CN100462424C

CN100462424C - Lubricating oil compositions

Info

Publication number: CN100462424C
Application number: CNB038219808A
Authority: CN
Inventors: 八木下和宏
Original assignee: Nippon Oil Corp
Current assignee: Eneos Corp
Priority date: 2002-08-05
Filing date: 2003-08-04
Publication date: 2009-02-18
Anticipated expiration: 2023-08-04
Also published as: EP1526169A4; EP1526169A1; WO2004013264A1; CN1681909A; EP1526169B1; AU2003252377A1

Abstract

A lubricating oil composition which comprises a base oil, (A) a specific alkali metal salicylate derivative, a specific alkaline earth metal salicylate derivative and/or their (per)basic salt in an amount of 0.005 to 5 mass % in terms of the amount of the metal element and (B) a phosphorus-containing wear inhibitor in an amount of 0.005 to 0.2 mass % in terms of the amount of phosphorus, has a total sulfur content of 0.3 mass % or less, and satisfies specific requirements, all the percentages being relative to the total amount of the composition. The lubricating oil composition is a low sulfur lubricating oil which is extremely excellent in wear inhibiting property and also excellent in long drain property and the like, and thus can be suitably used in particular for an internal combustion engine.

Description

Lubricating oil composition

Technical field

The present invention relates to the low sulfur lubricating oil composition, more particularly relate to the lubricating oil composition that is suitable for good resistance to abrasion of having of oil engine and long transsexual energy.

Background technology

Sulfur-bearing and phosphorus additive with good resistance to abrasion and antioxidant property are used for general lubricating oil as necessary basically additive as zinc dialkyl dithiophosphate, and particularly those are used for the lubricating oil of oil engine.But, present strong request lubricating oil comprises sulphur, phosphorus and ash content still less, because must alleviate to exhaust gas purifying catalyst such as three-way catalyst, oxide catalyst and NOx adsorbent, or to be contained in the exhaust aftertreatment device in the oil engine such as the harmful effect of Di Saier particulate filter (DPF) according to recent relevant problem of environment.

Disclosed up to now example low-phosphorous or without phosphorus oil comprises those that describe in the following Japanese Patent Laid-Open Publication: 62-253691,1-500912,6-41568,63-304095,63-304096,52-704,62-243692,62-501917,62-501572 and 2000-63862.The example of low ash content oil is included in those that describe in the following Japanese Patent Laid-Open Publication: 8-48989,8-253782,9-111275 and 2000-256690.But, comprise reduction when these known oil or when not comprising zinc dithiophosphate, they need be used to keep the sulfocompound of its abrasion resistance to mix, low ash content oil then must comprise zinc dithiophosphate.Up to now, almost there is not discovery to have the lubricating oil of sulphur, phosphorus and the ash oontent of good resistance to abrasion and reduction.

The inventor finds, contain P contained compound such as list or dialkyl group zinc phosphate, the low sulfur lubricating oil composition of dialkyl group single thiophosphate zinc or phosphotriester is when keeping abrasion resistance, compare with the composition that only contains zinc dithiophosphate, demonstrate better low friction performance, high temperature detergency, oxidative stability, and base number keeps performance, this low sulfur lubricating oil composition has been submitted to patent application (Japanese patent application 2002-015351,2001-315941,2002-086145,2002-086146,2002-086147,2002-191090,2002-191091 and 2002-191092).But, using the metal ratio is 5 or still less, particularly metal than be adjusted to 3 or still less the situation of Whitfield's ointment alkali purification agent as metal detergent under, can obtain low friction performance, high temperature detergency, oxidative stability and base number and keep the good especially composition of performance.Yet, have been found that, when the content that reduces sulfur-bearing and phosphorus anti-wear agent such as zinc dithiophosphate in order to reduce sulphur content or when using the phosphorous anti-wear agent of sulfur-bearing not, the composition of gained can not show that for the engine valve group be sufficient abrasion resistance, as for the wear resistance of rocking arm slurry with for the abrasion resistance of cam.

The present invention makes considering under the situation of above-mentioned requirements, and plans to provide a kind of length that contains Whitfield's ointment alkali purification agent and have good abrasion resistance low sulfur lubricating oil composition of remodeling.

Summary of the invention

Through deep research, can address the above problem and finished the present invention because discovery contains the lubricating oil composition of specific Whitfield's ointment alkali purification agent and phosphorous anti-wear agent.

That is, the present invention relates to a kind of lubricating oil composition, it comprises: lubricating base oil; (A) cross the salt or the basic salt of alkalization by the basic metal of following formula (1) expression or alkaline-earth metal salicylate and/or its, its amount is expressed as 0.005-5 quality % with metal, (B) phosphorous anti-wear agent, its amount is expressed as 0.005-0.2 quality % with phosphorus, and the total mass total amount that contains in composition is 0.3 quality % or sulphur still less, described salicylate be satisfy any salicylate that is selected from least one requirement in (I)-(IV) or salicylate mixture:

Wherein, R ¹It is the alkyl that contains 1-40 carbon atom; R ²Be hydrogen or the alkyl that contains 1-40 carbon atom, this alkyl can comprise oxygen or nitrogen; M is basic metal or alkaline-earth metal, and n depends on the valency of metal, is 1 or 2 integer;

(I) in the formula (1), R ¹Or R ²In one be the alkyl that contains 1-9 carbon atom, another is the alkyl that contains 10-40 carbon atom, and R ¹And R ²Between the difference of carbon number be 10 or more;

(II) by R wherein ¹And R ²Be formula (1) expression that contains the alkyl of 10-40 carbon atom salicylate component ratio be adjusted to 10 moles of % or more than;

(III) have an alkyl that contains 20-40 carbon atom salicylate component ratio be 85 moles of % or more than, wherein, by R wherein ¹Be alkyl, the R that contains 20-40 carbon atom ²Be hydrogen formula (1) expression salicylate component ratio be adjusted to 40 moles of % or more than;

(IV) have an alkyl that contains 10-19 carbon atom salicylate component ratio be 85 moles of % or more than, wherein, by R wherein ¹Be alkyl, the R that contains 10-19 carbon atom ²Be hydrogen formula (1) expression salicylate component ratio be adjusted to 55 moles of % or more than.

Component (B) is preferably at least a being selected from by the phosphorus compound of following formula (2) and (3) expression and the compound of its metal or amine salt:

Wherein, X ¹, X ²And X ³Be oxygen or sulphur independently of one another, R ³, R ⁴And R ⁵Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another; With

Wherein, X ⁴, X ⁵, X ⁶And X ⁷Be oxygen or sulphur independently of one another, R ⁶, R ⁷And R ⁸Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another.

Component (B) is preferably at least one class and is selected from wherein X ¹, X ²And X ³All be the formula (2) of oxygen and X wherein ⁴, X ⁵, X ⁶And X ⁷It all is the compound of phosphorus compound metal-salt of the formula (3) of oxygen.

Component (B) is preferably wherein X ⁴, X ⁵, X ⁶And X ⁷All be oxygen, R ⁶, R ⁷And R ⁸Be the phosphorus compound of formula (3) of the alkyl that contains 1-30 carbon atom independently of one another.

Component (B) is preferably wherein X ⁴, X ⁵, X ⁶And X ⁷In any two be the zinc salt of phosphorus compound of the formula (3) of oxygen.

The amount of the component that lubricating oil composition of the present invention comprises (B) is to represent with phosphorus, in the total mass 0.08 quality % of composition.

Lubricating oil composition of the present invention preferably comprises at least a being selected from (C) ashless dispersant and (D) additive of antioxidant.

The total sulfur content of lubricating base oil is 0.05 quality % or still less.

Lubricating oil composition is used for oil engine.

The sulfate ash content that is used for the lubricating oil composition of oil engine is preferably 1.0 quality % or still less.

The lubricating oil composition that is used for oil engine preferably satisfies or the multinomial requirement of the following stated: sulfate ash content is 0.5 quality % or still less, and total sulfur content is 0.05 quality % or still less, and phosphorus content is 0.05 quality % or still less.

The invention still further relates to and use described lubricating oil composition to prevent the method that engine valve group system avoids wearing and tearing.

Below described lubricating oil composition will be described in more detail.

There is no particular limitation to being used for lubricating base oil of the present invention.Therefore, can use any general mineral and/or the synthetic base oil that is used for lubricating oil.

The particular instance of mineral base oil comprises can be undertaken arbitrarily that one or more are selected from those base oils that solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing and hydrorefined processing obtain by the lubricating oil distillate that obtain the topped oil vacuum distilling that is produced by crude oil atmospheric distillation; The isomerized mineral oil of wax; With base oil by GTL WAX (gas-liquid wax) isomerization is obtained.

There is no particular limitation for the sulphur content of mineral base oil, as long as the total sulfur content of composition is 0.3 quality % or still less.The sulphur content of mineral oil is preferably 0.05 quality % or still less, more preferably 0.01 quality % or still less, preferred especially 0.005 quality % or still less.Can obtain having the lubricating oil composition of the transsexual energy of better length by the sulphur content that reduces mineral base oil.When this lubricating oil composition is used for oil engine, can avoid harmful effect as much as possible to exhaust aftertreatment device.

Although there is no particular limitation for total aromaticity content of mineral base oil, be preferably 10 quality % or still less, more preferably 6 quality % or still less, more preferably 3 quality % or still less also, preferred especially 2 quality % or still less.Be reduced to 10 quality % or lower by total aromaticity content, can obtain more excellent lubrication oil compositions of oxidative stability base oil.

Here the total aromaticity content ＂ of the term ＂ of Shi Yonging represents the aromatic fraction content according to ASTM D2549 mensuration.Aromatic fraction comprises alkylbenzene; Alkylnaphthalene; Anthracene, phenanthrene and its alkylate; 4 or the more phenyl ring compound of condensation each other wherein; And compound such as pyridine, quinoline, phenol and naphthols with assorted aromatic nucleus.

The particular instance of synthetic lubricating base oil comprises polybutene and its hydride; Poly-alpha-olefin such as 1-octene oligopolymer and 1-decene oligopolymer and its hydride; Diester such as pentanedioic acid two (tridecyl) ester, hexanodioic acid two-2-(ethyl hexyl) ester, diisodecyl adipate, hexanodioic acid two (tridecyl) ester and cebacate two-2-(ethyl hexyl) ester; Polyol ester such as DOPCP, trimethylolpropane caprylate, TriMethylolPropane(TMP) pelargonate, tetramethylolmethane-2-ethylhexanoate and tetramethylolmethane pelargonate; Aromatics synthetic oil such as alkylnaphthalene, alkylbenzene, and aromatic ester; With its mixture.

Above-mentioned mineral base oil or synthetic base oil any or the mixture that is selected from two or more types of these base oils can be used for the present invention.For example, being used for base oil of the present invention can be one or more mineral base oils or synthetic base oil, perhaps the mixing oil of one or more mineral base oils and one or more synthetic base oils.

Although there is no particular limitation for being used for the kinematic viscosity of lubricating base oil of the present invention under 100 ℃, be preferably 20mm ²/ s or lower, more preferably 10mm ²/ s or lower and preferred 1mm ²/ s or higher, more preferably 2mm ²/ s or higher.Preferably do not surpass 20mm 100 ℃ of following kinematic viscosity ²The lubricating base oil of/s because the low temperature viscosity characteristic of gained lubricating oil composition will be damaged, preferably is not lower than 1mm 100 ℃ of following kinematic viscosity simultaneously yet ²The lubricating base oil of/s is because the lubricity of gained lubricating oil composition will be big and relatively poor in the vaporization losses of lubricating inadequate oil film formation ability in position and base oil owing to it.

The vaporization losses that is used for base oil of the present invention by NOACK evaporation assay determination the time, will be preferably 20 quality % or lower, more preferably 16 quality % or lower, preferred especially 10 quality % or lower.Not preferred NOACK vaporization losses surpasses the lubricating base oil of 20 quality %, because the vaporization losses of base oil will be very big in the gained lubricating oil composition, if and composition is as internal combustion (IC) engine lubricating oil, sulphur compound in the composition, phosphorus compound or metal will accumulate on the exhaust gas purification device together with base oil so, will cause disadvantageous effect to the exhaust gas purification performance like this.The term ＂ NOACK evaporation ＂ that here uses is defined as according to ASTM D5800 and measures, and is retained under 250 ℃ the temperature when oil and 20mmH ₂The pressure of O (196Pa) is in the time of following 1 hour, and 60 restrain the loss amount of lubricating oil sample.

Although there is no particular limitation to the viscosity index of used lubricating base oil, in order to obtain viscosity characteristics good from low temperature to the pyritous, be preferably 80 or higher, more preferably 100 or higher, also more preferably 120 or higher.The preferred viscosities index is not lower than 80 lubricating base oil, because it will damage the low temperature viscosity characteristic of gained lubricating oil composition.

The component of lubricating oil composition of the present invention (A) is that one or more select the basic metal of free style (1) expression or alkaline-earth metal salicylate to cross the salt of alkalization or the compound of basic salt with it:

In the formula (1), R ¹It is the alkyl that contains 1-40 carbon atom; R ²Be hydrogen or the alkyl that contains 1-40 carbon atom, this alkyl can comprise oxygen or nitrogen; M is basic metal such as sodium and potassium or alkaline-earth metal such as magnesium, barium and calcium, and preferably magnesium and calcium, and n depends on the valency of metal " M ", is 1 or 2 integer.

The example that contains the alkyl of 1-40 carbon atom comprises alkyl, cycloalkyl, thiazolinyl, the cycloalkyl that alkyl replaces, aryl, the aryl that alkyl replaces, and aralkyl.Example comprises straight or branched alkyl such as the methyl that contains 1-40 carbon atom, ethyl, propyl group, butyl, amyl group more specifically, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl, and triacontyl; Cycloalkyl with 5-7 carbon atom, as cyclopentyl, cyclohexyl, and suberyl; Alkyl-cycloalkyl with 6-10 carbon atom, as methylcyclopentyl, dimethylcyclopentyl, the first and second basic ring amyl groups, the diethyl cyclopentyl, methyl cyclohexyl, Dimethylcyclohexyl, the first and second basic cyclohexyls, the diethyl cyclohexyl, methyl suberyl, dimethyl suberyl, with the first and second basic ring heptyl, wherein alkyl can be connected on the optional position of cycloalkyl; Straight or branched thiazolinyl such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, the decene base, undecenyl, laurylene base, tridecylene base, tetradecene base, ten pentaene bases, the hexadecylene base, 17 thiazolinyls, octadecylene base and 19 thiazolinyls, wherein the position of two keys can change; Aryl such as phenyl and naphthyl; Alkylaryl with 7-10 carbon atom, as tolyl, xylyl, the ethylbenzene base, propyl group phenyl, and butyl phenyl, wherein alkyl can be a straight or branched, and can be connected on the optional position of aryl; With aralkyl with 7-10 carbon atom, as benzyl, styroyl, hydrocinnamyl and benzene butyl, wherein alkyl can be a straight or branched.These alkyl can comprise oxygen or hydrogen.

In the present invention, component (A) need to satisfy at least one the requirement that be selected from the following requirement (I)-(IV), and can be satisfy separately these requirements salicylate mixture, wherein:

(III) have an alkyl that contains 20-40 carbon atom salicylate component ratio be 85 moles of % or more than, wherein, by R wherein ¹Be alkyl, the R that contains 20-40 carbon atom ²Be hydrogen formula (1) expression salicylate component ratio be adjusted to 40 moles of % or more than; With

In requiring (I), R ¹Or R ²In any be the alkyl that contains 1-9 carbon atom, preferably contain 1-5 carbon atom, especially preferably contain 1 carbon atom, other are the alkyl that contain 10-40 carbon atom, preferably contain the secondary alkyl of 10-30 carbon atom, in order to have the extremely good abrasion resistance of cam, the secondary alkyl that more preferably contains 20-30 carbon atom, in order to make water not too influence the antioxidant property of gained lubricating oil composition, preferably contain the secondary alkyl of 10-19 carbon atom, especially preferably contain the secondary alkyl of 14-18 carbon atom.And R ¹And R ²Between the difference of carbon number be 10 or more.

Particularly, described secondary alkyl is preferably the secondary alkyl that contains 10-40 carbon atom of being derived and being obtained by the polymkeric substance or the multipolymer of ethene, propylene or butylene.

The example that contains the alkyl of 1-9 carbon atom comprises alkyl such as methyl, ethyl, butyl and the tertiary butyl that contains 1-9 carbon atom, and it can comprise oxygen or nitrogen, for example-and COOH.The preferably tertiary butyl and methyl, most preferable.

The salicylate of (I) of meeting the demands is to have bought, because they also are not the commercially available prod now, but can use any known method to obtain, as disclosed method among Japanese Patent publication 48-35325 and the 50-3082.More specifically, at first, obtain wherein R by the following method ¹Or R ²In one be the alkyl that contains 10-40 carbon atom, another is the alkyl salicylate that contains the alkyl of 1-9 carbon atom: use to contain 10-40 carbon atom, the alkene of preferred 14-19 or 20-30 carbon atom, optionally to or the ortho position on raw material such as ortho-cresol or p-cresol or o-tert-butylphenol or p-tert-butylphenol alkylation, so that obtain 3-methyl-5-alkylphenol or 3-alkyl-5-methylphenol, perhaps the 3-tertiary butyl-5-alkylphenol or 3-alkyl-5-tert.-butyl phenol are used the carbon dioxide carboxylation afterwards; Perhaps with above-mentioned raw materials carboxylation and then alkylation.Afterwards, make the reaction of alkyl salicylate and metal base such as basic metal or alkaline earth metal oxide or oxyhydroxide or be converted into an alkali metal salt such as sodium or sylvite, this an alkali metal salt can further replace with alkaline-earth metal, thereby is met the salicylate of requirement (I).

In requiring (II), necessary wherein R ¹And R ²Be the formula (1) that contains the alkyl of 10-40 carbon atom salicylate component ratio be adjusted to 10 moles of % or more than.R ¹Or R ²Be preferably the secondary alkyl that contains 10-40 carbon atom, more preferably contain the secondary alkyl of 10-19 or 20-30 carbon atom, not too influence the antioxidant property of gained lubricating oil composition, especially preferably contain the secondary alkyl of 14-18 carbon atom in order to make water.It is desirable to R ¹And R ²Identical.

Described secondary alkyl is preferably the secondary alkyl that contains 10-40 carbon atom of being derived and being obtained by the polymkeric substance of ethene, propylene or butylene or multipolymer.

The salicylate of (II) of meeting the demands is to have bought, because they also are not the commercially available prod now, but can use any known method to obtain, as disclosed method among Japanese Patent publication 48-35325 and the 50-3082.For example, make its component ratio be 10 moles of % or more than, preferred 15 moles of % or more than, more preferably 20 moles of % or more than, even more preferably 40 moles of % or more than, 3 of preferred especially 100 moles of %, 5-dialkyl group Whitfield's ointment and metal base such as basic metal or alkaline earth metal oxide or oxyhydroxide reaction or be converted into an alkali metal salt such as sodium or sylvite, this an alkali metal salt can further replace with alkaline-earth metal, thereby is met the salicylate of requirement (II).

Above-mentioned 3 for preparation, there is no particular limitation for the salicylic method of 5-dialkyl group.For example, can be by using the 1.1-4 mole, preferred 2-4 mole, preferred especially 2-3 mole contains 10-40 carbon atom, and the alkene of individual or 20-30 the carbon atom of preferred 10-19 obtains 3,5-dialkyl group Whitfield's ointment with 1 mole alkylation of phenol, carry out carboxylation with carbon dioxide then, perhaps use the 1.1-4 mole, preferred 2-4 mole, the above-mentioned alkene of preferred especially 2-3 mole is with 1 mole Whitfield's ointment alkylation.

Perhaps, can be by optionally separating or concentrating commercially available a small amount of (being usually less than 10 moles of %) 3 that comprises in the neutral salicylate of monoalkyl salicylate as main ingredient as by product of containing, 5-dialkyl group salicylate, so that increase by 3,5-dialkyl group salicylate component ratio and obtain 3,5-dialkyl group Whitfield's ointment.

In requiring (III), require to have an alkyl that contains 20-40 carbon atom salicylate component ratio be 85 moles of % or more than, wherein, by R wherein ¹Be alkyl, the R that contains 20-40 carbon atom ²Be hydrogen formula (1) expression salicylate component ratio be adjusted to 40 moles of % or more than.

The example that contains the alkyl of 20-40 carbon atom comprises alkyl and thiazolinyl.More specifically, the example of alkyl comprises straight or branched alkyl such as eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl, and triacontyl; The example of thiazolinyl comprises straight or branched thiazolinyl such as eicosylene base, the heneicosene base, two dodecenyl succinic, tricosene base, the tetracosa carbon thiazolinyl, the ppentacosene base, cerotene base, cerotene base, two vaccenic acid bases, 29 carbene bases and triacontylene base, wherein the position of two keys can change.In the middle of these, especially preferably contain the alkyl and the thiazolinyl of 20-30 carbon atom, wherein the secondary alkyl of preferably deriving and obtaining by the polymkeric substance or the multipolymer of ethene, propylene or butylene.

For the salicylate of meet the demands (III) the preparation method there is no particular limitation.Be used to prepare the monoalkyl salicylate any known method all can use.For example, will carry out carboxylation with carbon dioxide then as the alkylation of phenol of raw material with the alkene that contains 20-40 carbon atom of equivalent, thereby obtain the monoalkyl Whitfield's ointment.Perhaps, the alkene with equivalent will obtain the monoalkyl Whitfield's ointment as the Whitfield's ointment alkylation of raw material.Gained monoalkyl Whitfield's ointment again with metal base such as basic metal or alkaline earth metal oxide or oxyhydroxide reaction, perhaps after being converted into an alkali metal salt such as sodium or sylvite, replace, thereby be met the salicylate of requirement (III) with alkaline-earth metal.The gained salicylate comprise 85 moles of % or more than, preferred 90 moles of % or above and 96 moles of % or following monoalkyl salicylate.But, if necessary, by separate and remove by product dialkyl group salicylate can make the monoalkyl salicylate purity be increased to 100 moles of %.

Need make wherein R ¹Be alkyl, the R that contains 20-40 carbon atom ²Be the salicylate of the formula (1) of hydrogen, promptly the component ratio of 3-alkylsalicylate be adjusted to 40 moles of % or more than.The component ratio of 3-alkylsalicylate be preferably 50 moles of % or more than, more preferably 55 moles of % or more than, purpose is further to increase abrasion resistance and good oil soluble.By the component ratio that makes the 3-alkylsalicylate be 80 moles of % or more than, can reduce the influence of water to antioxidant property.

In requiring (IV), must make salicylate with an alkyl that contains 10-19 carbon atom component ratio be 85 moles of % or more than, wherein, by R wherein ¹Be alkyl, the R that contains 10-19 carbon atom ²Be hydrogen formula (1) expression salicylate component ratio be adjusted to 55 moles of % or more than.

The alkyl that requires to contain 10-19 carbon atom in (IV) is preferably secondary alkyl, especially preferably contains the secondary alkyl of 14-18 carbon atom, and purpose is to reduce the influence of water to the resulting composition antioxidant property.

Described secondary alkyl is preferably the secondary alkyl of being derived and being obtained by the polymkeric substance of ethene, propylene or butylene or multipolymer.

For the salicylate of meet the demands (IV) the preparation method there is no particular limitation.Use any known be used to prepare the monoalkyl salicylate method so that its component ratio be adjusted to 85 moles of % or abovely all can obtain described salicylate.In the monoalkyl salicylate component ratio of 3-alkylsalicylate can be adjusted to by the following method 55 moles of % or more than.At first, on the ortho position, will use the carbon dioxide carboxylation then with the olefine selective ground that contains 10-19 carbon atom as the alkylation of phenol of raw material; With above-mentioned olefine selective ground on the 3-position with the Whitfield's ointment alkylation; From containing the monoalkyl salicylate as optionally separating or concentrated 3-alkyl salicylate the mixture of main ingredient; Or the 3-alkyl salicylate of this high density joined in the monoalkyl Whitfield's ointment in addition so that its component ratio become 55 moles of % or more than.Afterwards, any of these compounds and metal base such as basic metal or alkaline earth metal oxide or oxyhydroxide reaction perhaps replace with alkaline-earth metal after being converted into an alkali metal salt such as sodium or sylvite, thereby are met the salicylate of requirement (IV).

The salicylate that obtains like this except the 3-alkylsalicylate, comprises 4-alkylsalicylate, 5-alkylsalicylate, 3 usually, 5-dialkyl group salicylate, and 5-alkyl-4 hydroxyisophthalic acid salt is as by product.In the described salicylate monoalkyl salicylate total component ratio be 85 moles of % or more than, preferred 90 moles of % or more than, most preferably 100 moles of % or more than, but consider production cost, can be 96 moles of % or following.In the monoalkyl salicylate component ratio of 3-alkylsalicylate be 55 moles of % or more than, preferred 60 moles of % or more than, more preferably 80 moles of % or more than, 100 moles of % most preferably, but consider production cost can be 96 moles of % or following.By increasing the component ratio of 3-alkylsalicylate, can obtain having the lubricating oil composition of better abrasion resistance.

The preferred wherein component ratio of 3-alkylsalicylate is lower than the composition of 55 moles of %, because particularly when it is used for oil engine, it can not show sufficient abrasion resistance, starch wear resistance and for the abrasion resistance of cam for rocking arm.

The example of component of the present invention (A) also comprises by in the presence of water, and above-mentioned basic metal or alkaline-earth metal salicylate (neutral salt) are heated resulting basic salt with excess base metal or alkaline earth salt or basic metal or alkaline earth metal alkali (basic metal or alkaline earth metal hydroxides or oxide compound); With by make these neutral salt and alkali such as basic metal or alkaline earth metal hydroxides carbon dioxide, boric acid or boratory in the presence of the salt of crossing alkalization that obtains of reaction.

These reactions are carried out in solvent (aliphatic hydrocarbon solvent such as hexane, aromatic solvent such as dimethylbenzene, and light lubricating base oil) usually.Preferably use its metal content at 1.0-20 quality %, the compound in the preferred 2.0-16 quality % scope.

In the present invention, the base number of component (A) is generally 0-500mgKOH/g, preferred 20-450mgKOH/g.Component (A) can be the mixture of the compound of one or more its base numbers in this scope.Here the term ＂ base number ＂ of Shi Yonging represents according to the 7th part ＂ petroleum products of JIS K2501 and mensuration ＂ one literary composition of lubricant-neutralization value, by the base number of perchloric acid potentiometric determination.

For the metal of component (A) than there is no particular limitation.Usually, the metal that can use one or more types is than being 20 or following those components (A).In order to obtain good oxidative stability, high temperature detergency and low attriting performance, especially preferably using its metal ratio is 5 or lower, preferred 3 or lower, more preferably 2.3 or lower, preferred especially 1.5 or lower salicylate.When using the metal ratio is 5 or higher, and alkyl is have the monoalkyl salicylate that is lower than 20 carbon atoms the time, and the composition of gained may not can show for the wear resistance of rocking arm slurry with for the resistance to abrasion of cam.Therefore, its metal is useful especially than the component (A) in above-mentioned scope.Here by " content (mol%) of the content (mo1%) of the valency x metallic element of metallic element in the Whitfield's ointment alkali purification agent/soap base group " expression, wherein metallic element is a calcium to the term ＂ metal of Shi Yonging than ＂, magnesium, etc., soap base group is a salicyl etc.

In the present invention, the upper limit of component (A) content is the total mass in composition, 5 quality % or lower with regard to metal, preferred 1 quality % or lower, more preferably 0.4 quality % or lower.In addition, for the sulfate ash content of composition is reduced to 1.0 quality % or lower, the content of component (A) is preferably 0.3 quality % or lower.When lubricating oil composition of the present invention is used to the oil engine of exhaust aftertreatment device is housed, in order to avoid that as much as possible described device is caused harmful effect, thereby obtain its sulfate ash content is 0.5 quality % or lower lubricating oil composition, the content of component (A) is 0.2 quality % or lower, preferred 0.15 quality % or lower, most preferably 0.10 quality % or lower.The lower limit of component (A) content is the total mass in composition, 0.005 quality % or higher with regard to metal, preferred 0.01 quality % or higher, more preferably 0.02 quality % or higher, preferred especially 0.05 quality % or higher.When component (A) surpasses the above-mentioned upper limit, during particularly above 0.4 quality % with regard to metal, can increase the sulfate ash content of composition, and when composition is used for oil engine, may cause disadvantageous effect the exhaust aftertreatment device of oil engine.Component (A) is lower than and above-mentionedly down in limited time may not can shows its fundamental property feature as metal detergent, causes lubricating oil composition can not show that high temperature detergency and long transsexual energy such as oxidative stability and base number keep performance." sulfate ash content " used herein is by being measured by the described method of ＂ sulfated ash test method(s) ＂ of regulation among the JIS K 2,272 5, and mainly comes from containing metallic additive.

Component of the present invention (B) is phosphorous anti-wear agent.There is no particular limitation for this anti-wear agent, as long as they include phosphorus in molecule.

Be used for R ³-R ⁸The example of the alkyl that contains 1-30 carbon atom comprise alkyl, cycloalkyl, thiazolinyl, the cycloalkyl that alkyl replaces, aryl, the aryl that alkyl replaces, 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 comprises the cycloalkyl with 5-7 carbon atom, as cyclopentyl, and cyclohexyl, and suberyl.The example of alkyl-cycloalkyl comprises the alkyl-cycloalkyl with 6-11 carbon atom, as methylcyclopentyl, and dimethylcyclopentyl, the first and second basic ring amyl groups, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, the first and second basic ring hexyls, diethyl cyclohexyl, methyl suberyl, the dimethyl suberyl, the first and second basic ring heptyl and diethyl suberyl, wherein alkyl can be connected on the optional position of cycloalkyl.

The example of thiazolinyl comprises straight or branched thiazolinyl such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, the decene base, undecenyl, laurylene base, tridecylene base, tetradecene base, ten pentaene bases, the hexadecylene base, 17 thiazolinyls and octadecylene base, wherein the position of two keys can change.

The example of aryl comprises phenyl and naphthyl.The example of alkylaryl comprises those with 7-18 carbon atom, as tolyl, and xylyl, the ethylbenzene base, propyl group phenyl, butyl phenyl, the amyl group phenyl, hexyl phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl, the undecyl phenyl, and dodecylphenyl, wherein alkyl can be a straight or branched, and can be connected on the optional position of aryl.

The example of aralkyl comprises those with 7-12 carbon atom, as benzyl, and styroyl, hydrocinnamyl, the benzene butyl, benzene amyl group and benzene hexyl, wherein alkyl can be a straight or branched.

Be used for R ³-R ⁸The alkyl with 1-30 carbon atom preferably have the alkyl of 1-30 carbon atom and have the aryl of 6-24 carbon atom, more preferably have the alkyl of 3-18 carbon atom, more preferably have the alkyl of 4-12 carbon atom.

Example by the phosphorus compound of formula (2) expression comprises phosphorous acid; Single thiophosphorous acid; Dithio phosphorous acid; Trithio phosphorous acid; The phosphorous acid monoesters, single thiophosphorous acid monoesters, dithio phosphorous acid monoesters and trithio phosphorous acid monoesters, each all has an above-mentioned alkyl that contains 1-30 carbon atom; The phosphorous acid diester, single thiophosphorous acid diester, dithio phosphorous acid diester and trithio phosphorous acid diester, each all has two above-mentioned alkyl that contain 1-30 carbon atom; Tris phosphite, single thiophosphorous acid three esters, dithio tris phosphite and trithio tris phosphite, each all has 3 above-mentioned alkyl that contain 1-30 carbon atom; With its mixture.

In the present invention, two or more in the preferred formula (2), preferred especially all X ¹-X ³All be oxygen, purpose is further to strengthen high temperature detergency and long transsexual energy such as oxidative stability and base number maintenance performance.

Example by the phosphorus compound of formula (3) expression comprises phosphoric acid; Single thiophosphate; Phosphorodithioic acid; Trithio phosphoric acid, tetrathio phosphoric acid; Phosphate monoester, the single thiophosphate monoesters, the phosphorodithioic acid monoesters, trithio phosphate monoester and tetrathio phosphate monoester, each all has an above-mentioned alkyl that contains 1-30 carbon atom; Phosphodiester, the single thiophosphate diester, the phosphorodithioic acid diester, trithio phosphodiester and tetrathio phosphodiester, each all has two above-mentioned alkyl that contain 1-30 carbon atom; Phosphotriester, single thiophosphate three esters, phosphorodithioic acid three esters, trithio phosphotriester and tetrathio phosphotriester, each all has 3 above-mentioned alkyl that contain 1-30 carbon atom; With its mixture.

In the present invention, two or more in the preferred formula (3), more preferably three or more, preferred especially all X ⁴-X ⁷All be oxygen, purpose is further to strengthen high temperature detergency and long transsexual energy such as oxidative stability and base number maintenance performance.

Example by the salt of the phosphorus compound of formula (2) and (3) expression comprises, make metal base such as metal oxide, metal hydroxides, metal carbonate and metal chloride or nitrogenous compound such as ammonia and in its molecule, only contain the alkyl of 1-30 carbon atom or the amine compound of the alkyl that contains 1-30 carbon atom of hydroxyl and phosphorus compound reaction, so that the partly or entirely remaining acid-hydrolysis of neutralization and the salt that obtains.

The specific examples of the metal in the above-mentioned metal base comprises basic metal such as lithium, sodium, potassium, and caesium; Alkaline-earth metal such as calcium, magnesium, and barium; And heavy metal such as zinc, copper, iron, lead, nickel, silver, manganese, and molybdenum.In the middle of these metals, preferably basic metal such as lithium and sodium; Alkaline-earth metal such as magnesium and calcium, and zinc.

The number of contained OH in the valency of metal and the phosphorus compound or SH group is depended in the structural variation of the metal-salt of above-mentioned phosphorus compound.Therefore, the structure to the phosphorus compound metal-salt does not apply special qualification.For example, when 1 mole of zinc oxide and 2 mole of phosphoric acid diester (having an OH group) reaction, still also may there be polymerizable molecular in the compound that our conjecture obtains having the structure that is expressed from the next as main component:

Another example is that when 1 mole of zinc oxide and 1 mole of phosphoric acid monoesters (having two OH groups) reaction, still also may there be polymerizable molecular in the compound that our conjecture obtains having the structure that is expressed from the next as main component:

The particular instance of nitrogenous compound comprises ammonia, monoamine, diamines, and polyamines.Example comprises the alkylamine with the straight or branched alkyl that contains 1-30 carbon atom more specifically, as methylamine, and ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecylamine, amino dodecane, tridecyl amine, tetradecy lamine, pentadecyl amine, cetylamine, heptadecyl-amine, stearylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, two heptyl amices, the Di-Octyl amine nonyl amine, didecylamine, two heptadecyl-amines, two n-Laurylamines, diamin, two tetradecylamines, two pentadecyl amines, two cetylamines, two heptadecylamine (HDA)s, two octadecane amine, thyl methyl amine, first propylamine, the first butylamine, second propylamine, the second butylamine and third butylamine; Alkenyl amine with the straight or branched thiazolinyl that contains 2-30 carbon atom, as vinyl amine, propenyl amine, butenyl amine, octenyl amine, and oleyl amine; Alkanolamine with the straight or branched alkanol groups that contains 1-30 carbon atom, as carbinolamine, thanomin, Propanolamine, butanolamine, amylalcohol amine, hexanol amine, enanthol amine, octanol amine, nonyl alcohol amine, methanol amine, methyl alcohol Propanolamine, the methyl alcohol butanolamine, ethanol propanol amine, ethanol and butanol amine and propyl alcohol butanolamine; Alkylene diamines with the alkylene that contains 1-30 carbon atom, as methylene diamine, quadrol, propylene diamine, and butanediamine; Polyamines such as Diethylenetriaminee (DETA), triethylenetetramine, tetraethylenepentamine, and pentaethylene hexamine; Heterogeneous ring compound, as has a heterogeneous ring compound that is connected to the alkyl or alkenyl that contains 8-20 carbon atom on above-mentioned illustrative monoamine, diamines and the polyamines, the undecyl diethylamide is specifically arranged, the undecyl diethanolamine, the dodecyl dipropanolamine, oil base diethanolamine, oil base propylene diamine, with the stearyl tetraethylenepentamine, and N-hydroxyethyl oil-based imidazoline; Its oxyalkylene addition compound; With its mixture.

In the middle of these nitrogenous compounds, preferred examples comprises the fatty amine with the alkyl or alkenyl that contains 10-20 carbon atom, and this amine can be straight chain or side chain, as decyl amine, and amino dodecane, tridecyl amine, heptadecyl-amine, stearylamine, oleyl amine, and stearylamine.

Component (B) is preferably at least one class and is selected from compound as described below: by the metal-salt of the phosphorus compound of formula (2) expression, wherein all X ¹, X ²And X ³All be oxygen; With the metal-salt of the phosphorus compound of representing by formula (3), wherein all X ⁴, X ⁵, X ⁶And X ⁷All be oxygen, purpose is to obtain the excellent transsexual energy of length such as oxidative stability, high temperature detergency and low attriting performance.

Component (B) is preferably the phosphorus compound by formula (3) expression, wherein all X ⁴, X ⁵, X ⁶And X ⁷All be oxygen, and R ⁶, R ⁷And R ⁸For containing the alkyl of 1-30 carbon atom, purpose is to obtain the excellent transsexual energy of length such as oxidative stability and high temperature detergency, the ash oontent of low attriting performance and reduction independently of one another.

Component (B) is more preferably by the zinc salt of the phosphorus compound of formula (3) expression, wherein X ⁴, X ⁵, X ⁶And X ⁷In two be oxygen, purpose is the possibility that obtains excellent abrasion resistance and reduce phosphorus content.

By reference inventor's above-mentioned patent application, the above will become apparent.

In said components (B), preferably have two alkyl or the phosphorous acid diester of aryl and salt of zinc or calcium that contain 3-18 carbon atom; Have 3 alkyl or aryl that contain 3-18 carbon atom, preferred 3 tris phosphites that contain the alkyl of 6-12 carbon atom; Has alkyl or the phosphate monoester of aryl and the salt of zinc or calcium that contains 3-18 carbon atom; Have two alkyl or the phosphodiester of aryl and salt of zinc or calcium that contain 3-18 carbon atom; And have 3 alkyl or aryl that contain 3-18 carbon atom, preferred 3 phosphotriesters that contain the alkyl of 6-12 carbon atom.

The compound blend arbitrarily that belongs to component (B) of one or more types.

When use has the salt of the dithio phosphorous acid diester of two alkyl that contain 3-18 carbon atom or aryl and zinc, the content of this salt can further be reduced to, represent with phosphorus, total mass with composition is counted, 0.08 quality % or lower, preferred 0.05 quality % or lower is because this salt can keep the abrasion resistance for engine valve group system well.But, most preferably use the phosphorous anti-wear agent that does not comprise sulphur in the molecule, because it can further increase various characteristic performances such as oxidative stability, high temperature detergency and low friction performance.

In lubricating oil composition of the present invention, the content of component (B) is, represent with phosphorus, with the total mass of composition count 0.005 quality % or more than, preferred 0.01 quality % or more than, preferred especially 0.02 quality % or more than, be 0.2 quality % or following simultaneously, preferred 0.1 quality % or following, more preferably 0.08 quality % or following.With regard to phosphorus, then invalid aspect resistance to abrasion if component (B) is lower than 0.005 quality %, simultaneously, with regard to phosphorus,, may cause disadvantageous effect to exhaust aftertreatment device if component (B) surpasses 0.2 quality %.

Lubricating oil composition of the present invention has good abrasion resistance, and can show that low attriting performance, high temperature detergency and long transsexual energy such as base number keep performance and oxidative stability, be selected from (C) ashless dispersant and (D) compound of antioxidant but can comprise at least one class, be used for further improving the characteristic performance of composition.

Component (C), it is ashless dispersant, can be the ashless dispersant that is used for lubricating oil arbitrarily, as nitrogenous compound and its derivative that in molecule, has at least one straight or branched alkyl or alkenyl that contains 40-400 carbon atom, and the modified product of alkenyl succinimide.One or more these compounds may be mixed together arbitrarily.

The carbon number of alkyl or alkenyl is preferably 40-400, preferred 60-350.Have the alkyl or alkenyl that is lower than 40 carbon atoms and will damage the solvability of compound in lubricating base oil, contain the low-temperature fluidity that then will damage the gained lubricating oil composition greater than the alkyl or alkenyl of 400 carbon atoms.Described alkyl or alkenyl can be a straight or branched, but preferably stems from the oligopolymer of alkene such as propylene, 1-butylene and iso-butylene or stem from ethene and the branched-chain alkyl of the multipolymer of propylene or thiazolinyl.

The particular instance of component (C) comprises following compound, can use wherein one or more:

(C-1) in its molecule, contain the succinimide of at least one alkyl or alkenyl that contains 40-400 carbon atom and its derivative;

(C-2) in its molecule, contain the benzylamine of at least one alkyl or alkenyl that contains 40-400 carbon atom and its derivative; With

(C-3) in its molecule, contain the polyamines of at least one alkyl or alkenyl that contains 40-400 carbon atom and its derivative;

(C-1) particular instance of succinimide comprises the compound by following formula (4) and (5) expression:

R wherein ²⁰Be to contain 40-400, the alkyl or alkenyl of preferred 60-350 carbon atom, h is 1-5, the integer of preferred 2-4; With

Wherein, R ²¹And R ²²Be to contain 40-400 independently of one another, the alkyl or alkenyl of preferred 60-350 carbon atom, especially preferably polybutylene-based, i is the integer of 0-4, preferred 1-3.

Succinimide comprise suc as formula (4) represented wherein succinyl oxide be added to polyamines an end the monotype succinimide and be added to the dimorphism succinimide at the two ends of polyamines suc as formula (5) represented wherein succinyl oxide.Lubricating oil composition can comprise succinimide or its mixture of arbitrary type.

There is no particular limitation for the method for preparing these succinimides.For example, operable method is, make compound and maleic anhydride under 100-200 ℃ temperature, react alkyl or alkenyl succinimide and polyamines such as the diethylenetriamine that obtains by having the alkyl or alkenyl that contains 40-400 carbon atom, Triethylenetetramine (TETA), tetren or penten reaction.

(C-2) specific examples of benzylamine comprises the compound by following formula (6) expression:

R wherein ²³Be to contain 40-400, the alkyl or alkenyl of preferred 60-350 carbon atom, j is 1-5, the integer of preferred 2-4.

Although there is no particular limitation for the method for preparing benzylamine, but they can be by making the reaction of polyolefine such as oligomerization of propene thing, polybutene or ethene-alpha-olefin copolymer and phenol, to obtain alkylphenol, make alkylphenol and formaldehyde, polyamines such as Diethylenetriaminee (DETA), triethylenetetramine, tetraethylenepentamine or pentaethylene hexamine carry out Mannich reaction then and obtain.

(C-3) specific examples of polyamines comprises the compound by following formula (7) expression:

R ²⁴-NH-(CH ₂CH ₂NH) _K-H (7)

R wherein ²⁴Be to contain 40-400, the alkyl or alkenyl of preferred 60-350 carbon atom, k is 1-5, the integer of preferred 2-4.

There is no particular limitation for the method for preparing described polyamines.For example, this polyamines can be by with polyolefine such as oligomerization of propene thing, polybutene or ethene-alpha-olefin copolymer chlorination and make the chlorating polyolefine and ammonia or polyamines such as quadrol, Diethylenetriaminee (DETA), triethylenetetramine, tetraethylenepentamine or pentaethylene hexamine react and prepare.

Illustration is as the derivative of the nitrogenous compound of an example of component (C), its specific example comprises by making any above-mentioned nitrogenous compound and contain the monocarboxylic acid such as the lipid acid of 1-30 carbon atom, or contains the poly carboxylic acid of 2-30 carbon atom such as oxalic acid, phthalic acid, trimellitic acid and pyromellitic acid and react compound with the sour modification that neutralizes part or all of remaining amino and/or imino-or its amidation is obtained; By making above-mentioned nitrogenous compound and acid reaction compound with the boron modification that neutralizes partly or entirely remaining amino and/or imino-or its amidation is obtained; By making any above-mentioned nitrogenous compound and sulfocompound react the compound of the sulphur modification that obtains; And the modified product that obtains by two or more combined methods that are selected from sour modification, boron modification, the sulphur modification of above-mentioned nitrogenous compound.In the middle of these derivatives, the boric acid modified compound of alkenyl succinimide has good thermotolerance, antioxidant property and abrasion resistance, and the base number that therefore can improve the gained lubricating oil composition effectively keeps performance, high temperature detergency and abrasion resistance.

When lubricating oil composition of the present invention comprised component (C), its content was the total mass 0.01-20 quality % in composition, preferred 0.1-10 quality %.Aspect high temperature detergency, do not have effect when component (C) is lower than 0.01 quality %, and component (C) then can cause extreme damage to the low-temperature fluidity of gained lubricating oil composition during greater than 20 quality %.

Component (D), promptly antioxidant can be any phenol-based anti-oxidants, amido antioxidant and metal matrix antioxidant are as long as they are common in the lubricating oil.Add antioxidant and can improve the antioxidant property of lubricating oil composition, and therefore can improve its base number maintenance performance and high temperature detergency.

The example of phenol-based anti-oxidants comprises:

4,4 ＇-methylene-bis (2,6 di t butyl phenol),

4,4 ＇-two (2,6 di t butyl phenol),

4,4 ＇-two (2-methyl-6-tert butyl phenol),

2,2 ＇-methylene-bis(4-ethyl-6-t-butyl phenol),

2,2 ＇-methylene-bis (4-methyl-6-tert butyl phenol),

4,4 ＇-butylidene-bis(3-methyl-6-t-butyl phenol),

4,4 ＇-isopropylidene two (2,6 di t butyl phenol),

2,2 ＇-methylene-bis (4-methyl-6-nonyl phenol),

2,2 ＇-isobutyl fork base two (4, the 6-xylenol),

2,2 ＇-methylene-bis(4-methyl-6-cyclohexyl phenol),

2,6-di-t-butyl-4-cresols,

2,6-di-t-butyl-4-ethylphenol,

2,4 dimethyl 6 tert butyl phenol,

2,6-two uncles-alpha, alpha-dimethyl amino-p-cresol,

2,6-di-t-butyl-4-(N, N ＇-dimethylaminomethyl phenol),

4,4 ＇-sulfo-two (2-methyl-6-tert butyl phenol),

4,4 ＇-sulfo-two (3 methy 6 tert butyl phenol),

2,2 ＇-sulfo-two (4-methyl-6-tert butyl phenol),

Two (3-methyl-4-hydroxyl-5-tertiary butyl benzyl) sulfide,

Two (3,5-di-t-butyl-4-acrinyl) sulfide,

2,2 ＇-sulfo--di ethylene bis [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester],

Tridecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester,

Tetramethylolmethane-four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester],

Octyl group-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester,

Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, and

The fatty acid ester that the 3-methyl-5-tertiary butyl-4-hydroxyphenyl replaces.

Can use the mixture of two or more these compounds.

The example of amido antioxidant comprises phenyl-a-naphthylamine, alkyl phenyl-alpha-naphthylamine, and dialkyl diphenylamine.Two or more these compounds may be mixed together.

Phenol-based anti-oxidants and amido antioxidant can be used in combination.

When lubricating oil composition of the present invention comprised component (D), its content was the total mass 5 quality % or following in composition, preferred 3 quality % or following, more preferably 2.5 quality % or following.Component (D) can not obtain the sufficient antioxidant property that matches with content during greater than 5 quality %.Keep performance in order further to improve high temperature detergency in the lubricating oil deterioration process and long transsexual energy such as oxidative stability and base number, the content of component (D) be preferably 0.1 quality % or more than, preferred 1 quality % or more than.

In selection from component (B) is that solid is insoluble to or not too is dissolved in compound in the lubricating oil at normal temperatures, during as the dialkyl group zinc phosphate, for the solvability of component (B) and the manufacturing time of shortening gained lubricating oil composition, especially preferably with described compound and amine compound such as component (C), the amido antioxidant or its mixture that are selected from component (D) mix, or be dissolved in wherein or reaction with it, aforesaid operations is at organic solvent such as organic solvent such as hexane, toluene, or carry out in the naphthane, temperature is 15-150 ℃, preferred 30-120 ℃, preferred 40-90 ℃ especially, reaction times is 10 minutes-5 hours, preferred 20 minutes-3 hours, preferred especially 30 minutes-1 hour, and after solvent vacuum distilling with lubricating oil composition blend (referring to Japanese patent application 2002-191089) as oil soluble additive.

In order further to improve the performance characteristic of lubricating oil composition of the present invention, can it be used for lubricating oil additives and mix with any according to purpose.The example of this additive comprises the metal detergent that is different from component (A), is different from the anti-wear agent of component (B), friction modifiers, viscosity index improver, sanitas, rust-preventive agent, emulsion splitter, metal passivator, defoamer, and dyestuff.

The example that is different from the metal detergent of component (A) comprises basic metal or alkaline earth metal sulfonate, basic metal or alkaline-earth metal phenolate, with basic metal that is different from component (A) or alkaline-earth metal salicylate, that is, those have the salicylate of the alkyl of one or more 10-40 of containing carbon atom.The content that is different from the metal detergent of component (A) is, with regard to metal, in the total mass 0.005-5 quality % of composition.But when composition was used to the oil engine of exhaust aftertreatment device is housed, this content was preferably 0.4 quality % or following with regard to metal, more preferably accounted for 0.4 quality % or following in the total amount that contains component (A).

When the basic metal that is different from component (A) or alkaline-earth metal salicylate with component (A) when being used in combination, at least on the 3-position, has substituent salicylate, comprise component (A), component concentration be preferably 65 moles of % or more than, more preferably 70 moles of % or more than, preferred especially 80 moles of % or more than.

The example that is different from the anti-wear agent of component (B) comprises sulfocompound such as disulphide, alkene sulfide, sulfurized fat and oily, and zinc dithiocarbamate.These anti-wear agents can 0.005-5 quality % the amount blend, be 0.3 quality % or following degree to reach the total sulfur content that makes composition.But, preferably do not mix these anti-wear agents, so that reduce sulphur content and obtain long transsexual energy.

Friction modifiers can be any compound that is used as the lubricating oil friction modifiers usually.The example of this friction modifiers comprises molybdenum base friction modifiers such as molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum amine complex, molybdenum-succinimide complex compound, and molybdenumdisulphide; Ashless friction modifiers such as amine compound, fatty acid ester, fatty amide, lipid acid, fatty alcohol, and fatty ether, it has at least one alkyl or alkenyl that contains 6-30 carbon atom in molecule, especially preferably contain the straight chained alkyl or the thiazolinyl of 6-30 carbon atom.These friction modifiers can be with the amount blend of 0.1-5 quality %.

The sulfur-bearing molybdenum complex can be certain the amount blend, this consumption makes that the total sulfur content of composition is 0.3 quality % or following.In these ashless friction modifiers, use in fatty acid amide such as amine hydroxybenzene or fatty acid ester such as XU 61518.10 and the single oleic acid sorbitan ester any to distinguish further to improve abrasion resistance and friction reduces effect.Therefore, especially preferably use these ashless friction modifiers, bigger because their use can cause sulphur, phosphorus or the ash oontent of composition to be reduced to the level or the reduction degree that equate with the composition that uses in the embodiment of the invention.

The example of viscosity index improver comprises non-dispersive type viscosity index improver, is selected from the polymer of monomers or the multipolymer of various methacrylic esters or its hydride as one or more; Dispersion liquid type viscosity index improver is as the multipolymer of the various methacrylic esters that further comprise nitrogen compound; Wherein alpha-olefin can be non-dispersive liquid-or the dispersion liquid type ethene-alpha-olefin copolymer of propylene, 1-butylene or 1-amylene or its hydride; Polyisobutene or its hydride; Hydrogenant phenylethylene-dialkene multipolymer; The phenylethylene-maleic anhydride ester copolymer; With polyoxyethylene alkylphenyl ethene.

Must consider its shear stability when selecting the molecular weight of these viscosity index improvers.Specifically, the number-average molecular weight of non-dispersive liquid or dispersion liquid type polymethacrylate is 5,000-1, and 000,000, preferred 100,000-900,000.The number-average molecular weight of polyisobutene or its hydride is 800-5,000, and preferred 1,000-4,000.The number-average molecular weight of ethene-alpha-olefin copolymer or its hydride is 800-500,000, and preferred 3,000-200,000.

In the middle of these viscosity index improvers, use ethene-alpha-olefin copolymer or its hydride to help to form the special excellent lubrication oil compositions of shear stability.One or more compounds that are selected from above-mentioned viscosity index improver can be with amount mixing arbitrarily.The content of described viscosity index improver is normally in the total mass of composition, 0.1-20 quality %.

The example of sanitas comprise benzotriazole-, azimido-toluene-, thiadiazoles-and imidazo-5-yl-compound.

The example of rust-preventive agent comprises petroleum sulfonates, alkylbenzene sulfonate, dinonylnaphthalene sulfonic acid salt, alkenyl succinic acid ester, and polyol ester.

The example of emulsion splitter comprises polyglycol base nonionic surface active agent such as Voranol EP 2001, polyoxyethylene alkyl phenyl ether and polyxyethylated naphthyl ether.

The example of metal passivator comprises tetrahydroglyoxaline, pyrimidine derivatives, alkyl thiadiazoles, Thiotax, benzotriazole and its derivative, 1,3,4-thiadiazoles polysulfide, 1,3,4-thiadiazolyl group-2,5-two (dialkyl dithio amino formates), 2-(alkyl dithio) benzoglyoxaline, and β-(neighbour-carboxyl dibenzylsulfide generation) propionitrile.

The example of defoamer comprises polysiloxane, fluorosilicone, and fluoroalkyl ether.

When these additives mixed with lubricating oil composition of the present invention, the content of each all was selected from the total mass 0.005-5 quality % in composition in inhibiter, rust-preventive agent and the emulsion splitter.The content of metal passivator is selected from 0.005-1 quality %, and the content of defoamer then is selected from 0.0005-1 quality %.

Lubricating oil composition of the present invention is that sulphur content is 0.3 quality % or lubricating oil composition following, that have good resistance to abrasion, and by suitably selecting lubricating base oil, component (B) and various additive, can be so that the low sulfur lubricating oil composition has good abrasion resistance, its sulphur content can be reduced to 0.2 quality % or following, preferred 0.1 quality % or following, more preferably 0.05 quality % or following.It is 0.01 quality % or following that the present invention also can provide sulphur content, or even 0.005 quality % or following, or be substantially free of the lubricating oil composition of sulphur.

By regulating component (A) or (B) or the amount of other containing metallic additives, the sulfate ash content of lubricating oil composition of the present invention can be reduced to 1.0 quality % or following, 0.8 quality % or following, preferred 0.6 quality % or following, particularly 0.5 quality % or following.

Lubricating oil composition of the present invention is the low sulfur lubricating oil composition, not only abrasion resistance is good for it, and have good low friction performance, a long transsexual energy (oxidative stability, base number keeps performance) and high temperature detergency, therefore, can be preferred in petrol engine, diesel motor and the gas blowing engine of oil engine such as motorcycle, automobile, power generator and steamer.By reducing sulphur, phosphorus and ash oontent, it can be used for being equipped with the oil engine of exhaust aftertreatment device.In addition, it is 50 quality ppm or following that described lubricating oil composition can suitably be used to use sulphur content, preferred 30 quality ppm or following, preferred especially 10 quality ppm or following low-sulfur fuel such as gasoline, solar oil or kerosene, LPG, Sweet natural gas or be substantially free of the fuel of sulphur such as the oil engine of hydrogen, dme, alcohol and GTL (gas-liquid) in.

In addition, this lubricating oil composition can be suitably as requiring to have the lubricant of any above-mentioned characteristic performance, as be used for automatically or the lubricant of the drive system of manual transmission, grease, wet brake solution, hydraulic efficiency oil, turbine oil, compressor oil, bearing oil, refrigeration oil, or the like.

The invention effect

Lubricating oil composition of the present invention can show extremely good abrasion resistance, and can realize low-sulfur, ash content and phosphorus content, and low friction performance and the excellent transsexual energy of length.Therefore, lubricating oil composition of the present invention not only can be used as internal combustion (IC) engine lubricating oil, and can be used for those lubricating oil that requirement has these performances, as be used for automatically or the lubricating oil of the drive system of manual transmission, grease, wet brake solution, hydraulic efficiency oil, turbine oil, compressor oil, bearing oil, refrigeration oil, or the like.

Preferred forms of the present invention

Below, will be described in more detail the present invention by following examples and comparative example, these should not be considered to be limiting the scope of the invention.

Embodiment 1-6 and comparative example 1 and 2

As shown in table 1 below, preparation contain meet the requirements (I) salicylate lubricating oil composition (embodiment 1-6) and be used for correlated lubricating oil composition (comparative example 1 and 2).Carry out following performance estimation test for resulting composition.

(1) valve train rub(bing)test

Carry out the valve train rub(bing)test according to JASO M 328-95, so that measure rocking arm slurry wear area and the wearing and tearing of rocking arm and cam afterwards at 100 hours.The results are shown in table 1.Use sulphur content as 10ppm or following gasoline as test fuel

Apparent from result shown in the table 1, comprise the monoalkyl salicylate that contains an alkyl that contains 10-19 carbon atom comparative example 1 and 2 composition all have good abrasion resistance for rocking arm, but it is to the wear resistance of rocking arm slurry and relatively poor to the wear resistance of cam.

On the contrary, the lubricating oil composition of embodiment 1-6 is the low sulfur lubricating oil composition, and its each total sulfur content is 0.3 quality % or following.Even its total sulfur content and phosphorus content are reduced to 0.01 quality % or following and 0.08 quality % respectively or when following, and they also have extremely good abrasion resistance (to the wear resistance of rocking arm slurry with to the abrasion resistance of rocking arm and cam).Even be 0.5 quality % or when following (embodiment 1,2,4,5 and 6), they also show good performance characteristic at the sulfate ash content of composition.Be included in the composition (embodiment 2,3 and 5) of the component (A) that has the secondary alkyl that contains 10-40 carbon atom on the 3-position and have methyl on the 5-position, abrasion resistance is better.In addition, in comparative example 1 composition, there is 1/4 monoalkyl salicylate to replace under the situation of (embodiment 6) by component of the present invention (A), the component ratio of component in the calcium salicylate of composition (A) is 25 moles of %, like this, at least on the 3-position, has substituent salicylate, comprise component (A), total component ratio be 70 moles of %.Yet the abrasion resistance of composition but increases significantly.Our conjecture, this is because have on the 3-position at least due to the abrasion resistance of the less constituents for suppressing of substituent salicylate, particularly component (A) (B).

When using zinc dithiophosphate as component (B), even in the time that resulting composition comprises the salicylate that is used for comparative example's 2 uses, it also has sufficient abrasion resistance (referring to Japanese patent application 2002-015351) for valve train, comparative example 3 composition, phosphorus content: 0.11 quality %; rocking arm wear area: 2.8%, rocking arm wearing and tearing: 2.4 μ m, cam wear: 2.3 μ m).Therefore, we find that zinc dithiophosphate can keep abrasion resistance.But, for comprising the composition of component (A), coming compared with the composition of the salicylate that includes comparative example 2 with zinc dithiophosphate with the embodiment 1-5 of the combination of zinc phosphate, its abrasion resistance that demonstrates is better.Therefore, apparent, when anti-wear agent that uses component (A) and sulfur-bearing and phosphorus in the present invention such as zinc dithiophosphate, resulting composition is compared with the composition in the embodiment of the invention, and abrasion resistance is better.Therefore, we guess that can obtain phosphorus content and be reduced to 0.05 quality % or following, total sulfur content is reduced to 0.1 quality % or following, and sulfate ash content is reduced to 0.5 quality % or following, and has the composition of good abrasion resistance.

In addition, even in other components (B) of using the present invention's definition, during as metal-free phosphotriester, as long as component of being used in combination (A), just can with use comparative example 1 and 2 salicylate those situations compare, significantly improve abrasion resistance and reduce the ash content of resulting composition, because the abrasion resistance of the less constituents for suppressing of component (A) (B).

Embodiment 7 and comparative example 3

As shown in table 2 below, preparation contain meet the requirements (II) salicylate lubricating oil composition (embodiment 7) and be used for correlated lubricating oil composition (comparative example 3).As in Example 1, resulting composition is carried out identical performance estimation test.The result also is shown in table 2.

Apparent from result shown in the table 2, comprise the monoalkyl salicylate that contains an alkyl that contains 10-19 carbon atom comparative example 3 composition have good abrasion resistance for rocking arm, but it is to the wear resistance of rocking arm slurry and relatively poor to the wear resistance of cam.

On the contrary, the lubricating oil composition of embodiment 7 is the low sulfur lubricating oil composition, and its total sulfur content is 0.3 quality % or following.Even its total sulfur content and phosphorus content are reduced to 0.01 quality % or following and 0.08 quality % respectively or when following, it also has extremely good abrasion resistance (to the wear resistance of rocking arm slurry with to the abrasion resistance of rocking arm and cam).The sulfate ash content of composition can further be reduced to 0.5 quality % or following.Even a part of monoalkyl salicylate in comparative example's 3 compositions is replaced by component of the present invention (A) so that in the salicylate 3,5-dialkyl group salicylate component ratio be 10 moles of % or more than, preferred 20 moles of % or more than, or more preferably on the 3-position, has substituent salicylate at least, comprise component (A), total component ratio be 65 moles of % or more than, more preferably 70 moles of % or more than, under preferred especially 80 moles of % or the above situation, still generally acknowledge that resulting composition has the abrasion resistance of raising.Our conjecture, this is because have on the 3-position at least due to the abrasion resistance of the less constituents for suppressing of substituent salicylate, particularly component (A) (B).

When using sulfur-bearing and phosphorus anti-wear agent such as zinc dithiophosphate as component (B), resulting composition can show the abrasion resistance better than the embodiment of the invention 7, this be because, compare with the anti-wear agent of sulfur-bearing not, described anti-wear agent can keep abrasion resistance.Therefore, we guess that can obtain phosphorus content and be reduced to 0.05 quality % or following, total sulfur content is reduced to 0.1 quality % or following, and sulfate ash content is reduced to 0.5 quality % or following, and has the composition of good abrasion resistance.

In addition, even in other components (B) of using the present invention's definition, during as metal-free phosphotriester, as long as component of being used in combination (A), just can with the salicylate that uses comparative example 3 those situations compare, significantly improve abrasion resistance and reduce the ash content of resulting composition, because the abrasion resistance of the less constituents for suppressing of component (A) (B).

Embodiment 8 and 9 and comparative example 4 and 5

As shown in table 3 below, preparation contain meet the requirements (III) salicylate lubricating oil composition (embodiment 8 and 9) and be used for correlated lubricating oil composition (comparative example 4 and 5).As in Example 1, resulting composition is carried out identical performance estimation test.The result also is shown in table 3.

Apparent from result shown in the table 3, comprise the monoalkyl salicylate that contains an alkyl that contains 10-19 carbon atom comparative example 4 and 5 composition have good abrasion resistance for rocking arm, but it is to the wear resistance of rocking arm slurry and relatively poor to the wear resistance of cam.

On the contrary, embodiment 8 and 9 lubricating oil composition are the low sulfur lubricating oil compositions, and its each total sulfur content is 0.3 quality % or following.Even its total sulfur content and phosphorus content are reduced to 0.01 quality % or following and 0.08 quality % respectively or when following, they also have extremely good abrasion resistance (to the wear resistance of rocking arm slurry with to the abrasion resistance of rocking arm and cam).Particularly, its sulfate ash content be reduced to 0.5 quality % or following, only use metal than being 1.5 or the composition (embodiment 8) of following component (A), also show extremely good abrasion resistance.

Although not shown among the embodiment,, can have the abrasion resistance of raising by the composition that replaces a part of salicylate in comparative example 4 and 5 compositions with component of the present invention (A) and obtain.We guess to have the abrasion resistance of the less constituents for suppressing of salicylate (B) of high molecular alkyl.

When using sulfur-bearing and phosphorus anti-wear agent such as zinc dithiophosphate as component (B), resulting composition can show the abrasion resistance better than the embodiment of the invention 8, this be because, compare with the anti-wear agent of sulfur-bearing not, described anti-wear agent can keep abrasion resistance.Therefore, we guess that can obtain phosphorus content and be reduced to 0.05 quality % or following, total sulfur content is reduced to 0.1 quality % or following, and sulfate ash content is reduced to 0.5 quality % or following, and has the composition of good abrasion resistance.

In addition, even in other components (B) of using the present invention's definition, during as metal-free phosphotriester, as long as component of being used in combination (A), just can with use comparative example 4 and 5 salicylate those situations compare, significantly improve abrasion resistance and reduce the ash content of resulting composition, because the abrasion resistance of the less constituents for suppressing of component (A) (B).

Embodiment 10 and comparative example 6

As shown in table 4 below, preparation contain meet the requirements (IV) salicylate lubricating oil composition (embodiment 10) and be used for correlated lubricating oil composition (comparative example 6).As in Example 1, resulting composition is carried out identical performance estimation test.The result also is shown in table 4.

Apparent from result shown in the table 4, comprise the monoalkyl salicylate that contains an alkyl that contains 10-19 carbon atom comparative example 6 the composition (component ratio of 3-alkylsalicylate: 51 moles of %) have good abrasion resistance, but it is to the wear resistance of rocking arm slurry and relatively poor to the wear resistance of cam for rocking arm.

On the contrary, the monoalkyl salicylate that is comprised in the lubricating oil composition of the present invention (embodiment 10) is to prepare in addition isolating 3-alkylsalicylate in advance being joined the monoalkyl salicylate that uses among the comparative example 6, be 63 moles of % with regard to the component ratio that makes the 3-alkylsalicylate like this, we find, its abrasion resistance has especially been brought up to the wearing and tearing that make cam to the abrasion resistance of cam and has been reduced to the degree of half.Therefore, clearly, the abrasion resistance of the less constituents for suppressing of 3-alkylsalicylate (B), by further the component ratio of 3-alkylsalicylate being brought up to, for example 80 moles of % or more than, can obtain extremely good abrasion resistance.Lubricating oil composition of the present invention is the low sulfur lubricating oil composition, and its total sulfur content is 0.3 quality % or following.Even its total sulfur content and phosphorus content are reduced to 0.01 quality % or following and 0.08 quality % respectively or when following, it also has extremely good abrasion resistance (to the wear resistance of rocking arm slurry with to the abrasion resistance of rocking arm and cam).The sulfate ash content of composition can further be reduced to 0.5 quality % or following.

When using sulfur-bearing and phosphorus anti-wear agent such as zinc dithiophosphate as component (B), resulting composition can show the abrasion resistance better than the embodiment of the invention 10, this be because, compare with the anti-wear agent of sulfur-bearing not, described anti-wear agent can keep abrasion resistance.Therefore, we guess that can obtain phosphorus content and be reduced to 0.05 quality % or following, total sulfur content is reduced to 0.1 quality % or following, and sulfate ash content is reduced to 0.5 quality % or following, and has the composition of good abrasion resistance.

In addition, even in other components (B) of using the present invention's definition, during as metal-free phosphotriester, as long as component of being used in combination (A), just can compare with those situations of comparative example 6, significantly improve abrasion resistance and reduce the ash content of resulting composition, because the abrasion resistance of the less constituents for suppressing of component (A) (B).

1) mineral oil of hydrofinishing, total aromaticity content: 1.2 quality %, sulphur content: 0.001 quality %, the kinematic viscosity under 100 ℃: 5.6mm ²/ s, viscosity index: 125, NOACK vaporization losses: 8 quality %

2) 3-methyl-5-alkyl sodium salicylate: alkyl: secondary C14, C16, C18, the metal ratio: 1, Ca content: 2.0 quality %, sulfate ash: 6.8 quality %

3) 3-alkyl-5-cresotinic acid calcium: alkyl: secondary C14, C16, C18, the metal ratio: 1, Ca content: 2.0 quality %, sulfate ash: 6.8 quality %

4) 3-alkyl-5-cresotinic acid calcium: alkyl: secondary C14, C16, C18, the metal ratio: 2.7, Ca content: 6.2 quality %, sulfate ash: 21.1 quality %

5) 3-alkyl-5-tertiary butyl calcium salicylate: alkyl: secondary C14, C16, C18, the metal ratio: 1, Ca content: 2.0 quality %, sulfate ash: 6.8 quality %

6) 3-alkyl-5-cresotinic acid calcium: alkyl: secondary C20, C22, C24, C26, the metal ratio: 1, Ca content: 2.0 quality %, sulfate ash: 6.8 quality %

7) salicylic ratio of component: 3-alkyl salicylate: 51mol%; 5-alkyl salicylate: 35mol%; 4-alkyl salicylate: 6mol%; 3,5-dialkyl group Whitfield's ointment: 7mol%;

5-alkyl-4 hydroxyisophthalic acid: 1mol%; Alkyl: secondary C14, C16, C18, the metal ratio: 1, Ca content: 2.0 quality %, sulfate ash: 6.8 quality %

8) salicylic ratio of component: 3-alkyl salicylate: 51mol%; 5-alkyl salicylate: 35mol%; 4-alkyl salicylate: 6mol%; 3,5-dialkyl group Whitfield's ointment: 7mol%;

5-alkyl-4 hydroxyisophthalic acid: 1mol%; Alkyl: secondary C14, C16, C18, the metal ratio: 2.7, Ca content: 6.2 quality %, sulfate ash: 21.1 quality %

9) two (normal-butyl) zinc phosphate, phosphorus content: 13.2 quality %, sulphur content: 0 quality %, zinc content: 13.0 quality %, sulfate ash content: 19.5 quality %

10) polybutylene-based succinimide, polybutylene-based number-average molecular weight: 1,300

11) octyl group-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester and alkyl diphenyl base amine (1:1)

12) OCP, weight-average molecular weight: 150,000

13) polyglycol base

Table 2

		Embodiment 7	The comparative example 3
		Embodiment 7	The comparative example 3	Lubricating base oil ¹⁾	Quality %	Balance	Balance
(A) dialkyl group calcium salicylate ²⁾In metal	Quality % quality %	4 (0.08)	- -	Lubricating base oil ¹⁾	Quality %	Balance	Balance
(A) dialkyl group calcium salicylate ²⁾In metal	Quality % quality %	4 (0.08)	- -	The monoalkyl calcium salicylate ³⁾In metal	Quality % quality %	- -	4 (0.08)
(B) phosphorus compound ⁴⁾In phosphorus	Quality % quality %	0.6 (0.078)	0.6 (0.078)	The monoalkyl calcium salicylate ³⁾In metal	Quality % quality %	- -	4 (0.08)
(B) phosphorus compound ⁴⁾In phosphorus	Quality % quality %	0.6 (0.078)	0.6 (0.078)	(C) ashless dispersant ⁵⁾	Quality %	5	5
(D) antioxidant ⁶⁾	Quality %	2	2	(C) ashless dispersant ⁵⁾	Quality %	5	5
(D) antioxidant ⁶⁾	Quality %	2	2	Viscosity index improver ⁷⁾	Quality %	4	4
Emulsion splitter ⁸⁾	Quality %	0.01	0.01	Viscosity index improver ⁷⁾	Quality %	4	4
Emulsion splitter ⁸⁾	Quality %	0.01	0.01	Total sulfur content	Quality %	<0.01	<0.01
Sulfate ash content	Quality %	0.39	0.39	Total sulfur content	Quality %	<0.01	<0.01
Sulfate ash content	Quality %	0.39	0.39	The wearing and tearing of JASO valve train wearing test rocking arm wear area rocking arm wear cam	％ μm μm	3 0.8 2.3	77.5 5 31.1

2) 3,5-dialkyl group calcium salicylate: alkyl: secondary C14, C16, C18, the metal ratio: 1, Ca content: 2.0 quality %, sulfate ash: 6.8 quality %

3) salicylic ratio of component: 3-alkyl salicylate: 51mol%; 5-alkyl salicylate: 35mol%; 4-alkyl salicylate: 6mol%; 3,5-dialkyl group Whitfield's ointment: 7mol%;

4) two (normal-butyl) zinc phosphate, phosphorus content: 13.2 quality %, sulphur content: 0 quality %, zinc content: 13.0 quality %, sulfate ash content: 19.5 quality %

5) polybutylene-based succinimide, polybutylene-based number-average molecular weight: 1,300

6) octyl group-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester and alkyl diphenyl base amine (1:1)

7) OCP, weight-average molecular weight: 150,000

8) polyglycol base

Table 3

		Embodiment 8	Embodiment 9	The comparative example 4	The comparative example 5
		Embodiment 8	Embodiment 9	The comparative example 4	The comparative example 5	Lubricating base oil ¹⁾	Quality %	Balance	Balance	Balance	Balance
(A) monoalkyl calcium salicylate ²⁾In metal	Quality % quality %	4 (0.08)	- -	- -	- -	Lubricating base oil ¹⁾	Quality %	Balance	Balance	Balance	Balance
(A) monoalkyl calcium salicylate ²⁾In metal	Quality % quality %	4 (0.08)	- -	- -	- -	(A) monoalkyl calcium salicylate ³⁾In metal	Quality % quality %	- -	3 (0.25)	- -	- -
The monoalkyl calcium salicylate ⁴⁾In metal	Quality % quality %	- -	- -	4 (0.08)	- -	(A) monoalkyl calcium salicylate ³⁾In metal	Quality % quality %	- -	3 (0.25)	- -	- -
The monoalkyl calcium salicylate ⁴⁾In metal	Quality % quality %	- -	- -	4 (0.08)	- -	The monoalkyl calcium salicylate ⁵⁾In metal	Quality % quality %	- -	- -	- -	4 (0.25)
(B) phosphorus compound ⁶⁾In phosphorus	Quality % quality %	0.6 (0.078)	0.6 (0.078)	0.6 (0.078)	0.6 (0.078)	The monoalkyl calcium salicylate ⁵⁾In metal	Quality % quality %	- -	- -	- -	4 (0.25)
(B) phosphorus compound ⁶⁾In phosphorus	Quality % quality %	0.6 (0.078)	0.6 (0.078)	0.6 (0.078)	0.6 (0.078)	(C) ashless dispersant ⁷⁾	Quality %	5	5	5	5
(D) antioxidant ⁸⁾	Quality %	2	2	2	2	(C) ashless dispersant ⁷⁾	Quality %	5	5	5	5
(D) antioxidant ⁸⁾	Quality %	2	2	2	2	Viscosity index improver ⁹⁾	Quality %	4	4	4	4
Emulsion splitter ¹⁰⁾	Quality %	0.01	0.01	0.01	0.01	Viscosity index improver ⁹⁾	Quality %	4	4	4	4
Emulsion splitter ¹⁰⁾	Quality %	0.01	0.01	0.01	0.01	Total sulfur content	Quality %	<0.01	<0.01	<0.01	<0.01
Sulfate ash content	Quality %	0.39	0.96	0.39	0.96	Total sulfur content	Quality %	<0.01	<0.01	<0.01	<0.01
Sulfate ash content	Quality %	0.39	0.96	0.39	0.96	The wearing and tearing of JASO valve train wearing test rocking arm wear area rocking arm wear cam	％ μm μm	2 1.5 2.2	13.1 0 12.2	77.5 5 31.1	74.6 4.7 39.1

2) salicylic ratio of component: 3-alkyl salicylate: 55mol%; 5-alkyl salicylate: 34mol%; 4-alkyl salicylate: 5mol%; 3,5-dialkyl group Whitfield's ointment: 3mol%;

5-alkyl-4 hydroxyisophthalic acid: 3mol%; Alkyl: secondary C20, C22, C24, C26, the metal ratio: 1.2, Ca content: 2.0 quality %, sulfate ash: 6.8 quality %

3) salicylic ratio of component: 3-alkyl salicylate: 55mol%; 5-alkyl salicylate: 34mol%; 4-alkyl salicylate: 5mol%; 3,5-dialkyl group Whitfield's ointment: 3mol%;

5-alkyl-4 hydroxyisophthalic acid: 3mol%; Alkyl: secondary C20, C22, C24, C26, the metal ratio: 4.4, Ca content: 8.3 quality %, sulfate ash: 28.2 quality %

4) salicylic ratio of component: 3-alkyl salicylate: 51mol%; 5-alkyl salicylate: 35mol%; 4-alkyl salicylate: 6mol%; 3,5-dialkyl group Whitfield's ointment: 7mol%;

Stupid dioctyl phthalate: 1mol% between 5-alkyl-4-hydroxyl; Alkyl: secondary C14, C16, C18, the metal ratio: 1, Ca content: 2.0 quality %, sulfate ash: 6.8 quality %

5) salicylic ratio of component: 3-alkyl salicylate: 51mol%; 5-alkyl salicylate: 35mol%; 4-alkyl salicylate: 6mol%; 3,5-dialkyl group Whitfield's ointment: 7mol%;

6) two (normal-butyl) zinc phosphate, phosphorus content: 13.2 quality %, sulphur content: 0 quality %, zinc content: 13.0 quality %, sulfate ash content: 19.5 quality %

7) polybutylene-based succinimide, polybutylene-based number-average molecular weight: 1,300

8) octyl group-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester and alkyl diphenyl base amine (1:1)

9) OCP, weight-average molecular weight: 150,000

10) polyglycol base

Table 4

		Embodiment 10	The comparative example 6
		Embodiment 10	The comparative example 6	Lubricating base oil ¹⁾	Quality %	Balance	Balance
(A) calcium salicylate ²⁾In metal	Quality % quality %	4 (0.08)	- -	Lubricating base oil ¹⁾	Quality %	Balance	Balance
(A) calcium salicylate ²⁾In metal	Quality % quality %	4 (0.08)	- -	Calcium salicylate ³⁾In metal	Quality % quality %	- -	4 (0.08)
(B) phosphorus compound ⁴⁾In phosphorus	Quality % quality %	0.6 (0.078)	0.6 (0.078)	Calcium salicylate ³⁾In metal	Quality % quality %	- -	4 (0.08)
(B) phosphorus compound ⁴⁾In phosphorus	Quality % quality %	0.6 (0.078)	0.6 (0.078)	(C) ashless dispersant ⁵⁾	Quality %	5	5
(D) antioxidant ⁶⁾	Quality %	2	2	(C) ashless dispersant ⁵⁾	Quality %	5	5
(D) antioxidant ⁶⁾	Quality %	2	2	Viscosity index improver ⁷⁾	Quality %	4	4
Emulsion splitter ⁸⁾	Quality %	0.01	0.01	Viscosity index improver ⁷⁾	Quality %	4	4
Emulsion splitter ⁸⁾	Quality %	0.01	0.01	Total sulfur content	Quality %	<0.01	<0.01
Sulfate ash content	Quality %	0.39	0.39	Total sulfur content	Quality %	<0.01	<0.01
Sulfate ash content	Quality %	0.39	0.39	The wearing and tearing of JASO valve train wearing test rocking arm wear area rocking arm wear cam	％ μm μm	49.2 3.2 15.1	77.5 5 31.1

2) salicylic ratio of component: 3-alkyl salicylate: 63mol%; 5-alkyl salicylate: 28mol%; 4-alkyl salicylate: 4mol%; 3,5-dialkyl group Whitfield's ointment: 3mol%;

5-alkyl-4 hydroxyisophthalic acid: 2mol%; Alkyl: secondary C14, C16, C18, the metal ratio: 1, Ca content: 2.0 quality %, sulfate ash: 6.8 quality %

7) OCP, weight-average molecular weight: 150,000

8) polyglycol base

Claims

1. lubricating oil composition, it comprises:

Lubricating base oil,

(A) cross the salt or the basic salt of alkalization by the basic metal of following formula (1) expression or alkaline-earth metal salicylate and/or its, its amount with metal be expressed as 0.005-5 quality % and

(B) phosphorous anti-wear agent, its amount is expressed as 0.005-0.2 quality % with phosphorus,

And the total mass total amount that contains in composition is 0.3 quality % or sulphur still less, described salicylate be satisfy any salicylate that is selected from least one requirement in (I)-(IV) or salicylate mixture:

Wherein, R ¹It is the alkyl that contains 1-40 carbon atom; R ²Be hydrogen or the alkyl that contains 1-40 carbon atom, this alkyl contains or oxygen-free or nitrogen; M is basic metal or alkaline-earth metal, and n depends on the valency of metal, is 1 or 2 integer;

2. according to the lubricating oil composition of claim 1, wherein component (B) is selected from by the phosphorus compound of following formula (2) and (3) expression and the compound of its metal or amine salt at least a:

3. according to the lubricating oil composition of claim 2, wherein component (B) is selected from wherein X at least one class ¹, X ²And X ³All be the formula (2) of oxygen and X wherein ⁴, X ⁵, X ⁶And X ⁷It all is the compound of phosphorus compound metal-salt of the formula (3) of oxygen.

4. according to the lubricating oil composition of claim 2, wherein component (B) is X wherein ⁴, X ⁵, X ⁶And X ⁷All be oxygen, R ⁶, R ⁷And R ⁸Be the phosphorus compound of formula (3) of the alkyl that contains 1-30 carbon atom independently of one another.

5. according to the lubricating oil composition of claim 2, wherein component (B) is X wherein ⁴, X ⁵, X ⁶And X ⁷In any two be the zinc salt of phosphorus compound of the formula (3) of oxygen.

6. according to the lubricating oil composition of claim 1, wherein the amount of the component that is comprised (B) is represented to count 0.005-0.08 quality %. with the total mass of composition with phosphorus

7. according to the lubricating oil composition of claim 1, wherein lubricating oil composition comprises at least a being selected from (C) ashless dispersant and (D) additive of antioxidant.

8. according to the lubricating oil composition of claim 1, wherein the total sulfur content of lubricating base oil is 0.05 quality % or still less.

9. according to the lubricating oil composition of claim 1, wherein it is used for oil engine.

10. according to the lubricating oil composition of claim 9, wherein sulfate ash content is 1.0 quality % or still less.

11. according to the lubricating oil composition of claim 9, wherein it satisfies or the multinomial requirement of the following stated: sulfate ash content is 0.5 quality % or still less, and total sulfur content is 0.05 quality % or still less, and phosphorus content is 0.05 quality % or still less.

12. one kind is used the lubricating oil composition of claim 1 to prevent the method that engine valve group system weares and teares.