WO2011125879A1 - Lubricant composition for an internal combustion engine - Google Patents

Lubricant composition for an internal combustion engine

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Publication number
WO2011125879A1
WO2011125879A1 PCT/JP2011/058291 JP2011058291W WO2011125879A1 WO 2011125879 A1 WO2011125879 A1 WO 2011125879A1 JP 2011058291 W JP2011058291 W JP 2011058291W WO 2011125879 A1 WO2011125879 A1 WO 2011125879A1
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group
internal combustion
combustion engine
less
lubricating oil
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PCT/JP2011/058291
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French (fr)
Japanese (ja)
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一裕 手島
元治 石川
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出光興産株式会社
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102Aliphatic fractions
    • C10M2203/1025Aliphatic fractions used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic 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
    • C10M2205/0285Organic 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular 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
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2220/00Specified physical or chemical properties or characteristics, i.e. function, of single compounds in lubricating compositions
    • C10N2220/02Physico-chemical properties
    • C10N2220/022Viscosity
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/02Viscosity or viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/54Fuel economy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/74Noack Volatility
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2240/00Specified uses or applications of lubricating compositions
    • C10N2240/10Internal-combustion engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2270/00Specific manufacturing methods for lubricant compositions or compounds not covered by groups C10N2210/00 - C10N2260/00

Abstract

The disclosed lubricant composition for an internal combustion engine comprises: (A) a polyalphaolefin that has a kinetic viscosity at 100°C of at most 5.5 mm²/s, a CCS viscosity at −35°C of at most 3,000 mPa∙s, and a NOACK of at most 12 mass%; and (B) a mineral oil with a viscosity index of at least 120. Component (A) constitutes at least 25% of the entire composition by mass.

Description

Lubricating oil composition for an internal combustion engine

The present invention, lubricating oil compositions relating for an internal combustion engine.

Gasoline in an internal combustion engine such as an engine or a diesel engine, which may generate deposits of carbon, called coking within the engine during use occurs. When coking occurs may become in the engine cooling insufficient, and or flow of the lubricating oil itself is inhibited can lead to various disorders. In particular, in an engine equipped with a turbo mechanism, coking occurring in turbo bearing portion and the housing, or the oil supply passage has become a problem.
To prevent the occurrence of coking, it is effective to use evaporative low lubricating oil. The lubricating oil for low volatility of the internal combustion engine, the composition comprising a blend of PAO base oil and a low viscosity Group II or Group III in the API classification has been proposed (see Patent Documents 1 and 2).

JP-T 2008-533274 JP JP-T 2009-510214 JP

On the other hand, the internal combustion engine lubricating oil is important also fuel efficiency, low evaporation properties of the lubricating oil is generally higher viscosity, there is a possibility that the fuel economy is deteriorated. For even lubricating oil composition as described in Patent Documents 1 and 2, not necessarily sufficient with respect to the balance between the low volatility and fuel efficiency.

The present invention is excellent in anti-coking property a low volatility, and an object thereof is to further provide an internal combustion engine lubricating oil composition excellent in fuel economy.

In order to solve the above problem, the present invention is to provide an internal combustion engine lubricating oil composition as follows.
(1) (A) 100 kinematic viscosity at ℃ is 5.5 mm 2 / s or less, -35 CCS viscosity at ℃ is 3000 mPa · s or less, and poly α- olefin is NOACK is less 12 mass%, (B) viscosity index is blended with a mineral oil of 120 or more, the composition in the total amount of (a) the lubricating oil composition for an internal combustion engine, wherein the amount of the component is not less than 25 mass%.
(2) In the lubricating oil composition described above, the component (A) and (B) a kinematic viscosity at 100 ° C. of the base oil obtained by blending the components is less than 4.6 mm 2 / s internal combustion engine lubricating oil composition characterized.
(3) In the lubricating oil composition described above, NOACK of the composition is not more than 10 wt%, the lubricating oil for an internal combustion engine CCS viscosity equal to or less than 6000 mPa · s at -35 ° C. Composition.
(4) In the lubricating oil composition described above, wherein (B) for an internal combustion engine lubricating oil composition, wherein the amount of the component is not less than 20 wt% of the total amount of the composition.
(5) In the lubricating oil composition described above, the component (A) is an internal combustion engine lubricating oil composition characterized by being polymerized by a metallocene catalyst.
(6), characterized in that the internal combustion engine lubricating oil composition described above, wherein the component (A) is a poly α- olefin monomers one at least selected from α- olefins from 10 carbon atoms to 14 internal combustion engine lubricating oil composition to.
(7) In the internal combustion engine lubricating oil composition described above, wherein (A) an internal combustion engine lubricating oil composition characterized by component is trimer.

Internal combustion engine lubricating oil composition of the present invention, the mineral oil having specific properties and PAO having specific properties are blended, excellent coking resistance a low volatility, even more fuel efficiency Are better. Therefore, an internal combustion engine lubricating oil composition of the present invention is suitable also for a gasoline engine and a diesel engine with a turbo system.

Internal combustion engine lubricating oil composition of the present invention, as the component (A), 100 kinematic viscosity at ℃ is 5.5 mm 2 / s or less, -35 CCS viscosity at ℃ is 3000 mPa · s or less, NOACK is less 12 mass% and poly α- olefin is, is obtained by blending the mineral oil is (B) as component a viscosity index of 120 or more. It will be described in detail below.

(A) component:
(A) component in the present invention is a polymer of α- olefin poly α- olefin is (oligomer) (PAO).
Kinematic viscosity at 100 ° C. of PAO from the viewpoint of fuel economy, as the component (A) is required to be less 5.5 mm 2 / s. However, the kinematic viscosity is preferably from the viewpoint of lubricity is 3 mm 2 / s or more. Moreover, CCS viscosity at -35 ° C., it is necessary that the following 3000 mPa · s. Further, from the viewpoint of low volatility, it is also necessary NOACK is less than 12 wt%.
The number of carbon atoms of such is the monomers from which the PAO alpha-olefin, the viscosity index, low temperature properties such as pour point and low temperature viscosity, from 6 in view of the volatility to 20 preferably from 8 to 16 It is more preferable, particularly more preferably from 10 to 14. As the PAO, low volatility, although trimers of coking resistance and low fuel consumption point of view than the α- olefin is preferred, for the properties of interest, the number of carbon atoms of α- olefin and its mixing ratio, it is possible to adjust the degree of polymerization.
The polymerization catalyst of α- 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 catalyst, the 30 mm 2 / s or more low viscosity PAO is AlCl 3 catalysts have been used, low volatility, coking resistance and low fuel consumption point of view than the particular BF 3 catalyst, a metallocene catalyst is preferred.
BF 3 catalyst, water, an alcohol, are used together with the promoter such as an ester, of which viscosity index, low-temperature physical properties, from the point of view of yield, alcohol especially 1-butanol is preferable.

As the metallocene catalysts include catalysts comprising a combination of a metallocene compound and a cocatalyst. The metallocene compound, a metallocene compound represented by the following general formula (1) are preferred.
(RC 5 H 4) 2 MX 2 (1)
In the general formula (1), R is a hydrocarbon group having from 1 several hydrogen or C up to 10, M is a transition metal element of Group 4 of the periodic table, X is covalent or ionic bonding it is a ligand.

In the general formula (1), R is preferably a hydrocarbon group having 1 several hydrogen or C up to 4. Specific examples of M, titanium, zirconium, include hafnium, zirconium is preferred among these. Specific examples of X, a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group having from 1 to 20 carbon atoms (preferably from one to 10) from 1 to 20 carbon atoms (preferably 1 - 10), amino group, a phosphorus-containing hydrocarbon group having from 1 to 20 carbon atoms (preferably from 1 to 12) (eg, a diphenylphosphine group, etc.), a silicon-containing hydrocarbon having 1 to 20 carbon atoms (preferably from 1 to 12) hydrogen group (e.g., trimethylsilyl group), from 1 to 20 carbon atoms (preferably from 1 to 12) boron compound having a hydrocarbon group or a halogen (e.g., B (C 6 H 5) 4, BF 4 , etc. ) include the among these, a hydrogen atom, a halogen atom, a group selected from the group consisting of a hydrocarbon group and an alkoxy group are preferred.

Examples of the metallocene compounds represented by the general formula (1), for example, bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethyl cyclopentadienyl) zirconium dichloride, bis (an iso-propyl cyclopentadienyl) zirconium dichloride, bis (n- propyl cyclopentadienyl) zirconium dichloride, bis (n- butylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride , bis (thexyldimethylsilyl cyclopentadienyl) zirconium dichloride, bis (trimethylsilyl cyclopentadienyl) zirconium dichloride, bis (trimethylsilyl cyclopentadienyl) Jill Niumujikurorido, bis (cyclopentadienyl) zirconium chloro hydride, bis (cyclopentadienyl) methyl zirconium dichloride, bis (cyclopentadienyl) ethyl zirconium dichloride, bis (cyclopentadienyl) methoxy zirconium dichloride, bis (cyclo pentadienyl) phenyl zirconium dichloride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) di neopentyl zirconium, bis (cyclopentadienyl) dihydro zirconium, bis (cyclopentadienyl) dimethoxy zirconium, furthermore, the compounds described above, a chlorine atom and a bromine atom of these compounds, iodine atom, hydrogen atom, methyl , Those replaced with a phenyl group, also include those obtained by replacing the zirconium metal centers of the compounds titanium, hafnium.

As the co-catalyst, methylaluminoxane is preferable. Methylaluminoxane as can be used methyl aluminoxane known prior not particularly limited, for example, chain methylaluminoxane represented by the following general formula (2), the annular represented by the following general formula (3) methylaluminoxane and the like.

Formula (2) and the general formula (3), p represents the degree of polymerization is from usually 3 to 50, preferably from 7 to 40.

Methods for producing methylaluminoxane, may be mentioned a method of contacting with a condensing agent such trimethylaluminum and water, but is not particularly limited and means, may be reacted according to known methods.

The mixing ratio of the metallocene compound and methylaluminoxane, methylaluminoxane / metallocene compound (molar ratio) is from usually 15 to 150, it is preferably from 20 to 120, more preferably from 25 to 100. If the blending ratio is 15 or more, catalytic activity is expressed, also, alpha-dimers of olefins by generation, trimer or more yield suitable as base oil of lubricating oil is not lowered. On the other hand, if the blending ratio is 150 or less, it never demineralization removal of the catalyst may be incomplete.

The metallocene catalyst other than above such as for example a metallocene catalyst using a metallocene compound having a crosslinkable group. Preferably the metallocene compounds having two crosslinkable groups as the metallocene compounds, particularly metallocene compounds having the meso symmetry is preferred. The metallocene catalyst using a metallocene compound having the meso symmetry, for example, (a) a metallocene compound represented as a catalyst component by the following general formula (4), and, (b) said as the catalyst component (a) catalyst metallocene compound of the component or a derivative thereof and reacting with ionic compounds capable of forming a complex (b-1), and include a metallocene catalyst containing at least one component (b-2) selected from aluminoxane .

The compound represented by the general formula (4) is a compound of the meso symmetrical, in the general formula (4), M represents a metal element from Group III of the periodic table to Group 10. X represents a σ bonding ligand, and when X is plural, X may be the same or different, Y represents a Lewis base, if Y is plural, the plurality of Y be the same or different it may be. A is a hydrocarbon group having from 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having from 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 either the same or different from each other. R 1 represents a hydrogen atom, a halogen atom, a halogen-containing hydrocarbon group having from hydrocarbon group or 1 carbon atoms of from 1 to 20 carbon atoms to 20. q is an [(valence of M) -2] an integer from 1 to 5, r is an integer from 0 to 3. E is represented by the following general formula (5), a group represented by the following general formula (6), two E are identical.
Incidentally, the A meso symmetric compound, in binding mode of the two bridging groups (1,1 ') (2,2'), refers to transition metal compounds to crosslink two E.

In the general formula (5) and the general formula (6), R 2 is a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having from 1 to 4 carbon atoms, a silicon a group selected from the group consisting of-containing group and a heteroatom-containing group. When multiple R 2 are present, they may be the same or different from each other. Bond represented by the wavy line represents a bond between the bridging group A.

As the crosslinking group A in the general formula (4) is preferably a group represented by the following general formula (7).

In the general formula (7), B is the skeleton of the crosslinking group, 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, aromatic hydrocarbon group, an amine-containing group or a halogen-containing group. n is 1 or 2.

The metallocene compound represented by the general formula (4), for example, (1,1'-ethylene) (2,2'-ethylene) - bis (indenyl) zirconium dichloride, (1,1'-methylene) ( 2,2'-methylene) - (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-dimethyl indenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene) - bis (4,7-diisopropyl-indenyl) zirconium dichloride, (1, 1 ' - ethylene) (2,2'-ethylene) - bis (4-phenyl indenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene) - bis (3-methyl-4-isopropyl-indenyl ) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene) - bis (5,6-benzoindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'- dimethylsilylene) bis (cyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bis (indenyl) di Benzalkonium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene ) bis (3-n-butyl-indenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bis (3-i-propyl-indenyl) zirconium dichloride, (1, 1 ' - dimethylsilylene) (2,2'-dimethylsilylene) bis (3-trimethylsilyl-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bis (3-phenyl indenyl ) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bis (4,5 Benzoindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2 ' - dimethylsilylene) bis (5,6-dimethyl indenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bis (4,7-di--i- propyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bis (4-phenyl indenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bis (3-methyl -4-i-propyl-indenyl) zirconium dichloride, (1,1'-dimethylsilylene) ( 2,2'-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, and the like of the zirconium in these compounds obtained by substituting titanium or hafnium. Of course the present invention is not limited to these.

Examples of the (b-1) a catalyst component of the (b) catalyst component, wherein (a) reacts with the metallocene compound of the catalyst component, as long as the compound capable of forming an ionic complex, also any thing can be used, can be suitably used those represented by the following general formula (8) or the following general formula (9).
([L 1 -R 4] k +) a ([Z] -) b (8)
([L 2] k +) a ([Z] -) b (9)

In the general formula (8) and the general formula (9), L 1 is a Lewis base, L 2 denotes a M 2, R 5 R 6 M 3, R 7 3 C or R 8 M 3. [Z] - is a non-coordinating anion [Z 1] - or [Z 2] - shows the. Wherein [Z 1] - anion in which a plurality of groups are bonded to the element, i.e., [M 1 G 1 G 2 ··· G f] - ( wherein, M 1 is a Group 15 from Group 5 of the periodic table element up, preferably of group 13 in periodic table from group 15 to each element from .G 1 showing the up G f hydrogen atom, a halogen atom, an alkyl group having from 1 to 20 carbon atoms, having a carbon number of 2 dialkylamino groups of up to 40, an alkoxy group having from 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkyl aryl group having 7 carbon atoms up to 40, carbon arylalkyl groups having 7 to 40, a halogen-substituted hydrocarbon group having from 1 to 20 carbon atoms, heteroatom-containing acyloxy group having 1 to 20 carbon atoms, an organic metalloid group, or 2 carbon atoms, up to 20 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, It shows the salt. In addition, Lewis base may be coordinated. Further, R 4 is a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an aryl group, R 5 and R 6 are a cyclopentadienyl group , substituted cyclopentadienyl, indenyl group or fluorenyl group, R 7 represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having from 1 to 20 carbon atoms. R 8 is as tetraphenylporphyrin, a macrocyclic ligand such as phthalocyanine. k is [L 1 -R 4], is an integer of from 1 to ionic valence of [L 2] to 3, a is an integer of 1 or more, b = (k × a) . M 2 is, from the first periodic table to the third group, which includes the Group 11 to Group 13, and Group 17 element, M 3 is a seventh periodic table 12 It shows the elements up to the family.

Here, specific examples of L 1 include ammonia, methylamine, aniline, dimethylamine, diethylamine, N- methylaniline, diphenylamine, N, N- dimethylaniline, trimethylamine, triethylamine, tri -n- butylamine, methyl diphenylamine, pyridine, p- bromo -N, N-dimethyl aniline, p- nitro -N, N-amines such as dimethylaniline; thioethers such as tetrahydrothiophene; triethylphosphine, triphenylphosphine, phosphine such as diphenylphosphine benzoic esters such as ethyl; acetonitrile, and the like nitriles, such as benzonitrile.
Specific examples of R 4 include hydrogen, a methyl group, an ethyl group, a benzyl group, and a trityl group, specific examples of R 5, R 6 are, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, and the like pentamethylcyclopentadienyl group. Specific examples of R 7 include a phenyl group, p- tolyl group, and the like p- methoxyphenyl group, specific examples of R 8 can be mentioned tetraphenylporphyrin, phthalocyanine, allyl and methallyl. Specific examples of M 2 is, Li, Na, K, Ag , Cu, Br, mentioned and I, specific examples of M 3 include Mn, Fe, Co, Ni, Zn and the like. Also, [Z 1] -, i.e. in the [M 1 G 1 G 2 ··· G f], B Specific examples of M 1, Al, Si, P , As, Sb , etc., preferably B and Al and the like. Specific examples of the G 1 and G 2 to G f are a dialkylamino group include a dimethylamino group, a diethylamino group; an alkoxy group or a methoxy group as the aryloxy group, an ethoxy group, n- butoxy group, a phenoxy group, etc. ; methyl group as a hydrocarbon group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, n- octyl group, n- eicosyl group, a phenyl group, p- tolyl group, a benzyl group, 4- t- butylphenyl group, 3,5-dimethylphenyl group and the like; fluorine as the halogen atom, chlorine, bromine, and iodine; p-fluorophenyl group as hetero atom-containing hydrocarbon group, a 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 group, dicyclohexyl antimony group, such as diphenyl boron and the like.

Noncoordinating anions, i.e. pKa of -10 or less Bronsted acid alone, or a combination of Bronsted and Lewis acids conjugate base [Z 2] - Examples of trifluoromethanesulfonic acid anion (CF 3 SO 3) -, bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO 4) -, trifluoroacetic acid anion (CF 3 CO 2) - hexafluoroantimonate anion (SbF 6) -, fluorosulfonic acid anion (FSO 3) -, chlorosulfonic acid anion (ClSO 3) -, fluorosulfonic acid anion / antimony pentafluoride (FSO 3 / SbF 5) - , Fluorosulfonic acid anion / 5- fluoride arsenic (FSO 3 / AsF 5) - , trifluoromethanesulfonic acid / antimony pentafluoride (CF 3 SO 3 / SbF 5 ) - and the like, and the like.

Wherein (a) an ionic compound capable of reacting with the transition metal compound catalyst component to form an ionic complex, i.e., the specific examples of the (b-1) the catalyst component is tetrakis (pentafluorophenyl borate) N, N - dimethylanilinium tetraphenylborate, triethylammonium tetraphenylborate, tri -n- butylammonium tetraphenylborate trimethylammonium, tetraphenylborate, tetraethylammonium tetraphenylborate methyl (tri -n- butyl) ammonium tetraphenylborate, benzyl (tri -n- butyl) ammonium tetraphenylborate, dimethyl diphenyl ammonium, tetraphenyl borate triphenylmethyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methyl Rijiniumu, tetraphenylborate benzyl pyridinium tetraphenylborate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate triethylammonium tetrakis (pentafluorophenyl) borate tri -n- butylammonium tetrakis (pentafluorophenyl) borate triphenyl ammonium, tetrakis (pentafluorophenyl) borate tetra -n- butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate benzyl (tri -n- butyl) ammonium tetrakis (pentafluorophenyl ) borate methyldiphenyl ammonium tetrakis (pentafluorophenyl) borate tri phenyl (methyl) ammonium Arm, tetrakis (pentafluorophenyl) borate-methyl anilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium tetrakis (pentafluorophenyl) borate trimethyl anilinium tetrakis (pentafluorophenyl) borate methylpyridinium tetrakis (pentafluorophenyl ) borate benzyl pyridinium tetrakis (pentafluorophenyl) borate methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate methyl (4-cyano-pyridinium), tetrakis (pentafluorophenyl) borate triphenylphosphonium tetrakis [bis (3,5-di-fluoromethyl) phenyl] borate di Methyl anilinium tetraphenylborate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetrakis (pentafluorophenyl) borate ferrocenium tetrakis (pentafluorophenyl) borate (1,1'-dimethyl ferrocenium), tetrakis (pentafluorophenyl) borate decamethyltetrasiloxane ferrocenium tetrakis (pentafluorophenyl) borate and silver tetrakis (pentafluorophenyl) borate trityl tetrakis (pentafluorophenyl) borate lithium, tetrakis (pentafluorophenyl ) sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, hexafluoro phosphate Silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, and the like of silver trifluoromethanesulfonate. These (B-1) catalyst component may be used alone or may be used in combination of two or more.

On the other hand, the aluminoxanes of the (b-2) a catalyst component, for example, cyclic aluminoxane represented by the following general formula (10) include an annular aluminoxanes represented by the following general formula (11).

In the general formula (10) and the general formula (11), R 9 is or hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group having from 1 to 20 carbon atoms, preferably from 1 to 12 a halogen atom, w is represents an average degree of polymerization, is an integer of from generally 2 to 50, an integer of preferably from 2 to 40. Each R 9 may be the same or different.

Methods for producing the aluminoxanes, a method of contacting with a condensing agent such alkylaluminum and water can be mentioned, but is not particularly limited and means, may be reacted according to known methods.
For example, (1) an organoaluminum compound is dissolved in an organic solvent, a method of contacting it with water, (2) initial advance by adding an organic aluminum compound at the time of polymerization, a method of adding water after, (3) metal crystal water contained in the like salts, a method of reacting an organoaluminum compound adsorbed water to the inorganic or organic, is reacted with trialkyl aluminum (4) tetraalkyldialuminoxane, and the like further method of reacting water . The aluminoxanes may be insoluble in toluene. These aluminoxanes may be used singly or may be used in combination of two or more kinds.

The ratio of the above-mentioned (a) catalyst component and (b) catalyst component, when using (b-1) a catalyst component as (b) catalyst component, a molar ratio of 10: 1 to 1: 100 preferably in the range of 2: and more preferably ranges from 1 to 1:10. When departing from the above range, the catalyst cost per unit mass of the polymer becomes high, not practical. In the case of using the above-mentioned (b-2) catalyst component, a molar ratio of 1: 1 to 1: is preferably in the range of up to 1,000,000, 1: 10 to 1: and more preferably the range of up to 10000. If outside this range increases the catalyst cost per unit mass of the polymer is not practical. Further, above the (b) catalyst component can be used in combination (b-1) catalyst component and (b-2) a catalyst component alone or in combination.

In the present invention, the metallocene catalyst PAO (hereinafter, also referred to as "mPAO".) As monomers for the preparation of the preferred α- olefins from 10 carbon atoms to 14. From the viewpoint of viscosity index and low temperature properties, linear α- olefin is preferred. Specific examples include 1-decene, 1-dodecene, and 1-tetradecene and the like. Among these, 1-decene are particularly preferred.

Formula (1) or the general formula (4) metallocene compound represented by the alpha-olefin proportion [metallocene compound (mmol) / alpha-olefin (L)] is usually 0.01 0.4 is up, it is preferably from 0.05 to 0.3, more preferably from 0.1 to 0.2. The mixing ratio can be obtained a sufficient catalytic activity by 0.01 or more, whereas, if it is 0.4 or less, to improve the yield of trimer or higher oligomers suitable as base oil of lubricating oil, never demineralization removal of the catalyst may be incomplete.

Wherein the α- olefin polymerization is preferably carried out in the presence of hydrogen. The addition amount of hydrogen is generally not more than 0.1kPa least 50 kPa, preferably not more than 30kPa than 0.5 kPa, more preferably 1kPa or 10kPa or less. The addition amount of hydrogen that is sufficient catalytic activity can be obtained at least 0.1 kPa, whereas, if it is below 50 kPa, can reduce the generation of the saturation of the raw material α- olefin yield of mPAO of interest There is improved.

The polymerization of α- olefins is not limited to the reaction method may be conducted in the absence of a solvent, may be carried out in a solvent, any method may be used. When using a reaction solvent, such as benzene, toluene, xylene, aromatic hydrocarbons such as ethylbenzene, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclohexane, pentane, hexane, heptane, aliphatic hydrocarbons such as octane , chloroform, and halogenated hydrocarbons such as dichloromethane. Temperature of the polymerization reaction is usually 0 ℃ least 100 ° C. or less, preferably 20 ° C. or higher 80 ° C. or less, more preferably 30 ° C. or higher 70 ° C. or less. It said that it is the range, a sufficient catalytic activity can be obtained and thereby improving the yield of trimer or higher oligomers suitable as base oil of lubricating oil. The trimer or higher selectivity by carrying out the polymerization in a way that can be produced mPAO of 50% or more.

Depending on the purpose, it may be added to further process the mPAO obtained in the above manner, for example, in the case of improving the thermal stability and oxidation stability may be performed hydrotreating. Further, in the case of obtaining a lubricating base oil having the desired properties, it may be carried out distillation. The temperature of the hydrotreating is usually 50 ° C. or higher 300 ° C. or less, preferably 60 ° C. or higher 250 ° C. or less, and more preferably not more than 200 ° C. 70 ° C. or higher, the hydrogen pressure is usually 0.1MPa or more 10MPa or less , and the preferably at 0.5MPa or higher 2MPa or less, more preferably 0.7MPa or more 1.5MPa or less. In the hydrogenation process, it is possible to use a general hydrogenation catalyst, including Pd or Ni. Temperature in the distillation is usually 200 ° C. or higher 300 ° C. or less, preferably not more than 280 ° C. 220 ° C. or higher, more preferably not more 230 ° C. or higher 270 ° C. or less, the pressure is usually 0.1Pa than 15Pa or less, preferably is less 7Pa than 0.4 Pa, more preferably not more than 4Pa than 0.6 Pa.

mPAO after mPAO or hydrotreatment and distillation obtained in the above method, the short chain branching to about 1 per molecule (and usually 0.6 or more 1.2 or less, preferably 0.7 or and not more than 1.1 or less, and more preferably not more than 1.0 or 0.8 or more) with (in the present specification, referred methyl, ethyl group and propyl group and short chain branching.) . Furthermore, the short chain branching is predominantly methyl groups, the proportion of methyl groups are usually 80 mol% or more, preferably 85 mol% or more, more preferably 90 mol% or more.

In the present composition, the amount of the component (A), the total amount of the composition, it is necessary that not less than 25 mass%. In the blending amount is less than 25 wt%, it is impossible to sufficiently achieve the object of the present invention. Further, from the viewpoint that low volatility, (A) The amount of component, preferably 30 mass% or more, and more preferably at least 35 mass%. However, it is preferred that the solubility of the additives and the seal rubber 80 mass% or less than the compatibility viewpoint.

(B) component:
(B) component in the present invention is a viscosity index of 120 or more mineral oils. Such mineral oils, for example, hydrogenation refined mineral Group III in API classification is preferred.
Component (B), by being formulated with component (A), given an appropriate lubricity to the composition, it contributes to the improvement of fuel economy.
Further, by blending the component (B) improves the solubility of additives which are commonly used as for an internal combustion engine, resulting in contributing greatly to fuel efficiency.
Therefore, (B) component is preferably be formulated more than 20 mass% of the total amount of the composition, it is more preferable to be blended more than 25 wt%.

In the present invention, it is preferable that 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 that it is more preferably less.
When 100 ° C. kinematic viscosity of the mixed base oil is less than 4.6 mm 2 / s, contribute to the improvement of fuel economy. However, 100 ° C. kinematic viscosity of the mixed base oil in view of the volatility is preferably 3 mm 2 / s or more.

The composition is mainly composed of a mixed base oil as described above, NOACK of the composition is not more than 10 wt%, it is preferable CCS viscosity at -35 ° C. is not more than 6000 mPa · s. If CCS viscosity at NOACK and -35 ° C. is within this range, it is excellent in both fluidity (fuel efficiency) in coking resistance and low temperature, is suitable as a lubricating oil for internal combustion engine.

The lubricating oil composition of the present invention for the purpose is not impaired scope of the present invention, other additives as required, for example, viscosity index improvers, pour point depressants, detergent dispersants, antioxidants, antiwear-extreme pressure, friction modifiers, metal deactivators, can be appropriately blended rust, surfactants, demulsifiers, and antifoaming agents and the like.

Examples of the viscosity index improver include polymethacrylates, dispersion type polymethacrylates, olefin copolymers (e.g., ethylene - propylene copolymer), a dispersed olefin-based copolymer, a styrene-based copolymer (e.g., styrene - diene copolymers, styrene - isoprene copolymer) and the like. The amount of viscosity index improver, from the viewpoint of blending effects, the lubricating oil based on the total amount of the composition is preferably 0.5 wt% to 15 wt% or less, more preferably 10 mass% 1 mass% or more.

Examples of the pour point depressant, a weight average molecular weight and the like degree of polymethacrylate from 5000 to 50,000.
The amount of pour point depressant, from the viewpoint of blending effects, the lubricating oil based on the total amount of the composition is preferably 2 wt% or less than 0.1 wt%, more preferably less than 1 wt% 0.1 wt% is there.

The detergent dispersant, an ashless dispersant, it is possible to use a metal-based detergent.
The ashless dispersants, can be used any ashless dispersants used in lubricating oils, for example, monotype succinimide compound represented by the following general formula (II), or the general formula (III) They include succinic acid imide compound of bis type represented.

Above-mentioned formula (II), in (III), R 11, R 13 and R 14 are each an alkenyl group or an alkyl group having a number average molecular weight of 500 to 4,000, R 13 and R 14 are identical or different it may be. The number average molecular weight of R 11, R 13 and R 14 is preferably from 1,000 to 4,000.Also, R 12, R 15 and R 16 are each an alkylene group having from 2 carbon atoms up to 5, R 15 and R 16 may be the same or different, r is an integer of from 1 to 10, s is an integer of from 0 or 1 to 10.
When the number average molecular weight of the R 11, R 13 and R 14 is less than 500, decreases the solubility in the base oil, when it exceeds 4,000, detergency lowers, not the performance of the object is obtained I fear there is.
Also, the r is preferably from 2 to 5, more preferably from 3 to 4.
When r is less than 1, detergency deteriorates, when r is 11 or more, solubility in the base oil is deteriorated.
In the above formula (III), s is from preferably 1 to 4, more preferably 2 or 3.
Within the above range is preferred in terms of solubility in detergency and base oils.
The alkenyl group, a polybutenyl group, a polyisobutenyl group, an ethylene - can be mentioned propylene copolymer, the alkyl group are those they were hydrogenated.
Representative examples of suitable alkenyl groups include polybutenyl group or a polyisobutenyl group. Polybutenyl group is obtained as those obtained by polymerizing a mixture or high-purity isobutene of 1-butene and isobutene. Typical examples of suitable alkyl groups, is obtained by hydrogenating a polybutenyl group or a polyisobutenyl group.

The above alkenyl or alkyl succinimide compound is usually alkenylsuccinic anhydrides obtained by the reaction of a polyolefin with maleic anhydride, or an alkyl succinic anhydride obtained by hydrogenating, is reacted with a polyamine it can be produced by.
Additional monotype succinimide compound and succinimide compounds of bis type, can be produced by changing the reaction ratio of the alkenyl succinic anhydride or alkyl succinic anhydride with a polyamine.
The olefin monomer forming the polyolefin, can be used as a mixture of one or more of the α- olefin having a carbon number of 2 to 8, preferably using a mixture of isobutene and butene-1 be able to.

The polyamines, ethylene diamine, propylene diamine, butylene diamine, single diamines such pentylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, di (methylethylene) triamine, dibutyl triamine, tri-butylene tetramine , it may be mentioned polyalkylene polyamine, piperazine derivatives such as aminoethyl piperazine, such as penta pentylene hexamine.

Further, in addition to the above alkenyl or alkyl succinimide compound, a boron derivative, and these may be used either at least those modified with an organic acid.
Boron derivative of the alkenyl or alkyl succinimide compound may be used those produced by a conventional method.
For example, after the above-mentioned polyolefin is reacted with maleic anhydride and alkenyl succinic anhydrides, further said polyamines and boron oxide, boron halide, boric acid, boric anhydride, boric acid esters, and the boronic acid reacting a boron compound such as ammonium salt is reacted with an intermediate obtained by obtained by imidization.
The boron content in the boron derivative is not particularly limited, preferred boron content, 5 wt% or more 0.05 wt% or less, more preferably 3 wt% or less than 0.1 wt%.

The amount of the formula monotype succinimide compound represented by (II), or formula (III) above bis type succinimide compound represented by the total amount of the lubricating oil composition basis, 0.5 preferably wt% to 15 wt% or less, more preferably 10 mass% 1 mass% or more.
When the amount is less than 0.5 mass%, the effect is exhibited hardly, also the effect commensurate with the amount can not be obtained even exceed 15 wt%.
Further, the succinimide compound, as long as it contains the above defined amount may be used alone or in combination of two or more.

The metal-based detergent, any alkaline earth metal-based detergent used in lubricating oil may be used, for example, alkaline earth metal sulfonate, alkaline earth metal phenates, alkaline earth metal salicylates and among these two or more mixtures selected from the like.

The alkaline earth metal sulfonate, molecular weight 300 or more 1,500 or less, alkaline earth metal salts of alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound over 400 700 or less, particularly magnesium salts and / or calcium salts, and the like, among which calcium salt is preferably used.

The alkaline earth metal phenate, alkylphenol, alkylphenol sulfide, alkaline earth metal salts of the Mannich reaction product of alkylphenol, include particularly magnesium salts and calcium salts, among others calcium salt is preferably used.
The alkaline earth metal salicylate, alkaline earth metal salts of alkyl salicylic acids, in particular include magnesium salts, calcium salts and the like, among which calcium salt is preferably used.

The alkyl group constituting the alkaline earth metal-based detergent preferably has from 4 to 30 carbon atoms, a linear or branched alkyl group and more preferably from 6 to 18, it is linear it may be branched.
They also primary alkyl group or a secondary alkyl group or a tertiary alkyl group.
Further, alkaline earth metal sulfonate, the alkali earth metal phenates and alkaline earth metal salicylate, the alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, a Mannich reaction product of alkylphenol, such as direct alkyl salicylate, magnesium and / or or is reacted with an alkaline earth metal base of oxides and hydroxides of alkaline earth metals calcium, or is substituted with alkaline earth metal salts such as once after the alkali metal salts such as sodium salt and potassium salt by a neutral alkaline earth metal sulfonate obtained, not only the neutral alkaline earth metal phenate and neutral alkaline earth metal salicylate, neutral alkaline earth metal sulfonate, neutral alkaline earth metal phenates Obtained by and neutral alkaline earth metal salicylate with excess alkaline earth metal salt or an alkaline earth metal base is heated in the presence of water a basic alkaline earth metal sulfonate, basic alkaline earth metal phenate and and basic alkaline earth metal salicylate, the presence neutral alkaline earth metal sulfonate, neutral alkaline earth metal phenate and neutral alkaline earth metal alkaline earth carbonate or borate of a metal salicylate of the carbon dioxide overbased alkaline earth metal sulfonate obtained by reacting the overbased alkaline earth metal phenate and overbased alkaline earth metal salicylates also included.

The metallic detergent, said neutral salts, basic salts, and the like can be used overbased salts and mixtures thereof, especially overbased salicylates, overbased phenates, one overbased sulfonate above and mixing cleanliness of the neutral sulfonates are preferred in wear resistance.

Total base number of the metallic detergent is preferably at most 10 mgKOH / g or more 500 mgKOH / g, more preferably at most 15 mgKOH / g or more 450 mgKOH / g.
Here, the total base number referred, JIS K 2501 "Petroleum products and lubricants - neutralization number test method" 7. It means total base number by potentiometric titration as measured according to (base number-perchloric acid method).

The metallic detergent is not particularly limited to the metal ratio can be used as a mixture of 20 or less one or more, preferably, a metal ratio of 3 or less, more preferably 1.5 or less, particularly preferably it is an essential component 1.2 of the metal-based detergent, particularly preferred since it is excellent by stability and base number retention property oxidation and high-temperature detergency, and the like.
Herein, the term metal ratio is the valence × metal element content of the metal element in the metallic detergent (mol%) / soap group content expressed in (mol%), calcium and metal elements, magnesium, etc. , the soap group means a sulfonic acid group, a phenol group and salicylic acid groups.

Metallic detergents are generally are commercially available in a form diluted with a light lubricating base oil, the metal content is preferably has from 1 wt% to 20 wt%, 2 wt% to 16 wt% until things are more preferable. The amount of metallic detergent, the total amount of the composition, preferably 20 wt% or more 0.01 wt% or less, more preferably 0.1 mass% or more 10 wt% or less.
When the amount is less than 0.01 wt%, its effect is exhibited hardly, also effect can not be obtained commensurate with the addition even exceed 20 wt%.
The metal-based detergent, as long as it contains the above defined amount may be used alone or in combination of two or more.

As the antioxidant, phenol antioxidants, amine antioxidants, and molybdenum-amine complex-based antioxidant, and sulfur based antioxidants.
Examples of the phenolic antioxidant, for example, 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'-butylidene bis (3-methyl-6-t-butylphenol); 4,4'-isopropylidene-bis (2,6-di -t- butylphenol); 2,2'-methylenebis (4-methyl-6 - nonylphenol) 2,2'-iso butylidene bis (4,6-dimethylphenol) 2,2'-methylenebis (4-methyl-6-cyclohexylphenol); 2,6-di -t- butyl 4-methylphenol; 2,6-di -t- butyl-4-ethylphenol; 2,4-dimethyl -6-t-butylphenol, 2,6-di -t- amyl -p- cresol; 2,6 - di -t- butyl-4-(N, N'-dimethylaminomethyl phenol), 4,4'-thiobis (2-methyl -6-t-butylphenol); 4,4'-thiobis (3-methyl - 6-t-butylphenol); 2,2'-thiobis (4-methyl -6-t-butylphenol); bis (3-methyl-4-hydroxy -5-t-butylbenzyl) sulfide; bis (3,5 di -t- butyl-4-hydroxybenzyl) sulfide; n-octyl-3 (4-hydroxy-3,5-di -t- butyl phenyl) propionate; n-octadecyl-3- (4-hydroxy-3, 5-di -t- butyl phenyl) propionate; 2,2'-thio [diethyl - bis-3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate] and the like.
Among these, it is preferable particularly bisphenol-based and ester group-containing phenol.

As the amine antioxidant, for example, monooctyldiphenylamine; monoalkyl diphenylamine such as mono nonyl diphenylamine, 4,4'-dibutyl diphenylamine, 4,4'-dipentyl diphenylamine, 4,4'-dihexyl diphenylamine; 4,4'-heptyl diphenylamine, 4,4'-dioctyl diphenylamine, 4,4'-dialkyl diphenylamine such as di-nonyl diphenylamine, tetrabutyl diphenylamine; polyalkyl, such as tetra-nonyl diphenylamine; tetrahexyl diphenylamine; tetraoctyl diphenylamine diphenylamine, and those of naphthylamine, specifically, alpha-naphthylamine; phenyl -α- naphthylamine; more butylphenyl -α- naphthoquinone Triethanolamine; pentylphenyl -α- naphthylamine; hexylphenyl -α- naphthylamine; heptylphenyl -α- naphthylamine; octylphenyl -α- naphthylamine; and alkyl-substituted phenyl -α- naphthylamine, such as nonylphenyl -α- naphthylamine.
Among these, it is preferable that the dialkyl diphenylamine and naphthylamine.

The molybdenum-amine complex-based antioxidant, 6-valent molybdenum compounds, made by reacting at least one amine compound of molybdenum trioxide and molybdic acid in particular, for example, JP-A-2003-252887 it is possible to use a compound obtained by the process according to.
It is not particularly restricted but includes hexavalent amine compound to be reacted with the molybdenum compound, specifically, monoamines, diamines, polyamines and alkanolamines.
More specifically, with methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine, an alkyl group having 1 to 30 carbon atoms such as methyl propylamine (or of these alkyl groups and straight-chain or branched) alkylamine; Eteniruamin, propenylamine, butenylamine, Okuteniruamin, and alkenyl groups having 2 to 30 carbon atoms oleylamine (those alkenyl groups may be branched be linear) alkenyl amines having; methanol amine, ethanol amine , methanol ethanol amine, alkanol group having 1 to 30 carbon atoms such as methanol propanolamine (these alkanol groups may also be branched be linear) alkanolamine having; methylene diamine, ethylene diamine, propylene Amine, and alkylene diamine having an alkylene group having 1 to 30 carbon atoms, such as butylene diamine; diethylene triamine, triethylene tetramine, tetraethylene pentamine, polyamine such as pentaethylene hexamine; undecyl diethylamine, undecyl diethanolamine, dodecyl dipropanolamine , oleyl diethanolamine, oleyl propylenediamine, the monoamine such as stearyl tetraethylenepentamine, diamine compounds having an alkyl or alkenyl groups of the polyamine to the number 8 to 20 carbon or heterocyclic compounds imidazolines; alkylene of these compounds oxide adducts; and mixtures thereof and the like.
Further, sulfur-containing molybdenum complexes of succinimide described in KOKOKU 3-22438 and JP 2004-2866 publications can be exemplified.

As the sulfur-based antioxidant include phenothiazine, pentaerythritol - tetrakis - (3-laurylthiopropionate), didodecyl sulfide, dioctadecyl sulfide, didodecyl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, dodecyl octadecyl thiodipropionate, and 2-mercaptobenzimidazole and the like.
The amount of these antioxidants, the total amount of the composition, preferably 5 wt% or less than 0.1 wt%, and more preferably 3 mass% or less than 0.1 wt%.

The antiwear or extreme pressure agent, zinc dithiophosphate, zinc phosphate, zinc dithiocarbamate, disulfides, sulfurized olefins, sulfurized fats and oils, sulfurized esters, thiocarbonates, thiocarbamates, sulfur, such as polysulfides containing compounds; phosphites, phosphoric acid esters, phosphonic acid esters, and phosphorus-containing compounds such as amine salts thereof or metal salt; thiophosphite esters, thiophosphoric acid esters, thiophosphonic acid esters, and sulfur and phosphorous-containing antiwear agents, such as those amine salts or metal salts.
Preferred amount of the antiwear or extreme pressure agent, the total amount of the composition, 0.1 wt% or more, in the range of 20 wt% or less.
In the case of zinc-containing compound is preferably less 600 ppm by mass of zinc terms (the total amount of the composition), more preferably not more than 500 mass ppm, more preferably not more than 400 mass ppm. Also, in the case of the phosphorus-containing compound is preferably 500 ppm by mass or less of phosphorus terms (the total amount of the composition), more preferably not more than 400 mass ppm, further preferably 300 mass ppm or less. Zinc amount is 600 ppm by mass or less, the amount of the phosphorus is at most 500 ppm by mass, even using the present composition, Sarayu period consumed a basic compound such as that it becomes extremely short malfunction It does not occur.

The friction reducing agent, any compound which is generally used as a friction reducing agent for lubricating oil may be used, for example, at least one organic alkyl or alkenyl group having 6 carbon atoms to 30 in a molecule , fatty esters, fatty amides, fatty acids, fatty alcohols, ashless friction reducing agents such as aliphatic amines and aliphatic ethers.
The amount of friction reducing agent, the total amount of the composition, preferably 2 mass% or more 0.01% by mass or less, and more preferably not more than 1 mass% 0.01 mass% or more.

The metal deactivator, benzotriazole, tolyltriazole-based, thiadiazole-based, and imidazole-type compounds.
The amount of the metal deactivator, the total amount of the composition, preferably 3 mass% or more 0.01 wt% or less, and more preferably not more than 1 mass% 0.01 mass% or more.

Examples of the rust inhibitor include petroleum sulfonate, alkylbenzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinic acid esters, and polyhydric alcohol esters.
The amount of the rust inhibitor, from the viewpoint of blending effects, total amount of the lubricating oil composition basis, preferably from 1 mass% 0.01 mass%, more preferably 0.05 mass% to 0.5 mass% less.

As the surfactant or demulsifier, polyoxyethylene alkyl ethers, polyalkylene glycol-based non-ionic surfactants such as polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether and the like.
The amount of surfactant or demulsifier, the total amount of the composition, preferably 3 mass% or more 0.01 wt% or less, and more preferably not more than 1 mass% 0.01 mass% or more.

As the antifoaming agent, silicone oil, include fluorosilicone oils and fluoroalkyl ether, in view of balance between antifoaming effect and economical efficiency, the total amount of the composition, 0.005 wt% to 0.5 wt % or less, and more preferably 0.2 wt% or less than 0.01 mass%.

It will be described in more detail by the present invention through examples, but the present invention is not intended to restrict the scope.
Properties of the lubricating oil composition (sample oil) in each Example, and various performances (thin film evaporation characteristics, motoring characteristic) was determined by the following methods.

(1) was measured according to the method described in kinematic viscosity JIS K2283 at 100 ° C.. Incidentally, to measure the kinematic viscosity at 100 ° C. also mixed base oil.
(2) NOACK
It was measured evaporation loss in compliance with ASTM D 5800-08.
(3) CCS viscosity (cold cranking simulator viscosity)
In conformity with JIS K2010 to measure the shear viscosity at -35 ° C..
(4) in accordance with the method described in viscosity index JIS K2283, to calculate the viscosity index.
(5) The sample oil was 0.5g dropped in an aluminum container of the thin-film evaporation characteristics diameter 35 mm, was held 24 hours at 175 ° C. and placed in a hot-air constant temperature bath, and measuring the remaining mass of the sample oils, an evaporation rate calculated.
(6) motoring characteristic (fuel economy)
We were motoring test as described below.
Using the engine of the "in-line four-cylinder, DOHC, 1500cc", oil temperature 60 ° C., 80 ° C., and 100 ° C., the rotational speed 1500 rpm, measured driving torque for each condition of 2000 rpm, and 2500 rpm, all data (nine the average value of), was driving torque value of the sample oil. The commercial ACEA C2 5W-30 (100 Kinematic Viscosity at ℃; 10.29mm 2 /s,NOACK;14.3 wt%, CCS viscosity (-35 ℃); 7700mPa · s , viscosity index 172) based oil used, the driving torque value of the reference oil versus the torque improvement rate was evaluated motoring characteristic (fuel economy) according to the following criteria.
A: better than the reference oil. (Torque improvement rate of the reference oil compared: 1.5% or higher)
B: better than the reference oil. (Torque improvement rate of the reference oil Contrast: less than 1.5%)
C: less than the reference oil.

Among the base oil, MPAO described below were prepared as follows.
<Production Example: 1-decene oligomer (trimer) hydrogenated product prepared>
Three-necked flask oligomerization internal volume 5 l (a) decene, an inert gas stream, Desenmonoma (Idemitsu Kosan Co., Ltd.: Linearen 10) were charged 4 liters (21.4 mol), further, was dissolved in toluene biscyclopentadienyl zirconium dichloride (complex mass 1168Mg: 4 mmol) Like methylalumoxane (Al conversion: 40 mmol) dissolved in toluene was added. Maintaining the mixture thereof to 40 ° C., after stirring for 20 hours, methanol was added 20ml to stop the oligomerization reaction. Then, the reaction mixture was removed from the autoclave, to which was added 5 mol / aqueous sodium 4 liters hydroxide liter, after 4 hours the forced stirring at room temperature, was subjected to liquid separation operation. Removed upper organic layer was removed decene isomers of decene and side reaction products of unreacted stripped.
(B) the decene hydrogenation content volume of 5 liter autoclave oligomers, under a nitrogen stream, placed decene oligomer 3L prepared in (a), cobalt tris acetylacetonate dissolved in toluene (catalyst weight 3.0 g) and it was added triisobutylaluminum diluted with toluene (30 mmol). After the addition, the inside of the system from the substituted twice with hydrogen, the temperature was raised at a reaction temperature 80 ° C., and held the hydrogen pressure at 0.9 MPa. Hydrogenation proceeded immediately with exothermic, the temperature was lowered at the time of 4 hours after the reaction initiation, the reaction was stopped. Thereafter, depressurized, after taken out the contents, the reaction product was simply distilled, ranging from distillation temperature 240 ° C. to 270 ° C., a fraction (1-hydrogenated product of trimer decene pressure 530Pa ) were separated.

[Examples 1 to 4, Comparative Examples 1 to 4]
PAO, mineral oil and additives used, such as: lubricating oil composition of the formulation composition shown in Table 1 (sample oil) was prepared. It is shown in Table 1 together also for each sample oil properties, and various performances.
· PAO-1: INEOS Inc., Durasyn125 (kinematic viscosity at 100 ℃; 5.196mm 2 /s,NOACK;5.5 wt%, CCS viscosity (-35 ℃); 2490mPa · s , viscosity index; 143)
· PAO-2: INEOS Inc., Durasyn145 (kinematic viscosity at 100 ℃; 5.194mm 2 /s,NOACK;5.1 wt%, CCS viscosity (-35 ℃); 2570mPa · s , viscosity index; 145)
· PAO-3: the obtained in Preparation Example mPAO (100 Kinematic Viscosity at ℃; 3.458mm 2 /s,NOACK;11.1 wt%, CCS viscosity (-35 ℃); 800mPa · s , viscosity index; 127)

· PAO-4: INEOS Inc., Durasyn164 (100 Kinematic Viscosity at ℃; 3.893mm 2 /s,NOACK;14.0 wt%, CCS viscosity (-35 ℃); 1330mPa · s , viscosity index; 120)
· PAO-5: INEOS Inc., Durasyn166 (dynamic viscosity at 100 ℃; 5.824mm 2 /s,NOACK;6.0 wt%, CCS viscosity (-35 ℃); 3950mPa · s , viscosity index; 178)
Mineral oils -1: Hydrogenation refined mineral oil (kinematic viscosity at 100 ℃; 4.121mm 2 /s,NOACK;14.1 wt%, CCS viscosity (-35 ℃); 1870mPa · s , viscosity index; 122)
Mineral oils -2: Hydrogenation refined mineral oil (kinematic viscosity at 100 ℃; 6.483mm 2 /s,NOACK;7.5 wt%, CCS viscosity (-35 ℃); 10100mPa · s , viscosity index; 121)

Additive package: Infineum Co., infineum P6000
Viscosity index improvers: polymethacrylate (weight average molecular weight of 230,000, resin content 45 wt% (amount in Table 1 is the total amount of resin component was also included).)
· Pour point depressants: polymethyl methacrylates (weight average molecular weight of 6,000)

〔Evaluation results〕
As shown in Table 1, the sample oil from Example 1 with all of the configuration of the composition to 4, mineral oil having specific properties and PAO having specific properties are blended, low volatility it can be seen that excellent coking resistance is at. It is also excellent in fuel economy since a low viscosity. The excellent fuel economy will become obvious from the results of the motoring test. Thus, the composition, in addition to the normal internal combustion engine, is suitable also for a gasoline engine and a diesel engine with a turbo system.
On the other hand, each sample oil of Comparative Example, since neither given PAO is blended, it is impossible to satisfy both of fuel economy and low volatility (coking resistance).

Claims (7)

  1. (A) a kinematic viscosity at 100 ° C. is 5.5 mm 2 / s or less, -35 CCS viscosity at ° C. is 3000 mPa · s or less, and poly α- olefin is NOACK is less 12 mass%,
    (B) a viscosity index is blended with a mineral oil is 120 or more,
    Composition based on the total amount, (A) the lubricating oil composition for an internal combustion engine, wherein the amount of the component is not less than 25 mass%.
  2. In an internal combustion engine lubricating oil composition according to claim 1,
    Wherein components (A) and (B) an internal combustion engine lubricating oil composition characterized by kinematic viscosity at 100 ° C. of the base oil obtained by blending the components is less than 4.6 mm 2 / s.
  3. In an internal combustion engine lubricating oil composition according to claim 1 or claim 2,
    The NOACK composition is not more than 10 wt%, the internal combustion engine lubricating oil composition characterized by CCS viscosity at -35 ° C. is not more than 6000 mPa · s.
  4. In an internal combustion engine lubricating oil composition according to any one of claims 1 to 3,
    (B) the internal combustion engine lubricating oil composition, wherein the amount of the component is not less than 20 wt% of the total amount of the composition.
  5. In an internal combustion engine lubricating oil composition according to any one of claims 1 to 4,
    Wherein component (A) is an internal combustion engine lubricating oil composition characterized by being polymerized by a metallocene catalyst.
  6. In an internal combustion engine lubricating oil composition according to any one of claims 1 to 5,
    Wherein component (A) is an internal combustion engine lubricating oil composition characterized by either at least selected from α- olefins from 10 carbon atoms to 14 is poly α- olefin monomer.
  7. In an internal combustion engine lubricating oil composition according to any one of claims 1 to 6,
    (A) the lubricating oil composition for an internal combustion engine, wherein the component is a trimer.
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