CN100406543C - Lubricating oil compositions for automatic transmissions - Google Patents

Lubricating oil compositions for automatic transmissions Download PDF

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Publication number
CN100406543C
CN100406543C CNB028170113A CN02817011A CN100406543C CN 100406543 C CN100406543 C CN 100406543C CN B028170113 A CNB028170113 A CN B028170113A CN 02817011 A CN02817011 A CN 02817011A CN 100406543 C CN100406543 C CN 100406543C
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quality
lubricating oil
alkyl
phosphorus
composition
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CN1549853A (en
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有本直纯
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Eneos Corp
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Nippon Oil Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/108—Phenothiazine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/045—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

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  • Chemical & Material Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

A lubricating oil composition for an automatic transmission which has a mass ratio for phosphorus : calcium : boron : sulfur of 1 : 0.1 - 2 : 0.06 - 2 : 0.2 - 20, a concentration of phosphorus of 0.01 to 0.06 mass %, a concentration of the sulfur derived from a base oil of 0 to 0.1 mass %, a concentration of the sulfur derived from sulfur-containing additives of 0. 01 to 0.15 mass %, all ratios and concentrations being based on the total amount of the composition and determined by elemental analysis. The lubricating oil composition can be used for achieving the prevention of scratching phenomenon in a metal belt type automatic transmission even over a long period of time.

Description

The lubricating oil composition that is used for automatic transmission
Invention field
The present invention relates to be used for the lubricating oil composition of automatic transmission, be particularly related to the lubricating oil composition that is applicable to automobile-used belt continuously variable transmission device, μ-V feature that said composition can make the friction materials of automatic transmission demonstrate positive gradient prevents the scraping noise and makes positive gradient μ-V feature keep the longer time.
Background of invention
The automatic transmission that Hyundai Motor extensively adopts comprises gearshift and hydraulic control device, and gearshift is the combination of being furnished with the torque convertr of lock-up clutch, humid clutch and planetary set.But this automatic transmission has the fuel efficiency difference and collide the defective that the driver is felt under the weather because of gear shift due to the classification gear shift.Transmit energy by metal strip and realize the continuously variable transmission device (belt CVT) of the electrodeless variable-speed speed change gear of these defectives by way of compensation that come into operation.
Belt CVT comprises motion-work wheel, follow-up pulley and is used for energy-delivering metal strip that this metal strip is made up of a plurality of elements and the metal strip (steel band) that these elements are linked together.Also generally use automatic transmission fluid (ATF) commonly used in the stagewise automatic transmission among this belt CVT,, use many same parts among stagewise automatic transmission and the CVTs because this ATFs has cooling, lubricated and abrasion resistance.But find to have the automobile of some type belt CVTs to run into the phenomenon that especially when automobile sails garage or starting into, produces noise (scraping noise), i.e. so-called " scraping phenomenon " in recent years.
Found that this scraping phenomenon is that gear impact noise by the gear that places the CVTs back causes, is caused by the fluctuation in the follow-up pulley rotation process.The variation of also finding the frictional coefficient (μ) of metal strip and element this fluctuation occurs when being in antigradient with respect to the variation of sliding velocity (V), as disclosed among the JP-A-9-263782.μ-V feature of ATFs commonly used is not fine all the time among the belt CVT, and it alters a great deal when using for a long time, causes preventing the scraping noise fully.Therefore, the frequent scraping phenomenon that occurs.
For preventing the phenomenon of swiping fully, must develop a kind of ATF blending technology that can make friction materials demonstrate positive gradient μ-V feature all the time with this conventional ATFs.In addition, ATF must not only satisfy this necessary performance when fresh but also after using for some time, and keeps this performance for a long time.Have now found that lubricating oil deterioration by oxidation gradually after running for some time, the lubricating oil that particularly contains a large amount of sulphur is easy to take place μ-V feature decline.
Thereby, the purpose of this invention is to provide a kind of lubricating oil composition that is used for automatic transmission, said composition is applicable to belt CVTs, and the μ-V feature that can make friction materials demonstrate positive gradient prevents the scraping noise and makes positive gradient μ-V feature keep the longer time.
Summary of the invention
The present inventor finds to use and can realize above-mentioned purpose with element-specific than the composition that mixes special additive through after extensive investigations and the research, and the present invention is finished in this discovery substantially.
The invention provides a kind of lubricating oil composition that is used for automatic transmission, wherein by the definite phosphorus of ultimate analysis: calcium: boron: the mass ratio of sulphur is 1: (0.1 to 2): (0.06 to 2): (0.2 to 20), total amount based on composition, the concentration of phosphorus is 0.01 to 0.06% (quality), sulphur concentration from base oil is 0 to 0.1% (quality), is 0.01 to 0.15% (quality) from the sulphur concentration of sulfenyl additive.
Preferred lubricating oil composition of the present invention is the phosphorus of wherein determining by ultimate analysis: calcium: boron: the mass ratio of sulphur is 1: (0.1 to 1): (0.1 to 0.8): (0.4 to 5), total amount based on composition, the concentration of phosphorus is 0.02 to 0.05% (quality), sulphur concentration from base oil is 0 to 0.1% (quality), is 0.01 to 0.15% (quality) from the sulphur concentration of sulfenyl additive.
Contained sulfenyl additive is to be selected from (A) thiadiazoles and/or benzothiazole, (B) dithiocarbamate, (C) phosphorodithioate, (D) trithiophosphite, (E) polysulfide and (A) at least a compound of the derivative of (E) in the lubricating oil composition of the present invention.
Detailed Description Of The Invention
Be described in more detail below the present invention.
Except that lubricating base oil, lubricating oil composition of the present invention also comprises phosphorus, calcium, boron and sulphur.In these elements, sulphur is from base oil or additive such as sulfenyl additive and/or calcium base washing agent such as calcium sulphonate and calcium phenylate.Phosphorus is from phosphorus based additive and part sulfenyl additive.Calcium is from calcium base washing agent.Boron is from various additives such as boric acid modified succinimide and/or alkali metal borate or its hydrate.Each component of lubricating oil composition of the present invention is described below successively.
(1) base oil
The lubricating base oil that can be used for lubricating oil composition of the present invention can be any mineral base oil and/or the synthetic base oil that is commonly used for lubricant base.
The example of mineral base oil comprises paraffin or naphthenic oil, can be by for example solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrofining, sulfuric acid scrubbing and the clay treatment acquisition of one or more refining process of lubricating oil distillate process that crude oil atmospheric distillation or vacuum distilling are produced; With n-paraffin.
The example of synthetic base oil comprises poly-alpha-olefin such as 1-octene oligopolymer, 1-decene oligopolymer and ethylene-propylene oligopolymer and hydride thereof; Isobutylene oligomer and hydride thereof; Isoparaffin; Alkylbenzene; Alkylnaphthalene; Diester such as pentanedioic acid two (13) ester, di-2-ethylhexyl adipate, diisodecyl adipate, hexanodioic acid two (13) ester and Diisooctyl Sebacate; Polyol ester such as trimethylolpropane caprylate, TriMethylolPropane(TMP) pelargonate, tetramethylolmethane-2-ethylhexanoate and tetramethylolmethane pelargonate; The poly suboxygen alkyl glycol; Dialkyl diphenyl ether; And polyphenylene oxide.
The kinematic viscosity of lubricating base oil does not have particular restriction.But the kinematic viscosity of lubricating base oil under 100 ℃ is preferably 1 to 10mm 2/ s, more preferably 2 to 8mm 2/ s.
From the sulphur concentration of base oil is 0.1% (quality) or lower, preferred 0.05% (quality) or lower, more preferably 0.005% (quality) or lower.Sulphur concentration surpasses 0.1% (quality) and is difficult to μ-V feature of keeping stable for a long time.
(2) sulfenyl additive
Can be used for sulfenyl additive of the present invention is that any compound of the following stated (A) is to (E).
(A) thiadiazoles and/or benzothiazole
The specific examples of thiadiazoles comprises compound shown in the following formula:
Figure C0281701100051
In the formula (1), R 1For have 1 to 30, the straight or branched alkyl of preferred 6 to 24 carbon atoms, R 2For hydrogen or straight or branched alkyl, the preferred hydrogen of 1 to 30 carbon atom is arranged or the straight or branched alkyl of 1 to 24 carbon atom is arranged, a and b are 1,2 or 3, preferred 1 or 2 independently.
The specific examples of benzothiazole comprises compound shown in the following formula:
Figure C0281701100061
In the formula (2), R 3For straight or branched alkyl, preferable methyl and the ethyl of 1 to 4 carbon atom, R are arranged 4For have 1 to 30, the straight or branched alkyl of preferred 6 to 24 carbon atoms, c is 0 to 3 integer, preferred 0 or 1, d is 1 to 3 integer, preferred 1 or 2.
When mixing component (A) in the lubricating oil composition of the present invention, can use a kind of compound of the formula of being selected from (1) and (2) or two or the multiple compound that different structure is arranged that use is selected from formula (1) and (2).
(B) dithiocarbamate
Though can use any dithiocarbamate, its preferred embodiment comprises compound shown in formula (3) or (4):
In formula (3) and (4), R 5, R 6, R 7, R 8, R 9And R 10Independently for have 1 to 30, the alkyl of preferred 1 to 20 carbon atom, X is sulphur or methylene radical (CH 2-), e is 0 to 6 integer.
Be used for R 5To R 10The example of the alkyl that 1 to 30 carbon atom is arranged comprise alkyl, cycloalkyl, alkyl-cycloalkyl, alkenyl, aryl, alkaryl and aralkyl.
The example of alkyl comprises straight or branched alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
The example of cycloalkyl includes those of 5 to 7 carbon atoms, as cyclopentyl, cyclohexyl and suberyl.
The example of alkyl-cycloalkyl includes those of 6 to 11 carbon atoms, as methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl, diethyl cyclohexyl, methyl suberyl, dimethyl suberyl, methylethyl suberyl and diethyl suberyl, alkyl wherein can be bonded in any position of cycloalkyl.
The example of alkenyl comprises butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base and vaccenic acid base, can be straight or branched and also position of double bond can change.
The specific examples of aryl comprises phenyl and naphthyl.
The example of alkaryl includes those of 7 to 18 carbon atoms, as tolyl, xylyl, ethylbenzene base, propyl phenyl, butylbenzene base, penta phenyl, own phenyl, heptan phenyl, hot phenyl, nonyl phenyl, the last of the ten Heavenly stems phenyl, undecyl phenyl and dodecylphenyl, alkyl wherein can be a straight or branched, can be bonded in any position of aryl.
The specific examples of aralkyl includes those of 7 to 12 carbon atoms, and as benzyl, styroyl, hydrocinnamyl, benzene butyl, benzene amyl group and benzene hexyl, alkyl wherein can be a straight or branched.
One or more component (B) blending arbitrarily.
(C) phosphorodithioate
The example of phosphorodithioate comprises a kind of dialkyl dithiophosphate of being selected from compound shown in the following formula and two or the mixture of multiple dialkyl dithiophosphate:
Figure C0281701100081
In the formula (5), R 11And R 12Independently for have 2 to 30, the alkyl of preferred 3 to 20 carbon atoms.Be used for R 11And R 12The alkyl that 2 to 30 carbon atoms are arranged example with at R in the formula (3) 5To R 8Described identical.
(D) trithiophosphite
The example of trithiophosphite includes 2 to 30, the trithiophosphite compound of the alkyl of preferred 3 to 20 carbon atoms.Have 2 to 30 carbon atoms alkyl example with at R in the formula (3) 5To R 8Described identical.
(E) polysulfide
Polysulfide is the sulfur-based compound that is commonly referred to dialkyl thioether or olefine sulfide, represents with following formula:
R 13-S f-R 14 (6)
In the formula (6), R 13And R 14Independently for straight or branched alkyl, the aryl that 6 to 20 carbon atoms are arranged that 3 to 20 carbon atoms are arranged, the alkaryl of 6 to 20 carbon atoms is arranged or the aralkyl of 6 to 20 carbon atoms is arranged, f is 2 to 6 integer, preferred 2 to 5.
Be used for R 13And R 14The example of alkyl comprise n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, the straight or branched amyl group, the straight or branched hexyl, the straight or branched heptyl, the straight or branched octyl group, the straight or branched nonyl, the straight or branched decyl, the straight or branched undecyl, the straight or branched dodecyl, the straight or branched tridecyl, the straight or branched tetradecyl, the straight or branched pentadecyl, the straight or branched hexadecyl, the straight or branched heptadecyl, the straight or branched octadecyl, the straight or branched nonadecyl, with the straight or branched eicosyl.
Be used for R 13And R 14The example of aryl comprise phenyl and naphthyl.
Be used for R 13And R 14The example of alkaryl comprise tolyl (comprising all constitutional isomers), ethylbenzene base (comprising all constitutional isomers), straight or branched propyl group phenyl (comprising all constitutional isomers), straight or branched butyl phenyl (comprising all constitutional isomers), straight or branched amyl group phenyl (comprising all constitutional isomers), straight or branched hexyl phenyl (comprising all constitutional isomers), straight or branched heptyl phenyl (comprising all constitutional isomers), straight or branched octyl phenyl (comprising all constitutional isomers), straight or branched nonyl phenyl (comprising all constitutional isomers), straight or branched decyl phenyl (comprising all constitutional isomers), straight or branched undecyl phenyl (comprising all constitutional isomers), straight or branched dodecylphenyl (comprising all constitutional isomers), xylyl (comprising all constitutional isomers), ethyl methyl phenyl (comprising all constitutional isomers), diethyl phenyl (comprising all constitutional isomers), two (straight or branched) propyl group phenyl (comprising all constitutional isomers), two (straight or branched) butyl phenyl (comprising all constitutional isomers), methyl naphthyl (comprising all constitutional isomers), ethyl naphthyl (comprising all constitutional isomers), straight or branched propyl group naphthyl (comprising all constitutional isomers), straight or branched butyl naphthyl (comprising all constitutional isomers), dimethyl naphthyl (comprising all constitutional isomers), ethyl-methyl naphthyl (comprising all constitutional isomers), diethyl naphthyl (comprising all constitutional isomers), two (straight or branched) propyl group naphthyl (comprising all constitutional isomers), with two (straight or branched) butyl naphthyl (comprising all constitutional isomers).
Be used for R 13And R 14The example of aralkyl comprise benzyl, styroyl (comprising all isomer) and hydrocinnamyl (comprising all isomer).
R 13And R 14Be preferably by propylene, 1-butylene or iso-butylene deutero-have 3 to 18 carbon atoms alkyl, have 6 to 8 carbon atoms aryl, the alkaryl of 7 or 8 carbon atoms is arranged or the aralkyl of 7 or 8 carbon atoms is arranged.
The specific examples of this alkyl comprises sec.-propyl, side chain hexyl (comprising all branched isomers) by the propylene dimerization syntaxy, by Propylene trimers deutero-side chain nonyl (comprising all branched isomers), by propylene tetramer deutero-side chain dodecyl (comprising all branched isomers), by propylene pentamer deutero-side chain pentadecyl (comprising all branched isomers), by propylene six aggressiveness deutero-side chain octadecyls (comprising all branched isomers), sec-butyl, the tertiary butyl, by 1-butylene dimer deutero-side chain octyl group (comprising all branched isomers), by iso-butylene dimer deutero-side chain octyl group (comprising all branched isomers), by 1-butylene tripolymer deutero-branching dodecyl (comprising all branched isomers), by iso-butylene tripolymer deutero-side chain dodecyl (comprising all branched isomers), by 1-butylene tetramer deutero-side chain hexadecyl (comprising all branched isomers), with by iso-butylene tetramer deutero-side chain hexadecyl (comprising all branched isomers).The specific examples of this aryl comprises phenyl.The specific examples of this alkaryl comprises tolyl (comprising all constitutional isomers), ethylbenzene base (comprising all constitutional isomers) and xylyl (comprising all constitutional isomers).The specific examples of this aralkyl is benzyl and styroyl (comprising all constitutional isomers).
Can use in the lubricating oil composition of the present invention and be selected from above-mentioned sulfur-containing additive is component (A) one or more compound to (E) and derivative thereof.Among the present invention, the sulfenyl content of additive is 0.01 to 0.15% (quality) to the sulphur of (E) and derivative thereof with from total sulphur concentration of the sulphur of other additive based on the total amount of composition in such scope so that from component (A), is 0.01 to 0.06% (quality) to the phosphorus of (E) and derivative thereof with from the total phosphorus concentration of the phosphorus of phosphorus based additive based on the total amount of composition from component (A).The sulfenyl content of additive is pressed sulphur and is calculated less than 0.01% (quality) or when press phosphorus calculating less than 0.01% (quality), can not improve μ-V feature effectively.The sulfenyl content of additive is pressed sulphur and is calculated when surpassing 0.15% (quality) or pressing phosphorus calculating above 0.06% (quality), the oxidative stability of infringement gained lubricating oil composition.
For further improving μ-V feature, the sulfenyl content of additive is 0.01 to 0.15% (quality) to the sulphur of (E) and derivative thereof with from total sulphur concentration of the sulphur of other additive based on the total amount of composition in such scope so that from component (A) preferably, is 0.02 to 0.05% (quality) to the phosphorus of (E) and derivative thereof with from the total phosphorus concentration of the phosphorus of phosphorus based additive based on the total amount of composition from component (A).
(3) (F) phosphorus based additive
The example that can be used for phosphorus based additive of the present invention (hereinafter being called component (F)) is the salt of phosplate, bisphosphate, triguaiacyl phosphate, single phosphorous acid ester, diphosphites, GW-540, phosphoric acid ester and phosphorous acid ester, phosphoric acid, phosphorous acid, alkyl zinc dithiophosphate and composition thereof.In these components (component (F)), all be to contain 2 to 30 except that phosphoric acid and phosphorous acid, the compound of the alkyl of preferred 3 to 20 carbon atoms.
There is the example of the alkyl of 2 to 30 carbon atoms to comprise alkyl, cycloalkyl, alkyl-cycloalkyl, alkenyl, aryl, alkaryl and aralkyl.
The example of alkyl comprises ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, can be straight or branched.
The example of cycloalkyl includes those of 5 to 7 carbon atoms, as cyclopentyl, cyclohexyl and suberyl.
The example of alkyl-cycloalkyl includes those of 6 to 11 carbon atoms, wherein cycloalkyl can have the alkyl substituent in any position, as methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl, diethyl cyclohexyl, methyl suberyl, dimethyl suberyl, methylethyl suberyl and diethyl suberyl.
The example of alkenyl is butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base and vaccenic acid base, can be straight or branched and also position of double bond can change.
The example of aryl includes 6 to 18 carbon atoms, as phenyl and naphthyl.
The example of alkaryl includes those of 7 to 18 carbon atoms, as tolyl, xylyl, ethylbenzene base, propyl phenyl, butylbenzene base, penta phenyl, own phenyl, heptan phenyl, hot phenyl, nonyl phenyl, the last of the ten Heavenly stems phenyl, undecyl phenyl and dodecylphenyl, alkyl wherein can be a straight or branched, can be bonded in any position of aryl.
The example of aralkyl includes those of 7 to 12 carbon atoms, as benzyl, styroyl, hydrocinnamyl, benzene butyl, benzene amyl group and benzene hexyl, can be straight or branched.
Preferred compound as component (F) is a phosphoric acid; Phosphorous acid; Alkyl zinc dithiophosphate, alkyl wherein can be a straight or branched, as dipropyl zinc dithiophosphate, zinc dibutyldithiophosphate, diamyl disulfide for zinc phosphate, dihexyl zinc dithiophosphate, diheptyl zinc dithiophosphate and dioctyl zinc dithiophosphate; Mono alkyl phosphate, alkyl wherein can be straight or brancheds, as oneself ester of phosphoric acid one propyl ester, monobutyl phosphate, phosphoric acid one pentyl ester, phosphoric acid, phosphoric acid one heptyl ester and phosphoric acid one monooctyl ester; Mono phosphoric acid ester (alkyl) aryl ester such as phosphoric acid one phenyl ester and phosphoric acid one toluene ester; Phosphate dialkyl ester, alkyl wherein can be straight or brancheds, as di(2-ethylhexyl)phosphate propyl ester, dibutyl phosphate, di(2-ethylhexyl)phosphate pentyl ester, phosphoric acid dihexyl, di(2-ethylhexyl)phosphate heptyl ester and dioctylphosphoric acid ester; Di(2-ethylhexyl)phosphate (alkyl) aryl ester such as diphenyl phosphate and xylenylphosphate; Trialkylphosphate, alkyl wherein can be straight or brancheds, as tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate, tri hexyl phosphate, THP triheptylphosphate and trioctyl phosphate; Tricresyl phosphate (alkyl) aryl ester such as triphenylphosphate and Tritolyl Phosphate; Phosphorous acid mono alkyl ester, alkyl wherein can be straight or brancheds, as oneself ester of phosphorous acid one propyl ester, phosphorous acid one butyl ester, phosphorous acid one pentyl ester, phosphorous acid, phosphorous acid one heptyl ester and phosphorous acid one monooctyl ester; Phosphorous acid list (alkyl) aryl ester such as phosphorous acid one phenyl ester and phosphorous acid one toluene ester; Dialkyl phosphite, alkyl wherein can be straight or brancheds, as phosphorous acid dipropyl, dibutyl phosphite, phosphorous acid diamyl ester, phosphorous acid dihexyl, phosphorous acid two heptyl esters and dioctyl phosphite; Phosphorous acid two (alkyl) aryl ester such as phosphorous acid diphenyl ester and phosphorous acid diformazan phenyl ester; Trialkyl phosphite, alkyl wherein can be straight or brancheds, as tricresyl phosphite propyl ester, tributyl phosphate, tricresyl phosphite pentyl ester, the own ester of tricresyl phosphite, tricresyl phosphite heptyl ester and tricresyl phosphite monooctyl ester; Tricresyl phosphite (alkyl) aryl ester, wherein alkyl can be a straight or branched, as triphenyl phosphite and tricresyl phosphite; And composition thereof.
The specific examples of the salt of phosphoric acid ester and phosphorous acid ester comprises by phosplate, bisphosphate, single phosphorous acid ester or diphosphites and nitrogenous compound ammonia or the alkyl that contains 1-8 carbon atom is only arranged in its molecule or the aminated compounds reaction of the alkyl of hydroxyl obtains with all or part of remaining acid-hydrolysis that neutralizes for example.
The specific examples of nitrogenous compound comprises ammonia; Alkylamine, alkyl wherein can be a straight or branched, as Monomethylamine, monoethylamine, a propylamine, monobutylamine (MBA), an amylamine, a hexylamine, a heptyl amice, an octylame, dimethylamine, methyl ethyl-amine, diethylamine, methyl propylamine, ethyl propylamine, dipropyl amine, methylbutylamine, ethyl butyl amine, propyl group butylamine, dibutylamine, diamylamine, dihexylamine, two heptyl amices and Di-Octyl amine; Alkanolamine, alkanol groups wherein can be a straight or branched, as single carbinolamine, monoethanolamine, single Propanolamine, only son's hydramine, single amylalcohol amine, single hexanol amine, single enanthol amine, single octanol amine, single nonyl alcohol amine, dimethanolamine, methanol amine, diethanolamine, methyl alcohol Propanolamine, ethanol propanol amine, dipropanolamine, methyl alcohol butanolamine, ethanol and butanol amine, propyl alcohol butanolamine, two butanolamines, diamyl hydramine, two hexanol amine, two enanthol amine and two octanol amine; And composition thereof.
Lubricating oil composition of the present invention contains the component (F) of such amount so that is 0.01 to 0.06% (quality) from the phosphorus of component (F) with from the total phosphorus concentration of the phosphorus of other additive based on the total amount of composition.It is not preferred that phosphorus concentration is lower than 0.01% (quality), because the resistance to abrasion of resulting composition is bad, and phosphorus concentration is not preferred above 0.06% (quality) yet, because the oxidative stability of resulting composition is poor.For further improving μ-V feature, preferably contain the component (F) of such amount so that be 0.02 to 0.05% (quality) based on the total amount of composition from the phosphorus of component (F) with from the total phosphorus concentration of the phosphorus of other additive.
(4) (G) calcium base washing agent
The example that can be used for calcium base washing agent of the present invention (hereinafter referred to as component (G)) comprises that total basicnumber is generally 20 to 450mgKOH/g, preferred 50 to 400mgKOH/g alkaline calcium base washing agent.The total basicnumber that JIS K2501 (1992) the 7th part " mensuration of petroleum products and lubricant-neutralization value " is measured by the perchloric acid potentiometric titration is pressed in term used herein " total basicnumber " representative.
The specific examples of component (G) comprises one or more calcium base washing agent that is selected from following compound:
(G-1) total basicnumber is 20 to 450mgKOH/g calcium sulphonate;
(G-2) total basicnumber is 20 to 450mgKOH/g calcium phenylate; With
(G-3) total basicnumber is 20 to 450mgKOH/g calcium salicylate.
Particularly, component (G-1) is that calcium sulphonate can be to be the calcium salt of the alkyl aromatic sulfonic acid that obtains of 100 to 1500, preferred 200 to 700 Alkylaromatics sulfonation by molecular weight.The specific examples of alkyl aromatic sulfonic acid is mahogany acid and synthetic sulfonic acid.
Mahogany acid can be the mahogany acid that contained Alkylaromatics sulfonation obtains in the lubricant cut by mineral oil or the mahogany acid of by-product when producing white oil.Synthetic sulfonic acid can be that alkylbenzene (can be the alkylbenzene factory by-product as the detergent raw material) sulfonation that makes the straight or branched alkyl obtains or make polyolefine be alkylated into benzene or the sulfonation of dinonyl naphthalene is obtained.Though unrestricted, available oleum and sulfuric acid are as sulphonating agent.
Particularly, component (G-2) is that calcium phenylate can be to have that at least one contains 4 to 30, the calcium salt of the alkylphenol of the straight or branched alkyl of preferred 6 to 18 atoms; The calcium salt of the alkylphenol sulfide that this type of alkylphenol and reaction of Salmon-Saxl obtain; Or the calcium salt of the Mannich reaction product of the alkylphenol that obtains of alkylphenol and formaldehyde reaction.
Particularly, component (G-3) is that calcium salicylate can be to have that at least one contains 4 to 30, the calcium salt of the alkyl salicylate of the straight or branched alkyl of preferred 6 to 18 carbon atoms.
As long as component (G) be the total basicnumber of above-mentioned calcium sulphonate, calcium phenylate or calcium salicylate in 20 to 450mgKOH/g scope, then can be that Mannich reaction product by alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, alkylphenol or alkyl salicylate are directly with calcium oxide or calcium hydroxide reaction or changed into alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, the Mannich reaction product of alkylphenol or the salt that alkyl salicylate obtains of an alkali metal salt such as sodium salt or sylvite with the calcium salt replacement.Component (G) also can be that above-mentioned normal salt heats the basic calcium that obtains with excessive calcium salt or calcium hydroxide in the presence of water.Component (G) can also be that above-mentioned normal salt and above-mentioned basic calcium react the high alkaline calcium salt that obtains in the presence of carbonic anhydride.These are reflected at solvent and for example carry out in aliphatic hydrocarbon solvent such as hexane, aromatic hydrocarbon solvent such as dimethylbenzene or the lubricating base oil lighting end.
Metallo-detergent can be lubricated the form of base oil lighting end dilution be purchased.The preferred metallo-detergent of metal content in 1.0 to 20% (quality), preferred 2.0 to 16% (quality) scope that use.
The content of component (G) does not have particular restriction.But the content of component (G) is preferably 0.01 to 5.0% (quality), more preferably 0.05 to 4.0% (quality), based on the total amount of composition.Component (G) is less than 0.01% (quality) can not suppress humid clutch because of strength degradation due to the compression repeatedly, and component (G) surpasses the oxidative stability that 5.0% (quality) will reduce resulting composition.
(5) (H) boric acid modified succinimide
The example that can be used for boric acid modified succinimide (hereinafter referred to as component (H)) of the present invention comprises with boric acid obtains alkenyl succinimide modification that at least one alkyl that contains 40 to 400 carbon atoms or alkenyl are arranged in the molecule.Can mix one or more this type of succinimide in the lubricating oil composition of the present invention.
The carbon number of described alkyl or alkenyl is 40 to 400, preferred 60 to 350.There are the alkyl or the alkenyl that are less than 40 carbon atoms will reduce the solubleness of component (H) in lubricating base oil, and have alkyl or alkenyl will damage low-temperature fluidity more than 400 carbon atoms.
The specific examples that can be used for succinimide of the present invention comprises compound shown in formula (7) or (8):
Figure C0281701100141
R wherein 21For have 40 to 400, the alkyl or the alkenyl of preferred 60 to 350 carbon atoms, m is 1 to 5, preferred 2 to 4 integer; Or
Figure C0281701100151
R wherein 22And R 23Independently for have 40 to 400, the alkyl or the alkenyl of preferred 60 to 350 carbon atoms, n is 0 to 4, preferred 1 to 3 integer.
Succinimide is divided into shown in the formula (7) succinyl oxide wherein and adds to shown in single succinimide of polyamine one end and the formula (8) double amber imide that succinyl oxide wherein adds to the polyamine two ends.Among the present invention, this two classes succinimide and composition thereof all can be used as component (H).Boric acid modified succinimide used herein is the boron modified compound that above-mentioned succinimide and acid reaction obtain all or part of residue amino and/or imino-neutralization or amidation.
When lubricating oil composition of the present invention contained component (H), its content was generally 0.01 to 10.0% (quality), preferred 0.1 to 7.0% (quality), based on the gross weight of composition.Component (H) is less than 0.01% (quality) can not obtain enough detersive poweies, and component (H) will greatly be destroyed the low-temperature fluidity of resulting composition above 10.0% (quality).
(6) (I) alkali metal borate and hydride thereof
Component (I) is that the example of alkali metal borate and hydride thereof comprises hydrogenation lithium tetraborate, hydrogenation Sodium Tetraborate, hydrogenation potassium borate, hydrogenation boric acid rubidium and hydrogenation boric acid caesium.Particularly preferably be the hydrogenation potassium borate.
These alkali metal borates can obtain by the following method: the atomic ratio that makes potassium hydroxide or sodium hydroxide and boric acid water-soluble so that boric acid and basic metal (potassium/sodium) is in the scope of 2.0 to 4.5 (boron/basic metal); Add this solution in the oily solution that contains neutral alkaline earth metal sulfonate or succinimido ashless dispersant, vigorous stirring is to produce water-in-oil emulsion then; With make the dehydration of described emulsion obtain the dispersion agent of hydrogenation potassium borate or hydrogenation Sodium Tetraborate particulate.
In the described lubricating oil composition, the blended ratio of one or more component (I) can be selected arbitrarily, but preferably count 0.002% (quality) or higher, preferred 0.005% (quality) or higher and be 0.1% (quality) or lower, preferred 0.06% (quality) or lower, based on the total amount of composition by boron.Component (I) is lower than 0.002% (quality) by boron will make component (A) that the frictional property enhanced that makes between hardware composition can not be provided, and component (I) surpasses the stability in storage that 0.1% (quality) will reduce the gained lubricating oil composition by boron.
(7) other additive
Lubricating oil composition of the present invention can be used in combination with the anti-scratch of further enhancing with as other performance of lubricating oil with various additives known.This additive can be ashless dispersant, metallo-detergent, friction modifiers, antioxidant, viscosity index improver, defoamer and anti-wear agent except that component (G).
(J) ashless dispersant
The ashless dispersant that can be used in combination with lubricating oil composition of the present invention can be any compound that is used as ashless dispersant usually in lubricating oil.For example, can use has at least one alkyl that contains 40 to 400 carbon atoms or the nitrogenous compound of alkenyl in the molecule, if any those or derivatives thereofs of amino or imino-or the modified product of alkenyl succinimide.
Described alkyl or alkenyl can be straight or brancheds, preferably by the oligopolymer of alkene such as propylene, 1-butylene and iso-butylene or the low copolymer deutero-branched-chain alkyl or the thiazolinyl of ethene and propylene.Described alkyl or alkenyl have 40 to 400, preferred 60 to 350 carbon atoms.There are the alkyl or the alkenyl that are less than 40 carbon atoms that the solubleness of described compound in base oil is had disadvantageous effect, and the low-temperature fluidity that has alkyl or alkenyl more than 400 carbon atoms will destroy the gained lubricating oil composition.
The specific examples of the derivative of nitrogenous compound comprises nitrogenous compound and the monocarboxylic acid such as the formic acid of 2 to 30 carbon atoms is arranged or the polycarboxylic acid of 2 to 30 carbon atoms is arranged such as the oxygen modified compound that oxalic acid, phthalic acid, trimellitic acid and pyromellitic acid reaction obtain all or part of residue amino and/or imino-neutralization or amidation; The sulphur modified compound that nitrogenous compound and sulfocompound reaction obtain; With the modified product that nitrogenous compound is obtained through two or the multiple modification that is selected from oxygen modification and sulphur modification.
Though can mix one or more compound that is selected from above-mentioned ashless dispersant by arbitrary proportion among the present invention, the content of ashless dispersant is generally in the scope of 0.1 to 10% (quality), based on lubricating oil composition.
(K) metallo-detergent
The metallo-detergent except that component (G) that can be used in combination with lubricating oil composition of the present invention can be any compound that is used as metallo-detergent usually in lubricating oil.For example, can use basic metal or alkaline earth metal sulfonate, basic metal or alkaline-earth metal phenates, basic metal or alkaline-earth metal salicylate, and basic metal or alkaline-earth metal naphthenate.The use capable of being combined of one or more this compound.Alkali-metal example is sodium and potassium, and the example of alkaline-earth metal is a magnesium.The specific examples of preferable alloy washing agent is sulfonic acid magnesium, phenol magnesium and magnesium salicylate.The total basicnumber of these metallo-detergents and blended amount are selected arbitrarily according to the necessary performance characteristic of lubricating oil.
Though can mix one or more compound that is selected from above-mentioned metallo-detergent by arbitrary proportion among the present invention, its content is generally in the scope of 0.01 to 5% (quality), based on lubricating oil composition.
(L) friction modifiers
The friction modifiers that can be used in combination with lubricating oil composition of the present invention can be any compound that is used as friction modifiers usually in lubricating oil.For example, can use aminated compounds, fatty acid ester, fatty acid amide and fatty acid metal salt, intramolecularly all has at least one alkyl that contains 6 to 30 carbon atoms or alkenyl, preferably at least one contains the straight chained alkyl or the thiazolinyl of 6 to 30 carbon atoms.
The example of aminated compounds includes straight or branched (preferred straight chain) aliphatic monoamine of 6 to 30 carbon atoms, straight or branched (preferred straight chain) aliphatic polyamines that 6 to 30 carbon atoms are arranged and the alkylene oxide adduct of these aliphatic amines.The example of fatty acid ester includes straight or branched (preferred straight chain) lipid acid of 7 to 31 carbon atoms and the ester of aliphatic monohydric alcohol or aliphatic polyol.The example of fatty acid amide includes straight or branched (preferred straight chain) lipid acid of 7 to 31 carbon atoms and the acid amides of aliphatic monoamine or aliphatic polyamines.The example of fatty acid metal salt includes the alkaline earth salt (magnesium salts and calcium salt) or the zinc salt of straight or branched (preferred straight chain) lipid acid of 7 to 31 carbon atoms.
Though can mix one or more compound that is selected from above-mentioned friction modifiers by arbitrary proportion among the present invention, its content is generally in the scope of 0.01 to 5.0% (quality), preferred 0.03 to 3.0% (quality), based on the total amount of lubricating oil composition.
(M) antioxidant
The antioxidant that can be used in combination with lubricating oil composition of the present invention can be any conventional antioxidant such as phenolic group compound or the amino-complex that is used as antioxidant usually in lubricating oil.
The specific examples of antioxidant is that alkylphenol is as 2,6-di-tert-butyl-4-methy phenol, bis-phenol such as methylene radical-4,4-bis-phenol (2, the 6-di-tert-butyl-4-methy phenol), naphthylamines such as phenyl-a-naphthylamine, dialkyl diphenylamine, zinc dialkyl dithiophosphate are as two-2-ethylhexyl zinc dithiophosphate and (3,5-di-t-butyl-4-hydroxyphenyl) lipid acid such as propionic acid and monobasic or polyvalent alcohol such as methyl alcohol, Stearyl alcohol, 1, the ester of 6-hexylene glycol, neopentyl glycol, thiodiglycol, triglycol and tetramethylolmethane.
Though can mix one or more compound that is selected from above-mentioned antioxidant by arbitrary proportion among the present invention, its content is generally in the scope of 0.01 to 5.0% (quality), based on the total amount of lubricating oil composition.
(N) viscosity index improver
The viscosity index improver that can be used in combination with lubricating oil composition of the present invention can be non-decentralized viscosity index improver as one or more polymer of monomers that is selected from various methacrylic esters or its hydride or multipolymer and the decentralized viscosity index improver multipolymer as the various methacrylic esters that also contain nitrogen compound.Other example of viscosity index improver is non-decentralized or decentralized ethene-alpha-olefin copolymer (wherein said alpha-olefin can be propylene, 1-butylene or 1-amylene) or its hydride, polyisobutene or its hydrogenated products, phenylethylene-dialkene hydrogenated copolymer, styrene-maleic anhydride copolymer and polyoxyethylene alkylphenyl ethene.
Select the molecular weight of these viscosity index improvers need consider its shear stability.Particularly, the number-average molecular weight of non-dispersive type or decentralized polymethacrylate is preferably 5 000 to 150000, more preferably 5 000 to 35 000.The number-average molecular weight of polyisobutene or its hydride is 800 to 5 000, preferred 1 000 to 4 000.The number-average molecular weight of ethene-alpha-olefin copolymer and hydride thereof is 800 to 150 000, preferred 3 000 to 12 000.
In these viscosity index improvers, use ethene-alpha-olefin copolymer or its hydride to help to produce the splendid lubricating oil composition of shear stability.
Though can mix one or more compound that is selected from above-mentioned viscosity index improver by arbitrary proportion among the present invention, its content is generally in the scope of 0.1 to 40.0% (quality), based on the total amount of lubricating oil composition.
(O) defoamer
The defoamer that can be used in combination with lubricating oil composition of the present invention can be any conventional defoamer that is used as defoamer usually in lubricating oil.The specific examples of defoamer comprises siloxanes such as dimethyl siloxane and fluorosilicone.Though can mix one or more compound that is selected from above-mentioned defoamer by arbitrary proportion among the present invention, its content is generally in the scope of 0.001 to 0.05% (quality), based on the total amount of lubricating oil composition.
(P) sanitas
The sanitas that can be used in combination with lubricating oil composition of the present invention can be any conventional preservatives that is commonly used for the lubricating oil sanitas.Examples of preservatives comprises the compound based on benzotriazole, tolyl-triazole and imidazoles.Though can mix one or more compound that is selected from foregoing preservatives by arbitrary proportion among the present invention, its content is generally in the scope of 0.01 to 3.0% (quality), based on the total amount of lubricating oil composition.
It is 1 that lubricating oil composition of the present invention contains by the determination of elemental analysis mass ratio: (0.1-2): (0.06-2): phosphorus (0.2-20), calcium, boron and sulphur, and based on the total amount of composition.Described mass ratio is preferably 1: (0.1-1.0): (0.1-0.8): (0.4-5.0).
The total amount concentration that described lubricating oil composition contains based on composition is the phosphorus of 0.01 to 0.06% (quality), preferred 0.02 to 0.05% (quality).
It is that the sulphur and the concentration from base oil of 0 to 0.1% (weight) is the sulphur from the sulfenyl additive of 0.01 to 0.15% (quality) that described lubricating oil composition contains concentration.When p and s element mass ratio and concentration departed from above-mentioned scope respectively in above-mentioned base oil and the sulfenyl additive, the μ of described lubricating oil composition-V feature was with variation, thus the frequent scraping phenomenon that occurs.
Industrial applicibility
μ-V feature of using lubricating oil composition of the present invention can make interior metal strip of automatic transmission and element demonstrate positive gradient prevents the scraping phenomenon and can keep positive gradient μ-V feature for a long time.Thereby lubricating oil composition of the present invention is applicable to continuously variable transmission device such as belt CVTs.This lubricating oil composition also is applicable to stagewise automatic transmission and the final reduction drive gear of being furnished with limited-slip differential.
Preferred forms
Describe the present invention in more detail in conjunction with following invention and comparative example, but be not limited thereto.
Embodiment 1 to 8 and Comparative Examples 1 to 5
The lubricating oil composition of formulation embodiment 1 to 8 shown in the according to the form below 1 to 3 and Comparative Examples 1 to 5.Make each composition through following μ-V token test.
(μ-V token test)
Estimate μ-V feature by following rub(bing)test.
Device: Falex No.6 abrasion trier
Surface pressure: 3MPa
Oil temperature: 80 ℃
μ-V characteristic evaluating: frictional coefficient under the measurement 0.020m/s slip velocity and the frictional coefficient under the 0.005m/s slip velocity, calculate ratio (gradient) therebetween.Described gradient is just or negative relevant with the phenomenon that whether occurs swiping.Described gradient be on the occasion of the time, the phenomenon of swiping do not occur, and described gradient the phenomenon of swiping may appear when being negative value.
From table 1 to test-results shown in 3 as seen, lubricating oil composition of the present invention (embodiment 1 to 8) all demonstrates the μ-V feature of positive gradient.And wherein the element of phosphorus, calcium, boron and the sulphur lubricating oil composition that departs from the Comparative Examples 1 to 5 of the institute of the present invention range of definition than (mass ratio) does not demonstrate the μ-V feature of positive gradient.
Table 1
Figure C0281701100211
1) hydrocracking mineral oil A: base oil viscosity (100 ℃) 3.1mm 2/ s, sulphur content:＜0.001% (quality)
2) hydrocracking mineral oil B: base oil viscosity (100 ℃) 4.1mm 2/ s, sulphur content:＜0.001% (quality)
3) solvent treatment mineral oil A: base oil viscosity (100 ℃) 2.1mm 2/ s, sulphur content: 0.09% (quality)
4) decentralized polymethacrylate
5) non-dispersive type polymethacrylate
6) comprise ashless dispersant, phosphorus based additive, antioxidant and dilution wet goods
Phosphorus content and boron content in the ATF additive-package: 0.38% (quality), 0.013% (quality)
7) boric acid modified polybutylene-based succinimide, boron content: about 0.5% (quality)
8) total basicnumber: 300mgKOH/g, calcium contents: about 12% (quality)
9) sulphur content: 36% (quality)
10) sulphur content: 30% (quality)
11) sulphur content: 8.8% (quality), phosphorus content: 8.8% (quality)
12) sulphur content: 15% (quality), phosphorus content: 4% (quality)
13) sulphur content: 10% (quality)
14) sulphur content: 43% (quality)
15) Falex No.6 abrasion trier: 80 ℃ of oil temperature, surface pressure 3MPa, the Grad 0.005-0.020m/s between the slip velocity
Table 2
Figure C0281701100231
1)-15) with table 1 in identical
Table 3
Figure C0281701100241
1)-15) with table 1 in identical
Comparative Examples 6 and 7
For comparing, press the lubricating oil composition of the Comparative Examples of formulation shown in the table 46 and 7.Before running for some time and afterwards promptly they oxidized rotten before and estimate the μ-V feature of resulting composition among resulting composition and the embodiment 1 afterwards.Under 165.5 ℃ of oil temperature and 150 hours test condition of test period, make the rotten mode of each composition estimate oxidative stability by ISOT by JISK2514 (lubricating oil for IC engines oxidation stability test) regulation.The result also is shown in Table 4.
By result shown in the table 4 as seen, the composition of the embodiment of the invention 1 even after deterioration by oxidation, also keep the μ-V feature of positive gradient.On the contrary, wherein high and from the also high Comparative Examples 6 of the sulphur concentration of additive and composition μ-V feature variation of 7 from the sulphur concentration of base oil, demonstrate the μ-V feature of antigradient.
Table 4
Figure C0281701100261
1) hydrocracking mineral oil B: base oil viscosity (100 ℃) 4.1mm 2/ s, sulphur content:＜0.001% (quality)
2) hydrocracking mineral oil A: base oil viscosity (100 ℃) 2.1mm 2/ s, sulphur content: 0.09% (quality)
3) solvent treatment mineral oil B: base oil viscosity (100 ℃) 4.1mm 2/ s, sulphur content: 0.16% (quality)
4) decentralized polymethacrylate
5) non-dispersive type polymethacrylate
6) comprise ashless dispersant, phosphorus based additive, antioxidant and dilution wet goods
Phosphorus content and boron content in the ATF additive-package: 0.38% (quality), 0.013% (quality)
7) boric acid modified polybutylene-based succinimide, boron content: about 0.5% (quality)
8) total basicnumber: 300mgKOH/g, calcium contents: about 12% (quality)
9) sulphur content: 36% (quality)
10) sulphur content: 30% (quality)
11) sulphur content: 8.8% (quality), phosphorus content: 8.8% (quality)
12) sulphur content: 15% (quality), phosphorus content: 4% (quality)
13) sulphur content: 10% (quality)
14) sulphur content: 43% (quality)
15) Falex No.6 abrasion trier: 80 ℃ of oil temperature, surface pressure 3MPa, the Grad 0.005-0.020m/s between the slip velocity
16) Falex No.6 abrasion trier: 80 ℃ of oil temperature, surface pressure 3MPa, the Grad 0.005-0.020m/s between the slip velocity
ISOT handles (165.5 ℃ 150h) are estimated afterwards

Claims (2)

1. lubricating oil composition that is used for automatic transmission, described composition comprises base oil, at least aly be selected from following sulfenyl additive: (A) thiadiazoles and/or benzothiazole, (B) dithiocarbamate, (C) phosphorodithioate, (D) trithiophosphite, (E) polysulfide, (A) to the derivative of (E), (F) at least aly be selected from following phosphorus based additive: phosphoric acid ester and salt thereof, phosphorous acid ester and salt thereof, phosphoric acid, phosphorous acid, alkyl zinc dithiophosphate and their mixture, (G) calcium base washing agent, (H) boric acid modified succinimide and/or (I) alkali metal borate and hydride thereof, wherein by the definite phosphorus of ultimate analysis: calcium: boron: the mass ratio of sulphur is 1: (0.1 to 2): (0.06 to 2): (0.2 to 20), total amount based on composition, the concentration of phosphorus is 0.01 to 0.06 quality %, sulphur concentration from described base oil is 0 to 0.1 quality %, is 0.01 to 0.15 quality % from the sulphur concentration of described sulfenyl additive.
2. the lubricating oil composition of claim 1, wherein by the definite phosphorus of ultimate analysis: calcium: boron: the mass ratio of sulphur is 1: (0.1 to 1): (0.1 to 0.8): (0.4 to 5), total amount based on composition, the concentration of phosphorus is 0.02 to 0.05 quality %, sulphur concentration from base oil is 0 to 0.1 quality %, is 0.01 to 0.15 quality % from the sulphur concentration of sulfenyl additive.
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