CN102365354A - 齿轮油组合物 - Google Patents
齿轮油组合物 Download PDFInfo
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- CN102365354A CN102365354A CN2010800156448A CN201080015644A CN102365354A CN 102365354 A CN102365354 A CN 102365354A CN 2010800156448 A CN2010800156448 A CN 2010800156448A CN 201080015644 A CN201080015644 A CN 201080015644A CN 102365354 A CN102365354 A CN 102365354A
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- oil
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- ester
- base oil
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- 239000000203 mixture Substances 0.000 title claims abstract description 84
- 239000012208 gear oil Substances 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 239000002199 base oil Substances 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- -1 SULPHOSUCCINIC ACID ESTER Chemical class 0.000 claims description 59
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- 239000003921 oil Substances 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 239000004711 α-olefin Substances 0.000 claims description 10
- 125000004437 phosphorous atom Chemical group 0.000 claims description 8
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims description 7
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 abstract 1
- 239000000446 fuel Substances 0.000 abstract 1
- 239000005078 molybdenum compound Substances 0.000 abstract 1
- 150000002752 molybdenum compounds Chemical class 0.000 abstract 1
- 102000013563 Acid Phosphatase Human genes 0.000 description 25
- 108010051457 Acid Phosphatase Proteins 0.000 description 25
- GZCWLCBFPRFLKL-UHFFFAOYSA-N 1-prop-2-ynoxypropan-2-ol Chemical compound CC(O)COCC#C GZCWLCBFPRFLKL-UHFFFAOYSA-N 0.000 description 23
- 230000000694 effects Effects 0.000 description 16
- 239000002585 base Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- TYQTYRXEMJXFJG-UHFFFAOYSA-N phosphorothious acid Chemical compound OP(O)S TYQTYRXEMJXFJG-UHFFFAOYSA-N 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 8
- GBHRVZIGDIUCJB-UHFFFAOYSA-N hydrogenphosphite Chemical compound OP([O-])[O-] GBHRVZIGDIUCJB-UHFFFAOYSA-N 0.000 description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 7
- 238000005461 lubrication Methods 0.000 description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical group CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 150000001336 alkenes Chemical group 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005069 Extreme pressure additive Substances 0.000 description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 230000000994 depressogenic effect Effects 0.000 description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229940055577 oleyl alcohol Drugs 0.000 description 3
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229920001748 polybutylene Polymers 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229960001860 salicylate Drugs 0.000 description 3
- GAJQCIFYLSXSEZ-UHFFFAOYSA-L tridecyl phosphate Chemical compound CCCCCCCCCCCCCOP([O-])([O-])=O GAJQCIFYLSXSEZ-UHFFFAOYSA-L 0.000 description 3
- SPURMHFLEKVAAS-UHFFFAOYSA-N 1-docosene Chemical compound CCCCCCCCCCCCCCCCCCCCC=C SPURMHFLEKVAAS-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003939 benzylamines Chemical class 0.000 description 2
- 239000007998 bicine buffer Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LVZUNTGFCXNQAF-UHFFFAOYSA-N n-nonyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCC)C1=CC=CC=C1 LVZUNTGFCXNQAF-UHFFFAOYSA-N 0.000 description 2
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000005002 naphthylamines Chemical class 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229940095068 tetradecene Drugs 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- DUXYWXYOBMKGIN-UHFFFAOYSA-N trimyristin Chemical compound CCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCC DUXYWXYOBMKGIN-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RJDVGKCBHFINOK-UHFFFAOYSA-N tris(2-methylphenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound CC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C RJDVGKCBHFINOK-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 description 1
- IHWDIGHWDQPQMQ-UHFFFAOYSA-N 1-octadecylsulfanyloctadecane Chemical compound CCCCCCCCCCCCCCCCCCSCCCCCCCCCCCCCCCCCC IHWDIGHWDQPQMQ-UHFFFAOYSA-N 0.000 description 1
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- QVXGKJYMVLJYCL-UHFFFAOYSA-N 2,3-di(nonyl)-N-phenylaniline Chemical compound C(CCCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCCC QVXGKJYMVLJYCL-UHFFFAOYSA-N 0.000 description 1
- BKCNDTDWDGQHSD-UHFFFAOYSA-N 2-(tert-butyldisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSC(C)(C)C BKCNDTDWDGQHSD-UHFFFAOYSA-N 0.000 description 1
- NYLJHRUQFXQNPN-UHFFFAOYSA-N 2-(tert-butyltrisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSSC(C)(C)C NYLJHRUQFXQNPN-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical group CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- DAKZLOJXUDPQIL-UHFFFAOYSA-N 2-butyl-4-ethylphenol Chemical group CCCCC1=CC(CC)=CC=C1O DAKZLOJXUDPQIL-UHFFFAOYSA-N 0.000 description 1
- GTLMTHAWEBRMGI-UHFFFAOYSA-N 2-cyclohexyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C2CCCCC2)=C1 GTLMTHAWEBRMGI-UHFFFAOYSA-N 0.000 description 1
- YIKVZDICBNEEOZ-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphite Chemical compound CCCCC(CC)COP(O)O YIKVZDICBNEEOZ-UHFFFAOYSA-N 0.000 description 1
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- XDILCINHTMZTGG-UHFFFAOYSA-N 3-(3-dodecoxy-3-oxopropyl)sulfanylpropanoic acid Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(O)=O XDILCINHTMZTGG-UHFFFAOYSA-N 0.000 description 1
- VKJLYEDTHCTCOH-UHFFFAOYSA-N 3-(3-octadecoxy-3-oxopropyl)sulfanylpropanoic acid Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(O)=O VKJLYEDTHCTCOH-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical class C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 1
- 108050008598 Phosphoesterases Proteins 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- WYPOCAVDDXABIF-UHFFFAOYSA-N didecyl hydrogen phosphite Chemical compound CCCCCCCCCCOP(O)OCCCCCCCCCC WYPOCAVDDXABIF-UHFFFAOYSA-N 0.000 description 1
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- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
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- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-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
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- PPEZWDDRWXDXOQ-UHFFFAOYSA-N tributoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound CCCCOP(=S)(OCCCC)OCCCC PPEZWDDRWXDXOQ-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- SJDSOBWGZRPKSB-UHFFFAOYSA-N tricos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCC=C SJDSOBWGZRPKSB-UHFFFAOYSA-N 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BWPNIANVWARHPR-UHFFFAOYSA-N tridecyl dihydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)O BWPNIANVWARHPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- PTVDYMGQGCNETM-UHFFFAOYSA-N trityl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PTVDYMGQGCNETM-UHFFFAOYSA-N 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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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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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- 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
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- C10M2209/084—Acrylate; Methacrylate
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- 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
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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
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- 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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- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
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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
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- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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- 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
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- C—CHEMISTRY; METALLURGY
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
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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
- C10M2223/049—Phosphite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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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- 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
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Abstract
提供一种特定的齿轮油组合物,其混合(A)基础油、(B)乙烯-α烯烃共聚物、(C)含硫化合物、(D)有机钼化合物以及(E)含磷化合物而成,其极压性、剪切稳定性、耐磨性优异,且省油性亦优异。
Description
技术领域
本发明涉及齿轮油组合物,详细地涉及极压性、剪切稳定性、耐磨性优异、且省油性优秀的齿轮油组合物。
背景技术
齿轮油是齿轮装置用润滑油,用作汽车及其他高速高负荷齿轮用、普通机械的较轻负荷齿轮用、普通机械的较高负荷齿轮用等,用于防止齿轮的损伤·烧结(烧付)。这样的齿轮油中,通常要求其具有优异的极压性等,特别是在差动油中,与MTF(手动变速机油)相比,其极压性更受重视。此外,为了应对其他的用途,也要求着各种性能的提高,进行着各种技术开发。例如专利文献1和2中公开了含有特定的乙烯-α-烯烃共聚物的润滑油组合物。该润滑油组合物是一种温度特性优异、且剪切稳定性优秀的润滑油组合物。此外,对于齿轮油所要求的特性,除了上述之外,还可以列举有耐磨性、氧化稳定性、热稳定性等。
除了这些性能,近年来,在汽车用齿轮油等中,要求着提高省油性。作为提高省油性的方法,考虑有例如使用低粘度的齿轮油来减少粘性阻力,但此方法容易引起油膜破裂,致使耐烧结性下降、轴承或齿轮的疲劳寿命恶化等新问题。这样的话,很难兼顾提高省油性和作为齿轮油的基本性能,还要求进一步的技术开发。
现有技术文献
专利文献
专利文献1:日本专利特开昭63-280796号公报
专利文献2:日本专利特开平11-323370号公报
发明内容
本发明鉴于上述情况而成,其目的在于,提供一种尤其是极压性、剪切稳定性、耐磨性优异、且省油性优秀的齿轮油组合物。
本发明人注意到边界润滑条件中的摩擦系数、牵引系数(混合润滑领域中的摩擦系数),经过潜心研究,发现通过组合特定的基础油和特定的添加剂,可解决上述课题。本发明基于相关知识而完成。
即本发明提供:
1.一种齿轮油组合物,配合
(A)由选自100℃时的运动粘度为2~20mm2/s的矿物油和100℃时的运动粘度为2~20mm2/s的聚烯烃系合成油中的一种以上所构成的粘度指数在120以上的基础油、
(B)数均分子量为2000~10000的乙烯-α烯烃共聚物、
(C)下述通式(I)所表示的含硫化合物、
R1-Sx-R2…(I)
[通式(I)中,R1及R2各自独立地表示碳原子数4~16的烃基,x表示2~4的整数]
(D)有机钼化合物以及
(E)选自磷酸酯系化合物、亚磷酸酯系化合物、硫代磷酸酯系化合物和硫代亚磷酸酯系化合物的、具有碳原子数2~24的烃基的含磷化合物而成;
其中,以组合物总量为基准,(B)成分为3~10质量%、(C)成分换算成硫原子为1.2~2.0质量%、(D)成分换算成钼原子为100~300质量ppm、(E)成分换算成磷原子为0.15~0.2质量%,组合物中的硫原子与磷原子的质量比(S/P)为8~11。
2.根据上述1所述的齿轮油组合物,(A)成分基础油为以基础油总量为基准,配合粘度指数在125以上的矿物油以及/或者粘度指数在125以上的聚烯烃系合成油40质量%以上而成的基础油。
3.根据上述1或2所述的齿轮油组合物,(A)成分基础油为由矿物油构成的基础油。
4.根据上述1~3中任意一项所述的齿轮油组合物,其中(D)成分有机钼化合物为二硫代磷酸钼以及/或者二硫代氨基甲酸钼。
发明的效果
根据本发明,可提供一种极压性、剪切稳定性、耐磨性优异、且省油性优异的齿轮油组合物。
具体实施方式
本发明的齿轮油组合物混合(A)基础油、(B)乙烯-α烯烃共聚物、(C)含硫化合物、(D)有机钼化合物以及(E)含磷化合物而成。
本发明中的上述(A)成分的基础油是由选自100℃中的运动粘度为2~20mm2/s的矿物油和100℃中的运动粘度为2~20mm2/s的聚烯烃系合成油中的一种以上所构成的粘度指数在120以上的基础油。
当100℃中的运动粘度不足2mm2/s时,易发生高温时的油膜强度不足、蒸发损失变大等问题。而另一方面,超过20mm2/s时,由粘性阻力会增大动力损失。从该观点出发,优选100℃时的运动粘度为4~13mm2/s,更优选6~11mm2/s。
作为上述(A)成分基础油中所使用的矿物油,只要是能满足上述特性即无特别限制,例如可以列举,将对链烷烃基系原油或中间基系原油进行常压蒸馏或者对常压蒸馏的残渣油减压蒸馏获得的馏出油依照常法精制而得到的精制油、或者,精制后进一步进行深脱蜡处理获得的深脱蜡油等。此时的精制法无特别限制,可考虑各种方法。通常,单独进行(a)氢化处理、(b)脱蜡处理(溶剂脱蜡或加氢脱蜡)、(c)溶剂萃取处理、(d)碱蒸馏或硫酸清洗处理、(e)白土精制,或者以适当顺序组合进行。此外,将同一处理分成若干段反复进行也有效。例如,有(1)对馏出油进行氢化处理、或氢化处理后,进行碱蒸馏或硫酸清洗处理的方法;(2)对馏出油进行氢化处理后,进行脱蜡处理的方法;(3)对馏出油进行溶剂萃取处理后进行氢化处理的方法;(4)对馏出油进行两段或者三段氢化处理、或者在其之后进行碱蒸馏或硫酸清洗处理的方法,进一步还有(5)如上述(1)~(4)进行处理之后再次进行脱蜡处理,做成深脱蜡油的方法。无论是哪个方法,根据目的基础油的性状适当调整条件即可。
此外,作为上述聚烯烃系合成油,可例示例如α-烯烃的自聚体或共聚物、聚丁烯或它们的氢化物等,从粘度指数高的点,优选癸烯低聚物等碳原子数6~14的α-烯烃的低聚物、乙烯-丙烯共聚物等乙烯α-烯烃共聚物、聚丁烯或它们的氢化物。
本发明中的基础油可以使用1种上述矿物油,也可以两种以上组合使用。此外,还可以使用一种上述聚烯烃系合成油或两种以上组合使用。进一步,还可以将一种以上矿物油和一种以上聚烯烃系合成油组合使用。
本发明中使用粘度指数在120以上的基础油。通过将粘度指数120以上的基础油与(B)成分组合,可获得在牵引系数和剪切稳定性方面均优异的性能。
本发明使用的基础油优选由以基础油总量为基准,配合粘度指数在125以上的矿物油以及/或者粘度指数在125以上的聚烯烃系合成油40质量%以上而成,进一步优选配合60质量%以上而成的基础油。通过将满足该规定的基础油与(B)成分组合,可获得在牵引系数和剪切稳定性方面均优异的性能。
从经济性和各种添加剂的溶解性的观点考虑,本发明的(A)成分基础油优选由矿物油构成的基础油,尤其适宜通过深脱蜡处理获得的矿物油。该深脱蜡处理可通过在苛刻条件下的溶剂脱蜡处理法或使用沸石催化剂的接触加氢脱蜡处理法等进行。
本发明中的上述(B)成分乙烯-α烯烃共聚物是数均分子量为2000~10000的乙烯-α-烯烃共聚物。数均分子量不足2000时,粘度指数的提高效果不充分,超过10000时,剪切稳定性恶化,不理想。从该观点来看,更优选数均分子量为3000~8000。该乙烯-α-烯烃共聚物为乙烯与碳原子数3~20的α-烯烃、例如丙烯、1-丁烯、1-癸烯等的共聚物,其为不含极性基的聚合物。本发明中,(B)成分乙烯-α-烯烃共聚物可以单独使用一种,也可以组合两种以上使用。
本发明中,上述(B)成分的乙烯-α-烯烃共聚物以齿轮油组合物总量为基准,配合3~10质量%,优选配合4.5~8.5质量%。不足3质量%时,降低牵引系数的效果或粘度指数提高的效果不充分,超过10质量%时,无法获得与其混合量相称的效果,且剪切稳定性亦恶化。
在本发明中,使用(A)成分基础油与(B)成分乙烯-α-烯烃共聚物的组合。即,通过将这些并用,可在不降低剪切稳定性的同时降低牵引系数,获得提高省油性的效果。历来都知道,使用聚烯烃系合成油作为基础油会降低牵引系数,但在本发明中,即使是在使用矿物油作为基础油的情况下也能获得与现有技术同等的效果。因此,在此情况下,可获得如上所述的经济性和各种添加剂的溶解性的优点。
本发明中的上述(C)成分的含硫化合物为通式(I)所表示的含硫化合物。
R1-Sx-R2…(I)
通式(I)中,R1和R2各自独立地表示碳原子数4~16的烃基,可为直链状或支链状。碳原子数不足4时,耐磨性会下降,超过16时,氧化稳定性会降低。从该观点来看,更优选碳原子数为6~14,进一步优选为8~10。此外,从氧化稳定性优异的点,优选支链,具体地举例有叔丁基。通式(I)中,x表示2~4的整数。当X不足2时,极压性会下降,超过4时,氧化稳定性会降低。从该观点来看,x更优选为2或3。具体的化合物举例有二叔丁基二硫化物或二叔丁基三硫化物。在本发明中,(C)成分含硫化合物可单独使用一种,也可以两种以上组合使用。
本发明中,上述(C)成分含硫化合物以齿轮油组合物总量为基准,换算成硫原子,配合1.2~2.0质量%,优选配合1.6~1.9质量%。不足1.2质量%时,极压性会下降,超过2.0质量%时,油泥的产生会增多。
作为本发明中的上述(D)成分有机钼化合物,可使用传统用作润滑油用添加剂的有机钼化合物,例如列举有二硫代磷酸钼(MoDTP)或二硫代氨基甲酸钼(MoDTC)等,优选二硫代氨基甲酸钼。
作为二硫代氨基甲酸钼,可列举通式(II)所示的硫氧二硫代氨基甲酸钼。
[化1]
(式中,R3和R4分别表示碳原子数4~24的烃基,x和y分别表示1~3的数,x与y的和为4。)
此处,碳原子数4~24的烃基可列举,例如,碳原子数4~24的烷基、碳原子数4~24的链烯基、碳原子数6~24的芳基、碳原子数7~24的芳基烷基等。烃基的碳原子数在4以上时,在基础油中的溶解性良好,另,碳原子数在24以下时,发挥良好效果的同时,也容易得到。上述R3和R4相互可以相同也可以不同。
上述碳原子数4~24的烷基和碳原子数4~24的链烯基的可以是直链状、支链状和环状中的任一个,这样的基团可列举,例如正丁基、异丁基、仲丁基、叔丁基、各种己基、各种辛基、各种癸基、各种十二烷基、各种十四烷基、各种十六烷基、各种十八烷基、各种二十烷基、环戊基、环己基、油基、亚麻基等。此外,上述碳原子数6~24的芳基和碳原子数7~24的芳基烷基,可在其芳香环上导入1个以上的烷基等取代基,这样的基团列举有例如苯基、甲苯基、二甲苯基、萘基、丁基苯基、辛基苯基、壬基苯基、苯甲基、甲基苯甲基、丁基苯甲基、苯乙基、甲基苯乙基、丁基苯乙基等。
在本发明中,(D)成分有机钼化合物可单独使用一种,也可以两种以上组合使用。
本发明中,上述(D)成分有机钼化合物以齿轮油组合物总量为基准,换算成钼原子,为100~300质量ppm,优选150~200质量ppm。不足100质量ppm时,很难降低边界润滑条件中的摩擦系数,超过300质量ppm时,氧化稳定性和储藏稳定性会恶化。
本发明中的上述(E)成分含磷化合物为选自磷酸酯系化合物、亚磷酸酯系化合物、硫代磷酸酯系化合物和硫代亚磷酸酯系化合物的、具有碳原子数2~24的烃基的含磷化合物。
上述磷酸酯系化合物可列举例如通式(III)所示的磷酸三酯或酸性磷酸酯化合物。
(R5O)mP(=O)(OH)3-m…(III)
(式中,R5表示碳原子数2~24的烃基,m为1、2或者3。m为2或3时,R5O可相同或不同。)
上述通式(III)中,R5所示的碳原子数2~24的烃基可列举例如,碳原子数2~24的烷基和链烯基、碳原子数6~24的芳基、碳原子数7~24的芳烷基等。
上述烷基和链烯基可以是直链状、分支状、环状中的任一个,其例子可列举乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、各种戊基、各种己基、各种辛基、各种癸基、各种十二烷基、各种十四烷基、各种十六烷基、各种十八烷基、各种十九烷基、各种二十烷基、各种二十一烷基、各种二十二烷基、各种二十三烷基、各种二十四烷基、环戊基、环己基、烯丙基、丙烯基、各种丁烯基、各种己烯基、各种辛烯基、各种癸烯基、各种十二烯基、各种十四烯基、各种十六烯基、各种十八烯基、各种十九烯基、各种二十烯基、各种二十一烯基、各种二十二烯基、各种二十三烯基、各种二十四烯基、环戊烯基、环己烯基等。
碳原子数6~24的芳基可列举例如苯基、甲苯基、二甲苯基、萘基等,碳原子数7~24的芳烷基可列举例如苯甲基、苯乙基、萘基甲基、甲基苯甲基、甲基苯乙基、甲基萘基甲基等。
上述通式(III)所示的磷酸酯系化合物优选具有碳原子数2~18的烃基的化合物。
具体地,m=1的酸性磷酸单酯可列举酸性磷酸单乙酯、酸性磷酸单正丙酯、酸性磷酸单正丁酯、酸性磷酸单-2-乙基己酯、酸性磷酸单十二烷基酯(酸性磷酸单月桂酯)、酸性磷酸单十四烷基酯(酸性磷酸单肉豆蔻酯)、酸性磷酸单十六烷基酯、酸性磷酸单十八烷基酯(酸性磷酸单硬脂酰酯)、酸性磷酸单-9-十八烯酯(酸性磷酸单油醇酯)等。
又、m=2的酸性磷酸二酯可列举、酸性磷酸二-正丁酯、酸性磷酸二-2-乙基己酯、酸性磷酸二癸酯、酸性磷酸双十二烷基酯(酸性磷酸二月桂酯)、酸性磷酸二(十三烷基)酯、酸性磷酸双十八烷基酯(酸性磷酸双硬脂酰酯)、酸性磷酸二-9-十八烯酯(酸性磷酸二油醇酯)等。
进一步,m=3的磷酸三酯有磷酸三芳基酯、磷酸三烷基酯等,例如可以列举磷酸苯甲基二苯基酯、磷酸三苯酯、磷酸三甲苯酯、磷酸三丁酯、磷酸三癸酯、磷酸乙基二丁酯和磷酸三乙基苯酯等。
上述亚磷酸酯系化合物可列举例如通式(IV)或(V)所示的亚磷酸三酯或酸性亚磷酸酯化合物。
[化2]
(R6O)3P (IV)
(式中,R6表示碳原子数2~24的烃基,(V)式中的n为1或者2。n是2时,多个R6O可以相同或不同。)
上述通式(IV)和(V)中,R6所示的碳原子数2~24的烃基可列举同上述通式(III)中R5所表示的相同的基团。
上述通式(IV)所示的亚磷酸酯系化合物优选为具有碳原子数2~18的烃基的化合物。
亚磷酸三酯可以列举例如亚磷酸三苯酯、亚磷酸三乙酯、亚磷酸三异辛酯、亚磷酸三(2-乙基己基)酯、亚磷酸三异癸酯、亚磷酸三(十三烷基)酯、亚磷酸三油醇酯等。
此外,酸性亚磷酸酯可列举例如亚磷酸氢二正丁酯、亚磷酸氢二-2-乙基己酯、亚磷酸氢二癸酯、亚磷酸氢双十二烷基酯(亚磷酸氢双月桂酯)、亚磷酸氢双十八烷基酯(亚磷酸氢双硬脂酰酯)、亚磷酸氢二-9-十八烯酯(亚磷酸氢二油醇酯)、亚磷酸氢二苯酯等。
上述硫代磷酸酯系化合物可列举例如通式(VI)所示的硫代磷酸三酯或酸性硫代磷酸酯化合物。
[化3]
(式中,R7~R9表示氢原子或碳原子数2~24的烃基,至少一个为烃基。X1~X4表示氧原子或硫原子,至少一个为硫原子。)
具体的化合物可列举,硫代磷酸单丁酯、硫代磷酸单辛酯、硫代磷酸单十二烷基酯、硫代磷酸二丁酯、硫代磷酸二辛酯、硫代磷酸双十二烷基酯、硫代磷酸二苯酯、硫代磷酸三丁酯、硫代磷酸三辛酯、硫代磷酸三苯酯、硫代磷酸三(十二烷基)酯、二硫代磷酸二丙酯、二硫代磷酸单丙酯。
上述硫代亚磷酸酯系化合物可列举例如通式(VII)所示的硫代亚磷酸三酯或酸性硫代亚磷酸酯化合物。
[化4]
(式中,R10~R12表示氢原子或碳原子数2~24的烃基,至少一个为烃基。X5~X7表示氧原子或硫原子,至少一个为硫原子。)
具体的化合物可列举,硫代亚磷酸单丁酯、硫代亚磷酸单辛酯、硫代亚磷酸单十二烷基酯、硫代亚磷酸二丁酯、硫代亚磷酸二辛酯、硫代亚磷酸双十二烷基酯、硫代亚磷酸二苯酯、硫代亚磷酸三丁酯、硫代亚磷酸三辛酯、硫代亚磷酸三苯酯、硫代亚磷酸三(十二烷基)酯、三硫代亚磷酸三丁酯、硫代亚磷酸三(2-乙基己基)酯。
本发明的润滑油组合物中,可使用1种以上的上述磷酸酯系化合物、上述亚磷酸酯系化合物、上述硫代磷酸酯系化合物、上述硫代亚磷酸酯系化合物或将这些含磷化合物组合使用。进一步还可以使用这些含磷化合物的胺盐。
这些含磷化合物之中,优选磷酸酯系化合物或硫代磷酸酯系化合物,具体地列举有二硫代磷酸二丙酯、二硫代磷酸单丙酯、磷酸三癸酯、磷酸三甲苯酯等。
本发明中,上述(E)成分含磷化合物以齿轮油组合物总量为基准,换算成磷原子,配合0.15~0.2质量%,优选配合0.16~0.19质量%。当不足0.15质量%时,很难减少边界润滑条件中的摩擦系数,而且也难获得极压性的提高效果。另一方面,超过0.2质量%时,组合物的稳定性会下降,变得容易产生沉淀。
本发明的齿轮油组合物是组合物中的硫原子与磷原子的质量比(S/P)为8~11的齿轮油组合物。一般,含硫化合物或含磷化合物是被用作为极压添加剂等润滑油添加剂来使用,但在本发明中,特别通过(E)成分含磷化合物和(D)成分有机钼化合物的组合来获得效果,据此可达成边界润滑条件中的摩擦系数的减少化。上述硫原子与磷原子的质量比的范围即是为了得到该效果,当不足8时,很难减少边界润滑条件中的摩擦系数,且很难得到提高极压性的效果。另一方面,超过11时,不仅会发生与不足8时相同的麻烦,同时,组合物的稳定性也会下降、变得容易产生沉淀。润滑油添加剂的话,在市场出售有硫系极压添加剂与磷系极压添加剂的组合物作为齿轮油添加剂组件,在本发明中,只要满足上述规定即可使用这些添加剂组件。
如上所述,本发明注目于运动粘度、边界润滑条件中的摩擦系数、牵引系数,意图提高省油性,进一步,通过使用特定的添加剂、或利用特定的组合来提高极压性、剪切稳定性、耐磨性。因此,本发明的齿轮油组合物相比于使用一般经常使用的ZnDTP(二硫代磷酸锌)添加剂作为主要添加剂的情况时,其耐烧结性得到明显提高。
在不违反本发明目的的范围内,本发明的齿轮油组合物中可以适当的混合其他添加剂。
这样的添加剂可列举,例如,抗氧化剂、无灰系分散剂、金属系清洁剂、粘度指数改进剂、流点降低剂、金属减活剂、防锈剂、消泡剂等。
上述抗氧化剂举例有例如酚系抗氧化剂、胺系抗氧化剂、硫系抗氧化剂等。
酚系抗氧化剂可列举,例如、4,4′-亚甲基双-(2,6-二-叔丁基苯酚)、4,4′-双-(2,6-二-叔丁基苯酚)、4,4′-双-(2-甲基-6-叔丁基苯酚)、2,2′-亚甲基双-(4-乙基-6-叔丁基苯酚)、2,2′-亚甲基双-(4-甲基-6-叔丁基苯酚)、4,4′-亚丁基双-(3-甲基-6-叔丁基苯酚)、4,4′-异亚丙基双-(2,6-二-叔丁基苯酚)、2,2′-亚甲基双-(4-甲基-6-壬基苯酚)、2,2′-异亚丁基双-(4,6-二甲基苯酚)、2,2′-亚甲基双(4-甲基-6-环己基苯酚)、2,6-二-叔丁基-4-甲基苯酚、2,6-二-叔丁基-4-乙基苯酚、2,4-二甲基-6-叔丁基苯酚、2,6-二-叔戊基-对甲酚、2,6-二-叔丁基-4-(N,N′-二甲基氨基甲基苯酚)、4,4′-硫代双(2-甲基-6-叔丁基苯酚)、4,4′-硫代双(3-甲基-6-叔丁基苯酚)、2,2′-硫代双(4-甲基-6-叔丁基苯酚)、双(3-甲基-4-羟基-5-叔丁基苯甲基)硫化物、双(3,5-二-叔丁基-4-羟基苯甲基)硫化物、正辛基-3-(4-羟基-3,5-二-叔丁基苯基)丙酸酯、正十八(烷)基-3-(4-羟基-3,5-二-叔丁基苯基)丙酸酯、2,2′-硫代[二乙基-双-3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]等。其中,特别合适的是双酚系和含酯基的酚系。
此外,胺系抗氧化剂可列举,例如,单辛基二苯胺、单壬基二苯胺等单烷基二苯胺系;4,4′-二丁基二苯胺、4,4′-二戊基二苯胺、4,4′-二己基二苯胺、4,4′-二庚基二苯胺、4,4′-二辛基二苯胺、4,4′-二壬基二苯胺等二烷基二苯胺系;四丁基二苯胺、四己基二苯胺、四辛基二苯胺、四壬基二苯胺等聚烷基二苯胺系以及萘胺系,具体地有α-萘胺、苯基-α-萘基胺,还有丁基苯基-α-萘胺、戊基苯基-α-萘胺、己基苯基-α-萘胺、庚基苯基-α-萘胺、辛基苯基-α-萘胺;壬基苯基-α-萘胺等烷基取代苯基-α-萘胺等。其中,适宜选用二烷基二苯胺系和萘胺系。
硫系抗氧化剂可列举,例如吩噻嗪、季戊四醇-四-(3-月桂基硫代丙酸酯)、双十二烷基硫醚(ジドデシルサルフアイド)、双十八烷基硫醚、双十二烷基硫代二丙酸酯、双十八烷基硫代二丙酸酯、双肉豆蔻基硫代二丙酸酯、十二烷基十八烷基硫代二丙酸酯、2-巯基苯并咪唑等。
这些抗氧化剂可以单独使用一种,也可以混合两种以上使用。例如,从氧化稳定性效果的观点考虑,优选一种或两种以上酚系抗氧化剂与一种或两种以上胺系抗氧化剂的混合物。抗氧化剂的混合量以齿轮油组合物总量为基准,通常优选在0.1~5质量%范围,更优选0.1~3质量%。
无灰系分散剂可列举,例如,琥珀酰亚胺类、含硼琥珀酰亚胺类、苄胺类、含硼苄胺类、丁二酸酯类、脂肪酸或丁二酸所代表的一价或者二价羧酸酰胺类等。
此外,金属系清洁剂可列举,例如,钙等碱土类金属的中性金属磺酸盐、中性金属酚盐、中性金属水杨酸盐、中性金属膦酸盐、碱性金属磺酸盐、碱性金属酚盐、碱性金属水杨酸盐、过碱性(例如、总碱值是200~700mgKOH/g)金属磺酸盐、过碱性金属水杨酸盐、过碱性金属酚盐等。这些无灰系分散剂或金属系清洁剂的混合量,以齿轮油组合物总量为基准,通常为0.1~20质量%,理想的是0.5~10质量%。
粘度指数改进剂可列举,例如,聚甲基丙烯酸酯、分散型聚甲基丙烯酸酯、烯烃系共聚物、(例如,乙烯-丙烯共聚物等)、分散型烯烃系共聚物、苯乙烯系共聚物(例如,苯乙烯-二烯共聚物、苯乙烯-异戊二烯共聚物等)等。
粘度指数改进剂的混合量从混合效果这点,以齿轮油组合物总量为基准,通常在0.5~15质量%左右,优选1~10质量%。
流点降低剂可列举,例如,重均分子量在5000~50000左右的聚甲基丙烯酸酯等。
流点降低剂的混合量从混合效果这点,以齿轮油组合物总量为基准,通常在0.1~2质量%左右,优选0.1~1质量%。
金属减活剂可列举,苯并三唑系、甲苯基三唑系、噻二唑系和咪唑系化合物等。
金属减活剂的混合量以齿轮油组合物总量为基准,通常为0.01~3质量%,理想的是0.01~1质量%。
防锈剂可列举,石油磺酸盐、烷基苯磺酸盐、二壬基萘磺酸盐、链烯丁二酸酯、多元醇酯等。
从混合效果这点,以齿轮油组合物总量为基准,这些防锈剂的混合量通常在0.01~1质量%左右,优选0.05~0.5质量%。
消泡剂可列举,硅油、氟硅油和氟烷基醚等,从消泡效果和经济平衡性等观点,以齿轮油组合物总量为基准,通常为0.0005~0.5质量%、优选0.01~0.2质量%。
本发明的齿轮油组合物,其极压性、剪切稳定性、耐磨性优异,且省油性亦优异,适用于例如汽车用齿轮油、工业用齿轮油等,尤其优选用于汽车的差动齿轮的润滑。
实施例
接着,通过实施例对本发明进行更详细的说明,但本发明并不限定于此。
实施例1~5以及比较例1~6
用第1表-1中所示的混合量(质量%)调制齿轮油组合物。其性状见第1表-2。各成分的详细情况如下。
矿物油1:100℃时的运动粘度4.47mm2/s、粘度指数(VI)127的矿物油
矿物油2:100℃时的运动粘度10.89mm2/s、粘度指数(VI)107的矿物油
矿物油3:100℃时的运动粘度4.284mm2/s、粘度指数(VI)116的矿物油
OCP(烯烃共聚物):乙烯和丙烯的共聚物、数均分子量7700
PMA:聚甲基丙烯酸酯、数均分子量21000
含硫化合物:二-叔丁基二硫与二-叔丁基三硫的混合物(质量比7∶3)
有机钼化合物:含碳原子数为8的烷基的二硫代氨基甲酸钼
含磷化合物:磷酸酯化合物的混合物(二硫代磷酸二丙酯、二硫代磷酸单丙酯、磷酸三癸酯、磷酸三甲苯酯)
其他添加剂:分散剂(聚丁烯基琥珀酰亚胺)、摩擦调节剂(油酰胺)
上述矿物油、基础油和齿轮油组合物的性状测定按以下方法进行。
(1)运动粘度
依据JIS K 2283,测定40℃、100℃时的运动粘度。
(2)粘度指数(VI)
依据JIS K 2283进行测定。
(3)硫原子、磷原子、钼原子的含量
由ICP发光分析法求得。
对这些齿轮油组合物按照以下方法进行各种试验,评估其物性。评价结果示于表2中。
〔法列克司试验〕
使用法列克司试验机测定摩擦力的变化和磨耗量(销(pin)和块(block))
依据ASTMD2625-83,试验片:块使用SKH-51(HRC65)、销使用SUJ-2(HRC60),以转速1800rpm、负荷1179N、开始油温30℃后无降温调整、油量100ml的条件实施。负荷与转速达到规定设定值后,测定1200秒后的摩擦力和磨耗量。
〔剪切稳定性试验〕
依据JPI-5S-29-88“超声波、A法、60分钟、30ml”,测定剪切后100℃的运动粘度的降低率(%)。
〔牵引系数〕
使用MTM牵引力测量器测定牵引系数。
测定条件如下。(确认了负荷重量:20N,油温:100℃,滑动·滚动比:1~90%,平均旋转速度2m/s,SRR为20%的值)
〔高速蒂姆肯(チムケン)试验〕
依据JISK 2519,求出不引起烧结的最大负荷。转数为3600rpm、油温为40℃,最初负荷以阶梯性负荷从5LBS开始,当发生烧结时下降2.5LBS,无烧结时加重2.5LBS的负荷,重复进行该试验求得无烧结的合格负荷。此外,合格负荷为秤砣的值。
〔储藏稳定性〕
调制齿轮油组合物,按照以下基准观察1天后的状态。
○:无浑浊、无沉淀
△:浑浊、无沉淀
×:有沉淀
[表2]
第2表-1
第2表-2
产业上的可利用性
本发明的齿轮油组合物不仅实现低粘度化,而且极压性(耐烧结性)优异,还是一种剪切稳定性、耐磨性、省油性优异的齿轮油组合物。
Claims (4)
1.一种齿轮油组合物,配合
(A)由选自100℃时的运动粘度为2~20mm2/s的矿物油和100℃时的运动粘度为2~20mm2/s的聚烯烃系合成油中的一种以上所构成的粘度指数在120以上的基础油、
(B)数均分子量为2000~10000的乙烯-α烯烃共聚物、
(C)下述通式(I)所表示的含硫化合物、
R1-Sx-R2…(I)
通式(I)中,R1及R2各自独立地表示碳原子数4~16的烃基,x表示2~4的整数,
(D)有机钼化合物以及
(E)选自磷酸酯系化合物、亚磷酸酯系化合物、硫代磷酸酯系化合物和硫代亚磷酸酯系化合物的具有碳原子数2~24的烃基的含磷化合物而成;
以组合物总量为基准,(B)成分为3~10质量%、(C)成分换算成硫原子为1.2~2.0质量%、(D)成分换算成钼原子为100~300质量ppm、(E)成分换算成磷原子为0.15~0.2质量%,组合物中的硫原子与磷原子的质量比(S/P)为8~11。
2.根据权利要求1所述的齿轮油组合物,(A)成分的基础油为以基础油总量为基准,配合粘度指数在125以上的矿物油以及/或者粘度指数在125以上的聚烯烃系合成油40质量%以上而成的基础油。
3.根据权利要求1或2所述的齿轮油组合物,(A)成分的基础油为由矿物油构成的基础油。
4.根据权利要求1~3任意一项所述的齿轮油组合物,(D)成分的有机钼化合物为二硫代磷酸钼以及/或者二硫代氨基甲酸钼。
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CN107250331A (zh) * | 2015-02-27 | 2017-10-13 | Jxtg能源株式会社 | 齿轮油用润滑油组合物 |
CN107532106A (zh) * | 2015-03-30 | 2018-01-02 | 出光兴产株式会社 | 润滑油组合物 |
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US20120040874A1 (en) | 2012-02-16 |
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US9115328B2 (en) | 2015-08-25 |
JP2010229357A (ja) | 2010-10-14 |
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EP2412790A1 (en) | 2012-02-01 |
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