞれ調製した。得られた組成物について、以下の（１）〜（３）の評価を行い、その結果を表１に併記した。
(Examples 1-2, Comparative Examples 1-4)
Lubricating oil compositions (Examples 1 and 2) of the present invention having the compositions shown in Table 1 and comparative lubricating oil compositions (Comparative Examples 1 to 4) were prepared. About the obtained composition, the following (1)-(3) evaluation was performed and the result was written together in Table 1.
（１）貯蔵安定性
ＡＳＴＭ Ｄ−８９３に規定されている沈殿管に、供試油を１００ｃｃを採取し、６０℃に調整した空気恒温槽内に１ヶ月間静置させて、沈殿管底部に沈降した不溶分の容積を測定した。表１中、ＴＲは沈殿量が痕跡量又は沈殿を生じないことを示す。
（２）高温清浄性
ＪＰＩ−５Ｓ−５５９９に準拠し、ホットチューブ試験（３３０℃，１６ｈ）を行い、評点による高温清浄性を比較した。３３０℃において評点が７以上であれば、アスファルテンを含む高硫黄燃料を使用した場合でも優れた高温清浄性を示す潤滑油組成物であると判断した。
（３）すす分散性
供試油（新油）を５０ｇ採取し、乾燥させたカーボンブラック（三菱化学（株）製ＭＡ-１００）を３質量％配合して、ホモジナイザーで３分間撹拌させた。得られたカーボンブラック混合油について動粘度を測定し、粘度増加率を粘度比（（カーボンブラック混合油の動粘度−新油の動粘度）／新油の動粘度）で表した。粘度比が小さいほどすす分散性が良好であるとした。
(1) Storage stability 100 cc of sample oil was collected in a settling tube specified in ASTM D-893 and allowed to stand in an air thermostat adjusted to 60 ° C. for 1 month. The volume of the insoluble matter that settled was measured. In Table 1, TR indicates that the amount of precipitation does not cause a trace amount or precipitation.
(2) High temperature cleanliness Based on JPI-5S-5599, a hot tube test (330 ° C., 16 h) was performed, and the high temperature cleanliness by rating was compared. A rating of 7 or higher at 330 ° C. was judged to be a lubricating oil composition exhibiting excellent high temperature cleanliness even when using a high sulfur fuel containing asphaltenes.
(3) Soot dispersibility 50 g of test oil (new oil) was sampled and blended with 3% by mass of dried carbon black (MA-100 manufactured by Mitsubishi Chemical Corporation) and stirred with a homogenizer for 3 minutes. The kinematic viscosity of the obtained carbon black mixed oil was measured, and the rate of increase in viscosity was expressed as a viscosity ratio ((kinematic viscosity of carbon black mixed oil−dynamic viscosity of new oil) / dynamic viscosity of new oil). The smaller the viscosity ratio, the better the soot dispersibility.
表１より、本発明のサリシレート系清浄剤（Ａ）（１７０ｍｇＫＯＨ／ｇ）を含む潤滑油組成物（実施例１〜２）は、貯蔵安定性、高温清浄性、すす分散性のいずれにも優れることがわかる。また、炭素数１４〜１８のモノアルキルサリシレート（１７０ｍｇＫＯＨ／ｇ）を使用した組成物はいずれも沈殿量が多く、高温清浄性に劣ることがわかる。なお、この場合、無灰分散剤や高粘度基油の使用は、沈殿量を増加させることがわかる。 From Table 1, the lubricating oil compositions (Examples 1 and 2) containing the salicylate-based detergent (A) (170 mgKOH / g) of the present invention are excellent in all of storage stability, high-temperature cleanability, and soot dispersibility. I understand that. Moreover, it turns out that all the compositions using a C14-C18 monoalkyl salicylate (170 mgKOH / g) have a large amount of precipitation, and are inferior in high temperature cleanliness. In this case, it can be seen that the use of an ashless dispersant or a high-viscosity base oil increases the amount of precipitation.
Claims (3)
（Ａ）塩基価が２４０ｍｇＫＯＨ／ｇ未満及び／又は金属比が４．５未満であり、炭素数２０〜３０のαオレフィン（１００ｍｏｌ％）から誘導されるアルキル基からなる炭化水素基を１つ有するアルカリ金属サリシレート又はアルカリ土類金属サリシレート及び／又はその（過）塩基性塩、および
（Ｂ）塩基価が２４０ｍｇＫＯＨ／ｇ以上及び／又は金属比が４．５以上であり、炭素数１４〜１８のαオレフィン（１００ｍｏｌ％）から誘導されるアルキル基からなる炭化水素基を１つ有するアルカリ金属サリシレート又はアルカリ土類金属サリシレート及び／又はその（過）塩基性塩である（Ａ）成分以外のサリシレート系金属系清浄剤、とからなる金属系清浄剤を含有して成る、アスファルテン分や残留炭素分を含む重質燃料を使用する船舶、発電もしくは鉄道に使用される内燃機関用、内燃機関減速機用、又は内燃機関油圧作動器機用の潤滑油組成物。 In the base oil the total amount of 100 kinematic viscosity at ° C. is 4~17mm 2 / s less than the lubricating base oil 50 mass% or more and a kinematic viscosity at 100 ° C. 30 to 50 mm 2 / s bright stock or 10 wt% of the formulation To the lubricating base oil
(A) The base number is less than 240 mgKOH / g and / or the metal ratio is less than 4.5, and it has one hydrocarbon group composed of an alkyl group derived from an α-olefin (100 mol%) having 20 to 30 carbon atoms. Alkali metal salicylate or alkaline earth metal salicylate and / or (over) basic salt thereof, and (B) a base number of 240 mgKOH / g or more and / or a metal ratio of 4.5 or more, and having 14 to 18 carbon atoms Salicylate system other than (A) component which is an alkali metal salicylate or alkaline earth metal salicylate having one hydrocarbon group derived from an α-olefin (100 mol%) and / or an (over) basic salt thereof metallic detergents, comprising a metallic detergent consisting city, to use heavy fuel containing asphaltene component and carbon residue Ships, power generation or for internal combustion engines used in railroad, for an internal combustion engine speed reducer, or the internal combustion engine hydraulic equipment for lubricating oil compositions.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4994044B2 (en) | 2007-01-05 | 2012-08-08 | シェブロンジャパン株式会社 | Lubricating oil composition |
| JP5101915B2 (en) * | 2007-03-27 | 2012-12-19 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for diesel engines |
| US9175237B2 (en) * | 2007-12-12 | 2015-11-03 | Chevron Oronite Technology B.V. | Trunk piston engine lubricating oil compositions |
| US9175236B2 (en) * | 2008-05-08 | 2015-11-03 | Chevron Oronite Technology B.V. | Lubricating oil composition and method for use with low sulfur marine residual fuel |
| ES2641591T3 (en) * | 2008-05-20 | 2017-11-10 | Infineum International Limited | Marine Engine Lubrication |
| EP2135926A1 (en) * | 2008-05-20 | 2009-12-23 | Infineum International Limited | Marine engine lubrication |
| ES2644437T3 (en) * | 2008-05-20 | 2017-11-29 | Infineum International Limited | Marine Engine Lubrication |
| JP5642949B2 (en) * | 2009-08-04 | 2014-12-17 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
| JP4949510B2 (en) * | 2010-09-08 | 2012-06-13 | シェブロンジャパン株式会社 | Lubricating oil composition |
| JP4949509B2 (en) * | 2010-09-08 | 2012-06-13 | シェブロンジャパン株式会社 | Lubricating oil composition |
| JP5581296B2 (en) * | 2011-10-25 | 2014-08-27 | シェブロンジャパン株式会社 | Lubricating oil composition |
| JP5567538B2 (en) * | 2011-10-25 | 2014-08-06 | シェブロンジャパン株式会社 | Lubricating oil composition |
| US20130157910A1 (en) * | 2011-12-16 | 2013-06-20 | Chevron Oronite Company Llc | Diesel engine oils |
| US9102896B2 (en) * | 2012-12-17 | 2015-08-11 | Chevron Japan Ltd. | Fuel economical lubricating oil composition for internal combustion engines |
| US9506007B2 (en) * | 2014-11-14 | 2016-11-29 | Chevron Oronite Technology B.V. | Low sulfur marine distillate fuel trunk piston engine oil composition |
| JP6714423B2 (en) * | 2016-04-25 | 2020-06-24 | コスモ石油ルブリカンツ株式会社 | Diesel engine oil composition |
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| JPH05140575A (en) * | 1991-11-22 | 1993-06-08 | Kao Corp | Lubricating oil additive and lubricating oil composition containing the same |
| JPH1129784A (en) * | 1997-07-11 | 1999-02-02 | Nippon Oil Co Ltd | Lube oil composition for diesel engine |
| JPH1180771A (en) * | 1997-09-11 | 1999-03-26 | Nippon Oil Co Ltd | Lubricating oil composition for diesel engine |
| JP3992369B2 (en) * | 1998-07-17 | 2007-10-17 | 出光興産株式会社 | Lubricating oil composition for internal combustion engines |
| JP4393693B2 (en) * | 2000-11-01 | 2010-01-06 | コスモ石油ルブリカンツ株式会社 | Diesel engine oil composition |
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