WO2017109084A1 - Lubricating oil composition for internal combustion engines - Google Patents

Lubricating oil composition for internal combustion engines Download PDF

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Publication number
WO2017109084A1
WO2017109084A1 PCT/EP2016/082402 EP2016082402W WO2017109084A1 WO 2017109084 A1 WO2017109084 A1 WO 2017109084A1 EP 2016082402 W EP2016082402 W EP 2016082402W WO 2017109084 A1 WO2017109084 A1 WO 2017109084A1
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WO
WIPO (PCT)
Prior art keywords
internal combustion
combustion engines
lubricating oil
dlc
oil composition
Prior art date
Application number
PCT/EP2016/082402
Other languages
French (fr)
Inventor
Kenji Oohara
Kiyoshi Hanyuda
Kumiko KAMATA
Izumi Kobayashi
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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 B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Priority to US16/064,520 priority Critical patent/US20190002793A1/en
Priority to BR112018013044A priority patent/BR112018013044A2/en
Priority to RU2018126972A priority patent/RU2729063C2/en
Priority to EP16820273.7A priority patent/EP3394227B1/en
Priority to CN201680075362.4A priority patent/CN108431186A/en
Publication of WO2017109084A1 publication Critical patent/WO2017109084A1/en

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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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/46—Lubricating compositions characterised by the base-material being a macromolecular compound containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • 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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/04—Specified molecular weight or molecular weight distribution
    • 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
    • C10M2205/17—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
    • 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
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • 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
    • C10M2219/06—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
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • 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
    • 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
    • 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
    • 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
    • C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal

Definitions

  • the present invention relates to a lubricating oil composition for internal combustion engines, which contains prescribed components.
  • WO2005014763 proposes a lubricating oil that contains a lubricant base oil and a sulfur-containing molybdenum complex.
  • "Wear Analysis of DLC Coating in Oil Containing Mo-DTC” Takatoshi Shinyoshi, Yoshio Fuwa, Yoshinori Ozaki, JSAE 20077103 SAE 2007-01-1969 proposes a case in which wear of a film is facilitated when MoDTC is combined with a hydrogen-containing DLC film (a-C:H) .
  • the purpose of the present invention is to provide a lubricating oil composition for internal combustion engines, which can realize low friction in both internal combustion engines equipped with DLC and internal combustion engines not equipped with DLC.
  • the inventors of the present invention found that by blending a polyalkylene glycol (PAG) and a specific organic molybdenum compound as additional components in a lubricating oil composition for internal combustion engines, specifying the molecular weight of the PAG and specifying the blending quantity of the PAG, it was possible to realize low friction in internal combustion engines regardless of the presence or absence of DLC, and thereby completed the present invention.
  • PAG polyalkylene glycol
  • the present invention is a lubricating oil composition for internal combustion engines, which is characterized in that the lubricating oil composition for internal combustion engines is a composition obtained by blending a molybdenum dithiocarbamate (MoDTC) and a polyalkylene glycol (PAG) in a base oil, the weight average molecular weight of the polyalkylene glycol is 2750-4500, and the content of the polyalkylene glycol is not less than 0.005 mass% and less than 10 mass% relative to the total mass of the composition.
  • MoDTC molybdenum dithiocarbamate
  • PAG polyalkylene glycol
  • the lubricating oil composition for internal combustion engines of the present invention may be a lubricating oil composition for internal combustion engines that can be used in both internal combustion engines equipped with DLC and internal combustion engines not equipped with DLC (conventional internal combustion engines) .
  • a lubricating oil composition for internal combustion engines which can be used in both internal combustion engines equipped with DLC and internal combustion engines not equipped with DLC. Explanations will now be given of the constitution, properties and intended uses of lubricating oil compositions for internal combustion engines according to the present aspect .
  • a molybdenum dithiocarbamate (MoDTC) and a polyalkylene glycol (PAG) are blended in a base oil, and other additives may, if necessary, also be blended in the base oil.
  • MoDTC molybdenum dithiocarbamate
  • PAG polyalkylene glycol
  • the base oil used in the present aspect is not particularly limited, and mineral oils, synthetic oils, vegetable and animal oils and mixtures thereof used in conventional lubricating oils and grease compositions can be used as appropriate.
  • Specific examples thereof include base oils of groups 1 to 5 in the API (American Petroleum Institute) base oil categories.
  • API base oil categories are broad classifications of base oil materials defined by the American Petroleum Institute in order to prepare guidelines for lubricant base oils. In order to achieve excellent oxidation stability, a base oil belonging to group 3 is preferred.
  • the kinematic viscosity of the base oil is not particularly limited, but from practical perspectives such as preventing wear and achieving fuel efficiency, the kinematic viscosity at 100°C is preferably 2-32 mm 2 /s, and more preferably 3-8 mm 2 /s.
  • the viscosity index of the base oil is not particularly limited, but from practical perspectives such as preventing wear and achieving fuel efficiency, the viscosity index is preferably 10-200, and more preferably 100-200.
  • the molybdenum dithiocarbamate (MoDTC) used in the present aspect can be, for example, a molybdenum dialkyldithiocarbamate represented by formula (1) below.
  • R 1 to R 4 each denote an alkyl group
  • X 1 to X 4 each denote an oxygen atom or sulfur atom.
  • the alkyl groups R 1 , R 2 , R 3 and R 4 contained in the molybdenum dialkyldithiocarbamate represented by formula (1) are each independently a lipophilic group having 2-30 carbon atoms, and it is preferable for at least one of these four lipophilic groups to be a secondary lipophilic group.
  • the molybdenum dithiocarbamate (MoDTC) used in the present aspect is preferably a molybdenum
  • R 1 to R 4 each denote an alkyl group.
  • the content of the molybdenum dithiocarbamate used in the present aspect is not particularly limited, but is preferably 50-1500 ppm in terms of molybdenum content relative to the total mass of lubricating oil composition.
  • the polyalkylene glycol (PAG) is a compound in which a plurality of alkylene glycols are polymerized, and is represented by the general formula HO- ( C n H m O) S -H or the general formula HO- (C n H m O) s -OH, but is not particularly limited.
  • PAG polyalkylene glycol
  • the weight average molecular weight of the polyalkylene glycol according to the present aspect is 2750-4500, and preferably 3000-4000.
  • the polyalkylene glycol according to the present aspect is contained at a quantity of not less than 0.05 mass% and less than 10 mass%, preferably 0.5-8.0 mass%, and more preferably 1.0-5.0 mass%, relative to the total mass of the lubricating oil composition.
  • additives such as ash-free dispersing agents, wear prevention agents, extreme pressure additives, metal-based cleaning agents, antioxidants, viscosity index-improving agents, friction modifiers, rust inhibitors, non-ionic surfactants, demulsifiers, metal deactivating agents and anti-foaming agents, can be blended as optional components in the lubricating oil compositions according to the present aspect .
  • the HTHS viscosity of the lubricating oil composition of the present invention at 150°C and 10 6 s _1 is preferably 3.5 mPa-s or less, more preferably 3.0 mPa-s or less, further preferably 2.8 mPa-s or less, and particularly preferably 2.7 mPa-s or less.
  • this HTHS viscosity is preferably 1.4 mPa-s or more, more preferably 2.0 mPa-s or more, further preferably 2.3 mPa-s or more, particularly preferably 2.5 mPa-s or more, and most preferably 2.6 mPa-s or more.
  • this high temperature high shear viscosity is a numerical value determined using the test method disclosed in ASTM D5481.
  • lubricating oil compositions according to the present aspect is not particularly limited as long as the compositions are used in internal combustion engines .
  • the lubricating oil compositions according to the present aspect by setting the weight average molecular weight and content of the polyalkylene glycol to fall within specified ranges in the composition, which is obtained by blending a molybdenum dithiocarbamate and the polyalkylene glycol in a base oil, it is possible to reduce friction on surfaces not equipped with DLC as well as significantly reducing friction on surfaces equipped with DLC, and it is therefore possible to realize low friction regardless of the presence or absence of DLC .
  • the lubricating oil composition according to the present aspect can be used in both internal combustion engines equipped with DLC and internal combustion engines not equipped with DLC (that is, can be used as a lubricating oil composition for internal combustion engines equipped with DLC and internal combustion engines not equipped with DLC) .
  • an internal combustion engine equipped with DLC is an internal combustion engine in which all, or at least some, surfaces that are friction surfaces are coated with DLC.
  • DLC diamond-like carbon
  • DLC diamond-like carbon
  • the bonding between carbon atoms comprises both a diamond structure (SP3 bonds) and graphite bonds (SP2 bonds) .
  • SP3 bonds diamond structure
  • SP2 bonds graphite bonds
  • these include a-C (amorphous carbon) comprising only elemental carbon, hydrogen-containing a-C : H (hydrogenated amorphous carbon) and MeC, which partially contains a metal element such as titanium (Ti) or molybdenum (Mo) .
  • the coefficient of friction tends to increase as the content of hydrogen in DLC increases, but it is possible to select an arbitrary hydrogen content, such as 10 atom% or less, 5 atom% or less, or 0.5 atom% or less. Examples
  • the raw materials used in the working examples are as follows .
  • PEG#400 manufactured by NOF Corporation, PEG, weight average molecular weight 100
  • D-250 (manufactured by NOF Corporation, PPG, OH groups at both terminals, weight average molecular weight 250)
  • D-1000 (manufactured by NOF Corporation, PPG, OH groups at both terminals, weight average molecular weight 1000)
  • D-2000 (manufactured by NOF Corporation, PPG, OH groups at both terminals, weight average molecular weight 2000)
  • D-4000 (manufactured by NOF Corporation, PPG, OH groups at both terminals, weight average molecular weight 4000)
  • MB7 manufactured by NOF Corporation, PPG, OH group at one terminal, weight average molecular weight 700)
  • MB700 manufactured by NOF Corporation, PPG, OH group at one terminal, weight average molecular weight 3000
  • Sakuralube-165 manufactured by ADEKA, molybdenum content 4.5 mass%, sulfur content 5.0 massl
  • GF-5DI compositional details: metal cleaning agent, ash-free dispersing agent, zinc dithiophosphate, rust inhibitor, corrosion prevention agent, antioxidant, ash-free friction modifier, and the like.
  • Lubricating oil compositions were obtained by blending and formulating the raw materials mentioned above at the proportions (mass percentages) shown in the Tables. Tests
  • the lubricating oil compositions of the working examples and comparative examples were applied to sliding surfaces consisting of a DLC-coated sliding member, which was obtained by coating with a diamond-like carbon having a hydrogen content of 0.5 atom%, and a sliding member consisting of a SUJ2 material, and a friction test was carried out .
  • a friction test was carried out .
  • Using a cylinder-on-disk SRV friction tester (ASTM D 6425 ) the coefficient of friction was measured. The conditions are as follows: Temperature: 80°C, frequency: 50 Hz, load: 100 N.
  • the present invention achieves a friction-reducing effect on both metal contacting faces if a DLC film is present. Because a low coefficient of friction reduces the amount of frictional heat generated, it is possible to suppress softening of a surface caused by carbonization (an increase in the amount of SP2 bonding) caused by friction in the case of a DLC surface and improve the wear resistance of the DLC, and a reduction in frictional resistance leads to a reduction in stress within a DLC film and between a DLC film and the member therebelow, and lessens the problem of a DLC coating film detaching . In this way, the present invention contributes to fuel efficiency and maintenance of a favorable state in a DLC lubrication system.
  • the organic molybdenum compound exhibits functionality, a reduction in friction occurs and fuel efficiency is realized even in a non-DLC lubricating system.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)

Abstract

To provide a lubricating oil composition for internal combustion engines, which can realize low friction in both internal combustion engines equipped with a DLC and internal combustion engines not equipped with a DLC. [Solution] a lubricating oil composition for internal combustion engines, which is characterized in that the lubricating oil composition for internal combustion engines is a composition obtained by blending a molybdenum dithiocarbamate (MoDTC) and a polyalkylene glycol (PAG) in a base oil, the weight average molecular weight of the polyalkylene glycol is 2750-4500 and the content of the polyalkylene glycol is not less than 0.05 mass% and less than 10 mass% relative to the total mass of the composition.

Description

LUBRICATING OIL COMPOSITION FOR INTERNAL COMBUSTION
ENGINES
Field of the Invention
The present invention relates to a lubricating oil composition for internal combustion engines, which contains prescribed components.
Background of the Invention
Many lubricating oil compositions have been proposed in the past. For example, WO2005014763 proposes a lubricating oil that contains a lubricant base oil and a sulfur-containing molybdenum complex. Meanwhile, "Wear Analysis of DLC Coating in Oil Containing Mo-DTC", Takatoshi Shinyoshi, Yoshio Fuwa, Yoshinori Ozaki, JSAE 20077103 SAE 2007-01-1969 proposes a case in which wear of a film is facilitated when MoDTC is combined with a hydrogen-containing DLC film (a-C:H) .
In the case of the lubricating oil composition according to WO2005014763, however, evaluations are conducted using a real engine. Friction reduction performance evaluations are conducted on systems in which both DLC contacting faces and non-DLC contacting faces not having a DLC film, such as ordinary steel materials for engines, are simultaneously lubricated, but if a steel material lubrication effect is greater than a DLC contacting face lubrication effect, it is not clear whether this is suitable for DLC films. In addition, a means for solving the problem in "Wear Analysis of DLC Coating in Oil Containing Mo-DTC", Takatoshi Shinyoshi, Yoshio Fuwa, Yoshinori Ozaki, JSAE 20077103 SAE 2007-01-1969 is not given .
With these circumstances in mind, the purpose of the present invention is to provide a lubricating oil composition for internal combustion engines, which can realize low friction in both internal combustion engines equipped with DLC and internal combustion engines not equipped with DLC.
Summary of the Invention
As a result of diligent research carried out in order to achieve this purpose, the inventors of the present invention found that by blending a polyalkylene glycol (PAG) and a specific organic molybdenum compound as additional components in a lubricating oil composition for internal combustion engines, specifying the molecular weight of the PAG and specifying the blending quantity of the PAG, it was possible to realize low friction in internal combustion engines regardless of the presence or absence of DLC, and thereby completed the present invention. That is, the present invention is a lubricating oil composition for internal combustion engines, which is characterized in that the lubricating oil composition for internal combustion engines is a composition obtained by blending a molybdenum dithiocarbamate (MoDTC) and a polyalkylene glycol (PAG) in a base oil, the weight average molecular weight of the polyalkylene glycol is 2750-4500, and the content of the polyalkylene glycol is not less than 0.005 mass% and less than 10 mass% relative to the total mass of the composition.
Furthermore, the lubricating oil composition for internal combustion engines of the present invention may be a lubricating oil composition for internal combustion engines that can be used in both internal combustion engines equipped with DLC and internal combustion engines not equipped with DLC (conventional internal combustion engines) .
Detailed Description of the Invention
According to the present invention, it is possible to provide a lubricating oil composition for internal combustion engines, which can be used in both internal combustion engines equipped with DLC and internal combustion engines not equipped with DLC. Explanations will now be given of the constitution, properties and intended uses of lubricating oil compositions for internal combustion engines according to the present aspect .
In the lubricating oil compositions for internal combustion engines according to the present aspect, a molybdenum dithiocarbamate (MoDTC) and a polyalkylene glycol (PAG) are blended in a base oil, and other additives may, if necessary, also be blended in the base oil. A detailed explanation will now be given of the lubricating oil compositions for internal combustion engines according to the present aspect, but the present invention is in no way limited to these compositions.
The base oil used in the present aspect is not particularly limited, and mineral oils, synthetic oils, vegetable and animal oils and mixtures thereof used in conventional lubricating oils and grease compositions can be used as appropriate. Specific examples thereof include base oils of groups 1 to 5 in the API (American Petroleum Institute) base oil categories. Here, API base oil categories are broad classifications of base oil materials defined by the American Petroleum Institute in order to prepare guidelines for lubricant base oils. In order to achieve excellent oxidation stability, a base oil belonging to group 3 is preferred.
The kinematic viscosity of the base oil is not particularly limited, but from practical perspectives such as preventing wear and achieving fuel efficiency, the kinematic viscosity at 100°C is preferably 2-32 mm2/s, and more preferably 3-8 mm2/s.
The viscosity index of the base oil is not particularly limited, but from practical perspectives such as preventing wear and achieving fuel efficiency, the viscosity index is preferably 10-200, and more preferably 100-200.
The molybdenum dithiocarbamate (MoDTC) used in the present aspect can be, for example, a molybdenum dialkyldithiocarbamate represented by formula (1) below.
Figure imgf000006_0001
In formula 1, R1 to R4 each denote an alkyl group, and X1 to X4 each denote an oxygen atom or sulfur atom.
The alkyl groups R1, R2, R3 and R4 contained in the molybdenum dialkyldithiocarbamate represented by formula (1) are each independently a lipophilic group having 2-30 carbon atoms, and it is preferable for at least one of these four lipophilic groups to be a secondary lipophilic group.
Here, the molybdenum dithiocarbamate (MoDTC) used in the present aspect is preferably a molybdenum
dithiocarbamate represented by formula (2) below.
Figure imgf000007_0001
In formula (2), R1 to R4 each denote an alkyl group.
The content of the molybdenum dithiocarbamate used in the present aspect is not particularly limited, but is preferably 50-1500 ppm in terms of molybdenum content relative to the total mass of lubricating oil composition.
The polyalkylene glycol (PAG) is a compound in which a plurality of alkylene glycols are polymerized, and is represented by the general formula HO- ( CnHmO) S-H or the general formula HO- (CnHmO) s-OH, but is not particularly limited. In order to use a material having low oil solubility, it is preferable to use one or more compounds selected from among polyethylene glycol, polypropylene glycol and polybutylene glycol. From the perspective of compatibility with the base oil, polypropylene glycol and polybutylene glycol are more preferred. In addition, the weight average molecular weight of the polyalkylene glycol according to the present aspect is 2750-4500, and preferably 3000-4000. By setting the weight average molecular weight of the polyalkylene glycol to fall within such a range, compatibility with the base oil is improved and the coefficient of friction can be lowered.
Furthermore, the polyalkylene glycol according to the present aspect is contained at a quantity of not less than 0.05 mass% and less than 10 mass%, preferably 0.5-8.0 mass%, and more preferably 1.0-5.0 mass%, relative to the total mass of the lubricating oil composition. By setting the content of the polyalkylene glycol to fall within such a range, compatibility with the base oil is improved and the lubricating properties of the polyalkylene glycol can be exhibited.
One or more of a variety of additives, such as ash-free dispersing agents, wear prevention agents, extreme pressure additives, metal-based cleaning agents, antioxidants, viscosity index-improving agents, friction modifiers, rust inhibitors, non-ionic surfactants, demulsifiers, metal deactivating agents and anti-foaming agents, can be blended as optional components in the lubricating oil compositions according to the present aspect . The HTHS viscosity of the lubricating oil composition of the present invention at 150°C and 106 s_1 is preferably 3.5 mPa-s or less, more preferably 3.0 mPa-s or less, further preferably 2.8 mPa-s or less, and particularly preferably 2.7 mPa-s or less. In addition, this HTHS viscosity is preferably 1.4 mPa-s or more, more preferably 2.0 mPa-s or more, further preferably 2.3 mPa-s or more, particularly preferably 2.5 mPa-s or more, and most preferably 2.6 mPa-s or more. Moreover, this high temperature high shear viscosity is a numerical value determined using the test method disclosed in ASTM D5481.
The scope of use of the lubricating oil compositions according to the present aspect is not particularly limited as long as the compositions are used in internal combustion engines .
In particular, according to the lubricating oil compositions according to the present aspect, by setting the weight average molecular weight and content of the polyalkylene glycol to fall within specified ranges in the composition, which is obtained by blending a molybdenum dithiocarbamate and the polyalkylene glycol in a base oil, it is possible to reduce friction on surfaces not equipped with DLC as well as significantly reducing friction on surfaces equipped with DLC, and it is therefore possible to realize low friction regardless of the presence or absence of DLC . As a result, the lubricating oil composition according to the present aspect can be used in both internal combustion engines equipped with DLC and internal combustion engines not equipped with DLC (that is, can be used as a lubricating oil composition for internal combustion engines equipped with DLC and internal combustion engines not equipped with DLC) .
Moreover, an internal combustion engine equipped with DLC is an internal combustion engine in which all, or at least some, surfaces that are friction surfaces are coated with DLC. In addition, DLC (diamond-like carbon) generally means an amorphous substance constituted mainly from elemental carbon, and in which the bonding between carbon atoms comprises both a diamond structure (SP3 bonds) and graphite bonds (SP2 bonds) . Specifically, these include a-C (amorphous carbon) comprising only elemental carbon, hydrogen-containing a-C : H (hydrogenated amorphous carbon) and MeC, which partially contains a metal element such as titanium (Ti) or molybdenum (Mo) . Furthermore, the coefficient of friction tends to increase as the content of hydrogen in DLC increases, but it is possible to select an arbitrary hydrogen content, such as 10 atom% or less, 5 atom% or less, or 0.5 atom% or less. Examples
The present invention will now be explained in greater detail through the use of working examples and comparative examples, but is not limited to these examples. Preparation of lubricating oil composition
The raw materials used in the working examples are as follows .
Base oil
A GTL (gas-to-liquid) base oil synthesized by the Fischer-Tropsch process, which belongs to group 3, has a kinematic viscosity at 100°C of 7.58 mm2/s, and has a viscosity index of 141.
Additives
PAG
PEG#400 (manufactured by NOF Corporation, PEG, weight average molecular weight 100)
D-250 (manufactured by NOF Corporation, PPG, OH groups at both terminals, weight average molecular weight 250) D-1000 (manufactured by NOF Corporation, PPG, OH groups at both terminals, weight average molecular weight 1000) D-2000 (manufactured by NOF Corporation, PPG, OH groups at both terminals, weight average molecular weight 2000) D-4000 (manufactured by NOF Corporation, PPG, OH groups at both terminals, weight average molecular weight 4000) MB7 (manufactured by NOF Corporation, PPG, OH group at one terminal, weight average molecular weight 700)
MB700 (manufactured by NOF Corporation, PPG, OH group at one terminal, weight average molecular weight 3000)
50MB-2 (manufactured by NOF Corporation, PPG-PEG, weight average molecular weight 200)
MoDTC
Sakuralube-165 (manufactured by ADEKA, molybdenum content 4.5 mass%, sulfur content 5.0 massl)
1. Viscosity index improving agent
Polymethacrylate-based viscosity index improving agent Packaged additives
GF-5DI (compositional details: metal cleaning agent, ash-free dispersing agent, zinc dithiophosphate, rust inhibitor, corrosion prevention agent, antioxidant, ash-free friction modifier, and the like) .
Lubricating oil compositions were obtained by blending and formulating the raw materials mentioned above at the proportions (mass percentages) shown in the Tables. Tests
Friction test
The lubricating oil compositions of the working examples and comparative examples were applied to sliding surfaces consisting of a DLC-coated sliding member, which was obtained by coating with a diamond-like carbon having a hydrogen content of 0.5 atom%, and a sliding member consisting of a SUJ2 material, and a friction test was carried out . Using a cylinder-on-disk SRV friction tester (ASTM D 6425 ) , the coefficient of friction was measured. The conditions are as follows: Temperature: 80°C, frequency: 50 Hz, load: 100 N. A similar friction test was carried out by applying the lubricating oil compositions of the working examples and comparative examples to sliding surfaces consisting of a SUJ2 sliding member not coated with a DLC and a sliding member consisting of a SUJ2 material. The results are shown in the tables.
As shown in the tables, the present invention achieves a friction-reducing effect on both metal contacting faces if a DLC film is present. Because a low coefficient of friction reduces the amount of frictional heat generated, it is possible to suppress softening of a surface caused by carbonization (an increase in the amount of SP2 bonding) caused by friction in the case of a DLC surface and improve the wear resistance of the DLC, and a reduction in frictional resistance leads to a reduction in stress within a DLC film and between a DLC film and the member therebelow, and lessens the problem of a DLC coating film detaching . In this way, the present invention contributes to fuel efficiency and maintenance of a favorable state in a DLC lubrication system.
According to the present invention, in the case of metal surfaces also, the organic molybdenum compound exhibits functionality, a reduction in friction occurs and fuel efficiency is realized even in a non-DLC lubricating system.
Table 1 - comparative Examples 1-8 and working Examples 1-2
Figure imgf000015_0001
Table 2 - comparative Examples 9-16 and working Example 3
Figure imgf000016_0001

Claims

C L A I M S
1. A lubricating oil composition for internal combustion engines, which is characterized in that the lubricating oil composition for internal combustion engines is a composition obtained by blending a molybdenum
dithiocarbamate (MoDTC) and a polyalkylene glycol (PAG) in a base oil, the weight average molecular weight of the polyalkylene glycol is 2750-4500 and the content of the polyalkylene glycol is not less than 0.05 mass% and less than 10 mass% relative to the total mass of the composition.
2. The lubricating oil composition for internal combustion engines according to claim 1, which can be used in both internal combustion engines equipped with a DLC and internal combustion engines not equipped with a DLC.
3. The lubricating oil composition for internal combustion engines according to claim 1 or claim 2, wherein the polyalkylene glycol is polypropylene glycol (PPG) .
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