EP1707617B1 - Biodegradable lubricating oil composition - Google Patents
Biodegradable lubricating oil composition Download PDFInfo
- Publication number
- EP1707617B1 EP1707617B1 EP05709443.5A EP05709443A EP1707617B1 EP 1707617 B1 EP1707617 B1 EP 1707617B1 EP 05709443 A EP05709443 A EP 05709443A EP 1707617 B1 EP1707617 B1 EP 1707617B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricating oil
- oil composition
- ester
- test
- mass
- 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.)
- Not-in-force
Links
- 239000000203 mixture Substances 0.000 title claims description 76
- 239000010687 lubricating oil Substances 0.000 title claims description 72
- -1 aliphatic monocarboxylic acid Chemical class 0.000 claims description 49
- 238000012360 testing method Methods 0.000 claims description 44
- 150000002148 esters Chemical class 0.000 claims description 43
- 229920005862 polyol Polymers 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 239000002199 base oil Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 150000003077 polyols Chemical class 0.000 claims description 22
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 18
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000002530 phenolic antioxidant Substances 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 238000010998 test method Methods 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 241000276569 Oryzias latipes Species 0.000 claims description 10
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 238000006065 biodegradation reaction Methods 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 6
- 231100000215 acute (single dose) toxicity testing Toxicity 0.000 claims description 4
- 238000011047 acute toxicity test Methods 0.000 claims description 4
- KXZLHMICGMACLR-UHFFFAOYSA-N 2-(hydroxymethyl)-2-pentylpropane-1,3-diol Chemical compound CCCCCC(CO)(CO)CO KXZLHMICGMACLR-UHFFFAOYSA-N 0.000 claims description 3
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 claims description 3
- PKKMTXYTMIUYND-UHFFFAOYSA-N 2-[[3-hydroxy-2-(hydroxymethyl)-2-methylpropoxy]methyl]-2-methylpropane-1,3-diol Chemical compound OCC(C)(CO)COCC(C)(CO)CO PKKMTXYTMIUYND-UHFFFAOYSA-N 0.000 claims description 3
- AUYHMZGBIIEMRK-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2-(hydroxymethyl)-2-methylpropoxy]methyl]-2-methylpropoxy]methyl]-2-methylpropane-1,3-diol Chemical compound OCC(C)(CO)COCC(C)(CO)COCC(C)(CO)CO AUYHMZGBIIEMRK-UHFFFAOYSA-N 0.000 claims description 3
- HJIYDQCBJVTQAO-UHFFFAOYSA-N 2-butyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCCCC(CO)(CO)CO HJIYDQCBJVTQAO-UHFFFAOYSA-N 0.000 claims description 3
- VNAWKNVDKFZFSU-UHFFFAOYSA-N 2-ethyl-2-methylpropane-1,3-diol Chemical compound CCC(C)(CO)CO VNAWKNVDKFZFSU-UHFFFAOYSA-N 0.000 claims description 3
- QERPRBXFYXTKDD-UHFFFAOYSA-N 2-hexyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCCCCCC(CO)(CO)CO QERPRBXFYXTKDD-UHFFFAOYSA-N 0.000 claims description 3
- GRFUBKQMUNOERA-UHFFFAOYSA-N 3-(3-hydroxy-2,2-dimethylpropoxy)-2,2-dimethylpropan-1-ol Chemical compound OCC(C)(C)COCC(C)(C)CO GRFUBKQMUNOERA-UHFFFAOYSA-N 0.000 claims description 3
- UVCCXLWIORYUKI-UHFFFAOYSA-N 3-[3-(3-hydroxy-2,2-dimethylpropoxy)-2,2-dimethylpropoxy]-2,2-dimethylpropan-1-ol Chemical compound OCC(C)(C)COCC(C)(C)COCC(C)(C)CO UVCCXLWIORYUKI-UHFFFAOYSA-N 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 230000000813 microbial effect Effects 0.000 claims description 3
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 claims description 3
- 229950006800 prenderol Drugs 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000003921 oil Substances 0.000 description 25
- 235000019198 oils Nutrition 0.000 description 25
- 230000001590 oxidative effect Effects 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000012530 fluid Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000003566 sealing material Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- 231100000636 lethal dose Toxicity 0.000 description 6
- YVKVCTLHBOMQDA-GNOQXXQHSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;(z)-octadec-9-enoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O YVKVCTLHBOMQDA-GNOQXXQHSA-N 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 150000002763 monocarboxylic acids Chemical class 0.000 description 5
- 229940117969 neopentyl glycol Drugs 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005536 corrosion prevention Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 239000006078 metal deactivator Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- SXJBHJCKWQIWHA-UHFFFAOYSA-N 2-ethyl-2,3,3-trimethylbutanoic acid Chemical compound CCC(C)(C(O)=O)C(C)(C)C SXJBHJCKWQIWHA-UHFFFAOYSA-N 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000013556 antirust agent Substances 0.000 description 2
- 238000013475 authorization Methods 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- YYVJAABUJYRQJO-UHFFFAOYSA-N isomyristic acid Chemical compound CC(C)CCCCCCCCCCC(O)=O YYVJAABUJYRQJO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005555 metalworking Methods 0.000 description 2
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- ZONJATNKKGGVSU-UHFFFAOYSA-N 14-methylpentadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCC(O)=O ZONJATNKKGGVSU-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- NPMHELYJLOUPIZ-UHFFFAOYSA-N 2,2,3,4-tetramethylpentanoic acid Chemical compound CC(C)C(C)C(C)(C)C(O)=O NPMHELYJLOUPIZ-UHFFFAOYSA-N 0.000 description 1
- BTGGRPUPMPLZNT-PGEUSFDPSA-N 2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]butyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC BTGGRPUPMPLZNT-PGEUSFDPSA-N 0.000 description 1
- VUAXHMVRKOTJKP-UHFFFAOYSA-N 2,2-dimethylbutyric acid Chemical compound CCC(C)(C)C(O)=O VUAXHMVRKOTJKP-UHFFFAOYSA-N 0.000 description 1
- IKNDGHRNXGEHTO-UHFFFAOYSA-N 2,2-dimethyloctanoic acid Chemical compound CCCCCCC(C)(C)C(O)=O IKNDGHRNXGEHTO-UHFFFAOYSA-N 0.000 description 1
- OWEMTCOXFULTNW-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanoic acid Chemical compound CC(C)C(C)(C(C)C)C(O)=O OWEMTCOXFULTNW-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
- QHPKIUDQDCWRKO-UHFFFAOYSA-N 2,6-ditert-butyl-4-[2-(3,5-ditert-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 QHPKIUDQDCWRKO-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- AKNMPWVTPUHKCG-UHFFFAOYSA-N 2-cyclohexyl-6-[(3-cyclohexyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(C2CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1CCCCC1 AKNMPWVTPUHKCG-UHFFFAOYSA-N 0.000 description 1
- QFWGJUQOWNHFKT-UHFFFAOYSA-N 2-tert-butyl-2,5,5-trimethylhexanoic acid Chemical compound CC(C)(C)CCC(C)(C(O)=O)C(C)(C)C QFWGJUQOWNHFKT-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- BGWNOSDEHSHFFI-UHFFFAOYSA-N 2-tert-butyl-4-[(3-tert-butyl-4-hydroxy-5-methylphenyl)methylsulfanylmethyl]-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CSCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 BGWNOSDEHSHFFI-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- YGBSNORLROWMAY-UHFFFAOYSA-N 2-tert-butyl-6-(3,3-dimethylbutyl)phenol Chemical compound CC(C)(C)CCC1=CC=CC(C(C)(C)C)=C1O YGBSNORLROWMAY-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
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- C10M135/10—Sulfonic acids or derivatives thereof
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2207/0225—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2207/289—Partial esters containing free hydroxy groups
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2207/2895—Partial esters containing free hydroxy groups used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2219/046—Overbasedsulfonic acid salts
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N2020/01—Physico-chemical properties
- C10N2020/081—Biodegradable compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Definitions
- the present invention relates to a biodegradable lubricating oil composition. More specifically, it relates to a synthetic ester-based biodegradable lubricating oil composition which has excellent biodegradability, a high viscosity index, a low pour point, a high flash point, being satisfactory with lubricity, oxidative stability, property of preventing the corrosion of iron and non-ferrous metals, and suitability for use with sealing materials.
- Vegetable oils such as rapeseed oil, synthetic esters and polyalkyleneglycols have been used as a biodegradable base oil.
- vegetable oils have a problem of thermal or oxidative instability as well as unstable supply despite low cost
- polyalkyleneglycols have a problem of a poor suitability for use with sealing materials despite low cost and good thermal stability. Therefore, although synthetic esters are becoming more popular as biodegradable lubricating oils in Japan, they still have a substantial weakness against a mineral oil-based lubricating oil in terms of the cost and oxidative stability.
- a first component is a natural or synthetic oil component.
- One of the optional choices for such a natural or synthetic oil component is an ester compound containing methylol groups (column 8, lines 42 to 47).
- the composition contains additives, such as an antioxidant. Numerous phenolic antioxidants are mentioned, but other types of antioxidants are possible as well.
- the present invention was completed under these circumstances with an object to provide a biodegradable lubricating oil composition which has excellent biodegradability, a high viscosity index, a low pour point, a high flash point, being satisfactory with lubricity, oxidative stability, property of preventing the corrosion of iron and non-ferrous metals, and suitability for use with sealing materials.
- the present inventor studied intensively in order to develop a biodegradable lubricating oil composition which meets the aforementioned preferable properties, and found that a lubricating oil composition having a certain value or more of the biodegradability that is determined according to the OECD Test Guideline 301C method satisfies the purpose of the study, wherein the lubricating oil composition is composed of a synthetic ester base oil comprising mainly an ester composed of an aliphatic hindered polyol having a specific structure and an aliphatic monocarboxylic acid, to which a specific additive is admixed in a predetermined ratio.
- the present invention has been accomplished based on the aforementioned findings. That is, the present invention provides:
- the synthetic ester base oil used as component (A) of the present invention comprises at least 50 mass% hindered ester of an aliphatic monocarboxylic acid with an aliphatic hindered polyol which has one or more quaternary carbon atoms per molecule and in which at least one of the quaternary carbon atoms has one to four methylol groups bonded thereto.
- R 1 and R 2 independently represent a hydrocarbon group having 1 to 6 carbon atoms or a methylol group, and n is an integer of 0 to 4.
- hydrocarbon group having 1 to 6 carbon atoms among R 1 and R 2 in general formula (I) a linear or branched alkyl or alkenyl group is preferable, and especially, an alkyl group is preferable.
- neopentyl glycol 2-ethyl-2-methyl-1,3-propanediol; 2,2-diethyl-1,3-propanediol; trimethylolethane; trimethylolpropane; trimethylolbutane; trimethylolpentane; trimethylolhexane; trimethylolheptane; pentaerythritol; 2,2,6,6-tetramethyl-4-oxa-1,7-heptanediol; 2,2,6,6,10,10-hexamethyl-4,8-dioxa-1,11-undecanediol; 2,2,6,6,10,10,14,14-octamethyl-4,8,12-trioxa-1,15-pentadecanediol; 2,6-dihydroxymethyl-2,6-dimethyl-4-oxa-1,7-heptanediol; 2,6, 10-trihydroxymethyl-2,6, 10-
- the hindered polyols may be used singly or as a mixture of 2 or more thereof in the esterification.
- a preferable number of n is 0 to 2.
- Preferred hindered polyols are trimethylolpropane, neopentyl glycol, pentaerythritol and dehydrated condensates thereof, wherein preferable dehydrated condensates are bimolecular or trimolecular condensates.
- the above-described hindered polyols can be synthesized according to the conventional method.
- the dehydrated condensates of the hindered polyols can be synthesized by dehydration condensation of the hindered polyols in the presence of a catalyst at about 180°C by heating the hindered polyols at a temperature above the melting point and dispersing them in a solvent.
- aliphatic monocarboxylic acids used in the esterification of the aliphatic hindered polyols mentioned above saturated or unsaturated monocarboxylic acids having 6 to 22 carbon atoms are used preferably.
- the acyl group of the monocarboxylic acids may be linear or branched.
- aliphatic monocarboxylic acids examples include linear saturated monocarboxylic acids such as caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachic acid and behenic acid, linear unsaturated monocarboxylic acids such as undecenoic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassidic acid, linoleic acid and linolenic acid, branched saturated monocarboxylic acids such as isomyristic acid, isopalmitic acid, isostearic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2,2-dimethyloctanoic acid
- the hindered ester synthesized by esterification reaction of the above-mentioned hindered polyol with the aliphatic monocarboxylic acid may be a fully-esterified or partially-esterified compound.
- a preferable hindered ester is the fully-esterified compound.
- the hindered esters may be used singly or as a mixture of two or more thereof in the biodegradable lubricating oil composition of the present invention. Further, the amount of the hindered ester in the synthetic ester base oil is 50 mass% or more, preferably 70 mass% or more, and furthermore preferably 80 mass% or more in order to satisfy the predetermined properties of the biodegradable lubricating oil composition described below.
- Kinematic viscosity of the synthetic ester base oil used as the component (A) in the lubricating oil composition depends on the purpose of use of the lubricating oil composition, and is approximately in the range from 10 to 200 mm 2 /s at 40°C in general, preferably in the range from 10 to 100 mm 2 /s, and more preferably in the range from 15 to 80 mm 2 /s in the case of hydraulic fluid application.
- An acid value of the synthetic ester base oil is preferably 3 mg KOH/g or less and particularly preferably 1 mg KOH/g or less in terms of prevention of corrosion of machinery. Further, there is no particular limitation for a hydroxyl value, but it is preferably 50 mg KOH/g or less and particularly preferably 20 mg KOH/g or less from a viewpoint of lubricity.
- phenolic antioxidant as component (a) of the ingredient (B) is not particularly limited, and phenolic antioxidant known in the art can be used with suitable selection.
- phenolic antioxidant include 4,4'-methylenebis(2,6-di-t-butylphenol); 4,4'-bis(2,6-di-t-butylphenol); 4,4'-bis(2-methyl-6-t-butylphenol); 2,2'-methylenebis(4-ethyl-6-t-butylphenol); 2,2'-methylenebis(4-methyl-6-t-butylphenol); 4,4'-butylidenebis(3-methyl-6-t-butylphenol); 4,4'-isopropylidenebis(2,6-di-t-butylphenol); 2,2'-methylenebis(4-methyl-6-t-nonylphenol); 2,2'-isobutylidenebis(4,6-dimethylpenol); 2,2'-m
- these phenolic antioxidants may be used singly or in a combination of two or more thereof.
- the aforementioned hindered ester used for the synthetic ester base oil has satisfactory oxidative stability by itself, and the oxidative stability of the lubricating oil composition can further be improved by admixing such a phenolic antioxidant, which also results in the increase in thermal stability.
- the amount of the phenolic antioxidant added is in the range from 0.1 to 5.0 mass% based on the total amount of the present composition. When the amount of the phenolic antioxidant is in the range mentioned above, the effect of improvement in the oxidative stability is exhibited and the balance between cost and effectiveness becomes excellent.
- the preferable amount of the phenolic antioxidant admixed is in the range from 0.5 to 3.0 mass%.
- the phenolic antioxidants are used in the present invention from a viewpoint of impact on ecosystems.
- the low base number calcium sulfonate as the component (b) in the ingredient (B) is added to give anti-rust effect to the lubricating oil composition and has also detergency and dispersion function.
- the calcium sulfonate is a calcium salt of a sulfonated alkyl-substituted aromatic compound.
- the calcium sulfonate having a low base number such that the total base number (TBN) is in the range from 0 to 100 mg KOH/g (preferably in the range from 0 to 50 mg KOH/g) is used in the present invention.
- the low base number calcium sulfonates may be used singly or in a combination of two or more thereof.
- the amount of the calcium sulfonate added is in the range from 0.01 to 2.0 mass% based on the total amount of the composition.
- the amount of the low base number calcium sulfonate is preferably in the range from 0.05 to 1.0 mass%.
- the base oil itself has a level of lubricity equivalent to that of a conventional mineral oil-based antiwear hydraulic fluid, and in order to further improve the lubricity, an extreme-pressure agent and/or an antiwear agent may be added.
- sulfur-based or phosphorus-based extreme-pressure agents can be used.
- the sulfur-based extreme-pressure agent are sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, polysulfides, sulfurized olefins, thiocarbamates, thioterpenes, dialkylthiodipropionates and the like.
- sulfurized fats and oils, polysulfides and sulfurized olefins are preferred.
- examples of the antiwear agent are zinc dithiophosphate (ZnDTP), zinc dithiocarbamate (ZnDTC), sulfurized molybdenum dithiophosphate (MoDTP), sulfurized molybdenum dithiocarbamate (MoDTC), and the like.
- additives such as viscosity index improver, pour point depressant, ash-free dispersant, surfactant, anti-foaming agent, demulsifier and so on can be added in such a range of the amount that no drawback to the effect of the present invention is brought about.
- the degree of biodegradation of the lubricating oil composition as determined by the microbial degradation test of chemical substances according to the OECD Test Guideline 301C method is 70 % or more (the reference degree of biodegradability is 60 % or more), and has excellent biodegradability.
- the 96-h LC 50 value of the acute toxicity test for Japanese medaka (Oryzias latipes) as determined according to the JIS K 0102 standard is usually 100 mg/L or more, and has low impact on living organisms. Therefore, it can be said that the lubricating oil composition is a very environmentally friendly lubricating oil.
- the lubricating oil composition has such a low pour point as mentioned above so that machinery startability at lower temperatures is excellent with the present composition when it is used as a hydraulic fluid. Also, the present composition has such a high flash point as mentioned above so that it has high flame retardance and hence it belongs to the category of a safe combustible liquid having VG of 32 or more according to the Fire Service Law.
- the biodegradable lubricating oil composition of the present invention has excellent biodegradability, low impact to ecosystems, a high viscosity index, a low pour point, a high flash point, being satisfactory with lubricity, oxidative stability, property of preventing the corrosion of non-ferrous metals, and suitability for use with sealing materials. It has thus an excellent balance of those different properties.
- the lubricating oil composition is preferable, for example, as a hydraulic fluid that is a power transmission fluid used in power transmission, power control, shock absorption and the like in a hydraulic system such as hydraulic machinery or equipment, a lubricating oil for automobiles used in automatic transmission, buffer, driving machinery such as power steering, gears and the like, a metal-working oil for cutting, polishing or plasticizing, and the like.
- Examples 1 to 3 and Comparative examples 1 to 8 (1) Lubricating oil compositions with compositions shown in Tables 1-1 and 1-2 were prepared along with commercially-available products. General properties and biodegradability of these lubricating oil compositions are listed in Tables 2-1 and 2-2.
- Tables 1-1 and 1-2 PET denotes pentaerythritol
- TMP denotes trimethylolpropane
- NPG denotes neopentyl glycol
- ZnDTP denotes zinc dithiophosphate
- POE denotes polyoxyethylene.
- Table 3 Table 4 (2) Tables 3-1 and 3-2 indicate the test results of lubricity, oxidative stability and corrosion prevention of non-ferrous metals for each lubricating oil composition.
- Table 5 Table 6
- Table 4 indicates the test results of suitability for use with sealing materials of the lubricating oil composition of Example 1 and the lubricating oil compositions of Comparative examples I to 4.
- the lubricating oil compositions of the present invention have a well-balanced properties such as excellent biodegradability, a high viscosity index, a low pour point, a high flash point, being satisfactory with lubricity, oxidative stability, property of preventing the corrosion of iron and non-ferrous metals, and suitability for use with sealing materials.
- the biodegradable lubricating oil composition of the present invention comprises a synthetic ester base oil having excellent biodegradability, has well-balanced properties including lubricating performance, and is preferably used, for example, as a hydraulic fluid, automotive lubricating oil, metal-working oil, and so on.
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Description
- The present invention relates to a biodegradable lubricating oil composition. More specifically, it relates to a synthetic ester-based biodegradable lubricating oil composition which has excellent biodegradability, a high viscosity index, a low pour point, a high flash point, being satisfactory with lubricity, oxidative stability, property of preventing the corrosion of iron and non-ferrous metals, and suitability for use with sealing materials.
- In recent years, considerable attention has been paid to a biodegradable lubricating oil in the field of lubricant application due to environmental pollution-control measures. Research and development was started and commercially available products were manufactured in this field from early 1990's in Japan. However, biodegradable lubricating oils have not widely been used in Japan because of their higher cost compared with conventional mineral oil-based lubricating oils, in spite of high attention. Japan is far behind European countries where use of a biodegradable lubricating oil is made compulsory by law.
- Vegetable oils such as rapeseed oil, synthetic esters and polyalkyleneglycols have been used as a biodegradable base oil. However, vegetable oils have a problem of thermal or oxidative instability as well as unstable supply despite low cost, and polyalkyleneglycols have a problem of a poor suitability for use with sealing materials despite low cost and good thermal stability. Therefore, although synthetic esters are becoming more popular as biodegradable lubricating oils in Japan, they still have a substantial weakness against a mineral oil-based lubricating oil in terms of the cost and oxidative stability.
- Japan Environment Association has authorization standard, named "ECOMARK", for biodegradable hydraulic fluids. The authorization standard was drastically revised in July, 1998 for further severe control. The major changes were as follows:
- (1) The biodegradability standard was changed from the partial biodegradation test, "CEC Test Guideline" (reference degree of biodegradability: 67% or more) to the inherent biodegradation test, "OECD Test Guideline 301C method" (reference degree of biodegradability: 60% or more), and
- (2) The acute toxicity test for Japanese medaka (Oryzias latipes), JIS K 0102 (reference: LC50 ≥ 100 mg/L) was added.
- The following examples of a biodegradable lubricating oil have been disclosed:
- A lubricating oil composition comprising a polyol ester base oil composed of a carboxylic acid having 5 to 14 carbon atoms and a carboxylic acid having 15 to 38 carbon atoms in a weight ratio of 0.1:99.9 to 50:50, in which at least one of the compounds selected from the group consisting of a sulfonate, a condensate between an alkanolamine and a carboxylic acid having 5 to 14 carbon atoms and a polybutenyl succinimide is contained at 0.1 to 15 weight% (for example, Patent Document 1), a fire-resistant hydraulic fluid comprising a hydraulic base oil containing, as a main component, a polyol partial ester having a hydroxyl value of 35 mg KOH/g or more, a flash point of 290°C or more and a number-average molecular weight of 600 to 1500, wherein the ester is composed of a polyol having 3 to 12 carbon atoms and 3 to 6 total hydroxyl groups and a linear-chain monocarboxylic acid having 6 to 22 carbon atoms (for example, Patent Document 2), a lubricating oil comprising a synthetic ester having a kinematic viscosity of 20 to 40 mm2/s at 40°C, a viscosity index of 120 or more and a pour point of -30°C or less, wherein the ester is composed of a dimethylol alkane wherein the alkane has 5 to 7 carbon atoms and a linear-chain fatty acid having 10 to 20 carbon atoms (for example, Patent Document 3), a non-aqueous hydraulic fluid comprising a base oil composed of trimethylolpropane trioleate or neopentylglycol dioleate and a surfactant such as polyoxyethylene alkyl ether (for example, Patent Document 4) and the like.
- Although the above-mentioned biodegradable lubricating oils are satisfactory with respect to lubricity and oxidative stability, they still have problems of a high pour point, substantial metal dissolution of non-ferrous metals used for materials for hydraulic machinery, Lubricant compositions which are stabilized against destruction through heat and oxygen are described in Patent Document 5. The document describes compositions made from a number of different components. A first component is a natural or synthetic oil component. One of the optional choices for such a natural or synthetic oil component is an ester compound containing methylol groups (column 8, lines 42 to 47). Furthermore, the composition contains additives, such as an antioxidant. Numerous phenolic antioxidants are mentioned, but other types of antioxidants are possible as well. Other additives are "other metal deactivators, other corrosion inhibitors, viscosity improvers, dispersants, detergents, extreme pressure and antiwear additives and pour-point depressants", see column 6, lines 9 to 12. In the group of the "dispersants/depressants" calcium sulfonates are mentioned (column 8, lines 64/65). The feature of the total base number is not mentioned. The examples are compositions containing a vegetable oil (canola oil or sunflower oil) and a phenolic antioxidant.
Lubricants containing polyol esters are described in Patent Document 6.
Antioxidant compositions which are useful for gear lubricating oils are described in Patent Document 7. - In the further Patent Documents 8 to 10 lubricating oil compositions are described
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- Patent Document 1:
JP Kokai 1993-339591 - Patent Document 2:
JP Kokai 1994-228579 - Patent Document 3:
JP Kokai 1997-249889 - Patent Document 4:
JP kokai 1999-323373 - Patent Document 5:
US 5,580,482 A - Patent Document 6:
EP 0 712 834 A1 - Patent Document 7:
US 6,046,144 A - Patent Document 8:
JP 2002-097485 A - Patent Document 9:
JP 08-259980 A - Patent Document 10:
JP 2001-234187 A - The present invention was completed under these circumstances with an object to provide a biodegradable lubricating oil composition which has excellent biodegradability, a high viscosity index, a low pour point, a high flash point, being satisfactory with lubricity, oxidative stability, property of preventing the corrosion of iron and non-ferrous metals, and suitability for use with sealing materials.
- The present inventor studied intensively in order to develop a biodegradable lubricating oil composition which meets the aforementioned preferable properties, and found that a lubricating oil composition having a certain value or more of the biodegradability that is determined according to the OECD Test Guideline 301C method satisfies the purpose of the study, wherein the lubricating oil composition is composed of a synthetic ester base oil comprising mainly an ester composed of an aliphatic hindered polyol having a specific structure and an aliphatic monocarboxylic acid, to which a specific additive is admixed in a predetermined ratio. The present invention has been accomplished based on the aforementioned findings. That is, the present invention provides:
- (1) A biodegradable lubricating oil composition comprising (A) a synthetic ester base oil comprising at least 50 mass% hindered ester of an aliphatic monocarboxylic acid with an aliphatic hindered polyol represented by the general formula (I):
- (2) The biodegradable lubricating oil composition according to the aforementioned (1), wherein the 96-h LC50 value of the acute toxicity test for Japanese medaka (Oryzias latipes) according to the JIS K 0102 test method is 100 mg/L or more,
- (3) The biodegradable lubricating oil composition according to the aforementioned (1) or (2), wherein the viscosity index determined according to the JIS K 2283 method is 130 or more, the pour point determined according to the JIS K 2269 method is -40°C or less, and the flash point determined by using the Cleveland Open Cup (COC) tester according to the JIS K 2265 method is 250°C or more,
- (4) The biodegradable lubricating oil composition according to the aforementioned (1), wherein the aliphatic hindered polyol is at least one selected from neopentyl glycol; 2-ethyl-2-methyl-1-,3-propanediol; 2,2-diethyl-1,3-propanediol; trimethylolethane; trimethylolpropane; trimethylolbutane; trimethylolpentane; trimethylolhexane; trimethylolheptane; pentaerythritol; 2,2,6,6-tetramethyl-4-oxa-1,7-heptanediol; 2,2,6,6,10,10-hexamethyl-4, 8-dioxa-1,11-undecanediol; 2,2,6,6,10,10,14,14-octamethyl-4,8,12-trioxa-1,15-pentadecanediol; 2,6-dihydroxymethyl-2,6-dimethyl-4-oxa-1,7-heptanediol; 2,6,10-trihydroxymethyl-2,6,10-trimethyl-4,8-dioxa-1,11-undecanediol; 2,6,10,14-tetrahydroxymethyl-2,6,10,14-tetramethyl-4,8,12-trioxa-1,15-pentadecanedi ol; di(pentaerythritol); tri(pentaerythritol); tetra(pentaerythritol) and penta(pentaerythritol),
- (5) The biodegradable lubricating oil composition according to any of the aforementioned (1) to m(4), wherein the aliphatic monocarboxylic acid is a saturated or unsaturated monocarboxylic acid having 6 to 22 carbon atoms,
- (6) The biodegradable lubricating oil composition according to any of the aforementioned (1) to (3), wherein the hindered ester is at least one selected from an ester of a saturated or unsaturated monocarboxylic acid having 6 to 22 carbon atoms with pentaerythritol, and an ester of a saturated or unsaturated monocarboxylic acid having 6 to 22 carbon atoms with trimethylolpropane, and.
- (7) The biodegradable lubricating oil composition according to any of the aforementioned (1) to (6), which contains 0.1 to 5.0 mass% of an extreme-pressure agent and/or an antiwear agent as a component (B) (d) based on the total amount of the lubricating oil composition.
- According to the present invention, there is provided a synthetic ester-based biodegradable lubricating oil composition which has excellent biodegradability, a high viscosity index, a low pour point, a high flash point, being satisfactory with lubricity, oxidative stability, property of preventing the corrosion of iron and non-ferrous metals, and suitability for use with sealing materials.
- The biodegradable lubricating oil composition of the present invention comprises; (A) a synthetic ester base oil and (B) ingredients comprising a combination of (a) a phenolic antioxidant, (b) calcium sulfonate having a low base number and (c) a triazole compound.
- The synthetic ester base oil used as component (A) of the present invention comprises at least 50 mass% hindered ester of an aliphatic monocarboxylic acid with an aliphatic hindered polyol which has one or more quaternary carbon atoms per molecule and in which at least one of the quaternary carbon atoms has one to four methylol groups bonded thereto.
- The aliphatic hindered polyol which has one or more quaternary carbon atoms per molecule and in which at least one of the quaternary carbon atoms has one to four methylol groups bonded thereto of the present invention (which may be referred to simply as the hindered polyol hereinafter) is a compound represented by general formula (I):
- (wherein R1 and R2 independently represent a hydrocarbon group having 1 to 6 carbon atoms or a methylol group, and n is an integer of 0 to 4.)
- As the hydrocarbon group having 1 to 6 carbon atoms among R1 and R2 in general formula (I), a linear or branched alkyl or alkenyl group is preferable, and especially, an alkyl group is preferable.
- The compound represented by general formula (I) (hindered polyols) refers to a hindered polyol such as neopentyl glycol, trimethylolalkane (the alkane has 2 to 7 carbon atoms) and pentaerythritol or a dehydrated condensate thereof. Specific examples include neopentyl glycol; 2-ethyl-2-methyl-1,3-propanediol; 2,2-diethyl-1,3-propanediol; trimethylolethane; trimethylolpropane; trimethylolbutane; trimethylolpentane; trimethylolhexane; trimethylolheptane; pentaerythritol; 2,2,6,6-tetramethyl-4-oxa-1,7-heptanediol; 2,2,6,6,10,10-hexamethyl-4,8-dioxa-1,11-undecanediol; 2,2,6,6,10,10,14,14-octamethyl-4,8,12-trioxa-1,15-pentadecanediol; 2,6-dihydroxymethyl-2,6-dimethyl-4-oxa-1,7-heptanediol; 2,6, 10-trihydroxymethyl-2,6, 10-trimethyl-4,8-dioxa-1,11-undecanediol; 2,6,10,14-tetrahydroxymethyl-2,6,10,14-tetramethyl-4,8,12-trioxa-1,15-pentadecanediol; di(pentaerythritol); tri(pentaerythritol); tetra(pentaerythritol); penta(pentaerythritol) and the like.
- The hindered polyols may be used singly or as a mixture of 2 or more thereof in the esterification. In the above-described general formula (I), a preferable number of n is 0 to 2.
- Preferred hindered polyols are trimethylolpropane, neopentyl glycol, pentaerythritol and dehydrated condensates thereof, wherein preferable dehydrated condensates are bimolecular or trimolecular condensates.
- The above-described hindered polyols can be synthesized according to the conventional method. Also, the dehydrated condensates of the hindered polyols can be synthesized by dehydration condensation of the hindered polyols in the presence of a catalyst at about 180°C by heating the hindered polyols at a temperature above the melting point and dispersing them in a solvent.
- On the other hand, as the aliphatic monocarboxylic acids used in the esterification of the aliphatic hindered polyols mentioned above, saturated or unsaturated monocarboxylic acids having 6 to 22 carbon atoms are used preferably. The acyl group of the monocarboxylic acids may be linear or branched. Examples of the aliphatic monocarboxylic acids include linear saturated monocarboxylic acids such as caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachic acid and behenic acid, linear unsaturated monocarboxylic acids such as undecenoic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassidic acid, linoleic acid and linolenic acid, branched saturated monocarboxylic acids such as isomyristic acid, isopalmitic acid, isostearic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,3,3-trimethylbutanoic acid, 2,2,3,4-tetramethylpentanoic acid, 2,5,5-trimethyl-2-t-butylhexanoic acid, 2,3,3-trimethyl-2-ethylbutanoic acid, 2,3-dimethyl-2-isopropylbutanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid, and the like. The aliphatic monocarboxylic acids may be used singly or as a mixture of two or more kinds in the esterification.
- The hindered ester synthesized by esterification reaction of the above-mentioned hindered polyol with the aliphatic monocarboxylic acid may be a fully-esterified or partially-esterified compound. A preferable hindered ester is the fully-esterified compound.
- The hindered esters may be used singly or as a mixture of two or more thereof in the biodegradable lubricating oil composition of the present invention. Further, the amount of the hindered ester in the synthetic ester base oil is 50 mass% or more, preferably 70 mass% or more, and furthermore preferably 80 mass% or more in order to satisfy the predetermined properties of the biodegradable lubricating oil composition described below.
- As a synthetic ester base oil which can be used together with the hindered ester, there may be cited an ester composed of an aliphatic polyol other than the hindered polyol mentioned above and the above-described monocarboxylic acid from the viewpoint of biodegradability, etc. of the lubricating oil composition.
- Kinematic viscosity of the synthetic ester base oil used as the component (A) in the lubricating oil composition depends on the purpose of use of the lubricating oil composition, and is approximately in the range from 10 to 200 mm2/s at 40°C in general, preferably in the range from 10 to 100 mm2/s, and more preferably in the range from 15 to 80 mm2/s in the case of hydraulic fluid application.
- An acid value of the synthetic ester base oil is preferably 3 mg KOH/g or less and particularly preferably 1 mg KOH/g or less in terms of prevention of corrosion of machinery. Further, there is no particular limitation for a hydroxyl value, but it is preferably 50 mg KOH/g or less and particularly preferably 20 mg KOH/g or less from a viewpoint of lubricity.
- In the lubricating oil composition of the present invention, phenolic antioxidant as component (a) of the ingredient (B) is not particularly limited, and phenolic antioxidant known in the art can be used with suitable selection. Examples of the phenolic antioxidant include 4,4'-methylenebis(2,6-di-t-butylphenol); 4,4'-bis(2,6-di-t-butylphenol); 4,4'-bis(2-methyl-6-t-butylphenol); 2,2'-methylenebis(4-ethyl-6-t-butylphenol); 2,2'-methylenebis(4-methyl-6-t-butylphenol); 4,4'-butylidenebis(3-methyl-6-t-butylphenol); 4,4'-isopropylidenebis(2,6-di-t-butylphenol); 2,2'-methylenebis(4-methyl-6-t-nonylphenol); 2,2'-isobutylidenebis(4,6-dimethylpenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,6-di-t-butyl-4-methylphenol; 2,6-di-t-butyl-ethylphenol; 2,4-dimethyl-6-t-butylphenol; 2,6-di-t-amyl-p-cresol; 2,6-di-t-butyl-4-(N,N'-dimethylaminomethylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol); 4,4'-thiobis(3-methyl-6-t-butylphenol); 2,2'-thiobis(4-methyl-6-t-butylphenol); bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide; bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide; n-octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate; 2,2'-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and the like. Among them, those of bisphenol-based and ester-containing phenols are preferable.
- In the present invention, these phenolic antioxidants may be used singly or in a combination of two or more thereof. The aforementioned hindered ester used for the synthetic ester base oil has satisfactory oxidative stability by itself, and the oxidative stability of the lubricating oil composition can further be improved by admixing such a phenolic antioxidant, which also results in the increase in thermal stability. The amount of the phenolic antioxidant added is in the range from 0.1 to 5.0 mass% based on the total amount of the present composition. When the amount of the phenolic antioxidant is in the range mentioned above, the effect of improvement in the oxidative stability is exhibited and the balance between cost and effectiveness becomes excellent. The preferable amount of the phenolic antioxidant admixed is in the range from 0.5 to 3.0 mass%. In addition, although the effect of improvement in the oxidative stability can be obtained by adding an amine-based antioxidant as well, the phenolic antioxidants are used in the present invention from a viewpoint of impact on ecosystems.
- In the lubricating oil composition of the present invention, the low base number calcium sulfonate as the component (b) in the ingredient (B) is added to give anti-rust effect to the lubricating oil composition and has also detergency and dispersion function. The calcium sulfonate is a calcium salt of a sulfonated alkyl-substituted aromatic compound. When the base number of the calcium sulfonate is too large, its solubility in the synthetic ester base oil is not sufficient. Therefore, the calcium sulfonate having a low base number such that the total base number (TBN) is in the range from 0 to 100 mg KOH/g (preferably in the range from 0 to 50 mg KOH/g) is used in the present invention.
- The low base number calcium sulfonates may be used singly or in a combination of two or more thereof. The amount of the calcium sulfonate added is in the range from 0.01 to 2.0 mass% based on the total amount of the composition. When the amount of the low base number calcium sulfonate is in the range described above, satisfactory rust-prevention effect can be exhibited and excellent balance between cost and effectiveness is obtained. The amount of the low base number calcium sulfonate is preferably in the range from 0.05 to 1.0 mass%.
- In the lubricating oil composition of the present invention, the triazole compound as (c) component in the ingredient (B) is added as a metal deactivator and is used to give corrosion-prevention effect for non-ferrous metals to the lubricating oil composition. Examples of the triazole compounds are benzotriazole and its derivatives. The triazole compound may be used singly or in a combination of two or more kinds thereof. The amount of the triazole compound admixed is in the range from 0.01 to 1.0 mass% based on the total amount of the composition. When the amount of the triazole compound is in the aforementioned range, satisfactory corrosion-prevention effect can be exhibited and excellent balance between cost and effectiveness is obtained. The amount of the triazole compound admixed is preferably in the range from 0.05 to 0.5 mass%.
- In the lubricating oil composition of the present invention, the base oil itself has a level of lubricity equivalent to that of a conventional mineral oil-based antiwear hydraulic fluid, and in order to further improve the lubricity, an extreme-pressure agent and/or an antiwear agent may be added.
- As the extreme-pressure agent, sulfur-based or phosphorus-based extreme-pressure agents can be used. Examples of the sulfur-based extreme-pressure agent are sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, polysulfides, sulfurized olefins, thiocarbamates, thioterpenes, dialkylthiodipropionates and the like. Among them, sulfurized fats and oils, polysulfides and sulfurized olefins are preferred.
- Examples of the phosphorus-based extreme-pressure agent are phosphates, (mono-, di-, or tri-)thiophosphates, amine salts of acidic phosphates, amine salts of (mono-, or di-)thiophosphates, phosphites, (mono-, di-, or tri-)thiophosphites and the like.
- On the other hand, examples of the antiwear agent are zinc dithiophosphate (ZnDTP), zinc dithiocarbamate (ZnDTC), sulfurized molybdenum dithiophosphate (MoDTP), sulfurized molybdenum dithiocarbamate (MoDTC), and the like.
- The extreme-pressure agent or antiwear agent may be used singly or in a combination of two or more kinds thereof. Further, the total amount of these agents admixed is in the range from 0.1 to 5.0 mass% based on the total amount of the composition. When the amount of the extreme-pressure agent and/or antiwear agent is in the aforementioned range, improvement in the antiwear effect is exhibited and excellent balance between cost and effectiveness is obtained. The amount of the extreme-pressure agent and/or antiwear agent is preferably in the range from 0.5 to 3.0 mass%.
- In addition to the above-described additives, other additives such as viscosity index improver, pour point depressant, ash-free dispersant, surfactant, anti-foaming agent, demulsifier and so on can be added in such a range of the amount that no drawback to the effect of the present invention is brought about.
- The properties of the biodegradable lubricating oil composition of the present invention are explained below.
- The degree of biodegradation of the lubricating oil composition as determined by the microbial degradation test of chemical substances according to the OECD Test Guideline 301C method is 70 % or more (the reference degree of biodegradability is 60 % or more), and has excellent biodegradability. Further, the 96-h LC50 value of the acute toxicity test for Japanese medaka (Oryzias latipes) as determined according to the JIS K 0102 standard is usually 100 mg/L or more, and has low impact on living organisms. Therefore, it can be said that the lubricating oil composition is a very environmentally friendly lubricating oil.
- Also, the viscosity index is usually 130 or more, preferably 140 or more, the pour point is -40°C or lower, preferably -45°C or lower, and the flash point is usually 250°C or higher, preferably 260°C or higher. The synthetic ester base oil of the aforementioned component (A) has a viscosity index of 130 or more by itself, so addition of a viscosity index improver to the present composition is usually not necessary.
- The lubricating oil composition has such a low pour point as mentioned above so that machinery startability at lower temperatures is excellent with the present composition when it is used as a hydraulic fluid. Also, the present composition has such a high flash point as mentioned above so that it has high flame retardance and hence it belongs to the category of a safe combustible liquid having VG of 32 or more according to the Fire Service Law.
- The biodegradable lubricating oil composition of the present invention has excellent biodegradability, low impact to ecosystems, a high viscosity index, a low pour point, a high flash point, being satisfactory with lubricity, oxidative stability, property of preventing the corrosion of non-ferrous metals, and suitability for use with sealing materials. It has thus an excellent balance of those different properties.
- The lubricating oil composition is preferable, for example, as a hydraulic fluid that is a power transmission fluid used in power transmission, power control, shock absorption and the like in a hydraulic system such as hydraulic machinery or equipment, a lubricating oil for automobiles used in automatic transmission, buffer, driving machinery such as power steering, gears and the like, a metal-working oil for cutting, polishing or plasticizing, and the like.
- The present invention is further described by the following examples but not limited thereto.
- In addition, properties of the lubricating oil composition in each example were determined by the following methods:
- (1) General Properties:
- (a) Kinematic viscosity at 40°C: Determined according to JIS K 2283 test method.
- (b) Viscosity index: Determined according to JIS K 2283 test method.
- (c) Acid value: Determined according to JIS K 2501 test method.
- (d) Hydroxyl value: Determined by the pyridine-acetyl chloride method according to JIS K 0070 test method.
- (e) Flash point: Determined by using the Cleveland Open Cup (COC) tester according to JIS K 2265 test method.
- (f) Pour point: Determined according to JIS K 2269 test method.
- (g) Antirust performance: Determined according to JIS K 2510 test method, wherein the rust formation after 24 hours of the test initiation was inspected by visual observation using distilled water at 60°C.
- (2) Biodegradability:
- The degree of biodegradation was determined according to the modified MTTI test method, OECD301C. According to the authorized standard of "ECOMARK" revised in July, 1998, the degree of biodegradation is required to be 60 % or more.
- (3) Acute toxicity to fish:
- The half lethal concentration (LC50) after 96 hours was determined according to JIS K 0102 test method using Japanese medaka (Oryzias latipes). According to the authorized standards of "ECOMARK" revised in July, 1988, the LC50 value is required to be 100 mg/L or more.
- (4) Lubricity:
- (a) Shell Four-ball EP test (ASTM D2783): The load wear index (LWI) was determined from the last non-seizure load (LNL) and weld load (WL) values under the conditions including 1800 rpm and room temperature. The higher the LWI value, the better the load resistance.
- (b) Shell Four-ball wear test (ASTM D2783): The wear spot size was determined under the conditions including 1200 rpm, load of 294 N, temperature of 50°C and 30 minute test duration.
- (c) FZG Scouring test: The load stage of scouring was determined according to ASTM D5182-91 test method under the conditions including 90°C, 1450 rpm, 15 minute test duration, using the A-type gear.
- (d) Vane pump test (according to ASTM D2882): The degree of wear of vane and cam ring was determined by using a vane-type pump (Vickers Inc., V-104C Pump) after 250 hour operation under the conditions including 65°C, 13.7 MPa, 1200 rpm, 60 L oil volume and a flow rate of about 25 L/min.
- (5) Oxidative stability:
- (a) IOT:
- The relative kinematic viscosity at 40°C (kinematic viscosity after the test/kinematic viscosity before the test) was determined, wherein 300 mL of a sample oil filled in a cylinder (45 mm in diameter, 500 mm in length) was subjected to a test in the presence of copper and iron as a catalyst, under the conditions either at 130°C for 48 hours or at 150°C for 48 hours with air intake rate of 10 L/hour.
- (b) High pressure circulation test:
- The relative kinematic viscosity at 40°C (kinematic viscosity after the test/kinematic viscosity before the test) was determined after a test sample was subjected to a test under the following conditions:
- Pump type: (UCHIDA-REXROTH "A2FO-10/ 61R-PPB06"),
- Pump pressure: 35 MPa,
- Oil flow rate: 13.6 L/min,
- Oil temperature: 80°C,
- Air intake rate: 1 NL/h,
- Catalyst: Cu coil (1.6 mm in diameter, 60 m in length), and
- Test duration: 600 h.
Further, in the test described above, durability test was performed without limiting the test duration to measure the time when either the relative kinematic viscosity reaches 1.1, or the acid value reaches 2.0 mg KOH/g, or the Millipore value reaches 10 mg/100 mL of the sample (wherein the Millipore value is defined as a weight of fine powdery residue obtained by filtering out the residue with 0.8 µm membrane filter by vacuum filtration, followed by washing with n-hexane and drying), from which the service life was determined. - The relative kinematic viscosity at 40°C (kinematic viscosity after the test/kinematic viscosity before the test) was determined after a test sample was subjected to a test under the following conditions:
- (a) IOT:
- (6) Corrosion prevention for non-ferrous metals:
- After conducting a high-pressure circulation test for 600 hours in the manner similar to the aforementioned test (5), amounts of copper (dissolved from the catalyst) and zinc (dissolved from the piping material) in the sample oil were measured. In parallel to this method, a metal immersion test was also carried out according to the following procedure:
- (a) Put 100 g of a sample oil in a 200 mL mayonnaise bottle,
- (b) Weigh the test piece after polishing with sandpaper #240, washing with gasoline and drying,
- (c) Put one test piece into one sample bottle and heat at 100°C for 168 hours in a temperature-controlled bath,
- (d) Take out the test piece, wipe off the sample oil on the test piece using waste cloth, wash with gasoline, dry and weigh.
At this time, a metal immersion test as described above was carried out on a zinc test piece (1.0 mm × 26 mm × 60 mm) for the oil sample used in Comparative example 6, a weight loss of 0.47 % was observed. - (7) Suitability for use with sealing material:
- An immersion test was performed according to the JIS K 6258 method for nitrile-butadiene rubber (NBR) and polyurethane at 100°C for 240 hours and at 120°C for 240 hours, respectively, and the rate of change after the test with respect to values before the test was determined for each property: [mass change rate (%),
- volume change rate (%), hardness change (no units), change rate of tensile strength (%), and change rate of elongation at break (%)].
- Here, judgment criteria for evaluation of each of the aforementioned properties are as follows:
- ⊚ (excellent), ○(good), Δ (normal), and × (poor).
- After conducting a high-pressure circulation test for 600 hours in the manner similar to the aforementioned test (5), amounts of copper (dissolved from the catalyst) and zinc (dissolved from the piping material) in the sample oil were measured. In parallel to this method, a metal immersion test was also carried out according to the following procedure:
- Examples 1 to 3 and Comparative examples 1 to 8
(1) Lubricating oil compositions with compositions shown in Tables 1-1 and 1-2 were prepared along with commercially-available products. General properties and biodegradability of these lubricating oil compositions are listed in Tables 2-1 and 2-2.
Table 1Table 1-1 Examples Comparative examples 1 2 3 1 2 3 Prepared product or commercial product Prepared oil Prepared oil Prepared oil Commercial oil A Commercial oil B Commercial oil C Type of base oil Ester Ester Ester Ester Ester Ester Base oil (mass%) Hindered ester PET Ester 31.6 TMP Ester 50.1 TMP Ester 90.8 NPG dioleate 2.0 parts NPG dioleate 3.0 parts - TMP trioleate 66.2 TMP trioleate 47.2 TMP trioleate 6.5 TMP trioleate 8.0 parts TMP trioleate 8.0 parts - - - - - PET tetraoleate 1.0 part - Non-hindered ester - - Aliphatic ester Aliphatic ester Rapeseed oil Total 97.8 97.3 97.3 Antioxidant (mass%) Phenolic 1.4 Phenolic 1.4 Phenolic 1.4 Phenolic Amine-based Phenolic Antirust agent (mass%) Low base number Ca sulfonate 0.1 Low base number Ca sulfonate 0.1 Low base number Ca sulfonate 0.1 - - - Metal deactivator (mass%) Benzotriazole-based 0.1 Benzotriazole-based 0.1 Benzotriazole-based 0.1 - - - Extreme-pressure agent or antiwear agent (mass%) - S, P type 10 S, P type 1.0 ZnDTP Oleic acid, P type Oleic acid, P type Other additives (mass%) Methacrylate anti-foaming agent 0.6 Anti-foaming agent 0.1 Anti-foaming agent 0.1 Large base-number Ca sulfonate, imide-based friction modifier POE alkylether - Table 1-2 Comparative examples 4 5 6 7 8 Prepared product or commercial product Commercial oil D Commercial oil E Commercial oil F Prepared oil Commercial oil G Type of base oil Ester Ester Ester Ester Mineral oil-based Base oil (mass%) Hindered ester - TMP isostearate, oleate (partially-esterified) 2-butyl-2-ethyl-1,3-prop ane diol laurate and oleate mixture TMP trioleate 98.85 - - - - - - - Non-hindered ester Diisotridecyladipate - - - - Total 98.85 Antioxidant (mass%) Amine-based Amine-based 1.0 Phenolic Amine-based 1.0 Phenolic, amine-based Antirust agent (mass%) - Low base number Ca sulfonate 0.1 - Low base number Ca sulfonate 0.1 Polyol alkenyl succinate Metal deactivator (mass%) - Benzotriazole-based 0.05 - Benzotriazole-based 0.05 Triazole-based Extreme-pressure agent or antiwear agent (mass%) S, P type - Oleic acid - Tricresyl phosphate Other additives (mass%) Polybutene polymer Polymethacrylate - - Various additives*1 1 *1 Various additives: a pour point depressant, detergent dispersant, anti-foaming agent, demulsifier, etc.
In Tables 1-1 and 1-2, PET denotes pentaerythritol, TMP denotes trimethylolpropane, NPG denotes neopentyl glycol, ZnDTP denotes zinc dithiophosphate, and POE denotes polyoxyethylene.
Table 3 Table 4
(2) Tables 3-1 and 3-2 indicate the test results of lubricity, oxidative stability and corrosion prevention of non-ferrous metals for each lubricating oil composition. Table 5 Table 6
(3) Table 4 indicates the test results of suitability for use with sealing materials of the lubricating oil composition of Example 1 and the lubricating oil compositions of Comparative examples I to 4.
Table 7 - As is evident from the results of Tables 1 to 4, the lubricating oil compositions of the present invention (Examples 1 to 3) have a well-balanced properties such as excellent biodegradability, a high viscosity index, a low pour point, a high flash point, being satisfactory with lubricity, oxidative stability, property of preventing the corrosion of iron and non-ferrous metals, and suitability for use with sealing materials.
- The biodegradable lubricating oil composition of the present invention comprises a synthetic ester base oil having excellent biodegradability, has well-balanced properties including lubricating performance, and is preferably used, for example, as a hydraulic fluid, automotive lubricating oil, metal-working oil, and so on.
Claims (7)
- A biodegradable lubricating oil composition comprising(A) a synthetic ester base oil comprising at least 50 mass% hindered ester of an aliphatic monocarboxylic acid with an aliphatic hindered polyol represented by the general formula (I):(B) ingredients which arehaving a degree of biodegradation of 70 % or higher when examined by the test for the degree of microbial degradation of chemical substances according to the OECD Test Guideline 301C method.(a) 0.1 to 5.0 mass% phenolic antioxidant based on the total amount of the lubricating oil composition,(b) 0.01 to 2.0 mass% calcium sulfonate having a total base number in the range from 0 to 100 mg KOH/g based on the total amount of the lubricating oil composition, and(c) 0.01 to 1.0 mass% triazole compound based on the total amount of the lubricating oil composition, and
- The biodegradable lubricating oil composition according to claim 1, wherein the 96-h LC50 value of the acute toxicity test for Japanese medaka (Oryzias latipes) according to the JIS K 0102 test method is 100 mg/L or more.
- The biodegradable lubricating oil composition according to claim 1 or 2, wherein the viscosity index determined according to the JIS K 2283 method is 130 or more, the pour point determined according to the JIS K 2269 method is -40°C or less, and the flash point determined by using the Cleveland Open Cup (COC) tester according to the JIS K 2265 method is 250°C or more.
- The biodegradable lubricating oil composition according to Claim 1, wherein the aliphatic hindered polyol is at least one selected from neopentyl glycol; 2-ethyl-2-methyl-1,3-propanediol; 2,2-diethyl-1,3-propanediol; trimethylolethane; trimethylolpropane; trimethylolbutane; trimethylolpentane; trimethylolhexane; trimethylolheptane; pentaerythritol; 2,2,6,6-tetramethyl-4-oxa-1,7-heptanediol; 2,2,6,6,10,10-hexamethyl-4,8-dioxa-1,11-undecanediol; 2,2,6,6,10,10,14,14-octamethyl-4,8,12-trioxa-1,15-pentadecanediol; 2,6-dihydroxymethyl-2,6-dimethyl-4-oxa-1,7-heptanediol; 2,6,10-trihydroxymethyl-2,6,10-trimethyl-4,8-dioxa-1,11-undecanediol; 2,6,10,14-tetrahydroxymethyl-2,6,10,14-tetramethyl-4,8,12-trioxa-1,15-pentadecanediol; di(pentaerythritol); tri(pentaerythritol); tetra(pentaerythritol) and penta(pentaerythritol).
- The biodegradable lubricating oil composition according to any of claims 1 to 4, wherein the aliphatic monocarboxylic acid is a saturated or unsaturated monocarboxylic acid having 6 to 22 carbon atoms.
- The biodegradable lubricating oil composition according to any of claims 1 to 3, wherein the hindered ester is at least one selected from an ester of a saturated or unsaturated monocarboxylic acid having 6 to 22 carbon atoms with pentaerythritol, and an ester of a saturated or unsaturated monocarboxylic acid having 6 to 22 carbon atoms with trimethylolpropane.
- The biodegradable lubricating oil composition according to any of claims 1 to 6, which contains 0.1 to 5.0 mass% of an extreme-pressure agent and/or an antiwear agent as a component (B) (d) based on the total amount of the lubricating oil composition.
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JP2002212580A (en) * | 2001-01-19 | 2002-07-31 | Nippon Mitsubishi Oil Corp | Method for rustproofing refrigerator part |
US6919301B2 (en) * | 2001-10-16 | 2005-07-19 | Nsk Ltd. | Grease composition and rolling apparatus |
JP2004018531A (en) * | 2002-06-12 | 2004-01-22 | Nippon Oil Corp | Lubricating oil composition |
-
2004
- 2004-01-30 JP JP2004024291A patent/JP4827381B2/en not_active Expired - Fee Related
-
2005
- 2005-01-28 EP EP05709443.5A patent/EP1707617B1/en not_active Not-in-force
- 2005-01-28 WO PCT/JP2005/001216 patent/WO2005073353A1/en not_active Application Discontinuation
- 2005-01-28 US US10/585,203 patent/US20090176670A1/en not_active Abandoned
- 2005-01-28 CN CNB2005800031418A patent/CN100554388C/en not_active Expired - Fee Related
-
2014
- 2014-02-10 US US14/176,432 patent/US20140155307A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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None * |
Also Published As
Publication number | Publication date |
---|---|
US20140155307A1 (en) | 2014-06-05 |
US20090176670A1 (en) | 2009-07-09 |
CN100554388C (en) | 2009-10-28 |
EP1707617A4 (en) | 2010-05-26 |
JP2005213451A (en) | 2005-08-11 |
JP4827381B2 (en) | 2011-11-30 |
WO2005073353A1 (en) | 2005-08-11 |
EP1707617A8 (en) | 2006-12-06 |
CN1914303A (en) | 2007-02-14 |
EP1707617A1 (en) | 2006-10-04 |
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