EP1418221B1 - Lubricating oil composition for transmissions - Google Patents
Lubricating oil composition for transmissions Download PDFInfo
- Publication number
- EP1418221B1 EP1418221B1 EP03025453A EP03025453A EP1418221B1 EP 1418221 B1 EP1418221 B1 EP 1418221B1 EP 03025453 A EP03025453 A EP 03025453A EP 03025453 A EP03025453 A EP 03025453A EP 1418221 B1 EP1418221 B1 EP 1418221B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mass
- composition
- lubricating oil
- percent
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 74
- 239000010687 lubricating oil Substances 0.000 title claims description 34
- 230000005540 biological transmission Effects 0.000 title claims description 24
- -1 phosphorus compound Chemical class 0.000 claims description 85
- 239000002199 base oil Substances 0.000 claims description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims description 24
- 239000011574 phosphorus Substances 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 239000011593 sulfur Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 235000021317 phosphate Nutrition 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 claims description 4
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001177 diphosphate Substances 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000010688 mineral lubricating oil Substances 0.000 claims description 3
- 150000004712 monophosphates Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 2
- 239000001226 triphosphate Substances 0.000 claims description 2
- 235000011178 triphosphate Nutrition 0.000 claims description 2
- 125000002264 triphosphate group Chemical class [H]OP(=O)(O[H])OP(=O)(O[H])OP(=O)(O[H])O* 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 31
- 125000000217 alkyl group Chemical group 0.000 description 22
- 238000012360 testing method Methods 0.000 description 17
- 239000000654 additive Substances 0.000 description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000011707 mineral Substances 0.000 description 13
- 235000010755 mineral Nutrition 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000446 fuel Substances 0.000 description 11
- 238000007670 refining Methods 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 150000004678 hydrides Chemical class 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000004517 catalytic hydrocracking Methods 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 229920000193 polymethacrylate Polymers 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 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 3
- 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 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 230000006872 improvement Effects 0.000 description 3
- 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 3
- 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 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002948 undecyl 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])[H] 0.000 description 3
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 2
- RRZVGDGTWNQAPW-UHFFFAOYSA-N 4-[5-(1-methylpyrazol-4-yl)-3-[2-(1-methylpyrazol-4-yl)ethyl]imidazol-4-yl]benzonitrile Chemical compound C1=NN(C)C=C1CCN1C(C=2C=CC(=CC=2)C#N)=C(C2=CN(C)N=C2)N=C1 RRZVGDGTWNQAPW-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005069 Extreme pressure additive Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000003493 decenyl group Chemical group [H]C([*])=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 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002960 margaryl 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])[H] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000006384 methylpyridyl group Chemical group 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
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 2
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 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
- 125000002958 pentadecyl 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])[H] 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000004929 pyrrolidonyl group Chemical group N1(C(CCC1)=O)* 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 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 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 2
- 150000004867 thiadiazoles Chemical class 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 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 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
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 2
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- 125000005023 xylyl group Chemical group 0.000 description 2
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- UFFAFBPZFGAMJJ-UHFFFAOYSA-N (2-methoxy-4,6-dimethylphenyl)boronic acid Chemical compound COC1=CC(C)=CC(C)=C1B(O)O UFFAFBPZFGAMJJ-UHFFFAOYSA-N 0.000 description 1
- JNUCNIFVQZYOCP-UHFFFAOYSA-N (4-methylphenyl) dihydrogen phosphate Chemical compound CC1=CC=C(OP(O)(O)=O)C=C1 JNUCNIFVQZYOCP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
- NWPCFCBFUXXJIE-UHFFFAOYSA-N 2-(hydroxymethylamino)ethanol Chemical compound OCCNCO NWPCFCBFUXXJIE-UHFFFAOYSA-N 0.000 description 1
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- MLIOQLGKVQZBKL-UHFFFAOYSA-N 3-N-(dibutylamino)-3-N-(dipropylamino)-2-N,2-N-diethyl-1-N,1-N-dimethylbenzene-1,2,3-triamine Chemical compound CN(C)C=1C(=C(N(N(CCCC)CCCC)N(CCC)CCC)C=CC1)N(CC)CC MLIOQLGKVQZBKL-UHFFFAOYSA-N 0.000 description 1
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- 108010005254 Activating Transcription Factors Proteins 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 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 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- CERDIVAFXRCORQ-UHFFFAOYSA-O butoxy-hydroxy-oxophosphanium Chemical compound CCCCO[P+](O)=O CERDIVAFXRCORQ-UHFFFAOYSA-O 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- PAZHOQPRMVOBDD-RMRYJAPISA-N cyclopenta-1,3-diene;(1s)-1-(2-diphenylphosphanylcyclopenta-1,4-dien-1-yl)-n,n-dimethylethanamine;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1[C@@H](N(C)C)C PAZHOQPRMVOBDD-RMRYJAPISA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 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
- DVZIQPGIAQDYQH-UHFFFAOYSA-N diheptyl hydrogen phosphate Chemical compound CCCCCCCOP(O)(=O)OCCCCCCC DVZIQPGIAQDYQH-UHFFFAOYSA-N 0.000 description 1
- CUKQEWWSHYZFKT-UHFFFAOYSA-N diheptyl hydrogen phosphite Chemical compound CCCCCCCOP(O)OCCCCCCC CUKQEWWSHYZFKT-UHFFFAOYSA-N 0.000 description 1
- HUDSKKNIXMSHSZ-UHFFFAOYSA-N dihexyl hydrogen phosphate Chemical compound CCCCCCOP(O)(=O)OCCCCCC HUDSKKNIXMSHSZ-UHFFFAOYSA-N 0.000 description 1
- XFUSKHPBJXJFRA-UHFFFAOYSA-N dihexyl hydrogen phosphite Chemical compound CCCCCCOP(O)OCCCCCC XFUSKHPBJXJFRA-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- MGJHACFZFDVYIL-UHFFFAOYSA-N dipentyl hydrogen phosphite Chemical compound CCCCCOP(O)OCCCCC MGJHACFZFDVYIL-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- QVKQJEWZVQFGIY-UHFFFAOYSA-N dipropyl hydrogen phosphate Chemical compound CCCOP(O)(=O)OCCC QVKQJEWZVQFGIY-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- AJHVMIKRCDKKFP-UHFFFAOYSA-N heptyl dihydrogen phosphite Chemical compound CCCCCCCOP(O)O AJHVMIKRCDKKFP-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 description 1
- QXLBKTGZGPVJOO-UHFFFAOYSA-N hexyl dihydrogen phosphite Chemical compound CCCCCCOP(O)O QXLBKTGZGPVJOO-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical class C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 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
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- NJWMENBYMFZACG-UHFFFAOYSA-N n-heptylheptan-1-amine Chemical compound CCCCCCCNCCCCCCC NJWMENBYMFZACG-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- CWYZDPHNAGSFQB-UHFFFAOYSA-N n-propylbutan-1-amine Chemical compound CCCCNCCC CWYZDPHNAGSFQB-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- KCRLWVVFAVLSAP-UHFFFAOYSA-N octyl dihydrogen phosphite Chemical compound CCCCCCCCOP(O)O KCRLWVVFAVLSAP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- NVTPMUHPCAUGCB-UHFFFAOYSA-N pentyl dihydrogen phosphate Chemical compound CCCCCOP(O)(O)=O NVTPMUHPCAUGCB-UHFFFAOYSA-N 0.000 description 1
- YRODAVZDENZNAE-UHFFFAOYSA-N pentyl dihydrogen phosphite Chemical compound CCCCCOP(O)O YRODAVZDENZNAE-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical compound OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
- PRAHMDIEZMWIRW-UHFFFAOYSA-N propyl dihydrogen phosphite Chemical compound CCCOP(O)O PRAHMDIEZMWIRW-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- GSURLQOINUQIIH-UHFFFAOYSA-N triheptyl phosphate Chemical compound CCCCCCCOP(=O)(OCCCCCCC)OCCCCCCC GSURLQOINUQIIH-UHFFFAOYSA-N 0.000 description 1
- PPBMHSGZZYZYBO-UHFFFAOYSA-N triheptyl phosphite Chemical compound CCCCCCCOP(OCCCCCCC)OCCCCCCC PPBMHSGZZYZYBO-UHFFFAOYSA-N 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 description 1
- CVWUIWZKLYGDNJ-UHFFFAOYSA-N tripentyl phosphite Chemical compound CCCCCOP(OCCCCC)OCCCCC CVWUIWZKLYGDNJ-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
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- ZNCAMSISVWKWHL-UHFFFAOYSA-L zinc;butoxy-butylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCOP([O-])(=S)SCCCC.CCCCOP([O-])(=S)SCCCC ZNCAMSISVWKWHL-UHFFFAOYSA-L 0.000 description 1
- LZVDFWITYZHIEU-UHFFFAOYSA-L zinc;oxido-propoxy-propylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCOP([O-])(=S)SCCC.CCCOP([O-])(=S)SCCC LZVDFWITYZHIEU-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
Definitions
- This invention relates to lubricating oil compositions for transmissions, and more particularly to such lubricating oil compositions which are excellent in fuel consumption efficiency and extreme pressure properties and capable of providing gear and clutches with sufficient durabilities such that the long lasting gear change characteristics can be obtained.
- An automatic transmission is constituted by a torque converter, a wet clutch, a gear bearing mechanism, and a hydraulic control mechanism and will be contributive to the improvement of fuel efficiency using an ATF with a lower viscosity which can reduce the stirring resistance in the torque converter and the oil pump.
- a low viscosity ATF reduces the durability of gears determining the transmission ratios and shift clutches, leading to the poor durability of the gear change characteristics.
- Lowering the viscosity of an ATF reduces its extreme pressure properties and thus causes the gears to be seized, resulting in malfunctioning of the automatic transmission.
- the selection of gears determining transmission ratios is effected by allowing some of the wet clutches to be coupled and allowing the other to be idled.
- a low viscosity ATF reduces the durability of wet clutches, a dynamic friction coefficient necessary to couple the clutches is not generated, resulting in a possibility that the gear change may not work. Therefore, even though an ATF is lowered in viscosity, it must be capable of maintaining the durabilities of gears and wet clutches.
- EP 0 867 498 A1 discloses a transmission oil composition which comprises 0.05 to 2 % of at least one compound seleted from the group consisting of a metallic source of organic acids, particularly an alkaline-earth metal sort as component (A), 0.15 to 4 % of a specific polyamide compound as component (B) and 0.05 to 1.5 % of at least one compound selected from the group consisting of acid phosphate or acid phosphite esters as component (C).
- Additives may be further contained in said composition, wherein a viscosity index improver in an amount of 3 to 34 % by weight may be added.
- the kinematic viscosity of the base oil is in the range from 3 to 15 mm 2 /s and the base oil has a %Cp of less than 70.
- EP 0 978 555 A1 relates to a lubricating oil composition having a kinematic viscosity of at least 13.5 mm 2 /s at 100° C, wherein various types of sulfur-containing anti-wear and special extreme pressure agents may be added thereto.
- US 6,059,955 A discloses a low viscosity lube oil material having a saturate content greater than 98 % saturates, which is suitable for an automatic transmission fluid (ATF) basestock, which is of an isoparaffinic type and has a viscosity of 3.0 to 5.0 mm 2 /s at 100° C such that the automatic transmission fluid has a kinematic viscosity of at least 6.2 mm 2 /s at 100° C.
- ATF automatic transmission fluid
- Japanese Patent Laid-Open Publication No. 1-271494 discloses a transmission oil composition which comprises a specific amount of a base oil containing an ⁇ -olefin oligomer and a petroleum-based lubricant fraction and a specific amount of a polymethacrylate with a specific number-average molecular weight and has a kinematic viscosity of 7 cSt or greater at 140 °C.
- a power transmitting fluid whose main purpose is to improve the performance of a torque converter clutch in a slip mode and which comprises a base oil containing a hydrogenated mineral oil with a specific viscosity and a hydrogenated poly- ⁇ -olefin oligomer with a specific viscosity, an acrylic viscosity improver, and other additive components and has a viscosity of at least 6.8 cSt at 100 °C after 40 cycles in the FISST of ASTM D-5275 .
- these compositions each have a high viscosity while automobile transmission oils currently available on the market have generally a viscosity of from 7 - 9 mm 2 /s at 100 °C .
- a general object of the present invention is to provide a low viscosity transmission lubricating oil composition which is excellent in fuel efficiency and provides gears and wet clutches with sufficient durabilities such that the long lasting gear change characteristics can be obtained.
- a lubricating oil composition for transmissions having the features as defined in claim 1, wherein the mineral lubricating oil having a kinematic viscosity of from 2.3 to 3.4 mm 2 /s and a %Cp of 70 or higher defined by ASTM D 3238 is hereinafter referred to as "Component (A) " , wherein the phosphorus compound is hereinafter referred to as “Component (B)” , and wherein the viscosity index improver ishereinafter referred to as "Component (C)”.
- lubricating oil composition for transmissions (hereinafter may be referred to as "lubricating oil composition” or “lubricating oil”) of the present invention will be described in detail below.
- Component (A) for use in the present invention comprises a mineral oil having a kinematic viscosity of from 2.3 to 3.4 mm 2 /s and a %Cp of 70 or higher defined by ASTM D 3238.
- Component (A) comprising a mineral base oil meeting the above-described requirements, blended with Components (B) and (C) such that the sulfur content is adjusted to a specific amount, the resulting composition synergistically exhibits excellent fuel efficiency and extreme pressure properties and provides gears and wet clutches used under severe conditions with excellent durability.
- the upper limit kinematic viscosity of the mineral oil is 3.4 mm 2 /s, preferably 3.3 mm 2 /s at 100 °C, while the lower limit is 2.3 mm 2 /s, preferably 2.5 mm 2 /s at 100 °C.
- a kinematic viscosity in excess of 3.4 mm 2 /s at 100 °C is not preferred because it causes the increase of friction loss at the sites to be lubricated due to the increased fluid resistance, while a kinematic viscosity less than 2 . 3 mm 2 /s at 100°C is not also preferred because the resulting composition would be poor in lubricity due to insufficient oil film formation at the sites to be lubricated and encounters the evaporation loss of the base oil.
- the %Cp of the mineral base oil defined by ASTM D 3238 used in the present invention is preferably 71 or higher, more preferably 72 or higher, further more preferably 73 or higher, and still further preferably 74 or higher and is preferably 90 or lower, more preferably 85 or lower, and particularly preferably 82 or lower with the objective of obtaining an excellent solubility to additives.
- the %C p defined by ASTM D 3238 used herein refers to a percentage of paraffin carbon number to the total carbon number obtained by the ring analysis stipulated by this method.
- the viscosity index of mineral base oils used for Component (A) is preferably 50 or higher, more preferably 80 or higher, and further more preferably 100 or higher and is preferably 140 or lower and more preferably 130 or lower with the objective of more excellent low temperature properties.
- the use of a mineral base oil having a viscosity index of 50 or higher makes it possible to obtain a lubricating oil composition having the capabilities of both oil film formation and flow resistance reduction.
- the pour point of mineral base oils used for Component (A) is preferably 0 °C or lower, more preferably-5 °C or lower, and particularly preferably -10 °C .
- the use of a mineral base oil having a pour point of 0 °C or lower makes it possible to obtain a lubricating oil composition which is less preventive of the work of a machine at low temperatures.
- the mineral base oils may be paraffinic and naphthenic oils which can be obtained by subjecting a lubricating oil fraction produced by atmospheric- or vacuum- distilling a crude oil, to one or more refining processes such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid treating, and clay treatment.
- refining processes such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid treating, and clay treatment.
- These base oils may be used singlely or in combination mixed in an arbitrary proportion.
- More preferred methods of producing mineral base oils used in the present invention are as follows.
- the mineral base oils can be obtained by refining the starting oil or lubricant fractions recovered therefrom through usual refining processes and then recovering the lubricant fractions.
- the starting oil may be (1) distillate oils resulting from the atmospheric distillation of a paraffin based crude oil and/or of a mixed base crude oil; (2) vacuum distillate oils (WVGO) resulting from the vacuum distillation of the topped crude of a paraffin based crude oil and/or of a mixed base crude oil; (3) oils resulting from mild hydrocracking (MHC) of oils (1) and/or (2); (4) mixed oils of two or more selected from oils (1), (2), and (3); (5) deasphalted oils (DAO) of oils (1) to (4); (6) oils resulting from mild hydrocracking of oils (5); and (7) mixed oils of two or more selected from oils (1) to (6).
- WVGO vacuum distillate oils
- MHC mild hydrocracking
- DAO deasphalted oils
- refining processes mentioned above there is no restriction to the usual refining processes mentioned above which, therefore, may be any of the refining methods used upon production of lubricant base oils.
- refining methods are (a) hydro-refining such as hydrocracking and hydro-finishing; (b) solvent refining such as furfral extraction; (c) dewaxing such as solvent dewaxing and catalytic dewaxing; (d) clay treatment with acid clay or active clay; and (e) acid or alkali chemical refining such as sulfuric acid washing and caustic soda washing.
- hydro-refining such as hydrocracking and hydro-finishing
- solvent refining such as furfral extraction
- dewaxing such as solvent dewaxing and catalytic dewaxing
- clay treatment with acid clay or active clay and
- acid or alkali chemical refining such as sulfuric acid washing and caustic soda washing.
- one or more of these methods may be used in any combination in any order
- Particularly preferred mineral oils used in the present invention are starting oils selected from the above described (1) to (7); products obtained by hydrocracking lubricant fractions recovered from the starting oils; or components obtained by subjecting lubricant fractions recovered from the products to a dewaxing treatment such as solvent- or catalytic-dewaxing and then solvent-refining the resulting product, alternatively followed by a dewaxing treatment such as solvent- or catalytic-dewaxing.
- Component (A) used in the present invention may be a mixture of two or more mineral oils obtained by any of the above-described refining methods or a single kind of refined mineral oil.
- base oils used for Component (A) must meet the requirements that the kinematic viscosity is from 2.3 to 3.4 mm 2 /s at 100 °C and the %C P defined by ASTM D 3238 is 70 or higher.
- any kind of mineral oil can be used as Component (A).
- the mineral base oil used in the present invention may contain a small amount of synthetic oils such as poly- ⁇ -olefins and ester-based synthetic oils.
- Component (A) is contained in an amount of preferably at least 50 percent by mass, more preferably 60 percent by mass or more, further more preferably 75 percent by mass or more, and still further more preferably 80 percent by mass or more of the base oil.
- Component (B) contained in the lubricating oil composition of the present invention is a phosphorus compound.
- the content of Component (B) is from 0.025 to 0.05 percent by mass, preferably from 0.025 to 0.04 percent by mass, and particularly preferably from 0.03 to 0.035 in terms of phosphorus based on the total mass of the lubricating oil composition with the objective of imparting thereto excellent extreme pressure properties. Contents less than 0.025 percent by mass in terms of phosphorus are less effective to extreme pressure properties, while contents in excess of 0.05 percent by mass cause the deterioration of oxidation stability of the resulting composition and of durability of resin materials such as nylon.
- the phosphorus compound for Component (B) is selected by one of zinc alkyldithiophosphate, phosphoric acid, phosphorous acid, monophosphates, diphosphates, triphosphates, monophosphites, diphosphites, triphosphites, salts of phosphates and phosphites, thiophosphates, thiophosphites and esters thereof, and mixtures thereof.
- these components those other than phosphoric acid, thiophosphates, phosphorus acid, and thiophosphites are compounds containing a hydrocarbon group having 2 to 30, preferably 3 to 20 carbon atoms.
- hydrocarbon groups having 2 to 30 carbon atoms are alkyl, cycloalkyl, alkylcycloalkyl, aryl, alkylaryl, and arylalkyl groups.
- alkyl groups are ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups, all of which may be straight-chain or branched.
- cycloalkyl groups are those having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl, and cycloheptyl groups.
- alkylcycloalkyl groups are those having 6 to 11 carbon atoms, of which the cycloalkyl group may possess an alkyl substituent at any position, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethylcycloheptyl and diethylcycloheptyl groups.
- alkenyl groups are butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl groups, all of which may be straight-chain or branched and the position of which the double bond may vary.
- aryl groups are phenyl and naphthyl.
- alkylaryl groups are those having 7 to 18 carbon atoms, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, and dodecylphenyl groups, all of which the alkyl group may be straight-chain or branched and may bond to any position of the aryl group.
- arylalkyl groups are those having 7 to 12 carbon atoms, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl groups, all of which may be straight-chain or branched.
- Preferred compounds as Component (B) are phosphoric acid; phosphorus acid; zinc alkyldithiophosphates, of which the alkyl group may be straight-chain or branched, such as zinc dipropyldithiophosphate, zinc dibutyldithiophosphate, zinc dipentyldithiophospahte, zinc dihexyldithiophospahte, zinc diheptyldithiophospahte, and zinc dioctyldithiophospahte; monoalkyl phosphates, of which the alkyl group may be straight-chain or branched, such as monopropyl phosphate, monobutyl phosphate, monopentyl phosphate, monohexyl phosphate, monoheptyl phospahte and monooctyl phosphate; mono(alkyl)aryl phosphates such as monophenyl phospahte and monocresyl
- salts of phosphites and phosphates are those obtained by allowing a monophosphate, a diphosphate, a monophosphite, or a diphosphite to react with a nitrogen-containing compound such as ammonia or an amine compound having in its molecules only hydrocarbon or hydroxyl-containing groups having 1 to 8 carbon atoms so as to neutralize the whole or part of the remaining acid hydrogen.
- a nitrogen-containing compound such as ammonia or an amine compound having in its molecules only hydrocarbon or hydroxyl-containing groups having 1 to 8 carbon atoms
- nitrogen-containing compound examples include ammonia; alkylamines, of which the alkyl group may be straight-chain or branched, such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, monohexylamine, monoheptylamine, monooctylamine, dimethylamine, methylethylamine, diethylamine, methylpropylamine, ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine and dioctylamine; alkanolamines, of which the alkanol group may be straight-chain or branched, such as monomethanolamine, monoethanolamine, monopropanolamine, monobutanolamine, monopentanolamine, monohexanolamine;
- Phosphites and/or thiophosphites are preferably used as Component (B) of the lubricating oil composition of the present invention.
- Viscosity index improvers i.e., Component (C) are non-dispersion type and/or dispersion type viscosity index improvers.
- a lubricating oil composition comprising a dispersion type viscosity index improver is not claimed in the present invention.
- Said lubricating oil composition having the dispersion type viscosity index improver constitutes an example for supporting the understanding of the present invention.
- non-dispersion type-viscosity index improvers are copolymers of one or more monomers selected from the group consisting of compounds represented by formulas (1), (2) and (3) below, and hydrides of the copolymers:
- dispersion type-viscosity index improvers are copolymers of two or more monomers selected from the group consisting of compounds represented by formulas (4) and (5) below; ones obtained by introducing an oxygen-containing group into hydrides of the copolymers; copolymers of one or more monomers selected from the group consisting of compounds represented by formulas (1), (2) and (3) above with one or more monomers selected from the group consisting of compounds represented by formulas (4) and (5) below; and hydrides of the copolymers:
- R 1 is hydrogen or methyl
- R 2 is an alkyl group having 1 to 18 carbon atoms.
- alkyl groups having 1 to 18 carbon atoms for R 2 are alkyl groups, which may be straight-chain or branched, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.
- alkyl groups which may be straight-chain or branched, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexade
- R 3 is hydrogen or methyl
- R 4 is a hydrocarbon group having 1 to 12 carbon atoms.
- hydrocarbon groups having 1 to 12 carbon atoms for R 4 are alkyl groups, which may be straight-chain or branched, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups; alkenyl groups, which may be straight-chain or branched and the position of which the double bond may vary, such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups; cycloalkyl groups having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl, and cycloheptyl groups; alkylcycloalkyl groups, of which the alkyl group may bonded to any position of the cycl cycl
- X 1 and X 2 are each independently hydrogen, an alkoxy having 1 to 18 carbon atoms represented by the formula -OR 10 wherein R 10 is an alkyl group having 1 to 18 carbon atoms, or a monoalkylamine having 1 to 18 carbon atoms represented by the formula -NHR 11 wherein R 11 is an alkyl group having 1 to 18 carbon atoms.
- R 5 is hydrogen or methyl
- R 6 is an alkylene group having 1 to 18 carbon atoms
- Y 1 is an amine residue or heterocyclic residue having 1 or 2 nitrogen and 0 to 2 oxygen
- a is an integer of 0 or 1.
- alkylene groups having 1 to 18 carbon atoms for R 6 are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, and octadecylene groups, all of which may be straight-chain or branched.
- groups represented by Y 1 are dimethylamino, diethylamino, dipropylamino, dibutylamino, anilino, toluidino, xylidino, acetylamino, benzoilamino, morpholino, pyrrolyl, pyrrolino, pyridyl, methylpyridyl, pyrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino, and pyrazino groups.
- R 7 is hydrogen or methyl
- Y 2 is an amino- or heterocyclic- residue having 1 or 2 nitrogen and 0 to 2 oxygen.
- groups represented by Y 2 are dimethylamino, diethylamino, dipropylamino, dibutylamino, aniline, toluidino, xylidino, acetylamino, benzoilamino, morpholino, pyrrolyl, pyrrolino, pyridyl, methylpyridyl, pyrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino, and pyrazino groups.
- Preferred one or more monomers selected from compounds of formulas (1) - (3) above are alkylacrylates having 1 to 18 carbon atoms, alkylmethacrylates having 1 to 18 carbon atoms, olefins having 2 to 20 carbon atoms, styrene, methylstyrene, maleic anhydride ester, maleic an hydride amide, and mixtures thereof.
- Preferred one or more monomers selected from compounds of formulas (4) and (5) are dimethylaminomethylmethacrylate, diethylaminomethylmethacrylate, dimethylaminoethylmethacrylate, diethylaminoethylmethacrylate, 2-methyl-5-vinylpyridine, morpholinomethylmethacrylate, morpholinoethylmethacrylate, N-vinylpyrrolidone, and mixtures thereof.
- the molar ratio of the former to the latter is within the range of 80 : 20 to 95 : 5.
- a polymerization initiator such as benzoyl peroxide.
- viscosity index improvers are non-dispersion type- and dispersion type- polymethacrylates, non-dispersion type- and dispersion type- ethylene- ⁇ -olefin copolymers and hydrides thereof, polyisobutylene and hydrides thereof, styrene-diene hydrogenated copolymers, styrene-maleic anhydrides copolymers, and polyalkylstyrene.
- the molecular weight of Component (C) is preferably selected in view of shear stability. Specifically, it is desired that the dispersion type and non-dispersion type- polymethacrylates have a number-average molecular weight of 5,000 to 150,000, preferably 5,000 to 35,000. It is also desired that the polyisobutylnes and hydrides thereof have a number-average molecular weight of 800 to 5,000, preferably 2,000 to 4,000. Polyisobutylenes and hydrides thereof having a number-average molecular weight of less than 800 would be poor in thickening properties, while those having a number-average molecular weight in excess of 5,000 would deteriorate the shear stability and low-temperature flowability of the resulting lubricating oil composition.
- the lubricating oil composition of the present invention contains Component (C) in such an amount that the kinematic viscosity of the composition is made to from 5.0 to 6.0 mm 2 /s at 100°C.
- Component (C) in such an amount that the kinematic viscosity of the composition is made to from 5.0 to 6.0 mm 2 /s at 100°C.
- One or more compounds selected from these viscosity index improvers may be blended in an arbitrary amount.
- a lubricating oil composition with a kinematic viscosity less than 5.0 mm 2 /s at 100 °C is deteriorated in wear resistance, while one with a kinematic viscosity in excess of 6.0 mm 2 /s at 100 °C can not obtain a fuel efficiency as intended by the present invention.
- the lubricating oil composition of the present invention has a content of Component (C) from 0.1 to 20 percent by mass, based on the total mass of the composition.
- the upper limit sulfur content in the lubricating oil composition is 0.15 percent by mass, preferably 0.14 percent by mass, based on the total mass of the composition.
- a lubricating oil composition with a sulfur content in excess of 0.15 percent by mass reduces the durability of wet clutches.
- No particular limitation is imposed on the lower limit of sulfur content.
- the lower limit is preferably 0.02 percent by mass, more preferably 0.03 percent by mass, and particularly preferably 0.05 percent by mass with the objectives of producing a composition which is excellent in metal fatigue life and high in seizuring load.
- Examples of compounds containing sulfur are base oils containing sulfur contained in Component (A), phosphorus compounds containing sulfur contained in Component (B), compounds generally used in ATFs such as thiazole compounds, thiadiazole compounds, dithiocarbamate compounds, molybdenum dithiocarbamate compounds, dihydrocarbylpolysulfide compounds, sulfurized ester compounds, alkaline earth metal sulfonates, and alkaline earth metal phenates, or sulfuric compounds contained in diluent oils (light lubricant base oil or the like) for additives.
- ATFs such as thiazole compounds, thiadiazole compounds, dithiocarbamate compounds, molybdenum dithiocarbamate compounds, dihydrocarbylpolysulfide compounds, sulfurized ester compounds, alkaline earth metal sulfonates, and alkaline earth metal phenates, or sulfuric compounds contained in diluent oils (light lubricant base oil or the like) for
- a lubricating oil composition of the present invention which is excellent in fuel efficiency and extreme pressure properties for gears and capable of providing wet clutches with durability can be obtain by blending Component (A) as the base oil and Components (B) and (C) in specific amounts such that the kinematic viscosity of the resulting composition is made to from 5.0 to 6.0 mm 2 /s at 100°C and the sulfur content is made to 0.15 percent by mass or less, based on the total mass of the composition.
- ashless dispersants such as succinimides, metallic detergents such as calcium sulfonates, extreme pressure additives other than Component (B), friction modifiers, phenol- or amine-based oxidation inhibitors, rust inhibitors, corrosion inhibitors such as thiadiazoles, pour-point depressants, rubber swelling agents, antifoamers, and coloring agents.
- ashless dispersants such as succinimides, metallic detergents such as calcium sulfonates, extreme pressure additives other than Component (B), friction modifiers, phenol- or amine-based oxidation inhibitors, rust inhibitors, corrosion inhibitors such as thiadiazoles, pour-point depressants, rubber swelling agents, antifoamers, and coloring agents.
- additives may be used singlely or in combination.
- the amounts of these additives based on the total mass of the composition are from 0.1 to 10 percent by mass for ashless dispersants and metallic detergents, from 0.01 to 5 percent by mass for extreme pressure additives, friction modifiers, oxidation inhibitors, rust inhibitors, corrosion inhibitors, pour-point depressants, and rubber swelling agents, and from 0.0001 to 0.05 percent by mass for antifoamers and coloring agents.
- compositions were subjected to a test for evaluating its friction property for wet clutches.
- the extreme pressure property test was conducted using a Shell four-ball testing machine in accordance with ASTM D 2783 "Standard Test Method.for Measurement of Extreme-Pressure Property of Lubricating Fluids (Four-Ball Method)".
- One steel ball was fixed on the rotating axis and three steel balls were placed in the vessel such that all the four balls contact with each other.
- the vessel was filled with a sample oil. A load was applied to the three balls by pressing the ball on the rotation axis while the axis was held stationary.
- the rotation axis was rotated at a speed of 1,760 ⁇ 40 rpm for 10 seconds and the load was increased until welding occurs so as to obtain the last non-seizure load which is the last load at which the measured scar diameter is not more than 105 percent above the compensation scar diameter at the load.
- Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Component (A) Base Oil 1 1) mass% 70.1 40.0 63.6 29.7 63.6 63.6 Base Oil 2 2 ) mass% 13.4 46.9 12.7 21.2 12.7 12.7 Base Oil 3 3 ) mass% 0.0 0.0 8.5 17.0 8.5 8.5 Base Oil 4 4 ) mass% 0.0 0.0 0.0 17.0 0.0 0.0 Kinematic Viscosity of Component (A) (100°C) mm 2 /s
- the lubricating oil composition containing a mineral base oil whose %Cp was less than 70 (Comparative Example 1) and the composition containing a mineral base oil whose %Cp was less than 70 and containing more than 0.15 percent by mass of sulfur (Comparative Example 2) were large in the reduction of dynamic friction coefficient, while the composition containing a sulfur-containing phosphorus compound and thus containing sulfur in an amount of more than 0.15 percent by mass of the composition (Comparative Example 3) was high in extreme pressure properties but large in the reduction of dynamic friction coefficient.
- composition containing a phosphorus compound in an amount of less than 0.025 percent by mass in terms of phosphorus was significantly reduced in extreme pressure properties, while the composition whose Component (A) does not meet the requirements of the base oil kinematic viscosity and %Cp and sulfur content exceeds the range defined by the present invention (Comparative Example 5) was large in the reduction of dynamic friction coefficient and poor in extreme pressure properties.
- the lubricating oil composition of the present invention with the above described structure can not only be expected to make a transmission contributive to enhance the fuel efficiency due to its ability of reducing the stirring resistance in a torque converter or an oil pump but also provide wet clutches with a sufficient durability and obtain excellent extreme pressure properties. Therefore, the lubricating oil composition of the present invention is extremely useful as a fuel efficient type transmission oil composition which is completely different from the conventional ones.
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Description
- This invention relates to lubricating oil compositions for transmissions, and more particularly to such lubricating oil compositions which are excellent in fuel consumption efficiency and extreme pressure properties and capable of providing gear and clutches with sufficient durabilities such that the long lasting gear change characteristics can be obtained.
- In recent years, for the purpose of reducing the amount of carbon dioxide emission with the background of environmental issues, it becomes an urgent matter to improve the fuel economy of automobiles, resulting in a strong demand has been urged and resulted in a strong demand for automatic transmissions which are contributive to the improvement of fuel efficiency. There is one method of making an automatic transmission contributive to the improvement of fuel efficiency in which method to lower the viscosity of an automatic transmission fluid (ATF). An automatic transmission is constituted by a torque converter, a wet clutch, a gear bearing mechanism, and a hydraulic control mechanism and will be contributive to the improvement of fuel efficiency using an ATF with a lower viscosity which can reduce the stirring resistance in the torque converter and the oil pump.
- However, it is known that a low viscosity ATF reduces the durabilities of gears determining the transmission ratios and shift clutches, leading to the poor durability of the gear change characteristics. Lowering the viscosity of an ATF reduces its extreme pressure properties and thus causes the gears to be seized, resulting in malfunctioning of the automatic transmission. The selection of gears determining transmission ratios is effected by allowing some of the wet clutches to be coupled and allowing the other to be idled. However, since a low viscosity ATF reduces the durability of wet clutches, a dynamic friction coefficient necessary to couple the clutches is not generated, resulting in a possibility that the gear change may not work. Therefore, even though an ATF is lowered in viscosity, it must be capable of maintaining the durabilities of gears and wet clutches.
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EP 0 867 498 A1 discloses a transmission oil composition which comprises 0.05 to 2 % of at least one compound seleted from the group consisting of a metallic source of organic acids, particularly an alkaline-earth metal sort as component (A), 0.15 to 4 % of a specific polyamide compound as component (B) and 0.05 to 1.5 % of at least one compound selected from the group consisting of acid phosphate or acid phosphite esters as component (C). Additives may be further contained in said composition, wherein a viscosity index improver in an amount of 3 to 34 % by weight may be added. The kinematic viscosity of the base oil is in the range from 3 to 15 mm2/s and the base oil has a %Cp of less than 70. -
EP 0 978 555 A1 relates to a lubricating oil composition having a kinematic viscosity of at least 13.5 mm2/s at 100° C, wherein various types of sulfur-containing anti-wear and special extreme pressure agents may be added thereto. -
US 6,059,955 A discloses a low viscosity lube oil material having a saturate content greater than 98 % saturates, which is suitable for an automatic transmission fluid (ATF) basestock, which is of an isoparaffinic type and has a viscosity of 3.0 to 5.0 mm2/s at 100° C such that the automatic transmission fluid has a kinematic viscosity of at least 6.2 mm2/s at 100° C. - As one example of the conventional transmission oil compositions, there is known one disclosed in
Japanese Patent Laid-Open Publication No. 1-271494 Japanese Patent Laid-Open Publication No. 8-209174 - In view of the above-described circumstances, a general object of the present invention is to provide a low viscosity transmission lubricating oil composition which is excellent in fuel efficiency and provides gears and wet clutches with sufficient durabilities such that the long lasting gear change characteristics can be obtained.
- According to the present invention, there is provided a lubricating oil composition for transmissions having the features as defined in claim 1, wherein the mineral lubricating oil having a kinematic viscosity of from 2.3 to 3.4 mm2/s and a %Cp of 70 or higher defined by ASTM D 3238 is hereinafter referred to as "Component (A) " , wherein the phosphorus compound is hereinafter referred to as "Component (B)" , and wherein the viscosity index improver ishereinafter referred to as "Component (C)".
- The lubricating oil composition for transmissions (hereinafter may be referred to as "lubricating oil composition" or "lubricating oil") of the present invention will be described in detail below.
- Component (A) for use in the present invention comprises a mineral oil having a kinematic viscosity of from 2.3 to 3.4 mm2/s and a %Cp of 70 or higher defined by ASTM D 3238.
- Due to the use of Component (A) comprising a mineral base oil meeting the above-described requirements, blended with Components (B) and (C) such that the sulfur content is adjusted to a specific amount, the resulting composition synergistically exhibits excellent fuel efficiency and extreme pressure properties and provides gears and wet clutches used under severe conditions with excellent durabilities.
- The upper limit kinematic viscosity of the mineral oil is 3.4 mm2/s, preferably 3.3 mm2/s at 100 °C, while the lower limit is 2.3 mm2/s, preferably 2.5 mm2/s at 100 °C. A kinematic viscosity in excess of 3.4 mm2/s at 100 °C is not preferred because it causes the increase of friction loss at the sites to be lubricated due to the increased fluid resistance, while a kinematic viscosity less than 2 . 3 mm2/s at 100°C is not also preferred because the resulting composition would be poor in lubricity due to insufficient oil film formation at the sites to be lubricated and encounters the evaporation loss of the base oil.
- The %Cp of the mineral base oil defined by ASTM D 3238 used in the present invention is preferably 71 or higher, more preferably 72 or higher, further more preferably 73 or higher, and still further preferably 74 or higher and is preferably 90 or lower, more preferably 85 or lower, and particularly preferably 82 or lower with the objective of obtaining an excellent solubility to additives. The %Cp defined by ASTM D 3238 used herein refers to a percentage of paraffin carbon number to the total carbon number obtained by the ring analysis stipulated by this method.
- No particular limitation is imposed on the viscosity index of mineral base oils used for Component (A). However, the viscosity index is preferably 50 or higher, more preferably 80 or higher, and further more preferably 100 or higher and is preferably 140 or lower and more preferably 130 or lower with the objective of more excellent low temperature properties. The use of a mineral base oil having a viscosity index of 50 or higher makes it possible to obtain a lubricating oil composition having the capabilities of both oil film formation and flow resistance reduction.
- No particular limitation is imposed on the pour point of mineral base oils used for Component (A) as well. However, the pour point is preferably 0 °C or lower, more preferably-5 °C or lower, and particularly preferably -10 °C . The use of a mineral base oil having a pour point of 0 °C or lower makes it possible to obtain a lubricating oil composition which is less preventive of the work of a machine at low temperatures.
- No particular limitation is imposed on the method of producing mineral base oils used for Component (A). For example, the mineral base oils may be paraffinic and naphthenic oils which can be obtained by subjecting a lubricating oil fraction produced by atmospheric- or vacuum- distilling a crude oil, to one or more refining processes such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid treating, and clay treatment. These base oils may be used singlely or in combination mixed in an arbitrary proportion.
- More preferred methods of producing mineral base oils used in the present invention are as follows.
- For example, the mineral base oils can be obtained by refining the starting oil or lubricant fractions recovered therefrom through usual refining processes and then recovering the lubricant fractions. The starting oil may be (1) distillate oils resulting from the atmospheric distillation of a paraffin based crude oil and/or of a mixed base crude oil; (2) vacuum distillate oils (WVGO) resulting from the vacuum distillation of the topped crude of a paraffin based crude oil and/or of a mixed base crude oil; (3) oils resulting from mild hydrocracking (MHC) of oils (1) and/or (2); (4) mixed oils of two or more selected from oils (1), (2), and (3); (5) deasphalted oils (DAO) of oils (1) to (4); (6) oils resulting from mild hydrocracking of oils (5); and (7) mixed oils of two or more selected from oils (1) to (6).
- There is no restriction to the usual refining processes mentioned above which, therefore, may be any of the refining methods used upon production of lubricant base oils. Specific examples of such refining methods are (a) hydro-refining such as hydrocracking and hydro-finishing; (b) solvent refining such as furfral extraction; (c) dewaxing such as solvent dewaxing and catalytic dewaxing; (d) clay treatment with acid clay or active clay; and (e) acid or alkali chemical refining such as sulfuric acid washing and caustic soda washing. In the present invention, one or more of these methods may be used in any combination in any order.
- Particularly preferred mineral oils used in the present invention are starting oils selected from the above described (1) to (7); products obtained by hydrocracking lubricant fractions recovered from the starting oils; or components obtained by subjecting lubricant fractions recovered from the products to a dewaxing treatment such as solvent- or catalytic-dewaxing and then solvent-refining the resulting product, alternatively followed by a dewaxing treatment such as solvent- or catalytic-dewaxing.
- Component (A) used in the present invention may be a mixture of two or more mineral oils obtained by any of the above-described refining methods or a single kind of refined mineral oil. However, in either case, base oils used for Component (A) must meet the requirements that the kinematic viscosity is from 2.3 to 3.4 mm2/s at 100 °C and the %CP defined by ASTM D 3238 is 70 or higher. In other words, as long as the requirements are met, any kind of mineral oil can be used as Component (A).
- The mineral base oil used in the present invention may contain a small amount of synthetic oils such as poly-α-olefins and ester-based synthetic oils. However, in the lubricating oil composition of the present invention, Component (A) is contained in an amount of preferably at least 50 percent by mass, more preferably 60 percent by mass or more, further more preferably 75 percent by mass or more, and still further more preferably 80 percent by mass or more of the base oil.
- Component (B) contained in the lubricating oil composition of the present invention is a phosphorus compound.
- The content of Component (B) is from 0.025 to 0.05 percent by mass, preferably from 0.025 to 0.04 percent by mass, and particularly preferably from 0.03 to 0.035 in terms of phosphorus based on the total mass of the lubricating oil composition with the objective of imparting thereto excellent extreme pressure properties. Contents less than 0.025 percent by mass in terms of phosphorus are less effective to extreme pressure properties, while contents in excess of 0.05 percent by mass cause the deterioration of oxidation stability of the resulting composition and of durability of resin materials such as nylon.
- The phosphorus compound for Component (B) is selected by one of zinc alkyldithiophosphate, phosphoric acid, phosphorous acid, monophosphates, diphosphates, triphosphates, monophosphites, diphosphites, triphosphites, salts of phosphates and phosphites, thiophosphates, thiophosphites and esters thereof, and mixtures thereof. Among these components (Component (B)), those other than phosphoric acid, thiophosphates, phosphorus acid, and thiophosphites are compounds containing a hydrocarbon group having 2 to 30, preferably 3 to 20 carbon atoms.
- Examples of hydrocarbon groups having 2 to 30 carbon atoms are alkyl, cycloalkyl, alkylcycloalkyl, aryl, alkylaryl, and arylalkyl groups.
- Examples of alkyl groups are ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups, all of which may be straight-chain or branched.
- Examples of cycloalkyl groups are those having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl, and cycloheptyl groups.
- Examples of alkylcycloalkyl groups are those having 6 to 11 carbon atoms, of which the cycloalkyl group may possess an alkyl substituent at any position, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethylcycloheptyl and diethylcycloheptyl groups.
- Examples of alkenyl groups are butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl groups, all of which may be straight-chain or branched and the position of which the double bond may vary.
- Examples of aryl groups are phenyl and naphthyl. Examples of alkylaryl groups are those having 7 to 18 carbon atoms, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, and dodecylphenyl groups, all of which the alkyl group may be straight-chain or branched and may bond to any position of the aryl group.
- Examples of arylalkyl groups are those having 7 to 12 carbon atoms, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl groups, all of which may be straight-chain or branched.
- Preferred compounds as Component (B) are phosphoric acid; phosphorus acid; zinc alkyldithiophosphates, of which the alkyl group may be straight-chain or branched, such as zinc dipropyldithiophosphate, zinc dibutyldithiophosphate, zinc dipentyldithiophospahte, zinc dihexyldithiophospahte, zinc diheptyldithiophospahte, and zinc dioctyldithiophospahte; monoalkyl phosphates, of which the alkyl group may be straight-chain or branched, such as monopropyl phosphate, monobutyl phosphate, monopentyl phosphate, monohexyl phosphate, monoheptyl phospahte and monooctyl phosphate; mono(alkyl)aryl phosphates such as monophenyl phospahte and monocresyl phosphate; dialkyl phosphates, of which the alkyl group may be straight-chain or branched, such as dipropyl phosphate, dibutyl phosphate, dipentyl phospahte, dihexyl phosphate, diheptyl phosphate and dioctyl phospahte; di(alkyl)aryl phosphates such as diphenyl phosphate and dicresyl phospahte; trialkyl phosphates, of which the alkyl group may be straight-chain or branched, such as tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate and trioctyl phosphate; tri(alkyl)aryl phosphates such as triphenyl phosphate and tricresyl phosphate; monoalkyl phosphites, of which the alkyl group may be straight-chain or branched, such as monopropyl phosphite, monobutyl phosphite, monopentyl phosphite, monohexyl phosphite, monoheptyl phosphite and monooctyl phosphite; mono(alkyl)aryl phosphites such as monophenyl phosphite and monocresyl phosphite; dialkyl phosphites, of which the alkyl group may be straight-chain or branched, such as dipropyl phosphite, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite and dioctyl phosphite; di (alkyl) aryl phosphites such as diphenyl phosphite and dicresyl phosphite; trialkyl phosphites, of which the alkyl group may be straight-chain or branched, such as tripropyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite and trioctyl phosphite; tri(alkyl)aryl phosphites, of which the alkyl group may be straight-chain or branched, such as triphenyl phosphite and tricresyl phosphite; and mixtures thereof.
- Specific examples of salts of phosphites and phosphates are those obtained by allowing a monophosphate, a diphosphate, a monophosphite, or a diphosphite to react with a nitrogen-containing compound such as ammonia or an amine compound having in its molecules only hydrocarbon or hydroxyl-containing groups having 1 to 8 carbon atoms so as to neutralize the whole or part of the remaining acid hydrogen.
- Specific examples of the nitrogen-containing compound are ammonia; alkylamines, of which the alkyl group may be straight-chain or branched, such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, monohexylamine, monoheptylamine, monooctylamine, dimethylamine, methylethylamine, diethylamine, methylpropylamine, ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine and dioctylamine; alkanolamines, of which the alkanol group may be straight-chain or branched, such as monomethanolamine, monoethanolamine, monopropanolamine, monobutanolamine, monopentanolamine, monohexanolamine, monoheptanolamine, monooctanolamine, monononanolamine, dimethanolamine, methanolethanolamine, diethanolamine, methanolpropanolamine, ethanolpropanolamine, dipropanolamine, methanolbutanolamine, ethanolbutanolamine, propanolbutanolamine, dibutanolamine, dipentanolamine, dihexanolamine, diheptanolamine and dioctanolamine; and mixtures thereof. One or more of these Components (B) may be blended arbitrarily.
- Phosphites and/or thiophosphites are preferably used as Component (B) of the lubricating oil composition of the present invention.
- Viscosity index improvers, i.e., Component (C) are non-dispersion type and/or dispersion type viscosity index improvers.
- In this context, it is pointed out expressly that a lubricating oil composition comprising a dispersion type viscosity index improver is not claimed in the present invention. Said lubricating oil composition having the dispersion type viscosity index improver constitutes an example for supporting the understanding of the present invention.
- Specific examples of the non-dispersion type-viscosity index improvers are copolymers of one or more monomers selected from the group consisting of compounds represented by formulas (1), (2) and (3) below, and hydrides of the copolymers:
- Specific examples of dispersion type-viscosity index improvers are copolymers of two or more monomers selected from the group consisting of compounds represented by formulas (4) and (5) below; ones obtained by introducing an oxygen-containing group into hydrides of the copolymers; copolymers of one or more monomers selected from the group consisting of compounds represented by formulas (1), (2) and (3) above with one or more monomers selected from the group consisting of compounds represented by formulas (4) and (5) below; and hydrides of the copolymers:
- In formula (1) above, R1 is hydrogen or methyl, and R2 is an alkyl group having 1 to 18 carbon atoms.
- Specific examples of alkyl groups having 1 to 18 carbon atoms for R2 are alkyl groups, which may be straight-chain or branched, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.
- In formula (2) above, R3 is hydrogen or methyl, and R4 is a hydrocarbon group having 1 to 12 carbon atoms.
- Specific examples of hydrocarbon groups having 1 to 12 carbon atoms for R4 are alkyl groups, which may be straight-chain or branched, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups; alkenyl groups, which may be straight-chain or branched and the position of which the double bond may vary, such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups; cycloalkyl groups having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl, and cycloheptyl groups; alkylcycloalkyl groups, of which the alkyl group may bonded to any position of the cycloalkyl group, having 6 to 11 carbon atoms, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethylcycloheptyl, and diethylcycloheptyl groups; aryl groups such as phenyl and naphtyl groups; alkylaryl groups, of which the alkyl group may be straight-chain or branched and bond to any position of the aryl group, having 7 to 12 carbon groups, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, and hexylphenyl groups; and arylalkyl groups, of which the alkyl group may be straight-chain or branched, having 7 to 12 carbon atoms, such as benzyl, phenylethyl, phenylpropyl, phneylbutyl, phenylpentyl, and phenylhexyl groups.
- In formula (3) above, X1 and X2 are each independently hydrogen, an alkoxy having 1 to 18 carbon atoms represented by the formula -OR10 wherein R10 is an alkyl group having 1 to 18 carbon atoms, or a monoalkylamine having 1 to 18 carbon atoms represented by the formula -NHR11 wherein R11 is an alkyl group having 1 to 18 carbon atoms.
- In formula (4) above, R5 is hydrogen or methyl, R6 is an alkylene group having 1 to 18 carbon atoms, Y1 is an amine residue or heterocyclic residue having 1 or 2 nitrogen and 0 to 2 oxygen, and a is an integer of 0 or 1.
- Specific examples of alkylene groups having 1 to 18 carbon atoms for R6 are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, and octadecylene groups, all of which may be straight-chain or branched.
- Specific examples of groups represented by Y1 are dimethylamino, diethylamino, dipropylamino, dibutylamino, anilino, toluidino, xylidino, acetylamino, benzoilamino, morpholino, pyrrolyl, pyrrolino, pyridyl, methylpyridyl, pyrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino, and pyrazino groups.
- In formula (5), R7 is hydrogen or methyl, and Y2 is an amino- or heterocyclic- residue having 1 or 2 nitrogen and 0 to 2 oxygen.
- Specific examples of groups represented by Y2 are dimethylamino, diethylamino, dipropylamino, dibutylamino, aniline, toluidino, xylidino, acetylamino, benzoilamino, morpholino, pyrrolyl, pyrrolino, pyridyl, methylpyridyl, pyrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino, and pyrazino groups.
- Preferred one or more monomers selected from compounds of formulas (1) - (3) above are alkylacrylates having 1 to 18 carbon atoms, alkylmethacrylates having 1 to 18 carbon atoms, olefins having 2 to 20 carbon atoms, styrene, methylstyrene, maleic anhydride ester, maleic an hydride amide, and mixtures thereof.
- Preferred one or more monomers selected from compounds of formulas (4) and (5) are dimethylaminomethylmethacrylate, diethylaminomethylmethacrylate, dimethylaminoethylmethacrylate, diethylaminoethylmethacrylate, 2-methyl-5-vinylpyridine, morpholinomethylmethacrylate, morpholinoethylmethacrylate, N-vinylpyrrolidone, and mixtures thereof.
- When one or more monomers selected from compounds of formulas (1) - (3) is copolymerized with one or more monomers selected from compounds of formulas (4) and (5), the molar ratio of the former to the latter is within the range of 80 : 20 to 95 : 5. Although no particular limitation is imposed on the copolymerization method, such copolymers are generally obtained by radical-solution polymerization of the former with the latter in the presence of a polymerization initiator such as benzoyl peroxide.
- Specific examples of the viscosity index improvers are non-dispersion type- and dispersion type- polymethacrylates, non-dispersion type- and dispersion type- ethylene-α-olefin copolymers and hydrides thereof, polyisobutylene and hydrides thereof, styrene-diene hydrogenated copolymers, styrene-maleic anhydrides copolymers, and polyalkylstyrene.
- The molecular weight of Component (C) is preferably selected in view of shear stability. Specifically, it is desired that the dispersion type and non-dispersion type- polymethacrylates have a number-average molecular weight of 5,000 to 150,000, preferably 5,000 to 35,000. It is also desired that the polyisobutylnes and hydrides thereof have a number-average molecular weight of 800 to 5,000, preferably 2,000 to 4,000. Polyisobutylenes and hydrides thereof having a number-average molecular weight of less than 800 would be poor in thickening properties, while those having a number-average molecular weight in excess of 5,000 would deteriorate the shear stability and low-temperature flowability of the resulting lubricating oil composition.
- The lubricating oil composition of the present invention contains Component (C) in such an amount that the kinematic viscosity of the composition is made to from 5.0 to 6.0 mm2/s at 100°C. One or more compounds selected from these viscosity index improvers may be blended in an arbitrary amount. A lubricating oil composition with a kinematic viscosity less than 5.0 mm2/s at 100 °C is deteriorated in wear resistance, while one with a kinematic viscosity in excess of 6.0 mm2/s at 100 °C can not obtain a fuel efficiency as intended by the present invention. The lubricating oil composition of the present invention has a content of Component (C) from 0.1 to 20 percent by mass, based on the total mass of the composition.
- The upper limit sulfur content in the lubricating oil composition is 0.15 percent by mass, preferably 0.14 percent by mass, based on the total mass of the composition. A lubricating oil composition with a sulfur content in excess of 0.15 percent by mass reduces the durability of wet clutches. No particular limitation is imposed on the lower limit of sulfur content. However, the lower limit is preferably 0.02 percent by mass, more preferably 0.03 percent by mass, and particularly preferably 0.05 percent by mass with the objectives of producing a composition which is excellent in metal fatigue life and high in seizuring load. Examples of compounds containing sulfur are base oils containing sulfur contained in Component (A), phosphorus compounds containing sulfur contained in Component (B), compounds generally used in ATFs such as thiazole compounds, thiadiazole compounds, dithiocarbamate compounds, molybdenum dithiocarbamate compounds, dihydrocarbylpolysulfide compounds, sulfurized ester compounds, alkaline earth metal sulfonates, and alkaline earth metal phenates, or sulfuric compounds contained in diluent oils (light lubricant base oil or the like) for additives.
- In the present invention, a lubricating oil composition of the present invention which is excellent in fuel efficiency and extreme pressure properties for gears and capable of providing wet clutches with durability can be obtain by blending Component (A) as the base oil and Components (B) and (C) in specific amounts such that the kinematic viscosity of the resulting composition is made to from 5.0 to 6.0 mm2/s at 100°C and the sulfur content is made to 0.15 percent by mass or less, based on the total mass of the composition. In order to further enhance the properties, there may be added ashless dispersants such as succinimides, metallic detergents such as calcium sulfonates, extreme pressure additives other than Component (B), friction modifiers, phenol- or amine-based oxidation inhibitors, rust inhibitors, corrosion inhibitors such as thiadiazoles, pour-point depressants, rubber swelling agents, antifoamers, and coloring agents. These additives may be used singlely or in combination. The amounts of these additives based on the total mass of the composition are from 0.1 to 10 percent by mass for ashless dispersants and metallic detergents, from 0.01 to 5 percent by mass for extreme pressure additives, friction modifiers, oxidation inhibitors, rust inhibitors, corrosion inhibitors, pour-point depressants, and rubber swelling agents, and from 0.0001 to 0.05 percent by mass for antifoamers and coloring agents.
- The present invention will be further described in the following examples, but the present invention should not be construed as being limited thereto.
- Various lubricating oil compositions were prepared in accordance with the formulations shown in Tables 1 (Examples) and 2 (Comparative Examples). Various additives were added in amounts based on the total mass of the composition.
- Each of the resulting lubricating oil compositions was evaluated by (1) gear-shifting property test and (2) extreme pressure test, and the results were also shown in Tables 1 and 2.
- Each of the compositions was subjected to a test for evaluating its friction property for wet clutches.
- The friction property test for wet clutches was conducted in accordance with JASO M348-95 "Test Method for Friction Property of Automatic Transmission Fluids" using an SAE No. 2 test machine under the following conditions thereby evaluating the durability of the shifting properties of a clutch.
-
- Fluid Temperature : 120 °C
- Number of Revolutions : 5,000 rpm
- Moment of Inertia : 0.343 kg·m
- Pushing Load : 0.785 kPa
- Number of Tests : 2500
- Pressing Time : 4 seconds
- The rest of the conditions were determined in accordance with JASO M348-95.
- In this test, only the dynamic friction test was conducted wherein after the clutch was rotated at the constant speed of 5,000 rpm without load using flywheels with a moment of inertia of 0.343 kg · m, the clutch was stopped by applying a pressure thereto. The friction coefficient was calculated from the torque generated when the number of revolutions of the clutch was reduced to 1,800 rpm and was defied as the dynamic friction coefficient.
- 2,500 cycles of the dynamic friction test was conducted for each of the compositions such that the durability of shifting properties thereof was evaluated by the difference between the dynamic friction coefficient after 500 cycles and that after 2,500 cycles. When the difference was within 0.02, the composition was evaluated to be excellent in the durability.
- The extreme pressure property test was conducted using a Shell four-ball testing machine in accordance with ASTM D 2783 "Standard Test Method.for Measurement of Extreme-Pressure Property of Lubricating Fluids (Four-Ball Method)". One steel ball was fixed on the rotating axis and three steel balls were placed in the vessel such that all the four balls contact with each other. The vessel was filled with a sample oil. A load was applied to the three balls by pressing the ball on the rotation axis while the axis was held stationary. Thereafter, the rotation axis was rotated at a speed of 1,760±40 rpm for 10 seconds and the load was increased until welding occurs so as to obtain the last non-seizure load which is the last load at which the measured scar diameter is not more than 105 percent above the compensation scar diameter at the load. The higher the last non-seizure load, the better the extreme pressure properties of the sample.
Table 1. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Component (A) Base Oil 11) mass% 70.1 40.0 63.6 29.7 63.6 63.6 Base Oil 22) mass% 13.4 46.9 12.7 21.2 12.7 12.7 Base Oil 33) mass% 0.0 0.0 8.5 17.0 8.5 8.5 Base Oil 44) mass% 0.0 0.0 0.0 17.0 0.0 0.0 Kinematic Viscosity of Component (A) (100°C) mm2/s mm2/s 2.8 3.3 3 3 3 3 %Cp of Component (A) 74 76 73 71 73 73 Component (B) Phosphorus Additive 15) mass% 0.2 0.2 0.2 0.2 0.15 0.10 Phosphorus Additive 26) mass% 0.17 0.34 Phosphorus Content in Component (B) in mass% 0.03 0.03 0.03 0.03 0.03 0.03 Sulfur Content in Component (B) mass% 0.00 0.00 0.00 0.00 0.026 0.052 Component (C) Viscosity Index Improver7) mass% 12 8.6 10.7 10.7 10.7 10.7 Other Additives Ashless Dispersant8) mass% 3.0 3.0 3.0 3.0 3.0 3.0 Ca-based Detergent9) mass% 0.1 0.1 0.1 0.1 0.1 0.1 Friction Modifier10) mass% 0.1 0.1 0.1 0.1 0.1 0.1 Oxidation Inhibitor 111) mass% 0.5 0.5 0.5 0.5 0.5 0.5 Oxidation Inhibitor 212) mass% 0.5 0.5 0.5 0.5 0.5 0.5 Corrosion Inhibitor13) mass% 0.1 0.1 0.1 0.1 0.1 0.1 Antifoamer14) mass% 0.002 0.002 0.002 0.002 0.002 0.002 Kinematic Viscosity of Composition (100°C) mm2/s 5.5 5.5 5.5 5.5 5.5 5.5 Sulfur Content in Composition mass% 0.07 0.07 0.08 0.13 0.11 0.13 SAE No.2 Test Friction Coefficient after 500 cycles 0.12 0.12 0.12 0.12 0.12 0.12 Friction Coefficient after 2,500 cycles 0.11 0.11 0.11 0.11 0.11 0.11 Last Non-Seizure Load N 618 618 618 618 618 785 Table 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Component (A) Base Oil 11) mass% 33.9 0.0 63.6 63.7 0.0 Base Oil 22) mass% 8.5 0.0 12.7 12.7 0.0 Base Oil 33) mass% 25.4 46.6 8.5 8.5, 0.0 Base Oil 44) mass% 17.0 38.2 0.0 0.0 78.4 Kinematic Viscosity of Component (A) (100°C) mm2/s 3 3 3 3 2.1 %Cp of Component (A) 69 64 73 73 61 Component (B) Phosphorus Additive 15) mass% 0.2 0.2, 0.05 0.1 0.2 Phosphorus Additive 26) mass% 0.51 Phosphorus Content in Component (B) in mass% 0.03 0.03 0.03 0.02 0.03 Sulfur Content in Component (B) mass% 0.00 0.00 0.078 0.00 0.00 Component (C) Viscosity Index Improver7) mass% 10.7 10.7 10.7 10.7 17.1 Other Additives Ashless Dispersant8) mass% 3.0 3.0 3.0 3.0. 3.0 Ca-based Detergent9) mass% 0.1 0.1 0.1 0.1 0.1 Friction Modifier10) mass% 0.1 0.1 0.1 0.1 0.1 Oxidation Inhibitor 111) mass% 0.5 0.5 0.5 0.5 0.5 Oxidation Inhibitor 212) mass% 0.5 0.5 0.5 0.5 0.5 Corrosion Inhibitor13) mass% 0.1 0.1 0.1 0.1 0.1 Antifoamer14) mass% 0.002 0.002 0.002 0.002 0.002 Kinematic Viscosity of Composition (100°C) mm2/s 5.5 5.5 5.5 5.5 5.5 Sulfur Content in Composition mass% 0.14 0.22 0.16 0.07 0.23 SAE No.2 Test Friction Coefficient after 500 cycles 0.12 0.12 0.12 0.11 0.13 Friction Coefficient after 2,500 cycles 0.09 0.08 0.09 0.11 0:08 Last Non-Seizure Load N 618 618 785 392 392
1) Hydrogenated Refined Base Oil (viscosity index 105, %Cp 73)
2) Hydrogenated Refined Base Oil (viscosity index 125, %Cp 79)
3) Solvent Refined Base Oil (viscosity index 95, %Cp 67)
4) Solvent Refined Base Oil (viscosity index 95, %Cp 61)
5) Phosphite (phosphorus content 16.4mass%)
6) Trithiophosphite (phosphorus, content 4.9mass%, sulfur content 15.2mass%)
7) Non Dispersion Type Polymethacrylate (weight average molecular weight 20,000)
8) Polybutenyl Succinimide (bistype)
9) Calcium Sulfonate (total acid value 300mgKOH/g)
10) Amine-based
11) Dialkyldiphenylamine
12) Bis phenol-based
13) Thiadiazole-based
14) Polydiinethylsiloxane
1) Hydrogenated Refined Base Oil (viscosity index 105, %Cp 73)
2) Hydrogenated Refined Base Oil (viscosity index 125, %Cp 79)
3) Solvent Refined Base Oil (viscosity index 95, %Cp 67)
4) Solvent Refined Base Oil (viscosity index 95, %Cp 61)
5) Phosphite (phosphorus content 16.4mass%)
6) Trithiophosphite (phosphorus, content 4.9mass%, sulfur content 15.2mass%)
7) Non Dispersion Type Polymethacrylate (weight average molecular weight 20,000)
8) Polybutenyl Succinimide (bistype)
9) Calcium Sulfonate (total acid value 300mgKOH/g)
10) Amine-based
11) Dialkyldiphenylamine
12) Bis phenol-based
13) Thiadiazole-based
14) Polydiinethylsiloxane - As apparent from the test results shown in Tables 1 and 2, the lubricating oil compositions according to the present invention (Examples 1 to 6) were less in the reduction of dynamic friction coefficient and high in extreme pressure properties.
- Whereas, the lubricating oil composition containing a mineral base oil whose %Cp was less than 70 (Comparative Example 1) and the composition containing a mineral base oil whose %Cp was less than 70 and containing more than 0.15 percent by mass of sulfur (Comparative Example 2) were large in the reduction of dynamic friction coefficient, while the composition containing a sulfur-containing phosphorus compound and thus containing sulfur in an amount of more than 0.15 percent by mass of the composition (Comparative Example 3) was high in extreme pressure properties but large in the reduction of dynamic friction coefficient. The composition containing a phosphorus compound in an amount of less than 0.025 percent by mass in terms of phosphorus (Comparative Example 4) was significantly reduced in extreme pressure properties, while the composition whose Component (A) does not meet the requirements of the base oil kinematic viscosity and %Cp and sulfur content exceeds the range defined by the present invention (Comparative Example 5) was large in the reduction of dynamic friction coefficient and poor in extreme pressure properties.
- The lubricating oil composition of the present invention with the above described structure can not only be expected to make a transmission contributive to enhance the fuel efficiency due to its ability of reducing the stirring resistance in a torque converter or an oil pump but also provide wet clutches with a sufficient durability and obtain excellent extreme pressure properties. Therefore, the lubricating oil composition of the present invention is extremely useful as a fuel efficient type transmission oil composition which is completely different from the conventional ones.
Claims (2)
- A lubricating oil composition for transmissions which comprises(A) a mineral lubricating oil having a kinematic viscosity of from 2.3 to 3.4 mm2/s and a %Cp of 70 or higher defined by ASTM D 3238, as a base oil,(B) a phosphorus compound in an amount of from 0.025 to 0.05 percent by mass in terms of phosphorus based on the total mass of said composition, wherein said phosphorous compound is selected by one of zinc alkyldithiophosphate; phosphoric acid; phosphorous acid; monophosphates; diphosphates; triphosphates; monophosphites; diphosphites; triphosphites; salts of phosphates and phosphites; thiophosphates; thiophosphites or esters thereof; or mixtures thereof; wherein those other than phosphoric acid, phosphorous acid, thiophosphates and thiophosphites are compounds comprising a hydrocarbon group having 2 to 30 carbon atoms; and(C) a viscosity index improver of a non-dispersion type in an amount of from 0.1 to 20 percent by mass based on the total mass of the composition so that said composition has a kinematic viscosity of from 5.0 to 6.0 mm2/s, wherein sulfur being contained in an amount of 0.15 percent by mass or less in said composition.
- The lubricating oil composition for transmissions according to claim 1 which comprises(A) a mineral lubricating oil having a kinematic viscosity of from 2.5 to 3.3 mm2/s at 100°C and a %Cp of from 74 to 82 defined by ASTM D 3238, as a base oil,(B) a phosphorus compound in an amount of from 0.03 to 0.035 percent by mass in terms of phosphorus based on the total mass of said composition, and(C) sulfur being contained in an amount of from 0.05 to 0.14 percent by mass in said composition.
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| US (1) | US20040176256A1 (en) |
| EP (1) | EP1418221B1 (en) |
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| JP4907074B2 (en) * | 2004-10-22 | 2012-03-28 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for transmission |
| WO2006043709A1 (en) * | 2004-10-22 | 2006-04-27 | Nippon Oil Corporation | Lubricant composition for transmission |
| ES2540911T3 (en) | 2005-06-29 | 2015-07-14 | Nippon Oil Corporation | Base oil for hydraulic oil and hydraulic oil compositions |
| JP5213310B2 (en) * | 2006-04-20 | 2013-06-19 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition |
| US20090062163A1 (en) * | 2007-08-28 | 2009-03-05 | Chevron U.S.A. Inc. | Gear Oil Compositions, Methods of Making and Using Thereof |
| US20090062162A1 (en) * | 2007-08-28 | 2009-03-05 | Chevron U.S.A. Inc. | Gear oil composition, methods of making and using thereof |
| US7932217B2 (en) * | 2007-08-28 | 2011-04-26 | Chevron U.S.A., Inc. | Gear oil compositions, methods of making and using thereof |
| US20090088355A1 (en) * | 2007-09-27 | 2009-04-02 | Chevron U.S.A. Inc. | Gear Oil Compositions, Methods of Making and Using Thereof |
| US20090088356A1 (en) * | 2007-09-27 | 2009-04-02 | Chevron U.S.A. Inc. | Gear Oil Compositions, Methods of Making and Using Thereof |
| US20090298732A1 (en) * | 2008-05-29 | 2009-12-03 | Chevron U.S.A. Inc. | Gear oil compositions, methods of making and using thereof |
| FR2984348B1 (en) * | 2011-12-16 | 2015-02-27 | Total Raffinage Marketing | LUBRICATING COMPOSITIONS FOR TRANSMISSIONS |
| WO2014017558A1 (en) * | 2012-07-24 | 2014-01-30 | Ｊｘ日鉱日石エネルギー株式会社 | Poly(meth)acrylate viscosity index improver, and lubricating oil composition and lubricating oil additive containing said viscosity index improver |
| CN104395444B (en) | 2012-07-24 | 2018-10-16 | 吉坤日矿日石能源株式会社 | Poly- (methyl) acrylic ester viscosity index improver and the lube oil additive containing the viscosity index improver and lubricant oil composite |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169799A (en) * | 1976-12-27 | 1979-10-02 | Texaco Inc. | Lubricating oil composition |
| JP3608805B2 (en) * | 1993-04-30 | 2005-01-12 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
| US5578236A (en) | 1994-11-22 | 1996-11-26 | Ethyl Corporation | Power transmission fluids having enhanced performance capabilities |
| EP0858497B1 (en) * | 1995-11-03 | 2001-07-18 | Infineum USA L.P. | Automatic transmission fluids with improved transmission performance |
| CN1042949C (en) * | 1996-06-05 | 1999-04-14 | 中国石化兰州炼油化工总厂 | Lubricating oil compsn. |
| JP2000109876A (en) * | 1998-10-09 | 2000-04-18 | Tonen Corp | Hydraulic oil composition for buffer |
| JP3184113B2 (en) * | 1997-03-24 | 2001-07-09 | 東燃ゼネラル石油株式会社 | Lubricating oil composition for automatic transmission |
| US6059955A (en) * | 1998-02-13 | 2000-05-09 | Exxon Research And Engineering Co. | Low viscosity lube basestock |
| US6034040A (en) | 1998-08-03 | 2000-03-07 | Ethyl Corporation | Lubricating oil formulations |
| CA2374501A1 (en) * | 1999-05-24 | 2000-11-30 | The Lubrizol Corporation | Mineral gear oils and transmission fluids |
| US6482778B2 (en) * | 1999-08-11 | 2002-11-19 | Ethyl Corporation | Zinc and phosphorus containing transmission fluids having enhanced performance capabilities |
| JP2001262176A (en) * | 2000-03-21 | 2001-09-26 | Nippon Mitsubishi Oil Corp | Lubricant oil composition for transmission |
| GB0011115D0 (en) * | 2000-05-09 | 2000-06-28 | Infineum Int Ltd | Lubricating oil compositions |
| US6583092B1 (en) * | 2001-09-12 | 2003-06-24 | The Lubrizol Corporation | Lubricating oil composition |
| EP1439217B1 (en) * | 2001-10-12 | 2012-06-20 | Nippon Oil Corporation | Lubricating oil composition for internal combustion engine |
-
2003
- 2003-11-04 US US10/701,193 patent/US20040176256A1/en not_active Abandoned
- 2003-11-05 DE DE60335771T patent/DE60335771D1/en not_active Expired - Lifetime
- 2003-11-05 EP EP03025453A patent/EP1418221B1/en not_active Expired - Lifetime
- 2003-11-07 CN CNB2003101246693A patent/CN1301320C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1513960A (en) | 2004-07-21 |
| CN1301320C (en) | 2007-02-21 |
| EP1418221A3 (en) | 2004-06-23 |
| US20040176256A1 (en) | 2004-09-09 |
| EP1418221A2 (en) | 2004-05-12 |
| DE60335771D1 (en) | 2011-03-03 |
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