EP2880138B1 - Schmierstoffzusammensetzung für verbrennungsmotoren - Google Patents

Schmierstoffzusammensetzung für verbrennungsmotoren Download PDF

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Publication number
EP2880138B1
EP2880138B1 EP13742227.5A EP13742227A EP2880138B1 EP 2880138 B1 EP2880138 B1 EP 2880138B1 EP 13742227 A EP13742227 A EP 13742227A EP 2880138 B1 EP2880138 B1 EP 2880138B1
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Prior art keywords
mass
internal combustion
combustion engines
lubricating oil
group
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English (en)
French (fr)
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EP2880138A1 (de
Inventor
Kiyoshi Hanyuda
Kouichi Kubo
Kouji Murakami
Izumi Kobayashi
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/24—Emulsion properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/66—Hydrolytic stability
    • 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 an internal combustion engine lubricating oil composition designed for fuel economy and incorporating a monoglyceride with hydroxyl value of not less than 150 mgKOH/g (a glycerine fatty acid ester with the fatty acid ester bonded to one of the three hydroxyl groups of glycerine) as a friction modifier so as to realize fuel economy in internal combustion engines (hereinafter these may also be termed 'engines').
  • This provides a high-performance lubricating oil composition for internal combustion engines that causes condensed water from water vapour produced as a result of combustion of the fuel to be dispersed in the oil, so preventing corrosion or rusting of the engine.
  • renewable biofuels have increasingly been used in automotive gasoline and light oils in recent years from the standpoint of reducing carbon dioxide emissions to counter global warming.
  • biofuels specifically bioethanol or bioETBE (ethyl tert-butyl ether)
  • H/C hydrogen/carbon
  • the H/C (hydrogen/carbon) ratio of commercial premium gasoline and regular gasoline is respectively 1.763 and 1.875 calculated from the carbon concentrations shown in Table 2.4-1 of Oil Industry Promotion Center: 2005 Automotive Fuel Research Findings Report PEC-2005JC-16, 2-14. If 3% of such premium gasoline and regular gasoline were to be replaced with (bio)ethanol or similar, their H/C ratios would be respectively about 1.80 and 1.91.
  • ashless friction modifiers i.e. leaving no ash residue when combusted as they contain no elements such as metals or phosphorus
  • DPF diesel particulate filters
  • ashless friction modifiers added to engine lubricating oils contain neither metals nor elements such as phosphorus, they are known to have little effect on exhaust gas catalysts or exhaust gas post-treatment systems, and to be readily usable in engine lubricating oils.
  • they On the downside, they have a surfactant effect and, in some cases, this may intensify anti-emulsifying properties or water separability in the engine oil and cause water to deposit out on surfaces more readily. It has been feared that the deposited water would induce rusting or corrosion by coming into contact with the individual parts in the engine.
  • monoglyceride ashless friction modifiers are known to be highly effective for reducing friction and to be suitable for engine lubricating oil compositions, but if condensed water from water vapour associated with fuel combustion in the engine gets into the engine oil as described previously, it has been feared that this would increase anti-emulsifying properties or water separability.
  • WO2011/070141 discloses lubricating oil compositions that contain glycerol monoisostearate and fatty amines or alkanolamines. These lubricating oil compositions provide low friction coefficients and sea water stability.
  • Lubricating oil compositions for internal combustion engines that not only provide outstanding wear resistance and fuel economy (low-friction characteristics) but also cause condensed water from water vapour produced by fuel combustion to be dispersed through the oil to prevent corrosion or rusting of the engine have been sought for this reason.
  • the present inventors established that when condensed water from water vapour associated with fuel combustion in the engine becomes mixed in with the engine oil, monoglycerides with the said specific structure increase anti-emulsifying properties or water separability in connection with the aforesaid specific engine lubricating oils and make separation of the water onto surfaces more prone to occur.
  • the present inventors further undertook wide-ranging studies and research on ways of improving emulsion stability in the aforesaid specific engine lubricating oils. They discovered that upon adding an ethylene oxide adduct with a specific structure together with the aforesaid monoglyceride ashless friction modifiers with a specific structure to a certain specific quantity of lubricating oil composition, and also setting the quantities and/or quantitative ratio of the aforesaid monoglyceride with a specific structure and said ethylene oxide adduct to within specific ranges, the compositions exhibited improved emulsion stability in addition to outstanding wear resistance and fuel economy. They thus perfected the present invention.
  • the aforesaid monoglyceride is present at level in the range of from 0.3 to 2.0 mass% based on the total weight of the lubricating oil composition.
  • the ethylene oxide adduct (C) is a diethanolamine.
  • the ethylene oxide adduct (C) is oleyl diethanolamine.
  • the monoglyceride (B) is glycerine monooleate.
  • the lubricating oil composition has a kinematic viscosity at 100°C in the range of from 5.6 to 15 mm 2 /s.
  • the use of the lubricating oil composition for internal combustion engines using fuels with H/C ratios of from 1.93 to 4, internal combustion engines of vehicles fitted with idle-stop equipment, or internal combustion engines using fuels incorporating biofuels or biodiesel is disclosed.
  • lubricating oil compositions for internal combustion engines are obtained that, as well as providing outstanding wear resistance and fuel economy, also have the capacity to disperse condensed water due to water vapour produced as a result of combustion of the fuel as a stable emulsion through the oil and so prevent corrosion or rusting of the engine.
  • the mass ratio of the aforesaid monoglyceride (B) and aforesaid ethylene oxide adduct (C) is preferably in the range of from 0.5 to 2.7, more preferably in the range of from 1.0 to 2.5 and even more preferably in the range of from 1.2 to 2.25.
  • this embodiment is a lubricating oil for internal combustion engines characterised in that it contains:
  • the feature of this embodiment is thus the quantity and/or quantitative ratio of the aforesaid monoglyceride (B) and aforesaid ethylene oxide adduct (C) in lubricating oil compositions for internal combustion engines.
  • the base oils used for these lubricating oil compositions can be mineral oils and hydrocarbon synthetic oils known as highly refined base oils.
  • base oils belonging to Group 2, Group 3 or Group 4 in the base oil categories defined by the API may be used individually or as mixtures.
  • the base oils used herein should have kinematic viscosity at 100°C of from 3 to 12 mm 2 /s, preferably from 3 to 10 mm 2 /s and more preferably from 3 to 8 mm 2 /s.
  • Their viscosity index should be in the range of from 100 to 180, preferably in the range of from 100 to 160 and more preferably in the range of from 100 to 150.
  • Their sulphur content should not exceed 300 ppm, preferably not exceed 200 ppm, more preferably not exceed 100 ppm, and most preferably not exceed 50 ppm.
  • their 15°C density should be in the range of from 0.8 to 0.9 g/cm 3 , preferably in the range of from 0.8 to 0.865 g/cm 3 and more preferably in the range of from 0.81 to 0.83 g/cm 3 .
  • Their aromatic content (aromatic content in the present invention by n-d-M: measured in accordance with ASTM D3238) should be less than 3%, preferably less than 2% and more preferably less than 0.1%.
  • Group 2 base oils include, for example, paraffin-series mineral oils obtained by applying appropriate combinations of refining steps such as hydrorefining and dewaxing to lubricating oil fractions obtained by normal-pressure distillation of crude oil.
  • Group 2 base oils refined by the hydrorefining processes of Gulf Oil and so on have total sulphur contents of less than 10 ppm and aromatic contents of not more than 5% and are ideal for this embodiment.
  • the viscosity index is preferably in the range from 100 to 120 (viscosity index in the present invention is determined in accordance with ASTM D2270 and JIS K2283).
  • Kinematic viscosity at 100°C should preferably be in the range of from 3 to 12 mm 2 /s and more preferably in the range of from 3 to 9 mm 2 /s.
  • Their total sulphur content should be less than 300 ppm, preferably less than 200 ppm and still more preferably less than 10 ppm.
  • Their total nitrogen content should also be less than 10 ppm and preferably less than 1 ppm.
  • aniline points aniline point in the present invention is determined by ASTM D611 and JIS K2256) at 80 to 150°C and preferably 100 to 135°C should be used.
  • paraffin-series mineral oils produced by high-level hydrorefining of lubricating oil fractions obtained by normal-pressure distillation of crude oil base oils refined by the ISODEWAX process, which converts to isoparaffin and dewaxes the waxes formed in dewaxing processes, and base oils refined by the Mobil Wax Isomerization process are also ideal.
  • base oils correspond to API Group 2 and Group 3. There are no particular restrictions on their viscosity but their viscosity index should be in the range from 100 to 150 and preferably in the range of from 100 to 145.
  • Their kinematic viscosity at 100°C should preferably be in the range of from 3 to 12 mm 2 /s and more preferably in the range of from 3 to 9 mm 2 /s. Moreover, their sulphur content should be in the range of from 0 to 100 ppm and preferably less than 10 ppm. Their total nitrogen content should also be less than 10 ppm and preferably less than 1 ppm. Furthermore, those with aniline points at 80 to 150°C and preferably 110 to 135°C should be used.
  • GTL (gas to liquid) oils synthesized by the Fischer-Tropsch process are even better as base oils for this invention than mineral base oils refined from crude oil because they have very much lower sulphur contents or aromatic contents and very much higher paraffin component ratios and so provide outstanding oxidation stability and very low evaporation losses.
  • viscosity properties of GTL base oils but their usual viscosity index should be in the range of from 100 to 180 and more preferably in the range of from 100 to 150.
  • Their kinematic viscosity at 100°C should be in the range of from 3 to 12 mm 2 /s and more preferably in the range of from 3 to 9 mm 2 /s.
  • hydrocarbon synthetic oils examples include polyolefins, alkylbenzenes and alkylnaphthalenes, or mixtures of these.
  • the above polyolefins include polymers of all types of olefin or hydrides of these. Any desired olefin may be used, but examples include ethylene, propylene, butene and ⁇ -olefins with five or more carbons. To prepare polyolefins, one type of the above olefins may be used on its own or two or more types may be combined.
  • polyalphaolefins are ideal. These are Group 4 base oils. Polyalphaolefins may also be mixtures of two or more synthetic oils.
  • the density of these synthetic base oils at 15°C should be in the range of from 0.8000 to 0.8600g/cm 3 , preferably in the range of from 0.8100 to 0.8550g/cm 3 , and more preferably in the range of from 0.8250 to 0.8500g/cm 3 .
  • the hydrocarbon group moiety of the fatty acid in the monoglycerides used as ashless friction modifiers has from 8 to 22 carbons.
  • C 8 -C 22 hydrocarbon groups include alkyl groups such as the octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group or docosyl group (these alkyl groups may be straight-chain or branched), and alkenyl groups such as the octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl
  • the hydroxyl value is in the range of from 150 to 300 mgKOH/g and more preferably in the range of from 200 to 300 mgKOH/g based on the technique for determining hydroxyl values set out in JIS K0070.
  • Monoglyceride contents ranging from 0.3 to 2.0 mass%, preferably from 0.4 to 1.7 mass% and more preferably from 0.5 to 1.5 mass% based on the total mass of the composition may be cited.
  • Ethylene oxide adducts used in the present invention are at least one type of ethylene oxide adduct selected from the group consisting monoalkyl and monoalkenyl amine ethylene oxide adducts shown by Formula (1) below. wherein R is a C 14 -C 22 hydrocarbon group, n and m are independently either 1 or 2.
  • R is a hydrocarbon group with from 14 to 22 carbon atoms. Carbon numbers of from 16 to 20 are preferred for these C 14 -C 22 hydrocarbon groups and specific examples include alkyl groups such as the tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group or icosyl group (these alkyl groups may be straight-chain or branched), and alkenyl groups such as the tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group or icosenyl group (these alkenyl groups may be straight-chain or branched, and the double bond position may optionally be of the cis or trans form).
  • alkyl groups such as the tetradec
  • n and m each be either 1 or 2.
  • ethylene oxide adduct contents ranging from 0.4 to 1.5 mass%, preferably from 0.4 to 1.4 mass%, more preferably from 0.4 to 1.2 mass% based on the total mass of the composition may be cited.
  • additives besides the ingredients stated above may be used if necessary and as appropriate in order further to enhance performance.
  • examples of these include antioxidants, metal deactivators, anti-wear agents, antifoaming agents, viscosity index improvers, pour point reducers, cleansing dispersants, rust inhibitors and so on, and any other known additives for lubricating oils.
  • antioxidants used in lubricating oils are desirable in practical terms as antioxidants to be used in this embodiment, and examples include amine-series antioxidants, sulphur-series antioxidants, phenol-series antioxidants and phosphorus-series antioxidants. These antioxidants may be used individually or as combinations of several types in the range from 0.01 to 5 parts by weight relative to 100 parts by weight of base oil.
  • amine antioxidants examples include dialkyl-diphenylamines such as p , p '-dioctyl-diphenylamine (Seiko Chemical Co. Ltd: Nonflex OD-3), p,p' -di- ⁇ -methylbenzyl-diphenylamine or N- p -butylphenyl-N- p'- octylphenylamine; monoalkyldiphenylamines such as mono- t -butyldiphenylamine or monooctyldiphenylamine; bis(dialkylphenyl)amines such as di(2,4-diethylphenyl)amine or di(2-ethyl-4-nonylphenyl)amine; alkylphenyl-1-naphthylamines such as octylphenyl-1-naphthylamine or N-t-dodecylphenyl-1-naph
  • sulphur-series antioxidants include dialkylsulfides such as didodecylsulfide or dioctadecylsulfide; thiodipropionate esters such as idodecylthiodipropionate, dioctadecylthiodipropionate, dimyristilthiodipropionate or dodecyloctadecylthiodipropionate; and 2-mercaptobenzoimidazole, and so on.
  • dialkylsulfides such as didodecylsulfide or dioctadecylsulfide
  • thiodipropionate esters such as idodecylthiodipropionate, dioctadecylthiodipropionate, dimyristilthiodipropionate or dodecyloctadecylthiodipropionate
  • phenol antioxidants include 2,6-di- t- butyl-4-alkylphenols such as 2- t -butylphenol, 2- t -butyl-4-methylphenol, 2- t -butyl-5-methylphenol, 2,4-di- t -butylphenol, 2,4-dimethyl-6- t -butylphenol, 2- t- butyl-4-methoxyphenol, 3- t -butyl-4-methoxyphenol, 2,5-di t -butylhydroquinone (Kawaguchi Chemical Industry Co.
  • alkyl-3-(3,5-di- t -butyl-4-hydroxyphenyl)propionates such as 3,5-di- t -butyl-4-hydroxybenzylmercapto-octylacetate, n-octadecyl-3-(3,5-di- t -butyl-4-hydroxyphenyl)propionate (Yoshitomi Yakuhin Corporation: Yoshinox SS), n-dodecyl-3-(3,5-di- t -butyl-4-hydroxyphenyl)propionate, 2'-ethylhexyl-3-(3,5-di- t- butyl-4-hydroxyphenyl)propionate or benzenepropanate 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 side chain alkylester (Ciba Specialty Chemical Co.: Irganox L135); and 2,2'
  • polyphenols such as tetrakis[methylene -3-(3,5-di- t -butyl-4-hydroxyphenyl)propionate]methane (Chiba Specialty Chemical Co.: Irganox L101), 1,1,3-tris(2-methyl-4-hydroxy-5- t -butylphenyl)butane (Yoshitomiyakuhin Corporation: Yoshinox 930), 1,3,5-trimethyl-2,4,6-tris(3,5-di- t -butyl-4-hydroxybenzyl)benzene (Shell Japan: Ionox 330), bis-[3,3'-bis-(4'-hydroxy-3'- t- butylphenyl)butyric acid]glycol ester, 2-(3',5'-di- t- butyl-4-hydroxyphenyl)methyl-4-(2",4"-di- t -butyl-3"-hydroxyphenyl)
  • phosphorus-series antioxidants examples include triallyl phosphites such as triphenyl phosphite or tricresyl phosphite; trialkyl phosphites such as trioctadecyl phosphite or tridecyl phosphite; and tridodecyltrithio phosphite.
  • the amounts of sulphur- and phosphorus-series antioxidants incorporated need to be restricted in consideration of their effects on the exhaust gas control systems of internal combustion engines. It is preferable for the content of phosphorus in the lubricating oil overall not to exceed 0.10 mass% and of sulphur not to exceed 0.6 mass%, and more preferable for the phosphorus content not to exceed 0.08 mass% and the sulphur content not to exceed 0.5 mass%.
  • indazole and indazole derivatives such as toluindazoles such as 4-alkyl-indazole or 5-alkyl-indazole; and benzothiazole and benzothiazole derivatives such as 2-(alkyldithio)benzothiazoles such as 2-mercaptobenzothiazole derivative (Chiyoda Kagaku Co.
  • benzoxazole derivatives such as 2-(alkyldithio)-benzoxazoles such as 2-(octyldithio)benzoxazole, 2-(decyldithio)benzoxazole and 2-(dodecyldithio)benzoxazole; and 2-(alkyldithio)toluoxazoles such as 2-(octyldithio)toluoxazole, 2-(decyldithio)toluoxazole or 2-(dodecyldithio)toluoxazole; thiadiazole derivatives such as 2,5-bis(alkyldithio)-1,3,4-thiadiazoles such as 2,5-bis(heptyldithio)-1,3,4-thiadiazole, 2,5-bis(nonyldithio)-1,3,4-thiadiazole, 2,5-bis(d
  • metal deactivators may be used individually or as mixtures of multiple types in the range of from 0.01 to 0.5 parts by weight relative to 100 parts by weight of base oil.
  • Phosphorus compounds may also be added to lubricating oil compositions in this embodiment in order to impart wear resistance.
  • Zinc dithiophosphates and zinc phosphate may be cited as phosphorus compounds suitable for this embodiment. These phosphorus compounds may be used individually or as combinations of multiple types in the range from 0.01 to 2 mass% relative to 100 parts by mass of base oil, with a phosphorus content based on the lubricating oil overall preferably in the range from 0.05 to 0.10 mass% and, more preferably from 0.05 to 0.08 mass%.
  • Phosphorus content exceeding 0.10 mass% of the lubricating oil overall adversely affect catalysts and the like in exhaust gas control systems, but wear resistance as an engine oil cannot be maintained at phosphorus content below 0.05%.
  • Zinc dialkyl dithiophosphates zinc diallyl dithiophosphates, zinc allylalkyl dithiophosphates and so on may be cited as the above zinc dithiophosphates.
  • alkyl groups include primary or secondary alkyl groups having from 3 to 12 carbon atoms, and allyl groups may be the phenyl group or an alkylallyl group with the phenyl substituted by an alkyl group having from 1 to 18 carbon atoms.
  • Zinc dialkyl dithiophosphates with secondary alkyl groups are to be preferred among these zinc dithiophosphates, and these have from 3 to 12 carbon atoms, preferably from 3 to 8 carbon atoms and more preferably from 3 to 6 carbon atoms.
  • Viscosity index improvers may be added to lubricating oil compositions in this invention in order to improve their low-temperature pouring properties or viscosity characteristics.
  • Viscosity index improvers include, for example, polymethacrylates or olefin polymers such as ethylenepropylene copolymers, styrene-diene copolymers, polyisobutylene, polystyrene, and the like. The amount added may be in the range from 0.05 to 20 parts by weight relative to 100 parts by weight of base oil.
  • Polymers of the polymethacrylate series may be cited as examples of pour point reducers.
  • the amount added may be in the range of from 0.01 to 5 parts by weight relative to 100 parts by weight of base oil.
  • Antifoaming agents may also be added to lubricating oil compositions of the present invention in order to impart antifoaming properties.
  • antifoaming agents suitable for use herein include organosilicates such as dimethyl polysiloxane, diethyl silicate and fluorosilicone, and non-silicone antifoaming agents such as polyalkylacrylates.
  • the amount added may be in the range of from 0.0001 to 0.1 parts by weight relative to 100 parts by weight of base oil.
  • the viscosity index should be not less than 100, preferably not less than 110 and more preferably not less than 120.
  • the upper limit of the viscosity index should be, for example, not over 300.
  • Kinematic viscosity of the lubricating oil compositions at 100°C should be in the range of from 5.6 to 15 mm 2 /s, preferably in the range of from 5.6 to 12.5 mm 2 /s and more preferably in the range of from 5.6 to 9.3 mm 2 /s.
  • Lubricating oil compositions of the present invention are used as lubricating oil compositions for internal combustion engines.
  • Lubricating oil compositions of the present invention can be used in internal combustion engines burning fuels with H/C ratios of from 1.93 to 4 (preferably from 2.67 to 4).
  • Lubricating oil compositions of the present invention may also be used in the internal combustion engines of vehicles fitted with idle-stop apparatus.
  • lubricating oil compositions of the present invention are ideal for use in internal combustion engines using biofuels (e.g. bioethanol, ethyl tert-butylether, or cellulose-series ethanol) or biodiesel fuels (e.g. fuels incorporating hydroprocessed oils cracked and refined applying the hydroprocessing techniques for petroleum refining to fatty acid methylesters and raw oils and fats from plants or tallow, or synthetic oils prepared by synthesizing liquid hydrocarbons using catalyst reactions from carbon monoxide and hydrogen generated by applying the FT (Fischer-Tropsch) process to biomass thermal decomposition gas).
  • biofuels e.g. bioethanol, ethyl tert-butylether, or cellulose-series ethanol
  • biodiesel fuels e.g. fuels incorporating hydroprocessed oils cracked and refined applying the hydroprocessing techniques for petroleum refining to fatty acid methylesters and raw oils and fats from plants or tallow, or synthetic oils prepared by synth
  • the lubricating oil compositions of the present invention are ideal for use in internal combustion engines using fuels incorporating more than 3 vol%, preferably 5 vol% or more and more preferably 10 vol% or over of bioethanol in the fuel.
  • the lubricating oil compositions in this embodiment are ideal for use in internal combustion engines using fuels incorporating more than 5 mass%, preferably 7 mass% or over and more preferably 10 mass% or more of biodiesel in the fuel.
  • Base oils 1 to 4 used in the Examples and Comparative Examples had the properties set out in Table 1.
  • the values given herein for kinematic viscosity at 40°C and 100°C had been determined in accordance with JIS K 2283 "Crude Oil and Petroleum Products - Kinematic Viscosity Test Method and Determination of Viscosity Index".
  • the values cited for viscosity index had also been obtained in accordance with JIS K 2283 "Crude Oil and Petroleum Products - Kinematic Viscosity Test Method and Determination of Viscosity Index”.
  • Pour point (PP) was determined in accordance with JIS K 2269, flash point with JIS K 2265-4 (COC: Cleveland Open Cup technique), and sulphur content with JIS K 2541 (radioexcitation technique).
  • ASTM D3238 was used as regards %C A , %C N and %C P .
  • Lubricating oil compositions were prepared in Examples 1 to 8 and Comparative Examples 1 to 13 using the above constituents to have the formulations shown in Tables 2 and 3.
  • Shell four-ball testing was carried out in accordance with ASTM D4172 under conditions of 1800 rpm, oil temperature 50°C and load 40 kgf for periods of 30 minutes. After testing, the test balls were removed, the wear scars were measured and the diameter shown as the result.
  • the friction coefficient was determined and evaluated using the Cameron-Plint TE77 tester employed in ASTM-G-133 (American Society for Testing and Materials) in order to observe the friction characteristics.
  • the upper test piece was an SK-3 steel cylinder 6 mm in diameter and 16 mm long, and the lower test piece an SK-3 steel plate. Tests were conducted for ten minutes at a test temperature of 80°C, load 300 N, amplitude 15 mm and frequency 10 Hz, and the mean friction coefficient measured in the final minute when it had stabilized was recorded. The smaller the friction coefficient, the better the friction reduction properties were.
  • Evaluation tests were carried out taking simulated E85 fuel and distilled water and using a commercial highspeed blender, for example, a Waring Blender 7011H (currently 7011S) with a stainless steel container from MFI K.K. in this series of tests.
  • the test procedures were as follows.
  • test oil to be evaluated was measured out into a 200 mL measuring cylinder and poured into the 7011H blender.
  • 15mL of simulated E85 fuel was measured out into a 100 mL measuring cylinder and poured into the 7011H blender, and finally 15 mL of distilled water was measured out into a 100 mL measuring cylinder and poured into the 7011H.
  • the cover was put on the container immediately afterwards and the materials were blended at 15000 rpm for 60 seconds.
  • the simulated E85 fuel used was prepared by measuring out 150 mL of commercial JIS1 automotive gasoline and 850 mL of special-grade ethanol from Wako Pure Chemical Industries into a measuring cylinder and mixing them at ambient temperature.
  • the tests were completed in times shorter than the designated time and the samples were held in a cool, dark place indoors in containers that could be tightly sealed so as to prevent volatilization of light compounds during use.
  • Wear resistance is unsatisfactory with materials giving results of 0.50 mm or over in Shell four-ball wear tests.
  • wear scar diameter was 0.39 mm. Where wear scarring was larger than this, functioning of the anti-wear agent would have been impaired so that wear had increased and worsened. It therefore was unsatisfactory.
  • Comparative Example 8 and Comparative Example 12 it was difficult to overcome water separability associated with glycerine monooleate at concentrations of the oleylamine ethylene oxide adduct of less than 0.4 mass%.
  • amine ethylene oxide adduct is within a defined range of concentration, it is possible to maintain good wear resistance and friction reduction while overcoming water separability and maintaining emulsion-retention even in base oils synthesized by the Fischer-Tropsch process.
  • Base oil 1 Base oil 2
  • Base oil 3 Base oil 4
  • Base oil group (API class) Group 3 Group 3
  • Group 3 Kinematic 100°C viscosity 40°C mm 2 /sec 4.2 7.6 3.1 5.0 mm 2 /sec 19.4 45.6 12.4 23.7
  • Viscosity index 123 133 104 146 Pour point °C -15.0 -12.5 -32.5 -20.0 Flash point °C 214 240 194 232 Sulphur content mass% 0.0008 0.0010 ⁇ 0.01 ⁇ 0.01 ASTM D3238-95 %C A 0 0 0 0 %C N 22.4 20.4 31.1 7 %C P 77.6 79.6 69.9
  • Table 3 Comp Ex 1 Comp Ex 2 Comp Ex 3 Comp Ex 4
  • Comp Ex 5 Comp Ex 6
  • SAE viscosity grade 0W-20 0W-20 0W-20 5W-30 5W-30 5W-30 5W-30
  • Base oil 1 mass% 74.41 73

Claims (7)

  1. Schmierölzusammensetzung für Verbrennungsmotoren, dadurch gekennzeichnet, dass sie enthält:
    (A) wenigstens ein Grundöl ausgewählt aus der Gruppe bestehend aus Grundölen der Gruppen 2, 3 und 4 der Grundölkategorien des American Petroleum Institute mit einer kinematischen Viskosität von 3 bis 12 mm2/s bei 100 °C und einem Viskositätsindex von 100 bis 180,
    (B) ein Monoglycerid mit einer Kohlenwasserstoffgruppe mit 8 bis 22 Kohlenstoffatomen, das ein Glycerin-Fettsäureester ist, bei dem der Fettsäureester an eine der drei Hydroxygruppen des Glycerins gebunden ist, wobei das Monoglycerid einen Hydroxywert von 150 bis 300 mg KOH/g aufweist und wobei das Monoglycerid in einer Menge von 0,3 bis 2,0 Masse-% bezogen auf die Gesamtmasse der Zusammensetzung vorhanden ist, und
    (C) wenigstens ein Ethylenoxid-Addukt ausgewählt aus der Gruppe bestehend aus Monoalkyl- und Monoalkenylamin-Ethylenoxid-Addukten dargestellt durch die nachstehende Formel (1):
    Figure imgb0013
    wobei R eine C14-C22-Kohlenwasserstoffgruppe ist, n und m unabhängig 1 oder 2 sind,
    wobei das Ethylenoxid-Addukt in einer Menge von 0,4 bis 1,5 Masse-% bezogen auf die Gesamtmasse der Zusammensetzung vorhanden ist.
  2. Schmierölzusammensetzung für Verbrennungsmotoren gemäß Anspruch 1, dadurch gekennzeichnet, dass das Masseverhältnis des genannten Monoglycerids (B) und des genannten Ethylenoxid-Addukts (C) (Masse-% Monoglycerid B / Masse% Ethylenoxid-Addukt C) in dem Bereich von 0,5 bis 2,7 liegt.
  3. Schmierölzusammensetzung für Verbrennungsmotoren gemäß Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass das Ethylenoxid-Addukt (C) ein Diethanolamin ist.
  4. Schmierölzusammensetzung für Verbrennungsmotoren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Ethylenoxid-Addukt (C) Oleyldiethanolamin ist.
  5. Schmierölzusammensetzung für Verbrennungsmotoren gemäß einem der Ansprüche 1 und 4, dadurch gekennzeichnet, dass das Monogylcerid (B) Glycerinmonooleat ist.
  6. Schmierölzusammensetzung für Verbrennungsmotoren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass ihre kinematische Viskosität bei 100 °C in dem Bereich von 5,6 bis 15 mm2/s liegt.
  7. Verwendung einer Schmierölzusammensetzung für Verbrennungsmotoren gemäß einem der Ansprüche 1 bis 6 in Verbrennungsmotoren, die Kraftstoffe mit H/C-Verhältnissen von 1,93 bis 4 verwenden, in Verbrennungsmotoren von Fahrzeugen, die mit Leerlauf-Stopp-Vorrichtungen ausgestattet sind, oder Verbrennungsmotoren, die Kraftstoffe verwenden, die Biokraftstoffe oder Biodiesel enthalten.
EP13742227.5A 2012-07-30 2013-07-29 Schmierstoffzusammensetzung für verbrennungsmotoren Revoked EP2880138B1 (de)

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EP3063257B1 (de) * 2013-10-29 2019-08-21 Croda, Inc. Schmierstoffzusammensetzung enthaltend reibwertverminderer auf basis eines derivats einer hydroxycarbonsäure
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