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WO2013037932A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
WO2013037932A1
WO2013037932A1 PCT/EP2012/068037 EP2012068037W WO2013037932A1 WO 2013037932 A1 WO2013037932 A1 WO 2013037932A1 EP 2012068037 W EP2012068037 W EP 2012068037W WO 2013037932 A1 WO2013037932 A1 WO 2013037932A1
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WO
WIPO (PCT)
Prior art keywords
lubricating oil
mass
constituent
oil composition
group
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.)
Ceased
Application number
PCT/EP2012/068037
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English (en)
Inventor
Tetsuo Wakizono
Kiyoshi Hanyuda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to RU2014115198A priority Critical patent/RU2615511C2/ru
Priority to BR112014005905A priority patent/BR112014005905A2/pt
Priority to EP12761725.6A priority patent/EP2748293A1/fr
Priority to CN201280044741.9A priority patent/CN103797100A/zh
Priority to US14/344,347 priority patent/US20140342956A1/en
Publication of WO2013037932A1 publication Critical patent/WO2013037932A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C10M141/12—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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • 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
    • C10M141/10—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 phosphorus-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
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • 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
    • 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—Overbased sulfonic acid salts
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/252—Diesel engines
    • 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
    • C10N2040/255—Gasoline engines

Definitions

  • the present invention relates to a lubricating oil composition and in particular relates to a lubricating oil composition for an internal combustion engine having an improved friction lowering effect and an improved corrosion prevention effect.
  • a coating is applied to the catalyst in the DPF itself, in order to discharge soot that has been deposited in the DPF from the system, by continuous combustion (this is called continuous
  • Sulphur-containing compounds such as zinc
  • dithiophosphate are effective in regard to prevention of corrosion friction of lead-containing materials, and have shown excellent benefits in terms of preventing lead corrosion friction in conventional engine oil.
  • an anti-wear coating an oily film or reactive coating
  • the corrosion-preventing agents and rust inhibitors prevent such action of the extreme pressure agents and anti-wear agents.
  • an object of the present invention is to provide a lubricating oil composition of a type meeting environmental regulations and with
  • the present inventors discovered that, while maintaining the friction-reducing effect, the problems of lead corrosion and copper corrosion could be solved by conjoint use in the lubricating oil base oil of (a) specified fatty acid glyceride compounds and (b) specified triazole derivatives in a certain ratio, and including (c) specified zinc dialkyl dithiophosphates , each of these being present in small quantities.
  • the invention provides a lubricating oil composition containing, as constituent (a), 0.5 to 1.5 mass% of a mono or diester of glycerin and a straight-chain or branched fatty acid of carbon number 6 to 20 having a saturated hydrocarbyl group; as constituent (b) , 0.1 to 0.5 mass% of a triazole derivative represented by general formula ( 1 ) :
  • R 1 is hydrogen or a hydrocarbyl group of carbon number 1 to 3
  • R2 and R3 are respectively independently hydrogen or a hydrocarbyl group of carbon number 1 to 20, which may contain an oxygen atom, sulphur atom or
  • constituent (c) 0.01 to 0.2 mass%, calculated as phosphorus, of a mixture of primary zinc dialkyl dithiophosphate whose alkyl group is a primary
  • hydrocarbyl group hereinbelow sometimes referred to as primary ZnDTP
  • secondary zinc dialkyl dithiophosphate whose alkyl group is a secondary hydrocarbyl group
  • This lubricating oil composition constitutes a lubricating oil composition for internal combustion engines of a type conforming to environmental regulations, which need not contain a molybdenum-based friction reducing agent, which has low ash, low phosphorus and low sulphur, and improved
  • lubricating oil composition can be widely employed with internal combustion engines such as gasoline engines, diesel engines, or engines whose fuel is dimethyl ether, or gas engines or the like.
  • base oils that is employed in the lubricating oil composition according to the present invention
  • mineral oils, synthetic oils, or various mixtures of these that are normally employed in lubricating oil may be suitably used: base oils of group 1, group 2, group 3, group 4 and group 5 in the base oil category of the API (American Petroleum Institute) may be employed alone or in the form of mixtures thereof; in particular, base oils of group 2, group 3 and group 4 are preferably employed.
  • Group 1 base oils comprise for example paraffin- based mineral oils obtained by suitable combination of refining means such as solvent refining, hydrogenation refining and dewaxing, in respect of lubricating oil fractions obtained by reduced-pressure distillation of crude oil.
  • refining means such as solvent refining, hydrogenation refining and dewaxing
  • the viscosity index may be 80 to 120,
  • the dynamic viscosity at 100°C is preferably 2 to 40mm 2 /s, more preferably 3 to 15mm 2 /s.
  • the total nitrogen content may be less than lOOppm, preferably less than 50ppm.
  • oil of aniline point 80 to 150°C, preferably 90 to 135°C may be
  • Group 2 base oils comprise for example paraffin- based mineral oils obtained by suitable combination of refining means such as hydrogenation refining and
  • Group 2 base oils refined by the hydrogenation refining method of for example the Gulf Company are of total sulphur less than lOppm, aromatics less than 5 mass% and can be applied to the present invention.
  • the viscosity of these base oils is not particularly restricted, but the viscosity index may be 80 to 120, preferably 100 to 120.
  • the dynamic viscosity at 100°C may preferably be 2 to 40mm 2 /s, more preferably 3 to 15mm 2 /s, and particularly preferably 3.5 to 12mm 2 /s.
  • oil of total sulphur less than 300ppm, preferably less than lOOppm and even more preferably less than lOppm may be employed.
  • the total nitrogen may also be less than lOppm, preferably less than lppm.
  • oil of aniline point 80 to 150°C, preferably 100 to 135°C may be employed.
  • base oils called group 2 plus base oils are preferable, whose viscosity
  • group 3 base oils for example in regard to the lubricating oil fraction obtained by reduced-pressure distillation of crude oil, there are available paraffin- based mineral oils manufactured by high-hydrogenation refining, base oils refined by the ISODEWAX process, in which wax generated by the dewaxing process is converted to isoparaffins and these are dewaxed, or base oils refined using the Mobil WAX isomerisation process: these also may suitably be employed in the present invention.
  • the viscosity of these base oils there is no particular restriction on the viscosity of these base oils, and a viscosity index of 120 to 160, preferably 120 to 150, may be employed.
  • the dynamic viscosity at 100°C is preferably 2 to 40mm 2 /s, more preferably 3 to 15mm 2 /s, and particularly preferably 3.5 to 12mm 2 /s.
  • the total sulphur may be less than 300ppm, preferably less than lOOppm and even more
  • the total nitrogen may also be less than lOppm, preferably less than lppm.
  • oil whose aniline point is 80 to 150°C, preferably 110 to 135°C may be employed.
  • group 3 base oils preferable base oils, called group 3 plus base oils, may be mentioned, which have a viscosity index of at least 130.
  • PAO poly- -olefin
  • group 5 base oils there may be mentioned by way of example polyolefins apart from the aforementioned PAO, alkyl benzenes, alkyl naphthalenes, esters,
  • polyoxyalkylene glycols polyphenyl ethers, dialkyl diphenyl ethers, fluorine-containing compounds
  • polystyrene resin perfluoropolyethers, fluorinated polyolefins etc
  • silicones perfluoropolyethers, fluorinated polyolefins etc
  • polyolefins polymers of various types of polyolefins or hydrides of these are included. Any desired olefin may be employed: examples include
  • polyolefins one of the aforementioned olefins may be used alone, or two or more may be used in combination.
  • the GTL (gas to liquid) base oil that is synthesised by the Fischer-Tropsch method in the technique of
  • such base oil can therefore be suitably employed as base oil in the present invention.
  • the viscosity of the GTL base oil may be 115 to 180, preferably 125 to 175 or more preferably 130 to 160.
  • the dynamic viscosity at 100°C may be 2 to 12mm 2 /s, preferably 2.5 to 8.5 mm 2 /s.
  • the total sulphur is less than lOppm and the total nitrogen is less than lppm.
  • SHELL XHVI Registered Trademark
  • the base oil oil of various types may be employed alone, or may be employed in the form of a suitable mixture: the sulphur of such a base oil may be less than 50ppm, preferably less than lOppm; even more preferably, the degree of freedom in blending design may often be increased by making the sulphur content Oppm.
  • base oil of suitable viscosity may be employed, depending on the application of the lubricating oil composition; usually, the dynamic viscosity at 100°C is 2 to 40mm 2 /s, preferably 3 to 15mm 2 /s and particularly preferably 3.5 tol2 mm 2 /s. If the dynamic viscosity at 100°C is 2mm 2 /s or more, there is little evaporation loss, and if it is less than 40mm 2 /s, loss of power due to lowered viscosity is suppressed: a beneficial effect in terms of improved fuel efficiency may therefore be obtained .
  • the aforementioned (a) according to the present invention are fatty acid glyceride compounds, and are mono or diesters of glycerin and fatty acids of carbon number 6 to 20 having a straight-chain or branched saturated hydrocarbyl group.
  • the fatty acid glyceride compounds of (a) may be employed on their own or in the form of a combination of two or more of these.
  • the blending amount thereof is preferably at least 0.5 mass%, more preferably at least 0.7 mass%, from the point of view of the friction reduction effect. Regarding the upper limit of the blending amount, this is less than 1.5 mass%, from the point of view of metal corrosion, oxidative degradation of the lubricating oil and economy.
  • Ri is hydrogen or a hydrocarbyl group of carbon number 1 to 3, preferably hydrogen.
  • R 2 and R 3 are respectively independently hydrogen or hydrocarbyl groups of carbon number 1 to 20, preferably hydrocarbyl groups of carbon number 6 to 12, which may contain an oxygen atom, sulphur atom, or nitrogen atom.
  • R 2 and R 3 do not contain an oxygen atom, sulphur atom, or nitrogen atom.
  • R 2 and R 3 may be respectively the same or different.
  • triazole derivative from the point of view of the beneficial effect thereof, 0.1 to 0.5 mass% may be used. Also, for this triazole derivative, a single type thereof may be employed, or two or more types thereof may be employed in combination. In addition, this may be employed in combination with other metal deactivators.
  • ZnDTP zinc dialkyl dithiophosphate
  • R 4 , R 5 , R 6 and R 7 are respectively independently straight-chain or branched saturated hydrocarbyl groups of carbon number 3 to 20.
  • the carbon number of the saturated hydrocarbyl groups is preferably 3 to 12, and more preferably 3 to 8.
  • R 4 to R 7 are respectively independent, but their structure is the same.
  • R 4 is a primary
  • R 5 to R 7 are also primary hydrocarbyl groups, and, in the case where R 4 is a secondary hydrocarbyl group, the remaining R 5 to R 7 are also secondary hydrocarbyl groups.
  • primary zinc dialkyl dithiophosphates primary ZnDTP
  • secondary ZnDTP secondary zinc dialkyl dithiophosphates
  • the contents of the mixture of primary ZnDTP and secondary ZnDTP may be 0.01 to 0.2 mass%, referred to (calculated as) the amount of phosphorus, preferably 0.05 to 0.15 mass%, more preferably 0.05 to 0.12 mass%. If the content of primary and secondary ZnDTP is too small, sufficient friction preventing performance is not
  • the ratio of primary ZnDTP may be 10 to 60 mass% of the total ZnDTP referred to (calculated as) the amount of phosphorus, preferably 30 to 55 mass%, and more preferably 33 to 50 mass%, while the ratio of secondary ZnDTP may be 40 to 90 mass%, preferably 45 to 70 mass% and more preferably 50 to 67 mass%.
  • constituent (b) may be made about 1.5 to 8: a synergistic effect is thereby achieved, and an excellent friction reduction effect and corrosion preventing effect, which cannot be achieved by these on their own are
  • additives apart from the constituents (a) , (b) , (c) may be suitably blended, such as, for example, viscosity index improvers, pour point depressants, metal cleaning agents, ashless dispersants, antioxidants, friction modifiers, metal deactivators, anti-wear agents or extreme pressure agents, rust inhibitors, surfactants or anti-emulsifiers or defoamers.
  • non-dispersion type polymethacrylate dispersion type polymethacrylate
  • non-dispersion type olefin-based copolymers such as for example ethylene- propylene copolymer
  • dispersion-type olefin-based copolymers such as for example styrene-based copolymers, or styrene-isoprene
  • the blending amount of these viscosity index improvers will usually be about 0.1 to 15 mass%, referred to the total amount of the lubricating oil composition.
  • pour point depressants there may be mentioned by way of example polymethacrylates of weight average molecular weight about 5000 to 50,000.
  • any of the alkaline earth metal cleaning agents that are employed in lubricating oils may be used, such as for example alkaline earth metal sulphonates, alkaline earth metal phenates, alkaline earth metal salicylates and mixtures of two or more of these.
  • salicylates magnesium or calcium, preferably calcium, may be employed.
  • these metal cleaning agents apart from neutral salts as mentioned above, for example basic salts, over-based salts and mixtures of these may be employed: in particular, calcium salicylate is preferable on account of its cleaning performance and anti-wear properties .
  • the content of the aforementioned metal cleaning agents is usually less than 1 mass%, calculated in terms of the metallic element, and preferably less than 0.5 mass%. Preferably the content thereof is less than 0.3 mass%, in order to keep the sulphated ash in the
  • lubricating oil composition below 1 mass%. Also, in order to obtain oxidation stability, and maintain the total base number and high-temperature cleaning performance, the content should be at least 0.05 mass%, preferably at least 0.1 mass%.
  • the aforementioned sulphated ash is a value measured by "5. Method of testing sulphated ash" of JIS K 2272 and is chiefly due to additives containing metals: based on this, it is possible to learn the amount of metal additives in the composition.
  • ashless dispersant examples include succinimide-based compounds of the mono-imide type or bis-imide type, benzylamine-type compounds, or alkenamine-type compounds.
  • succinimide-type compounds and particularly preferably alkenyl succinimides are employed.
  • the aforementioned ashless dispersants are present in the content of 0.1 to 15 mass%, preferably 0.2 to 10 mass% in the composition. If the aforementioned content is less than 0.1 mass%, a sufficient beneficial effect is not found; if the content exceeds 15 mass%, the beneficial effect is saturated and further addition is economically disadvantageous.
  • a single type of the aforementioned ashless dispersants may be employed, but it is also possible to employ a mixture of two or more types thereof in a suitable ratio.
  • antioxidants there may be employed for example phenolic antioxidants, amine-based antioxidants, molybdenum amino complex-based
  • antioxidants or sulphur-based antioxidants.
  • phenolic antioxidants there may be mentioned for example 4,4 ' -methylenebis ( 2 , 6-di-t-butylphenol ) , 2,2'- methylenebis ( 4-methyl-6-t-butylphenol ) , 4,4 '-bis (2,6- di-t-butylphenol ) , 4,4 '-bis ( 2-methyl-6-t-butylphenol ) , 2 , 2 ' -methylenebis ( 4-ethyl-6-t-butylphenol ) , 4,4 '- isopropylidene-bis ( 2 , 6-di-t-butylphenol ) , 4,4'- butylidenebis ( 3-methyl-6-t-butylphenol ) , 2,2 '- methylenebis ( 4-methyl-6-nonylphenol ) , 2, 2'- isobutylidenebis (4, 6-dimethyl phenol), 2,2'- methylenebis ( 4-methyl-6-cyclohexyl
  • phenolic antioxidants are suitable which are of the bisphenolic type or ester-group-containing
  • phenolic type also, a mixture of two or more of these may be employed.
  • amine-based antioxidants there may be mentioned by way of example: alkyl-substituted
  • phenylaniline-based antioxidants such as hexyl
  • phenylaniline or octyl phenylaniline bis (alkyl- substituted phenyl) amines such as bis (butylphenyl ) amine, bis (neopentylphenyl ) amine, bis (hexylphenyl ) amine, bis (heptylphenyl ) amine, bis ( octylphenyl ) amine, or bis (nonylphenyl ) amine; bis (dialkyl-substituted phenyl) amines such as bis (dibutylphenyl ) amine, bis (di-hexylphenyl ) amine, bis (di-octylphenyl ) amine, or bis (dinonylphenyl ) amine; and naphthylamine-based antioxidants, specifically, 2-naphthylamine, N-2- naphthylamine, or N-alkyl-sub
  • molybdenum amino complex-based antioxidants there may be mentioned hexavalent molybdenum compounds such as for example compounds obtained by reaction of molybdenum trioxide and/or molybdic acid with an amine compound. There is no particular restriction regarding the amine compounds that may be reacted with the amine compound.
  • hexavalent molybdenum compound examples that may be mentioned include monoamines, diamines, polyamines, alkanolamines , or heterocyclic compounds such as
  • dialkyl sulphides such as didodecyl sulphide, or dioctadecyl sulphide
  • thiodipropionic acid esters such as didodecyl thiodipropionate, or dioctadecyl thiodipropionate, dimyristyl thiodipropionate, or dodecyl octadecyl thiodipropionate
  • 2-mercaptobenzo imidazole 2-mercaptobenzo imidazole
  • any compound that is ordinarily employed as an anti-wear agent or extreme pressure agent in lubricating oil may be employed as an anti-wear agent or extreme pressure agent: examples include zinc phosphate, zinc dialkyl phosphate, zinc dialkyl monothiophosphate, zinc dithiocarbamine, disulphides, vulcanised olefins, vulcanised fats and oils, vulcanised esters, thiocarbonates , thiocarbamates or the like sulphur-containing compounds, phosphorus- containing compounds such as phosphorous acid esters, phosphoric acid esters, phosphonic acid esters and the amine salts or metal salts or the like thereof, or sulphur and phosphorus-containing anti-wear agents such as thiophosphorous acid esters, thiophosphoric acid esters, thiophosphonic acid esters, and the amine salts or metal salts or the like thereof, alkal
  • any compound that is ordinarily employed as a friction- reducing agent in lubricating oil may be employed:
  • examples include ashless friction-reducing agents such as fatty acid esters, aliphatic amines, acid amides, fatty acids, aliphatic alcohols, or aliphatic ethers having at least one alkyl group or alkenyl group in the molecule, of carbon number 6 to 30.
  • ashless friction-reducing agents such as fatty acid esters, aliphatic amines, acid amides, fatty acids, aliphatic alcohols, or aliphatic ethers having at least one alkyl group or alkenyl group in the molecule, of carbon number 6 to 30.
  • Metal-containing friction- reducing agents such as molybdenum complexes having an organic ligand may also be mentioned.
  • any compound that is ordinarily employed as a metal is ordinarily employed as a metal
  • deactivator in lubricating oil examples include oxazole-based compounds, thiazole-based
  • rust inhibitors petroleum sulphonates, alkyl benzene sulphonate, dinonyl naphthalene sulphonate, alkenyl succinic acid esters, or polyhydric alcohol esters and the like may be mentioned by way of example.
  • surfactants or anti-emulsifiers there may be mentioned by way of example polyalkylene glycol-based non-ionic surfactants, such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, or
  • polyoxyethylene alkylnaphthyl ether polyoxyethylene alkylnaphthyl ether.
  • defoaming agents there may be mentioned by way of example silicone oil, fluorosilicone oil and fluoroalkyl ethers.
  • the sulphur content in the lubricating oil composition should be kept below 0.5 mass%, preferably below 0.4 mass%. If the sulphur content is less than 0.5 mass%, deterioration of performance of the exhaust gas cleaning catalyst can be suppressed. Also, the sulphur content in the lubricating oil composition should be kept below 0.5 mass%, preferably below 0.4 mass%. If the sulphur content is less than 0.5 mass%, deterioration of performance of the exhaust gas cleaning catalyst can be suppressed. Also, the
  • phosphorous content should be kept to 0.01 to 0.2 mass%, preferably 0.05 to 0.15 mass% and more preferably 0.05 to 0.12 mass%. If the phosphorus content is less than 0.2 mass%, as mentioned above, deterioration of performance of the exhaust gas cleaning catalyst can be suppressed. Also, the sulphated ash should be kept below 1.1 mass%, preferably below 1.0 mass%. If the sulphated ash is less than 1.1 mass%, the drop in performance of the DPF can be suppressed. Specifically, the amount of ash deposited in the DPF is small, making it possible to suppress clogging of this filter by the ash, and so making it possible to prolong the useful life of the DPF.
  • Lubricating oil compositions according to practical examples and comparative examples were prepared having the compositions shown in Table 1 to Table 3.
  • the constituents used in preparation of the lubricating oil compositions were as follows.
  • Base oil 1 group 3 base oil of Fischer-Tropsch origin (characteristics: 100°C dynamic viscosity
  • Base oil 2 group 3 base oil of Fischer-Tropsch origin (characteristics: 100°C dynamic viscosity
  • Base oil 3 group 3 base oil (characteristics: 100°C dynamic viscosity 4.250mm 2 /s, viscosity index 125, %CA no more than 1, sulphur content 40ppm)
  • Base oil 4 group 3 base oil (characteristics: 100°C dynamic viscosity 7.600mm 2 /s, viscosity index 133,
  • Base oil 5 group 2 base oil (characteristics: 100°C dynamic viscosity 5.357mm 2 /s, viscosity index 109, %CA no more than 1, sulphur content less than lOOppm) (6)
  • Base oil 6 group 2 base oil (characteristics:
  • Glyceride 1 glyceryl mono-isostearate (GM I)
  • Glyceride 2 mixture of glyceryl mono-octanate and dioctanate, mono-units: di-units 4:6 to 6:4
  • Glyceride 3 glyceryl mono-oleate (GMO)
  • GMO glyceryl mono-oleate
  • Triazole compound 1- (di- ( 2-ethyl hexyl) aminoethyl) 1, 2, 4-triazole (Irgamet 30 manufactured by BASF)
  • Ca salicylate Ca content 8% by mass, total base number 230mgKOH/g
  • Ca sulphonate Ca content 12.5 mass%, total base number 320mgKOH/g
  • dispersant phenolic antioxidant, amine-based antioxidant and viscosity index improver.
  • test piece a cylindrical test piece manufactured in accordance with SK-3, of diameter 6mm, length 16 mm was employed; for the lower test piece, a test plate manufactured in accordance with SK-3 was employed, with a test temperature of 100°C, load 300N, vibration amplitude 15mm, reciprocatory frequency 10Hz, duration of test 10 min: the coefficient of friction obtained was used as an index of fuel
  • composition was placed in a glass beaker and a steel plate, copper plate and lead plate were immersed in this test oil, and an oxidation stability test was conducted for 168 hours at 150°C: the amounts (ppm) of copper and lead leached into the degraded test oil after the test were measured.
  • the copper and lead contents in the oxidation-degraded oil were measured in accordance with
  • Copper content 50ppm or less.
  • Lead content 30ppm or less.
  • test was conducted using test equipment based on "Piston under-crown cumulative test device for lubricating oil" as set out in JP 2004-092601.
  • test conditions were set as: piston top and temperature 275°C, oil temperature 100°C, oil spray rate 90 ml/minute, and test time 48 hours; the percentage increase of the 40°C dynamic viscosity after the test was measured: values below 5% were regarded as pass values.
  • test temperature The test conditions were set as: test temperature
  • test time 16 hours sample oil feed rate 0.3 ml/hour, air flow rate 10 ml/hour; a colour phase
  • glyceride 1 glyceride mono- isostearate
  • glyceride 2 C8 mono-diglyceride
  • triazole compound keeping the amounts of secondary and primary ZnDTP, Ca salicylate and other additives (including succinimide dispersant, phenolic and amino antioxidant and viscosity index improver) fixed at the same amounts.
  • the primary and secondary ZnDTP were employed mixed in a ratio of 1:2, referred to the amount of phosphorus.
  • comparative example 1 contained a triazole compound:
  • Comparative example 2 is a prescription in which the ratio of glyceride and triazole compound was more than 8: the frictional coefficient in the reciprocatory frictional test satisfied the pass criterion, but the amount of leached copper and the amount of leached lead in the copper and lead corrosion test did not satisfy the pass criteria.
  • Comparative example 3 is a prescription in which the ratio of
  • glyceride and triazole compound was less than 1.5: the amount of leached copper and the amount of leached lead in the copper and lead corrosion tests satisfied the pass criteria, but the frictional coefficient in the
  • comparative example 3 by addition of 0.5 mass% of GMI and 0.5 mass% of triazole compound, the leached amounts of copper and lead are reduced to a level satisfying the pass criteria, but the frictional coefficient does not satisfy the pass criterion. Also, even if triazole compound is used, as in comparative example 4, if GMI is not added, the frictional coefficient is high, so that the pass criterion is not satisfied.
  • Comparative example 5 and comparative example 8 show cases in which the ratio of glycerides 1, 2 and triazole compound is 5: however, in a prescription in which only primary ZnDTP is employed as the ZnDTP, the pass
  • the pass criterion is not met in the anti-wear test, while, in a prescription in which only secondary ZnDTP is employed as the ZnDTP, the pass criterion is not met in the
  • glyceride 2 shown in practical example 5 satisfies the pass criterion in respect of each of the test items, in the same way as glyceride 1.
  • glyceride 3 GMO having an unsaturated hydrocarbyl group
  • a benzotriazole compound which is widely employed as a copper deactivator, is employed instead of the triazole compound: it can be seen that the copper and lead
  • GMO glyceride 3
  • Table 3 indicate that the test in question was not in fact carried out, since it was known that the pass criteria in the tests that had already been implemented were not satisfied.

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

Abstract

L'invention concerne une huile lubrifiante pour un moteur à combustion interne. L'huile lubrifiante permet une réduction des frottements et satisfait les réglementations environnementales requérant un effet anticorrosion important. La composition d'huile lubrifiante contient un mono- ou diester de glycérine et un acide gras linéaire ou ramifié en C6 à 20 contenant un groupe hydrocarbyle saturé ; un dérivé de triazole ; et un mélange de dithiophosphate de dialkyle de zinc primaire et de dithiophosphate de dialkyle de zinc secondaire.
PCT/EP2012/068037 2011-09-16 2012-09-14 Composition d'huile lubrifiante Ceased WO2013037932A1 (fr)

Priority Applications (5)

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RU2014115198A RU2615511C2 (ru) 2011-09-16 2012-09-14 Композиция смазочного масла
BR112014005905A BR112014005905A2 (pt) 2011-09-16 2012-09-14 composição de óleo lubrificante
EP12761725.6A EP2748293A1 (fr) 2011-09-16 2012-09-14 Composition d'huile lubrifiante
CN201280044741.9A CN103797100A (zh) 2011-09-16 2012-09-14 润滑油组合物
US14/344,347 US20140342956A1 (en) 2011-09-16 2012-09-14 Lubricating oil composition

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JP2011203583A JP5771103B2 (ja) 2011-09-16 2011-09-16 潤滑油組成物
JP2011-203583 2011-09-16

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CN104451055A (zh) * 2014-12-01 2015-03-25 昌利锻造有限公司 一种模具钢用淬火油及其制备方法
WO2019236441A1 (fr) 2018-06-08 2019-12-12 The Lubrizol Corporation Inhibition de la corrosion en phase vapeur
EP3587541A4 (fr) * 2017-02-21 2020-12-16 Kyodo Yushi Co., Ltd. Composition lubrifiante pour réducteur de vitesse, et réducteur de vitesse

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AU2016307780B2 (en) * 2015-08-14 2019-02-21 Vanderbilt Chemicals, Llc Additive for lubricant compositions comprising an organomolybdenum compound, and a derivatized triazole
EP3255129B1 (fr) * 2016-06-06 2024-01-24 The Lubrizol Corporation Adduits thiol-carboxyliques comme additifs de lubrification
JP2018062551A (ja) * 2016-10-11 2018-04-19 出光興産株式会社 潤滑油組成物
WO2020218025A1 (fr) * 2019-04-26 2020-10-29 Ｋｙｂ株式会社 Composition lubrifiante pour amortisseurs, additif pour ajustement de frottement, additif lubrifiant, amortisseur et procédé d'ajustement de frottement pour une composition lubrifiante pour des amortisseurs
JP2024108867A (ja) * 2023-01-31 2024-08-13 出光興産株式会社 潤滑油組成物

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CN104451055A (zh) * 2014-12-01 2015-03-25 昌利锻造有限公司 一种模具钢用淬火油及其制备方法
EP3587541A4 (fr) * 2017-02-21 2020-12-16 Kyodo Yushi Co., Ltd. Composition lubrifiante pour réducteur de vitesse, et réducteur de vitesse
US11053451B2 (en) 2017-02-21 2021-07-06 Kyodo Yushi Co., Ltd. Lubricant composition for a speed reducer, and speed reducer
WO2019236441A1 (fr) 2018-06-08 2019-12-12 The Lubrizol Corporation Inhibition de la corrosion en phase vapeur
EP3802750A1 (fr) * 2018-06-08 2021-04-14 The Lubrizol Corporation Inhibition de la corrosion en phase vapeur

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US20140342956A1 (en) 2014-11-20
BR112014005905A2 (pt) 2017-04-04
JP2013064073A (ja) 2013-04-11
RU2014115198A (ru) 2015-10-27
JP5771103B2 (ja) 2015-08-26
CN103797100A (zh) 2014-05-14

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