EP2878655B1 - Engine oil composition - Google Patents
Engine oil composition Download PDFInfo
- Publication number
- EP2878655B1 EP2878655B1 EP13822656.8A EP13822656A EP2878655B1 EP 2878655 B1 EP2878655 B1 EP 2878655B1 EP 13822656 A EP13822656 A EP 13822656A EP 2878655 B1 EP2878655 B1 EP 2878655B1
- Authority
- EP
- European Patent Office
- Prior art keywords
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- viscosity
- mass
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- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 78
- 239000010705 motor oil Substances 0.000 title claims description 57
- 239000002199 base oil Substances 0.000 claims description 126
- 230000001050 lubricating effect Effects 0.000 claims description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- 239000010687 lubricating oil Substances 0.000 claims description 36
- 238000012360 testing method Methods 0.000 claims description 26
- 229920000193 polymethacrylate Polymers 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000000446 fuel Substances 0.000 description 43
- 150000002430 hydrocarbons Chemical group 0.000 description 39
- 238000000034 method Methods 0.000 description 32
- 239000003921 oil Substances 0.000 description 28
- 239000004215 Carbon black (E152) Substances 0.000 description 25
- 229930195733 hydrocarbon Natural products 0.000 description 25
- 238000005461 lubrication Methods 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 24
- 239000000654 additive Substances 0.000 description 23
- 239000000178 monomer Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- -1 alkaline earth metal borate Chemical class 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 238000007670 refining Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 238000004517 catalytic hydrocracking Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 230000001603 reducing effect Effects 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 5
- 150000004678 hydrides Chemical class 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000006735 deficit Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 239000002518 antifoaming agent Substances 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
- 239000002585 base Substances 0.000 description 2
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000006384 methylpyridyl group Chemical group 0.000 description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 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
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 2
- 125000004929 pyrrolidonyl group Chemical group N1(C(CCC1)=O)* 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- UUGXDEDGRPYWHG-UHFFFAOYSA-N (dimethylamino)methyl 2-methylprop-2-enoate Chemical compound CN(C)COC(=O)C(C)=C UUGXDEDGRPYWHG-UHFFFAOYSA-N 0.000 description 1
- OBDUMNZXAIUUTH-HWKANZROSA-N (e)-tetradec-2-ene Chemical group CCCCCCCCCCC\C=C\C OBDUMNZXAIUUTH-HWKANZROSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-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
- MNZNJOQNLFEAKG-UHFFFAOYSA-N 2-morpholin-4-ylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCOCC1 MNZNJOQNLFEAKG-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
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 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
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 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
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010718 automatic transmission oil Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000010710 diesel engine oil Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- KPGRTCPQLMJHFQ-UHFFFAOYSA-N diethylaminomethyl 2-methylprop-2-enoate Chemical compound CCN(CC)COC(=O)C(C)=C KPGRTCPQLMJHFQ-UHFFFAOYSA-N 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
- 239000000839 emulsion Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010711 gasoline engine oil Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- RZRFZEDWURIJRY-UHFFFAOYSA-N morpholin-4-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCN1CCOCC1 RZRFZEDWURIJRY-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
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 238000012546 transfer Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
- C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/073—Star shaped polymers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/54—Fuel economy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
Definitions
- the present invention relates to an engine oil composition.
- lubricating oils are used for internal combustion engines, transmissions, and other machine apparatuses to smooth their action.
- engine oil lubricating oil for internal combustion engines
- various additives such as anti-wear agents, metallic detergents, ash-free dispersants, and antioxidants are blended with the conventional engine oil (for example, see Patent Literatures 1 to 3 below).
- the fuel efficiency required for the lubricating oil is increasing recently. For this reason, examinations have been conducted into ways of application of high viscosity index base oil and application of a variety of friction modifiers (for example, see Patent Literature 4 below).
- EP 2522709 A1 relates to a lubricant composition
- a lubricant composition comprising a lubricating base oil with a 100°C kinematic viscosity of 1 to 20 mm 2 /s, a viscosity index improver having a ratio in M1/M2 of 0.2 or greater, between the total area of the peaks between chemical shifts of 36 to 38 ppm M1 in the total area of the peaks between the chemical shifts of 64 to 66 ppm M2, with respect to the total area of all the peaks, in the spectrum obtained by 13 C-NMR, further a friction modifier and an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate.
- US 2010/190671 A1 relates to an additive for reducing fuel consumption of a vehicle, comprising a comb polymer, comprising in the main chain repeat units which are derived from polyolefin-based macromonomers and repeat units which are derived from low molecular weight monomers for reducing the fuel consumption of vehicles.
- a reduction in the kinematic viscosity of the lubricating oil and an increase in the viscosity index multi-grading by a combination of low viscosity base oils with viscosity index improvers
- blending of friction reducing agents are known.
- the lubrication performance is reduced under severe lubrication conditions (under high temperature high shear conditions) due to a reduction of the viscosity of the lubricating oil or the base oil that forms the lubricating oil, occurrence of failures such as wear, burning, and fatigue breaking is concerned.
- ash-free friction modifiers and molybdenum friction modifiers are known, but there is demand for an oil with fuel efficiency superior to that of standard oils having theses friction reducing agents.
- HTHS viscosity is also referred to as "high temperature high shear viscosity"
- high temperature high shear viscosity a kinematic viscosity at 40°C, a kinematic viscosity at 100°C, and an HTHS viscosity at 100°C
- the HTHS viscosity at 150°C can be further reduced while maintaining the durability of the engine, and the kinematic viscosity can be reduced more significantly than ever.
- an engine oil having an HTHS viscosity at 150°C of lower than 2.6 mPa ⁇ s, which is the lower limit of the HTHS viscosity at 150°C of an SAE 0W-20 engine oil is developed and being used.
- the lubrication state of the engine oil to be used is severer than ever, it is important to maintain the HTHS viscosity at 150°C reduced by usage at a constant level or more. Moreover, it is important to reduce the kinematic viscosity as much as possible while reducing the coefficient of friction in a boundary lubrication region.
- the present invention has been made in consideration of such circumstances, and an object of the present invention is to provide an engine oil composition excellent in fuel efficiency in which in an engine oil having an HTHS viscosity at 150°C of less than 2.6 mPa ⁇ s, a kinematic viscosity at 40°C and a kinematic viscosity at 100°C may be sufficiently reduced from the beginning of usage after usage for a long time, and an increase in a coefficient of friction in a boundary lubrication region may be sufficiently suppressed.
- the present invention provides an engine oil composition including a lubricating base oil having a kinematic viscosity at 100°C of 1 to 5 mm 2 /s, a poly(meth)acrylate viscosity index improver (A) containing a structural unit represented by the following formula (1) in a proportion of 30 to 90 mol%, a structural unit represented by the following Formula (3) in a proportion of 0.5 to 70 mol%, and having a PSSI in an ultrasonic shear test of 15 or less measured according to JASO M347-95 under the condition that only the volume of a sample is increased, wherein the viscosity index improver has a ratio of the molecular weight to the PSSI (Mw/PSSI) of 1 ⁇ 10 4 or more; and from 0.01% by mass to 0.1% by mass of molybdenum dithiocarbamate, based on the total amount of the lubricating oil composition in terms of the molybdenum element, as a friction modifier
- the viscosity index improver (A) be a viscosity index improver having a PSSI of 10 or less.
- the PSSI in the ultrasonic shear test in the present invention designates the reduction rate in the viscosity of the viscosity index improver evaluated according to JASO M347-95 (automatic transmission oil shear stability test method) under the condition where only the volume of a sample is increased. More specifically, it means a permanent shear stability index of a polymer (Permanent Shear Stability Index) obtained by adjusting an output with Standard oil A specified in the ASTM test method, performing a shear test at an amplitude of 28 ⁇ m, a vibration number of 10 KHz, an irradiation time of 10 minutes, and the volume of the sample of 60 mL, and calculating the measured kinematic viscosity.
- Permanent Shear Stability Index obtained by adjusting an output with Standard oil A specified in the ASTM test method, performing a shear test at an amplitude of 28 ⁇ m, a vibration number of 10 KHz, an irradiation time of 10 minutes, and the volume of the sample of 60 m
- the PSSI is calculated from ((V1 - V2)/V1 ⁇ 100) (%) based on the viscosity (V1) at 100°C per amount of the viscosity index improver to be added which is measured before the shear test and the viscosity (V2) at 100°C per amount of the viscosity index improver to be added which is measured after the shear test.
- an engine oil composition excellent in fuel efficiency in which in an engine oil having an HTHS viscosity at 150°C of 2.4 mPa ⁇ s or less, the kinematic viscosity at 40°C and the kinematic viscosity at 100°C may be sufficiently reduced from the beginning of usage after usage for a long time, and an increase in the coefficient of friction in the boundary lubrication region may be sufficiently suppressed can be provided.
- the engine oil composition according to the present invention may be suitably used not only for gasoline engines, diesel engines, gas engines, and the like for bicycles, automobiles, power generation, cogeneration, and the like but also for a variety of engines using fuels having a sulfur content of 50 mass ppm or less.
- the lubricating oil composition according to the present invention is also useful for a variety of engines for ships and outboard motors.
- the engine oil composition according to the present embodiment includes a lubricating base oil having a kinematic viscosity at 100°C of 1 to 5 mm 2 /s, a poly(meth)acrylate viscosity index improver (A) containing one or two more of structural unit represented by the following formula (1) in a proportion of 30 to 90 mol% and having a PSSI in an ultrasonic shear test of 15 or less, and a friction modifier (B).
- R 1 represents hydrogen or a methyl group
- R 2 represents a linear or branched hydrocarbon group having a carbon number of 6 or less.
- a lubricating base oil having a kinematic viscosity at 100°C of 1 to 5 mm 2 /s (hereinafter referred to as a "lubricating base oil according to the present embodiment") is used.
- Examples of the lubricating base oil according to the present embodiment include those having a kinematic viscosity at 100°C of 1 to 5 mm 2 /s among paraffin mineral oils, normal paraffin base oils, and isoparaffin base oils obtainable by refining a lubricating oil fraction obtainable by normal pressure distillation and/or reduced pressure distillation of a crude oil using one or two or more refining treatments selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, and the like.
- Preferable examples of the lubricating base oil according to the present embodiment may include base oils obtainable by using the base oils (1) to (8) shown below as the raw material, and refining the raw material oil and/or a lubricating oil fraction recovered from the raw material oil by a predetermined refining method to recover a lubricating oil fraction:
- hydrorefining such as hydrocracking and hydrofinishing
- solvent refining such as furfural solvent extraction
- dewaxing such as solvent dewaxing and catalytic dewaxing
- white clay refining with acid clay or activated clay and chemical (acid or alkali) washing such as sulfuric acid washing and sodium hydroxide washing are preferable.
- one method may be used alone, or two or more may be used in combination. If two or more refining methods are combined, the order is not particularly limited, and can be properly selected.
- a base oil selected from the base oils (1) to (8) or the following base oil (9) or (10) obtainable by performing a predetermined treatment on the lubricating oil fraction recovered from the base oil is particularly preferable:
- a solvent refining treatment and/or a hydrofinishing step may be included as preferably steps when necessary.
- the catalyst used in the hydrocracking and hydrogenation isomerization is not particularly limited, and hydrocracking catalysts in which a carrier is a composite oxide having cracking activity (such as silica alumina, alumina boria, and silica zirconia) or one or more of the composite oxides in combination bounded by a binder, and a metal having a hydrogenation activity (such as one or more metals in Groups VIa and VIII in the periodic table) is carried to the carrier; or hydrogenation isomerization catalysts in which a metal containing at least one metal among metals in Group VIII and having a hydrogenation activity is carried to a carrier containing zeolite (such as ZSM-5, zeolite beta, and SAPO-11) are preferably used.
- the hydrocracking catalyst and the hydrogenation isomerization catalyst may be used in combination by stacking or mixing.
- reaction conditions in hydrocracking and hydrogenation isomerization are not particularly limited, and a hydrogen partial pressure of 0.1 to 20 MPa, an average reaction temperature of 150 to 450°C, an LHSV of 0.1 to 3.0 hr -1 , and the hydrogen/oil ratio of 50 to 20000 scf/b are preferred.
- the kinematic viscosity at 100°C of the lubricating base oil according to the present embodiment needs to be 5 mm 2 /s or less, preferably 4.5 mm 2 /s or less, more preferably 4 mm 2 /s or less, still more preferably 3.8 mm 2 /s or less, particularly preferably 3.7 mm 2 /s or less, and most preferably 3.6 mm 2 /s or less.
- the kinematic viscosity at 100°C needs to be 1 mm 2 /s or more. It is preferable that the kinematic viscosity at 100°C be 1.5 mm 2 /s or more.
- the kinematic viscosity at 100°C is more preferably 2 mm 2 /s or more, still more preferably 2.5 mm 2 /s or more, and particularly preferably 3 mm 2 /s or more.
- the kinematic viscosity at 100°C here designates the kinematic viscosity at 100°C specified in ASTM D-445. In the case where the kinematic viscosity at 100°C of the lubricating base oil exceeds 5 mm 2 /s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained.
- the kinematic viscosity at 40°C of the lubricating base oil according to the present embodiment is preferably 40 mm 2 /s or less, more preferably 30 mm 2 /s or less, still more preferably 25 mm 2 /s or less, particularly preferably 20 mm 2 /s or less, and most preferably 17 mm 2 /s or less.
- the kinematic viscosity at 40°C is preferably 6.0 mm 2 /s or more, more preferably 8.0 mm 2 /s or more, still more preferably 10 mm 2 /s or more, particularly preferably 12 mm 2 /s or more, and most preferably 14 mm 2 /s or more.
- kinematic viscosity at 40°C of the lubricating base oil exceeds 40 mm 2 /s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained.
- a kinematic viscosity of 6.0 mm 2 /s or less formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition may be increased.
- the viscosity index of the lubricating base oil according to the present embodiment be 100 or more.
- the viscosity index is more preferably 105 or more, still more preferably 110 or more, particularly preferably 115 or more, and most preferably 120 or more. If the viscosity index is less than 100, not only viscosity-temperature properties, heat and oxidation stability, and anti-volatilization are reduced, but also the coefficient of friction tends to be increased; and resistance against wear tends to be reduced.
- the viscosity index in the present invention means the viscosity index measured according to JIS K 2283-1993.
- the lubricating base oil in the engine oil composition according to the present embodiment be a mixture of a first lubricating base oil component having a kinematic viscosity at 100°C of 3.5 mm 2 /s or more and having a viscosity index of 120 or more and a second lubricating base oil component having a kinematic viscosity at 100°C of less than 3.5 mm 2 /s.
- the density ( ⁇ 15 ) at 15°C of the first lubricating base oil component used in the engine oil composition according to the present embodiment is preferably 0.860 or less, more preferably 0.850 or less, still more preferably 0.840 or less, and particularly preferably 0.822 or less.
- the density at 15°C in the present invention means a density measured at 15°C according to JIS K 2249-1995.
- the pour point of the first lubricating base oil component used in the engine oil composition according to the present embodiment is preferably -10°C or less, more preferably -12.5°C or less, still more preferably -15°C or less, and particularly preferably -20°C or less. If the pour point exceeds the upper limit value, the fluidity at a low temperature of the entire lubricating oil using the lubricating base oil tends to be reduced.
- the pour point in the present invention means the pour point measured according to JIS K 2269-1987.
- the kinematic viscosity at 100°C of the first lubricating base oil component used in the engine oil composition according to the present embodiment be 5 mm 2 /s or less.
- the kinematic viscosity is more preferably 4.5 mm 2 /s or less, still more preferably 4.0 mm 2 /s or less, and particularly preferably 3.9 mm 2 /s or less.
- the kinematic viscosity at 100°C be 3.5 mm 2 /s or more.
- the kinematic viscosity is more preferably 3.6 mm 2 /s or more, still more preferably 3.7 mm 2 /s or more, and particularly preferably 3.8 mm 2 /s or more.
- kinematic viscosity at 100°C exceeds 5 mm 2 /s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained.
- a kinematic viscosity less than 3.5 mm 2 /s formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the engine oil composition may be increased.
- the kinematic viscosity at 40°C of the first lubricating base oil component used in the engine oil composition according to the present embodiment is preferably 40 mm 2 /s or less, more preferably 30 mm 2 /s or less, still more preferably 25 mm 2 /s or less, particularly preferably 20 mm 2 /s or less, and most preferably 17 mm 2 /s or less.
- the kinematic viscosity at 40°C is preferably 6.0 mm 2 /s or more, more preferably 8.0 mm 2 /s or more, still more preferably 10 mm 2 /s or more, particularly preferably 12 mm 2 /s or more, and most preferably 14 mm 2 /s or more.
- kinematic viscosity at 40°C exceeds 40 mm 2 /s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained.
- a kinematic viscosity of 6.0 mm 2 /s or less formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition may be increased.
- the viscosity index of the first lubricating base oil component used in the engine oil composition according to the present embodiment be 100 or more.
- the viscosity index is more preferably 110 or more, still more preferably 120 or more, particularly preferably 130 or more, and most preferably 140 or more.
- the viscosity index is preferably 170 or less, more preferably 160 or less, still more preferably 155 or less, and particularly preferably 150 or less. If the viscosity index is less than 100, not only viscosity-temperature properties, heat and oxidation stability, and anti-volatilization are reduced, but also the coefficient of friction tends to be increased; and resistance against wear tends to be reduced. If the viscosity index exceeds 170, low temperature viscosity tends to be increased to reduce the fuel efficiency at low oil temperatures. Moreover, startability tends to be reduced.
- the density ( ⁇ 15 ) at 15°C of the second lubricating base oil component used in the engine oil composition according to the present embodiment is preferably 0.860 or less, more preferably 0.850 or less, still more preferably 0.840 or less, and particularly preferably 0.835 or less.
- the pour point of the second lubricating base oil component used in the engine oil composition according to the present embodiment is preferably -10°C or less, more preferably -12.5°C or less, still more preferably -15°C or less, and particularly preferably -20°C or less. If the pour point exceeds the upper limit value, the fluidity at a low temperature of the entire lubricating oil using the lubricating base oil tends to be reduced.
- the kinematic viscosity at 100°C of the second lubricating base oil component used in the engine oil composition according to the present embodiment be less than 3.5 mm 2 /s.
- the kinematic viscosity is more preferably 3.4 mm 2 /s or less, and still more preferably 3.3 mm 2 /s or less.
- the kinematic viscosity at 100°C be 2 mm 2 /s or more, and the kinematic viscosity is more preferably 2.5 mm 2 /s or more, and still more preferably 3.0 mm 2 /s or more.
- kinematic viscosity at 100°C exceeds 3.5 mm 2 /s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained.
- a kinematic viscosity less than 2 mm 2 /s formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition may be increased.
- the kinematic viscosity at 40°C of the second lubricating base oil component used in the engine oil composition according to the present embodiment is preferably 20 mm 2 /s or less, more preferably 18 mm 2 /s or less, still more preferably 16 mm 2 /s or less, and particularly preferably 14 mm 2 /s or less.
- the kinematic viscosity at 40°C is preferably 6.0 mm 2 /s or more, more preferably 8.0 mm 2 /s or more, still more preferably 10 mm 2 /s or more, particularly preferably 12 mm 2 /s or more, and most preferably 13 mm 2 /s or more.
- kinematic viscosity at 40°C exceeds 20 mm 2 /s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained.
- a kinematic viscosity of 6.0 mm 2 /s or less formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition may be increased.
- the viscosity index of the second lubricating base oil component used in the engine oil composition according to the present embodiment be 100 or more.
- the viscosity index is more preferably 105 or more, and still more preferably 110 or more.
- the viscosity index is preferably 160 or less, more preferably 150 or less, still more preferably 140 or less, and particularly preferably 135 or less. If the viscosity index is less than 100, not only viscosity-temperature properties, heat and oxidation stability, and anti-volatilization are reduced, but also the coefficient of friction tends to be increased. Moreover, resistance against wear tends to be reduced. If the viscosity index exceeds 160, low temperature viscosity tends to be increased to reduce the fuel efficiency at low oil temperatures. Moreover, startability tends to be reduced.
- the sulfur content of the lubricating base oil used in the present embodiment depends on the sulfur content of the raw material.
- the lubricating base oil containing substantially no sulfur may be obtainable.
- the sulfur content of the lubricating base oil to be obtainable is usually 100 mass ppm or more.
- the sulfur content be 100 mass ppm or less, it is more preferable that the sulfur content be 50 mass ppm or less, it is still more preferable that the sulfur content be 10 mass ppm or less, and it is particularly preferable that the sulfur content be 5 mass ppm or less.
- the nitrogen content of the lubricating base oil used in the present embodiment is preferably 7 mass ppm or less, more preferably 5 mass ppm or less, and still more preferably 3 mass ppm or less. If the nitrogen content exceeds 5 mass ppm, heat and oxidation stability tends to be reduced.
- the nitrogen content in the present invention means the nitrogen content measured according to JIS K 2609-1990.
- %C p of the lubricating base oil used in the present embodiment be 70 or more.
- %C p is preferably 80 or more, more preferably 85 or more, still more preferably 87 or more, and particularly preferably 90 or more.
- %C p is preferably 99.9 or less, more preferably 98 or less, still more preferably 96 or less, and particularly preferably 94 or less. If %C p of the lubricating base oil is less than the lower limit value, viscosity-temperature properties, heat and oxidation stability, and friction properties tend to be reduced; furthermore, if an additive is blended with the lubricating base oil, the effect of the additive tends to be reduced. If %C p of the lubricating base oil exceeds the upper limit value, the solubility of the additive tends to be reduced.
- %C A of the lubricating base oil used in the present embodiment be 2 or less. %C A is more preferably 1 or less, still more preferably 0.8 or less, and particularly preferably 0.5 or less. If %C A of the lubricating base oil exceeds the upper limit value, viscosity-temperature properties, heat and oxidation stability, and fuel efficiency tend to be reduced.
- %C N of the lubricating base oil used in the present embodiment be 30 or less.
- %C N is preferably 25 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 10 or less.
- %C N is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and particularly preferably 6 or more. If %C N of the lubricating base oil exceeds the upper limit value, viscosity-temperature properties, heat and oxidation stability, and friction properties tend to be reduced. If %C N is less than the lower limit value, the solubility of the additive tends to be reduced.
- %C p , %C N , and %C A in the present invention mean the percentage of the number of paraffin carbon atoms to the total number of carbon atoms, the percentage of the number of naphthene carbon atoms to the total number of carbon atoms, and the percentage of the number of aromatic carbon atoms to the total number of carbon atoms, respectively, which are determined by the method (n-d-M ring analysis) according to ASTM D 3238-85.
- %C P , %C N , and %C A above described are based on the values determined by the method above; for example, even in a lubricating base oil containing no naphthene content, %C N determined by the method may indicate a value more than zero.
- the content of the saturates in the lubricating base oil used in the present embodiment is preferably 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more based on the total amount of the lubricating base oil; the proportion of the cyclic saturates in the saturates is preferably 40% by mass or less, preferably 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 21% by mass or less.
- the proportion of the cyclic saturates in the saturates is preferably 5% by mass or more, and more preferably 10% by mass or more.
- viscosity-temperature properties and heat and oxidation stability may be improved; if an additive is blended with the lubricating base oil, the function of the additive may be demonstrated at a higher level while the additive is sufficiently stably dissolved in the lubricating base oil.
- the friction properties of the lubricating base oil itself may be improved; as a result, an improvement in a friction reducing effect and thus an improvement in energy saving properties may be attained.
- the saturates in the present invention are measured by the method described in ASTM D 2007-93 above.
- the aromatic content of the lubricating base oil used in the present embodiment is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less based on the total amount of the lubricating base oil, and is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more based on the total amount of the lubricating base oil. If the content of the aromatics exceeds the upper limit value, viscosity-temperature properties, heat and oxidation stability, friction properties, anti-volatilization, and low temperature viscosity properties tend to be reduced; if an additive is blended with the lubricating base oil, the effect of the additive tends to be reduced.
- the lubricating base oil according to the present embodiment may be a lubricating base oil containing no aromatics, but the content of the aromatics in the range of the lower limit value or more can further enhance the solubility of the additive.
- the aromatic content in the present invention means the value measured according to ASTM D 2007-93.
- the aromatics usually include alkylbenzene and alkylnaphthalene; anthracene, phenanthrene, and alkylated products thereof; compounds in which four or more benzene rings are condensed; and aromatic compounds having a heteroatom such as pyridines, quinolines, phenols, and naphthols.
- a synthetic base oil may be used as the lubricating base oil according to the present embodiment.
- the synthetic base oil are base oils having a kinematic viscosity at 100°C of 1 to 20 mm 2 /s.
- the examples include poly- ⁇ -olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffin, alkylbenzene, alkylnaphthalene, diesters (such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, and di-2-ethylhexylcebacate), polyol esters (such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, and pentaerythritol pelargonate), polyoxyal
- poly- ⁇ -olefins typically include oligomers or co-oligomers of ⁇ -olefins having a carbon number of 2 to 32, preferably a carbon number of 6 to 16 (such as 1-octene oligomer, decene oligomer, and ethylene-propylene co-oligomer) and hydrides thereof.
- the method for producing poly- ⁇ -olefin is not particularly limited, and examples thereof include a method for polymerizing ⁇ -olefin in the presence of a polymerization catalyst containing a complex of aluminum trichloride or boron trifluoride, water, an alcohol (such as ethanol, propanol, and butanol), and carboxylic acid or an ester thereof, such as a Friedel-Crafts catalyst.
- a polymerization catalyst containing a complex of aluminum trichloride or boron trifluoride, water, an alcohol (such as ethanol, propanol, and butanol), and carboxylic acid or an ester thereof, such as a Friedel-Crafts catalyst.
- the lubricating base oil according to the present embodiment may be used alone, or the lubricating base oil according to the present embodiment may be used in combination with one or two or more of other base oils.
- the proportion of the lubricating base oil according to the present embodiment in the mixed base oils be 30% by mass or more, it is more preferable that the proportion of the lubricating base oil according to the present embodiment in the mixed base oils be 50% by mass or more, and it is still more preferable that the proportion of the lubricating base oil according to the present embodiment in the mixed base oils be 70% by mass or more.
- the other base oils used in combination with the lubricating base oil according to the present embodiment is not particularly limited, and examples of a mineral oil-based base oil include solvent refined mineral oils, hydrocracked mineral oils, hydrorefined mineral oils, and solvent dewaxed base oils whose kinematic viscosity at 100°C is 5 mm 2 /s or more and 100 mm 2 /s or less.
- Examples of the other synthetic base oils used in combination with the lubricating base oil according to the present embodiment include the synthetic base oils described above whose kinematic viscosity at 100°C is out of the range of 1 to 5 mm 2 /s.
- the engine oil composition according to the present embodiment contains a poly(meth)acrylate viscosity index improver (A) (hereinafter referred to as "viscosity index improver according to the present embodiment" for convenience) containing one or two or more of the structural units represented by the following formula (1) in a proportion of 30 to 90 mol% and having the PSSI in the ultrasonic shear test of 15 or less.
- A poly(meth)acrylate viscosity index improver
- the compound has any form as long as the compound satisfies the condition that the compound is a poly(meth)acrylate viscosity index improver having the structural unit represented by the following formula (1) in the proportion of 30 to 90 mol% and having the PSSI in the ultrasonic shear test of 15 or less.
- Specific examples of the compound are non-dispersive or dispersive poly(meth)acrylate viscosity index improvers, (meth)acrylate-olefin copolymers, or a mixture thereof: wherein R 1 represents hydrogen or a methyl group; and R 2 represents a linear or branched hydrocarbon group having a carbon number of 6 or less.
- R 2 in the structural unit represented by the formula (1), as described above, is a linear or branched hydrocarbon group having a carbon number of 6 or less and may be one hydrocarbon group or a mixture of two or more thereof;
- R 2 is preferably a linear or branched hydrocarbon having a carbon number of 4 or less, still more preferably a linear or branched hydrocarbon having a carbon number of 3 or less, and more preferably a hydrocarbon group having a carbon number of 2 or less.
- the proportion of the (meth)acrylate structural unit represented by the formula (1) in a polymer is 30 to 90 mol% as described above, preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, and particularly preferably 60 mol% or less.
- the proportion is preferably 32 mol% or more, more preferably 35 mol% or more, and still more preferably 40 mol% or more.
- the solubility in the base oil, the effect of improving viscosity temperature properties, and low temperature viscosity properties may be inferior; at a proportion less than 20 mol%, the effect of improving viscosity temperature properties may be inferior.
- the viscosity index improver is a copolymer having (meth)acrylate structural unit.
- a copolymer is obtainable by copolymerizing one or two or more of monomers represented by the following formula (3) (hereinafter referred to as "Monomer (M-1)") and a monomer other than Monomer (M-1).
- M-1 monomers represented by the following formula (3)
- R 3 represents a hydrogen atom or a methyl group
- R 4 represents a linear or branched hydrocarbon group having a carbon number of 7 or more.
- R 4 in the structural unit represented by the formula (3) is a linear or branched hydrocarbon group having a carbon number of 7 or more, preferably a linear or branched hydrocarbon having a carbon number of 10 or more, more preferably a linear or branched hydrocarbon having a carbon number of 15 or more, and still more preferably a branched hydrocarbon group having a carbon number of 18 or more.
- the upper limit of the hydrocarbon group represented as R 4 is not particularly limited, and it is preferable that it be a linear or branched hydrocarbon group having a carbon number of 2000 or less.
- the (meth)acrylate structural unit represented by the formula (3) in the polymer may be one or two or more mixtures, and the proportion is from 0.5 to 70 mol%, the proportion is preferably 60 mol% or less, more preferably 50 mol% or less, particularly preferably 40 mol% or less, and most preferably 30 mol% or less.
- the proportion is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and particularly preferably 10 mol% or more.
- the effect of improving viscosity temperature properties and low temperature viscosity properties may be inferior; at a proportion less than 0.5 mol%, the effect of improving viscosity temperature properties may be inferior.
- the other monomers used in combination with Monomer (M-1) be one or two or more selected from the monomer represented by the following formula (4) (hereinafter referred to as "Monomer (M-3)”) and the monomer represented by the following formula (5) (hereinafter referred to as “Monomer (M-4)").
- a copolymer of Monomers (M-1) and (M-3) and/or (M-4) is the so-called dispersive poly(meth)acrylate viscosity index improver.
- the dispersive poly(meth)acrylate viscosity index improver may further contain Monomer (M-2) as the constitutional monomer.
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents an alkylene group having a carbon number of 1 to 18
- E 1 represents an amine residue or heterocycle residue having a nitrogen number of 1 to 2 and an oxygen number of 0 to 2
- a represents 0 or 1
- Examples of the alkylene group having a carbon number of 1 to 18 represented by R 6 specifically may include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group (these alkylene groups may be linear or branched).
- Examples of the group represented by E 1 specifically can include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, a morpholino group, a pyrrolyl group, a pyrrolino group, a pyridyl group, a methylpyridyl group, a pyrrolidinyl group, a piperidinyl group, a quinonyl group, a pyrrolidonyl group, a pyrrolidono group, an imidazolino group, and a pyrazino group.
- R 7 represents a hydrogen atom or a hydrocarbon group
- E 2 represents a hydrocarbon group or an amine residue or heterocycle residue having a nitrogen number of 1 to
- Examples of the group represented by E 2 specifically can include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, a morpholino group, a pyrrolyl group, a pyrrolino group, a pyridyl group, a methylpyridyl group, a pyrrolidinyl group, a piperidinyl group, a quinonyl group, a pyrrolidonyl group, a pyrrolidono group, an imidazolino group, and a pyrazino group.
- Monomers (M-3) and (M-4) specifically may include dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinyl pyridine, morpholinomethyl methacrylate, morpholinoethyl methacrylate, N-vinylpyrrolidone, and mixtures thereof.
- the method for producing the viscosity index improver according to the present embodiment is not particularly limited, and examples thereof include a method in which using a control radical polymerization process, an alkyl methacrylate serving as an arm portion (polymerization chain of alkyl methacrylate) is polymerized, and the polyalkyl methacrylate is then reacted with a polyfunctional compound having two or more ethylenic unsaturated double bonds.
- control radical polymerization process involves an atom transfer radical polymerization (ATRP) process, a reversible addition-fragmentation chain transfer (RAFT) process, or a nitroxide mediated polymerization process.
- ATRP atom transfer radical polymerization
- RAFT reversible addition-fragmentation chain transfer
- nitroxide mediated polymerization process a nitroxide mediated polymerization process.
- the synthesis can be performed as a batch operation, a semi-batch operation, a continuous step, a feed step, or a bulk step.
- the synthesis may be performed in an emulsion, a solution, or a suspension.
- the average molecular weight of the polymethacrylate or viscosity index improver to be produced may be adjusted.
- the reaction rate to the viscosity index improver using the synthesized arm portion is 70% or more, preferably 80% or more, and more preferably 85% or more based on the amount of the polymer reacted to become the viscosity index improver. If the reaction rate is low, the arm portion remains, and the molecular weight cannot be increased.
- the PSSI in the ultrasonic shear test (shear stability index) of the viscosity index improver according to the present embodiment is 15 or less, preferably 12 or less, more preferably 10 or less, and still more preferably 5 or less. If the PSSI in the ultrasonic shear test exceeds 15, shear stability is poor, and initial viscosity temperature properties and fuel efficiency are reduced in order to keep the kinematic viscosity and the HTHS viscosity after usage at a constant level or more.
- the PSSI (Permanent Shear Stability Index) of the viscosity index improver according to the present embodiment in a diesel injector method is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, particularly preferably 5 or less, and most preferably 3 or less. If the PSSI exceeds 20, shear stability is poor, and to keep the kinematic viscosity and the HTHS viscosity after usage at a constant level or more, the initial fuel efficiency may be reduced.
- PSSI in the diesel injector method here means the permanent shear stability index of the polymer (Permanent Shear Stability Index) calculated based on the data measured by ASTM D 6278-02 (Test Method for Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus) in accordance with ASTM D 6022-01 (Standard Practice for Calculation of Permanent Shear Stability Index).
- the weight average molecular weight (M W ) of the viscosity index improver according to the present embodiment be 100,000 or more, and the weight average molecular weight is more preferably 200,000 or more, still more preferably 300,000 or more, and particularly preferably 400,000 or more. It is preferable that the weight average molecular weight be 1,000,000 or less, and the weight average molecular weight is more preferably 900,000 or less, still more preferably 700,000 or less, and particularly preferably 600,000 or less.
- the weight average molecular weight is less than 100,000, the effect of improving a viscosity index when the viscosity index improver is dissolved in the lubricating base oil is small; not only fuel efficiency and low temperature viscosity properties are inferior but also cost may increase. If the weight average molecular weight exceeds 1,000,000, the effect of increasing viscosity is excessively increased; not only fuel efficiency and low temperature viscosity properties are inferior, but also shear stability, the solubility in the lubricating base oil, and storage stability are reduced.
- the ratio of the weight average molecular weight of the viscosity index improver according to the present embodiment to the PSSI in the ultrasonic shear test is 1.0 ⁇ 10 4 or more, and the ratio is more preferably 2.0 ⁇ 10 4 or more, still more preferably 5.0 ⁇ 10 4 or more, and particularly preferably 8.0 ⁇ 10 4 or more. If M W /PSSI is less than 1.0 ⁇ 10 4 , fuel efficiency and low temperature startability, namely, viscosity temperature properties and low temperature viscosity properties may be reduced.
- the ratio of the weight average molecular weight to the PSSI in the diesel injector method of the viscosity index improver according to the present embodiment (M W /PSSI) be 1.0 ⁇ 10 4 or more, and the ratio is more preferably 2.0 ⁇ 10 4 or more, still more preferably 5.0 ⁇ 10 4 or more, and particularly preferably 8.0 ⁇ 10 4 or more. If M W /PSSI is less than 1.0 ⁇ 10 4 , fuel efficiency and low temperature startability, namely, viscosity temperature properties and low temperature viscosity properties may be reduced.
- the ratio (M W /M N ) of the weight average molecular weight (M W ) to the number average molecular weight (M N ) of the viscosity index improver according to the present embodiment be 5.0 or less, and the ratio is more preferably 4.0 or less, still more preferably 3.5 or less, particularly preferably 3.0 or less, and most preferably 2.0 or less. It is preferable that M W /M N be 1.0 or more, and the ratio is more preferably 1.1 or more, and still more preferably 1.2 or more. If M W /M N is 4.0 or more or 1.0 or less, solubility and the effect of improving viscosity temperature properties may be reduced so that sufficient storage stability and fuel efficiency cannot be maintained.
- the hydrocarbon main chain ratio of the viscosity index improver according to the present embodiment is preferably 0.3 or less, more preferably 0.2 or less, more preferably 0.18 or less, still more preferably 0.16 or less, still more preferably 0.14 or less, particularly preferably 0.10 or less, and most preferably 0.05 or less.
- the hydrocarbon main chain ratio is preferably 0.005 or more, more preferably 0.01 or more, and still more preferably 0.02 or more. If the hydrocarbon main chain ratio exceeds 0.3, shear stability is reduced, and viscosity temperature properties and fuel efficiency may be reduced. If the hydrocarbon main chain ratio is less than 0.01, the solubility in the base oil is reduced, and viscosity temperature properties and fuel efficiency may be reduced.
- the "hydrocarbon main chain ratio" in the present invention means the proportion of the carbon number of the polymethacrylic acid main chain of the total number of carbon atoms of the molecule (the ratio, that is, the carbon number of the poly(meth)acrylic acid main chain/the total number of carbon atoms in the molecule).
- the poly(meth)acrylate viscosity index improver is a mixture of a plurality of polymers having different structures or molecular weights, the proportion is calculated as an average value of the poly(meth)acrylate viscosity index improver. If two or more poly(meth)acrylic acid chains are present in the molecule, a longer chain of these poly(meth)acrylic acid chains is the "poly(meth)acrylic acid main chain.”
- the influences of the core portion is small, and the core portion is excluded from the calculation.
- the molecular weight of each arm portion is substantially equal, and the weight average molecular weight of the arm portion measured by GPC analysis (standard substance: polystyrene) is used in calculation of the carbon number of the arm portion in the main chain.
- the average polymerization number (A1) of each monomer in the molecule is calculated. From A1, the total carbon number (B1) and the carbon number (C1) of the polymethacrylic acid main chain in one molecule are calculated, and C1/B1 is calculated. C1/B1 is the hydrocarbon main chain ratio.
- the number of arm portions (D) defined by the number average molecular weight of the poly(meth)acrylate viscosity index improver/the number average molecular weight of the arm portion is calculated, and C1/(B1 ⁇ D) is calculated.
- C1/(B1 ⁇ D) is the hydrocarbon main chain ratio of the poly(meth)acrylate viscosity index improver having a star structure.
- the content of the viscosity index improver according to the present embodiment is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, still more preferably 1 to 30% by mass, particularly preferably 5 to 20% by mass based on the total amount of the composition. If the content of the viscosity index improver is less than 0.1% by mass, the effect of improving the viscosity index and the effect of reducing the viscosity of a product are reduced, and fuel efficiency may not be improved.
- the cost of the product is significantly increased, and the viscosity of the base oil needs to be reduced; for this reason, the lubrication performance under severe lubrication conditions (high temperature high shear conditions) may be reduced, causing deficits such as wear, seizure, and fatigue breaking.
- the engine oil composition according to the present embodiment may further contain a non-dispersive or dispersive poly(meth)acrylate, a non-dispersive or dispersive ethylene- ⁇ -olefin copolymer or a hydride thereof, polyisobutylene or a hydride thereof, a styrene-diene hydrogenation copolymer, a styrene-maleic anhydride ester copolymer, polyalkylstyrene and the like usually used.
- a non-dispersive or dispersive poly(meth)acrylate a non-dispersive or dispersive ethylene- ⁇ -olefin copolymer or a hydride thereof, polyisobutylene or a hydride thereof, a styrene-diene hydrogenation copolymer, a styrene-maleic anhydride ester copolymer, polyalkylstyrene and the like usually used.
- the content of the viscosity index improver in the engine oil composition according to the present embodiment be 0.1 to 50% by mass based on the total amount of the composition, and the content is preferably 0.5 to 20% by mass, more preferably 1.0 to 15% by mass, and still more preferably 1.5 to 12% by mass based on the total amount of the composition. If the content is less than 0.1% by mass, low temperature properties may be insufficient; if the content exceeds 50% by mass, the shear stability of the composition may be reduced.
- the engine oil composition according to the present embodiment contains molybdenum dithiocarbamate as a friction modifier (B). Thereby, fuel efficiency performance may be increased compared to the case where the present configuration is not included.
- the content of the friction modifier is 0.01% by mass or more, and preferably 0.03% by mass or more, and 0.1% by mass or less, preferably 0.08% by mass or less, and particularly preferably 0.06% by mass or less based on the total amount of the lubricating oil composition in terms of the molybdenum element. If the content is less than 0.01% by mass, the effect of reducing friction by addition thereof tends to be insufficient, and the fuel efficiency and heat and oxidation stability of the lubricating oil composition tend to be insufficient. If the content exceeds 0.1% by mass, the effect corresponding to the content is not obtained, and the storage stability of the lubricating oil composition tends to be reduced.
- any additives usually used in the lubricating oil may be contained in the engine oil composition according to the present embodiment according to the purpose.
- additives may include additives such as a metallic detergent besides the first and the second perbasic metal salts, an ash-free dispersant, an anti-wear agent (or extreme-pressure agent), an antioxidant, a corrosion inhibitor, a rust inhibitor, an antiemulsifier, a metal deactivator, and an antifoaming agent.
- each additive is contained in the engine oil composition according to the present embodiment, it is preferable that the content of each additive be 0.01 to 10% by mass based on the total amount of the lubricating oil composition.
- the kinematic viscosity at 100°C of the engine oil composition according to the present embodiment is 4 to 7 mm 2 /s, and particularly preferably 6.8 mm 2 /s or less.
- the kinematic viscosity at 100°C of the engine oil composition according to the present embodiment is preferably 4.5 mm 2 /s or more, more preferably 5.0 mm 2 /s or more, still more preferably 5.5 mm 2 /s or more, particularly preferably 6.0 mm 2 /s or more.
- the kinematic viscosity at 100°C here designates a kinematic viscosity at 100°C specified in ASTM D-445.
- kinematic viscosity at 100°C is less than 4 mm 2 /s, insufficient lubrication may be caused; at a kinematic viscosity more than 12 mm 2 /s, necessary low temperature viscosity and sufficient fuel efficiency performance may not be obtainable.
- the kinematic viscosity at 40°C of the engine oil composition according to the present embodiment be 4 to 50 mm 2 /s, and the kinematic viscosity is preferably 40 mm 2 /s or less, more preferably 35 mm 2 /s or less, particularly preferably 30 mm 2 /s or less, and most preferably 28 mm 2 /s or less.
- the kinematic viscosity at 40°C of the engine oil composition according to the present embodiment is preferably 15 mm 2 /s or more, more preferably 18 mm 2 /s or more, still more preferably 20 mm 2 /s or more, particularly preferably 22 mm 2 /s or more, and most preferably 25 mm 2 /s or more.
- the kinematic viscosity at 40°C here designates a kinematic viscosity at 40°C specified in ASTM D-445. If the kinematic viscosity at 40°C is less than 4 mm 2 /s, insufficient lubrication may be caused; at a kinematic viscosity more than 50 mm 2 /s, necessary low temperature viscosity and sufficient fuel efficiency performance may not be obtainable.
- the viscosity index of the engine oil composition according to the present embodiment be in the range of 140 to 400, and the viscosity index is preferably 180 or more, more preferably 190 or more, still more preferably 200 or more, particularly preferably 210 or more, and most preferably 215 or more. If the viscosity index of the lubricating oil composition is less than 140, it may be difficult to improve fuel efficiency while maintaining the HTHS viscosity at 150°C, and to reduce the low temperature viscosity at -35°C. If the viscosity index of the lubricating oil composition exceeds 400 and more, evaporation properties may be reduced, and deficits due to insufficient solubility of the additive and matching properties with a seal material may be caused.
- the HTHS viscosity at 100°C of the engine oil composition according to the present embodiment be 5.5 mPa ⁇ s or less, and the HTHS viscosity is more preferably 5.0 mPa ⁇ s or less, still more preferably 4.7 mPa ⁇ s or less, particularly preferably 4.5 mPa ⁇ s or less, and most preferably 4.4 mPa ⁇ s or less.
- the HTHS viscosity is preferably 3.0 mPa ⁇ s or more, still more preferably 3.5 mPa ⁇ s or more, particularly preferably 4.0 mPa ⁇ s or more, and most preferably 4.1 mPa ⁇ s or more.
- the HTHS viscosity at 100°C in the present invention designates a high temperature high shear viscosity at 100°C specified in ASTM D4683. If the HTHS viscosity at 100°C is less than 3.0 mPa ⁇ s, insufficient lubrication may be caused; at an HTHS viscosity more than 5.5 mPa ⁇ s, necessary low temperature viscosity and sufficient fuel efficiency performance may not be obtainable.
- the HTHS viscosity at 150°C of the engine oil composition according to the present embodiment is 2.4 mPa ⁇ s or less.
- the HTHS viscosity is preferably 2.0 mPa ⁇ s or more, more preferably 2.1 mPa ⁇ s or more, still more preferably 2.2 mPa ⁇ s or more, and particularly preferably 2.3 mPa ⁇ s or more.
- the HTHS viscosity at 150°C here designates a high temperature high shear viscosity at 150°C specified in ASTM D4683.
- the HTHS viscosity at 150°C is less than 2.0 mPa ⁇ s, insufficient lubrication may be caused; at an HTHS viscosity more than 2.6 mPa ⁇ s, sufficient fuel efficiency performance may not be obtainable.
- the ratio of the HTHS viscosity at 150°C to HTHS viscosity at 100°C of the engine oil composition according to the present embodiment (HTHS viscosity at 150°C/HTHS viscosity at 100°C) be 0.50 or more, and the ratio is more preferably 0.52 or more, still more preferably 0.53, and particularly preferably 0.54 or more. If the ratio is less than 0.50, necessary low temperature viscosity and sufficient fuel efficiency performance may not be obtainable.
- the engine oil composition according to the present embodiment may sufficiently reduce the kinematic viscosity at 40°C, kinematic viscosity at 100°C and HTHS viscosity at 100°C in an engine oil having an HTHS viscosity at 150°C of less than 2.6 mPa ⁇ s, may sufficiently suppress an increase in the coefficient of friction in the boundary lubrication region, and has high fuel efficiency.
- the lubricating oil composition according to the present embodiment having such high properties may be suitably used as energy saving engine oils such as energy saving gasoline engine oils and energy saving diesel engine oils.
- the weight average molecular weight of the obtained arm molecule was 87400
- the number average molecular weight (Mn) was 62000
- the degree of dispersion (Mw/Mn) was 1.41.
- Non-dispersive PMA viscosity index improver A-1 a target star polymer
- the weight average molecular weight (Mw) of the obtained Non-dispersive PMA viscosity index improver A-1 was 570000
- the number average molecular weight (Mn) was 470000
- the degree of dispersion (Mw/Mn) was 1.23
- PSSI was 10.8
- Mw/PSSI was 5.3 ⁇ 10 4 .
- the arm conversion rate of the Non-dispersive PMA viscosity index improver A-1 was 64% by mass
- the average number of arms was 8, and the hydrocarbon main chain ratio was 0.025.
- the weight average molecular weight and the number average molecular weight are the weight average molecular weight and the number average molecular weight in terms of polystyrene measured by using an HLC-8220 GPC apparatus made by Tosoh Corporation having 3 TSKgel Super MultiPore HZ-M columns made by Tosoh Corporation (4.6 mm ID ⁇ 15 cm) in series and tetrahydrofuran as a solvent at a temperature of 40°C, a flow rate of 0.35 mL/min, a sample concentration of 1% by mass, an amount of sample injection of 5 ⁇ L with a detector deference refractive index meter (RI).
- HLC-8220 GPC apparatus made by Tosoh Corporation having 3 TSKgel Super MultiPore HZ-M columns made by Tosoh Corporation (4.6 mm ID ⁇ 15 cm) in series and tetrahydrofuran as a solvent at a temperature of 40°C, a flow rate of 0.35 mL/min, a sample concentration of
- Non-dispersive PMA viscosity index improver A-2 A star polymer (hereinafter referred to as "Non-dispersive PMA viscosity index improver A-2”) was synthesized in the same manner as in Synthesis Example 1 except that instead of the arm molecule solution in Synthesis Example 1, an arm molecule solution containing an arm molecule including 70 mol% methyl methacrylate and 30 mol% methacrylate in which R 4 in the formula (4) was an alkyl group having 18 carbon atoms (weight average molecular weight: 49600, number average molecular weight (Mn): 40000, degree of dispersion (Mw/Mn): 1.24) was used.
- the Mw of the obtained non-dispersive PMA viscosity index improver A-2 was 370000, Mn was 320000, Mw/Mn was 1.15, PSSI was 4.5, Mw/PSSI was 8.2 ⁇ 10 4 , and the hydrocarbon main chain ratio was 0.025.
- Non-dispersive PMA viscosity index improver A-3 A star polymer (hereinafter referred to as "Non-dispersive PMA viscosity index improver A-3”) was synthesized in the same manner as in Synthesis Example 1 except that instead of the arm molecule solution in Synthesis Example 1, an arm molecule solution containing an arm molecule including 70 mol% methyl methacrylate and 30 mol% methacrylate in which R 4 in the formula (4) was an alkyl group having 18 carbon atoms (weight average molecular weight: 54000, number average molecular weight (Mn): 42000, degree of dispersion (Mw/Mn): 1.29) was used.
- Non-dispersive PMA viscosity index improver A-3 obtained was 490000, Mn was 410000, Mw/Mn was 1.19, PSSI was 6.7, Mw/PSSI was 7.3 ⁇ 10 4 , and the hydrocarbon main chain ratio was 0.020.
- the engine oil compositions in Examples 1 to 4 including all the components (A) and (B), whose kinematic viscosity at 100°C is 4 to 8 mm 2 /s, and whose HTHS viscosity at 150°C is adjusted to be less than 2.6 mPa ⁇ s show that kinematic viscosity and HTHS viscosity at 100°C are lower and fuel efficiency is higher than those of the engine oil compositions in Comparative Examples 1 to 3 in which HTHS viscosities at 150°C after the ultrasonic shear test are substantially the same and which do not include the component (A) and the engine oil composition whose HTHS viscosity at 150°C is adjusted to be 2.7 mPa ⁇ s.
- the motoring friction improving rate of the engine oil composition in Comparative Example 5 not containing the component (B) is significantly poor.
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Description
- The present invention relates to an engine oil composition.
- In the related art, lubricating oils are used for internal combustion engines, transmissions, and other machine apparatuses to smooth their action. Particularly in lubricating oil for internal combustion engines (engine oil), high performance is required with higher performance of the internal combustion engines, higher outputs, severer operation conditions, and the like. Accordingly, to meet such required performances, various additives such as anti-wear agents, metallic detergents, ash-free dispersants, and antioxidants are blended with the conventional engine oil (for example, see Patent Literatures 1 to 3 below). Moreover, the fuel efficiency required for the lubricating oil is increasing recently. For this reason, examinations have been conducted into ways of application of high viscosity index base oil and application of a variety of friction modifiers (for example, see Patent Literature 4 below).
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- Patent Literature 1: Japanese Patent Application Laid-Open No.
2001-279287 - Patent Literature 2: Japanese Patent Application Laid-Open No.
2002-129182 - Patent Literature 3: Japanese Patent Application Laid-Open No.
08-302378 - Patent Literature 4: Japanese Patent Application Laid-Open No.
06-306384 -
EP 2522709 A1 relates to a lubricant composition comprising a lubricating base oil with a 100°C kinematic viscosity of 1 to 20 mm2/s, a viscosity index improver having a ratio in M1/M2 of 0.2 or greater, between the total area of the peaks between chemical shifts of 36 to 38 ppm M1 in the total area of the peaks between the chemical shifts of 64 to 66 ppm M2, with respect to the total area of all the peaks, in the spectrum obtained by 13C-NMR, further a friction modifier and an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate. -
US 2010/190671 A1 relates to an additive for reducing fuel consumption of a vehicle, comprising a comb polymer, comprising in the main chain repeat units which are derived from polyolefin-based macromonomers and repeat units which are derived from low molecular weight monomers for reducing the fuel consumption of vehicles. - However, it cannot be said that the conventional lubricating oils are not sufficient in fuel efficiency.
- For example, as a standard method for fuel efficiency, a reduction in the kinematic viscosity of the lubricating oil and an increase in the viscosity index (multi-grading by a combination of low viscosity base oils with viscosity index improvers), and blending of friction reducing agents are known. In the case of a reduction in viscosity, the lubrication performance is reduced under severe lubrication conditions (under high temperature high shear conditions) due to a reduction of the viscosity of the lubricating oil or the base oil that forms the lubricating oil, occurrence of failures such as wear, burning, and fatigue breaking is concerned. Moreover, for blending of friction reducing agents, ash-free friction modifiers and molybdenum friction modifiers are known, but there is demand for an oil with fuel efficiency superior to that of standard oils having theses friction reducing agents.
- To prevent deficits in the reduction in viscosity and give fuel efficiency while maintaining durability, it is effective to increase an HTHS viscosity at 150°C ("HTHS viscosity" is also referred to as "high temperature high shear viscosity") while reducing a kinematic viscosity at 40°C, a kinematic viscosity at 100°C, and an HTHS viscosity at 100°C; however, it is very difficult for the conventional lubricating oil to satisfy these requirements all.
- Because of recent progress in the engine technique, the HTHS viscosity at 150°C can be further reduced while maintaining the durability of the engine, and the kinematic viscosity can be reduced more significantly than ever. For further improvement in fuel efficiency, an engine oil having an HTHS viscosity at 150°C of lower than 2.6 mPa·s, which is the lower limit of the HTHS viscosity at 150°C of an SAE 0W-20 engine oil is developed and being used. However, because for the engine oil having an HTHS viscosity at 150°C of lower than 2.6 mPa·s, the lubrication state of the engine oil to be used is severer than ever, it is important to maintain the HTHS viscosity at 150°C reduced by usage at a constant level or more. Moreover, it is important to reduce the kinematic viscosity as much as possible while reducing the coefficient of friction in a boundary lubrication region.
- The present invention has been made in consideration of such circumstances, and an object of the present invention is to provide an engine oil composition excellent in fuel efficiency in which in an engine oil having an HTHS viscosity at 150°C of less than 2.6 mPa·s, a kinematic viscosity at 40°C and a kinematic viscosity at 100°C may be sufficiently reduced from the beginning of usage after usage for a long time, and an increase in a coefficient of friction in a boundary lubrication region may be sufficiently suppressed.
- To solve the above problems, the present invention provides an engine oil composition including a lubricating base oil having a kinematic viscosity at 100°C of 1 to 5 mm2/s, a poly(meth)acrylate viscosity index improver (A) containing a structural unit represented by the following formula (1) in a proportion of 30 to 90 mol%, a structural unit represented by the following Formula (3) in a proportion of 0.5 to 70 mol%, and having a PSSI in an ultrasonic shear test of 15 or less measured according to JASO M347-95 under the condition that only the volume of a sample is increased, wherein the viscosity index improver has a ratio of the molecular weight to the PSSI (Mw/PSSI) of 1 × 104 or more; and from 0.01% by mass to 0.1% by mass of molybdenum dithiocarbamate, based on the total amount of the lubricating oil composition in terms of the molybdenum element, as a friction modifier (B), wherein the engine oil composition has a kinematic viscosity at 100°C of 4 to 7 mm2/s, and an HTHS viscosity at 150°C of 2.4 mPa·s or less:
- It is preferable that the viscosity index improver (A) be a viscosity index improver having a PSSI of 10 or less.
- Here, the PSSI in the ultrasonic shear test in the present invention designates the reduction rate in the viscosity of the viscosity index improver evaluated according to JASO M347-95 (automatic transmission oil shear stability test method) under the condition where only the volume of a sample is increased. More specifically, it means a permanent shear stability index of a polymer (Permanent Shear Stability Index) obtained by adjusting an output with Standard oil A specified in the ASTM test method, performing a shear test at an amplitude of 28 µm, a vibration number of 10 KHz, an irradiation time of 10 minutes, and the volume of the sample of 60 mL, and calculating the measured kinematic viscosity. The PSSI is calculated from ((V1 - V2)/V1 × 100) (%) based on the viscosity (V1) at 100°C per amount of the viscosity index improver to be added which is measured before the shear test and the viscosity (V2) at 100°C per amount of the viscosity index improver to be added which is measured after the shear test.
- As above, according to the present invention, an engine oil composition excellent in fuel efficiency in which in an engine oil having an HTHS viscosity at 150°C of 2.4 mPa·s or less, the kinematic viscosity at 40°C and the kinematic viscosity at 100°C may be sufficiently reduced from the beginning of usage after usage for a long time, and an increase in the coefficient of friction in the boundary lubrication region may be sufficiently suppressed can be provided.
- Moreover, the engine oil composition according to the present invention may be suitably used not only for gasoline engines, diesel engines, gas engines, and the like for bicycles, automobiles, power generation, cogeneration, and the like but also for a variety of engines using fuels having a sulfur content of 50 mass ppm or less. The lubricating oil composition according to the present invention is also useful for a variety of engines for ships and outboard motors.
- Hereinafter, suitable Embodiment of the present invention will be described in detail.
- The engine oil composition according to the present embodiment includes a lubricating base oil having a kinematic viscosity at 100°C of 1 to 5 mm2/s, a poly(meth)acrylate viscosity index improver (A) containing one or two more of structural unit represented by the following formula (1) in a proportion of 30 to 90 mol% and having a PSSI in an ultrasonic shear test of 15 or less, and a friction modifier (B).
- In the engine oil composition according to the present embodiment, a lubricating base oil having a kinematic viscosity at 100°C of 1 to 5 mm2/s (hereinafter referred to as a "lubricating base oil according to the present embodiment") is used.
- Examples of the lubricating base oil according to the present embodiment include those having a kinematic viscosity at 100°C of 1 to 5 mm2/s among paraffin mineral oils, normal paraffin base oils, and isoparaffin base oils obtainable by refining a lubricating oil fraction obtainable by normal pressure distillation and/or reduced pressure distillation of a crude oil using one or two or more refining treatments selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, and the like.
- Preferable examples of the lubricating base oil according to the present embodiment may include base oils obtainable by using the base oils (1) to (8) shown below as the raw material, and refining the raw material oil and/or a lubricating oil fraction recovered from the raw material oil by a predetermined refining method to recover a lubricating oil fraction:
- (1) Distilled oil obtainable by normal pressure distillation of a paraffinic crude oil and/or a mixed-base crude oil,
- (2) Distilled oil obtainable by reduced pressure distillation of a paraffinic crude oil and/or a normal pressure distillation residue oil of a mixed-base crude oil (WVGO),
- (3) Waxes obtainable by a lubricating oil dewaxing step (such as slack wax) and/or synthetic waxes obtainable by a gas-to-liquid (GTL) process or the like (such as Fischer-Tropsch wax and GTL wax),
- (4) One or two or more mixed oils selected from the base oils (1) to (3) and/or a mild hydrocracked oil of the mixed oil,
- (5) Two or more mixed oils selected from the base oils (1) to (4),
- (6) Deasphalted oil (DAO) of the base oil (1), (2), (3), (4) or (5),
- (7) Mild hydrocracked oil (MHC) of the base oil (6), and
- (8) Mixed oil of two or more selected from the base oils (1) to (7).
- For the predetermined refining method, hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; white clay refining with acid clay or activated clay; and chemical (acid or alkali) washing such as sulfuric acid washing and sodium hydroxide washing are preferable. In the present embodiment, among these refining methods, one method may be used alone, or two or more may be used in combination. If two or more refining methods are combined, the order is not particularly limited, and can be properly selected.
- Furthermore, for the lubricating base oil according to the present embodiment, a base oil selected from the base oils (1) to (8) or the following base oil (9) or (10) obtainable by performing a predetermined treatment on the lubricating oil fraction recovered from the base oil is particularly preferable:
- (9) Hydrocracking base oils obtainable by hydrocracking the base oil selected from the base oils (1) to (8) or the lubricating oil fraction recovered from the base oil, and performing a dewaxing treatment such as solvent dewaxing and catalytic dewaxing on the product or the lubricating oil fraction recovered from the product by distillation or the like, or performing distillation after the dewaxing treatment, and
- (10) Hydrogenation isomerized base oils obtainable by hydrogenation isomerizing the base oil selected from the base oils (1) to (8) or the lubricating oil fraction recovered from the base oil, and performing a dewaxing treatment such as solvent dewaxing and catalytic dewaxing on the product or the lubricating oil fraction recovered from the product by distillation or the like, or performing distillation after the dewaxing treatment.
- In production of the lubricating base oil (9) or (10), a solvent refining treatment and/or a hydrofinishing step may be included as preferably steps when necessary.
- The catalyst used in the hydrocracking and hydrogenation isomerization is not particularly limited, and hydrocracking catalysts in which a carrier is a composite oxide having cracking activity (such as silica alumina, alumina boria, and silica zirconia) or one or more of the composite oxides in combination bounded by a binder, and a metal having a hydrogenation activity (such as one or more metals in Groups VIa and VIII in the periodic table) is carried to the carrier; or hydrogenation isomerization catalysts in which a metal containing at least one metal among metals in Group VIII and having a hydrogenation activity is carried to a carrier containing zeolite (such as ZSM-5, zeolite beta, and SAPO-11) are preferably used. The hydrocracking catalyst and the hydrogenation isomerization catalyst may be used in combination by stacking or mixing.
- The reaction conditions in hydrocracking and hydrogenation isomerization are not particularly limited, and a hydrogen partial pressure of 0.1 to 20 MPa, an average reaction temperature of 150 to 450°C, an LHSV of 0.1 to 3.0 hr-1, and the hydrogen/oil ratio of 50 to 20000 scf/b are preferred.
- The kinematic viscosity at 100°C of the lubricating base oil according to the present embodiment needs to be 5 mm2/s or less, preferably 4.5 mm2/s or less, more preferably 4 mm2/s or less, still more preferably 3.8 mm2/s or less, particularly preferably 3.7 mm2/s or less, and most preferably 3.6 mm2/s or less. The kinematic viscosity at 100°C needs to be 1 mm2/s or more. It is preferable that the kinematic viscosity at 100°C be 1.5 mm2/s or more. The kinematic viscosity at 100°C is more preferably 2 mm2/s or more, still more preferably 2.5 mm2/s or more, and particularly preferably 3 mm2/s or more. The kinematic viscosity at 100°C here designates the kinematic viscosity at 100°C specified in ASTM D-445. In the case where the kinematic viscosity at 100°C of the lubricating base oil exceeds 5 mm2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained. At a kinematic viscosity of 1 mm2/s or less, formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition may be increased.
- The kinematic viscosity at 40°C of the lubricating base oil according to the present embodiment is preferably 40 mm2/s or less, more preferably 30 mm2/s or less, still more preferably 25 mm2/s or less, particularly preferably 20 mm2/s or less, and most preferably 17 mm2/s or less. The kinematic viscosity at 40°C is preferably 6.0 mm2/s or more, more preferably 8.0 mm2/s or more, still more preferably 10 mm2/s or more, particularly preferably 12 mm2/s or more, and most preferably 14 mm2/s or more. In the case where the kinematic viscosity at 40°C of the lubricating base oil exceeds 40 mm2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained. At a kinematic viscosity of 6.0 mm2/s or less, formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition may be increased.
- It is preferable that the viscosity index of the lubricating base oil according to the present embodiment be 100 or more. The viscosity index is more preferably 105 or more, still more preferably 110 or more, particularly preferably 115 or more, and most preferably 120 or more. If the viscosity index is less than 100, not only viscosity-temperature properties, heat and oxidation stability, and anti-volatilization are reduced, but also the coefficient of friction tends to be increased; and resistance against wear tends to be reduced.
- The viscosity index in the present invention means the viscosity index measured according to JIS K 2283-1993.
- It is preferable that the lubricating base oil in the engine oil composition according to the present embodiment be a mixture of a first lubricating base oil component having a kinematic viscosity at 100°C of 3.5 mm2/s or more and having a viscosity index of 120 or more and a second lubricating base oil component having a kinematic viscosity at 100°C of less than 3.5 mm2/s. By using the mixture of the first lubricating base oil component and the second lubricating base oil component, high viscosity temperature properties may be given to improve fuel efficiency more significantly.
- The density (ρ15) at 15°C of the first lubricating base oil component used in the engine oil composition according to the present embodiment is preferably 0.860 or less, more preferably 0.850 or less, still more preferably 0.840 or less, and particularly preferably 0.822 or less.
- The density at 15°C in the present invention means a density measured at 15°C according to JIS K 2249-1995.
- The pour point of the first lubricating base oil component used in the engine oil composition according to the present embodiment is preferably -10°C or less, more preferably -12.5°C or less, still more preferably -15°C or less, and particularly preferably -20°C or less. If the pour point exceeds the upper limit value, the fluidity at a low temperature of the entire lubricating oil using the lubricating base oil tends to be reduced. The pour point in the present invention means the pour point measured according to JIS K 2269-1987.
- It is preferable that the kinematic viscosity at 100°C of the first lubricating base oil component used in the engine oil composition according to the present embodiment be 5 mm2/s or less. The kinematic viscosity is more preferably 4.5 mm2/s or less, still more preferably 4.0 mm2/s or less, and particularly preferably 3.9 mm2/s or less. It is preferable that the kinematic viscosity at 100°C be 3.5 mm2/s or more. The kinematic viscosity is more preferably 3.6 mm2/s or more, still more preferably 3.7 mm2/s or more, and particularly preferably 3.8 mm2/s or more. If the kinematic viscosity at 100°C exceeds 5 mm2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained. At a kinematic viscosity less than 3.5 mm2/s, formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the engine oil composition may be increased.
- The kinematic viscosity at 40°C of the first lubricating base oil component used in the engine oil composition according to the present embodiment is preferably 40 mm2/s or less, more preferably 30 mm2/s or less, still more preferably 25 mm2/s or less, particularly preferably 20 mm2/s or less, and most preferably 17 mm2/s or less. The kinematic viscosity at 40°C is preferably 6.0 mm2/s or more, more preferably 8.0 mm2/s or more, still more preferably 10 mm2/s or more, particularly preferably 12 mm2/s or more, and most preferably 14 mm2/s or more. In the case where the kinematic viscosity at 40°C exceeds 40 mm2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained. At a kinematic viscosity of 6.0 mm2/s or less, formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition may be increased.
- It is preferable that the viscosity index of the first lubricating base oil component used in the engine oil composition according to the present embodiment be 100 or more. The viscosity index is more preferably 110 or more, still more preferably 120 or more, particularly preferably 130 or more, and most preferably 140 or more. The viscosity index is preferably 170 or less, more preferably 160 or less, still more preferably 155 or less, and particularly preferably 150 or less. If the viscosity index is less than 100, not only viscosity-temperature properties, heat and oxidation stability, and anti-volatilization are reduced, but also the coefficient of friction tends to be increased; and resistance against wear tends to be reduced. If the viscosity index exceeds 170, low temperature viscosity tends to be increased to reduce the fuel efficiency at low oil temperatures. Moreover, startability tends to be reduced.
- The density (ρ15) at 15°C of the second lubricating base oil component used in the engine oil composition according to the present embodiment is preferably 0.860 or less, more preferably 0.850 or less, still more preferably 0.840 or less, and particularly preferably 0.835 or less.
- The pour point of the second lubricating base oil component used in the engine oil composition according to the present embodiment is preferably -10°C or less, more preferably -12.5°C or less, still more preferably -15°C or less, and particularly preferably -20°C or less. If the pour point exceeds the upper limit value, the fluidity at a low temperature of the entire lubricating oil using the lubricating base oil tends to be reduced.
- It is preferable that the kinematic viscosity at 100°C of the second lubricating base oil component used in the engine oil composition according to the present embodiment be less than 3.5 mm2/s. The kinematic viscosity is more preferably 3.4 mm2/s or less, and still more preferably 3.3 mm2/s or less. It is preferable that the kinematic viscosity at 100°C be 2 mm2/s or more, and the kinematic viscosity is more preferably 2.5 mm2/s or more, and still more preferably 3.0 mm2/s or more. If the kinematic viscosity at 100°C exceeds 3.5 mm2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained. At a kinematic viscosity less than 2 mm2/s, formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition may be increased.
- The kinematic viscosity at 40°C of the second lubricating base oil component used in the engine oil composition according to the present embodiment is preferably 20 mm2/s or less, more preferably 18 mm2/s or less, still more preferably 16 mm2/s or less, and particularly preferably 14 mm2/s or less. The kinematic viscosity at 40°C is preferably 6.0 mm2/s or more, more preferably 8.0 mm2/s or more, still more preferably 10 mm2/s or more, particularly preferably 12 mm2/s or more, and most preferably 13 mm2/s or more. If the kinematic viscosity at 40°C exceeds 20 mm2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency may not be obtained. At a kinematic viscosity of 6.0 mm2/s or less, formation of an oil film in a lubrication place is insufficient; for this reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition may be increased.
- It is preferable that the viscosity index of the second lubricating base oil component used in the engine oil composition according to the present embodiment be 100 or more. The viscosity index is more preferably 105 or more, and still more preferably 110 or more. The viscosity index is preferably 160 or less, more preferably 150 or less, still more preferably 140 or less, and particularly preferably 135 or less. If the viscosity index is less than 100, not only viscosity-temperature properties, heat and oxidation stability, and anti-volatilization are reduced, but also the coefficient of friction tends to be increased. Moreover, resistance against wear tends to be reduced. If the viscosity index exceeds 160, low temperature viscosity tends to be increased to reduce the fuel efficiency at low oil temperatures. Moreover, startability tends to be reduced.
- The sulfur content of the lubricating base oil used in the present embodiment depends on the sulfur content of the raw material. For example, in the case where a raw material containing substantially no sulfur as a synthetic wax component obtainable by the Fischer-Tropsch reaction or the like is used, the lubricating base oil containing substantially no sulfur may be obtainable. In the case where a raw material containing sulfur such as slack wax produced in the refining process of the lubricating base oil and microcrystalline wax produced in the wax refining process thereof is used, the sulfur content of the lubricating base oil to be obtainable is usually 100 mass ppm or more. In the lubricating base oil according to the present embodiment, from the viewpoint of further improvement in heat and oxidation stability and a reduction in sulfur, it is preferable that the sulfur content be 100 mass ppm or less, it is more preferable that the sulfur content be 50 mass ppm or less, it is still more preferable that the sulfur content be 10 mass ppm or less, and it is particularly preferable that the sulfur content be 5 mass ppm or less.
- The nitrogen content of the lubricating base oil used in the present embodiment is preferably 7 mass ppm or less, more preferably 5 mass ppm or less, and still more preferably 3 mass ppm or less. If the nitrogen content exceeds 5 mass ppm, heat and oxidation stability tends to be reduced. The nitrogen content in the present invention means the nitrogen content measured according to JIS K 2609-1990.
- It is preferable that %Cp of the lubricating base oil used in the present embodiment be 70 or more. %Cp is preferably 80 or more, more preferably 85 or more, still more preferably 87 or more, and particularly preferably 90 or more. %Cp is preferably 99.9 or less, more preferably 98 or less, still more preferably 96 or less, and particularly preferably 94 or less. If %Cp of the lubricating base oil is less than the lower limit value, viscosity-temperature properties, heat and oxidation stability, and friction properties tend to be reduced; furthermore, if an additive is blended with the lubricating base oil, the effect of the additive tends to be reduced. If %Cp of the lubricating base oil exceeds the upper limit value, the solubility of the additive tends to be reduced.
- It is preferable that %CA of the lubricating base oil used in the present embodiment be 2 or less. %CA is more preferably 1 or less, still more preferably 0.8 or less, and particularly preferably 0.5 or less. If %CA of the lubricating base oil exceeds the upper limit value, viscosity-temperature properties, heat and oxidation stability, and fuel efficiency tend to be reduced.
- It is preferable that %CN of the lubricating base oil used in the present embodiment be 30 or less. %CN is preferably 25 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 10 or less. %CN is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and particularly preferably 6 or more. If %CN of the lubricating base oil exceeds the upper limit value, viscosity-temperature properties, heat and oxidation stability, and friction properties tend to be reduced. If %CN is less than the lower limit value, the solubility of the additive tends to be reduced.
- %Cp, %CN, and %CA in the present invention mean the percentage of the number of paraffin carbon atoms to the total number of carbon atoms, the percentage of the number of naphthene carbon atoms to the total number of carbon atoms, and the percentage of the number of aromatic carbon atoms to the total number of carbon atoms, respectively, which are determined by the method (n-d-M ring analysis) according to ASTM D 3238-85. Namely, preferable ranges of %CP, %CN, and %CA above described are based on the values determined by the method above; for example, even in a lubricating base oil containing no naphthene content, %CN determined by the method may indicate a value more than zero.
- The content of the saturates in the lubricating base oil used in the present embodiment is preferably 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more based on the total amount of the lubricating base oil; the proportion of the cyclic saturates in the saturates is preferably 40% by mass or less, preferably 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 21% by mass or less. The proportion of the cyclic saturates in the saturates is preferably 5% by mass or more, and more preferably 10% by mass or more. If the content of the saturates and the proportion of the cyclic saturates in the saturates each satisfy the conditions above, viscosity-temperature properties and heat and oxidation stability may be improved; if an additive is blended with the lubricating base oil, the function of the additive may be demonstrated at a higher level while the additive is sufficiently stably dissolved in the lubricating base oil. Furthermore, according to the present embodiment, the friction properties of the lubricating base oil itself may be improved; as a result, an improvement in a friction reducing effect and thus an improvement in energy saving properties may be attained.
- The saturates in the present invention are measured by the method described in ASTM D 2007-93 above.
- In the method for separating the saturates or in composition analysis of the cyclic saturates, a noncyclic saturates, or the like, similar methods that give similar results can be used. Examples of the methods, besides the method above, can include the method described in ASTM D 2425-93, the method described in ASTM D 2549-91, the method by a high performance liquid chromatography (HPLC), or the modified methods thereof.
- The aromatic content of the lubricating base oil used in the present embodiment is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less based on the total amount of the lubricating base oil, and is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more based on the total amount of the lubricating base oil. If the content of the aromatics exceeds the upper limit value, viscosity-temperature properties, heat and oxidation stability, friction properties, anti-volatilization, and low temperature viscosity properties tend to be reduced; if an additive is blended with the lubricating base oil, the effect of the additive tends to be reduced. The lubricating base oil according to the present embodiment may be a lubricating base oil containing no aromatics, but the content of the aromatics in the range of the lower limit value or more can further enhance the solubility of the additive.
- The aromatic content in the present invention means the value measured according to ASTM D 2007-93. The aromatics usually include alkylbenzene and alkylnaphthalene; anthracene, phenanthrene, and alkylated products thereof; compounds in which four or more benzene rings are condensed; and aromatic compounds having a heteroatom such as pyridines, quinolines, phenols, and naphthols.
- A synthetic base oil may be used as the lubricating base oil according to the present embodiment. Examples of the synthetic base oil are base oils having a kinematic viscosity at 100°C of 1 to 20 mm2/s. The examples include poly-α-olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffin, alkylbenzene, alkylnaphthalene, diesters (such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, and di-2-ethylhexylcebacate), polyol esters (such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, and pentaerythritol pelargonate), polyoxyalkylene glycol, dialkyldiphenyl ether, polyphenyl ether; among these, poly-α-olefins are preferable. Examples of poly-α-olefins typically include oligomers or co-oligomers of α-olefins having a carbon number of 2 to 32, preferably a carbon number of 6 to 16 (such as 1-octene oligomer, decene oligomer, and ethylene-propylene co-oligomer) and hydrides thereof.
- The method for producing poly-α-olefin is not particularly limited, and examples thereof include a method for polymerizing α-olefin in the presence of a polymerization catalyst containing a complex of aluminum trichloride or boron trifluoride, water, an alcohol (such as ethanol, propanol, and butanol), and carboxylic acid or an ester thereof, such as a Friedel-Crafts catalyst.
- In the engine oil composition according to the present embodiment, the lubricating base oil according to the present embodiment may be used alone, or the lubricating base oil according to the present embodiment may be used in combination with one or two or more of other base oils. In the case where the lubricating base oil according to the present embodiment is used in combination with the other base oil(s), it is preferable that the proportion of the lubricating base oil according to the present embodiment in the mixed base oils be 30% by mass or more, it is more preferable that the proportion of the lubricating base oil according to the present embodiment in the mixed base oils be 50% by mass or more, and it is still more preferable that the proportion of the lubricating base oil according to the present embodiment in the mixed base oils be 70% by mass or more.
- The other base oils used in combination with the lubricating base oil according to the present embodiment is not particularly limited, and examples of a mineral oil-based base oil include solvent refined mineral oils, hydrocracked mineral oils, hydrorefined mineral oils, and solvent dewaxed base oils whose kinematic viscosity at 100°C is 5 mm2/s or more and 100 mm2/s or less.
- Examples of the other synthetic base oils used in combination with the lubricating base oil according to the present embodiment include the synthetic base oils described above whose kinematic viscosity at 100°C is out of the range of 1 to 5 mm2/s.
- Moreover, the engine oil composition according to the present embodiment contains a poly(meth)acrylate viscosity index improver (A) (hereinafter referred to as "viscosity index improver according to the present embodiment" for convenience) containing one or two or more of the structural units represented by the following formula (1) in a proportion of 30 to 90 mol% and having the PSSI in the ultrasonic shear test of 15 or less. Thereby, the fuel efficiency, the maintenance of fuel efficiency, and the durability may be enhanced more significantly compared to the case where the present configuration is not included. The compound has any form as long as the compound satisfies the condition that the compound is a poly(meth)acrylate viscosity index improver having the structural unit represented by the following formula (1) in the proportion of 30 to 90 mol% and having the PSSI in the ultrasonic shear test of 15 or less. Specific examples of the compound are non-dispersive or dispersive poly(meth)acrylate viscosity index improvers, (meth)acrylate-olefin copolymers, or a mixture thereof:
- R2 in the structural unit represented by the formula (1), as described above, is a linear or branched hydrocarbon group having a carbon number of 6 or less and may be one hydrocarbon group or a mixture of two or more thereof; R2 is preferably a linear or branched hydrocarbon having a carbon number of 4 or less, still more preferably a linear or branched hydrocarbon having a carbon number of 3 or less, and more preferably a hydrocarbon group having a carbon number of 2 or less.
- In the viscosity index improver according to the present embodiment, the proportion of the (meth)acrylate structural unit represented by the formula (1) in a polymer is 30 to 90 mol% as described above, preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, and particularly preferably 60 mol% or less. The proportion is preferably 32 mol% or more, more preferably 35 mol% or more, and still more preferably 40 mol% or more. At a proportion more than 90 mol%, the solubility in the base oil, the effect of improving viscosity temperature properties, and low temperature viscosity properties may be inferior; at a proportion less than 20 mol%, the effect of improving viscosity temperature properties may be inferior.
- Besides the (meth)acrylate structural unit represented by the formula (1), the viscosity index improver according to the present embodiment is a copolymer having (meth)acrylate structural unit. Such a copolymer is obtainable by copolymerizing one or two or more of monomers represented by the following formula (3) (hereinafter referred to as "Monomer (M-1)") and a monomer other than Monomer (M-1).
- R4 in the structural unit represented by the formula (3) is a linear or branched hydrocarbon group having a carbon number of 7 or more, preferably a linear or branched hydrocarbon having a carbon number of 10 or more, more preferably a linear or branched hydrocarbon having a carbon number of 15 or more, and still more preferably a branched hydrocarbon group having a carbon number of 18 or more. The upper limit of the hydrocarbon group represented as R4 is not particularly limited, and it is preferable that it be a linear or branched hydrocarbon group having a carbon number of 2000 or less. It is more preferably a linear or branched hydrocarbon having a carbon number of 500 or less, still more preferably a linear or branched hydrocarbon having a carbon number of 100 or less, particularly preferably a branched hydrocarbon having a carbon number of 50 or less, and most preferably a branched hydrocarbon having a carbon number of 25 or less.
- In the viscosity index improver according to the present embodiment, the (meth)acrylate structural unit represented by the formula (3) in the polymer may be one or two or more mixtures, and the proportion is from 0.5 to 70 mol%, the proportion is preferably 60 mol% or less, more preferably 50 mol% or less, particularly preferably 40 mol% or less, and most preferably 30 mol% or less. The proportion is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and particularly preferably 10 mol% or more. At a proportion more than 70 mol%, the effect of improving viscosity temperature properties and low temperature viscosity properties may be inferior; at a proportion less than 0.5 mol%, the effect of improving viscosity temperature properties may be inferior.
- It is suitable that the other monomers used in combination with Monomer (M-1) be one or two or more selected from the monomer represented by the following formula (4) (hereinafter referred to as "Monomer (M-3)") and the monomer represented by the following formula (5) (hereinafter referred to as "Monomer (M-4)"). A copolymer of Monomers (M-1) and (M-3) and/or (M-4) is the so-called dispersive poly(meth)acrylate viscosity index improver. The dispersive poly(meth)acrylate viscosity index improver may further contain Monomer (M-2) as the constitutional monomer.
- Examples of the alkylene group having a carbon number of 1 to 18 represented by R6 specifically may include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group (these alkylene groups may be linear or branched).
- Examples of the group represented by E1 specifically can include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, a morpholino group, a pyrrolyl group, a pyrrolino group, a pyridyl group, a methylpyridyl group, a pyrrolidinyl group, a piperidinyl group, a quinonyl group, a pyrrolidonyl group, a pyrrolidono group, an imidazolino group, and a pyrazino group.
- Examples of the group represented by E2 specifically can include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, a morpholino group, a pyrrolyl group, a pyrrolino group, a pyridyl group, a methylpyridyl group, a pyrrolidinyl group, a piperidinyl group, a quinonyl group, a pyrrolidonyl group, a pyrrolidono group, an imidazolino group, and a pyrazino group.
- Preferable examples of Monomers (M-3) and (M-4) specifically may include dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinyl pyridine, morpholinomethyl methacrylate, morpholinoethyl methacrylate, N-vinylpyrrolidone, and mixtures thereof.
- The copolymerization molar ratio of a copolymer of Monomer (M-1) and Monomers (M-2) to (M-4) is not particularly limited, and Monomer (M-1): Monomers (M-2) to (M-4) = 20:80 to 90:10 or so is preferable, and the ratio is more preferably 30:70 to 80:20, and still more preferably 40:60 to 70:30.
- The method for producing the viscosity index improver according to the present embodiment is not particularly limited, and examples thereof include a method in which using a control radical polymerization process, an alkyl methacrylate serving as an arm portion (polymerization chain of alkyl methacrylate) is polymerized, and the polyalkyl methacrylate is then reacted with a polyfunctional compound having two or more ethylenic unsaturated double bonds.
- The control radical polymerization process involves an atom transfer radical polymerization (ATRP) process, a reversible addition-fragmentation chain transfer (RAFT) process, or a nitroxide mediated polymerization process.
- The discussion on the polymer mechanism of the ATRP polymerization is shown in Matyjaszewski et al., Reaction scheme 11.1, p. 524; Reaction scheme 11.4, p. 566; Reaction scheme 11, 7, p. 571; Reaction scheme 11.8, p. 572; and Reaction scheme 11.9, p. 575.
- The discussion on the polymer mechanism of the RAFT polymerization is shown in Matyjaszewski et al., section 12.4.4, pp. 664 to 665.
- The detailed description of nitroxide mediated polymerization (Chapter 10, pp. 463 to 522), ATRP (Chapter 11, pp. 523 to 628), and RAFT (Chapter 12, pp. 629 to 690) are shown in "Handbook of Radical Polymerization" (Krzysztof Matyjaszewski and Thomas P. Davis, copyright 2002, published by John Wiley and Sons Inc. (hereinafter referred to as "Matyjaszewski et al.").
- The synthesis can be performed as a batch operation, a semi-batch operation, a continuous step, a feed step, or a bulk step. The synthesis may be performed in an emulsion, a solution, or a suspension.
- In the synthesis, by changing the amounts of an initiator and the polyfunctional compound having two or more ethylenic unsaturated double bonds to be used, the average molecular weight of the polymethacrylate or viscosity index improver to be produced may be adjusted.
- The reaction rate to the viscosity index improver using the synthesized arm portion is 70% or more, preferably 80% or more, and more preferably 85% or more based on the amount of the polymer reacted to become the viscosity index improver. If the reaction rate is low, the arm portion remains, and the molecular weight cannot be increased.
- The PSSI in the ultrasonic shear test (shear stability index) of the viscosity index improver according to the present embodiment is 15 or less, preferably 12 or less, more preferably 10 or less, and still more preferably 5 or less. If the PSSI in the ultrasonic shear test exceeds 15, shear stability is poor, and initial viscosity temperature properties and fuel efficiency are reduced in order to keep the kinematic viscosity and the HTHS viscosity after usage at a constant level or more.
- The PSSI (Permanent Shear Stability Index) of the viscosity index improver according to the present embodiment in a diesel injector method is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, particularly preferably 5 or less, and most preferably 3 or less. If the PSSI exceeds 20, shear stability is poor, and to keep the kinematic viscosity and the HTHS viscosity after usage at a constant level or more, the initial fuel efficiency may be reduced.
- The "PSSI in the diesel injector method" here means the permanent shear stability index of the polymer (Permanent Shear Stability Index) calculated based on the data measured by ASTM D 6278-02 (Test Method for Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus) in accordance with ASTM D 6022-01 (Standard Practice for Calculation of Permanent Shear Stability Index).
- It is preferable that the weight average molecular weight (MW) of the viscosity index improver according to the present embodiment be 100,000 or more, and the weight average molecular weight is more preferably 200,000 or more, still more preferably 300,000 or more, and particularly preferably 400,000 or more. It is preferable that the weight average molecular weight be 1,000,000 or less, and the weight average molecular weight is more preferably 900,000 or less, still more preferably 700,000 or less, and particularly preferably 600,000 or less. If the weight average molecular weight is less than 100,000, the effect of improving a viscosity index when the viscosity index improver is dissolved in the lubricating base oil is small; not only fuel efficiency and low temperature viscosity properties are inferior but also cost may increase. If the weight average molecular weight exceeds 1,000,000, the effect of increasing viscosity is excessively increased; not only fuel efficiency and low temperature viscosity properties are inferior, but also shear stability, the solubility in the lubricating base oil, and storage stability are reduced.
- The ratio of the weight average molecular weight of the viscosity index improver according to the present embodiment to the PSSI in the ultrasonic shear test (MW/PSSI) is 1.0 × 104 or more, and the ratio is more preferably 2.0 × 104 or more, still more preferably 5.0 × 104 or more, and particularly preferably 8.0 × 104 or more. If MW/PSSI is less than 1.0 × 104, fuel efficiency and low temperature startability, namely, viscosity temperature properties and low temperature viscosity properties may be reduced.
- It is preferable that the ratio of the weight average molecular weight to the PSSI in the diesel injector method of the viscosity index improver according to the present embodiment (MW/PSSI) be 1.0 × 104 or more, and the ratio is more preferably 2.0 × 104 or more, still more preferably 5.0 × 104 or more, and particularly preferably 8.0 × 104 or more. If MW/PSSI is less than 1.0 × 104, fuel efficiency and low temperature startability, namely, viscosity temperature properties and low temperature viscosity properties may be reduced.
- It is preferable that the ratio (MW/MN) of the weight average molecular weight (MW) to the number average molecular weight (MN) of the viscosity index improver according to the present embodiment be 5.0 or less, and the ratio is more preferably 4.0 or less, still more preferably 3.5 or less, particularly preferably 3.0 or less, and most preferably 2.0 or less. It is preferable that MW/MN be 1.0 or more, and the ratio is more preferably 1.1 or more, and still more preferably 1.2 or more. If MW/MN is 4.0 or more or 1.0 or less, solubility and the effect of improving viscosity temperature properties may be reduced so that sufficient storage stability and fuel efficiency cannot be maintained.
- The hydrocarbon main chain ratio of the viscosity index improver according to the present embodiment is preferably 0.3 or less, more preferably 0.2 or less, more preferably 0.18 or less, still more preferably 0.16 or less, still more preferably 0.14 or less, particularly preferably 0.10 or less, and most preferably 0.05 or less. The hydrocarbon main chain ratio is preferably 0.005 or more, more preferably 0.01 or more, and still more preferably 0.02 or more. If the hydrocarbon main chain ratio exceeds 0.3, shear stability is reduced, and viscosity temperature properties and fuel efficiency may be reduced. If the hydrocarbon main chain ratio is less than 0.01, the solubility in the base oil is reduced, and viscosity temperature properties and fuel efficiency may be reduced.
- The "hydrocarbon main chain ratio" in the present invention means the proportion of the carbon number of the polymethacrylic acid main chain of the total number of carbon atoms of the molecule (the ratio, that is, the carbon number of the poly(meth)acrylic acid main chain/the total number of carbon atoms in the molecule).
- Because usually the poly(meth)acrylate viscosity index improver is a mixture of a plurality of polymers having different structures or molecular weights, the proportion is calculated as an average value of the poly(meth)acrylate viscosity index improver. If two or more poly(meth)acrylic acid chains are present in the molecule, a longer chain of these poly(meth)acrylic acid chains is the "poly(meth)acrylic acid main chain."
- For the poly(meth)acrylate viscosity index improver having a star structure (structure in which a plurality of arm portions as the poly(meth)acrylic acid chain is connected to a core portion, also referred to as a "star-like structure"), the influences of the core portion is small, and the core portion is excluded from the calculation. Usually the molecular weight of each arm portion is substantially equal, and the weight average molecular weight of the arm portion measured by GPC analysis (standard substance: polystyrene) is used in calculation of the carbon number of the arm portion in the main chain.
- Specifically, first, from the weight average molecular weight measured by GPC analysis (standard substance: polystyrene), the blending ratio of monomers or the weight average molecular weight of the arm portion measured by GPC analysis (standard substance: polystyrene) and the blending ratio of monomers, the average polymerization number (A1) of each monomer in the molecule is calculated. From A1, the total carbon number (B1) and the carbon number (C1) of the polymethacrylic acid main chain in one molecule are calculated, and C1/B1 is calculated. C1/B1 is the hydrocarbon main chain ratio.
- For the poly(meth)acrylate viscosity index improver having a star structure, the number of arm portions (D) defined by the number average molecular weight of the poly(meth)acrylate viscosity index improver/the number average molecular weight of the arm portion is calculated, and C1/(B1 × D) is calculated. C1/(B1 × D) is the hydrocarbon main chain ratio of the poly(meth)acrylate viscosity index improver having a star structure.
- The content of the viscosity index improver according to the present embodiment is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, still more preferably 1 to 30% by mass, particularly preferably 5 to 20% by mass based on the total amount of the composition. If the content of the viscosity index improver is less than 0.1% by mass, the effect of improving the viscosity index and the effect of reducing the viscosity of a product are reduced, and fuel efficiency may not be improved. At a content more than 50% by mass, the cost of the product is significantly increased, and the viscosity of the base oil needs to be reduced; for this reason, the lubrication performance under severe lubrication conditions (high temperature high shear conditions) may be reduced, causing deficits such as wear, seizure, and fatigue breaking.
- Besides the viscosity index improver according to the present embodiment, the engine oil composition according to the present embodiment may further contain a non-dispersive or dispersive poly(meth)acrylate, a non-dispersive or dispersive ethylene-α-olefin copolymer or a hydride thereof, polyisobutylene or a hydride thereof, a styrene-diene hydrogenation copolymer, a styrene-maleic anhydride ester copolymer, polyalkylstyrene and the like usually used.
- It is preferable that the content of the viscosity index improver in the engine oil composition according to the present embodiment be 0.1 to 50% by mass based on the total amount of the composition, and the content is preferably 0.5 to 20% by mass, more preferably 1.0 to 15% by mass, and still more preferably 1.5 to 12% by mass based on the total amount of the composition. If the content is less than 0.1% by mass, low temperature properties may be insufficient; if the content exceeds 50% by mass, the shear stability of the composition may be reduced.
- The engine oil composition according to the present embodiment contains molybdenum dithiocarbamate as a friction modifier (B). Thereby, fuel efficiency performance may be increased compared to the case where the present configuration is not included.
- In the engine oil composition according to the present embodiment, the content of the friction modifier is 0.01% by mass or more, and preferably 0.03% by mass or more, and 0.1% by mass or less, preferably 0.08% by mass or less, and particularly preferably 0.06% by mass or less based on the total amount of the lubricating oil composition in terms of the molybdenum element. If the content is less than 0.01% by mass, the effect of reducing friction by addition thereof tends to be insufficient, and the fuel efficiency and heat and oxidation stability of the lubricating oil composition tend to be insufficient. If the content exceeds 0.1% by mass, the effect corresponding to the content is not obtained, and the storage stability of the lubricating oil composition tends to be reduced.
- To further improve the performance, any additives usually used in the lubricating oil may be contained in the engine oil composition according to the present embodiment according to the purpose. Examples of such additives may include additives such as a metallic detergent besides the first and the second perbasic metal salts, an ash-free dispersant, an anti-wear agent (or extreme-pressure agent), an antioxidant, a corrosion inhibitor, a rust inhibitor, an antiemulsifier, a metal deactivator, and an antifoaming agent.
- If these additives are contained in the engine oil composition according to the present embodiment, it is preferable that the content of each additive be 0.01 to 10% by mass based on the total amount of the lubricating oil composition.
- The kinematic viscosity at 100°C of the engine oil composition according to the present embodiment is 4 to 7 mm2/s, and particularly preferably 6.8 mm2/s or less. The kinematic viscosity at 100°C of the engine oil composition according to the present embodiment is preferably 4.5 mm2/s or more, more preferably 5.0 mm2/s or more, still more preferably 5.5 mm2/s or more, particularly preferably 6.0 mm2/s or more. The kinematic viscosity at 100°C here designates a kinematic viscosity at 100°C specified in ASTM D-445. If the kinematic viscosity at 100°C is less than 4 mm2/s, insufficient lubrication may be caused; at a kinematic viscosity more than 12 mm2/s, necessary low temperature viscosity and sufficient fuel efficiency performance may not be obtainable.
- It is preferable that the kinematic viscosity at 40°C of the engine oil composition according to the present embodiment be 4 to 50 mm2/s, and the kinematic viscosity is preferably 40 mm2/s or less, more preferably 35 mm2/s or less, particularly preferably 30 mm2/s or less, and most preferably 28 mm2/s or less. The kinematic viscosity at 40°C of the engine oil composition according to the present embodiment is preferably 15 mm2/s or more, more preferably 18 mm2/s or more, still more preferably 20 mm2/s or more, particularly preferably 22 mm2/s or more, and most preferably 25 mm2/s or more. The kinematic viscosity at 40°C here designates a kinematic viscosity at 40°C specified in ASTM D-445. If the kinematic viscosity at 40°C is less than 4 mm2/s, insufficient lubrication may be caused; at a kinematic viscosity more than 50 mm2/s, necessary low temperature viscosity and sufficient fuel efficiency performance may not be obtainable.
- It is preferable that the viscosity index of the engine oil composition according to the present embodiment be in the range of 140 to 400, and the viscosity index is preferably 180 or more, more preferably 190 or more, still more preferably 200 or more, particularly preferably 210 or more, and most preferably 215 or more. If the viscosity index of the lubricating oil composition is less than 140, it may be difficult to improve fuel efficiency while maintaining the HTHS viscosity at 150°C, and to reduce the low temperature viscosity at -35°C. If the viscosity index of the lubricating oil composition exceeds 400 and more, evaporation properties may be reduced, and deficits due to insufficient solubility of the additive and matching properties with a seal material may be caused.
- It is preferable that the HTHS viscosity at 100°C of the engine oil composition according to the present embodiment be 5.5 mPa·s or less, and the HTHS viscosity is more preferably 5.0 mPa·s or less, still more preferably 4.7 mPa·s or less, particularly preferably 4.5 mPa·s or less, and most preferably 4.4 mPa·s or less. The HTHS viscosity is preferably 3.0 mPa·s or more, still more preferably 3.5 mPa·s or more, particularly preferably 4.0 mPa·s or more, and most preferably 4.1 mPa·s or more. The HTHS viscosity at 100°C in the present invention designates a high temperature high shear viscosity at 100°C specified in ASTM D4683. If the HTHS viscosity at 100°C is less than 3.0 mPa·s, insufficient lubrication may be caused; at an HTHS viscosity more than 5.5 mPa·s, necessary low temperature viscosity and sufficient fuel efficiency performance may not be obtainable.
- The HTHS viscosity at 150°C of the engine oil composition according to the present embodiment is 2.4 mPa·s or less. The HTHS viscosity is preferably 2.0 mPa·s or more, more preferably 2.1 mPa·s or more, still more preferably 2.2 mPa·s or more, and particularly preferably 2.3 mPa·s or more. The HTHS viscosity at 150°C here designates a high temperature high shear viscosity at 150°C specified in ASTM D4683. If the HTHS viscosity at 150°C is less than 2.0 mPa·s, insufficient lubrication may be caused; at an HTHS viscosity more than 2.6 mPa·s, sufficient fuel efficiency performance may not be obtainable.
- It is preferable that the ratio of the HTHS viscosity at 150°C to HTHS viscosity at 100°C of the engine oil composition according to the present embodiment (HTHS viscosity at 150°C/HTHS viscosity at 100°C) be 0.50 or more, and the ratio is more preferably 0.52 or more, still more preferably 0.53, and particularly preferably 0.54 or more. If the ratio is less than 0.50, necessary low temperature viscosity and sufficient fuel efficiency performance may not be obtainable.
- The engine oil composition according to the present embodiment may sufficiently reduce the kinematic viscosity at 40°C, kinematic viscosity at 100°C and HTHS viscosity at 100°C in an engine oil having an HTHS viscosity at 150°C of less than 2.6 mPa·s, may sufficiently suppress an increase in the coefficient of friction in the boundary lubrication region, and has high fuel efficiency. The lubricating oil composition according to the present embodiment having such high properties may be suitably used as energy saving engine oils such as energy saving gasoline engine oils and energy saving diesel engine oils.
- Hereinafter, the present invention will be more specifically described based on Examples and Comparative Example, but the present invention will not be limited to Examples below.
- To a 300 ml 5-necked separable flask having an anchor metallic stirring blade (with a vacuum seal), a Dimroth condenser, a 3-necked cock for introducing nitrogen, and a sample introduction port mounted thereon, 25.2 parts by mass of methyl methacrylate, 36.5 parts by mass of methacrylate in which R4 in the formula (3) was an alkyl group having a carbon number of 18, and 120 parts by mass of a hydrocarbon solvent (SAE10) as a solvent were placed, and a uniform solution was prepared under stirring. The solution was cooled to 0°C with an ice bath, and vacuum degassing/nitrogen purging of the reaction system was performed 5 times using a diaphragm pump. Under a nitrogen stream, 0.27 parts by mass of azobisisobutyronitrile (AIBN) as a radical initiator, 0.013 parts by mass of 1,4-cyclohexadiene, and 0.11 parts by mass of iodine were charged from the sample introduction port; then, polymerization was performed under a nitrogen atmosphere at a solution temperature of 80°C for 12 hours to prepare an arm molecule solution.
- As a result of GPC analysis (standard substance: polystyrene), the weight average molecular weight of the obtained arm molecule was 87400, the number average molecular weight (Mn) was 62000, and the degree of dispersion (Mw/Mn) was 1.41.
- To the arm solution, 0.07 parts by mass of azobisisobutyronitrile (AIBN) and 2.14 parts by mass of ethylene glycol dimethacrylate were added, and polymerization was performed under a nitrogen atmosphere at a solution temperature of 80°C for 12 hours to prepare a solution of a target star polymer (hereinafter referred to as "Non-dispersive PMA viscosity index improver A-1").
- As a result of GPC analysis (standard substance: polystyrene), the weight average molecular weight (Mw) of the obtained Non-dispersive PMA viscosity index improver A-1 was 570000, the number average molecular weight (Mn) was 470000, the degree of dispersion (Mw/Mn) was 1.23, PSSI was 10.8, and Mw/PSSI was 5.3 × 104. The arm conversion rate of the Non-dispersive PMA viscosity index improver A-1 was 64% by mass, the average number of arms was 8, and the hydrocarbon main chain ratio was 0.025.
-
- The weight average molecular weight and the number average molecular weight are the weight average molecular weight and the number average molecular weight in terms of polystyrene measured by using an HLC-8220 GPC apparatus made by Tosoh Corporation having 3 TSKgel Super MultiPore HZ-M columns made by Tosoh Corporation (4.6 mm ID × 15 cm) in series and tetrahydrofuran as a solvent at a temperature of 40°C, a flow rate of 0.35 mL/min, a sample concentration of 1% by mass, an amount of sample injection of 5 µL with a detector deference refractive index meter (RI).
- A star polymer (hereinafter referred to as "Non-dispersive PMA viscosity index improver A-2") was synthesized in the same manner as in Synthesis Example 1 except that instead of the arm molecule solution in Synthesis Example 1, an arm molecule solution containing an arm molecule including 70 mol% methyl methacrylate and 30 mol% methacrylate in which R4 in the formula (4) was an alkyl group having 18 carbon atoms (weight average molecular weight: 49600, number average molecular weight (Mn): 40000, degree of dispersion (Mw/Mn): 1.24) was used.
- The Mw of the obtained non-dispersive PMA viscosity index improver A-2 was 370000, Mn was 320000, Mw/Mn was 1.15, PSSI was 4.5, Mw/PSSI was 8.2 × 104, and the hydrocarbon main chain ratio was 0.025.
- A star polymer (hereinafter referred to as "Non-dispersive PMA viscosity index improver A-3") was synthesized in the same manner as in Synthesis Example 1 except that instead of the arm molecule solution in Synthesis Example 1, an arm molecule solution containing an arm molecule including 70 mol% methyl methacrylate and 30 mol% methacrylate in which R4 in the formula (4) was an alkyl group having 18 carbon atoms (weight average molecular weight: 54000, number average molecular weight (Mn): 42000, degree of dispersion (Mw/Mn): 1.29) was used.
- The Mw of Non-dispersive PMA viscosity index improver A-3 obtained was 490000, Mn was 410000, Mw/Mn was 1.19, PSSI was 6.7, Mw/PSSI was 7.3 × 104, and the hydrocarbon main chain ratio was 0.020.
- In Examples 1 to 4, Illustrative Example 5, and 5 and Comparative Examples 1 to 5, base oils and additives shown below were used to prepare engine oil compositions having compositions shown in Table 2. The properties of Base oils O-1, O-2, and O-3 are shown in Table 1.
-
- O-1 (Base oil 1): mineral oil prepared by hydrocracking /hydrogenation isomerization of a n-paraffin containing oil
- O-2 (Base oil 2): hydrocracked mineral oil
- O-3 (Base oil 3): hydrocracked mineral oil
-
- A-1: non-dispersive PMA viscosity index improver prepared in Synthesis Example 1 (copolymer prepared by reacting 70 mol% methyl methacrylate, 30 mol% methacrylate in which R4 in the formula (3) was an alkyl group having a carbon number of 18, a small amount of a polymerization initiator, and ethylene glycol dimethacrylate. Mw = 570000, Mn = 470000, Mw/Mn = 1.23, PSSI in the ultrasonic shear test = 10.8, Mw/PSSI = 5.3 × 104, PSSI in the diesel injector method = 3.8, hydrocarbon main chain ratio = 0.025)
- A-2: non-dispersive PMA viscosity index improver prepared in Synthesis Example 2 (copolymer prepared by reacting 70 mol% methyl methacrylate, 30 mol% methacrylate in which R4 in the formula (3) was an alkyl group having a carbon number of 18, a small amount of a polymerization initiator, and ethylene glycol dimethacrylate. Mw = 370000, Mn = 320000, Mw/Mn = 1.15, PSSI in the ultrasonic shear test = 4.5, Mw/PSSI = 8.2 × 104, PSSI in the diesel injector method= 2.2, hydrocarbon main chain ratio = 0.025)
- A-3: non-dispersive PMA viscosity index improver prepared in Synthesis Example 3 (copolymer prepared by reacting 70 mol% methyl methacrylate, 30 mol% methacrylate in which R4 in the formula (3) was an alkyl group having a carbon number of 18, a small amount of a polymerization initiator, and ethylene glycol dimethacrylate. Mw = 490000, Mn = 410000, Mw/Mn = 1.19, PSSI in the ultrasonic shear test = 6.7, Mw/PSSI = 7.3 × 104, hydrocarbon main chain ratio = 0.020)
- a-1: dispersive PMA viscosity index improver (copolymer prepared by reacting 20 mol% methyl methacrylate, 80 mol% methacrylate in which R4 in the formula (3) was an alkyl group having a carbon number of 12 to 15, and small amounts of a dispersive group and a polymerization initiator. Mw = 300000, Mn = 70000, Mw/Mn = 4.0, PSSI in the ultrasonic shear test = 43, Mw/PSSI = 7.0 × 103, hydrocarbon main chain ratio = 0.13)
- a-2: dispersive PMA viscosity index improver (copolymer prepared by reacting 20 mol% methyl methacrylate, 80 mol% methacrylate in which R4 in the formula (3) was an alkyl group having a carbon number of 12 to 15, and small amounts of a dispersive group and a polymerization initiator. Mw = 80000, Mn = 30000, Mw/Mn = 2.7, PSSI in the ultrasonic shear test = 18, Mw/PSSI = 4.4 × 103, hydrocarbon main chain ratio = 0.13)
- a-3: non-dispersive PMA viscosity index improver (copolymer prepared by reacting 30 mol% methyl methacrylate, 70 mol% methacrylate in which R4 in the formula (3) was an alkyl group having a carbon number of 12 to 15, and a small amount of a polymerization initiator. Mw = 400000, Mn = 110000, Mw/Mn = 3.9, PSSI in the ultrasonic shear test = 49, Mw/PSSI = 8.2 × 103, hydrocarbon main chain ratio = 0.16)
- B-1: MoDTC (alkyl group chain length: C8/C13, Mo content: 10 mass%, sulfur content: 11 mass%)
- B-2: glycerol monooleate
- C-1: other additives (such as a succinimide dispersant, ZnDTP, an antioxidant, an anti-wear agent, a pour-point depressant, and an antifoaming agent).
- In the engine oil compositions in Examples 1 to 4, Illustrative Example 5, and Comparative Examples 1 to 4, the kinematic viscosity at 40°C or 100°C, the viscosity index, the HTHS viscosity at 100°C or 150°C, and the HTHS viscosity after the ultrasonic shear test were measured The obtained results are shown in Table 2.
- (1) Kinematic viscosity: ASTM D-445
- (2) Viscosity index: JIS K 2283-1993
- (3) HTHS viscosity: ASTM D-4683
- (4) Ultrasonic shear test: according to JASO M347-95, an output was adjusted with Standard oil A specified in the ASTM test method, and a shear test was performed at an amplitude of 28 µm, the vibration number of 10 KHz, an irradiation time of 10 minutes, and a sample volume of 60 mL. The PSSI was calculated from ((V1 - V2)/V1 × 100) (%) based on the viscosity (V1) at 100°C per amount of the viscosity index improver to be added which was measured before the shear test and the viscosity (V2) at 100°C per amount of the viscosity index improver to be added which was measured after the shear test.
- (5) Valve train motoring friction test: using an apparatus that could measure the friction torque of a pair of a cam and a tappet of a valve train in a direct-acting 4-cylinder engine, a friction torque at an oil temperature of 100°C and the number of rotation of 350 rpm was measured. A motoring friction improving rate where Comparative Example 5 was used as a standard oil was calculated.
- As shown in Table 2, the engine oil compositions in Examples 1 to 4 including all the components (A) and (B), whose kinematic viscosity at 100°C is 4 to 8 mm2/s, and whose HTHS viscosity at 150°C is adjusted to be less than 2.6 mPa·s show that kinematic viscosity and HTHS viscosity at 100°C are lower and fuel efficiency is higher than those of the engine oil compositions in Comparative Examples 1 to 3 in which HTHS viscosities at 150°C after the ultrasonic shear test are substantially the same and which do not include the component (A) and the engine oil composition whose HTHS viscosity at 150°C is adjusted to be 2.7 mPa·s. The motoring friction improving rate of the engine oil composition in Comparative Example 5 not containing the component (B) is significantly poor.
O-1 | O-2 | O-3 | |||
Base oil 1 | Base oil 2 | Base oil 3 | |||
Density | (15°C) | g/cm3 | 0.820 | 0.835 | 0.8320 |
Kinematic viscosity | (40°C) | mm2/s | 15.8 | 20.0 | 13.5 |
(100°C) | mm2/s | 3.85 | 4.29 | 3.27 | |
Viscosity index | 141 | 123 | 112 | ||
Pour point | °C | -22.5 | -17.5 | -22.5 | |
Aniline point | °C | 119 | 116 | 109 | |
Iodine number | 0.06 | 0.05 | 5.38 | ||
Sulfur content | massppm | <1 | <1 | <1 | |
Nitrogen content | massppm | <3 | <3 | <3 | |
n-d-M analysis | %CP | 93.3 | 80.7 | 72.6 | |
%CN | 6.7 | 19.3 | 23.4 | ||
%CA | 0 | 0 | 0 | ||
Separation by chromatography mass% | Saturate content | 99.6 | 99.7 | 99.6 | |
Aromatic content | 0.2 | 0.2 | 0.3 | ||
Resin content | 0.1 | 0.1 | 0.1 | ||
Recover rate | 99.9 | 100 | 100 | ||
Paraffin content based on saturate content | mass% | 87.1 | 53.8 | 50.7 | |
Naphthene content based on saturate content | mass% | 12.9 | 46.2 | 49.3 |
Base oil | Based on total amount of base oil | Example 1 | Example 2 | Example 3 | Example 4 | Illustrative Example 5 | Comparative Example 1 | Comparative Example 2 | Comparative Example 3 | Comparative Example 4 | Comparative Example 5 | ||
O-1 | Base oil 1 | % by mass | 50 | ||||||||||
O-2 | Base oil 2 | % by mass | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | ||
O-3 | Base oil 3 | % by mass | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | |
Viscosity of base oil (40°C) | mm2/s | 14.7 | 16.2 | 16.2 | 16.2 | 16.2 | 16.2 | 16.2 | 16.2 | 16.2 | 16.2 | ||
Viscosity of base oil (100°C) | 3.6 | 3.7 | 3.7 | 3.7 | 3.7 | 3.7 | 3.7 | 3.7 | 3.7 | 3.7 | |||
Viscosity index of base oil | 124 | 117 | 117 | 117 | 117 | 117 | 117 | 117 | 117 | 117 | |||
Additives | Based on total amount of composition | ||||||||||||
A-1 | Viscosity index improver 1 | % by mass | 9.3 | 8.5 | 8.8 | 11.3 | |||||||
A-2 | Viscosity index improver 2 | % by mass | 9.7 | ||||||||||
A-3 | Viscosity index improver 3 | % by mass | 9.5 | ||||||||||
a-1 | Viscosity index improver 4 | % by mass | 5.5 | 5.5 | |||||||||
a-2 | Viscosity index improver 5 | % by mass | 5.9 | ||||||||||
a-3 | Viscosity index improver 6 | % by mass | 5.8 | ||||||||||
B-1 | MoDTC | % by mass | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | |||
B-2 | Ester | % by mass | 0.5 | ||||||||||
C-1 | Other additives | % by mass | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | |
Results of evaluation | |||||||||||||
Kinematic viscosity | 40°C | mm2/s | 25.2 | 26.9 | 26.7 | 27.7 | 26.4 | 35.9 | 32.3 | 35.4 | 30.4 | 36.2 | |
100°C | mm2/s | 6.3 | 6.4 | 6.2 | 6.4 | 6.3 | 8.5 | 7.0 | 8.4 | 7.4 | 8.6 | ||
Viscosity index | 216 | 202 | 195 | 195 | 203 | 225 | 185 | 226 | 224 | 228 | |||
HTHS viscosity | 100°C | mPa·s | 4.30 | 4.37 | 4.57 | 4.49 | 4.35 | 5.00 | 4.95 | 5.51 | 4.79 | 4.97 | |
HTHS viscosity | 150°C | mPa·s | 2.34 | 2.35 | 2.33 | 2.33 | 2.35 | 2.48 | 2.36 | 2.50 | 2.70 | 2.48 | |
HTHS viscosity (150°C)/HTHS viscosity (100°C) | 0.54 | 0.54 | 0.51 | 0.52 | 0.54 | 0.50 | 0.48 | 0.45 | 0.56 | 0.50 | |||
HTHS viscosity after ultrasonic shear | 150°C | mPa·s | 2.30 | 2.30 | 2.30 | 2.30 | 2.30 | 2.30 | 2.30 | 2.30 | - | 2.30 | |
The motoring friction improving rate | % | 14 | 14 | - | - | - | - | - | - | - | 0 |
Claims (2)
- An engine oil composition comprising:a lubricating base oil having a kinematic viscosity at 100°C of 1 to 5 mm2/s;a poly(meth)acrylate viscosity index improver containing a structural unit represented by the following formula (1) in a proportion of 30 to 90 mol%, a structural unit represented by the following Formula (3) in a proportion of 0.5 to 70 mol%, and having a PSSI in an ultrasonic shear test of 15 or less measured according to JASO M347-95 under the condition that only the volume of a sample is increased; wherein the viscosity index improver has a ratio of a molecular weight to the PSSI(MW/PSSI) of 1 x 104 or more; andfrom 0.01% by mass to 0.1% by mass of molybdenum dithiocarbamate, based on the total amount of the lubricating oil composition in terms of the molybdenum element, as a friction modifier,wherein the engine oil composition has a kinematic viscosity at 100°C of 4 to 7 mm2/s, and an HTHS viscosity at 150°C of 2.4 mPa·s or less:
- The engine oil composition according to claim 1, wherein the viscosity index improver is a viscosity index improver having a PSSI in the ultrasonic shear test of 10 or less measured according to JASO M347-95 under the condition that only the volume of a sample is increased.
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EP2980193A4 (en) * | 2013-03-28 | 2016-11-16 | Jx Nippon Oil & Energy Corp | Fuel-efficient engine oil composition |
US10443013B2 (en) | 2014-09-17 | 2019-10-15 | Nippon Shokubai Co., Ltd. | Viscosity index improver, method for producing the same and lubricating oil composition |
US10759888B2 (en) | 2016-01-12 | 2020-09-01 | Kuraray Co., Ltd. | (Meth) acrylate polymers |
JP6992958B2 (en) * | 2016-03-25 | 2022-02-04 | 出光興産株式会社 | Lubricating oil composition, internal combustion engine, and method of lubricating internal combustion engine |
WO2018056316A1 (en) | 2016-09-21 | 2018-03-29 | 株式会社日本触媒 | Viscosity index improver and lubricant oil composition |
JP6749851B2 (en) | 2017-01-20 | 2020-09-02 | 出光興産株式会社 | Lubricating oil composition, method for producing lubricating oil composition, and transmission |
US20180258366A1 (en) * | 2017-03-08 | 2018-09-13 | Chevron Japan Ltd. | Low viscosity lubricating oil composition |
CN110869478A (en) * | 2017-06-27 | 2020-03-06 | 路博润公司 | Lubricating composition and method for internal combustion engine |
JP2020158784A (en) * | 2020-06-30 | 2020-10-01 | 出光興産株式会社 | Lubricant composition, internal combustion engine and lubrication method of internal combustion engine |
US11732207B2 (en) | 2020-08-31 | 2023-08-22 | Eneos Corporation | Lubricating oil composition for internal combustion engine |
US11987766B2 (en) | 2020-08-31 | 2024-05-21 | Eneos Corporation | Lubricating oil composition for internal combustion engine |
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JP4416261B2 (en) | 2000-03-29 | 2010-02-17 | 新日本石油株式会社 | Engine oil composition |
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DE102005041528A1 (en) * | 2005-08-31 | 2007-03-01 | Rohmax Additives Gmbh | Multi-arm star-shaped polymer for use as lubricating oil additive, e.g. viscosity modifier or dispersant, has at least three arms containing units derived from esters of higher alkanols and unsaturated carboxylic acids |
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