Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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)
• bioETBE ethyl tert-butyl ether
• H/C hydrogen
• Emulsion retention is a test with evaluation procedures laid down in ASTM D7563. This is a test to check and evaluate the stability of engine oil in respect of whether any (condensed) water or E85 fuel and the like that has become mixed with it does not deposit out on surfaces but remains incorporated in emulsion form without separating out, so that the individual engine components do not rust or corrode.
• ashless friction modifiers such as fatty acid esters have come to be added to engine lubricating oils so as to reduce friction between metals in the engine and improve fuel economy
• 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
• 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 invention was devised in the light of the above situation and seeks to provide a lubricating oil composition for internal combustion engines that, as well as providing outstanding wear resistance and fuel economy, causes condensed water etc. from water vapour produced as a result of fuel combustion to be dispersed in the oil, so preventing corrosion or rusting of the engine .
• 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
• compositions exhibited improved emulsion stability in addition to outstanding wear resistance and fuel economy. They thus perfected the present invention.
• (C) at least one ethylene oxide adduct selected from the group consisting of monoalkyl and monoalkenyl amine ethylene oxide adducts having Formula (1) below, wherein the ethylene oxide adduct is present at a level of from
• R is a C14-C22 hydrocarbon group
• n and m are independently either 1 or 2.
• the mass ratio of the aforesaid monoglyceride (B) and aforesaid ethylene oxide adduct (C) is in the range of from 0.5 to 2.7.
• the lubricating oil composition contains:
• (C) at least one ethylene oxide adduct selected from the group consisting of monoalkyl and monoalkenyl amine ethylene oxide adducts shown by Formula (1) below,
• R is a C14-C22 hydrocarbon group
• n and m are independently either 1 or 2 and the mass ratio of the aforesaid monoglyceride (B) and aforesaid ethylene oxide adduct (C) (mass% of monoglyceride B / mass% of ethylene oxide adduct C) is in the range of from 0.5 to 2.7.
• 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, and the aforesaid ethylene oxide adduct is present at a level in the range of from 0.4 to 1.5 mass% relative to 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.
• lubricating oil composition is employed in 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.
• 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 .
• (C) at least one ethylene oxide adduct selected from the group consisting of monoalkyl and monoalkenyl amine ethylene oxide adducts shown by Formula (1) below, wherein the ethylene oxide adduct is present at a level of from 0.4 to 1.5 mass% based on the total mass of the composition .
• R is a C14-C22 hydrocarbon group
• n and m are independently either 1 or 2.
• 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 :
• (C) at least one ethylene oxide adduct selected from the group consisting of monoalkyl and monoalkenyl amine ethylene oxide adducts shown by Formula (1) below, Formula ( 1 ) :
• R is a C14-C22 hydrocarbon group
• n and m are independently either 1 or 2 and the mass ratio of the aforesaid monoglyceride (B) and aforesaid ethylene oxide adduct (C) (mass% of monoglyceride B / mass% of ethylene oxide adduct C) is in the range of from 0.5 to 2.7.
• the mass ratio of the aforesaid monoglyceride (B) and aforesaid ethylene oxide adduct (C) is preferably in the range of from 1.0 to 2.5 and more preferably in the range of from 1.2 to 2.25. It is ideal for these
• lubricating oil compositions for internal combustion engines to contain the aforesaid monoglyceride at a level of from 0.3 to 2.0 mass% based on the total mass of the composition, and the aforesaid ethylene oxide adduct at a level of from 0.4 to 1.5 mass% based on the total quantity of the composition.
• the feature of this embodiment is thus the quantity and/or quantitative ratio of the aforesaid monoglyceride
• compositions can be mineral oils and hydrocarbon
• 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.
• 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 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 .
• Group 2 base oils include, for example, paraffin-series mineral oils obtained by applying
• 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
• D445 and JIS K2283 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 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
• base oils refined by the Mobil Wax are examples of 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
• base oils refined by the Mobil Wax base oils refined by the Mobil Wax
• 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.
• SHELL XHVI (registered trade mark) may be cited as an example of such GTL base oil products.
• 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 CC-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.
• polyolefins known as
• polyalphaolefins are ideal. These are Group 4 base oils. Polyalphaolefins may also be mixtures of two or more synthetic oils.
• viscosity of these synthetic oils should be in the range from 3 to 12 mm 2 /s, preferably in the range from 3 to 10 mm 2 /s and more preferably in the range from 3 to 8 mm 2 /s.
• the viscosity index of these synthetic base oils should be in the range of from 100 to 170, preferably in the range of from 110 to 170 and more preferably in the range of from 110 to 155.
• 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.
• C8-C22 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
• 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
• composition 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.
• R is a C14-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 C14-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,
• n and m each to 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
• 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 ⁇ , ⁇ ' -dioctyl-diphenylamine
• monoalkyldiphenylamines such as mono-t-butyldiphenylamine or monooctyldiphenylamine ;
• dialkylphenyl ) amines such as di(2,4- diethylphenyl ) amine or di ( 2-ethyl-4-nonylphenyl ) amine ; alkylphenyl-l-naphthylamines such as octylphenyl-1- naphthylamine or N-t-dodecylphenyl-l-naphthylamine ;
• allyl-naphthylamines such as 1-naphthylamine, phenyl-1- naphthylamine, phenyl-2-naphthylamine, N-hexylphenyl-2- naphthylamine or N-octylphenyl-2-naphthylamine ;
• phenylenediamines such as N, N ' -diisopropyl-p- phenylenediamine or N, ' -diphenyl-p-phenylenediamine ; and phenothiazines such as phenothiazine (Hodogaya Chemical Co. Ltd: phenothiazine) or 3 , 7-dioctylphenothiazine, and so on .
• sulphur-series antioxidants examples include dialkylsulfides such as didodecylsulfide or
• thiodipropionate esters such as idodecylthiodipropionate, dioctadecylthiodipropionate, dimyristilthiodipropionate or dodecyloctadecylthiodipropionate ;
• phenol antioxidants examples include 2,6-di-t- butyl-4-alkylphenols such as 2-t-butylphenol ,
• 6-di-t-butyl-4-alkoxyphenols such as 2 , 6-di-t-butyl-4- methoxyphenol or 2 , 6-di-t-butyl-4-ethoxyphenol .
• 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
• phenolaldehyde condensates such as condensates of p-t- butylphenol with formaldehyde, or condensates of p-t- butylphenol with acetaldehyde .
• phosphorus-series antioxidants examples include triallyl phosphites such as triphenyl phosphite or tricresyl phosphite; trialkyl phosphites such as
• trioctadecyl phosphite or tridecyl 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%.
• metal deactivators examples include benzotriazole and benzotriazole derivatives such as 4- alkyl-benzotriazoles such as 4-methyl-benzotriazole or 4- ethyl-benzotriazole ;
• 5-alkyl-benzotriazoles such as 5-methyl-benzotriazole or 5-ethyl-benzotriazole ;
• 1-alkyl-benzotriazoles such as l-dioctylaminomethyl-2 , 3- benzotriazole ; or
• 1-alkyl-tolutriazoles such as l-dioctylaminomethyl-2 , 3- tolutriazole ; and benzoimidazole and benzoimidazole derivatives such as 2- ( alkyldithio ) -benzoimidazoles such as 2- (octyldithio) -benzoimidazole, 2- (decyldithio ) - benzoimidazole or 2- (dodecyldithio ) -benzoimidazole ; and 2- ( alkyldithio ) -toluimidazoles such as 2- ( octyldithio ) - toluimidazole, 2- (decyldithio ) -toluimidazole or 2- (dodecyldithio ) -toluimidazole .
• toluindazoles such as 4-alkyl- indazole or 5-alkyl-indazole
• benzothiazole and benzothiazole derivatives such as 2- ( alkyldithio ) benzothiazoles such as 2- mercaptobenzothiazole derivative (Chiyoda Kagaku Co. Ltd:
• 2- (N, N-dialkyldithiocarbamyl ) -toludithiazoles such as 2- (N, N-diethyldithiocarbamyl ) toluthiazole, 2-(N,N- dibutyldithiocarbamyl ) toluthiazole or 2-(N,N- dihexyldithiocarbamyl ) toluthiazole.
• benzoxazole derivatives such as 2- ( alkyldithio ) -benzoxazoles such as 2- (octyldithio) benzoxazole, 2- (decyldithio ) benzoxazole and
• thiadiazole derivatives such as 2 , 5-bis ( alkyldithio ) -
• 4-thiadiazoles such as 2 , 5-bis (heptyldithio ) -1 , 3 , 4- thiadiazole, 2, 5-bis (nonyldithio) -1, 3, 4-thiadiazole, 2,5- bis (dodecyldithio ) -1 , 3 , 4-thiadiazole or 2,5- bis ( octadecyldithio ) -1,3, 4-thiadiazole ;
• triazole derivatives such as l-alkyl-2 , 4-triazoles such as l-di-octylaminomethyl-2 , 4-triazole.
• 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
• 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%.
• 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.
• pour point reducers or viscosity index improvers may be added to lubricating oil compositions in this
• Viscosity index improvers include, for example,
• polymethacrylates or olefin polymers such as ethylene- propylene copolymers, styrene-diene copolymers,
• 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
• 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
• 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 is used as lubricating oil compositions for internal combustion engines.
• Lubricating oil is used as lubricating oil compositions for internal combustion engines.
• 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).
• fuels with H/C ratios of from 1.93 to 4 include fuels in which 5% of JIS2 diesel light oil has been replaced with methyl stearate as a typical biodiesel fuel
• Lubricating oil compositions of the present invention may also be used in the internal combustion engines of vehicles fitted with idle-stop apparatus. Furthermore, 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
• 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
• 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.
• compositions of the present invention for internal combustion engines that, as well as providing outstanding wear resistance and fuel economy, also cause condensed water from water vapour produced by fuel combustion to be dispersed through the oil and prevent corrosion or rusting of the engine.
• the present invention is not restricted in any way by these.
• copolymer with molar mass >1000 g/mol produced by reaction between a surfactant, condensed 12- hydroxystearic acid and polyethylene oxide.
• Additive A6 Polyethylene-polyoxypropylene condensate (ADEKA Co. surfactant for cleansing agents, commercially available from ADEKA Co. under the tradename Adeka Pluronic L101)
• Weight-average molecular weight 3800
• Additive B was set at 9.05 mass% meeting the ILSAC GF-5 standards, but there is no particular restriction on the content of Additive B.
• Polymethacrylate series viscosity index improver Non- dispersion type.
• R is a Ci to Cis alkyl group.
• Olefin copolymer viscosity index improver Non dispersing type .
• Antifoaming agent solution comprising 3 mass% of a dimethyl polysiloxane type of silicone oil dissolved in light oil.
• Lubricating oil compositions were prepared in
• 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.
• 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. Then 15mL of simulated E85 fuel was measured out into a 200 mL measuring cylinder and poured into the 7011H blender. Then 15mL of simulated E85 fuel was measured out into a 200 mL measuring cylinder and poured into the 7011H blender. Then 15mL of simulated E85 fuel was measured out into a
• the simulated E85 fuel used was prepared by
• 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.
• Comparative Example 1 was an engine oil containing no glycerine monooleate and showed no water separation in the emulsification tests. However, because it contained no glycerine monooleate, it had a high friction
• Comparative Examples 2 and 3 were OW-20 grade engine oils with different viscosity improvers. Friction coefficients not exceeding 0.1 were achieved on adding glycerine monooleate to each of those, and advantages in terms of fuel economy associated with reduced friction coefficients were obtained. On the other hand, however, it was evident that the water and oil separated out relatively quickly due to potent surface chemical activity in these types of oil containing glycerine monooleate .
• Examples 2, 3 and 4 established that there were no differences in emulsifying performance attributable to differences in the type (poly (meth) acrylate, olefin copolymer) or concentration of the non-dispersion type viscosity index improver used.
• 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.
• glycerine monooleate at concentrations of the oleylamine ethylene oxide adduct of less than 0.4 mass% .
• Example 1 taking Group 2, 3 and 4 base oils with low unsaturation levels and sulphur contents, adding 0.4 mass% or more of an oleylamine ethylene oxide adduct overcame water separability due to the potent surface activity effect of glycerine monooleate and served to improve emulsion-retention. It was also clear that wear resistance and the friction coefficient reduction could also be maintained.
• a GTL (gas to liquid) base oil synthesized by the Fischer-Tropsch process was used from among API Group 3 base oils showing defined properties .

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• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)

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• 2012
  • 2012-07-30 JP JP2012168934A patent/JP5943252B2/ja active Active
• 2013
  • 2013-07-29 WO PCT/EP2013/065884 patent/WO2014019975A1/en active Application Filing
  • 2013-07-29 RU RU2015106989A patent/RU2641104C2/ru active
  • 2013-07-29 CN CN201380046934.2A patent/CN104619818B/zh active Active
  • 2013-07-29 EP EP13742227.5A patent/EP2880138B1/en not_active Revoked
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