WO2011125881A1 - 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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- WO2011125881A1 WO2011125881A1 PCT/JP2011/058293 JP2011058293W WO2011125881A1 WO 2011125881 A1 WO2011125881 A1 WO 2011125881A1 JP 2011058293 W JP2011058293 W JP 2011058293W WO 2011125881 A1 WO2011125881 A1 WO 2011125881A1
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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
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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- 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
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- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/02—Carbon; Graphite
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
- C10M105/46—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
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- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/06—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
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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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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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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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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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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
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- C10N2030/54—Fuel economy
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Definitions
- the present invention relates to a lubricating oil composition for an internal combustion engine.
- coking In an internal combustion engine such as a gasoline engine or a diesel engine, carbon deposition called coking may occur inside the engine during use. When coking occurs, there is a possibility of causing various obstacles due to insufficient cooling inside the engine or obstruction of the flow of the lubricating oil itself. In particular, in an engine equipped with a turbo mechanism, coking that occurs in a turbo bearing portion, a housing, or an oil supply passage is a problem. In addition, coking is more likely to occur when using a low viscosity and easy to mist lubricant. Therefore, in order to prevent the occurrence of mist and coking, it is effective to use a lubricating oil having a low evaporation property.
- An object of the present invention is to provide a lubricating oil composition for an internal combustion engine that has low evaporation properties, is excellent in mist resistance and coking resistance, and is also excellent in fuel efficiency.
- the present invention provides the following lubricating oil composition for an internal combustion engine.
- a lubricating oil composition for an internal combustion engine wherein the blending amount of component A) is 25% by mass or more.
- Lubricating oil composition for engines (3) In the lubricating oil composition for an internal combustion engine described above, the kinematic viscosity at 100 ° C. of a base oil obtained by blending the component (A) and the component (B) is 4.6 mm 2 / s or less.
- a lubricating oil composition for an internal combustion engine is 4.6 mm 2 / s or less.
- the NOACK of the composition is 10% by mass or less
- the CCS viscosity at ⁇ 35 ° C. is 6000 mPa ⁇ s or less
- the MR viscosity at ⁇ 40 ° C. is 30,
- a lubricating oil composition for an internal combustion engine having a viscosity of 000 mPa ⁇ s or less.
- the above lubricating oil composition for internal combustion engines wherein the blending amount of the component (B) is 20% by mass or more based on the total amount of the composition.
- the component (A) is a polyalphaolefin having at least one selected from alphaolefins having 10 to 14 carbon atoms as a monomer.
- Lubricating oil composition for internal combustion engines (8) The lubricating oil composition for internal combustion engines, wherein the component (A) is a trimer.
- the lubricating oil composition for an internal combustion engine of the present invention is formulated with a polyisobutylene having a predetermined mass average molecular weight with respect to a mixed base oil obtained by blending PAO having a specific property and mineral oil having a specific property. Therefore, it has low evaporation, excellent mist resistance and caulking resistance, and is also excellent in fuel economy. Therefore, the lubricating oil composition for an internal combustion engine of the present invention is suitable for a gasoline engine or a diesel engine having a turbo mechanism.
- the lubricating oil composition for internal combustion engines of the present invention uses a mixed base oil obtained by blending the following components (A) and (B) as a base oil.
- the mineral oil which is 120 or more is described in detail below.
- the component (A) in the present invention is poly ⁇ -olefin (PAO) which is a polymer (oligomer) of ⁇ -olefin.
- PAO poly ⁇ -olefin
- the kinematic viscosity at 100 ° C. of PAO as component (A) needs to be 5.5 mm 2 / s or less.
- this kinematic viscosity is preferably 3 mm 2 / s or more from the viewpoint of lubricity.
- the CCS viscosity at ⁇ 35 ° C. needs to be 3000 mPa ⁇ s or less.
- NOACK is required to be 12% by mass or less from the viewpoint of low evaporation.
- the number of carbon atoms of the ⁇ -olefin, which is a monomer for obtaining such PAO, is preferably from 6 to 20 from the viewpoint of low temperature properties such as viscosity index, pour point and low temperature viscosity, and evaporation, but from 8 to 16 Is more preferable, and 10 to 14 is particularly preferable.
- the PAO is preferably an ⁇ -olefin trimer from the viewpoints of low evaporation, coking resistance and low fuel consumption, but in order to obtain the desired properties, the carbon number of the ⁇ -olefin and its blending ratio, The degree of polymerization can be adjusted.
- the polymerization catalyst of ⁇ - olefin, BF 3 catalyst, AlCl 3 catalyst may be used Ziegler catalysts, such as metallocene catalysts, conventionally, the low viscosity PAO below 100 ° C.
- kinematic viscosity of 30mm 2 / s BF 3 AlCl 3 catalysts have been used for low-viscosity PAOs with a catalyst of 30 mm 2 / s or more, but BF 3 catalysts and metallocene catalysts are particularly preferred from the viewpoints of low evaporation, coking resistance, and low fuel consumption.
- the BF 3 catalyst is used together with a promoter such as water, alcohol, ester, etc. Among them, alcohol, particularly 1-butanol, is preferable from the viewpoint of viscosity index, low temperature physical properties, and yield.
- the metallocene catalyst examples include a catalyst containing a combination of a metallocene compound and a promoter.
- a metallocene compound represented by the following general formula (1) is preferable.
- R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- M is a transition metal element of Group 4 of the periodic table
- X is covalent bond or ionic bond It is a ligand.
- R is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
- M include titanium, zirconium, and hafnium. Among these, zirconium is preferable.
- Specific examples of X include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10), an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10), Amino group, phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12) (for example, diphenylphosphine group), silicon-containing carbon atom having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms)
- a hydrogen group for example, trimethylsilyl group
- a group for example, trimethyl
- Examples of the metallocene compound represented by the general formula (1) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, and bis.
- methylaluminoxane is preferable.
- limiting in particular as methylaluminoxane A conventionally well-known methylaluminoxane can be used, for example, the chain
- p represents the degree of polymerization and is usually from 3 to 50, preferably from 7 to 40.
- Examples of the method for producing methylaluminoxane include a method in which methylaluminum is brought into contact with a condensing agent such as water, but the means is not particularly limited, and the reaction may be carried out according to a known method.
- the compounding ratio of the metallocene compound and methylaluminoxane is usually from 15 to 150, preferably from 20 to 120, more preferably from 25 to 100, as the methylaluminoxane / metallocene compound (molar ratio).
- the blending ratio is 15 or more, catalytic activity is exhibited, and the yield of trimer or more suitable as a base oil for lubricating oil does not decrease due to the formation of ⁇ -olefin dimer.
- the blending ratio is 150 or less, deashing and removal of the catalyst will not be incomplete.
- metallocene catalysts other than the above include metallocene catalysts that use a metallocene compound having a crosslinking group.
- a metallocene compound having two crosslinking groups is preferable, and a metallocene compound having meso symmetry is particularly preferable.
- the metallocene catalyst using the metallocene compound having meso symmetry include (a) a metallocene compound represented by the following general formula (4) as a catalyst component, and (b) the catalyst (a) as a catalyst component.
- Examples thereof include a compound (b-1) capable of forming an ionic complex by reacting with a component metallocene compound or a derivative thereof, and a metallocene catalyst containing at least one component (b-2) selected from aluminoxane. .
- the compound represented by the general formula (4) is a mesosymmetric compound, and in the general formula (4), M represents a metal element from group 3 to group 10 of the periodic table.
- X represents a ⁇ -binding ligand, and when there are a plurality of X, a plurality of X may be the same or different, Y represents a Lewis base, and when there are a plurality of Y, a plurality of Y are the same or different It may be.
- A represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—. , -SO 2 -, - Se - , - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - and -AlR 1 - shows a bridging group selected from the two a They may be the same or different.
- R 1 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms.
- q is an integer from 1 to 5 and represents [(valence of M) -2], and r represents an integer from 0 to 3.
- E is a group represented by the following general formula (5) and the following general formula (6), and the two Es are the same.
- the mesosymmetric compound refers to a transition metal compound in which two bridging groups bridge two Es in a bonding mode of (1,1 ′) (2,2 ′).
- R 2 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 4 carbon atoms, silicon A group selected from the group consisting of a containing group and a heteroatom-containing group is shown. When several R ⁇ 2 > exists, they may mutually be same or different.
- the bond indicated by the wavy line represents the bond with the bridging group A.
- the crosslinkable group A in the general formula (4) is preferably a group represented by the following general formula (7).
- B is a skeleton of a bridging group and represents a carbon atom, a silicon atom, a boron atom, a nitrogen atom, a germanium atom, a phosphorus atom, or an aluminum atom.
- R 3 represents a hydrogen atom, a carbon atom, an oxygen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an amine-containing group, or a halogen-containing group.
- n is 1 or 2.
- Examples of the metallocene compound represented by the general formula (4) include (1,1′-ethylene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) ( 2,2′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1′-ethylene) ( 2,2′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, ( 1,1′-ethylene) (2,2′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,1′-ethylene (2,2'-ethylene) -bis (5,6-dimethylindenyl
- the catalyst component (b-1) of the catalyst component (b) is any compound that can react with the metallocene compound of the catalyst component (a) to form an ionic complex. Although it can be used, what is represented by the following general formula (8) or the following general formula (9) can be preferably used. ([L 1 ⁇ R 4 ] k + ) a ([Z] ⁇ ) b (8) ([L 2 ] k + ) a ([Z] ⁇ ) b (9)
- L 1 represents a Lewis base
- L 2 represents M 2 , R 5 R 6 M 3 , R 7 3 C or R 8 M 3
- [Z] ⁇ represents a non-coordinating anion [Z 1 ] ⁇ or [Z 2 ] ⁇ .
- [Z 1 ] ⁇ is an anion in which a plurality of groups are bonded to the element, that is, [M 1 G 1 G 2 ... G f ] ⁇ (where M 1 is group 5 to group 15 of the periodic table).
- G 1 to G f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 2 to C atoms.
- Two or more of the .G 1 illustrating a hydrocarbon group to G f may optionally form a ring .f is an integer of [(valence of central metal M 1) +1].), [Z 2] - is the reciprocal of the logarithm (pKa) is -10 or less Bronsted acid alone, or a combination of Bronsted acids and Lewis acids conjugate base of the acid dissociation constant or generally conjugate acid is defined as super acid, Indicates salt. In addition, a Lewis base may be coordinated.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group
- R 5 and R 6 are each a cyclopentadienyl group.
- R 7 represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group.
- R 8 represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine.
- M 2 includes elements from Group 1 to Group 3 of the Periodic Table, Group 11 to Group 13 and Group 17 of the Periodic Table, and M 3 includes Groups 7 to 12 of the Periodic Table. Indicates elements up to group.
- L 1 examples include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine; thioethers such as tetrahydrothiophene; Examples include esters such as ethyl acid; nitriles such as acetonitrile and benzonitrile.
- R 4 include hydrogen, methyl group, ethyl group, benzyl group, and trityl group.
- R 5 and R 6 include cyclopentadienyl group, methylcyclopentadienyl group, Examples thereof include an ethylcyclopentadienyl group and a pentamethylcyclopentadienyl group.
- R 7 include phenyl group, p-tolyl group, p-methoxyphenyl group and the like, and specific examples of R 8 include tetraphenylporphyrin, phthalocyanine, allyl, methallyl and the like.
- M 2 include Li, Na, K, Ag, Cu, Br, I, and the like.
- M 3 include Mn, Fe, Co, Ni, Zn, and the like.
- [Z 1 ] ⁇ that is, [M 1 G 1 G 2 ... G f ]
- specific examples of M 1 include B, Al, Si, P, As, Sb, etc., preferably B and Al.
- G 1 and G 2 to G f include a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group and the like as an alkoxy group or an aryloxy group.
- Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4- t-butylphenyl group, 3,5-dimethylphenyl group, etc .; halogen, fluorine, chlorine, bromine, iodine, etc .; heteroatom-containing hydrocarbon group, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl Group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3, - bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) such as a methyl group; pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine
- non-coordinating anions that is, Bronsted acids having a pKa of ⁇ 10 or less or conjugate bases [Z 2 ] — in combination with Bronsted acids and Lewis acids
- trifluoromethanesulfonic acid anions CF 3 SO 3 ) ⁇
- bis (trifluoromethanesulfonyl) methyl anion bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide
- perchlorate anion (ClO 4 ) ⁇ trifluoroacetate anion (CF 3 CO 2 ) ⁇
- Hexafluoroantimony anion SBF 6 ) ⁇
- fluorosulfonate anion FSO 3 ) ⁇
- chlorosulfonate anion ClSO 3 ) ⁇
- fluorosulfonate anion / 5-antimony fluoride FSO 3 / S
- An ionic compound that reacts with the transition metal compound of the catalyst component (a) to form an ionic complex is tetrakis (pentafluorophenylboric acid) N, N -Dimethylanilinium, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (Tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methyl
- examples of the aluminoxane as the catalyst component (b-2) include a chain aluminoxane represented by the following general formula (10) and a cyclic aluminoxane represented by the following general formula (11).
- R 9 is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 alkyl group, alkenyl group, aryl group, arylalkyl group or the like, or Represents a halogen atom, and w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably an integer of 2 to 40.
- Each R 9 may be the same or different.
- Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means is not particularly limited and may be reacted according to a known method.
- a method in which an organoaluminum compound is dissolved in an organic solvent and contacting it with water (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) metal There are a method of reacting crystallization water contained in a salt or the like, water adsorbed on an inorganic or organic substance with an organoaluminum compound, and (4) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water.
- the aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.
- the use ratio of the above-mentioned (a) catalyst component and (b) catalyst component is from 10: 1 to 1: 100 in molar ratio when (b-1) catalyst component is used as (b) catalyst component.
- the range of 2: 1 to 1:10 is more preferable. If it deviates from the above range, the catalyst cost per unit mass polymer increases, which is not practical.
- the molar ratio is preferably in the range of 1: 1 to 1: 1000000, and more preferably in the range of 1:10 to 1: 10000. When deviating from this range, the catalyst cost per unit mass polymer becomes high, which is not practical.
- the (b) catalyst component the (b-1) catalyst component and the (b-2) catalyst component may be used alone or in combination of two or more.
- an ⁇ -olefin having 10 to 14 carbon atoms is preferred as a monomer for producing PAO (hereinafter also referred to as “mPAO”) using a metallocene catalyst.
- mPAO PAO
- a linear ⁇ -olefin is preferable.
- Specific examples include 1-decene, 1-dodecene, 1-tetradecene, and the like. Of these, 1-decene is particularly preferred.
- the blending ratio of the metallocene compound represented by the general formula (1) or the general formula (4) and the ⁇ -olefin [metallocene compound (mmol) / ⁇ -olefin (L)] is usually 0.01 to 0.4. Up to, preferably from 0.05 to 0.3, more preferably from 0.1 to 0.2. Sufficient catalytic activity is obtained when the blending ratio is 0.01 or more, whereas when it is 0.4 or less, the yield of oligomers of trimer or more suitable as a base oil of the lubricating oil is improved, There is no incomplete removal of the catalyst.
- the polymerization of the ⁇ -olefin is preferably performed in the presence of hydrogen.
- the amount of hydrogen added is usually from 0.1 kPa to 50 kPa, preferably from 0.5 kPa to 30 kPa, and more preferably from 1 kPa to 10 kPa.
- the amount of hydrogen added is 0.1 kPa or more, sufficient catalytic activity can be obtained.
- it is 50 kPa or less, the production of a raw material ⁇ -olefin saturated product can be reduced, and the desired yield of mPAO is obtained. Will improve.
- the polymerization of the ⁇ -olefin is not limited in the reaction method, and may be performed in the absence of a solvent or in a solvent, and any method may be used.
- a reaction solvent for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane and octane Halogenated hydrocarbons such as chloroform and dichloromethane.
- the temperature of the polymerization reaction is usually 0 ° C.
- the mPAO obtained by the above method may be further treated.
- hydrogenation may be performed in order to improve thermal stability or oxidation stability.
- the temperature of the hydrogenation treatment is usually 50 ° C. or more and 300 ° C. or less, preferably 60 ° C. or more and 250 ° C. or less, more preferably 70 ° C. or more and 200 ° C. or less
- the hydrogen pressure is usually 0.1 MPa or more and 10 MPa or less.
- it is 0.5 MPa or more and 2 MPa or less, More preferably, it is 0.7 MPa or more and 1.5 MPa or less.
- a general hydrogenation catalyst containing Pd, Ni, or the like can be used.
- the temperature in distillation is usually 200 ° C. or more and 300 ° C. or less, preferably 220 ° C. or more and 280 ° C. or less, more preferably 230 ° C. or more and 270 ° C. or less, and the pressure is usually 0.1 Pa or more and 15 Pa or less, preferably Is 0.4 Pa or more and 7 Pa or less, more preferably 0.6 Pa or more and 4 Pa or less.
- the mPAO obtained by the above method, mPAO after hydrogenation treatment or distillation has about 1 short chain branch per molecule (usually 0.6 or more and 1.2 or less, preferably 0.7). It is 1.1 or less, more preferably 0.8 or more and 1.0 or less.
- a methyl group, an ethyl group, and a propyl group are referred to as short-chain branches.
- the short chain branch is mainly a methyl group, and the proportion of the methyl group is usually 80 mol% or more, preferably 85 mol% or more, more preferably 90 mol% or more.
- the blending amount of the component (A) needs to be 25% by mass or more based on the total amount of the composition. If the blending amount is less than 25% by mass, the object of the present invention cannot be sufficiently achieved. Further, from the viewpoint of low evaporation, the blending amount of the component (A) is preferably 30% by mass or more, and more preferably 35% by mass or more. However, it is preferably 80% by mass or less from the viewpoint of the solubility of the additive and the compatibility with the seal rubber.
- the component (B) in the present invention is a mineral oil having a viscosity index of 120 or more.
- mineral oil for example, Group III hydrorefined mineral oil in the API classification is suitable.
- the component (B) is blended with the component (A), thereby imparting appropriate lubricity to the composition and contributing to improvement in fuel economy.
- blending (B) component the solubility of the additive generally used for internal combustion engines improves, and it contributes also greatly to fuel-saving property as a result. Therefore, the component (B) is preferably blended in an amount of 20% by mass or more, more preferably 25% by mass or more based on the total amount of the composition.
- kinematic viscosity at 100 ° C. in the mixed base oil by blending the above components (A) and component (B) is less than 4.6mm 2 / s, 4.4mm 2 / s
- the following is more preferable.
- the mixed base oil has a 100 ° C. kinematic viscosity of 4.6 mm 2 / s or less, it contributes to an improvement in fuel economy.
- the 100 ° C. kinematic viscosity of the mixed base oil is preferably 3 mm 2 / s or more from the viewpoint of evaporability.
- This composition is obtained by blending polyisobutylene (PIB) having a mass average molecular weight (Mw) of 500,000 or more with the above-mentioned predetermined mixed base oil.
- PIB polyisobutylene
- Mw mass average molecular weight
- the mass average molecular weight of the polyisobutylene is more preferably 600,000 or more, and particularly preferably 700,000 or more.
- the upper limit of the weight average molecular weight of polyisobutylene is not particularly limited, but is preferably 3 million or less, more preferably 2 million or less, and particularly preferably 1.5 million or less from the viewpoint of availability and shear stability of the polymer.
- the mass average molecular weight of polyisobutylene is a value determined from a calibration curve measured using gel permeation chromatography and prepared using standard polystyrene.
- polystyrene resin there is no restriction
- the reaction temperature is usually in the range of ⁇ 100 ° C. to 70 ° C.
- one of the above polyisobutylenes may be selected, or two or more polyisobutylenes having different molecular weights may be combined and blended.
- the blending amount of these polyisobutylenes is preferably 0.01% by mass or more and 0.2% by mass or less, more preferably 0.015% by mass or more and 0.15% by mass or less, particularly preferably as a resin component, based on the total amount of the composition. Is 0.025 mass% or more and 0.1 mass% or less. If the blending amount of polyisobutylene is 0.01% by mass or more as a resin component, the mist prevention effect is remarkably recognized, and if it is 0.2% by mass or less, the low temperature characteristics of the composition can be kept good.
- This composition is obtained by blending a predetermined polyisobutylene with the above-mentioned mixed base oil as a main component, and the NOACK of this composition is 10% by mass or less, and the CCS viscosity at ⁇ 35 ° C. is 6000 mPa ⁇
- the MR viscosity at ⁇ 40 ° C. is preferably 30,000 mPa ⁇ s or less. If NOACK and the CCS viscosity at ⁇ 35 ° C. and this range are both excellent in coking resistance and low-temperature fluidity (fuel saving performance), it is suitable as a lubricating oil for an internal combustion engine.
- a viscosity index improver such as a pour point depressant, a cleaning dispersant, an antioxidant, as necessary, as long as the object of the present invention is not impaired.
- An antiwear agent / extreme pressure agent, a friction reducing agent, a metal deactivator, a rust inhibitor, a surfactant / demulsifier, an antifoaming agent, and the like can be appropriately blended.
- the viscosity index improver examples include polymethacrylate, dispersed polymethacrylate, olefin copolymer (for example, ethylene-propylene copolymer), dispersed olefin copolymer, styrene copolymer (for example, Styrene-diene copolymer, styrene-isoprene copolymer, etc.).
- the blending amount of the viscosity index improver is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less based on the total amount of the lubricating oil composition from the viewpoint of the blending effect.
- pour point depressant examples include polymethacrylate having a weight average molecular weight of about 5000 to 50,000.
- the blending amount of the pour point depressant is preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less, based on the total amount of the lubricating oil composition, from the viewpoint of the blending effect. is there.
- an ashless dispersant and a metal-based cleaning agent can be used.
- the ashless dispersant any ashless dispersant used in lubricating oils can be used.
- a monotype succinimide compound represented by the following general formula (II) or a general formula (III) The bis-type succinimide compound represented is mentioned.
- R 11 , R 13 and R 14 are each an alkenyl group or alkyl group having a number average molecular weight of 500 to 4,000, and R 13 and R 14 are the same or different. May be.
- the number average molecular weight of R 11 , R 13 and R 14 is preferably from 1,000 to 4,000.
- R 12 , R 15 and R 16 are each an alkylene group having 2 to 5 carbon atoms, R 15 and R 16 may be the same or different, and r represents an integer of 1 to 10, s represents 0 or an integer from 1 to 10.
- the r is preferably 2 to 5, more preferably 3 to 4.
- s is preferably 1 to 4, more preferably 2 or 3. If it is in the said range, it is preferable at the point of the cleanability and the solubility with respect to base oil.
- alkenyl group examples include a polybutenyl group, a polyisobutenyl group, and an ethylene-propylene copolymer, and the alkyl group is a hydrogenated form thereof.
- suitable alkenyl groups include polybutenyl or polyisobutenyl groups.
- the polybutenyl group can be obtained by polymerizing a mixture of 1-butene and isobutene or high-purity isobutene.
- a representative example of a suitable alkyl group is a hydrogenated polybutenyl group or polyisobutenyl group.
- the above alkenyl or alkyl succinimide compound is usually prepared by reacting an alkenyl succinic anhydride obtained by reaction of polyolefin with maleic anhydride, or an alkyl succinic anhydride obtained by hydrogenating it with a polyamine. Can be manufactured.
- the mono-type succinimide compound and the bis-type succinimide compound described above can be produced by changing the reaction ratio of alkenyl succinic anhydride or alkyl succinic anhydride and polyamine.
- the olefin monomer forming the polyolefin one or more of ⁇ -olefins having 2 to 8 carbon atoms can be mixed and used, but a mixture of isobutene and butene-1 is preferably used. be able to.
- Polyamines include ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, and other single diamines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di (methylethylene) triamine, dibutylenetriamine, and butylenetetramine.
- polyalkylene polyamines such as pentapentylenehexamine and piperazine derivatives such as aminoethylpiperazine.
- boron derivatives thereof and those modified with organic acids may be used.
- the boron derivative of the alkenyl or alkyl succinimide compound those produced by a conventional method can be used. For example, after reacting the above polyolefin with maleic anhydride to form an alkenyl succinic anhydride, the polyamine and boron oxide, boron halide, boric acid, boric anhydride, boric acid ester, and boric acid It is obtained by reacting with an intermediate obtained by reacting a boron compound such as an ammonium salt and imidizing.
- a boron compound such as an ammonium salt and imidizing.
- the blending amount of the monotype succinimide compound represented by the above formula (II) or the bis type succinimide compound represented by the above formula (III) is 0.5% based on the total amount of the lubricating oil composition.
- the content is preferably from 15% by mass to 15% by mass, and more preferably from 1% by mass to 10% by mass. If the blending amount is less than 0.5% by mass, the effect is hardly exhibited, and if it exceeds 15% by mass, an effect commensurate with the blending amount cannot be obtained.
- a succinimide compound may be used alone or in combination of two or more as long as it contains the specified amount.
- any alkaline earth metal detergent used for lubricating oils can be used, for example, alkaline earth metal sulfonates, alkaline earth metal phenates, alkaline earth metal salicylates, and the like. And a mixture of two or more selected from.
- Alkaline earth metal sulfonates include alkaline earth metal salts of alkyl aromatic sulfonic acids, particularly magnesium salts, obtained by sulfonating alkyl aromatic compounds having a molecular weight of 300 to 1,500, preferably 400 to 700. And / or calcium salts and the like, among which calcium salts are preferably used.
- alkaline earth metal phenates include alkylphenols, alkylphenol sulfides, alkaline earth metal salts of Mannich reactants of alkylphenols, particularly magnesium salts and calcium salts, among which calcium salts are particularly preferably used.
- alkaline earth metal salicylates include alkaline earth metal salts of alkyl salicylic acid, particularly magnesium salts and calcium salts, among which calcium salts are preferably used.
- the alkyl group constituting the alkaline earth metal detergent is preferably an alkyl group having 4 to 30 carbon atoms, more preferably a linear or branched alkyl group having 6 to 18 carbon atoms, It may be a branch. These may also be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups.
- the alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate the above alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, Mannich reaction product of alkylphenol, alkylsalicylic acid, etc.
- alkaline earth metal bases such as alkaline earth metal oxides and hydroxides of calcium, or once replaced with alkaline earth metal salts such as sodium salts and potassium salts, etc.
- alkaline earth metal bases such as alkaline earth metal oxides and hydroxides of calcium, or once replaced with alkaline earth metal salts such as sodium salts and potassium salts, etc.
- the above neutral salts, basic salts, overbased salts, and mixtures thereof can be used, and in particular, one of overbased salicylates, overbased phenates, and overbased sulfonates. Mixing the above with neutral sulfonate is preferable in terms of cleanliness and wear resistance.
- the total base number of the metal detergent is preferably 10 mgKOH / g or more and 500 mgKOH / g or less, more preferably 15 mgKOH / g or more and 450 mgKOH / g or less.
- the total base number referred to here is JIS K 2501 “Petroleum products and lubricants—Test method for neutralization number”. Means the total base number by potentiometric titration method (base number / perchloric acid method) measured according to the above.
- the metal detergent is not particularly limited in its metal ratio, and can be used by mixing one or more of 20 or less, preferably the metal ratio is 3 or less, more preferably 1.5 or less, In particular, it is particularly preferable to use a metal-based detergent of 1.2 or less as an essential component because it is excellent in oxidation stability, base number maintenance, high-temperature cleanability, and the like.
- the metal ratio here is expressed by the valence of the metal element in the metal-based detergent ⁇ the metal element content (mol%) / the soap group content (mol%).
- the metal elements are calcium, magnesium, and the like.
- the soap group means a sulfonic acid group, a phenol group, a salicylic acid group, and the like.
- the metal detergent is generally marketed in a state diluted with a light lubricating base oil or the like, and preferably has a metal content of 1% by mass to 20% by mass, preferably 2% by mass to 16% by mass. Those up to are more preferred.
- the compounding amount of the metal detergent is preferably 0.01% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, based on the total amount of the composition. If the blending amount is less than 0.01% by mass, the effect is hardly exhibited, and even if it exceeds 20% by mass, an effect commensurate with the addition cannot be obtained. Moreover, as long as a metal type detergent contains said prescribed amount, you may use it individually or in combination of 2 or more types.
- antioxidants examples include phenol-based antioxidants, amine-based antioxidants, molybdenum amine complex-based antioxidants, and sulfur-based antioxidants.
- phenolic antioxidant examples include 4,4′-methylenebis (2,6-di-t-butylphenol); 4,4′-bis (2,6-di-t-butylphenol); 4,4 ′ -Bis (2-methyl-6-t-butylphenol); 2,2'-methylenebis (4-ethyl-6-t-butylphenol); 2,2'-methylenebis (4-methyl-6-t-butylphenol); 4,4′-butylidenebis (3-methyl-6-tert-butylphenol); 4,4′-isopropylidenebis (2,6-di-tert-butylphenol); 2,2′-methylenebis (4-methyl-6) -Nonylphenol); 2,2'-isobutylidenebis (4,6-dimethylphenol); 2,2'-methylenebis (4-methyl-6-cyclohex
- amine-based antioxidants include monooctyl diphenylamine; monoalkyl diphenylamines such as monononyl diphenylamine; 4,4′-dibutyldiphenylamine; 4,4′-dipentyldiphenylamine; 4,4′-dihexyldiphenylamine; 4,4′-diheptyldiphenylamine; 4,4′-dioctyldiphenylamine; dialkyldiphenylamines such as 4,4′-dinonyldiphenylamine, tetrabutyldiphenylamine; tetrahexyldiphenylamine; tetraoctyldiphenylamine; polyalkyl such as tetranonyldiphenylamine Diphenylamine type and naphthylamine type, specifically ⁇ -naphthylamine; phenyl- ⁇ -naphthylamine; and butyl
- a hexavalent molybdenum compound specifically, a product obtained by reacting at least one of molybdenum trioxide and molybdic acid with an amine compound, for example, JP-A-2003-252887
- the compound obtained by the production method described in 1. can be used. Although it does not restrict
- 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 1-30 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; alkylenes of these compounds Examples thereof include oxide adducts; and mixtures thereof. Examples thereof include a sulfur-containing molybdenum complex of succinimide described in JP-B-3-22438 and JP-A-2004-2866
- sulfur-based antioxidants include phenothiazine, pentaerythritol-tetrakis- (3-laurylthiopropionate), didodecyl sulfide, dioctadecyl sulfide, didodecylthiodipropionate, dioctadecylthiodipropionate, dimyristyl.
- examples thereof include thiodipropionate, dodecyl octadecyl thiodipropionate, and 2-mercaptobenzimidazole.
- the blending amount of these antioxidants is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, based on the total amount of the composition.
- Antiwear or extreme pressure agents include zinc dithiophosphate, zinc phosphate, zinc dithiocarbamate, disulfides, sulfurized olefins, sulfurized fats and oils, sulfurized esters, thiocarbonates, thiocarbamates, polysulfides, etc. Containing compounds; phosphorous esters, phosphate esters, phosphonate esters, and phosphorus-containing compounds such as amine salts or metal salts thereof; thiophosphites, thiophosphates, thiophosphonates, And sulfur and phosphorus containing antiwear agents such as amine salts or metal salts thereof.
- a preferable blending amount of the antiwear agent or extreme pressure agent is in the range of 0.1% by mass or more and 20% by mass or less based on the total amount of the composition.
- a zinc-containing compound it is preferably 600 ppm by mass or less, more preferably 500 ppm by mass or less, and still more preferably 400 ppm by mass or less in terms of zinc (based on the total amount of the composition).
- 500 mass ppm or less is preferable in phosphorus conversion (composition whole quantity basis), More preferably, it is 400 mass ppm or less, More preferably, it is 300 mass ppm or less.
- the blending amount of zinc is 600 mass ppm or less and the blending amount of phosphorus is 500 mass ppm or less, there is a problem that even if this composition is used, the basic compound is consumed and the oil renewal period becomes extremely short. Does not occur.
- any compound generally used as a friction reducing agent for lubricating oils can be used.
- it has at least one alkyl group or alkenyl group having 6 to 30 carbon atoms in the molecule.
- Ashless friction reducing agents such as fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols, aliphatic amines, and aliphatic ethers.
- the blending amount of the friction reducing agent is preferably 0.01% by mass or more and 2% by mass or less, more preferably 0.01% by mass or more and 1% by mass or less, based on the total amount of the composition.
- the metal deactivator examples include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
- the compounding amount of the metal deactivator is preferably 0.01% by mass or more and 3% by mass or less, more preferably 0.01% by mass or more and 1% by mass or less, based on the total amount of the composition.
- rust preventive agent examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, and polyhydric alcohol ester.
- the blending amount of these rust preventives is preferably 0.01% by weight or more and 1% by weight or less, more preferably 0.05% by weight or more and 0.5% by weight, based on the total amount of the lubricating oil composition, from the viewpoint of blending effects. It is as follows.
- the surfactant or demulsifier examples include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether and polyoxyethylene alkyl naphthyl ether.
- the blending amount of the surfactant or the demulsifier is preferably 0.01% by mass or more and 3% by mass or less, more preferably 0.01% by mass or more and 1% by mass or less, based on the total amount of the composition.
- antifoaming agent examples include silicone oil, fluorosilicone oil, and fluoroalkyl ether, and 0.005% by mass or more and 0.5% by mass on the basis of the total amount of the composition from the viewpoint of balance of defoaming effect and economy. % Or less, more preferably 0.01% by mass or more and 0.2% by mass or less.
- Mist ratio (mist mass / sample oil mass) ⁇ 100 Test device: TACO mist measuring device (model number: C3-0807) Air pressure: 0.2MPa Sample oil amount: 40 g
- the driving torque value compared to the reference oil was used as the torque improvement rate, and the motoring characteristics (fuel economy) were evaluated according to the following criteria.
- reaction product is subjected to simple distillation, and a fraction at a pressure of 530 Pa in the range of a distillation temperature from 240 ° C. to 270 ° C. (1-decene trimer hydrogenated product) ).
- Example oils having the composition shown in Tables 1 and 2 were prepared. Tables 1 and 2 also show the properties and various performances of each sample oil.
- PAO-1 INEOS, Durasyn 145 (kinematic viscosity at 100 ° C .; 5.194 mm 2 / s, NOACK; 5.1% by mass, CCS viscosity ( ⁇ 35 ° C.); 2570 mPa ⁇ s, viscosity index; 145)
- PAO-2 mPAO obtained in the above production example (kinematic viscosity at 100 ° C .; 3.458 mm 2 / s, NOACK; 11.1% by mass, CCS viscosity ( ⁇ 35 ° C.); 800 mPa ⁇ s, viscosity index; 127)
- PAO-3 manufactured by INEOS, Durasyn 164 (kinematic viscosity at 100 ° C .; 3.893 mm 2 / s, NOACK; 14.0% by mass, CCS viscosity ( ⁇ 35 ° C.); 1330 mPa ⁇ s, viscosity index; 120)
- PAO-4 manufactured by INEOS, Durasyn 166 (kinematic viscosity at 100 ° C .; 5.824 mm 2 / s, NOACK; 6.0% by mass, CCS viscosity ( ⁇ 35 ° C.); 3950 mPa ⁇ s, viscosity index; 178)
- Mineral oil-1 hydrorefined mineral oil (kinematic viscosity at 100 ° C .; 4.121 mm 2 / s, NOACK; 14.1% by mass, CCS viscosity ( ⁇ 35 ° C.); 1870 mPa ⁇ s or less, viscosity index; 122)
- Mineral oil-2 hydrorefined mineral oil (kinematic viscosity at 100 ° C .; 6.483 mm 2 / s, NOACK; 7.5 mass%, CCS viscosity ( ⁇ 35 ° C.); 10100 mPa ⁇ s or less, viscosity index: 121)
- Polyisobutylene mass average molecular weight 760,0000, resin content 4.9% by mass
- Additive package Infineum P6000 manufactured by Infineum Viscosity index improver: polymethacrylate (mass average molecular weight 230,000, resin content 45% by mass
- Pour point depressant polyalkyl methacrylate (mass average molecular weight 6,000)
Abstract
Description
従って、ミスト化やコーキングの発生を防止するには、蒸発性の低い潤滑油を使用することが効果的である。低蒸発性の内燃機関用潤滑油としては、API分類におけるグループIIあるいはグループIIIの基油と低粘度のPAOとのブレンドを含む組成物が提案され
ている(特許文献1、2参照)。
(1)(A)成分:100℃における動粘度が5.5mm2/s以下、-35℃におけるCCS粘度が3000mPa・s以下、NOACKが12質量%以下であるポリアルファオレフィン
(B)成分:粘度指数が120以上である鉱油
前記(A)成分と(B)成分とを含む基油に、質量平均分子量が50万以上であるポリイソブチレンを配合してなり、潤滑油全量基準で、前記(A)成分の配合量が25質量%以上であることを特徴とする内燃機関用潤滑油組成物。
(2)上述の内燃機関用潤滑油組成物において、前記ポリイソブチレンの配合量が組成物全量基準で樹脂分として0.005質量%以上、0.2質量%以下であることを特徴とする内燃機関用潤滑油組成物。
(3)上述の内燃機関用潤滑油組成物において、前記(A)成分と(B)成分とを配合してなる基油の100℃における動粘度が4.6mm2/s以下であることを特徴とする内燃機関用潤滑油組成物。
(4)上述の内燃機関用潤滑油組成物において、該組成物のNOACKが10質量%以下であり、-35℃におけるCCS粘度が6000mPa・s以下であり、-40℃におけるMR粘度が30,000mPa・s以下であることを特徴とする内燃機関用潤滑油組成物。
(5)上述の内燃機関用潤滑油組成物において、前記(B)成分の配合量が組成物全量基準で20質量%以上であることを特徴とする内燃機関用潤滑油組成物。
(6)上述の内燃機関用潤滑油組成物において、前記(A)成分がメタロセン触媒により重合してなることを特徴とする内燃機関用潤滑油組成物。
(7)上述の内燃機関用潤滑油組成物において、前記(A)成分が炭素数10から14までのアルファオレフィンから選ばれた少なくともいずれかをモノマーとするポリアルファオレフィンであることを特徴とする内燃機関用潤滑油組成物。
(8)上述の内燃機関用潤滑油組成物において、前記(A)成分が3量体であることを特徴とする内燃機関用潤滑油組成物。
(A)成分:100℃における動粘度が5.5mm2/s以下、-35℃におけるCCS粘度が3000mPa・s以下、NOACKが12質量%以下であるポリα-オレフィン
(B)成分:粘度指数が120以上である鉱油
以下、詳細に説明する。
本発明における(A)成分は、α-オレフィンの重合体(オリゴマー)であるポリα-オレフィン(PAO)である。
省燃費性の観点より、(A)成分であるPAOの100℃における動粘度は、5.5mm2/s以下であることが必要である。ただし、この動粘度は、潤滑性の観点より3mm2/s以上であることが好ましい。また、-35℃におけるCCS粘度は、3000mPa・s以下であることが必要である。さらに、低蒸発性の観点より、NOACKが12質量%以下であることも必要である。
このようなPAOを得るためのモノマーであるα-オレフィンの炭素数としては、粘度指数、流動点及び低温粘度等の低温物性、蒸発性の観点より6から20までが好ましいが、8から16までがより好ましく、特に10から14までがさらに好ましい。また、PAOとしては、低蒸発性、耐コーキング性および低燃費性の観点よりα-オレフィンの3量体が好ましいが、目的とする性状にするため、α-オレフィンの炭素数とその配合比、重合度を調節することができる。
α-オレフィンの重合触媒としては、BF3触媒、AlCl3触媒、チーグラー型触媒、メタロセン触媒などが使用可能であり、従来、100℃動粘度が30mm2/s未満の低粘度PAOにはBF3触媒が、30mm2/s以上の低粘度PAOにはAlCl3触媒が使用されてきたが、低蒸発性、耐コーキング性および低燃費性の観点より特にBF3触媒、メタロセン触媒が好ましい。
BF3触媒は、水、アルコール、エステルなどのプロモーターとともに使用されるが、このうち、粘度指数、低温物性、収率の点より、アルコール特に1-ブタノールが好ましい。
(RC5H4)2MX2 (1)
前記一般式(1)中、Rは水素原子または炭素数1から10までの炭化水素基であり、Mは周期律表第4族の遷移金属元素であり、Xは共有結合性またはイオン結合性の配位子である。
なお、前記メソ対称型の化合物とは、2つの架橋基が(1,1’)(2,2’)の結合様式で、2つのEを架橋する遷移金属化合物のことをいう。
([L1-R4]k+)a([Z]-)b (8)
([L2]k+)a([Z]-)b (9)
R4の具体例としては、水素、メチル基、エチル基、ベンジル基、トリチル基などを挙げられ、R5、R6の具体例としては、シクロペンタジエニル基、メチルシクロペンタジエニル基、エチルシクロペンタジエニル基、ペンタメチルシクロペンタジエニル基などを挙げられる。R7の具体例としては、フェニル基、p-トリル基、p-メトキシフェニル基などを挙げられ、R8の具体例としてはテトラフェニルポルフィリン、フタロシアニン、アリル、メタリルなどを挙げられる。また、M2の具体例としては、Li、Na、K、Ag、Cu、Br、Iなどを挙げられ、M3の具体例としては、Mn、Fe、Co、Ni、Znなどを挙げられる。また、[Z1]-、即ち[M1G1G2・・・Gf]において、M1の具体例としてはB、Al、Si、P、As、Sbなど、好ましくはBおよびAlが挙げられる。また、G1およびG2からGfまでの具体例としては、ジアルキルアミノ基としてジメチルアミノ基、ジエチルアミノ基など;アルコキシ基若しくはアリールオキシ基としてメトキシ基、エトキシ基、n-ブトキシ基、フェノキシ基など;炭化水素基としてメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、n-オクチル基、n-エイコシル基、フェニル基、p-トリル基、ベンジル基、4-t-ブチルフェニル基、3,5-ジメチルフェニル基など;ハロゲン原子としてフッ素、塩素、臭素、ヨウ素など;ヘテロ原子含有炭化水素基としてp-フルオロフェニル基、3,5-ジフルオロフェニル基、ペンタクロロフェニル基、3,4,5-トリフルオロフェニル基、ペンタフルオロフェニル基、3,5-ビス(トリフルオロメチル)フェニル基、ビス(トリメチルシリル)メチル基など;有機メタロイド基としてペンタメチルアンチモン基、トリメチルシリル基、トリメチルゲルミル基、ジフェニルアルシン基、ジシクロヘキシルアンチモン基、ジフェニル硼素などが挙げられる。
例えば、(1)有機アルミニウム化合物を有機溶剤に溶解しておき、これを水と接触させる方法、(2)重合時に当初有機アルミニウム化合物を加えておき、後に水を添加する方法、(3)金属塩などに含有されている結晶水、無機物や有機物への吸着水を有機アルミニウム化合物と反応させる方法、(4)テトラアルキルジアルミノキサンにトリアルキルアルミニウムを反応させ、さらに水を反応させる方法などがある。なお、アルミノキサンとしては、トルエン不溶性のものであってもよい。これらのアルミノキサンは1種用いてもよく、2種以上を組み合わせて用いてもよい。
本発明における(B)成分は、粘度指数120以上の鉱油である。このような鉱油としては、例えば、API分類におけるグループIIIの水素化精製鉱油が好適である。
(B)成分は、(A)成分とともに配合されることにより、適度な潤滑性を組成物に与え、省燃費性の向上に寄与する。
また、(B)成分を配合することにより、内燃機関用として汎用される添加剤の溶解性が向上し、結果的に省燃費性にも大きく寄与する。
それ故、(B)成分は、組成物全量基準で20質量%以上配合されることが好ましく、25質量%以上配合されることがより好ましい。
この混合基油の100℃動粘度が4.6mm2/s以下であると、省燃費性の向上に寄与する。ただし、蒸発性の観点より混合基油の100℃動粘度は、3mm2/s以上であることが好ましい。
なお、ポリイソブチレンの質量平均分子量は、ゲルパーミエーションクロマトグラフィーにより測定し、標準ポリスチレンを用いて作成した検量線から求めた値である。
本発明においては、上述のポリイソブチレンを1種選択し、または分子量が異なるポリイソブチレンを2種以上組み合せて配合してもよい。これらポリイソブチレンの配合量は、組成物全量基準で、樹脂分として好ましくは0.01質量%以上0.2質量%以下、より好ましくは0.015質量%以上0.15質量%以下、特に好ましくは0.025質量%以上0.1質量%以下である。ポリイソブチレンの配合量が樹脂分として0.01質量%以上であれば、顕著にミスト防止効果が認められ、0.2質量%以下であると組成物の低温特性を良好に保つことができる。
流動点降下剤の配合量は、配合効果の点から、潤滑油組成物全量基準で、0.1質量%以上2質量%以下が好ましく、より好ましくは0.1質量%以上1質量%以下である。
無灰分散剤としては、潤滑油に用いられる任意の無灰分散剤を用いることができるが、例えば、下記一般式(II)で表されるモノタイプのコハク酸イミド化合物、または一般式(III)で表されるビスタイプのコハク酸イミド化合物が挙げられる。
上記R11、R13およびR14の数平均分子量が500未満であると、基油への溶解性が低下し、4,000を超えると、清浄性が低下し、目的の性能が得られないおそれがある。
また、上記rは、好ましくは2から5まで、より好ましくは3から4までである。
rが1未満であると、清浄性が悪化し、rが11以上であると、基油に対する溶解性が悪くなる。
上記式(III)において、sは好ましくは1から4まで、より好ましくは2か3である。
上記範囲内であれば、清浄性および基油に対する溶解性の点で好ましい。
アルケニル基としては、ポリブテニル基、ポリイソブテニル基、エチレン-プロピレン共重合体を挙げることができ、アルキル基としてはこれらを水添したものである。
好適なアルケニル基の代表例としては、ポリブテニル基またはポリイソブテニル基が挙げられる。ポリブテニル基は、1-ブテンとイソブテンの混合物あるいは高純度のイソブテンを重合させたものとして得られる。また、好適なアルキル基の代表例としては、ポリブテニル基またはポリイソブテニル基を水添したものである。
上記のモノタイプのコハク酸イミド化合物およびビスタイプのコハク酸イミド化合物は、アルケニルコハク酸無水物若しくはアルキルコハク酸無水物とポリアミンとの反応比率を変えることによって製造することができる。
上記ポリオレフィンを形成するオレフィン単量体としては、炭素数2から8までのα-オレフィンの1種または2種以上を混合して用いることができるが、イソブテンとブテン-1の混合物を好適に用いることができる。
アルケニル若しくはアルキルコハク酸イミド化合物のホウ素誘導体は、常法により製造したものを使用することができる。
例えば、上記のポリオレフィンを無水マレイン酸と反応させてアルケニルコハク酸無水物とした後、更に上記のポリアミンと酸化ホウ素、ハロゲン化ホウ素、ホウ酸、ホウ酸無水物、ホウ酸エステル、およびホウ素酸のアンモニウム塩等のホウ素化合物を反応させて得られる中間体と反応させてイミド化させることによって得られる。
このホウ素誘導体中のホウ素含有量には、特に制限はないが、好ましいホウ素含有量は、0.05質量%以上5質量%以下、より好ましくは0.1質量%以上3質量%以下である。
配合量が0.5質量%未満であると、その効果が発揮されにくく、また15質量%を超えてもその配合量に見合った効果は得られない。
また、コハク酸イミド化合物は、上記の規定量を含有する限り、単独または2種以上を組み合わせて用いてもよい。
アルカリ土類金属サリシレートとしては、アルキルサリチル酸のアルカリ土類金属塩、特にマグネシウム塩やカルシウム塩等が挙げられ、中でもカルシウム塩が好ましく用いられる。
これらはまた1級アルキル基、2級アルキル基または3級アルキル基でもよい。
また、アルカリ土類金属スルフォネート、アルカリ土類金属フェネートおよびアルカリ土類金属サリシレートとしては、前記のアルキル芳香族スルフォン酸、アルキルフェノール、アルキルフェノールサルファイド、アルキルフェノールのマンニッヒ反応物、アルキルサリチル酸等を直接、マグネシウムおよび/またはカルシウムのアルカリ土類金属の酸化物や水酸化物等のアルカリ土類金属塩基と反応させたり、または一度ナトリウム塩やカリウム塩等のアルカリ金属塩としてからアルカリ土類金属塩と置換させること等により得られる中性アルカリ土類金属スルフォネート、中性アルカリ土類金属フェネートおよび中性アルカリ土類金属サリシレートだけでなく、中性アルカリ土類金属スルフォネート、中性アルカリ土類金属フェネートおよび中性アルカリ土類金属サリシレートと過剰のアルカリ土類金属塩やアルカリ土類金属塩基を水の存在下で加熱することにより得られる塩基性アルカリ土類金属スルフォネート、塩基性アルカリ土類金属フェネートおよび塩基性アルカリ土類金属サリシレートや、炭酸ガスの存在下で中性アルカリ土類金属スルフォネート、中性アルカリ土類金属フェネートおよび中性アルカリ土類金属サリシレートをアルカリ土類金属の炭酸塩またはホウ酸塩を反応させることにより得られる過塩基性アルカリ土類金属スルフォネート、過塩基性アルカリ土類金属フェネートおよび過塩基性アルカリ土類金属サリシレートも含まれる。
なお、ここでいう全塩基価とは、JIS K 2501「石油製品および潤滑油-中和価試験方法」の7.に準拠して測定される電位差滴定法(塩基価・過塩素酸法)による全塩基価を意味する。
なお、ここでいう金属比とは、金属系清浄剤における金属元素の価数×金属元素含有量(モル%)/せっけん基含有量(モル%)で表され、金属元素とはカルシウム、マグネシウム等、せっけん基とは、スルフォン酸基、フェノール基およびサリチル酸基等を意味する。
金属系清浄剤の配合量は、組成物全量基準で、好ましくは0.01質量%以上20質量%以下、より好ましくは0.1質量%以上10質量%以下である。
配合量が0.01質量%未満であると、その効果が発揮されにくく、また20質量%を超えてもその添加に見合った効果は得られない。
また、金属系清浄剤は、上記の規定量を含有する限り、単独または2種以上を組み合わせて用いてもよい。
フェノール系酸化防止剤としては、例えば、4,4’-メチレンビス(2,6-ジ-t-ブチルフェノール);4,4’-ビス(2,6-ジ-t-ブチルフェノール);4,4’-ビス(2-メチル-6-t-ブチルフェノール);2,2’-メチレンビス(4-エチル-6-t-ブチルフェノール);2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール);4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェノール);4,4’-イソプロピリデンビス(2,6-ジ-t-ブチルフェノール);2,2’-メチレンビス(4-メチル-6-ノニルフェノール);2,2’-イソブチリデンビス(4,6-ジメチルフェノール);2,2’-メチレンビス(4-メチル-6-シクロヘキシルフェノール);2,6-ジ-t-ブチル-4-メチルフェノール;2,6-ジ-t-ブチル-4-エチルフェノール;2,4-ジメチル-6-t-ブチルフェノール;2,6-ジ-t-アミル-p-クレゾール;2,6-ジ-t-ブチル-4-(N,N’-ジメチルアミノメチルフェノール);4,4’-チオビス(2-メチル-6-t-ブチルフェノール);4,4’-チオビス(3-メチル-6-t-ブチルフェノール);2,2’-チオビス(4-メチル-6-t-ブチルフェノール);ビス(3-メチル-4-ヒドロキシ-5-t-ブチルベンジル)スルフィド;ビス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)スルフィド;n-オクチル-3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオネート;n-オクタデシル-3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオネート;2,2’-チオ[ジエチル-ビス-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]などが挙げられる。
これらの中で、特にビスフェノール系およびエステル基含有フェノール系のものが好適である。
これらの中で、ジアルキルジフェニルアミン系およびナフチルアミン系のものが好適である。
6価のモリブデン化合物と反応させるアミン化合物としては特に制限されないが、具体的には、モノアミン、ジアミン、ポリアミンおよびアルカノールアミンが挙げられる。
より具体的には、メチルアミン、エチルアミン、ジメチルアミン、ジエチルアミン、メチルエチルアミン、メチルプロピルアミン等の炭素数1~30のアルキル基(これらのアルキル基は直鎖状でも分枝状でもよい)を有するアルキルアミン;エテニルアミン、プロペニルアミン、ブテニルアミン、オクテニルアミン、およびオレイルアミン等の炭素数2~30のアルケニル基(これらのアルケニル基は直鎖状でも分枝状でもよい)を有するアルケニルアミン;メタノールアミン、エタノールアミン、メタノールエタノールアミン、メタノールプロパノールアミン等の炭素数1~30のアルカノール基(これらのアルカノール基は直鎖状でも分枝状でもよい)を有するアルカノールアミン;メチレンジアミン、エチレンジアミン、プロピレンジアミン、およびブチレンジアミン等の炭素数1~30のアルキレン基を有するアルキレンジアミン;ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等のポリアミン;ウンデシルジエチルアミン、ウンデシルジエタノールアミン、ドデシルジプロパノールアミン、オレイルジエタノールアミン、オレイルプロピレンジアミン、ステアリルテトラエチレンペンタミン等の上記モノアミン、ジアミン、ポリアミンに炭素数8から20までのアルキル基またはアルケニル基を有する化合物やイミダゾリン等の複素環化合物;これらの化合物のアルキレンオキシド付加物;およびこれらの混合物等が例示できる。
また、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。
これらの酸化防止剤の配合量は、組成物全量基準で、0.1質量%以上5質量%以下が好ましく、より好ましくは0.1質量%以上3質量%以下である。
耐摩耗剤または極圧剤の好ましい配合量は、組成物全量基準で、0.1質量%以上、20質量%以下の範囲である。
なお、亜鉛含有化合物の場合、亜鉛換算(組成物全量基準)で600質量ppm以下が好ましく、より好ましくは500質量ppm以下であり、さらに好ましくは400質量ppm以下である。また、リン含有化合物の場合、リン換算(組成物全量基準)で500質量ppm以下が好ましく、より好ましくは400質量ppm以下であり、さらに好ましくは300質量ppm以下である。亜鉛の配合量が600質量ppm以下、リンの配合量が500質量ppm以下であると、本組成物を用いても、塩基性化合物を消耗し更油期間が極端に短くなるというような不具合が生じない。
摩擦低減剤の配合量は、組成物全量基準で、好ましくは0.01質量%以上2質量%以下、より好ましくは0.01質量%以上1質量%以下である。
金属不活性剤の配合量は、組成物全量基準で、0.01質量%以上3質量%以下が好ましく、より好ましくは0.01質量%以上1質量%以下である。
これら防錆剤の配合量は、配合効果の点から、潤滑油組成物全量基準で、0.01質量%以上1質量%以下が好ましく、より好ましくは0.05質量%以上0.5質量%以下である。
界面活性剤または抗乳化剤の配合量は、組成物全量基準で、0.01質量%以上3質量%以下が好ましく、より好ましくは0.01質量%以上1質量%以下である。
各例における潤滑油組成物(試料油)の性状、および各種性能(ミスト化率、モータリング特性)は以下に示す方法で求めた。
JIS K2283に記載の方法に準拠して測定した。なお、混合基油についても100℃における動粘度を測定した。
(2)NOACK
ASTM D 5800-08に準拠して蒸発損失量を測定した。
(3)CCS粘度(コールドクランキングシミュレータ粘度)
JIS K2010に準拠して-35℃におけるせん断粘度を測定した。
(4)MR粘度(低温ポンピング粘度)
ASTM D 4684-08に準拠して-40℃における見かけ粘度を測定した。
(5)粘度指数
JIS K2283に記載の方法に準拠して、粘度指数を算出した。
(6)ミスト化率
以下に示すようなミスト化試験を行った。
圧縮空気と各試料油とを混合してミスト化し、浮遊ミスト化した油量(ミスト化質量)を測定し、試験油の質量で割り返すことでミスト化率を測定した。このミスト化率が低いほど浮遊ミストが少ないことを意味する。
ミスト化率(質量%)=(ミスト化質量/試料油の質量)×100
試験装置:TACOミスト測定装置(型式番号:C3-0807)
空気圧力:0.2MPa
試料油量:40g
以下に示すようなモータリング試験を行った。
「直列4気筒、DOHC、1500cc」のエンジンを用いて、油温60℃,80℃,および100℃、回転数1500rpm,2000rpm,および2500rpmの各条件で駆動トルクを測定し、全データ(9つ)の平均値を、試料油の駆動トルク値とした。そして、市販ACEA C2 5W-30(100℃における動粘度;10.29mm2/s、NOACK;14.3質量%、CCS粘度(-35℃);7700mPa・s、粘度指数172)を基準油として用い、基準油対比の駆動トルク値をトルク改善率とし、以下に示す基準でモータリング特性(省燃費性)を評価した。
A:基準油より優れる。(基準油対比のトルク改善率:1.5%以上)
B:基準油より優れる。(基準油対比のトルク改善率:1.5%未満)
C:基準油より劣る。
<製造例:1-デセンオリゴマー(3量体)水素添加物の製造>
(a)デセンのオリゴマー化
内容積5リットルの三つ口フラスコに、不活性ガス気流下、デセンモノマー(出光興産(株)製:リニアレン10)4リットル(21.4モル)を仕込み、更に、トルエンに溶解したビスシクロペンタジエニルジルコニウムジクロリド(錯体質量1168mg:4ミリモル)と同じくトルエンに溶解したメチルアルモキサン(Al換算:40ミリモル)を添加した。これらの混合物を40℃に保ち、20時間攪拌を行った後、メタノール20mlを添加してオリゴマー化反応を停止させた。次いで、反応混合物をオートクレーブから取出し、これに5モル/リットルの水酸化ナトリウム水溶液4リットルを添加し、室温で強制攪拌を4時間した後、分液操作を行なった。上層の有機層を取出し、未反応のデセンおよび副反応生成物のデセン異性体をストリッピングして除去した。
(b)デセンオリゴマーの水素化
内容積5リットルのオートクレーブに、窒素気流下、(a)で製造したデセンオリゴマー3リットルを入れ、トルエンに溶解させたコバルトトリスアセチルアセトナート(触媒重量3.0g)とトルエンで希釈したトリイソブチルアルミニウム(30ミリモル)を添加した。添加後、水素で系内を2回置換してから、昇温し、反応温度80℃で、水素圧を0.9MPaに保持した。水素化は発熱を伴いながら直ちに進行し、反応開始後4時間の時点で降温し、反応を停止した。その後、脱圧し、内容物を取出してから、反応生成物を単蒸留し、留出温度240℃から270℃までの範囲で、圧力530Paの留分(1-デセンの3量体の水素添加物)を分離した。
以下のようなPAO、鉱油および添加剤を用い、表1および表2に示す配合組成の潤滑油組成物(試料油)を調製した。各試料油の性状、および各種性能についても併せて表1、表2に示す。
・PAO-1:INEOS社製、Durasyn145(100℃における動粘度;5.194mm2/s、NOACK;5.1質量%、CCS粘度(-35℃);2570mPa・s、粘度指数;145)
・PAO-2:上記製造例で得られたmPAO(100℃における動粘度;3.458mm2/s、NOACK;11.1質量%、CCS粘度(-35℃);800mPa・s、粘度指数;127)
・PAO-4:INEOS社製、Durasyn166(100℃における動粘度;5.824mm2/s、NOACK;6.0質量%、CCS粘度(-35℃);3950mPa・s、粘度指数;178)
・鉱油-2:水素化精製鉱油(100℃における動粘度;6.483mm2/s、NOACK;7.5質量%、CCS粘度(-35℃);10100mPa・s以下、粘度指数;121)
・添加剤パッケージ:Infineum社製、infineum P6000
・粘度指数向上剤:ポリメタクリレート(質量平均分子量230,000、樹脂分45質量%
・流動点降下剤:ポリアルキルメタクリレート(質量平均分子量6,000)
表1に示すように、本組成物の構成を全て備えた実施例1から5までの試料油は、特定の性状を有するPAOと特定の性状を有する鉱油に加え、さらに所定の質量平均分子量を有するポリイソブチレンが配合されている。それ故、低蒸発性であって耐ミスト性および耐コーキング性に優れ、さらに低粘度であることから省燃費性にも優れることが理解できる。それ故、本組成物は、通常の内燃機関だけでなく、ターボ機構を備えたガソリンエンジンやディーゼルエンジンに対しても好適である。
一方、表2に示すように、比較例の各試料油は、いずれも上述した配合組成を有していないので、低蒸発性、耐ミスト性、耐コーキング性および省燃費性のすべてを満足することはできない。
Claims (8)
- (A)成分:100℃における動粘度が5.5mm2/s以下、-35℃におけるCCS粘度が3000mPa・s以下、NOACKが12質量%以下であるポリアルファオレフィン
(B)成分:粘度指数が120以上である鉱油
前記(A)成分と(B)成分とを含む基油に、
質量平均分子量が50万以上であるポリイソブチレンを配合してなり、
潤滑油全量基準で、前記(A)成分の配合量が25質量%以上である
ことを特徴とする内燃機関用潤滑油組成物。 - 請求項1に記載の内燃機関用潤滑油組成物において、
前記ポリイソブチレンの配合量が組成物全量基準で樹脂分として0.005質量%以上、0.2質量%以下である
ことを特徴とする内燃機関用潤滑油組成物。 - 請求項1または請求項2に記載の内燃機関用潤滑油組成物において、
前記(A)成分と(B)成分とを配合してなる基油の100℃における動粘度が4.6mm2/s以下である
ことを特徴とする内燃機関用潤滑油組成物。 - 請求項1から請求項3までのいずれか1項に記載の内燃機関用潤滑油組成物において、
該組成物のNOACKが10質量%以下であり、-35℃におけるCCS粘度が6000mPa・s以下であり、-40℃におけるMR粘度が30000mPa・s以下である
ことを特徴とする内燃機関用潤滑油組成物。 - 請求項1から請求項4までのいずれか1項に記載の内燃機関用潤滑油組成物において、
前記(B)成分の配合量が組成物全量基準で20質量%以上である
ことを特徴とする内燃機関用潤滑油組成物。 - 請求項1から請求項5までのいずれか1項に記載の内燃機関用潤滑油組成物において、
前記(A)成分がメタロセン触媒により重合してなる
ことを特徴とする内燃機関用潤滑油組成物。 - 請求項1から請求項6までのいずれか1項に記載の内燃機関用潤滑油組成物において、
前記(A)成分が炭素数10から14までのアルファオレフィンから選ばれた少なくともいずれかをモノマーとするポリアルファオレフィンである
ことを特徴とする内燃機関用潤滑油組成物。 - 請求項1から請求項7までのいずれか1項に記載の内燃機関用潤滑油組成物において、
前記(A)成分が3量体である
ことを特徴とする内燃機関用潤滑油組成物。
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US11155764B2 (en) | 2016-05-05 | 2021-10-26 | Afton Chemical Corporation | Lubricants for use in boosted engines |
US10858610B2 (en) * | 2017-03-24 | 2020-12-08 | Exxonmobil Chemical Patents Inc. | Cold cranking simulator viscosity boosting base stocks and lubricating oil formulations containing the same |
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Cited By (6)
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WO2013055482A1 (en) | 2011-10-10 | 2013-04-18 | Exxonmobil Research And Engineering Company | Lubricating compositions |
WO2013055480A1 (en) | 2011-10-10 | 2013-04-18 | Exxonmobil Research And Engineering Company | Low viscosity engine oil compositions |
WO2013055481A1 (en) | 2011-10-10 | 2013-04-18 | Exxonmobil Research And Engineering Company | High efficiency engine oil compositions |
US9234151B2 (en) | 2011-10-10 | 2016-01-12 | Exxonmobil Research And Engineering Company | Lubricating compositions |
US9234150B2 (en) | 2011-10-10 | 2016-01-12 | Exxonmobil Research And Engineering Company | Low viscosity engine oil compositions |
US9234152B2 (en) | 2011-10-10 | 2016-01-12 | Exxonmobil Research And Engineering Company | High efficiency engine oil compositions |
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JP5878863B2 (ja) | 2016-03-08 |
KR101771764B1 (ko) | 2017-08-25 |
JPWO2011125881A1 (ja) | 2013-07-11 |
EP2554647A4 (en) | 2013-10-09 |
US20130030226A1 (en) | 2013-01-31 |
EP2554647A1 (en) | 2013-02-06 |
KR20130023236A (ko) | 2013-03-07 |
US9023190B2 (en) | 2015-05-05 |
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