WO2015022976A1 - Composition d'huile lubrifiante pour moteur à combustion interne - Google Patents

Composition d'huile lubrifiante pour moteur à combustion interne Download PDF

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Publication number
WO2015022976A1
WO2015022976A1 PCT/JP2014/071388 JP2014071388W WO2015022976A1 WO 2015022976 A1 WO2015022976 A1 WO 2015022976A1 JP 2014071388 W JP2014071388 W JP 2014071388W WO 2015022976 A1 WO2015022976 A1 WO 2015022976A1
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Prior art keywords
group
mass
less
oil composition
internal combustion
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PCT/JP2014/071388
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English (en)
Japanese (ja)
Inventor
大也 宮本
慎太郎 楠原
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Ｊｘ日鉱日石エネルギー株式会社
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Application filed by Ｊｘ日鉱日石エネルギー株式会社 filed Critical Ｊｘ日鉱日石エネルギー株式会社
Priority to CN201480041176.XA priority Critical patent/CN105452427B/zh
Priority to MX2016001860A priority patent/MX2016001860A/es
Priority to US14/904,496 priority patent/US20160152920A1/en
Priority to CA2921209A priority patent/CA2921209A1/fr
Priority to JP2015531829A priority patent/JP6270226B2/ja
Priority to EP14835748.6A priority patent/EP3037505A4/fr
Priority to KR1020167004328A priority patent/KR102075820B1/ko
Publication of WO2015022976A1 publication Critical patent/WO2015022976A1/fr

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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • C10M133/18—Amides; Imides of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • C—CHEMISTRY; METALLURGY
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
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    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
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    • 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
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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    • 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
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    • 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
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    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
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    • 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
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    • 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
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
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    • 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 for an internal combustion engine with improved fuel economy.
  • Patent Document 1 discloses a specific additive (such as a base oil having a kinematic viscosity at 100 ° C. of 2 to 8 mm 2 / s and an aromatic content of 15% by mass).
  • Patent Document 2 discloses a kinematic viscosity at 100 ° C. of 3 to 8 mm 2 / s.
  • Lubricating oil composition for internal combustion engines comprising a lubricating base oil containing an ester based lubricating base oil and a molybdenum based friction modifier or an ester-based or amine-based ashless friction modifier and an overbased Ca salicylate
  • Patent Document 3 combines sulfurized oxymolybdenum dithiocarbamate with an ashless friction modifier such as an acid amide compound, an aliphatic partial ester compound and / or an aliphatic amine compound.
  • a lubricating oil composition for an internal combustion engine that has been blended is proposed.
  • JP-A-8-302378 Japanese Patent Laid-Open No. 2005-41998 JP 2008-106199 A JP-A-9-316475 JP 2008-179669 A JP 2005-290181 A
  • the present invention solves the above-mentioned problems, and the problem to be solved by the present invention is to provide a lubricating oil composition for an internal combustion engine that further reduces friction and is excellent in fuel efficiency.
  • the present invention relates to (A) a lubricant base oil having a kinematic viscosity at 100 ° C. of 2.0 to 5.0 mm 2 / s, and (B) a molybdenum friction modifier as 0.005 as the amount of molybdenum based on the total amount of the composition. ⁇ 0.2% by mass, (C) 0.01 to 1% by mass of metal detergent based on the total amount of the composition, and (D) an alkyl group, alkenyl group or acyl group having 6 to 24 carbon atoms A lubricating oil composition for an internal combustion engine containing 0.01 to 10% by mass of one or more compounds selected from amino acids and / or derivatives thereof.
  • the metallic detergent contains at least a salicylate detergent, and the kinematic viscosity at 100 ° C. of the lubricating oil composition for an internal combustion engine is 4.0 to 12.5 mm 2 / s. Further, the lubricating oil composition for an internal combustion engine further contains 0.02 to 0.2% by mass of zinc dialkyldithiophosphate (ZnDTP) based on the total amount of the composition, based on the amount of phosphorus.
  • ZnDTP zinc dialkyldithiophosphate
  • the lubricating oil composition for an internal combustion engine of the present invention has a remarkable effect that it has a low coefficient of friction and excellent fuel efficiency.
  • the lubricating base oil in the present invention is not particularly limited as long as it is a lubricating base oil having a kinematic viscosity at 100 ° C. of 2.0 to 5.0 mm 2 / s. Any mineral oil and synthetic oil can be used as long as they are used as the lubricating base oil of the lubricating oil composition for internal combustion engines.
  • the kinematic viscosity of this lubricating base oil at 100 ° C. is preferably in the range of 2.5 to 4.5 mm 2 / s, more preferably 3.0 mm 2 / s or more, and even more preferably 3. 5 mm 2 / s or more. When the kinematic viscosity at 100 ° C.
  • the kinematic viscosity at 100 ° C. is the kinematic viscosity at 100 ° C. as defined in ASTM D-445.
  • the lubricating base oil of the present invention preferably has a viscosity index of 90 or more, more preferably 100 or more.
  • the viscosity index means a viscosity index measured in accordance with JIS K2283-1993.
  • a mineral base oil or a synthetic base oil can be used alone, or two or more mineral base oils, or It may be a mixture of two or more kinds of synthetic base oils, or may be a mixture of mineral oil base oils and synthetic oil base oils. And the mixing ratio of 2 or more types of base oil in the said mixture can be chosen arbitrarily.
  • mineral base oils lubricating oil fractions obtained by subjecting crude oil to atmospheric distillation and reduced pressure distillation are subjected to solvent deburring, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid Examples thereof include paraffinic and naphthenic lubricating base oils and the like, which are refined by appropriately combining purification treatments such as washing and clay treatment.
  • Synthetic base oils include poly- ⁇ -olefins (eg polybutene, 1-octene oligomers, 1-decene oligomers, ethylene-propylene oligomers) or their hydrides, isobutene oligomers or their hydrides, isoparaffins, alkylbenzenes, alkyls Naphthalene, diesters (eg, dibutyl maleate, ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate), co-weight of ⁇ -olefin and diester Coalesced, polyol esters (eg, trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythr
  • the lubricating base oil of the present invention is preferably a base oil having a saturated hydrocarbon content of 90% or more in the mineral base oil.
  • this saturated hydrocarbon content means a value measured by ASTM D-2007.
  • the base oils are preferably those classified into group III or higher based on the base oil classification by API (American Petroleum Institute), and base oils obtained by isomerizing wax. There are no particular restrictions on the method for producing this base oil, but atmospheric residual oil obtained by atmospheric distillation of crude oil is desulfurized, hydrocracked and fractionated into a set viscosity grade, or the residual oil. It is preferable to use a base oil obtained by solvent dewaxing or catalytic dewaxing and, if necessary, solvent extraction and hydrogenation. Of these, base oils obtained by catalytic dewaxing are preferred.
  • the above-mentioned lube base oil has been further subjected to distillation under reduced pressure at atmospheric distillation residue, fractionated to the required viscosity grade, and then subjected to processes such as solvent refining and hydrorefining to dewax the solvent.
  • GTL WAX gas Also included are GTL-based wax isomerized lubricating base oils and the like produced by isomerizing (Turi Liquid Wax).
  • the basic production process of the wax isomerized lubricating base oil is the same as that of the hydrocracking base oil.
  • The% C A of the base oil is not particularly limited, is preferably less than 3, more preferably 2 or less, even more preferably 1 or less, and most preferably substantially zero. If it exceeds 10, the improvement of heat resistance, which is one of the objects of the present invention, becomes insufficient. Note that the% C A means a value measured by a method in accordance with ASTM D3238-85 (n-d-M ring analysis).
  • the sulfur content of the base oil is not particularly limited, but is preferably 0.03% by mass or less, more preferably 0.01% by mass or less, and particularly preferably one containing substantially no sulfur.
  • the method for measuring the sulfur content is not particularly limited, but JIS K2541-1996 is generally used.
  • molybdenum friction modifier in the present invention includes, for example, molybdenum dithiocarbamate (MoDTC) and molybdenum dithiophosphate (MoDTP).
  • MoDTC molybdenum dithiocarbamate
  • MoDTP molybdenum dithiophosphate
  • Specific examples of molybdenum dithiocarbamate include compounds represented by the following general formula (1).
  • Specific examples of molybdenum dithiophosphate include compounds represented by the following general formula (2).
  • R 1 to R 8 each independently represent a hydrocarbon group having 1 to 24 carbon atoms
  • Preferred examples of the hydrocarbon group having 1 to 24 carbon atoms represented by R 1 to R 8 in the general formulas (1) and (2) are each linear or branched having 1 to 24 carbon atoms.
  • the alkyl group or alkenyl group may be primary, secondary, or tertiary.
  • the molybdenum friction modifier in the lubricating oil composition of the present invention includes, for example, basic nitrogen compounds such as succinimide, acidic molybdenum compounds such as molybdenum trioxide, and sulfur such as hydrogen sulfide and phosphorus pentasulfide.
  • basic nitrogen compounds such as succinimide
  • acidic molybdenum compounds such as molybdenum trioxide
  • sulfur such as hydrogen sulfide and phosphorus pentasulfide.
  • An organic molybdenum complex which is a reaction product with a compound is also a preferred example.
  • the content of the molybdenum-based friction modifier is 0.005 mass% or more and 0.2 mass% or less, preferably 0 or less, in terms of molybdenum element, based on the total amount of the composition. 0.01% by mass or more.
  • the content of the molybdenum-based friction modifier is less than 0.005% by mass in terms of molybdenum element, a remarkable fuel saving effect cannot be obtained, while the content of the molybdenum-based friction modifier is less than the elemental molybdenum.
  • the converted amount exceeds 0.2% by mass, it is not preferable because an improvement in the fuel saving effect corresponding to the content cannot be obtained.
  • molybdenum dithiophosphate and molybdenum dithiocarbamate are preferably used, but because of the synergistic effect with other components, the fuel saving performance can be significantly improved from low to high temperatures. It is particularly preferred.
  • metal-based detergent As the metal-based detergent of the present invention, any compound usually used in lubricating oils can be used, for example, having a linear or branched hydrocarbon group, An overbased compound of an oil-soluble metal salt having an OH group and / or a carbonyl group can be used. Also, alkaline earth metal sulfonates, alkaline earth metal carboxylates, alkaline earth metal salicylates, alkaline earth metal phenates, alkaline earth metal phosphonates and other overbased metal salts, alkaline earth metal hydroxides or oxides If necessary, an overbased metal salt that can be obtained by reacting boric acid or boric anhydride can be used.
  • alkaline earth metals examples include magnesium, calcium, barium and the like, with calcium being preferred.
  • the overbased metal salt it is more preferable to use an oil-soluble metal salt of a compound containing an OH group and / or a carbonyl group overbased with an alkaline earth metal borate or an alkaline earth metal carbonate.
  • an alkaline earth metal salicylate from the viewpoint of excellent fuel economy, and it is more preferable to use an alkaline earth metal salicylate overbased with an alkaline earth metal borate.
  • the metal-based detergent of the present invention preferably has a base number of 50 mgKOH / g or more, more preferably 100 mgKOH / g or more, further preferably 120 mgKOH / g or more, and 140 mgKOH / g or more. It is particularly preferred. Moreover, it is preferable that it is 300 mgKOH / g or less, and it is more preferable that it is 200 mgKOH / g or less.
  • the base number is less than 50 mgKOH / g, the increase in the viscosity is increased, so that the fuel efficiency is deteriorated and the friction reducing effect due to the addition tends to be insufficient.
  • the base number in the present invention is a value measured according to JIS K 2501 5.2.3.
  • the method for producing the metal detergent used in the present invention is arbitrary.
  • the oil-soluble metal salt, alkaline earth metal hydroxide or oxide, if necessary, boric acid or anhydrous boric acid, water, methanol The reaction is carried out in the presence of an alcohol such as ethanol, propanol or butanol and a diluting solvent such as benzene, toluene or xylene at 20 to 200 ° C. for 2 to 8 hours, and then heated to 100 to 200 ° C. with water and if necessary It is obtained by removing the alcohol and diluting solvent.
  • an alcohol such as ethanol, propanol or butanol
  • a diluting solvent such as benzene, toluene or xylene
  • the metal detergent of the present invention preferably has a metal ratio of 4.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less. When the metal ratio exceeds 4.0, there is a possibility that the friction torque is reduced, that is, the fuel saving performance is insufficient.
  • the metal ratio is preferably 1.0 or more, more preferably 1.1 or more, and even more preferably 1.5 or more. If the metal ratio is less than 1.0, the kinematic viscosity or low temperature viscosity of the lubricating oil composition for internal combustion engines becomes high, which may cause problems in fuel saving and startability.
  • the metal ratio referred to in the present invention is represented by the valence of the metal element in the metal detergent ⁇ the metal element content (mol%) / the soap group content (mol%), and the metal element is calcium,
  • a soap group such as magnesium means a sulfonic acid group, a phenol group, a salicylic acid group, or the like.
  • the linear or branched hydrocarbon group of the metal detergent of the present invention is preferably an alkyl group or an alkenyl group, and the alkyl group or alkenyl group preferably has 8 or more carbon atoms, more preferably 10 or more, Preferably it is 12 or more, and 19 or less is preferable. A carbon number of less than 8 is not preferable because the oil solubility is not sufficient.
  • it may be linear or branched, but is preferably linear, and these may be a primary alkyl group, alkenyl group, secondary alkyl group, alkenyl group, tertiary alkyl group or alkenyl group, but secondary In the case of an alkyl group, an alkenyl group, a tertiary alkyl group or an alkenyl group, the position of branching is preferably only carbon bonded to an aromatic group.
  • the content of the metal detergent is 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more, in terms of metal element, based on the total amount of the lubricating oil composition. 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.4% by mass or less, still more preferably 0.3% by mass or less, particularly preferably 0.25% by mass or less, and most preferably Is 0.22 mass% or less.
  • the content is less than 0.01% by mass, the friction reduction effect due to the addition tends to be insufficient, and the fuel economy, thermal / oxidation stability and cleanliness of the lubricating oil composition are insufficient. There is a tendency.
  • the content exceeds 1% by mass, the friction reduction effect due to the addition tends to be insufficient, and the fuel economy of the lubricating oil composition tends to be insufficient.
  • the content of the boron-containing metallic detergent is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and still more preferably in terms of boron element based on the total amount of the lubricating oil composition. Is 0.04% by mass or more, particularly preferably 0.05% by mass or more, preferably 0.2% by mass or less, more preferably 0.10% by mass or less, and further preferably 0.08% by mass or less. Especially preferably, it is 0.07 mass% or less.
  • the content is less than 0.01% by mass, the friction reduction effect due to the addition tends to be insufficient, and the fuel economy, thermal / oxidation stability and cleanliness of the lubricating oil composition are insufficient. There is a tendency.
  • the content exceeds 0.2% by mass the effect of reducing friction due to the addition tends to be insufficient, and the fuel efficiency of the lubricating oil composition tends to be insufficient.
  • the metal-based detergent containing boron has a ratio (MB1) / (MB2) of the weight (MB1) of the metal element contained in the detergent to the weight (MB2) of the boron element contained in the detergent, Preferably it is 1 or more, More preferably, it is 2 or more, More preferably, it is 2.5 or more. If (MB1) / (MB2) is less than 1, it is not preferable because fuel economy may be deteriorated.
  • (MB1) / (MB2) is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and particularly preferably 5 or less. If (MB1) / (MB2) exceeds 20, the fuel economy may be deteriorated, which is not preferable.
  • the ashless friction modifier contains at least one or more amino acids and / or derivatives thereof having an alkyl group, alkenyl group or acyl group having 6 to 24 carbon atoms.
  • the compound include compounds represented by the following general formula (3).
  • R 9 is an alkyl group, alkenyl group or acyl group having 6 to 24 carbon atoms
  • R 10 is an alkyl group having 1 to 4 carbon atoms or hydrogen
  • R 11 is hydrogen or 1 to 10 carbon atoms. It is an alkyl group.
  • the alkyl group may include a linear, branched or cyclic structure, and the carbon atom may be substituted with a heteroatom, or may be modified with a functional group such as a hydroxyl group, a carboxyl group, or an amino group. Good.
  • R 12 is an alkyl group having 1 to 4 carbon atoms or hydrogen, n is 0 or 1, and X is a functional group having active hydrogen or a hydrocarbon having the functional group and a metal salt or ethanolamine of the functional group A salt or a methoxy group.
  • R 9 in the general formula (3) is more preferably an alkyl group, an alkenyl group, or an acyl group having 11 or more carbon atoms from the viewpoint of solubility in a base oil. Moreover, 20 or less carbon atoms are more preferable from points, such as storage stability. Furthermore, it is preferable that it is linear from a viewpoint of a friction reduction effect.
  • alkyl group, alkenyl group, and acyl group include, for example, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group.
  • Alkyl groups such as hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group (these alkyl groups may be linear or branched), hexenyl group, Heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, henecocenyl, dococenyl Alkenyl groups such as lycocenyl and tetracosenyl groups (these alkenyl groups
  • R 10 in the general formula (3) is more preferably an alkyl group having 4 or less carbon atoms, more preferably 3 or less carbon atoms, and particularly preferably 2 or less carbon atoms from the viewpoint of storage stability.
  • the alkyl group of R 11 may contain a linear, branched or cyclic structure, the carbon atom may be substituted with a hetero atom, and is modified with a functional group such as a hydroxyl group, a carboxyl group or an amino group. May be. From the viewpoint of friction reduction effect and solubility in base oil, an alkyl group having 2 or less carbon atoms is more preferable, 1 or less carbon atoms is more preferable, and hydrogen is particularly preferable.
  • R 12 is more preferably an alkyl group having 4 or less carbon atoms, more preferably 3 or less carbon atoms, particularly preferably 2 or less carbon atoms, and most preferably hydrogen from the viewpoint of storage stability.
  • a hydroxyl group, an amino group and the like are preferable.
  • amino group primary and secondary amines are preferable, and primary amines are particularly preferable.
  • the metal salt of the active hydrogen group include a metal salt of a hydroxyl group.
  • —COX in formula (3) is preferably a carboxyl group.
  • Specific examples of the hydrocarbon having a hydroxyl group which is a functional group having active hydrogen include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, and 1,6.
  • Examples of the metal of the hydroxyl group metal salt include alkali metal or alkaline earth metal and zinc, and examples of the alkali metal or alkaline earth metal include sodium, potassium, magnesium, calcium and the like. Among these, alkaline earth metals and zinc are preferable from the viewpoint of improving the sustainability of the friction characteristic effect.
  • the metal salt among the general formula (3), a carboxylate in which —COX of the general formula (3) is a carboxy group structure is preferable.
  • the ashless friction modifier of the present invention is preferably at least one compound selected from the general formula (3) from the viewpoint of improving the durability of the friction characteristic effect, and the general formula (3). Only one compound selected from among them may be used alone, or a mixture of two or more compounds may be used.
  • N-acyl sarcosine in particular, R 9 is an acyl group having 18 carbon atoms, R 10 is a methyl group, R 11 is hydrogen, X is a hydroxyl group, N-oleoyl sarcosine where n is 0, R 9 is a lauroyl group which is an acyl group having 12 carbon atoms, R 10 is a methyl group, R 11 is hydrogen, R 12 is hydrogen, X is a hydroxyl group, n is 1
  • N-lauroyl-N-methyl- ⁇ -alanine is mentioned.
  • the content of the above ashless friction modifier is 0.01 to 10% by mass, preferably 5% by mass or less, more preferably 2% by mass or less, based on the total amount of the composition.
  • the content exceeds 10% by mass, the frictional properties corresponding to the content are not further improved, and the storage stability is lowered, which is not preferable.
  • 0.05% by mass or more is preferable, and more preferably 0.1% by mass. If this content is less than 0.01% by mass, the effect of improving the friction characteristics is not seen, which is not preferable.
  • (E) Antiwear agent It is preferable to add zinc dialkyldithiophosphate (ZnDTP) of general formula (4) to the lubricating oil composition for an internal combustion engine of the present invention as an antiwear agent in addition to the above additives.
  • ZnDTP zinc dialkyldithiophosphate
  • R 13 to R 16 are each independently hydrogen or a linear or branched alkyl group having at least one of 1 to 24 carbon atoms.
  • the first grade, the second grade, or the third grade may be used.
  • these zinc dialkyldithiophosphates may be used alone or in combination of two or more, but zinc dithiophosphate having a primary alkyl group (primary ZnDTP) or second A zinc dithiophosphate (secondary ZnDTP) containing a secondary alkyl group is preferred, and a secondary alkyl group containing zinc dithiophosphate as a main component is particularly preferred because it increases wear resistance.
  • the content of the zinc dialkyldithiophosphate is preferably 0.02 to 0.2% by mass, more preferably 0.03 to 0.1% as the amount of phosphorus, based on the total amount of the composition. It is good to mix
  • a viscosity index improver In the lubricating oil composition for internal combustion engines of the present invention, other additives such as a viscosity index improver, a pour point depressant, an antioxidant, an abrasion resistance are added as necessary, as long as the object of the present invention is not impaired.
  • An agent or extreme pressure agent, a friction reducing agent, a dispersant, a rust inhibitor, a surfactant or a demulsifier, an antifoaming agent, and the like can be appropriately blended.
  • a non-dispersed viscosity index improver or a dispersed viscosity index improver can be used as the viscosity index improver.
  • a non-dispersed or dispersed polymethacrylate or olefin copolymer, or polyisobutene, Polystyrene, ethylene-propylene copolymer, styrene-diene copolymer and hydride thereof can be used.
  • weight average molecular weights are generally 5,000 to 1,000,000, but in order to further improve fuel efficiency, the weight average molecular weight is 100,000 to 1,000,000, preferably 200,000 to It is desirable to use the above viscosity index improvers which are 900,000, particularly preferably 400,000 to 800,000.
  • the proportion of the structural unit represented by the following general formula (5) is 30 to 90 mol%
  • the proportion of the structural unit represented by the following general formula (6) is 0.1 to 50 mol. %
  • a viscosity index improver that is a poly (meth) acrylate viscosity index improver having a hydrocarbon main chain ratio of 0.18 or less is preferable for improving fuel economy.
  • R 17 represents hydrogen or a methyl group
  • R 18 represents a linear or branched hydrocarbon group having 6 or less carbon atoms
  • R 19 in the general formula (6) Represents hydrogen or a methyl group
  • R 20 represents a linear or branched hydrocarbon group having 16 or more carbon atoms.
  • the viscosity index improver preferably has a PSSI (Permanent Cystability Index) in the diesel injector method of 30 or less. When PSSI exceeds 30, the shear stability is poor, and the kinematic viscosity after use and the HTHS viscosity are kept at a certain level or more, so that the initial fuel economy may be deteriorated.
  • PSSI Permanent Cystability Index
  • PSSI in the diesel injector method is based on ASTM D6022-01 (Standard Practice for Calculation of Permanent Shear Stability Index), and ASTM D6278-02 (Test Method for Shear Stability of Polymer Containing Fluids Using a Means the Permanent Shear Stability Index of the polymer calculated on the basis of data measured by the European Diesel Injector Apparatus.
  • a polymethacrylate polymer for example, a polymethacrylate polymer, an alkylated aromatic compound, a fumarate-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer, and the like that are compatible with the lubricating base oil to be used can be used.
  • the detergent / dispersant succinimide, benzylamine, alkylpolyamine, polybuteneamine, modified products of these boron compounds and sulfur compounds, alkenyl succinates, and the like can be used.
  • This detergent-dispersant is preferably a mono-type or bis-type succinimide, and more preferably a bis-type succinimide. Further, a bis-type succinimide containing no boron is particularly preferable. Further, the detergent-dispersant preferably has a molecular weight of 1000 or more, more preferably 5000 or more, more preferably 7000 or more, and further preferably 9000 or more.
  • the molecular weight is 1000 or less, the cleanliness may be insufficient.
  • the molecular weight exceeds 30000, the fuel economy of the engine oil composition may be significantly deteriorated.
  • the content of the cleaning dispersant is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1.0 to 8% by mass, based on the total amount of the engine oil composition. is there.
  • the content of the cleaning dispersant is less than 0.1% by mass, the cleanability may be insufficient.
  • the content exceeds 15% by mass the fuel efficiency of the engine oil composition is greatly deteriorated. There is a risk.
  • the N content of the cleaning dispersant is preferably 0.1 or more, more preferably 0.3 or more, more preferably 0.4 or more, and further preferably 0.5 or more.
  • the N content is 0.1 or less, the cleanliness may be insufficient.
  • the N content exceeds 2.0, the fuel economy of the engine oil composition may be significantly deteriorated. is there.
  • any of those generally used in lubricating oils such as phenolic compounds and amine compounds, can be used.
  • 2,6-di-tert-butyl-4 Alkylphenols such as methylphenol, bisphenols such as methylene-4,4-bis (2,6-di-tert-butyl-4-methylphenol), naphthylamines such as phenyl- ⁇ -naphthylamine, dialkyldiphenylamines, Phenothiazines can be used.
  • extreme pressure additives and antiwear agents include phosphorus compounds such as phosphate esters, phosphites and salts thereof, and sulfur compounds such as disulfides, sulfurized olefins and sulfurized fats and oils.
  • phosphorus compounds such as phosphate esters, phosphites and salts thereof
  • sulfur compounds such as disulfides, sulfurized olefins and sulfurized fats and oils.
  • rust inhibitor for example, alkenyl succinic acid, alkenyl succinic acid ester, polyhydric alcohol ester, petroleum sulfonate, dinonyl naphthalene sulfonate and the like can be used.
  • the corrosion inhibitor for example, benzotriazole, thiadiazole, and imidazole compounds can be used.
  • silicone compounds such as a dimethyl silicone and a fluoro silicone, can be used, for example.
  • the additive amount of these additives is arbitrary, but the content of the antifoaming agent is usually 0.0005 to 0.01% by mass and the content of the viscosity index improver is 0.05 to 20 based on the total amount of the composition.
  • the content of the corrosion inhibitor is 0.005 to 0.2% by mass, and the content of other additives is about 0.05 to 10% by mass, respectively.
  • Kinematic viscosity at 100 ° C. for an internal combustion engine lubricating oil composition of the present invention is preferably 4.0 mm 2 / s or more, more preferably 6.0 mm 2 / s or higher, more preferably 6.1 mm 2 / s or more, most preferably 6.2 mm 2 / s or more, preferably 12.5 mm 2 / s or less, more preferably 9.3 mm 2 / s or less, and still more preferably 8.5 mm 2. / S or less.
  • the kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445. If the kinematic viscosity at 100 ° C.
  • the kinematic viscosity at 40 ° C. of the lubricating oil composition is preferably 4 to 50 mm 2 / s, preferably 40 mm 2 / s or less, more preferably 35 mm 2 / s or less.
  • the kinematic viscosity at 40 ° C. is preferably 15 mm 2 / s or more, more preferably 18 mm 2 / s or more, still more preferably 20 mm 2 / s or more, particularly preferably 22 mm 2 / s or more, and most preferably 25 mm 2 / s. s or more.
  • the kinematic viscosity at 40 ° C. here refers to the kinematic viscosity at 40 ° C.
  • the viscosity index of the lubricating oil composition is 120 or more, preferably 400 or less, preferably 190 or more, more preferably 200 or more, particularly preferably 230 or more, and most preferably 240 or more.
  • the viscosity index is less than 120, it may be difficult to improve fuel economy while maintaining the HTHS viscosity at 150 ° C.
  • the viscosity index exceeds 400, the evaporability may be deteriorated, and further, there may be a problem due to insufficient solubility of the additive and compatibility with the sealing material.
  • HTHS viscosity is also called “high temperature high shear viscosity”
  • it is effective to lower the kinematic viscosity at 40 ° C., the kinematic viscosity at 100 ° C., and the HTHS viscosity at 100 ° C., but it has been very difficult to satisfy all these requirements with conventional lubricating oils.
  • the HTHS viscosity at 100 ° C. of the lubricating oil composition is preferably 5.5 mPa ⁇ s or less, more preferably 5.0 mPa ⁇ s or less, still more preferably 4.7 mPa ⁇ s or less, and particularly preferably 4.5 mPa ⁇ s. ⁇ S or less, most preferably 4.4 mPa ⁇ s or less. Further, it is preferably 3.0 mPa ⁇ s or more, more preferably 3.5 mPa ⁇ s or more, particularly preferably 4.0 mPa ⁇ s or more, and most preferably 4.1 mPa ⁇ s or more.
  • referred to in the present invention indicates a high temperature and high shear viscosity at 100 ° C. as defined in ASTM D4683. If the HTHS viscosity at 100 ° C. is less than 3.0 mPa ⁇ s, there is a risk of insufficient lubricity, and if it exceeds 5.5 mPa ⁇ s, the necessary low temperature viscosity and sufficient fuel saving performance cannot be obtained. There is a fear.
  • the ratio of the HTHS viscosity at 150 ° C. to the HTHS viscosity at 100 ° C. of the lubricating oil composition of the present invention is preferably 0.45 or more. Preferably it is 0.475 or more, more preferably 0.50, even more preferably 0.515 or more, particularly preferably 0.53 or more. If the ratio is less than 0.45, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained.
  • Molybdenum-based friction modifier molybdenum dithiocarbamate In general formula (1), R 1 to R 4 are alkyl groups having 8 or 13 carbon atoms, a and b are 2, and the concentration of molybdenum element is 10% by mass, 11% by mass of sulfur (C) Metal-based detergent (C-1) Overbased Ca salicylate: metal ratio 2.3, alkyl group carbon number 14-18, Ca content 6.2 mass%, base number 180 mgKOH / g (C-2) Overbased boric acid Ca salicylate: metal ratio of 2.5, alkyl group having 14 to 18 carbon atoms, Ca content of 6.8% by mass, B content of 2.7% by mass, base number of 190 mgKOH / g (C-3) Overbased Ca salicylate borate: metal ratio of 1.5, alkyl group having 14 to 28 carbon atoms, Ca content of 5.0% by
  • the prepared lubricating oil composition was subjected to a motoring friction test under the following conditions, and the friction torque was measured.
  • the average friction torque was calculated.
  • the obtained results are shown in% in Table 1 together with the physical properties of the lubricating oil composition. (Test conditions) Use engine: Inline 4-cylinder, 1800cc, roller rocker arm type engine Oil temperature: 100 ° C Rotation speed: 1000rpm
  • the lubricating oil composition for an internal combustion engine of the present invention can be suitably used as a fuel-saving engine oil such as a fuel-saving gasoline engine oil or a fuel-saving diesel engine oil.

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Abstract

La présente invention concerne une composition d'huile lubrifiante pour moteur à combustion interne, qui peut réduire plus avant les frottements et présente d'excellentes performances d'économie de consommation de carburant. La présente invention concerne une composition d'huile lubrifiante pour moteur à combustion interne, qui comprend (A) une huile de base d'huile lubrifiante présentant une viscosité cinématique comprise entre 2,0 et 5,0 mm2/s à 100 °C, (B) un modificateur de frottement contenant du molybdène à une teneur comprise entre 0,005 et 0,2 % en masse en termes de teneur en molybdène par rapport à la quantité totale de la composition, (C) un agent nettoyant contenant un métal à une teneur comprise entre 0,01 et 1 % en masse en termes de teneur en métal par rapport à la quantité totale de la composition, et (D) au moins un composé choisi parmi les acides aminés, chacun comportant un groupement alkyle, alcényle ou acyle en C6-24 et/ou des dérivés des acides aminés à une teneur comprise entre 0,01 et 10 % en masse.
PCT/JP2014/071388 2013-08-16 2014-08-13 Composition d'huile lubrifiante pour moteur à combustion interne WO2015022976A1 (fr)

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CN201480041176.XA CN105452427B (zh) 2013-08-16 2014-08-13 内燃机用润滑油组合物
MX2016001860A MX2016001860A (es) 2013-08-16 2014-08-13 Composicion de aceite lubricante para motor de combustion interna.
US14/904,496 US20160152920A1 (en) 2013-08-16 2014-08-13 Lubricant oil composition for internal combustion engine
CA2921209A CA2921209A1 (fr) 2013-08-16 2014-08-13 Composition d'huile lubrifiante pour moteur a combustion interne
JP2015531829A JP6270226B2 (ja) 2013-08-16 2014-08-13 内燃機関用潤滑油組成物
EP14835748.6A EP3037505A4 (fr) 2013-08-16 2014-08-13 Composition d'huile lubrifiante pour moteur à combustion interne
KR1020167004328A KR102075820B1 (ko) 2013-08-16 2014-08-13 내연 기관용 윤활유 조성물

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016129465A1 (fr) * 2015-02-13 2016-08-18 Ｊｘエネルギー株式会社 Composition d'huile lubrifiante pour moteur à combustion interne
WO2016158971A1 (fr) * 2015-03-31 2016-10-06 出光興産株式会社 Composition d'huile lubrifiante et procédé de réduction de frottement de moteur à combustion interne
EP3115444A4 (fr) * 2014-03-04 2017-11-01 Idemitsu Kosan Co., Ltd Composition d'huile lubrifiante
CN108699473A (zh) * 2016-02-24 2018-10-23 出光兴产株式会社 润滑油组合物、和该润滑油组合物的制造方法
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EP3115444A4 (fr) * 2014-03-04 2017-11-01 Idemitsu Kosan Co., Ltd Composition d'huile lubrifiante
WO2016129465A1 (fr) * 2015-02-13 2016-08-18 Ｊｘエネルギー株式会社 Composition d'huile lubrifiante pour moteur à combustion interne
WO2016158971A1 (fr) * 2015-03-31 2016-10-06 出光興産株式会社 Composition d'huile lubrifiante et procédé de réduction de frottement de moteur à combustion interne
CN108699473A (zh) * 2016-02-24 2018-10-23 出光兴产株式会社 润滑油组合物、和该润滑油组合物的制造方法
WO2022138292A1 (fr) * 2020-12-21 2022-06-30 出光興産株式会社 Composition d'huile lubrifiante

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KR20160042909A (ko) 2016-04-20
CN105452427B (zh) 2018-04-10
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EP3037505A1 (fr) 2016-06-29
CA2921209A1 (fr) 2015-02-19
US20160152920A1 (en) 2016-06-02
MX2016001860A (es) 2016-05-16
KR102075820B1 (ko) 2020-02-10
EP3037505A4 (fr) 2017-01-18
JP6270226B2 (ja) 2018-01-31

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