WO2014021350A1 - 内燃機関用潤滑油組成物 - Google Patents
内燃機関用潤滑油組成物 Download PDFInfo
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- WO2014021350A1 WO2014021350A1 PCT/JP2013/070661 JP2013070661W WO2014021350A1 WO 2014021350 A1 WO2014021350 A1 WO 2014021350A1 JP 2013070661 W JP2013070661 W JP 2013070661W WO 2014021350 A1 WO2014021350 A1 WO 2014021350A1
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- 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
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- 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
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- 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
- C10M135/12—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
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- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—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
- C10M145/12—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 monocarboxylic
- C10M145/14—Acrylate; Methacrylate
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- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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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
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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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
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
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- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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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
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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
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C10M2215/28—Amides; Imides
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- 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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- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
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- C10M2227/09—Complexes with metals
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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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
- C10N2030/02—Pour-point; Viscosity index
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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
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10N2030/54—Fuel economy
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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
- C10N2030/68—Shear stability
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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
- C10N2030/74—Noack Volatility
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Definitions
- the present invention relates to a lubricating oil composition for an internal combustion engine, and more particularly to a lubricating oil composition for an internal combustion engine having a reduced viscosity.
- Patent Document 1 discloses a fuel efficiency of an internal combustion engine by adding a polymethacrylate viscosity index improver, a salicylate metal detergent, and a molybdenum friction modifier to a mineral oil base oil having a relatively low viscosity.
- a lubricating oil composition for an internal combustion engine having a high-temperature high-shear degree at 150 ° C. of 2.6 mPa ⁇ s and a high-temperature high-shear viscosity at 100 ° C. of 5.5 to 5.9 mPa ⁇ s is disclosed.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide low fuel consumption, wear prevention, and high-temperature oxidation stability of a lubricating oil composition used in an internal combustion engine and reduced in viscosity. Is to improve the performance.
- the inventors of the present invention have added a specific metal detergent, an organomolybdenum compound, and a viscosity index improver to the lubricating oil composition for internal combustion engines that has been reduced in viscosity. It was found that the problem can be solved by blending the following, and the following invention was completed. That is, the present invention provides the following (1) to (3).
- a lubricating base oil composed of mineral oil and / or synthetic oil (A) an overbased calcium sulfonate and / or an overbased calcium phenate having a total base number of 200 mgKOH / g or more by the perchloric acid method, (B) a dinuclear organomolybdenum compound represented by the general formula (I) and / or a trinuclear organomolybdenum compound represented by the general formula (II), and (C) a polysiloxane having an SSI (Shear Stability Index) of 30 or less.
- SSI Shear Stability Index
- the total molybdenum content derived from the binuclear and trinuclear organomolybdenum compounds is 0.025% by mass or more based on the total amount of the composition
- the high-temperature high-shear viscosity at 100 ° C. is 4.0 to 5.0 mPa ⁇ s
- the high-temperature high-shear viscosity at 150 ° C. is 2.5 mPa ⁇ s or less
- the NOACK evaporation 250 ° C., 1 hour
- R 1 to R 4 represent a hydrocarbon group having 4 to 22 carbon atoms, and R 1 to R 4 may be the same or different.
- X 1 to X 4 represents a sulfur atom or an oxygen atom, respectively.
- Mo 3 Sk L n Q z (II) (In Formula (II), each L is independently a ligand having an organic group containing carbon atoms, and there are at least 21 carbon atoms in total in all of the organic groups of the ligand; n is 1 To 4; k is 4 to 7; Q is a compound that donates neutral electrons; z is 0 to 5 and includes non-stoichiometric values) (2)
- low fuel consumption, wear prevention, and high-temperature oxidation stability can be improved in the lubricating oil composition for internal combustion engines with reduced viscosity.
- the lubricating oil composition for internal combustion engines of the present embodiment includes (A) an overbased calcium sulfonate as a metallic detergent and / or Or an overbased calcium phenate, (B) an organomolybdenum compound containing at least a binuclear organomolybdenum compound and / or a trinuclear organomolybdenum compound as a friction modifier, and (C) a polyalkyl (meta) as a viscosity index improver. ) Acrylate is blended.
- the lubricating oil composition has a high temperature high shear viscosity (HTHS viscosity) at 150 ° C. of 2.5 mPa ⁇ s or less. Further, the high temperature high shear viscosity (HTHS viscosity) at 100 ° C. is 4.0 to 5.0 mPa ⁇ s. When the lubricating oil composition has an HTHS viscosity at 150 ° C. and 100 ° C. within these ranges, the fuel efficiency of the lubricating oil composition is easily improved.
- the HTHS viscosity at 150 ° C. is preferably 2.0 to 2.5 mPa ⁇ s, more preferably 2.2 to 2.5 mPa ⁇ s.
- the HTHS viscosity at 100 ° C. is preferably 4.0 to 4.75 mPa ⁇ s.
- the NOACK evaporation amount (250 ° C., 1 hour) of the lubricating oil composition is 15% by mass or less. When the NOACK evaporation amount is larger than 15% by mass, the high-temperature oxidation stability is deteriorated, and the viscosity of the lubricating oil composition tends to increase.
- the NOACK evaporation amount (250 ° C., 1 hour) is preferably 10% by mass or more in order to improve fuel efficiency.
- lubricating base oil there is no restriction
- mineral oil for example, a lubricating oil fraction obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil can be desolvated, solvent extracted, hydrocracked, solvent dewaxed, catalytic dehydrated.
- Mineral oil refined by one or more treatments such as wax, hydrorefining, or the like, or mineral oil produced by isomerizing wax, GTL WAX, and the like.
- examples of synthetic oils include polyolefins such as polybutene, ⁇ -olefin homopolymers and copolymers (for example, ethylene- ⁇ -olefin copolymers), such as polyol esters, dibasic acid esters, and phosphoric acid esters.
- polyolefins such as polybutene, ⁇ -olefin homopolymers and copolymers (for example, ethylene- ⁇ -olefin copolymers), such as polyol esters, dibasic acid esters, and phosphoric acid esters.
- esters for example, various ethers such as polyphenyl ether, polyglycol, alkylbenzene, alkylnaphthalene and the like.
- polyolefins and polyol esters are particularly preferable.
- the mineral oil may be used alone or in combination of two or more.
- the said synthetic oil may be used 1 type and may be used in combination of 2 or more type.
- one or more mineral oils and one or more synthetic oils may be used in combination.
- the viscosity of the lubricating base oil is not particularly limited, but the kinematic viscosity at 100 ° C. is preferably in the range of 2.0 to 10 mm 2 / s, more preferably 2.2 to 6.5 mm 2 / s. Range. By setting the kinematic viscosity at 100 ° C. within these ranges, the lubricating oil composition can be lowered in viscosity, and the HTHS viscosity at 100 ° C. and 150 ° C. of the lubricating oil composition can be easily set within the predetermined range described above. Furthermore, the viscosity index of the lubricating base oil is preferably 100 or more, more preferably 120 or more, and still more preferably 130 or more.
- the% C p by ring analysis is preferably 75% or more, more preferably 80% or more, and further preferably 85% or more. By setting% Cp to 75% or more, high-temperature oxidation stability in the lubricating oil composition can be improved.
- The% C p by ring analysis shows a proportion of paraffin component calculated in ring analysis n-d-M method (percentage), is a value measured in accordance with ASTM D-3238.
- the overbased calcium sulfonate and / or the overbased calcium phenate blended in the lubricating base oil of the present invention has a TBN of 200 mgKOH / g or more.
- TBN is the total base number measured by JIS K-2501: perchloric acid method.
- the total base number (TBN) of the component (A) is preferably 200 to 500 mgKOH / g, more preferably 300 to 450 mgKOH / g. If TBN is less than 200 mgKOH / g, the fuel efficiency is insufficient. Moreover, when it is 500 mgKOH / g or less, oxidation stability improves and it is preferable. Also, the combined use of neutral calcium sulfonate of 30 mgKOH / g or less is effective from the viewpoint of improving the oxidation stability.
- the overbased calcium phenate is usually obtained by overbasing the calcium salt using an alkylphenol having 1 to 50 carbon atoms, preferably an alkyl group having 10 to 30 carbon atoms, or a sulfurized alkylphenol as phenol.
- an alkylphenol having 1 to 50 carbon atoms preferably an alkyl group having 10 to 30 carbon atoms, or a sulfurized alkylphenol as phenol.
- the overbased calcium sulfonate calcium salts of various sulfonic acids can be used, and usually obtained by a method of carbonating calcium salts of various sulfonic acids.
- the sulfonic acid include aromatic petroleum sulfonic acid, alkyl sulfonic acid, aryl sulfonic acid, alkyl aryl sulfonic acid and the like.
- dodecyl benzene sulfonic acid dilauryl cetyl benzene sulfonic acid, paraffin wax-substituted benzene sulfone.
- examples thereof include acid, polyolefin-substituted benzenesulfonic acid, polyisobutylene-substituted benzenesulfonic acid, and naphthalenesulfonic acid.
- the overbased calcium sulfonate and / or the overbased calcium phenate is used in combination with a dinuclear and / or trinuclear organomolybdenum compound described later, Thickening and the like can be suppressed without deteriorating oxidation stability.
- the overbased calcium sulfonate and / or overbased calcium phenate having a TBN of 200 mgKOH / g or more is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 3.3% by weight based on the total amount of the composition. 0 mass% is mix
- the organic molybdenum compound as the component (B) includes a dinuclear organic molybdenum compound and / or a trinuclear organic molybdenum compound.
- the dinuclear organic molybdenum compound is represented by the following general formula (I)
- the trinuclear organic molybdenum compound is represented by the following general formula (II).
- R 1 to R 4 represent a hydrocarbon group having 4 to 22 carbon atoms, and R 1 to R 4 may be the same or different.
- the carbon number is 3 or less, the oil solubility is poor, and when it is 23 or more, the melting point becomes high, handling becomes worse, and the friction reducing ability is lowered.
- the carbon number is preferably 4 to 18 carbon atoms, more preferably 8 to 13 carbon atoms.
- hydrocarbon group examples include an alkyl group, an alkenyl group, an alkylaryl group, a cycloalkyl group, and a cycloalkenyl group, and a branched or straight chain alkyl group or alkenyl group is preferable, and a branched or straight chain group is preferred.
- An alkyl group is more preferred.
- the branched or straight chain alkyl group having 8 to 13 carbon atoms include n-octyl group, 2-ethylhexyl group, isononyl group, n-decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group and the like. It is done.
- R 1 and R 2 are the same alkyl group
- R 3 and R 4 are the same alkyl group from the viewpoint of solubility in base oil, storage stability and friction reducing ability
- the alkyl groups of R 3 and R 4 are preferably different.
- X 1 to X 4 represent a sulfur atom or an oxygen atom
- X 1 to X 4 may be the same or different.
- all of X 1 to X 4 may be sulfur atoms or oxygen atoms.
- each L is independently a selected ligand having an organic group containing carbon atoms; n is from 1 to 4; k varies from 4 to 7; Are selected from the group of compounds that donate neutral electrons, for example, each independently selected from water, amines, alcohols, ethers, etc .; z ranges from 0 to 5; And non-stoichiometric values.
- the organic groups of the ligand at least a total of 21 to make the compound oil-soluble, such as at least 25 carbon atoms, at least 30 carbon atoms, or at least 35 carbon atoms. There should be carbon atoms.
- the ligand is selected, for example, from the group consisting of the following ligands and mixtures thereof.
- X, X 1 , X 2 , and Y are each independently selected from the group of oxygen and sulfur, and R 1 , R 2 , and R are independently hydrogen and organic groups These may be the same or different.
- the organic group is a hydrocarbyl group such as an alkyl, aryl, substituted aryl, and ether group (eg, the carbon atom bonded to the remainder of the ligand is primary or secondary). More preferably, each ligand has the same hydrocarbyl group.
- hydrocarbyl refers to a substituent having a carbon atom that is directly bonded to the remainder of the ligand, and within the scope of the present invention, the property is primarily hydrocarbyl.
- substituents include the following: 1. Hydrocarbon substituents, ie, aliphatic substituents (eg, alkyl or alkenyl), alicyclic substituents (eg, cycloalkyl or cycloalkenyl), aromatic groups—, aliphatic groups—, and alicyclics Aromatic nuclei etc. substituted by groups-as well as cyclic groups in which the ring is completed via another position in the ligand (ie any two indicated substituents together form an alicyclic group You may).
- Substituted hydrocarbon substituents ie, those that contain, within the scope of the present invention, non-hydrocarbon groups that do not alter the predominantly hydrocarbyl properties of the substituent.
- non-hydrocarbon group include halo such as chloro and fluoro, amino, alkoxy, mercapto, alkyl mercapto, nitro, nitroso, sulfoxy and the like.
- the organic group of the ligand has a sufficient number of carbon atoms to render the compound oil soluble.
- the number of carbon atoms in each group generally ranges from 1 to about 100, preferably 1 to 30, and more preferably 4 to 20.
- Preferred ligands include alkyl xanthates, carboxylates, dialkyldithiocarbamates, and mixtures thereof. Most preferred is a dialkyldithiocarbamate.
- formation of the compound requires the selection of a ligand with an appropriate charge so that the nuclear charge is balanced.
- a compound having the formula Mo 3 S k L n Qz has a cationic nucleus surrounded by an anionic ligand, which has a net +4 charge and has the structure shown below: Indicated.
- the total charge in all ligands must be -4.
- Four monoanionic ligands are preferred. If you do not wish to be bound by any theory, two or more trinuclear nuclei may be bound by one or more ligands or connected to each other by one or more ligands. May be multivalent (ie, having a plurality of linkages to one or more nuclei). Oxygen and / or selenium may substitute for sulfur in the nucleus.
- Oil-soluble trinuclear organomolybdenum compounds are preferred, and in a suitable liquid / solvent, a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 .n (H 2 O), where n is 0 and 2 And including non-stoichiometric values) can be prepared by reacting with a suitable ligand source such as tetraalkyl thiuram disulfide.
- a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 .n (H 2 O), where n is 0 and 2 And including non-stoichiometric values
- trinuclear molybdenum compounds include a source of molybdenum such as (NH 4 ) 2 Mo 3 S 13 .n (H 2 O) in a suitable solvent; a source of ligand such as tetraalkylthiuram disulfide and dialkyldithiocarbamic acid And sulfur extractants such as cyanide ions and sulfite ions can be reacted.
- a source of molybdenum such as (NH 4 ) 2 Mo 3 S 13 .n (H 2 O) in a suitable solvent
- ligand such as tetraalkylthiuram disulfide and dialkyldithiocarbamic acid
- sulfur extractants such as cyanide ions and sulfite ions can be reacted.
- trinuclear molybdenum-sulfur halogen such as [M ′] 2 [Mo 3 S 7 A 6 ] (where M ′ is a counter ion and A is
- the chloride salt may be reacted with a ligand source such as dialkyldithiocarbamic acid in a suitable liquid / solvent to form an oil-soluble trinuclear molybdenum compound.
- a ligand source such as dialkyldithiocarbamic acid
- suitable liquid / solvents can be, for example, aqueous or organic.
- the selected ligand must have a sufficient number of carbon atoms to dissolve the compound in the lubricating oil composition.
- oil soluble does not necessarily indicate that the compound or additive is completely soluble in the oil. Such terms mean that they dissolve during use, transport and storage.
- the dinuclear and / or trinuclear organomolybdenum compound is mixed with the above-described specific metal detergent (component (A)) and the specific viscosity described later.
- component (C) index improver
- the total molybdenum content derived from the binuclear and trinuclear organic molybdenum compounds is 0.025% by mass or more based on the total amount of the composition.
- the amount is less than 0.025% by mass, the driving torque at the time of low engine rotation increases, and it becomes difficult to realize fuel efficiency reduction.
- it is less than 0.025% by mass, even when the molybdenum content in the composition is increased by blending, for example, the following mononuclear organomolybdenum compound other than binuclear and trinuclear, the engine is driven at low engine speed. Torque cannot be reduced.
- the lubricating oil composition may be formed by blending a mononuclear organic molybdenum compound in addition to the above-described binuclear and / or trinuclear organic molybdenum compound.
- a mononuclear organomolybdenum compound cannot reduce the drive torque at low engine speeds when used alone, but when used in combination with the above-mentioned binuclear and / or trinuclear organomolybdenum compounds, The driving torque is reduced, the fuel efficiency is improved, and the high-temperature oxidation stability is improved to prevent thickening.
- a mononuclear organic molybdenum compound containing a compound of the following general formula (III) and / or a compound of the general formula (IV) can be exemplified.
- a mixture of the compound of general formula (III) and the compound of general formula (IV) is obtained by sequentially reacting fatty oil, diethanolamine and a molybdenum source by, for example, a condensation method described in JP-A No. 62-108891.
- R represents a fatty oil residue, and the fatty oil contains at least 12 carbon atoms and may contain 22 or more carbon atoms. It is.
- esters are generally known as vegetable and animal oils. Examples of useful vegetable oils are derived from coconut, corn, cottonseed, linseed oil, peanut, soybean, and sunflower seeds. Similarly, animal fats such as tallow may be used.
- the molybdenum source may be an oxygen-containing molybdenum compound that can react with an intermediate reaction product of fatty oil and diethanolamine to form an ester-type molybdenum complex. Molybdenum sources include in particular ammonium molybdate, molybdenum oxide, and mixtures thereof.
- a hexavalent molybdenum compound specifically, a compound obtained by reacting molybdenum trioxide and / or molybdic acid with an amine compound, for example, described in JP-A No. 2003-252887
- the compound obtained by the production method can also be used.
- limit especially as an amine compound made to react with a hexavalent molybdenum compound Specifically, a monoamine, diamine, a polyamine, and an alkanolamine are mentioned.
- alkyl group having 1 to 30 carbon atoms such as methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine, methylpropylamine and the like (these alkyl groups may be linear or branched).
- alkanol groups may be linear or branched; methylenediamine, ethylenediamine, propylene Amines and alkylenediamines having 1 to 30 carbon atoms such as butylenediamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine; undecyldiethylamine, undecyldiethanolamine, dodecyldipropanolamine , Oleyldiethanolamine, oleylpropylenediamine, stearyltetraethylenepentamine and other monoamines, diamines, polyamines having a C8-20 alkyl group or alkenyl group, and heterocyclic compounds such as imidazoline; alkylene oxides of these compounds And adducts; and mixtures thereof.
- the mononuclear organic molybdenum compound include sulfur-containing molybdenum complexes of succinimide described in JP-B-
- the organomolybdenum compound is preferably blended in an amount of 0.04 to 0.1% by mass, based on the total amount of the composition, and 0.05 to 0.09. More preferably, it is blended by mass%.
- a friction reduction characteristic can be improved and low fuel consumption can be implement
- the effect corresponding to the compounding quantity can be exhibited by setting it as 0.1 mass% or less.
- the total molybdenum content derived from the mononuclear organic molybdenum compound is preferably 0.075% by mass or less, more preferably 0.015 to 0.07% by mass, and particularly preferably 0.05 to 0.07% by mass based on the total amount of the composition. 0.07% by mass.
- the molybdenum content derived from one nucleus is within this range, the friction reducing property of the lubricating oil composition is sufficiently enhanced by the combined use with a binuclear and / or trinuclear organic molybdenum compound.
- the molybdenum content derived from the dinuclear and trinuclear organomolybdenum compounds should be reduced for example, even when the content is less than the molybdenum content derived from a mononuclear organic molybdenum compound, the high-temperature oxidation stability and the friction reduction characteristics are enhanced, and fuel consumption can be reduced.
- the total molybdenum content derived from binuclear and trinuclear organomolybdenum compounds may be about 0.025 to 0.05 mass% when used in combination with mononuclear organomolybdenum compounds.
- the total molybdenum content should be 0.040% by mass or more. It is preferably 0.04 to 0.1% by mass, more preferably 0.05 to 0.09% by mass.
- Component (C) As (C) component mix
- SSI means a shear stability index (Shear Stability Index) and indicates the ability to resist the decomposition of the polymer (component (C)). The higher the SSI, the more unstable the polymer is to shear and the easier it is to degrade.
- Kv 0 is a value of 100 ° C. kinematic viscosity of a mixture obtained by adding a polyalkyl (meth) acrylate to a base oil.
- Kv 1 is the value of the 100 ° C. kinematic viscosity after passing the mixture of the base oil plus polyalkyl (meth) acrylate through a 30 cycle high shear Bosch diesel injector according to the procedure of ASTM D6278.
- Kv oil is the value of the 100 ° C. kinematic viscosity of the base oil.
- As the base oil a Group II base oil having a dynamic viscosity of 100 ° C. of 5.35 mm 2 / s and a viscosity index of 105 is used.
- the wear resistance of the lubricating oil composition can be enhanced.
- the high-temperature oxidation stability of the lubricating oil composition can be improved and the fuel efficiency can be improved. it can.
- the SSI of the component (C) is preferably 1 to 25. By making SSI 25 or less, the wear prevention property of a lubricating oil composition can be improved more.
- the monomer constituting the polyalkyl (meth) acrylate of the component (C) is an alkyl (meth) acrylate, and preferably an alkyl (metha) of a linear alkyl group having 1 to 18 carbon atoms or a branched alkyl group having 3 to 34 carbon atoms. ) Acrylate.
- alkyl (meth) acrylate for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, Examples include hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, and the like. Two or more of these monomers may be used as a copolymer.
- the alkyl group of these monomers may be linear or branched.
- the polyalkyl (meth) acrylate is preferably (a) having a weight average molecular weight of 10,000 to 1,000,000, more preferably 30,000 to 500,000. When the polyalkyl (meth) acrylate is in this molecular weight range, the SSI is easily set to 30 or less.
- the weight average molecular weight is a value obtained by measuring by GPC and using polystyrene as a calibration curve, and is specifically measured under the following conditions. Column: TSK gel GMH6 2 Measurement temperature: 40 ° C Sample solution: 0.5 mass% THF solution Detector: Refractive index detector Standard: Polystyrene
- the polyalkyl (meth) acrylate having an SSI of 30 or less is preferably blended in an amount of 2 to 20% by weight, more preferably 5 to 15% by weight, based on the total amount of the composition.
- the lubricating oil composition may further comprise other components other than the components (A) to (C).
- Other components include friction modifiers that also function as antioxidants such as zinc dialkyldithiophosphate, various antioxidants, ashless dispersants, ashless friction modifiers, metal deactivators, pour point depressants Agents, antifoaming agents and the like.
- a zinc dialkyldithiophosphate having a primary or secondary alkyl group having 3 to 22 carbon atoms and an alkylaryl group substituted with an alkyl group having 3 to 18 carbon atoms is used. These may be used alone or in combination of two or more.
- antioxidant blended in the lubricating oil composition examples include amine-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. These can be arbitrarily selected from known antioxidants conventionally used as antioxidants for lubricating oils.
- amine antioxidants include diphenylamines, diphenylamines such as alkylated diphenylamines having an alkyl group having 3 to 20 carbon atoms; ⁇ -naphthylamines, alkyl substituted phenyl- ⁇ -naphthylamines having 3 to 20 carbon atoms, and the like. A naphthylamine type thing is mentioned.
- phenolic antioxidants examples include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, octadecyl-3- (3,5 Monophenolic compounds such as -di-tert-butyl-4-hydroxyphenyl) propionate; 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-ethyl- 6-tert-butylphenol) and the like.
- sulfur-based antioxidant examples include dilauryl-3,3′-thiodipropionate
- examples of the phosphorus-based antioxidant include phosphite.
- ashless dispersant examples include polybutenyl succinimide having a polybutenyl group having a number average molecular weight of 900 to 3,500, polybutenylbenzylamine, polybutenylamine, and derivatives thereof such as boric acid-modified products. Can be mentioned. These ashless dispersants can be blended singly or in any combination.
- ashless friction modifiers include, for example, partial ester compounds obtained by reaction of fatty acids and aliphatic polyhydric alcohols. Use ester friction modifier.
- the fatty acid is preferably a fatty acid having a linear or branched hydrocarbon group having 6 to 30 carbon atoms, and the hydrocarbon group has more preferably 8 to 24 carbon atoms, particularly preferably 10 to 20 carbon atoms.
- the aliphatic polyhydric alcohol is a divalent to hexavalent alcohol, and examples thereof include ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and the like.
- the metal deactivator include benzotriazole, triazole derivatives, benzotriazole derivatives, thiadiazole derivatives, and the like.
- pour point depressant examples include ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, condensate of chlorinated paraffin and phenol, polymethacrylate, polyalkylstyrene, etc. Methacrylate is preferably used.
- the antifoaming agent examples include dimethylpolysiloxane and polyacrylate.
- the lubricating oil composition may contain these components (components (A) to (C)), and at least some of the blended components (components (A) to (C)) have reacted. One or more of the components (A) to (C) may be reacted with a part of any combination component other than these components (components (A) to (C)).
- the evaluation method of the lubricating oil composition of each example and comparative example is as follows. (1) Motoring driving torque Using the lubricating oil compositions of the examples and comparative examples, the camshaft of a 2 liter SOHC engine is driven by a motor, and the torque applied to the camshaft at that time is measured. The value was evaluated by motoring drive torque. At this time, the rotational speed of the camshaft was 550 rpm, and the engine oil temperature was 100 ° C. (2) Abrasion prevention test The lubricating oil composition was confirmed by measuring the kinematic viscosity at 100 ° C after shearing 30 times with a diesel injector according to ASTM D6287-07. The lower the 100 ° C.
- Examples 1 to 6, Comparative Examples 1 to 7 According to the composition of Table 1, lubricating oil compositions of Examples and Comparative Examples were prepared, and the properties of the lubricating oil compositions were measured. Moreover, according to the said evaluation method, the lubricating oil composition of each Example and the comparative example was evaluated.
- Lubricating base oil base oil A Group III 100N hydrorefined base oil, 100 ° C kinematic viscosity 4.2mm 2 / s, viscosity index 132, NOACK evaporation (250 ° C, 1 hour) 13.5% by mass, ndM ring analysis % Cp.85.5%
- Base oil B Group II 70N hydrorefined base oil, 100 ° C kinematic viscosity 3.10mm 2 / s, viscosity index 103, NOACK evaporation (250 ° C, 1 hour) 39.7% by mass, ndM ring analysis% Cp71.0%
- Metal detergent A Overbased calcium sulfonate, TBN (perchloric acid method) 300mgKOH / g, calcium content 11.1% by mass, sulfur content 1.49% by mass
- Metal-based detergent B Overbased calcium phenate, TBN (perchloric acid method) 255 mg
- SAKURA-LUBE 515 manufactured by ADEKA Co., Ltd.
- Infineum C9455B (manufactured by INFINEUM), trinuclear molybdenum dithiocarbamate represented by general formula (II), molybdenum content 5.27 mass%, sulfur content 9.04 mass% Mononuclear molybdenum compound (1): Trade name.
- MOLYVAN 855 (RT Vanderbilt Company Inc.), [2,2 '-(dodecanoylimino) diethanolato] dioxomolybdenum (VI) and [3- (dodecanoyloxy) -1,2-propanediolato] dioxo Molybdenum (VI) mixture, molybdenum content 7.9% by mass, nitrogen content 2.8% by mass Mononuclear molybdenum compound (2): Trade name.
- Other zinc dialkyldithiophosphates ZnDTP: zinc content 9.0% by mass, phosphorus content 8.2% by mass, sulfur content 17.1% by mass, alkyl group; mixture amine of secondary butyl group and secondary hexyl group
- Antioxidants Dialkyldiphenylamine, nitrogen content 4.62% by mass Phenol-based antioxidant: octadecyl-3- (3,5-di-tert-butyl 4-
- the lubricating oil compositions of the respective examples were able to reduce the viscosity and reduce the motoring drive torque, and were able to improve fuel efficiency. Further, as is apparent from the results of the anti-wear test, it was possible to prevent wear due to shear, and the rate of increase in kinematic viscosity (%) at high temperatures was low, and the high-temperature oxidation stability was excellent. On the other hand, in the lubricating oil composition of each comparative example in which any of the components (A) to (C) of the present invention is not blended or the blending amount of the component (B) is low, fuel efficiency, wear resistance, One of the high-temperature oxidation stability deteriorated.
- the lubricating oil composition for an internal combustion engine of the present invention has low fuel consumption, improved wear resistance, and high-temperature oxidation stability, and is suitable for an internal combustion engine, particularly an internal combustion engine with high fuel efficiency. Can be used.
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Abstract
Description
例えば、特許文献1には、比較的低粘度の鉱油系基油に、ポリメタアクリレート系の粘度指数向上剤、サリチレート系金属清浄剤、モリブデン系摩擦調整剤を添加することにより、内燃機関の燃費を向上できる、150℃における高温高せん断度が2.6mPa・s、100℃における高温高せん断粘度が5.5~5.9mPa・sの内燃機関用潤滑油組成物が開示されている。
しかし、例えば、特許文献1の配合をそのまま利用して潤滑油を更に低粘度化すると、燃費、特にエンジン低回転時の燃費が十分に向上するとはいえず、また、摺動部での摩耗が増大したり、高温酸化安定性が悪化したりするなどの弊害が生じる。
すなわち、本発明は、以下の(1)~(3)を提供するものである。
(1)鉱油及び/又は合成油からなる潤滑油基油に、
(A)過塩素酸法による全塩基価が200mgKOH/g以上の過塩基性カルシウムスルホネート及び/または過塩基性カルシウムフェネート、
(B)一般式(I)で示される二核の有機モリブデン化合物及び/又は一般式(II)で示される三核の有機モリブデン化合物、及び
(C)SSI(Shear Stability Index)が30以下のポリアルキル(メタ)アクリレートを配合してなり、
前記二核及び三核の有機モリブデン化合物由来のモリブデン含有量合計が、組成物全量に対して0.025質量%以上であり、
100℃における高温高せん断粘度が4.0~5.0mPa・s、150℃における高温高せん断粘度が2.5mPa・s以下であり、かつNOACK蒸発量(250℃、1時間)が15質量%以下である内燃機関用潤滑油組成物。
Mo3SkLnQz (II)
(式(II)において、Lはそれぞれ独立に、炭素原子を含有する有機基を有する、リガンドであり、リガンドの有機基全ての中には少なくとも合計21個の炭素原子が存在し;nは1から4であり;kは4から7であり;Qは、中性電子を供与する化合物であり;zは0から5であり、且つ非化学量論の値を含む)
(2)有機モリブデン化合物を組成物全量に対してモリブデン含有量で0.04~0.1質量%配合してなる上記(1)に記載の内燃機関用潤滑油組成物。
(3)前記ポリアルキル(メタ)アクリレートを組成物全量に対して2~20質量%配合してなる(1)又は(2)に記載の内燃機関用潤滑油組成物。
[内燃機関用潤滑油組成物]
本実施形態の内燃機関用潤滑油組成物(以下、単に「潤滑油組成物」と称することもある)は、潤滑油基油に、(A)金属系清浄剤として過塩基性カルシウムスルホネート及び/または過塩基性カルシウムフェネート、(B)摩擦調整剤として二核の有機モリブデン化合物及び/又は三核の有機モリブデン化合物を少なくとも含む有機モリブデン化合物、及び(C)粘度指数向上剤としてポリアルキル(メタ)アクリレートを配合してなるものである。
150℃におけるHTHS粘度は、好ましくは2.0~2.5mPa・s、より好ましくは2.2~2.5mPa・sである。また、100℃におけるHTHS粘度は、好ましくは4.0~4.75mPa・sである。
潤滑油組成物のNOACK蒸発量(250℃、1時間)は、15質量%以下となる。NOACK蒸発量が15質量%より大きくなると、高温酸化安定性が悪化して、潤滑油組成物の増粘等が起こりやすくなる。NOACK蒸発量(250℃、1時間)は、10質量%以上であることが低燃費性向上のためには好ましい。
本発明において用いる潤滑油基油としては、特に制限はなく、従来、潤滑油の基油として使用されている鉱油や合成油の中から任意のものを適宜選択して用いることができる。
鉱油としては、例えば、原油を常圧蒸留して得られる常圧残油を減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製等のうちの1つ以上の処理を行って精製した鉱油、あるいはワックスや、GTL WAXを異性化することによって製造される鉱油等が挙げられる。
100℃における動粘度をこれら範囲とすることにより、潤滑油組成物を低粘度化し、潤滑油組成物の100℃、150℃におけるHTHS粘度を上記した所定の範囲にしやすくなる。
さらに、潤滑油基油の粘度指数は、100以上が好ましく、より好ましくは120以上、さらに好ましくは130以上である。粘度指数を100以上と高くすることで、潤滑油基油の温度変化に伴って起こる粘度変化が小さくなる。
また、潤滑油基油としては、環分析による%Cpが75%以上であることが好ましく、より好ましくは80%以上、さらに好ましくは85%以上である。%Cpを75%以上とすることで、潤滑油組成物における高温酸化安定性を良好にすることができる。環分析による%Cpとは、環分析n-d-M法にて算出したパラフィン分の割合(百分率)を示し、ASTM D-3238に従って測定されたものである。
本発明の潤滑油基油に配合される過塩基性カルシウムスルホネート及び/または過塩基性カルシウムフェネートは、TBNが200mgKOH/g以上のものである。TBNは、JIS K-2501:過塩素酸法で測定された全塩基価である。
(A)成分の全塩基価(TBN)は、200~500mgKOH/gが好ましく、300~450mgKOH/gがより好ましい。TBNが200mgKOH/g未満では、低燃費性が不充分になる。また、500mgKOH/g以下とすると、酸化安定性が向上し好ましい。
また、30mgKOH/g以下の中性カルシウムスルホネートの併用も酸化安定性が向上の観点で有効である。
また、過塩基性カルシウムスルホネートは、各種スルホン酸のカルシウム塩が使用でき、通常、各種スルホン酸のカルシウム塩を炭酸化する方法により得られる。スルホン酸としては、芳香族石油スルホン酸、アルキルスルホン酸、アリールスルホン酸、アルキルアリールスルホン酸等があり、具体的には、例えばドデシルベンゼンスルホン酸、ジラウリルセチルベンゼンスルホン酸、パラフィンワックス置換ベンゼンスルホン酸、ポリオレフィン置換ベンゼンスルホン酸、ポリイソブチレン置換ベンゼンスルホン酸、ナフタレンスルホン酸などを挙げることができる。
本発明では、低粘度化された潤滑組成物において、過塩基性カルシウムスルホネート及び/または過塩基性カルシウムフェネートを、後述する二核及び/又は三核の有機モリブデン化合物と併用しても、高温酸化安定性を悪化させずに増粘等を抑えることができる。
(B)成分の有機モリブデン化合物は、二核の有機モリブデン化合物及び/又は三核の有機モリブデン化合物を含むものである。本発明において、二核の有機モリブデン化合物は、下記一般式(I)で示されるものであり、また、三核の有機モリブデン化合物は、下記一般式(II)で示されるものである。
式(I)においてX1~X4は硫黄原子又は酸素原子を表し、X1~X4は同一であってもよいし、異なっていてもよい。好ましくは硫黄原子と酸素原子の比が、硫黄原子/酸素原子=1/3~3/1、より好ましくは1.5/2.5~3/1である。上記範囲内であれば、耐腐食性や、基油に対する溶解性の面で良好な性能が得られる。また、X1~X4の全てが硫黄原子又は酸素原子であってもよい。
一般式(II)において、Lはそれぞれ独立に、炭素原子を含有する有機基を有する、選択されたリガンドであり;nは1から4であり;kは4から7の中で変化し;Qは中性電子を供与する化合物の群から選択されるものであり、例えばそれぞれ独立に、水、アミン、アルコール、及びエーテル等から選択されるものであり;zは0から5の範囲であり、且つ非化学量論の値を含む。リガンドの有機基全ての中には、例えば、少なくとも25個の炭素原子、少なくとも30個の炭素原子、又は少なくとも35個の炭素原子といったように、上記化合物を油溶性とするのに、少なくとも合計21個の炭素原子が存在しているべきである。
上記リガンドは、例えば、以下のリガンド及びその混合物からなる群から選択される。
1.炭化水素置換基、即ち、脂肪族の置換基(例えば、アルキル又はアルケニル)、脂環式の置換基(例えば、シクロアルキル又はシクロアルケニル)、芳香族基-、脂肪族基-、及び脂環式基-に置換された芳香核等、並びに環がリガンド中のもう一つの箇所を介して完結している環式基(即ち、任意の2つの示された置換基がともに脂環式基を形成してもよい)。
2.置換された炭化水素置換基、即ち、本発明の範囲内において、置換基の主にヒドロカルビルの特性を変化させない非炭化水素基を含むもの。非炭化水素基としては、例えば、特にクロロ、フルオロ等のハロ、アミノ、アルコキシ、メルカプト、アルキルメルカプト、ニトロ、ニトロソ、スルホキシ等が挙げられる。
式Mo3SkLnQzを有する化合物は、アニオン性のリガンドに囲まれたカチオン性の核を有し、そのカチオン性の核は、正味+4の電荷を有する以下に示すような構造により示される。
選択されたリガンドは、上記化合物を潤滑油組成物に溶解させる上で十分な数の炭素原子を有していなければならない。本明細書で使用される「油溶性」なる用語は、必ずしも化合物や添加物が完全に油に溶解することを示すものではない。斯かる用語は、それらが使用時、輸送時、及び保存時に溶解することを意味する。
一核の有機モリブデン化合物としては、例えば、下記一般式(III)の化合物及び/又は一般式(IV)の化合物を含む一核の有機モリブデン化合物が例示できる。これら一般式(III)の化合物と一般式(IV)の化合物の混合物は、例えば特開昭62-108891号公報に記載された縮合方法により脂肪油、ジエタノールアミン及びモリブデン源を逐次反応させることにより得られるものである。
モリブデン源は、脂肪油及びジエタノールアミンの中間反応生成物と反応しエステル型モリブデン錯体を形成できる酸素含有モリブデン化合物でよい。モリブデン源は、特にモリブデン酸アンモニウム、酸化モリブデン、及びそれらの混合物を含む。
また、一核の有機モリブデン化合物としては、特公平3-22438号公報および特開2004-2866公報に記載されているコハク酸イミドの硫黄含有モリブデン錯体等が例示できる。
また、一核の有機モリブデン化合物と、二核及び/又は三核の有機モリブデン化合物とを併用する場合、二核及び三核の有機モリブデン化合物由来のモリブデン含有量は、その配合量を少なくして、例えば、一核の有機モリブデン化合物由来のモリブデン含有量より少なくしても、高温酸化安定性及び摩擦低減特性が高められ、低燃費化が実現できる。具体的には、二核及び三核の有機モリブデン化合物由来のモリブデン含有量合計は、一核の有機モリブデン化合物と併用する場合には、0.025~0.05質量%程度であってもよい。
一方で、一核の有機モリブデン化合物を使用しない場合には、二核及び三核の有機モリブデン化合物は、配合量を高めたほうが良く、そのモリブデン含有量合計を0.040質量%以上としたほうがよく、好ましくは0.04~0.1質量%、より好ましくは0.05~0.09質量%である。
潤滑油組成物に配合される(C)成分としては、SSI30以下のポリアルキル(メタ)アクリレートを使用する。ここで、SSIとは、せん断安定性指数(Shear Stability Index)を意味し、ポリマー((C)成分)の分解に抵抗する能力を示す。SSIが大きいほど、ポリマーはせん断に対して不安定で、より分解されやすい。
(C)成分のSSIは、好ましくは1~25である。SSIを25以下とすることで、潤滑油組成物の磨耗防止性をより高めることができる。
アルキル(メタ)アクリレートを構成する好ましいモノマーとして、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、ヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、オクチル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレートなどが挙げられ、これらモノマーを2種類以上使用してコポリマーとしてもよい。これらモノマーのアルキル基は直鎖状でもよいし、分岐鎖状のものでもよい。
なお、重量平均分子量は、GPCによって測定され、ポリスチレンを検量線として得られる値であり、詳細には以下の条件で測定されるものである。
カラム : TSK gel GMH6 2本 測定温度 : 40℃
試料溶液 : 0.5質量%のTHF溶液 検出装置 : 屈折率検出器
標準 : ポリスチレン
潤滑油組成物は、上記(A)~(C)成分以外のその他成分をさらに配合してなるものであってもよい。その他成分としては、ジアルキルジチオリン酸亜鉛等の酸化防止剤としの機能も兼ね備える摩擦調整剤、各種酸化防止剤、無灰系分散剤、無灰系摩擦調整剤、金属不活性化剤、流動点降下剤、消泡剤等が挙げられる。
アミン系酸化防止剤としては、例えばジフェニルアミン、炭素数3~20のアルキル基を有するアルキル化ジフェニルアミン等のジフェニルアミン系のもの;α-ナフチルアミン、炭素数3~20のアルキル置換フェニル-α-ナフチルアミンなどのナフチルアミン系のものが挙げられる。
また、フェノール系酸化防止剤としては、例えば、2,6-ジ-tert-ブチル-4-メチルフェノール、2,6-ジ-tert-ブチル-4-エチルフェノール、オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネートなどのモノフェノール系のもの;4,4'-メチレンビス(2,6-ジ-tert-ブチルフェノール)、2,2'-メチレンビス(4-エチル-6-tert-ブチルフェノール)などのジフェノール系のもの等を挙げられる。
また硫黄系酸化防止剤としてジラウリル-3,3'-チオジプロピオネイト等、リン系酸化防止剤としてはホスファイト等が挙げられる。
これらの酸化防止剤は単独で又は複数種を任意に組合せて含有させることができるが、通常2種以上を組み合わせて使用するのが好ましい。
無灰系摩擦調整剤としては、例えば脂肪酸と脂肪族多価アルコールとの反応により得られる部分エステル化合物等のエステル系摩擦調整剤を使用する。上記脂肪酸は好ましくは炭素数6~30の直鎖状又は分岐状炭化水素基を有する脂肪酸であり、該炭化水素基の炭素数はより好ましくは8~24、特に好ましくは10~20である。また、上記脂肪族多価アルコールは2~6価のアルコールであり、エチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール等が挙げられる。
金属不活性化剤としては、ベンゾトリアゾール、トリアゾール誘導体、ベンゾトリアゾール誘導体、チアジアゾール誘導体等が挙げられる。
流動点降下剤としては、例えばエチレン-酢酸ビニル共重合体、塩素化パラフィンとナフタレンとの縮合物、塩素化パラフィンとフェノールとの縮合物、ポリメタクリレート、ポリアルキルスチレン等が挙げられ、特に、ポリメタクリレートが好ましく用いられる。
消泡剤としては、例えば、ジメチルポリシロキサン、ポリアクリレート等が挙げられる。
なお、本明細書において、成分(例えば、(A)~(C)成分)を配合してなるとは、潤滑油基油に、これら成分((A)~(C)成分)を配合することにより、潤滑油組成物が、これら成分((A)~(C)成分)を含むものであってもよく、配合した成分((A)~(C)成分)の少なくとも一部が反応しているものでもよく、(A)~(C)成分のいずれか一種以上とこれら成分((A)~(C)成分)以外の任意の配合成分の一部が反応しているものでもよい。
(1)動粘度
JIS K2283-1983に準じ、ガラス製毛管式粘度計を用いて測定した値である。
(2)粘度指数
JIS K 2283に準拠して測定した値である。
(3)NOACK蒸発量
ASTM D5800に規定の方法に従って測定した値である。
(4)高温高せん断粘度(HTHS粘度)
ASTM D4683及びASTM D6616の方法により、TBS粘度計(Tapered Bearing Simulator Viscometer)を用いて測定した。試験条件を以下に示す。
・せん断速度 :106sec-1
・回転数(モーター) :3000rpm
・間隔(ローター/ステーター):3μm
・油温:100℃及び150℃
(1)モータリング駆動トルク
各実施例、比較例の潤滑油組成物を用いて、排気量2LのSOHCエンジンのカムシャフトをモータで駆動し、その際にカムシャフトにかかるトルクを測定し、その値をモータリング駆動トルクで評価した。このとき、カムシャフトの回転数は、550rpm、エンジン油温は100℃とした。
(2)磨耗防止性試験
潤滑油組成物について、ASTM D6287-07に従って、ディーゼルインジェクタで30回せん断した後の100℃動粘度を測定することにより確認した。100℃動粘度が低いほど磨耗防止性が低くなる。
(3)高温酸化安定性試験
潤滑油組成物について、NOACK(250℃、4時間)の方法に従い高温酸化させ、高温酸化前と高温酸化後の動粘度(40℃)を測定して、動粘度(40℃)増加率を測定した。
表1の配合に従って、各実施例、比較例の潤滑油組成物を作製し、その潤滑油組成物の性状を測定した。また、上記評価方法に従って、各実施例、比較例の潤滑油組成物を評価した。
(1)潤滑油基油
基油A:GroupIII 100N水素化精製基油、100℃動粘度 4.2mm2/s、粘度指数132、NOACK蒸発量(250℃、1時間)13.5質量%, n-d-M環分析 %Cp.85.5%
基油B:GroupII 70N水素化精製基油、100℃動粘度 3.10mm2/s、粘度指数103、NOACK蒸発量(250℃、1時間)39.7質量%, n-d-M環分析 %Cp71.0%
(2)金属系清浄剤(成分(A))
金属系清浄剤A:過塩基性カルシウムスルホネート、TBN(過塩素酸法)300mgKOH/g、カルシウム含有量11.1質量%、硫黄含有量1.49質量%
金属系清浄剤B:過塩基性カルシウムフェネート、TBN(過塩素酸法)255mgKOH/g、カルシウム含有量9.3質量%、硫黄含有量3.0質量%
金属系清浄剤C:過塩基性カルシウムサリシレート、TBN(過塩素酸法)225mgKOH/g、カルシウム含有量7.8質量%、硫黄含有量0.2質量%
(3)有機モリブデン化合物((B)成分)
二核モリブデン化合物:商品名.SAKURA-LUBE 515(株式会社ADEKA製)、R1~R4それぞれの炭素数が8又は13であり、X1~X4が酸素原子である一般式(I)で示される二核モリブデンジチオカルバメート、モリブデン含有量10.0質量%、硫黄含有量11.5質量%
三核モリブデン化合物:商品名.Infineum C9455B(INFINEUM社製)、一般式(II)で示される三核モリブデンジチオカルバメート、モリブデン含有量5.27質量%、硫黄含有量9.04質量%
一核モリブデン化合物(1):商品名.MOLYVAN 855(R. T. Vanderbilt Company Inc.製)、[2,2´‐(ドデカノイルイミノ)ジエタノラト]ジオキソモリブデン(VI)と[3-(ドデカノイルオキシ)-1,2-プロパンジオラト]ジオキソモリブデン(VI)の混合物、モリブデン含有量7.9質量%、窒素含有量2.8質量%
一核モリブデン化合物(2):商品名.SAKURA-LUBE S-710(株式会社ADEKA製)、モリブデン酸ジイソトリデシルアミン、モリブデン含有量10.0質量%
(4)粘度指数向上剤(成分(C))
粘度指数向上剤A:ポリアルキル(メタ)アクリレート、質量平均分子量38万、SSI=20
粘度指数向上剤B:ポリアルキル(メタ)アクリレート、質量平均分子量42万、SSI=53
(5)その他
ジアルキルジチオリン酸亜鉛(ZnDTP):亜鉛含有量9.0質量%、リン含有量8.2質量%、硫黄含有量17.1質量%、アルキル基;第2級ブチル基と第2級ヘキシル基の混合物
アミン系酸化防止剤:ジアルキルジフェニルアミン、窒素含有量4.62質量%
フェノール系酸化防止剤:オクタデシル-3-(3,5-ジ-tert-ブチル4-ヒドロキシフェニル)プロピオネート
ポリブテニルコハク酸ビスイミド:ポリブテニル基の数平均分子量2300、窒素含有量1.0質量%、塩素含有量0.01質量%以下
エステル系摩擦調整剤:グリセリンモノオレート
表1中のその他の添加剤としては、金属不活性化剤、流動点降下剤及び消泡剤を配合した。
Claims (3)
- 鉱油及び/又は合成油からなる潤滑油基油に、
(A)過塩素酸法による全塩基価が200mgKOH/g以上の過塩基性カルシウムスルホネート及び/または過塩基性カルシウムフェネート、
(B)下記の一般式(I)で示される二核の有機モリブデン化合物、及び/又は下記一般式(II)で示される三核の有機モリブデン化合物、及び
(C)SSI30以下のポリアルキル(メタ)アクリレートを配合してなり、
前記二核及び三核の有機モリブデン化合物由来のモリブデン含有量合計が、組成物全量に対して0.025質量%以上であり、
100℃における高温高せん断粘度が4.0~5.0mPa・s、150℃における高温高せん断粘度が2.5mPa・s以下であり、かつNOACK蒸発量(250℃、1時間)が15質量%以下である内燃機関用潤滑油組成物。
Mo3SkLnQz (II)
(式(II)において、Lはそれぞれ独立に、炭素原子を含有する有機基を有する、リガンドであり、リガンドの有機基全ての中には少なくとも合計21個の炭素原子が存在し;nは1から4であり;kは4から7であり;Qは、中性電子を供与する化合物であり;zは0から5であり、且つ非化学量論の値を含む) - 有機モリブデン化合物を組成物全量に対してモリブデン含有量で0.04~0.1質量%配合してなる請求項1に記載の内燃機関用潤滑油組成物。
- 前記ポリアルキル(メタ)アクリレートを組成物全量に対して2~20質量%配合してなる請求項1又は2に記載の内燃機関用潤滑油組成物。
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JP2017171864A (ja) * | 2016-03-25 | 2017-09-28 | 出光興産株式会社 | 潤滑油組成物、内燃機関、及び内燃機関の潤滑方法 |
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US10920167B2 (en) | 2016-07-11 | 2021-02-16 | Adeka Corporation | Lubricant composition and lubricating oil composition |
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Also Published As
Publication number | Publication date |
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EP2883946A1 (en) | 2015-06-17 |
CN104508098A (zh) | 2015-04-08 |
TW201410864A (zh) | 2014-03-16 |
US9587200B2 (en) | 2017-03-07 |
JP6097296B2 (ja) | 2017-03-15 |
EP2883946B1 (en) | 2019-06-12 |
CN104508098B (zh) | 2018-04-10 |
EP2883946A4 (en) | 2016-05-11 |
KR20150036227A (ko) | 2015-04-07 |
JPWO2014021350A1 (ja) | 2016-07-21 |
US20150175927A1 (en) | 2015-06-25 |
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