CN100554388C - Biodegradable lubricating oil composition - Google Patents
Biodegradable lubricating oil composition Download PDFInfo
- Publication number
- CN100554388C CN100554388C CNB2005800031418A CN200580003141A CN100554388C CN 100554388 C CN100554388 C CN 100554388C CN B2005800031418 A CNB2005800031418 A CN B2005800031418A CN 200580003141 A CN200580003141 A CN 200580003141A CN 100554388 C CN100554388 C CN 100554388C
- Authority
- CN
- China
- Prior art keywords
- lubricating oil
- oil composition
- biodegradable lubricating
- ester
- test
- 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 - Fee Related
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 62
- 238000012360 testing method Methods 0.000 claims abstract description 36
- -1 aliphatic monocarboxylic acid Chemical class 0.000 claims abstract description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- 150000002148 esters Chemical class 0.000 claims abstract description 24
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 21
- 239000002199 base oil Substances 0.000 claims abstract description 19
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 12
- 238000010998 test method Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 239000005069 Extreme pressure additive Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- 241000276569 Oryzias latipes Species 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 229940059574 pentaerithrityl Drugs 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 231100000403 acute toxicity Toxicity 0.000 claims description 4
- 230000007059 acute toxicity Effects 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 230000006866 deterioration Effects 0.000 claims description 3
- 230000002906 microbiologic effect Effects 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003566 sealing material Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
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- 230000000813 microbial effect Effects 0.000 abstract 1
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- 239000002530 phenolic antioxidant Substances 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 23
- 235000019198 oils Nutrition 0.000 description 23
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- 230000001590 oxidative effect Effects 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 5
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- 238000013475 authorization Methods 0.000 description 4
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- 239000005864 Sulphur Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000010720 hydraulic oil Substances 0.000 description 3
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- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- 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
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 238000005516 engineering process Methods 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
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
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- 239000002480 mineral oil Substances 0.000 description 2
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- 238000002156 mixing 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
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
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- RHHHGLCTQKINES-UHFFFAOYSA-M sodium;5-amino-2-methoxy-4-sulfobenzenesulfonate Chemical compound [Na+].COC1=CC(S(O)(=O)=O)=C(N)C=C1S([O-])(=O)=O RHHHGLCTQKINES-UHFFFAOYSA-M 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
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- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
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- 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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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- 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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- 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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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
- 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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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
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- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
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- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
- C10M2207/2895—Partial esters containing free hydroxy groups used as base material
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- 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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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/081—Biodegradable compounds
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/64—Environmental friendly compositions
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
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- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
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Abstract
The present invention provides a biodegradable lubricating oil composition which is a synthetic ester-based biodegradable lubricating oil composition having excellent biodegradability, high viscosity index, low pour point, and high flash point, and which is satisfactory in lubricity, oxidation stability, corrosion resistance against ferrous and nonferrous metals, and suitability for use in combination with sealing materials. [ MEANS FOR SOLVING PROBLEMS ] the biodegradable lubricating oil composition comprises a synthetic ester-base oil comprising at least 50 mass% of a hindered ester of an aliphatic monocarboxylic acid and an aliphatic hindered polyol having one or more quaternary carbon atoms per molecule and wherein at least one of the quaternary carbon atoms has 1 to 4 methylol groups bonded thereto, and (B) 0.1 to 5.0 mass% of a phenolic antioxidant, (B)0.01 to 2.0 mass% of a calcium sulfonate having a low base number, and (C)0.01 to 1.0 mass% of a triazole compound, and has a biodegradability of 60% or more when tested according to the chemical substance microbial degradability test according to OECD test criterion 301C.
Description
Technical field
[0001] the present invention relates to Biodegradable lubricating oil composition.More particularly, it relates to a kind of synthetic ester-based, biodegradable lubricating oil composition with excellent biological degradability, high viscosity index (HVI), low pour point, high flash point, its oilness, oxidative stability, prevent iron and non-ferrous metal corrosive performance, and the suitability that the fitted seal material uses is satisfactory.
Background technology
[0002] in recent years, in field of lubricant, Biodegradable lubricant oil as environmental pollution-measure of control, receives sizable concern.In Japan, the research and development in relevant this field has just begun and has produced the available commercial product from eighties of last century the beginning of the nineties.Yet Biodegradable lubricant oil is not used widely so far, and reason is to compare the cost height with traditional mineral oil-based lubricating oil, although shown great attention to.Japan far lags behind European countries, and the application of Biodegradable lubricant oil has been enforceable by legal provisions in those countries.
Vegetables oil such as rapeseed oil, synthetic ester and polyalkane glycol have been used as biodegradable base oil.Yet, although vegetables oil exists heat or oxidative instability and supply problem of unstable cost low, although there is the low and Heat stability is good of problem cost poor for applicability that is used for sealing material in the polyalkane glycol simultaneously.Therefore, although synthetic ester is just becoming more and more welcome in Japan,, compare them with mineral oil based lubricating oil and still have serious weakness from cost or oxidative stability.
[0003] Japanese environment association has the authorization standard at biodegradable hydraulic efficiency oil, " ECOMARK " by name.This authorization standard was done material alteration to reach stricter control in July, 1998.Main variation is as follows:
(1) the biological degradability standard from part biological degraded test " CEC test rule " (with reference to biodegradation intensity: 67% or higher) change into intrinsic biodegradation test " OECD test rule 301C method " (with reference to biodegradation intensity: 60% or higher), and
(2) increased the test of Japanese medaka (Oryzias latipes) acute toxicity, and JIS K0102 (reference: LC50 〉=100mg/L).
The example of following Biodegradable lubricant oil is disclosed: a kind of lubricating oil composition, comprise polyol ester basis oil, by the carboxylic acid of 5～14 carbon atoms and the carboxylic acid of 15～38 carbon atoms, the two weight ratio was between 0.1: 99.9～50: 50, form, wherein contain the condenses between at least a carboxylic acid that is selected from sulfonate, alkanolamine and 5～14 carbon atoms of 0.1～15 weight % and the compound (for example, patent documentation 1) of polybutylene-based succinimide; A kind of anti-retardant hydraulic oil, comprise the hydraulic pressure base oil, it comprises, as main ingredient, a kind of part ester of polyvalent alcohol, its hydroxyl value are 35mgKOH/g or higher, 290 ℃ of flash-points or higher, with number-average molecular weight 600～1500, wherein this ester is formed (for example, patent documentation 2) by the polyvalent alcohol of 3～12 carbon atoms and 3～6 total oh groups and the linear chain monocarboxylic acid of 6～22 carbon atoms; A kind of lubricating oil comprises synthetic ester, and its viscosity of 40 ℃ is 20～40mm
2/ s, viscosity index 120 or higher, and pour point-30 ℃ or lower, wherein this ester comprises the dihydroxymethyl alkane, and wherein alkane has the linear chain lipid acid (for example, patent documentation 3) of 5～7 carbon atoms and 10～20 carbon atoms; A kind of non-aqueous hydraulic comprises the base oil of being made up of trimethylolpropane tris oleic acid ester or neopentyl glycol dioleate and tensio-active agent such as Voranol EP 2001 (for example, patent documentation 4), and the like.
[0004] though, Biodegradable lubricant oil above-mentioned is satisfactory on oilness or oxidative stability, but they still exist high pour point, to hydraulic machinery with the employed non-ferrous metal of material have sizable dissolving metal amount, to the problems such as extreme run-inflation effect of sealing material.
[0005] patent documentation 1:JP Kokai 1993-339591
Patent documentation 2:JP Kokai 1994-228579
Patent documentation 3:JP Kokai 1997-249889
Patent documentation 4:JP Kokai 1999-323373
Summary of the invention
The problem that invention will solve
[0006] the present invention finishes under such environment, its purpose is to provide a kind of Biodegradable lubricating oil composition, it has the synthetic ester-based, biodegradable lubricating oil composition of excellent biological degradability, high viscosity index (HVI), low pour point, high flash point, its oilness, oxidative stability, prevent iron and non-ferrous metal corrosive performance, and the suitability that the fitted seal material uses is satisfactory.
The measure of dealing with problems
[0007] but the Biodegradable lubricating oil composition that the inventor meets above-mentioned people's performance for research and development done further investigation and found, a kind of have be equal to or greater than, measure according to OECD test rule 301C method, the Biodegradable lubricating oil composition of a certain biological degradability numerical value can satisfy this research purpose, wherein this lubricating oil composition is made up of a kind of synthetic ester-base oil, the latter mainly comprises the ester that aliphatic steric hindrance polyvalent alcohol with ad hoc structure and mono carboxylic acid of aliphatic series are formed, and ratio is mixed a kind of special additive according to the rules therein.The present invention finishes on the basis of above-mentioned discovery.In other words, the invention provides:
(1) a kind of Biodegradable lubricating oil composition, comprise (A) synthetic ester-base oil, the latter comprises the hindered ester of at least 50 quality % mono carboxylic acid of aliphatic series and aliphatic steric hindrance polyvalent alcohol, this polyvalent alcohol per molecule has one or more quaternary carbon atoms, and wherein quaternary carbon atom has one of at least 1～4 bonding methylol groups thereon, and (B) following ingredients, (a) 0.1～5.0 quality % phenol antioxidant, (b) 0.01～2.0 quality % has the calcium sulphonate of low alkali value, (c) 0.01～1.0 quality % triazole compounds, and when having 60% or higher biological degradability according to according to the chemical substance microbiological deterioration degree experimental test of OECD test rule 301C the time
(2) according to the Biodegradable lubricating oil composition of (1) above-mentioned, wherein according to JISK 0102 test method, Japanese medaka (Oryzias latipes) acute toxicity is tested, 96-hLC
50Value is equal to or greater than 100mg/L,
(3) according to the Biodegradable lubricating oil composition of (1) above-mentioned or (2), wherein viscosity index is equal to or greater than 130, and pour point is-40 ℃ or lower, and flash-point is 250 ℃ or higher,
(4) according to any one Biodegradable lubricating oil composition in (1) above-mentioned～(3), wherein aliphatic steric hindrance polyvalent alcohol is the compound by general formula (I) representative:
[0008]
[general formula 1]
[0009] R wherein
1And R
2Represent the hydrocarbyl group or the methylol groups of 1～6 carbon atom independently, and n is 0～4 integer,
(5) according to the Biodegradable lubricating oil composition of (4) above-mentioned, wherein aliphatic steric hindrance polyvalent alcohol is TriMethylolPropane(TMP), neopentyl glycol, tetramethylolmethane, or its dehydration condensation,
(6) according to any one Biodegradable lubricating oil composition in (1) above-mentioned～(5), wherein mono carboxylic acid of aliphatic series is the saturated or unsaturated monocarboxylic of 6～22 carbon atoms,
(7) according to any one Biodegradable lubricating oil composition in (1) above-mentioned～(6), wherein have total basicnumber between 0～100mg KOH/g as low alkali value component (B) calcium sulphonate (b), and
(8) according to any one Biodegradable lubricating oil composition in (1) above-mentioned～(7), it comprises 0.1～5.0 quality % extreme pressure additive and/or anti-wear agent as component (B) (d).
The advantage of invention
[0010] according to the present invention, a kind of synthetic ester-based, biodegradable lubricating oil composition is provided, it has excellent biological degradability, high viscosity index (HVI), low pour point, high flash point, in oilness, oxidative stability, prevent iron and non-ferrous metal corrosive performance, and satisfactory on the suitability used of fitted seal material.
The invention optimum implementation
[0011] Biodegradable lubricating oil composition of the present invention comprises: (A) synthetic ester-base oil and the composition that (B) comprises following combination, (a) phenol antioxidant, (b) low alkali value calcium sulphonate and (c) triazole compounds.
The hindered ester that comprises at least 50 quality % mono carboxylic acid of aliphatic series and aliphatic steric hindrance polyvalent alcohol as the synthetic ester-base oil of component of the present invention (A), this polyvalent alcohol has one or more quaternary carbon atom per molecules, and wherein quaternary carbon atom has one of at least 1～4 bonding methylol groups thereon.
Have one or more quaternary carbon atom per molecules, and quaternary carbon atom the present invention's aliphatic series steric hindrance polyvalent alcohol (following can be referred to as the steric hindrance polyvalent alcohol simply) compound of general formula (I) representative preferably of having one of at least 1～4 bonding methylol groups thereon wherein:
[0012] [general formula 2]
[0013] R wherein
1And R
2Represent the hydrocarbyl group or the methylol groups of 1～6 carbon atom independently, and n is 0～4 integer
As, in general formula (I), at R
1And R
2The hydrocarbyl group of 1～6 central carbon atom is preferably line style or branched-alkyl or kiki alkenyl group, especially the preferred alkyl group.
[0014] compound (steric hindrance polyvalent alcohol) of general formula (I) representative refers to such steric hindrance polyvalent alcohol, for example, and neopentyl glycol, trimethylol alkanes (alkane has 2～7 carbon atoms) or tetramethylolmethane or its dehydration condensation.Object lesson comprises neopentyl glycol; 2-ethyl-2-methyl isophthalic acid, ammediol; 2,2-diethyl-1, ammediol; Trimethylolethane; TriMethylolPropane(TMP); Tri hydroxy methyl butane; The trishydroxymethyl pentane; Trimethylolhexane; The trishydroxymethyl heptane; Tetramethylolmethane; 2,2,6,6-tetramethyl--4-oxa--1,7-heptanediol; 2,2,6,6,10,10-hexamethyl-4,8-two oxa-s-1,11-undecane glycol; 2,2,6,6,10,10,14,14-prestox-4,8,12-trioxa-1,15-pentadecane glycol; 2,6-dihydroxymethyl-2,6-dimethyl-4-oxa--1,7-heptane glycol; 2,6,10-trishydroxymethyl-2,6,10-trimethylammonium-4,8-two oxa-s-1,11-undecane glycol; 2,6,10,14-tetra methylol-2,6,10,14-tetramethyl--4,8,12-trioxa-1,15-pentadecane glycol; Two (tetramethylolmethanes); Three (tetramethylolmethanes); Four (tetramethylolmethanes); Five (tetramethylolmethanes) and the like.
[0015] the steric hindrance polyvalent alcohol can be separately or with 2 or the form of more kinds of its mixtures be used for esterification.In the general formula of Miao Shuing (I), the preferred value of n is 0～2 in the above.
Preferred steric hindrance polyvalent alcohol is TriMethylolPropane(TMP), neopentyl glycol, tetramethylolmethane or its dehydration condensation, and wherein preferred dehydration condensation is bimolecular or three molecule condensess.
Above-described steric hindrance polyvalent alcohol can be synthetic according to traditional method.Equally, the dehydration condensation of steric hindrance polyvalent alcohol also can make the steric hindrance polyvalent alcohol carry out dehydrating condensation at about 180 ℃ in the presence of catalyzer to synthesize by the steric hindrance polyvalent alcohol is dispersed in the temperature heating that is higher than fusing point and with them in the solvent.
[0016] on the other hand, the mono carboxylic acid of aliphatic series that uses in the esterification as aliphatic steric hindrance polyvalent alcohol above-mentioned preferably uses the saturated or unsaturated monocarboxylic of 6～22 carbon atoms.The carboxyl groups of monocarboxylic acid can be line style or branching.The example of mono carboxylic acid of aliphatic series comprises line style saturated mono carboxylic acid such as caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, palmitinic acid, margaric acid, stearic acid, nondecylic acid, eicosanoic acid, docosoic acid, line style unsaturated monocarboxylic such as undecylenic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassidic acid, linolic acid or linolenic acid, branching saturated mono carboxylic acid such as different tetradecanoic acid, different palmitinic acid, Unimac 5680,2, the 2-acid dimethyl, 2,2-dimethyl valeric acid, 2, the 2-dimethyl is sad, 2-ethyl-2,3,3-trimethylammonium butyric acid, 2,2,3,4-tetramethyl-valeric acid, 2,5,5-trimethylammonium-2-tertiary butyl caproic acid, 2,3,3-trimethylammonium-2 Ethylbutanoic acid, 2,3-dimethyl-2-sec.-propyl butyric acid, 2 ethyl hexanoic acid or 3,5, the 5-tri-methyl hexanoic acid, and the like.Mono carboxylic acid of aliphatic series can also can be used as separately 2 or more kinds of mixtures be used for esterification.
[0017] can be the compound of full esterification or partial esterification by the esterification synthetic hindered ester between steric hindrance polyvalent alcohol above-mentioned and the mono carboxylic acid of aliphatic series.Preferred hindered ester is the compound of full esterification.
Hindered ester can also can be used as separately its 2 or more kinds of mixtures be used for Biodegradable lubricating oil composition of the present invention.Alkane, the quantity in the hindered ester in synthetic ester-base oil is equal to or greater than 50 quality %, preferably is equal to or greater than 70 quality %, more preferably is equal to or greater than 80 quality % so that satisfy the regulation performance of the Biodegradable lubricating oil composition that describes below.
As the synthetic ester-base oil that can cooperate hindered ester to use together, consider to enumerate the aliphatic polyol except that steric hindrance polyvalent alcohol above-mentioned and the ester of above-described monocarboxylic acid generation from the angle of the biological degradability of lubricating oil composition.
The kinematic viscosity of the synthetic ester-base oil that uses as the component in the lubricating oil composition (A) depends on the application target of lubricating oil composition, generally at 40 ℃ between about 10～200mm
2The scope of/s is preferably at 10～100mm
2The scope of/s is more preferably at 15～80mm
2The scope of/s is under situation about using as hydraulic efficiency oil.
The acid number of synthetic ester-base oil preferably is equal to or less than 3mg KOH/g, especially preferably is equal to or less than 1mg KOH/g, considers from preventing etching apparatus.In addition, be not particularly limited, but preferably be equal to or less than 50mg KOH/g, especially preferably be equal to or less than 20mgKOH/g, from the angle of oilness for hydroxyl value.
[0018] in lubricating oil composition of the present invention, phenol antioxidant, the component (a) as composition (B) is not subjected to specific limited, can use technology on known phenol antioxidant, need only suitably select.The example of phenol antioxidant comprises 4; 4,4 '-two (2,6 di t butyl phenols); 4,4 '-two (2-methyl-6-tert butyl phenol); 2; 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol); 4,4 '-Ding fork two (3 methy 6 tert butyl phenol); 4,4 '-isopropylidene two (2,6 di t butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert nonylphenol); 2,2 '-isobutyl fork two (4, the 6-xylenol); 2; 2,6 di tert butyl 4 methyl phenol; 2,6-di-t-butyl-ethylphenol; 2,4 dimethyl 6 tert butyl phenol; 2,6-two tert-pentyls-p-cresol; 2,6-di-t-butyl-4-(N, N '-dimethylaminomethylphenol), 4,4 '-thiobis (2-methyl-6-tert butyl phenol); 4,4 '-thiobis (3 methy 6 tert butyl phenol); 2,2 '-thiobis (4-methyl-6-tert butyl phenol); Two (3-methyl-4-hydroxyl-5-tertiary butyl benzyl) thioether; Two (3,5-di-t-butyl-4-acrinyl) thioether; Octadecane base-3-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propane; 2,2 '-sulfo-[diethyl-two-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] and the like.In the middle of them, be preferably based on bis-phenol and comprise those of phenols of ester.
[0019] in the present invention, these phenol antioxidant can be separately also can its 2 or more kinds of being used in combination.The hindered ester itself that is used for synthetic ester-base oil above-mentioned just has satisfied oxidative stability, and the oxidative stability of lubricating oil composition also can further improve by this kind of blending phenol antioxidant, does the raising that also causes thermostability like this.The add-on of phenol antioxidant is benchmark between the scope of 0.1～5.0 quality % in present composition total amount.When in the scope that the quantity of phenol antioxidant is mentioned in the above, the improvement of oxidative stability will show, simultaneously cost and balance between the rendeing a service brilliance that becomes.The preferred amount of the phenol antioxidant of blending is in the scope of 0.5～3.0 quality %.In addition, though the improvement effect of oxidative stability also can obtain by the antioxidant that adds based on amine, the angle to ecosystem influence adopts phenol antioxidant in the present invention.
[0020] in lubricating oil composition of the present invention, adding low alkali value calcium sulphonate so that give the lubricating oil composition rust-proof effect, also has decontamination and divergent function as the component (b) in the composition (B) simultaneously.This calcium sulphonate is the calcium salt of the aromatic substance of sulfonation, alkyl-replacement.When the base number of calcium sulphonate is excessive, its solubleness deficiency in synthetic ester-base oil.Therefore, adopt the low alkali value calcium sulphonate in the present invention, control total basicnumber (TBN) is between the scope of 0～100mg KOH/g (preferably 0～50mg KOH/g scope).
The low alkali value calcium sulphonate can be separately also can 2 or more kinds of array configurations use.The add-on of calcium sulphonate is between the scope of 0.01～2.0 quality %, is benchmark in the total alkali content of composition.When in the scope that the quantity of low alkali value calcium sulphonate is described in the above, will show satisfied rust-proof effect and obtain balance between excellent cost and the effectiveness.The consumption of low alkali value calcium sulphonate is preferably between the scope of 0.05～1.0 quality %.
[0021] in lubricating oil composition of the present invention, as (c) in the composition (B), add triazole compounds, be used as the metal activation agent, and give lubricating oil composition and prevent corrosive nature non-ferrous metal.The example of triazole compounds is benzotriazole and derivative thereof.Triazole compounds can be separately also can its 2 or more kinds of array configurations use.The mixed volume of triazole compounds is benchmark between 0.01～1.0 quality % in the total composition.When in the scope that the quantity of triazole compounds is mentioned in the above, can show satisfied anticorrosion ability and obtain balance between excellent cost and the effectiveness.The mixed volume of triazole compounds is preferably between 0.05～0.5 quality %.
In lubricating oil composition of the present invention, base oil itself have with based on traditional mineral oil-the suitable lubricity levels of antiwear hydraulic oil, and, can add a kind of extreme pressure additive and/or anti-wear agent for further improvement oilness.
As extreme pressure additive, can use based on sulphur or based on the extreme pressure additive of phosphorus.Example based on the extreme pressure additive of sulphur is sulfurized fatty or oil, sulfide aliphatic acid, sulfuration ester, polysulfide, olefine sulfide, thiocarbamate, sulfo-terpenes, dialkyl group thiodipropionate etc.In the middle of them, sulfurized fatty or oil, polysulfide or olefine sulfide are preferred.
Based on the example of the extreme pressure additive of sulphur is amine salt, phosphorous acid ester, (single-, two-or three-) thiophosphite etc. of amine salt, (single-, two-or three-) thiophosphatephosphorothioate of phosphoric acid ester, (single-, two-or three-) thiophosphatephosphorothioate, acid phosphatase.
On the other hand, the example of anti-wear agent is zinc dithiophosphate (ZnDTP), zinc dithiocarbamate (ZnDTC), sulfurized molybdenum dithiophosphate (MoDTP), sulfurized molybdenum dithiocarbamate (MoDTC) etc.
[0022] extreme pressure additive or anti-wear agent can be separately also can its 2 or more kinds of being used in combination.In addition, the total amount of these blended additives is benchmark between 0.1～5.0 quality % in the total composition.When in the scope that the quantity of extreme pressure additive and/or anti-wear agent is mentioned in the above, the improvement that shows anti-wear effect, obtain cost simultaneously and render a service between splendid balance.The consumption of extreme pressure additive and/or anti-wear agent is preferably between 0.5～3.0 quality %.
Except above-described additive, other additive such as viscosity index improver, pour point depressant, ashless dispersant, tensio-active agent, defoamer, emulsion splitter etc. also can add, as long as its consumption does not hinder the performance of effect of the present invention.
[0023] performance of explained later Biodegradable lubricating oil composition of the present invention.
The biological degradability of lubricating oil composition according to the chemical substance microbiological deterioration test determination of OECD test rule 301C method, is 70% or higher (is 60% or higher with reference to biological degradability), and has excellent biological degradability.In addition, the 96-h LC of acute toxicity test
50Value is generally 100mg/L or higher, and biology is had low influence.Therefore, we can say that this lubricating oil composition is a kind of very eco-friendly lubricating oil.
Also have, viscosity index is generally 130 or higher, and preferred 140 or higher, pour point is-40 ℃ or lower, preferred-45 ℃ or lower, and flash-point is generally 250 ℃ or higher, preferred 260 ℃ or higher.The viscosity index of the synthetic ester-base oil of component above-mentioned (A) itself is 130 or higher, therefore, does not need usually to add viscosity index improver in the present composition.
Lubricating oil composition has as mentioned above so low pour point, so that when with it during as hydraulic efficiency oil, the low temperature machine startup of the present composition is splendid.Also have, the present composition has high like this flash-point as mentioned above, causes it to have very high flame retardant and therefore, and according to the Fire-Fighting Service method, it belongs to VG and equals 32 or the classification of higher safe flammable liquid.
[0024] Biodegradable lubricating oil composition of the present invention has excellent biological degradability, low ecosystem influence, high viscosity index (HVI), low pour point, high flash point, in oilness, oxidative stability, to prevent that non-ferrous metal corrodibility and cooperation are used for aspect the suitability of sealing material satisfactory.Therefore, it has balance splendid between those different performances.
This lubricating oil composition preferably, for example, as hydraulic efficiency oil, that is, a kind of power transmission fluids that is used for transmission of power, power control, shock absorption etc. is used in hydraulic efficiency system such as hydraulic machinery or the equipment; Be used for automatic transmission, vibroshock, steering device such as power steering, the gear etc. of automobile as lubricating oil, metalworking fluid, for example, cutting, polishing or plasticising etc.
Example
[0025] the present invention will be described further by following example but be not limited to these examples.
In addition, the performance demands of the lubricating oil in each example adopts following method to determine:
(1) general property:
(a) 40 ℃ kinematic viscosity: determine according to JIS K 2283 test methods.
(b) viscosity index: determine according to JIS K 2283 test methods.
(c) acid number: determine according to JIS K 2501 test methods.
(d) hydroxyl value: adopt pyridine-Acetyl Chloride 98Min. method to determine according to JIS K 0070 test method.
(e) flash-point: adopt the Cleveland to open cup (COC) tester according to JIS K 2265 test methods and determine.
(f) pour point: determine according to JIS K 2269 test methods.
(g) rustless property: determine according to JIS K 2510 test methods, wherein adopt 60 ℃ of distilled water, with the situation of getting rusty behind the visual inspection on-test 24h.
[0026] (2) biological degradability:
Biological degradability is determined according to the MITI test method OECD301C of improvement." ECOMARK " authorization standard according to revising in July, 1998 requires biological degradability to be equal to or greater than 60%.
(3) to the acute toxicities of fish:
Toxic limit medium dose (LC behind the 96h
50), adopt Japanese medaka (oryzias latipes) to determine according to JIS K 0102 test method." ECOMARK " authorization standard according to revising in July, 1998 requires LC
50Value is equal to or greater than 100mg/L.
(4) oilness:
(a) Shell four ball EP tests (ASTM D2783): determine load abrasion index (LWI), block load (LNL) and welding load (WL) value according to last nothing under the condition that comprises 1800rpm and room temperature.The LWI value is high more, and anti-loading capacity is good more.
(b) (a) Shell four-ball wear test (ASTM D2783): under the condition of the load that comprises 1200rpm, 294N, 50 ℃ temperature and 30min test period, determine the wearing and tearing spot size.
(c) FZG washout test: measure and to wash away the load platform,, adopt A-type mechanism comprising under 90 ℃, the condition of 1450rpm, 15min test period according to ASTM D5182-91 test method.
(d) vane pump test (according to ASTM D2882): measure the blade and the cam ring degree of wear, adopt vane pump (Vickers company, the V-104C pump), under the condition that comprises 65 ℃, 13.7MPa, 1200rpm, 60L oil volume and about 25L/min flow rate through the 250h operation after.
[0027] (5) oxidative stability:
(a)IOT：
Be determined at 40 ℃ relative movement viscosity (kinematic viscosity before test back kinematic viscosity/test), wherein 300mL fills with cylinder (45mm diameter, 500mm length) sample oil is in the presence of copper and iron as catalyzer, at 130 ℃ and 48h, perhaps 150 ℃ and 48h, under the air imbibed quantity 10L/h condition, reception test.
(b) cycle of higher pressure test:
Be determined at 40 ℃ relative movement viscosity (kinematic viscosity before test back kinematic viscosity/test), test sample carries out after the following condition of acceptance is handled:
Pump type: (UCHIDA-REXROTH " A2FO-10/61R-PPB06 "),
Pumping pressure: 35MPa,
Oil flow rate: 13.6L/min,
The oil temperature: 80 ℃,
Air sucks speed: 1NL/h,
Catalyzer: bronze pan tube (1.6mm diameter, 60m is long), and
Test period: 600h.
In addition, in the above in the test of Miao Shuing, under the condition of clipping time not, carry out serviceability test, to measure one of following time: when relative movement viscosity reaches 1.1, perhaps reach 2.0mg KOH/g when acid number, perhaps the micropore value reaches the 10mg/100mL sample (wherein the micropore value is defined as, and leaches after the residue with 0.8 μ m membrane filter by vacuum filtration, wash the weight of also dry resulting Powdered residue again with normal hexane), determine work-ing life thus.
[0028] (6) prevent the corrosion to non-ferrous metal
According to after having carried out the 600h cycle of higher pressure in the mode that is similar to test above-mentioned (5), the quantity of copper in the working sample oil (dissolving) and zinc (dissolving) from pipeline material from catalyzer.In parallel therewith method, implement the metal soak test according to following program again:
(a) 100g sample oil is put in the 200mL mayonnaise bottle,
(b) in the standard of using sand paper #240 polishing, with gasoline washing and the dry weight that takes by weighing sample afterwards,
(c) a slice sample is put in the sample bottle and in temperature control is bathed, is heated 168h at 100 ℃,
(d) take out sample, wipe sample oil on the dry sample,, dryly also weigh with the gasoline washing with useless cloth.
This moment, at the sample oil that uses in the Comparative Examples 6, (1.0mm * 26mm * 60mm) implement metal soak test as described above observes 0.47% weight saving to the zinc sample.
[0029] (7) are for the suitability of sealing material:
According to JIS K 6258 methods, implement 100 ℃ and 240h respectively at paracril (NBR) and urethane, and the soak test of 120 ℃ and 240h, the numerical value change rate of every kind of character before and after the confirmed test: [mass change (%), volume change (%), changes in hardness (no unit), tensile strength velocity of variation (%) and extension at break velocity of variation (%)].
Here, the judging criterion to every kind of character assessment above-mentioned is as follows:
◎ (excellent), zero (very), △ (generally), * (poor).
[0030] example 1～3 and Comparative Examples 1～8
(1) prepared the lubricating oil composition of forming shown in table 1-1 and 1-2, together with the product of available commercial.The general aspects of these lubricating oil compositions and biological degradability are stated among table 2-1 and the 2-2.
[0033] annotate:
In table 1-1 and 1-2, PET represents tetramethylolmethane, and TMP represents TriMethylolPropane(TMP), and NPG represents neopentyl glycol, and ZnDTP represents zinc dithiophosphate, and POE represents polyoxyethylene.
[0034] table 3
Table 2-1
[0035] table 4
Table 2-2
[0036] (2) table 3-1 and 3-2 provide oilness, oxidative stability and the anti-non-ferrous metal corrosive test-results of every kind of lubricating oil composition.
[0037] table 5
Table 3-1
* 1: zinc dissolved numerical value is not measured, because added ZnDTP.
[0038] table 6
Table 3-2
* 2: through at 100 ℃, significantly corrosion is found in the immersion of 168h.
[0039] (3) table 4 provides the test-results that example 1 lubricating oil composition and Comparative Examples 1～4 lubricating oil composition are used for the suitability of sealing material.
[0040] table 7
Table 4
[0041] finds out as result from table 1～4, lubricating oil composition of the present invention (example 1～3) has isostatic performance well, for example, excellent biological degradability, high viscosity index (HVI), low pour point, high flash point, in oilness, oxidative stability, prevent iron and non-ferrous metal corrosive performance, and it is satisfactory to be used for the aspects such as suitability of sealing material.
Commercial Application
[0042] Biodegradable lubricating oil composition of the present invention comprises and a kind ofly has excellent biology and fall Synthetic ester-the base oil of solution property, it has well balanced performance, comprises greasy property, and And be preferred for, for example, as hydraulic oil, automobile oil, Metalworking fluid etc.
Claims (8)
1. Biodegradable lubricating oil composition, comprise (A) synthetic ester-base oil, should synthesize the hindered ester that ester-base oil comprises at least 50 quality % mono carboxylic acid of aliphatic series and aliphatic steric hindrance polyvalent alcohol, this polyvalent alcohol per molecule has one or more quaternary carbon atoms, and wherein quaternary carbon atom has one of at least 1～4 bonding methylol groups thereon, and (B) following ingredients, (a) 0.1～5.0 quality % phenol antioxidant, (b) 0.01～2.0 quality % has the calcium sulphonate of low alkali value, (c) 0.01～1.0 quality % triazole compounds, and when having 60% or higher biological degradability according to according to the chemical substance microbiological deterioration degree experimental test of OECD test rule 301C method the time.
2. according to the Biodegradable lubricating oil composition of claim 1, wherein according to JIS K0102 test method, Japanese medaka (Oryzias latipes) acute toxicity is tested, 96-hLC
50Value is equal to or greater than 100mg/L.
3. according to the Biodegradable lubricating oil composition of claim 1 or 2, wherein viscosity index is equal to or greater than 130, and pour point is-40 ℃ or lower, and flash-point is 250 ℃ or higher.
4. according to the Biodegradable lubricating oil composition of claim 1 or 2, wherein aliphatic steric hindrance polyvalent alcohol is the compound by general formula (I) representative:
R wherein
1And R
2Represent the hydrocarbyl group or the methylol groups of 1～6 carbon atom independently, and n is 0～4 integer.
5. according to the Biodegradable lubricating oil composition of claim 4, wherein aliphatic steric hindrance polyvalent alcohol is TriMethylolPropane(TMP), neopentyl glycol, tetramethylolmethane, or its dehydration condensation.
6. according to the Biodegradable lubricating oil composition of claim 1 or 2, wherein mono carboxylic acid of aliphatic series is the saturated or unsaturated monocarboxylic of 6～22 carbon atoms.
7. according to the Biodegradable lubricating oil composition of claim 1 or 2, wherein has total basicnumber between 0～100mgKOH/g as low alkali value component (B) calcium sulphonate (b).
8. according to the Biodegradable lubricating oil composition of claim 1 or 2, it comprises 0.1～5.0 quality % extreme pressure additive and/or anti-wear agent as component (B) (d).
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| JP2006104231A (en) * | 2004-09-30 | 2006-04-20 | Hitachi Ltd | Hydraulic fluid for shock absorber and hydraulic shock absorber equipped with the same |
| JP4684951B2 (en) * | 2006-06-16 | 2011-05-18 | トヨタ紡織株式会社 | Lubricating oil for processing metal material and method for processing metal material using the same |
| JP5095177B2 (en) * | 2006-11-06 | 2012-12-12 | 出光興産株式会社 | Biodegradable lubricating oil composition |
| JP5140070B2 (en) * | 2007-03-29 | 2013-02-06 | 出光興産株式会社 | Gear oil composition |
| JP2010052242A (en) * | 2008-08-28 | 2010-03-11 | Nippon Koyu Ltd | Ink backflow inhibitor composition for ballpoint pen |
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- 2005-01-28 CN CNB2005800031418A patent/CN100554388C/en not_active Expired - Fee Related
- 2005-01-28 WO PCT/JP2005/001216 patent/WO2005073353A1/en not_active Application Discontinuation
- 2005-01-28 EP EP05709443.5A patent/EP1707617B1/en not_active Not-in-force
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| CN1346872A (en) | 2000-09-22 | 2002-05-01 | 日石三菱株式会社 | Lubricating oil composition for papermaker |
Also Published As
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|---|---|
| EP1707617B1 (en) | 2017-03-15 |
| CN1914303A (en) | 2007-02-14 |
| WO2005073353A1 (en) | 2005-08-11 |
| EP1707617A1 (en) | 2006-10-04 |
| US20090176670A1 (en) | 2009-07-09 |
| JP4827381B2 (en) | 2011-11-30 |
| EP1707617A8 (en) | 2006-12-06 |
| US20140155307A1 (en) | 2014-06-05 |
| EP1707617A4 (en) | 2010-05-26 |
| JP2005213451A (en) | 2005-08-11 |
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