CN101495607A - lubricating oil composition - Google Patents

lubricating oil composition Download PDF

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Publication number
CN101495607A
CN101495607A CNA2007800287743A CN200780028774A CN101495607A CN 101495607 A CN101495607 A CN 101495607A CN A2007800287743 A CNA2007800287743 A CN A2007800287743A CN 200780028774 A CN200780028774 A CN 200780028774A CN 101495607 A CN101495607 A CN 101495607A
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lubricating oil
ester
oil composition
oil
quality
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山田亮
高仓丰
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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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
    • C10M143/00Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/02Polyethene
    • 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
    • C10M171/00Lubricating 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
    • 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
    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32Heterocyclic sulfur, selenium or tellurium compounds
    • C10M135/36Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
    • 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
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • 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
    • C10M161/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • 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
    • C10M2205/022Ethene
    • 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
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106Thiadiazoles
    • 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
    • C10M2225/00Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02Pour-point; 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08Resistance to extreme temperature
    • 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40Low content or no content compositions
    • C10N2030/43Sulfur free or low sulfur content compositions
    • 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
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

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

Abstract

A lubricating oil composition comprising a lubricating base oil and 0.5 to 10 mass% of an ethylene-alpha-olefin copolymer having a number average molecular weight of 2800 to 8000, wherein the lubricating base oil has a kinematic viscosity at 100 ℃ of 1.5 to 40mm2A lubricating base oil having a viscosity index of 100 or more, a pour point of-25 ℃ or less and a sulfur content of 0.01 mass% or less. The lubricating oil composition has a low viscosity, excellent low-temperature fluidity and oxidation stability, and a long metal fatigue life, and is particularly suitable for use as a transmission lubricating oil for automobiles.

Description

Lubricating oil composition
Technical field
The present invention relates to a kind of lubricating oil composition, in more detail, it is low to relate to a kind of viscosity, and low-temperature fluidity, oxidative stability excellence, simultaneously the metal fatigue life-span long, the variator that is particularly suitable as automobile is with the lubricating oil composition that lubricates wet goods.
Background technology
In recent years, at environmental problem, energy-conservationization of automobile and construction machinery, agricultural machine etc. promptly economized burnup and changed into and be the task of top priority, is starved of devices such as helping energy-conservation engine, variator, final stage step-down gear, compressor, oil gear.Therefore, install employed lubricating oil, than needed to reduce stirring resistance and friction resistance more in the past for these.
For example, as one of province's burnup method of variator and final stage step-down gear, can enumerate the method that makes the lubricating oil lowering viscousity.Automatic transmission that automobile is used in variator or buncher have torque transfer machine, wet clutch, gear-bearing mechanism, oil pump, oil pressure controlling organization etc., in addition, manual transmission or final stage step-down gear have gear-bearing mechanism, by making these install more lowering viscousity of employed lubricating oil, reduce the stirring resistance and the friction resistance of torque transfer machine, wet clutch, gear-bearing mechanism and oil pump etc., improve the efficiency of conversion of power, thereby improve the specific fuel consumption of automobile.
Yet, when particularly under high humidity environment, using the lubricating oil of lowering viscousity, cause the vaporization losses of lubricating oil easily, and, can produce the problems such as frictional coefficient increase of oil-bound film on the contrary along with lowering viscousity.Its result causes significantly reduce fatigue lifetime sometimes, produce to burn phenomenons such as sticking, causes variator etc. to be not in good state.When particularly cooperating Phosphorus extreme-pressure additive, can cause significantly worsen fatigue lifetime, be difficult to carry out lowering viscousity usually for the extreme pressure property that improves low viscosity oil.
For example, for automobile transmission oil in the past, as the automobile transmission oil that can keep various performances such as speed change characteristic for a long time, disclose the lubricant base of synthetic oil and/or mineral oils, anti-wear agent, extreme-pressure additive, metal species purification agent, ashless dispersant, friction regulator, viscosity index improver etc. have been carried out the material (for example, with reference to patent documentation 1 and 2) that forms after the best fit.Yet all these compositions to Fatigue Life, are not discussed when making the lubricating oil lowering viscousity fully.
Patent documentation 1: Japanese kokai publication hei 7-268375 communique
Patent documentation 2: TOHKEMY 2000-63869 communique
Summary of the invention
In this case, the object of the present invention is to provide a kind of viscosity low and low-temperature fluidity and oxidative stability excellence, metal fatigue life-span while is long, is particularly suitable as the lubricating oil composition of the variator of automobile with lubricating oil.
The inventor etc. further investigate in order to develop the lubricating oil composition with above-mentioned premium properties, found that, by base oil with specific trait is cooperated the ethene-alpha-olefin copolymer of the molecular weight with specified range with the ratio of regulation, can realize this purpose.The present invention just is being based on above-mentioned discovery and is finishing.
That is, the invention provides:
(1) lubricating oil composition, it is characterized in that: (A) number-average molecular weight that contains lubricant base and 0.5~10 quality % is 2800~8000 ethene-alpha-olefin copolymer, and as described lubricant base, using 100 ℃ of following kinematic viscosity is 1.5~40mm 2/ s, viscosity index are more than 100, pour point for below-25 ℃ and sulphur content be the following lubricant base of 0.01 quality %;
(2) above-mentioned (1) described lubricating oil composition wherein, further contain (B) Phosphorus extreme-pressure additive and/or sulphur class extreme-pressure additive 0.01~2.0 quality %, and the sulphur total content is below the 0.15 quality %;
(3) above-mentioned (1) or (2) described lubricating oil composition, it further contains (C) and is selected from least a additive in antioxidant, other extreme-pressure additive, anti-wear agent, oiliness improver, detergent-dispersant additive and the pour point depressant; And,
(4) each described lubricating oil composition in above-mentioned (1) to (3), it is as the variator lubricating oil of automobile.
According to the present invention, can provide a kind of viscosity low and low-temperature fluidity and oxidative stability excellence, metal fatigue life-span while is long, is particularly suitable as the lubricating oil composition of the variator of automobile with lubricated wet goods.
Embodiment
In the lubricating oil composition of the present invention,, can use base oil with proterties as follows as base oil.
Kinematic viscosity under 100 ℃ of this base oils must be at 1.5~40mm 2In the scope of/s.If this kinematic viscosity is 1.5mm 2More than/the s, then vaporization losses is few; If kinematic viscosity is 40mm on the other hand 2Below/the s, then the power waste that is caused by viscous resistance is also not too large, can access the effect of improving of specific fuel consumption (combustion Charges).Kinematic viscosity is preferably 2~25mm 2/ s is preferably 2~10mm especially 2/ s.
The viscosity index of this base oil must be more than 100, and pour point must be below-25 ℃.If viscosity index is more than 100, then the viscosity that is caused by temperature variation changes little.This viscosity index is preferably more than 105, more preferably more than 110.In addition, if pour point is below-25 ℃, even then the lubricating oil composition of gained also has sufficient flowability under low temperature environment.This pour point is preferably below-30 ℃, more preferably-40 ℃ below.
In addition, above-mentioned kinematic viscosity and viscosity index value, the value of pour point for measuring according to JIS K 2265 for measuring according to JIS K 2283.
In addition, the sulphur content of this base oil must be below 0.01 quality %.If this sulphur content is that then the oxidative stability of the lubricating oil composition of gained is good below the 0.01 quality %.In addition, the value of this sulphur content for measuring according to JIS K 2541.
As this base oil, its kind is not particularly limited, can use any of mineral oil and synthetic oil.Wherein as mineral oil, can use the known various mineral oil of prior art, for example can enumerate: paraffin base class mineral oil, middle base class mineral oil, cycloalkanes base class mineral oil etc., as concrete example, can enumerate the lightweight neutral oil that obtains by solvent treatment, hydrofining etc., middle matter neutral oil, heavy neutral oil or bright stock (bright stock), and the mineral wet goods that obtains of the isomerization by wax.
In addition, as synthetic oil, can use the known various synthetic oils of prior art equally, for example can use: poly-alpha olefins, polybutene, polyol ester, diester, phosphoric acid ester, polyphenylene oxide, alkylbenzene, alkylnaphthalene, polyether polyols, neopentyl glycol, silicone oil, TriMethylolPropane(TMP), tetramethylolmethane and the ester that is obstructed (Hindered ester) etc.These base oils may be used singly or in combination of two or more, and mineral oil and synthetic oil can also be used in combination.
Being characterized as of lubricating oil composition of the present invention, contain base oil with above-mentioned proterties and (A) number-average molecular weight of 0.5~10 quality % be 2800~8000 ethene-alpha-olefin copolymer.
In the lubricating oil composition of the present invention, ethene-alpha-olefin copolymer as the use of (A) composition, its number-average molecular weight if this number-average molecular weight is more than 2800, then can be brought into play the effect of the viscosity index raising of the lubricating oil composition that makes gained in 2800~8000 scope; On the other hand, if number-average molecular weight is below 8000, then the shear stability of the lubricating oil composition of gained is good.From the viewpoint that viscosity index improves effect and gives good shear stability, this number-average molecular weight is preferably 3000~7000.
In addition, the value of above-mentioned number-average molecular weight for adopting vapor pressure osmolarity measuring method to record.
Alpha-olefin as constituting this ethene-alpha-olefin copolymer can use carbonatoms to be preferably 3~20, more preferably 3~10 alpha-olefin.As such alpha-olefin, for example can enumerate: propylene, 1-butylene, iso-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene etc.These alpha-olefins can use a kind of, also can be used in combination of two or more, and consider especially preferably to use propylene from aspect of performance.
In addition, consider that from aspect of performance the content of ethylene unit is preferably 15~85 moles of % in this ethene-alpha-olefin copolymer, more preferably 20~80 moles of %.Be not particularly limited for the copolymerization form, random copolymerization and block copolymerization all can.
In the lubricating oil composition of the present invention,, can use a kind of above-mentioned ethene-alpha-olefin copolymer, also can be used in combination of two or more as (A) composition.Should (A) composition be the composition that is coupled in order to reach following purpose in the base oil: promptly in order to make lubricating oil composition of the present invention have the low and low-temperature fluidity of viscosity and oxidative stability excellence, long performance of metal fatigue life-span simultaneously.
Therefore, from the viewpoint of above-mentioned performance, the content of above-mentioned (A) composition is benchmark with the total composition, is 0.5~10 quality %, is preferably 0.5~6 quality %, more preferably 0.5~4.5 quality %.
In the lubricating oil composition of the present invention, can further contain Phosphorus extreme-pressure additive and/or sulphur class extreme-pressure additive as (B) composition.
As above-mentioned Phosphorus extreme-pressure additive, for example can enumerate: phosphoric acid ester, acid phosphoric acid ester, acid phosphate amine salt, phosphorous acid ester, acid phosphorous acid ester and acid phosphorous acid ester amine salt etc.
As phosphoric acid ester, triaryl phosphate is for example arranged, trialkylphosphate, the tricresyl phosphate alkyl aryl ester, the tricresyl phosphate alkyl aryl, tricresyl phosphate alkenyl esters etc. for example can be enumerated: triphenylphosphate, Tritolyl Phosphate, phosphoric acid benzyl diphenyl ester, phosphoric acid ethyl diphenyl ester, tributyl phosphate, phosphoric acid ethyl dibutylester, cresyl diphenyl phosphate, di(2-ethylhexyl)phosphate cresols phenyl ester, phosphoric acid ethylphenyl diphenyl ester, di(2-ethylhexyl)phosphate (ethylphenyl) phenyl ester, phosphoric acid propyl group phenyl diphenyl ester, di(2-ethylhexyl)phosphate (propyl group phenyl) phenyl ester, tricresyl phosphate ethyl phenyl ester, tricresyl phosphate propyl group phenyl ester, phosphoric acid butyl phenyl diphenyl ester, di(2-ethylhexyl)phosphate (butyl phenyl) phenyl ester, tricresyl phosphate butyl phenyl ester, tri hexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, the tricresyl phosphate Lauryl Ester, tricresyl phosphate myristyl ester, tricresyl phosphate palmityl ester, the tricresyl phosphate stearyl, tricresyl phosphate oleyl ester etc.
As acid phosphoric acid ester, for example can enumerate: acid di(2-ethylhexyl)phosphate-2-ethylhexyl, acid di(2-ethylhexyl)phosphate decyl ester, acid di(2-ethylhexyl)phosphate (dodecyl) ester (acid dilauryl phosphate), acid tricresyl phosphate decyl ester, acid di(2-ethylhexyl)phosphate (octadecyl) ester (the hard ester group ester of acid di(2-ethylhexyl)phosphate), acid di(2-ethylhexyl)phosphate-9-vaccenic acid base ester (acid di(2-ethylhexyl)phosphate oleyl ester) etc.; As phosphorous acid ester, for example can enumerate: triethyl-phosphite, tributyl phosphate, triphenyl phosphite, tricresyl phosphite, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (2-ethylhexyl) ester, tridecyl phosphite, tricresyl phosphite Lauryl Ester, tricresyl phosphite isooctyl acrylate, phosphorous acid phenylbenzene isodecyl ester, tricresyl phosphite stearyl, tricresyl phosphite oleyl ester etc.
As acid phosphorous acid ester, for example can enumerate: hydrogen phosphite (hydrogen phosphite) two-2-ethylhexyl, hydrogen phosphite didecyl ester, hydrogen phosphite two (dodecyl) ester (hydrogen phosphite dilauryl ester), hydrogen phosphite two (octadecyl) ester (hydrogen phosphite two hard ester group esters), hydrogen phosphite two-9-vaccenic acid base ester (hydrogen phosphite two oleyl esters), hydrogen phosphite diphenyl ester etc.
As acid phosphate amine salt and acid phosphorous acid ester amine salt, can enumerate above-mentioned acid phosphoric acid ester and acid phosphorous acid ester respectively with the formed salt of following amine.As amine, can use single amine, two that replaces to replace amine or three replacement amine.
As single example that replaces amine, can enumerate: butylamine, amylamine, hexylamine, hexahydroaniline, octylame, lauryl amine, stearylamine, oleyl amine, benzylamine etc.; As the example of two replacement amine, can enumerate: dibutylamine, diamylamine, dihexylamine, dicyclohexyl amine, Di-Octyl amine, dilaurylamine, distearyl amine, two oleyl amines, dibenzylamine, stearyl-monoethanolamine, decyl-monoethanolamine, hexyl-Propanolamine, benzyl-monoethanolamine, phenyl-monoethanolamine, tolyl-single Propanolamine etc.; As the example of three replacement amine, can enumerate: Tributylamine, triamylamine, trihexylamine, tricyclohexyltin amine, trioctylamine, trilaurylamine (Tridodecylamine, three stearylamines, three oleyl amines, tribenzylamine, two oleyls-monoethanolamine, dilauryl-single Propanolamine, dioctyl-monoethanolamine, dihexyl-single Propanolamine, dibutyl-Propanolamine, oleyl-diethanolamine, stearyl-dipropanolamine, lauryl-diethanolamine, octyl group-dipropanolamine, butyl-diethanolamine, benzyl-diethanolamine, phenyl-diethanolamine, tolyl-dipropanolamine, xylyl-diethanolamine, trolamine, tripropanol amine etc.
In addition, as acid phosphate amine salt, can use phosphoric acid hydrogen (hydrogenphosphate) mono-methyl, phosphoric acid hydrogen mono ethyl ester, phosphoric acid hydrogen list propyl ester, phosphoric acid hydrogen mono, phosphoric acid hydrogen list-acid phosphatase monoesters and formed salt of above-mentioned amine such as 2-ethylhexyl.
Among the present invention, these phosphate compounds can be used alone, and also can be used in combination of two or more.
On the other hand, as sulphur class extreme-pressure additive, so long as intramolecularly has sulphur atom, solubilized or be dispersed in the lubricant base oil can be brought into play extreme-pressure additive and excellent rubbing characteristics gets final product.As such sulphur class extreme-pressure additive, for example can enumerate: sulfuration grease, sulfide aliphatic acid, sulfuration ester, olefine sulfide, dialkyl polysulphide, thiadiazole compound, thiophosphatephosphorothioate (thiophosphite, thiophosphatephosphorothioate), alkylthio carbamino compound, thiocarbamate (salt) compound, sulfo-terpene compound, dialkyl group thiodipropionate (salt) compound etc.Here, the sulfuration grease is to react by the compound of sulphur or sulfur-bearing and grease (lard, whale oil, vegetables oil, fish oil etc.) to obtain, and the content of this sulphur has no particular limits, and generally is preferably 5~30 quality %.As its concrete example, can enumerate: sulfuration lard, sulfuration rapeseed oil, sulfuration castor seeds oil, sulfurized soybean oil, sulfuration rice bran wet goods.As the example of sulfide aliphatic acid, can enumerate sulfuration oleic acid etc.; As the example of sulfuration ester, can enumerate: sulfuration Witconol 2301, the misery ester of sulfuration rice bran fats etc.
As olefine sulfide, for example, can enumerate by the compound of following general formula (I) expression etc.:
[changing 1]
R 1-S q-R 2…(I)
(in the formula, R 1The expression carbonatoms is 2~15 thiazolinyl, R 2The expression carbonatoms is 2~15 alkyl or alkenyl; Q represents 1~8 integer.)。Alkene or the vulcanizing agent reactions such as its two~tetramer and sulphur, sulfur subchloride of this compound by making carbonatoms 2~15 make, as this alkene, and preferred propylene, iso-butylene, diisobutylene etc.
As the dialkyl polysulphide, for example, can enumerate compound by following general formula (II) expression:
[changing 2]
R 3-S r-R 4…(II)
(in the formula, R 3And R 4Represent the alkyl or cycloalkyl of carbonatoms 1~20, the aryl of carbonatoms 6~20, the alkylaryl of carbonatoms 7~20 or the arylalkyl of carbonatoms 7~20 respectively, the two can be identical or different; R represents 1~8 integer.)。Wherein, when R3 and R4 are alkyl, be called alkyl sulfide (alkyl sulfide).
As dialkyl polysulphide, for example can preferably enumerate: dibenzyl polysulphide, various dinonyl polysulphide, various two (dodecyl) polysulphide, various dibutyl polysulphide, various dioctyl polysulphide, phenylbenzene polysulphide, dicyclohexyl polysulphide etc. by above-mentioned general formula (II) expression.
As thiadiazole compound, for example can preferably enumerate: 2, two (the n-hexyl dithio)-1,3 of 5-, the 4-thiadiazoles, 2, two (the n-octyl dithio)-1,3 of 5-, 4-thiadiazoles, 2, two (the n-nonyl dithio)-1,3 of 5-, the 4-thiadiazoles, 2,5-two (1,1,3,3-tetramethyl butyl dithio)-1,3, the 4-thiadiazoles, 3, two (the n-hexyl dithio)-1,2 of 5-, 4-thiadiazoles, 3, two (the n-octyl dithio)-1,2 of 6-, the 4-thiadiazoles, 3, two (the n-nonyl dithio)-1 of 5-, 2, the 4-thiadiazoles, 3,5-two (1,1,3,3-tetramethyl butyl dithio)-1,2, the 4-thiadiazoles, 4, two (the n-octyl dithio)-1,2 of 5-, the 3-thiadiazoles, 4, two (the n-nonyl dithio)-1,2 of 5-, the 3-thiadiazoles, 4,5-two (1,1,3,3-tetramethyl butyl dithio)-1,2,3-thiadiazoles etc.
As thiophosphatephosphorothioate, can enumerate: alkyl trithiophosphite, aryl or alkylaryl thiophosphatephosphorothioate, dilauryl zinc dithiophosphate etc., preferred especially lauryl trithiophosphite, triphenyl thiophosphatephosphorothioate.
As the alkylthio carbamino compound, for example can preferably enumerate: two (dimethyl thiocarbamoyl) single sulfide, two (dibutyl thiocarbamoyl) single sulfide, two (dimethyl thiocarbamoyl) disulphide, two (dibutyl thiocarbamoyl) disulphide, two (diamyl thiocarbamoyl) disulphide, two (dioctyl thiocarbamoyl) disulphide etc.
In addition, as thiocarbamate (salt) compound, for example can enumerate zinc dialkyl dithiocarbamate; As the sulfo-terpene compound, for example can enumerate the reactant of thiophosphoric anhydride and firpene; As dialkyl group thiodipropionate (salt) compound, for example can enumerate: dilauryl thiodipropionate, distearyl thiodipropionate etc.Wherein, consider preferred thiadiazole compound, benzyl sulfide from the aspects such as oxidative stability of extreme pressure property, rubbing characteristics, heat.
These sulphur class extreme-pressure additives can be used alone, and also can be used in combination.
In the lubricating oil composition of the present invention,, can only use above-mentioned Phosphorus extreme-pressure additive, can also only use sulphur class extreme-pressure additive, perhaps Phosphorus extreme-pressure additive and sulphur class extreme-pressure additive can also be used in combination as (B) composition.
From as the effect of extreme-pressure additive and the viewpoints such as balance of economy, be somebody's turn to do the content of (B) composition, be benchmark with the lubricating oil composition total amount, be generally 0.01~2.0 quality %, be preferably 0.05~1.5 quality %.
In addition, when using sulphur class extreme-pressure additive,, preferably adjust use level so that the sulphur total content in the composition is preferably below the 0.15 quality %, more preferably below the 0.10 quality % from etch-proof viewpoint.
In the lubricating oil composition of the present invention, further,, can contain at least a additive that is selected from antioxidant, other extreme-pressure additive, anti-wear agent, oiliness improver, detergent-dispersant additive and the pour point reducer as (C) composition.
As examples of antioxidants, can enumerate: amine antioxidants, phenol antioxidant and sulphur class antioxidant etc.
As amine antioxidants, for example can enumerate: monoalkyl diphenylamines such as single octyl diphenylamine, single nonyl diphenylamine; 4,4 '-dibutyl pentanoic, 4,4 '-diamyl pentanoic, 4,4 '-dihexyl pentanoic, 4,4 '-diheptyl pentanoic, 4,4 '-dioctyl diphenylamine, 4, dialkyl diphenylamine classes such as 4 '-dinonyldiphenylamine; Many alkyl diphenyls amines such as tetrabutyl pentanoic, four hexyl pentanoic, four octyl diphenylamines, four nonyl diphenylamine; Naphthylamines classes such as alpha-naphthylamine, phenyl-a-naphthylamine, butyl phenyl-alpha-naphthylamine, amyl group phenyl-a-naphthylamine, hexyl phenyl-a-naphthylamine, heptyl phenyl-a-naphthylamine, octyl phenyl-alpha-naphthylamine, nonyl phenyl-a-naphthylamine, wherein preferred dialkyl diphenylamine class.
As the phenol antioxidant, for example can enumerate: 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-monophenol classes such as 4-ethylphenol; 4,4 '-methylene-bis (2,6 di t butyl phenol), 2, hexichol phenols such as 2 '-methylene-bis(4-ethyl-6-t-butyl phenol).
As sulphur class antioxidant, for example can enumerate: thiodiphenylamine, tetramethylolmethane-four-(3-lauryl thiopropionate), two (3, the 5-tertiary butyl-4-acrinyl) (3-(3 for sulfide, sulfo-di ethylene bis, 5-di-t-butyl-4-hydroxyphenyl)) propionic ester, 2,6-di-t-butyl-4-(4, two (the octylsulfo)-1,3,5-triazines of 6--2-methylamine) phenol etc.
These antioxidants can be used alone, and also can be used in combination.In addition, its use level is a benchmark with the lubricating oil composition total amount, is chosen to be 0.01~10 quality % usually, preferably is chosen to be the scope of 0.03~5 quality %.
As other extreme-pressure additive, anti-wear agent, oiliness improver, for example can enumerate: zinc dithiophosphate (ZnDTP), zinc dithiocarbamate (ZnDTC), dithio organic phosphoric acid sulfuration oxygen molybdenum (sulfuration オ キ シ モ リ Block デ Application オ Le ガ ノ ホ ス ホ ロ ジ チ オ エ one ト) (MoDTP), dithiocarbamic acid sulfuration oxygen molybdenum organo-metallic compounds such as (MoDTC).The use level of these compounds is a benchmark with the lubricating oil composition total amount, is generally 0.05~5 quality %, is preferably 0.1~3 quality %.
In addition, oiliness improver can be enumerated: the saturated and unsaturated monocarboxylic of aliphatics such as stearic acid, oleic acid; Polymerized fatty acid such as dimeracid, hydrogenated dimer acids; Hydroxy fatty acids such as ricinolic acid, 12-oxystearic acid; Saturated and the unsaturated single alcohol of aliphatics such as lauryl alcohol, oleyl alcohol; Saturated and the unsaturated monoamine of aliphatics such as stearylamine, oleyl amine; Saturated and unsaturated monocarboxylic acid amides of aliphatics such as lauric amide, amine hydroxybenzene etc.
The preferred use level of these oiliness improvers is a benchmark with the lubricating oil composition total amount, is the scope of 0.01~10 quality %, the scope of preferred especially 0.1~5 quality %.
As detergent-dispersant additive, for example can enumerate: the benzylamine class of the succinimide class of succinimide class, boracic, benzylamine class, boracic, succinate class, be ashless class dispersion agents such as the monovalence of representative or dibasic carboxylic acid amides with lipid acid or succsinic acid; Neutral metal sulfonate, neutral metal phenates, neutral metal salicylate, neutral metal phosphonate, alkaline sulfonate, alkaline phenates, alkaline salicylate, metal species purification agent such as overbased sulfonate, high alkaline salicylate, high alkalinity phosphonate.Its use level is a benchmark with the lubricating oil composition total amount, is generally 0.1~20 quality %, is preferably 0.5~10 quality %.
As pour point reducer, can use weight-average molecular weight is polymethacrylate of about 50,000~150,000 etc.
As required, can contain the additive except that above-mentioned additive in the lubricating oil composition of the present invention, for example rust-preventive agent, metal passivator, defoamer, tensio-active agent etc.
As rust-preventive agent, for example can use alkenyl succinic acid or its part ester etc.; As corrosion inhibitor for metal, for example can use: benzotriazole category, benzimidazoles, benzothiazoles, thiadiazole etc.; As metal passivator, for example can use: benzotriazole, benzotriazole derivatives, benzothiazole, benzothiazole derivant, triazole, triazole derivative, dithiocarbamate (salt), dithiocarbamate (salt) derivative, imidazoles, imdazole derivatives etc.As defoamer, for example can use dimethyl polysiloxane, polyacrylic ester etc.; As tensio-active agent, for example can use polyoxyethylene alkyl phenyl ether etc.
Lubricating oil composition of the present invention has viscosity low and low-temperature fluidity and features such as oxidative stability excellence, metal fatigue life-span while length,, shock absorber fluid oily with oil, power steering gear applicable to the variator of for example automobile, engine oil and automobile-industrial gear oil, oil pressure oil, bearing wet goods, the automatic transmission, manual transmission, buncher iso-variable velocity device that is especially suitable for use as automobile is with oil.
Embodiment
Below, the present invention will be described in more detail by embodiment, but the present invention is not subjected to the qualification of these embodiment.
In addition, obtain the rerum natura of base oil and lubricating oil composition according to following method.
<base oil and lubricating oil composition 〉
(1) kinematic viscosity (40 ℃, 100 ℃)
Measure according to JIS K 2283.
(2) viscosity index (VI)
Measure according to JIS K 2283.
(3) sulphur content
Measure according to JIS K 2541.
<base oil 〉
(4) pour point
Measure according to JIS K 2265.
<lubricating oil composition 〉
(5) low temperature viscosity (40 ℃)
According to ASTM D 2983, the brookfield viscosity under measuring-40 ℃.
(6) fatigue lifetime
Use four balls to rotate (four ball translocation Move) protracted test machine, measure fatigue lifetime according to following main points.
(bearing)
Material: bearing steel
Sample: φ 60 * thickness 5mm
3/8 inch (3/8 * 2.54cm) of test ball size: φ
(test conditions)
Load: 147N
Speed of rotation: 2200rpm
Oil temperature: 120 ℃
The time till sample is peeled off of will arriving is as fatigue lifetime, calculates L50 (mean value) from the result of 6 tests.
(7) oxidative stability
According to JIS K 2514, make test oil force deterioration by ISOT test (150 ℃), viscosity velocity of variation (40 ℃, 100 ℃), the acid number measured after 144 hours increase total amount, base number, normal heptane not meltage and copper increasing amount.
The kind of each composition that is used to prepare lubricating oil composition is as described below.
Base oil A~F
Proterties is as shown in table 1.
Table 1
Figure A20078002877400131
Ethene-alpha-olefin copolymer I
Mitsui Chemicals society system, trade(brand)name " Le one カ Application ト HC600 ", number-average molecular weight are that 2600,100 ℃ of following kinematic viscosity are 600mm 2/ s, viscosity index are 240, sulphur content is less than 0.1 quality %
Ethene-alpha-olefin copolymer II
Mitsui Chemicals society system, trade(brand)name " Le one カ Application ト HC2000 ", number-average molecular weight are that 3700,100 ℃ of following kinematic viscosity are 2000mm 2/ s, viscosity index are 300, sulphur content is less than 0.1 quality %
Ethene-alpha-olefin copolymer III (comprising the thinning oil that concentration is 50 quality %)
Mitsui Chemicals society system, trade(brand)name " Le one カ Application ト HS4010M ", number-average molecular weight are that 6600,100 ℃ of following kinematic viscosity are 2000mm 2/ s, viscosity index are 335, sulphur content is less than 0.1 quality %
Viscosity index improver I
Romax society system, trade(brand)name " VISCOPLEX 0-050 ", polymethacrylate number-average molecular weight are that 18000,100 ℃ of following kinematic viscosity are 450mm 2/ s
Viscosity index improver II
It is that 45000,100 ℃ of following kinematic viscosity are 852mm that Sanyo changes into society's system, trade(brand)name " ア Network Le one Block C728 ", polymethacrylate number-average molecular weight 2/ s
Pour point reducer
Sanyo changes into society's system, trade(brand)name " ア Network Le one Block C728 ", polymethacrylate
Extreme-pressure additive: thiadiazoles
ATF additive packing (パ Star ケ one ジ)
イ Application Off イ ニ ア system society system, commodity " Infineum T4261 " contain Phosphorus extreme-pressure additive, sulphur class extreme-pressure additive, detergent-dispersant additive, friction modulator (Mo Ca Tone System drug), antioxidant
Embodiment 1~4 and comparative example 1~6
Preparation has the lubricating oil composition of composition as shown in table 2, estimates the rerum natura except that oxidation stability.Its result is as shown in table 2.
Estimate oxidative stability at embodiment 1 and comparative example 1.Its result is as shown in table 3.
Figure A20078002877400151
Figure A20078002877400161
Table 3
Figure A20078002877400171
Table 2 is the result show, the low temperature viscosity (40 ℃) of lubricating oil composition of the present invention (embodiment 1~4) is less than 10000 all, and surpasses 150 minutes fatigue lifetime [L50], and low-temperature fluidity is good, and the metal fatigue life-span is long.Relative with it, the fatigue lifetime [L50] of comparative example 1~4 and comparative example 6 is less than 150 all, and the metal fatigue life-span is short; And the low temperature viscosity of comparative example 1,4 and 6 (40 ℃) surpasses 10000, and low-temperature fluidity is poor.
On the other hand, surpass 150 the fatigue lifetime of comparative example 5 [L50], and the metal fatigue life-span is long, but the low-temperature fluidity extreme difference; In addition, table 3 is the result show, compares with embodiment 1, and the oxidative stability of comparative example 5 is poor.
Industrial usability
Low and the low temperature flow of lubricant oil composite viscosity of the present invention and oxidation-stabilized property are excellent Different, simultaneously the metal fatigue life-span long, applicable speed changer in for example automobile turns to oily, power , engine oil oily to device oil, damper, automobile-industrial gear oil, oil pressure oil and Bearing oil etc.

Claims (4)

1. lubricating oil composition, it is characterized in that: (A) number-average molecular weight that contains lubricant base and 0.5~10 quality % is 2800~8000 ethene-alpha-olefin copolymer, and as described lubricant base, using 100 ℃ of following kinematic viscosity is 1.5~40mm 2/ s, viscosity index are more than 100, pour point for below-25 ℃ and sulphur content be the following lubricant base of 0.01 quality %.
2. the described lubricating oil composition of claim 1 wherein, further contain (B) Phosphorus extreme-pressure additive and/or sulphur class extreme-pressure additive 0.01~2.0 quality %, and the sulphur total content is below the 0.15 quality %.
3. the described lubricating oil composition of claim 2, it further contains (C) and is selected from least a additive in antioxidant, other extreme-pressure additive, anti-wear agent, oiliness improver, detergent-dispersant additive and the pour point depressant.
4. each described lubricating oil composition in the claim 1 to 3, it is as the variator lubricating oil of automobile.
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