CN102639684A

CN102639684A - Lubricating oil composition

Info

Publication number: CN102639684A
Application number: CN2010800551447A
Authority: CN
Inventors: 镰野秀树
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2009-12-03
Filing date: 2010-12-01
Publication date: 2012-08-15
Also published as: KR20120099065A; US20120238481A1; WO2011068137A1; EP2508590A1; JPWO2011068137A1; EP2508590A4

Abstract

A lubricating oil composition which has excellent wear resistance even with low phosphorus content, low sulfur content and low sulfated ash content and which exhibits excellent friction reducing effect even when used in DLC-treated sliding parts, is provided by mixing a specific sulfur-containing compound and a specific polar group-containing compound into a base oil.

Description

Lubricating oil composition

Technical field

The present invention relates to lubricating oil composition.Say that in further detail even relate to low-phosphorous branch, low sulphur content, low sulfuric acid ash content, wear resistance is still excellent, and also can embody the lubricating oil composition that excellent friction reduces effect when promptly being used in the slide unit of handling through quasi-diamond (DLC).

Background technology

In the present motor car engine,, using oxide catalyst, three-way catalyst, NO for purification of exhaust gas _XSorption-type reducing catalyst, diesel particulate filter (DPF) etc.Known these exhaust gas purifiers can receive metal ingredient, the phosphorus branch in the engine oil, the detrimentally affect of sulphur content, and on the countermeasure of anti-locking apparatus deterioration, it is necessary reducing these compositions.

In addition, in recent years, be purpose to practice thrift oil consumption, automobile etc. is being carried out various technological development, can enumerate the process for treating surface of the slide unit of mover for example etc.

In the past; As the anti-wear agent of employed lubricating oil for IC engines in petrol engine, diesel motor, the gas engine etc. the inhibitor of holding concurrently; Use zinc dithiophosphate (Zn-DTP) all the year round, also be considered to necessary additive important in the lubricating oil for IC engines now.

But, produce sulfuric acid and phosphoric acid owing to zinc dithiophosphate if decompose meeting, the basic cpd in the consumption of engine oil, the deterioration of promotion lubricating oil shortens the drain period sometimes terrifically.In addition, zinc dithiophosphate also exists greasy filthization under the hot conditions, worsens the problem of engine interior cleanliness.And, owing in the zinc dithiophosphate molecule when containing metal ingredient (zinc), also contain a large amount of phosphorus and divide and sulphur content, therefore be considered to bring dysgenic reason to exhaust gas purifier.Therefore, even the lubricating oil composition that does not use zinc dithiophosphate, wear resistance also excellent is developed in expectation.

In addition, in view of the development progress situation of above-mentioned slide unit process for treating surface, lubricating oil composition also needs further improvement.For example, if when lubricating oil that will be in the past is used to apply the slide unit that DLC handles, the friction that can not embody desired degree sometimes reduces effect.Therefore, in order to reach further low burnupization, when expectation promptly is used in the slide unit of handling through DLC, also can embody the lubricating oil composition that excellent friction reduces effect.

In order to solve such problem, the various additive for lubricant of proposition and lubricating oil composition are arranged all always.For example, having put down in writing in the patent documentation 1～3 with the disulfide compound with ad hoc structure is the additive for lubricant and the lubricating oil composition of principal constituent.Put down in writing in the patent documentation 4 and reduced sulphur, phosphorus, and wearing and tearing prevent the engine oil of excellent performance as the poisoning material of reducing catalyst.Having put down in writing in the patent documentation 5 to have uses lubricating oil composition that adamantine slipping plane, order contain special additive between wherein low Frictional Slipping structure.

The prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid is opened the 2004-262964 communique

Patent documentation 2: Japanese Patent Laid is opened the 2004-262965 communique

Patent documentation 3: Japanese Patent Laid is opened the 2008-056876 communique

Patent documentation 4: Japanese Patent Laid is opened the 2007-131792 communique

Patent documentation 5: Japanese Patent Laid is opened the 2008-56735 communique

Summary of the invention

The problem that invention will solve

Though the exploitation of various additive for lubricant and lubricating oil composition is carried out so far; But for lubricating oil; Usually numerous requirements such as performance, wear resistance and friction minimizing effect of relevant poisoning of catalyst are satisfied in requirement simultaneously, and the lubricating oil composition of therefore putting down in writing in the above-mentioned document also is far from being enough outstanding.Especially because zinc dithiophosphate is an additive very useful when improving wear resistance with oxidation-resistance, had so will not use this compound with in the past equal or than in the past better the lubricating oil composition of performance be difficult.

In view of the foregoing, the objective of the invention is to, even low-phosphorous branch, low sulphur content, low sulfuric acid ash content are provided, wear resistance is still excellent, and also can embody the lubricating oil composition that excellent friction reduces effect when promptly being used in the slide unit of handling through DLC.

Solve the means of problem

People of the present invention concentrate on studies repeatedly, and the result finds to pass through and with specific sulfocompound and specific polar functionalities compound, can achieve the above object.The present invention is based on this understanding and accomplishes.

Just, the present invention provides:

1, a kind of lubricating oil composition; It is characterized in that; In base oil, mix (A) and be selected from formula (I) and the sulfocompound of (II) representing at least a kind; The polar functionalities compound that (B) has an alkyl of at least a kind of polar group being selected from amino, carboxamido-group and hydroxyl and carbonatoms 3～24 forms

[changing 1]

R ¹-Y-(CH ₂) _n-S _x-(CH ₂) _n-Y-R ² (1)

(R ¹～R ¹²Represent Wasserstoffatoms respectively independently; Be selected from the alkyl of alkyl, naphthenic base, thiazolinyl, cycloalkenyl group and aryl; Or comprise the heteroatom group that contains that the atom that is selected from Sauerstoffatom, nitrogen-atoms and sulphur atom forms in these alkyl, Y respectively independently expression be selected from-O-,-S-,-SO-,-SO ₂-,-(C=O) O-,-(C=O) NH-,-O (C=O) NH-,-C (=O)-,-N (H)-,-NHCONH-,-N=N-,-NH-C (=NH)-NH-,-S-C (=O)-,-NH-C (=S)-with-NH-C (=S)-divalent group of NH-.X is 1～3 integer, and n is respectively 1～5 integer independently.)

2, the lubricating oil composition of record in above-mentioned 1; It is characterized in that the polar functionalities compound that above-mentioned (B) has an alkyl of at least a kind of polar group being selected from amino, carboxamido-group and hydroxyl and carbonatoms 3～24 is at least a kind of compound that is selected from the group that glycerine partial fatty acid ester, glycerol monoethers compound, amine compound and amide compound form.

3, the lubricating oil composition of record in above-mentioned 1; It is characterized in that; The polar functionalities compound that above-mentioned (B) has an alkyl of at least a kind of polar group being selected from amino, carboxamido-group and hydroxyl and carbonatoms 3～24 is the formula (III) or (IV) monoglyceride of expression; Formula (V) or (VI) expression the glycerol monoethers compound

[changing 2]

(R ¹³And R ¹⁴The alkyl of representing carbonatoms 3～24 respectively independently.)

4, the lubricating oil composition of record in above-mentioned 1; It is characterized in that; The polar functionalities compound that above-mentioned (B) has the alkyl of at least a kind of polar group being selected from amino, carboxamido-group and hydroxyl and carbonatoms 3～24 is the amine compound of formula (VII) expression or the amide compound of formula (VIII) expression

[changing 3]

(R ¹⁵And R ¹⁷The alkyl of representing carbonatoms 3～24 respectively independently, R ¹⁶And R ¹⁸The terminal Wasserstoffatoms of representing the straight chained alkyl of Wasserstoffatoms or carbonatoms 2～4 is respectively independently replaced the group that forms by hydroxyl.)

5, the lubricating oil composition of any record of above-mentioned 1～4 is characterized in that, is benchmark with the lubricating oil composition total amount, and phosphorus content is below 0.5 quality %, and sulphated ash is below 0.6 quality %.

6, the lubricating oil composition of any record of above-mentioned 1～5 is characterized in that, is benchmark with the lubricating oil composition total amount, and phosphorus content is 0 quality %, and sulphated ash is below 0.1 quality %.

7, the lubricating oil composition of any record of above-mentioned 1～6 is characterized in that, is that the slide unit of implementing quasi-diamond DLC processing is used lubricating oil composition.

The effect of invention

Even low-phosphorous branch, low sulphur content, low sulfuric acid ash content can be provided according to the present invention, wear resistance is still excellent, and also can embody the lubricating oil composition that excellent friction reduces effect when promptly being used in the slide unit of handling through DLC.

Embodiment

Lubricating oil composition of the present invention is characterised in that, is in base oil, to mix specific sulfocompound and specific polar functionalities compound forms.

(base oil)

As base oil used in the present invention, there is not restriction especially, can be suitably from always using as selecting arbitrarily employed MO of lubricant base and the synthetic oil.

Above-mentioned MO can be given an example; For example; Carry out the resulting lubricating oil distillate of underpressure distillation again to crude oil being carried out the resulting atmospheric resids of air distillation; Carry out the processing more than 1 among solvent deasphalting, SX, hydrogenolysis, solvent dewaxing, contact dewaxing, the hydrofinishing etc., the refining MO that obtains, perhaps mineral wet goods through paraffin, GTL WAX isomerizing manufacturing are formed.

On the other hand; As said synthetic oil, can enumerate, for example; [alpha-olefin homo and multipolymer are (for example for polybutylenes, polyolefine; Ethene-alpha-olefin copolymer) etc.], various ester (for example, polyol ester, dibasic acid esters, SULPHOSUCCINIC ACID ESTER etc.), various ether (for example, ppe etc.), polyglycol, korenyl, alkylnaphthalene etc.In the middle of these synthetic oils, special preferred polyolefm, polyol ester.

Base oil among the present invention can use a kind of above-mentioned MO separately, also can make up use more than 2 kinds.In addition, can also use a kind of above-mentioned synthetic oil, or combination is used more than 2 kinds.More can MO more than a kind and the combination of the synthetic oil more than a kind be used.

The not special restriction of above-mentioned basic oil viscosity, the kinematic viscosity in the time of preferred 100 ℃ is at 2～30mm ²The scope of/s is more preferably at 3～15mm ²The scope of/s is further preferably at 4～10mm ²The scope of/s.

If the kinematic viscosity in the time of 100 ℃ is 2mm ²More than/the s, then vaporization losses is few, in addition, if at 30mm ²Below/the s, then can suppress the power waste that causes by viscous resistance, obtain oil consumption and improve effect.

In addition, as base oil, preferably use according to carbon type analysis (ring analysis) %C _ABelow 3.0, the base oil of content below 50 quality ppm of sulphur content.Here, the %C that obtains according to the carbon type analysis _AExpression, the ratio (percentage ratio) of the aromatic component of calculating through carbon type analysis n-d-M method.In addition, sulphur content is the value of measuring according to JIS K 2541.

%CA below 3.0, the base oil of sulphur content below 50 quality ppm have good oxidative stability, can provide a kind of and can suppress the acid number lubricating oil composition with the greasy filth generation that rises.Preferred %C _ABelow 1.0, further preferred below 0.5, more preferably sulphur content is below the 30 quality ppm in addition.

Further, the viscosity index of base oil is preferred more than 70, and is more preferably more than 100, further preferred more than 120.Along with temperature variation, viscosity changes little this viscosity index at the base oil more than 70.

(sulfocompound)

In the lubricating oil composition of the present invention, mix formula (I) or (II) represented sulfocompound.

[changing 4]

R ¹-Y-(CH ₂) _n-S _x-(CH ₂) _n-Y-R ² (I)

General formula (I) or (II) in, R ¹～R ¹²Represent Wasserstoffatoms respectively independently, be selected from the alkyl of alkyl, naphthenic base, thiazolinyl, cycloalkenyl group and aryl, or comprise the heteroatom group that contains that the atom that is selected from Sauerstoffatom, nitrogen-atoms and sulphur atom forms in these alkyl.

R ¹～R ¹²The alkyl of expression, the alkyl of preferred carbonatoms 1～30, the more preferably alkyl of carbonatoms 1～24.The object lesson of alkyl for example can be enumerated, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, various hexyl, various octyl group, various decyl, various dodecyl, various tetradecyl, various hexadecyl, various octadecyl and various eicosyls etc.In addition, also can be replaced on the alkyl, can enumerate for example benzyl, styroyl etc. by aromatic group.

R ¹～R ¹²The naphthenic base of expression, the naphthenic base of preferred carbonatoms 3～30, the more preferably naphthenic base of carbonatoms 3～24.The object lesson of naphthenic base can be enumerated cyclopropyl, cyclopentyl, cyclohexyl, methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethylammonium cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl and diethylammonium cyclohexyl etc.In addition, also can be replaced on the naphthenic base, can enumerate for example benzyl ring amyl group, benzyl ring hexyl etc. by aromatic group.

R ¹～R ¹²The thiazolinyl of expression, the thiazolinyl of preferred carbonatoms 2～30, the more preferably thiazolinyl of carbonatoms 2～24.The object lesson of thiazolinyl can be enumerated for example vinyl, allyl group, 1-butylene base, crotyl, 3-crotonyl, 1-methyl ethylene, 1-methacrylic, 1,1-dimethyl-allyl, 2-methacrylic, nonene base, decene base, octadecylene base etc.In addition, also can be replaced on the thiazolinyl by aromatic group.

R ¹～R ¹²The cycloalkenyl group of expression, the cycloalkenyl group of preferred carbonatoms 3～30, the more preferably cycloalkenyl group of carbonatoms 3～24.The object lesson of cycloalkenyl group can be enumerated cyclobutene base, methyl cyclobutene base etc.In addition, also can be replaced on the cycloalkenyl group by aromatic group.

R ¹～R ¹²The aryl of expression, the aryl of preferred carbonatoms 6～30, the more preferably aryl of carbonatoms 6～24.The object lesson of aryl can be enumerated phenyl, tolyl, xylyl, naphthyl, butyl phenyl, octyl phenyl, nonyl phenyl etc.

General formula (I) or (II) in, Y respectively independently the expression be selected from-O-,-S-,-SO-,-SO ₂-,-(C=O) O-,-(C=O) NH-,-O (C=O) NH-,-C (=O)-,-N (H)-,-NHCONH-,-N=N-,-NH-C (=NH)-NH-,-S-C (=O)-,-NH-C (=S)-with-NH-C (=S)-divalent group of NH-.

General formula (I) or (II) in, x is 1～3 integer, preferred 2.N is respectively 1～5 integer independently, preferred 1 or 2.

The sulfocompound of general formula (I) expression can be enumerated the for example compound shown in the following formula.

[changing 5]

[changing 6]

[changing 7]

[changing 8]

[changing 9]

[changing 10]

[changing 11]

[changing 12]

In addition; Following compound also is the example of compound shown in the general formula (I); For example: two (methoxycarbonyl methyl) disulfide, two (ethoxy carbonyl methyl) disulfide, two (positive propoxy carbonyl methyl) disulfide, two (isopropoxy carbonyl methyl) disulfide, two (n-butoxy carbonyl methyl) disulfide, two (n-octyloxy carbonyl methyl) disulfide, two (n-dodecane oxygen base carbonyl methyl) disulfide, two (ring propoxycarbonyl methyl) disulfide, 1; Two (the 2-methoxycarbonyl ethyl) disulfides, 1 of 1-; Two (the 3-methoxycarbonyl n-propyl) disulfides, 1 of 1-; Two (the 4-methoxycarbonyl normal-butyl) disulfides, 1 of 1-, two (the 2-ethoxy carbonyl ethyl) disulfides, 1 of 1-, two (the 2-positive propoxy carbonyl ethyl) disulfides, 1 of 1-; Two (the 2-isopropoxy carbonyl ethyl) disulfides, 1 of 1-, 1-two (2-ring propoxycarbonyl ethyl) disulfide etc.

Object lesson as the compound shown in the general formula (II); Can enumerate; Dithio oxysuccinic acid tetramethyl ester, dithio oxysuccinic acid tetra-ethyl ester, dithio oxysuccinic acid four-1-propyl ester, dithio oxysuccinic acid four-2-propyl ester, dithio oxysuccinic acid four-1-butyl ester, dithio oxysuccinic acid four-2-butyl ester, dithio oxysuccinic acid four isobutylates, the own ester of dithio oxysuccinic acid four-1-, dithio oxysuccinic acid four-1-monooctyl ester, the own ester of dithio oxysuccinic acid four-1-(2-ethyl), dithio oxysuccinic acid four-1-(3; 5; The 5-trimethylammonium) own ester, dithio oxysuccinic acid four-1-ester in the last of the ten Heavenly stems, dithio oxysuccinic acid four-1-dodecyl ester; Dithio oxysuccinic acid four-1-cetyl ester, dithio oxysuccinic acid four-1-stearyl, dithio oxysuccinic acid four benzyl esters, dithio oxysuccinic acid four-α-(methyl) benzyl ester, dithio oxysuccinic acid four α, alpha-alpha-dimethyl benzyl ester, dithio oxysuccinic acid four-1-(2-methoxyl group) ethyl ester, dithio oxysuccinic acid four-1-(2-oxyethyl group) ethyl ester, dithio oxysuccinic acid four-1-(2-butoxy) ethyl ester, dithio oxysuccinic acid four-1-(2-oxyethyl group) ethyl ester, dithio oxysuccinic acid four-1-(2-butoxy butoxy) ethyl ester, dithio oxysuccinic acid four-1-(2-phenoxy) ethyl ester etc.

Among the present invention, these general formulas (I) or (II) shown in sulfocompound can a kind use separately, also can mix use more than 2 kinds.In addition, the combined amount of this sulfocompound is benchmark with the total composition, is preferably 0.01～5.0 quality %, more preferably 0.1～2.0 quality %.Through making combined amount more than 0.01 quality %, can obtain sufficient abrasion resistance, if surpass 5.0 quality %, can not obtain the effect that matches with addition sometimes.

(polar functionalities compound)

In the lubricating oil composition of the present invention, be mixed with the polar functionalities compound of the alkyl of carbonatoms with at least a kind of polar group being selected from amino, carboxamido-group and hydroxyl and specified range.

The polar functionalities compound that uses among the present invention is to have carbonatoms 3～24, the compound of the alkyl of preferred carbonatoms 8～20.If carbonatoms less than 3, then the solvability of this compound is low.In addition,, can obtain more excellent friction usually and reduce effect though be accompanied by the increase of carbonatoms, if surpass 24, the effect that matches with regard to the increase that is difficult to obtain with carbonatoms.

Said polar functionalities compound for example can be enumerated, and is selected from the group that glycerine partial fatty acid ester, glycerol monoethers compound, amine compound and amide compound are formed, and contains the compound of said alkyl.

Said glycerine partial fatty acid ester for example is glycerine and the resulting compound of fatty acid response; This lipid acid can be enumerated, acetate, propionic acid, butyric acid (butyric acid), valeric acid (valeric acid), isovaleric acid (isovaleric acid), caproic acid (caproic acid), enanthic acid, isoamyl acetic acid, sad (caprylic acid), 2 ethyl hexanoic acid, isocaprylic acid, n-nonanoic acid (sunflower acid), different n-nonanoic acid, capric acid (capric acid), isodecyl acid, undeeanoic acid, different undeeanoic acid, laurostearic acid (LAURIC ACID 99 MIN), different laurostearic acid, tridecylic acid, different tridecylic acid, TETRADECONIC ACID (tetradecanoic acid), palmitic acid (palmitinic acid), stearic acid (Triple Pressed Stearic Acid), Unimac 5680,20 acid (eicosanoic acid), behenic acid (mountain Yu acid), tetracosanoic acid (lignoceric acid), hydroxyhexacosanoic acid (cerinic acid), octacosanoic acid (montanic acid), 10-undecylenic acid, hexadecylenic acid, oleic acid, elaidic acid, linolic acid, linolenic acid, sweet carbon enoic acid, sinapinic acid, zoomaric acid etc.Also can be the mixed fatty acid that obtains from natural fats and oils in addition.In these lipid acid, consider the lipid acid of preferred carbonatoms 10～18, the more preferably sfas of carbonatoms 10～12, further preferred oleic acid and elaidic acid, most preferably oleic acid from the viewpoint of reducing friction of lubricating oil.

Said glycerine partial fatty acid ester can enumerate formula (III) for example and (IV) shown in monoglyceride.These compounds can obtain through the direct esterification reaction of lipid acid and glycerine or the transesterification reaction of grease and glycerine etc.

[changing 13]

General formula (III) and (IV) in, R ¹³The alkyl of representing carbonatoms 3～24 respectively independently.Formula of of the present invention (III) or (IV) shown in monoglyceride can use separately, also can use their mixture.Moreover, when using these monoglycerides, can also sneak into glycerol-fatty acid diester or glycerine fatty acid three esters.

Said glycerol monoethers compound for example is the compound that glycerine and fatty alcohol reaction obtain, and this fatty alcohol can be enumerated propyl alcohol, butanols, oleyl alcohol, VLTN 6 etc.Wherein, consider the pure and mild VLTN 6 of preferred oil, preferred especially oleyl alcohol from the viewpoint of reducing friction of lubricating oil.

Said glycerol monoethers compound can enumerate formula (V) for example and (VI) shown in the glycerol monoethers compound.

[changing 14]

Logical formula V with (VI) in, R ¹⁴The alkyl of representing carbonatoms 3～24 respectively independently.Formula of of the present invention (V) or (VI) shown in the glycerol monoethers compound can use separately, also can use their mixture.Moreover, when using these glycerol monoethers compounds, can also sneak into glycerine diether or glycerine three ethers.

Said amine compound can be enumerated for example alkyl ammonium compounds or fatty alcohol amine compound.Alkyl in the alkyl ammonium compounds can be enumerated alkyl contained in the said lipid acid.This amine compound for example can be enumerated, the amine compound shown in the formula (VII).

[changing 15]

In the general formula (VII), R ¹⁵The alkyl of expression carbonatoms 3～24.R ¹⁶Represent independently respectively Wasserstoffatoms or carbonatoms 2～4 straight chained alkyl terminal Wasserstoffatoms by hydroxyl replace the group form (for example ,-(CH ₂) ₂-OH).Amine compound shown in the formula of of the present invention (VII) can use separately, also can use their mixture.

The object lesson of said amine compound can be enumerated monoethanolamine, diethylolamine, trolamine, N-Mono Methyl Ethanol Amine, N; N-dimethylethanolamine, N-ehtylethanolamine, N; N-diethylethanolamine, N-isopropyl alcohol amine, N, N-diisopropyl ethanolamine, monoisopropanolamine, HSDB 338, tri-isopropanolamine, N-methyl isopropyl hydramine, N, N-dimethylisopro panolamine, N-ethyl Yi Bingchunan, N; N-diethylammonium Yi Bingchunan, N-isopropyl Propanolamine, N; N-di-isopropyl Yi Bingchunan, single n-propyl alcohol amine, two n-propyl alcohol amine, three n-propyl alcohol amine, N-methyl n-propyl alcohol amine, N, N-dimethyl n Propanolamine, N-ethyl n-propyl alcohol amine, N, N-diethylammonium n-propyl alcohol amine, N-sec.-propyl n-propyl alcohol amine, N; N-di-isopropyl n-propyl alcohol amine, only son's hydramine, two butanolamines, three butanolamines, N-methyl butanol amine, N; N-dimethyl butyrate hydramine, N-ethyl butanol amine, N, N-diethylammonium butanolamine, N-sec.-propyl butanolamine, N, N-di-isopropyl butanolamine etc.

Said amide compound can be enumerated 1～4 yuan of carboxylic acid and alkylamine or the reaction of aliphatics hydramine and the compound that obtains.

Constitute said monocarboxylic alkyl and for example can enumerate hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, cerylic, heptacosyl, octacosyl, nonacosyl and triacontyl etc.

Monocarboxylic acid can be enumerated caproic acid, caprylic acid, capric acid, LAURIC ACID 99 MIN, tetradecanoic acid, palmitinic acid, Triple Pressed Stearic Acid, eicosanoic acid, mountain Yu acid and lignoceric acid etc., and 2～4 yuan of carboxylic acids can be enumerated polycarboxylic acids such as oxalic acid, phthalic acid, trimellitic acid, Pyromellitic Acid in addition.

Said amide compound for example can be enumerated, the amide compound shown in the formula (VIII).

[changing 16]

In the general formula (VIII), R ¹⁷The alkyl of expression carbonatoms 3～24.R ¹⁸Represent independently respectively Wasserstoffatoms or carbonatoms 2～4 straight chained alkyl terminal Wasserstoffatoms by the substituted group of hydroxyl (for example ,-(CH ₂) ₂-OH).Amide compound shown in the formula of of the present invention (VIII) can use separately, also can use their mixture.

The object lesson of said amide compound can be enumerated, oleoyl monoethanolamine, oleoyl diethylolamine, oleoyl list Propanolamine, oleoyl dipropanolamine etc.

Polar functionalities compound among the present invention also can be the reaction of said polar functionalities compound and molybdenum compound and the compound that obtains.This molybdenum compound can be enumerated for example molybdenum oxide, halogenation molybdenum, molybdic acid etc.In this reaction, molybdenum compound is according to respect to 1 mole of said polar functionalities compound, preferred 0.01～10 mole mol ratio, and more preferably 0.05～5 mole mol ratio is used.

In the said reaction, solvent can use for example organic solvents such as hydrocarbon-type oil, hexane, heptane, octane, toluene, YLENE.

The not special restriction of the temperature of reaction of said reaction, preferred 50～250 ℃, more preferably 100～200 ℃.

Polar functionalities compound among the present invention also can be the reaction of said polar functionalities compound and boron cpd and the compound that obtains.This boron cpd can be enumerated like boron oxide, halogenation boron, boric acid, boron trioxide, boric acid ester etc.In this reaction, boron cpd is according to respect to 1 mole of said polar functionalities compound, preferred 0.01～10 mole mol ratio, and more preferably 0.05～5 mole mol ratio is used.

In the present invention, above-mentioned polar functionalities compound can use a kind separately, also can mix use more than 2 kinds.In addition, the combined amount of polar functionalities compound is a benchmark with the total composition, is preferably 0.01～5.0 quality %, more preferably 0.1～2.0 quality %.Through making combined amount is to obtain the effect of friction minimizing fully more than the 0.01 quality %, if reach more than the 5.0 quality %, the generation dissolving is remaining sometimes.

In the lubricating oil composition of the present invention, can also in the scope that does not hinder its effect, mix known additive in the past.Additive can be enumerated, for example, inhibitor, ashless be that dispersion agent, metal are sanitising agent, viscosity index improver, pour point depressor, metal passivator, rust-preventive agent and skimmer etc.

As above-mentioned inhibitor, preferred phosphorated inhibitor not, for example can enumerate phenol is that inhibitor, amine are that inhibitor, the complexing of molybdenum amine are that inhibitor, sulphur are inhibitor etc.

As inhibitor phenol being arranged for example is that inhibitor and amine are inhibitor.As phenol is inhibitor, can enumerate, for example, 4; 4 '-methylene radical two (2,6 di t butyl phenol), 4,4 '-two (2,6 di t butyl phenols), 4; 4 '-two (2-methyl-6-tert butyl phenol), 2,2 '-methylene radical two (4-ethyl-6-tert.-butyl phenol), 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol), 4; 4 '-butylidene two (3 methy 6 tert butyl phenol), 4,4 '-isopropylidene two (2,6 di t butyl phenol), 2; 2 '-methylene radical two (4-methyl-6-nonylphenol), 2,2 '-isobutylene two (4, the 6-xylenol), 2; 2 '-methylene radical two (4-methyl-6-cyclohexylphenol), 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-4-ethylphenol, 2; 4-dimethyl--6-tert.-butyl phenol, 2,6-two tert-pentyl p-cresol, 2,6-di-t-butyl-4-(N; N '-dimethyl amine methylphenol), 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, n-octyl-3-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic ester, Octadecane base-3-(4-hydroxyl-3; The 5-di-tert-butyl-phenyl) propionic ester, 2,2 '-sulfo-[diethylammonium two-3-(3,5-di-t-butyl-4-phenylor) propionic ester] etc.

Wherein, it is desirable to the phenol system that bis-phenol is and contains ester group especially.

In addition, amine is that inhibitor for example has monoalkyl p-diaminodiphenyl systems such as single octyl group p-diaminodiphenyl, single nonyl p-diaminodiphenyl; 4,4 '-dibutyl p-diaminodiphenyl, 4,4 '-diamyl p-diaminodiphenyl, 4,4 '-dihexyl p-diaminodiphenyl, 4,4 '-diheptyl p-diaminodiphenyl, 4,4 '-dioctyl p-diaminodiphenyl, 4, dialkyl group p-diaminodiphenyl such as 4 '-dinonyl p-diaminodiphenyl system; Many alkyl biphenyls amine such as tetrabutyl p-diaminodiphenyl, four hexyl biphenyl amine, four octyl group p-diaminodiphenyl, four nonyl p-diaminodiphenyl system; And alpha-naphthylamine, PA; Also have alkyl-substituted phenyl-alpha-naphthylamines such as butyl phenyl-alpha-naphthylamine, amyl group PA, hexyl PA, heptyl PA, octyl phenyl-alpha-naphthylamine, nonyl PA etc.

Wherein, it is desirable to dialkyl group p-diaminodiphenyl system and naphthylamines based compound.

Complexing is an inhibitor as molybdenum amine; Can use 6 valency molybdenum compounds, particularly, like the resultant of reaction of molybdic oxide and/or molybdic acid and amine compound; For example, open the compound of the working method gained that the 2003-252887 communique put down in writing according to Japanese Patent Laid.

Amine compound as with said 6 valency molybdenum compounds reaction does not have special restriction, can enumerate monoamine, diamines, polyamines and aliphatics hydramine particularly.More specifically can enumerate the alkylamine that methylamine, ethamine, dimethyl amine, DIETHANOL AMINE, methylethyl amine, methyl-propyl amine etc. have the alkyl (these alkyl can be straight chain shape or branched) of carbonatoms 1～30; Vinyl-amine, allylamine, butenylamine, octene amine and oleyl amine etc. have the alkenyl amine of the thiazolinyl (these thiazolinyls can be straight chain shape or branched) of carbonatoms 2～30; Carbinolamine, thanomin, methanol amine and methyl alcohol Propanolamine etc. have the aliphatics hydramine of the fatty alcohol radical (these fatty alcohol radicals can be straight chain shape or branched) of carbonatoms 1～30; Methanediamine, quadrol, tn and tetramethylenediamine etc. have the Alkylenediamine of the alkylidene group of carbonatoms 1～30; Polyamines such as NSC 446, Triethylenetetramine (TETA), tetren, penten; The heterogeneous ring compound such as compound or tetrahydroglyoxaline that has the alkyl or alkenyl of carbonatoms 8～20 in above-mentioned monoamine, diamines, the polyamines such as undecyl DIETHANOL AMINE, undecyl diethylolamine, dodecyl dipropanolamine, oleyl diethylolamine, oleyl tn, octadecyl tetren; The alkylene oxide adduct of these compounds; And their mixture etc.

In addition, can enumerate, fair 3-22438 communique of Japanese Patent Laid and Japanese Patent Laid are opened the sulfur-bearing molybdenum complex of the described succinimide of 2004-2866 communique etc.

Said sulphur is that inhibitor can be enumerated, for example Vermitin, tetramethylolmethane four (3-dodecyl thiopropionate), two dodecyl thioether, two octadecyl thioether, two dodecyl thiodipropionate, two octadecyl thiodipropionate, two tetradecyl thiodipropionate, dodecyl octadecyl thiodipropionate, 2-mercaptobenzimidazole etc.

Among such inhibitor, from reducing the viewpoint of metal ingredient or sulphur content, preferred phenol is that inhibitor and amine are inhibitor.In addition, above-mentioned inhibitor can use a kind of separately, also can mix two or more uses.Wherein, consider from the viewpoint of oxidative stability effect, preferred a kind of or more than two kinds phenol be inhibitor and a kind of or more than two kinds amine be the mixture of inhibitor.

The combined amount of inhibitor is that benchmark is usually preferably in 0.1～5 quality % scope, more preferably in 0.1～3 quality % scope with the total composition.

In addition, above-mentioned ashless dispersant can use employed any ashless dispersant in the lubricating oil, for example can enumerate the monotype succinimide compound shown in the formula (IX), or the dimorphism succinimide compound shown in the formula (X).

[changing 17]

Among above-mentioned general formula (IX), (X), R ¹⁹, R ²¹And R ²⁴Be respectively the thiazolinyl or the alkyl of number-average molecular weight 500～4000, R ²¹And R ²⁴Can be the same or different.R ¹⁹, R ²¹And R ²⁴Number-average molecular weight be preferably 1000～4000.

Above-mentioned R ¹⁹, R ²¹And R ²⁴If number-average molecular weight more than 500, if the favorable solubility in base oil then below 4000, is not then worried dispersed decline.

In addition, R ²⁰, R ²²And R ²³Be respectively the alkylidene group of carbonatoms 2～5, R ²²And R ²³Can be the same or different, r representes 1～10 integer, and s representes 0 or 1～10 integer.In addition, above-mentioned r is preferred 2～5, and more preferably 3～4.R is 1 when above, good dispersibility, and r is 10 when following, and the solvability in base oil is also good.

Further, in general formula (X), s is preferred 1～4, and more preferably 2～3.Based on deliquescent viewpoint dispersed and in base oil, s is comparatively desirable in 1～4 scope the time.

As above-mentioned thiazolinyl, can enumerate polybutylene-based, polyisobutenyl, ethylene-propylene copolymer, alkyl is their hydrogenation products.Suitable thiazolinyl typical example has polybutylene-based or polyisobutenyl for example.This is polybutylene-based to be to obtain through mixture or the highly purified isobutene polymerisation that makes 1-butylene and iso-butylene.

In addition, the typical example of suitable alkyl has, the hydrogenation products of polybutylene-based or polyisobutenyl.

Above-mentioned alkenyl succinimide compound or alkyl succinimide compound usually can be through making with the alkenyl succinic anhydride of polyolefine and maleic anhydride reaction generation or with alkyl succinic anhydride and polyamines reaction that its hydrogenation obtains.In addition, above-mentioned monotype succinimide compound and dimorphism succinimide compound can make through the reactive ratio that changes above-mentioned alkenyl succinic anhydride or alkyl succinic anhydride and polyamines.

As the olefinic monomer that forms said polyolefins, can use terminal olefin a kind of of carbonatoms 2～8 or mix more than two kinds, but the suitable mixture that uses iso-butylene and 1-butylene.

In addition; Above-mentioned polyamines can be enumerated single diamines such as quadrol, tn, tetramethylenediamine and pentamethylene diamine; Polyalkylene polyamines such as NSC 446, Triethylenetetramine (TETA), tetren, penten, two (methyl ethylidene) triamine, two butylidene triamines, three butylidene tetramines and five pentylidene hexamines, bridged piperazine derivatives such as aminoethylpiperazine etc.

In addition, ashless dispersant is except above-mentioned thiazolinyl or alkyl succinimide compound, can also use its boron derivative and/or through organic acid it carried out the compound after the modification.

The boron derivative of thiazolinyl or alkyl succinimide compound can use the product by the ordinary method preparation.For example; After making the reaction of said polyolefins and maleic anhydride generate alkenyl succinic anhydride, will make itself and above-mentioned polyamines and boron cpds such as boron oxide, halogenation boron, boric acid, boron trioxide, boric acid ester, boric acid ammonium salt react the midbody generation imidization reaction of acquisition again and obtain.

The not special restriction of boron content in this boron derivative, in boron, the scope of preferred 0.05～5 quality %, the more preferably scope of 0.1～3 quality %.

In addition, the combined amount of above-mentioned ashless dispersant is a benchmark with the lubricating oil composition total amount, the scope of preferred 0.5～15 quality %, the more preferably scope of 1～10 quality %, the further scope of preferred 3～7 quality %.

When combined amount less than 0.5 quality %, little for the effect of the base number maintenance under the high temperature, on the other hand, when combined amount was crossed 15 quality %, the low-temperature fluidity of lubricating oil composition can worsen significantly, and was all undesirable.

As above-mentioned metal is sanitising agent; Can use that employed any alkaline-earth metal is a sanitising agent in the lubricating oil, for example can enumerate alkaline-earth metal sulphonate, alkaline-earth metal phenates, alkaline-earth metal salicylate and be selected from mixture more than 2 kinds wherein etc.

As above-mentioned alkaline-earth metal sulphonate; Can enumerate, molecular weight is preferred 300～1500, the more preferably alkali earth metal salt of the alkyl aryl sulfonate of 400～700 alkyl aromatic compound sulfonation gained; Particularly magnesium salts and/or calcium salt etc., central preferred use calcium salt.

Said alkaline-earth metal phenates can be enumerated, the alkali earth metal salt, particularly magnesium salts and/or calcium salt etc. of the Mannich reaction thing of alkylphenol, alkylphenol thioether, alkylphenol, central special preferred calcium salt.

Said alkaline-earth metal salicylate can be enumerated, the alkali earth metal salt of alkyl salicylate, particularly magnesium salts and/or calcium salt etc., central preferred use calcium salt.

As constituting above-mentioned alkaline-earth metal is the alkyl of purificant, and preferred carbonatoms is 4～30 alkyl, more preferably 6～18 straight chain or branched-chain alkyl, and it is that straight chain, side chain all can.

In addition, they can be primary alkyl, secondary alkyl or tertiary alkyl.

In addition; As alkaline-earth metal sulphonate, alkaline-earth metal phenates and alkaline-earth metal salicylate; Except the Mannich reaction thing that makes abovementioned alkyl aromatic sulphonic acid, alkylphenol, alkylphenol thioether, alkylphenol, alkyl salicylate etc.; Directly and alkaline-earth metal alkali such as the oxide compound of the alkaline-earth metal of magnesium and/or calcium or oxyhydroxide react; Perhaps make it to generate an alkali metal salts such as sodium salt or sylvite earlier; Replace the neutral alkaline-earth metal sulphonate obtained, neutral alkaline-earth metal phenates with alkali earth metal salt again and beyond the neutral alkaline-earth metal salicylate; Also comprise; Alkali base great soil group metal sulfonate, alkali base great soil group metal phenates and alkali base great soil group metal salicylate salt that neutral alkaline-earth metal sulphonate, neutral alkaline-earth metal phenates and neutral alkaline-earth metal salicylate obtain through heating in the presence of water with excessive alkali earth metal salt or alkaline-earth metal alkali; And in the presence of carbonic anhydride, parlkaline alkaline-earth metal sulphonate, parlkaline alkaline-earth metal phenates and parlkaline alkaline-earth metal salicylate that neutral alkaline-earth metal sulphonate, neutral alkaline-earth metal phenates and neutral alkaline-earth metal salicylate are obtained with the carbonate of alkaline-earth metal or borate reaction.

As employed metal among the present invention is purificant, is purpose with the sulphur content that reduces in the compsn, preferred bases great soil group metal salicylate salt or alkaline-earth metal phenates, wherein preferred parlkaline salicylate or parlkaline phenates, especially preferred parlkaline SAP 002.

Employed metal is the scope of the preferred 10～500mgKOH/g of total basicnumber of purificant among the present invention, and the more preferably scope of 15～450mgKOH/g can therefrom be selected a kind of or more than two kinds and use.

In addition, said here total basicnumber is meant the total basicnumber of measuring (base number perchloric acid method) based on the potentiometric titration of measuring according to 7. of JIS K 2501 " petroleum product and lubricating oil-neutralization value TP ".

In addition; As the metal that uses among the present invention is sanitising agent, and its metal ratio does not have special restriction, can use a kind of below 20 usually or it is mixed use more than two kinds; But in order to obtain more excellent oxidative stability, base number maintenance and high-temperature cleaning property etc.; The preferred metal ratio that uses is below 3, and more preferably below 1.5, the preferred especially metal below 1.2 is a sanitising agent.

In addition; Said here metal is (valency of metallic element) * (metal element content (mole %))/(soap base content (the mole %)) in the sanitising agent than being expressed as metal; So-called metallic element is meant calcium, magnesium etc., and so-called soap base is meant sulfonic group, phenolic group and salicyl etc.

Said metal is that the combined amount of sanitising agent is a benchmark with the lubricating oil composition total amount, the scope of preferred 0.01～20 quality %, the more preferably scope of 0.1～10 quality %, the further scope of preferred 0.5～5 quality %.

When combined amount less than 0.01 quality %, be difficult to obtain performances such as high-temperature cleaning property, oxidative stability, base number maintenance, so not preferred.On the other hand, if when 20 quality % are following, can obtain the effect that matches with its addition usually, but this metal is the upper limit of sanitising agent combined amount, is not limited to above-mentioned scope, importantly reduces combined amount as much as possible.In view of the above, reduce the metal ingredient of lubricating oil composition, i.e. sulphated ash can prevent the deterioration of automobile emission gas refining plant.

In addition, metal is that sanitising agent needs only in afore mentioned rules content, can separately or make up more than two kinds and use.

Particularly, above-mentioned metal is among the sanitising agent, preferred especially parlkaline SAP 002 or parlkaline calcium phenylate, above-mentioned ashless be among the dispersion agent, preferred especially above-mentioned polybutylene-based succsinic acid imide.In addition, the scope of the preferred 100～500mgKOH/g of total basicnumber of above-mentioned parlkaline SAP 002 and parlkaline calcium phenylate, the more preferably scope of 200～500mgKOH/g.

As said viscosity index improver; Can enumerate as: Rohm tech inc, decentralized Rohm tech inc, olefin copolymer are (for example; Ethylene-propylene copolymer etc.), decentralized olefin copolymer, styrene based copolymer (for example, vinylbenzene-diene copolymers, styrene-isoprene multipolymer etc.) etc.

The combined amount of viscosity index improver is benchmark from the mixed effect this point with the lubricating oil composition total amount, the scope of preferred 0.5～15 quality %, the more preferably scope of 1～10 quality %.

As said pour point depressor, for example can enumerate: the Rohm tech inc of weight-average molecular weight about 5000～50000 etc.

The combined amount of pour point depressor is benchmark from the mixed effect this point with the lubricating oil composition total amount, the scope of preferred 0.1～2 quality %, the more preferably scope of 0.1～1 quality %.

Said metal passivator can be enumerated, for example benzotriazole system, tolyl-triazole system, thiadiazoles system and imidazole compound etc.

The combined amount of metal passivator is a benchmark with the lubricating oil composition total amount, the scope of preferred 0.01～3 quality %, the more preferably scope of 0.01～1 quality %.

Said rust-preventive agent can be enumerated, for example sulfonated petro-leum, sulfonated alkylbenzene, dinonylnaphthalene sulfonic acid salt, alkenyl succinic acid ester, polyol ester etc.

The combined amount of these rust-preventive agent is benchmark from the mixed effect this point with the lubricating oil composition total amount, the scope of preferred 0.01～1 quality %, the more preferably scope of 0.05～0.5 quality %.

Above-mentioned skimmer can be enumerated; For example silicone oil, fluorosilicon oil and fluoroalkyl ether etc., its combined amount is benchmark from the viewpoints such as balance of defoaming effect and economy with the lubricating oil composition total amount; The scope of preferred 0.005～0.5 quality, the more preferably scope of 0.01～0.2 quality %.

In the lubricating oil composition of the present invention, as required, further all right mixed friction improving agent, anti-wear agent, extreme-pressure additive.In addition this friction improver be meant except that of the present invention must composition-compound the polar functionalities compound.The combined amount of friction improver is a benchmark with the lubricating oil composition total amount, the scope of preferred 0.01～2 quality %, the more preferably scope of 0.01～1 quality %.

Said anti-wear agent or extreme-pressure additive can be enumerated: zinc dithiophosphate, zn phosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate, disulfide class (refer to except that general formula used in the present invention (I) or the material the sulfocompound (II), can enumerate for example benzyldithio toluene.), sulfocompounds such as olefine sulfide class, vulcanized oil lipid, sulfuration ester class, thiocarbonic ester class, thiocarbamates, polysulfide ether; Phosphorous acid esters, phosphoric acid ester, phosphonic acid ester and P contained compounds such as amine salt or metal-salt thereof; Anti-wear agent of sulfur-bearings such as thiophosphite class, group thiophosphate, Thiophosphonate class and amine salt or metal-salt and phosphorus etc.

Under the situation that is mixed with anti-wear agent or extreme-pressure additive, the content that its combined amount must be careful the phosphorus branch, sulphur content and the metal ingredient that do not make in the lubricating oil becomes excessive because of mixing anti-wear agent or extreme-pressure additive.

Lubricating oil composition of the present invention is by constituting above the composition, and what time following its proterties preferably satisfy.

(1) sulphated ash (JIS K 2272) is below 0.6 quality %, more preferably below 0.1 quality %.And,

(2) phosphorus content (JIS-5S-38-92) is below 0.5 quality %, more preferably below 0 quality %.

Except above some, below further more preferably it satisfies some.

(3) sulphur content (JIS K 2541) is below 0.4 quality %, more preferably below 0.2 quality %.

(4) boron content is below 0.4 quality %, more preferably below 0.2 quality %.

The lubricating oil composition of the present invention that satisfies these proterties can suppress oxide catalyst, three-way catalyst, the NO of motor car engine _XThe deterioration of sorption-type reducing catalyst, diesel particulate filter (DPF) etc.

Above-mentioned sulfocompound and polar functionalities compound are used in lubricating oil composition of the present invention collocation, and the result of itself and usefulness is to embody the wear resistance and friction minimizing effect that surpasses when using separately respectively far away.Therefore,, also can obtain enough lubricating oil compositions of excellence of lubricity, reach the proterties of above-mentioned sulphated ash etc. more easily even do not mix the zinc dithiophosphate of making oil dope in the past commonly used.Further, as mentioned below, when lubricating oil composition of the present invention promptly is used in the slide unit that applied the DLC processing, can show that also excellent friction reduces effect.

Lubricating oil composition of the present invention is suitable for lubricating oil for IC engines such as petrol engine, diesel motor, gas engine such as using as cart, brougham, generating with, boats and ships; Owing to be low-phosphorous branch, low sulphur content, low sulfuric acid ash content, be particularly suitable for being mounted with the oil engine usefulness of exhaust gas purifier.

Lubricating oil composition of the present invention in addition also is suitable for the purposes beyond above-mentioned.Especially; Because embodying excellent abrasive, lubricating oil composition reduces effect with friction; For example can be used for oil engine, automatic transmission, buncher, manual transmission, power steering stgear, snubber, compressor, coolant compressor, refrigerator, hydraulic oil pump and clutch pulley etc. lubricated.That is, lubricating oil composition of the present invention can be used as I. C. engine oil, automatic transmission fluid, buncher oil, manual transmission is oily, power steering stgear is oily, snubber is oily, compressor oil, refrigerator oil, hydraulic oil pump oil, clutch pulley be with lubricating oil and railway grease etc.

Lubricating oil composition of the present invention is under the situation of metal such as steel at slipping plane not only, and has at least a portion of slipping plane and all can embody friction under the situation of DLC film and reduce effect and excellent abrasive.

The viewpoint consideration that this DLC film reduces effect from improving friction is preferably the material of hydrogen richness below 40 atom %, and more preferably the material below 30 atom % is preferably the material below 20 atom % especially.

Having the not special restriction of the other side's member of the sliding component of DLC film for slipping plane, for example, can be the sliding component that has the DLC film equally, also can be iron or organic materialss such as iron alloy member, aluminium alloy element or resin or elastomeric material.

Embodiment

The present invention will be described in more detail then to pass through embodiment and comparative example, but the present invention is not limited to these embodiment.

< measuring method of proterties, performance >

Following embodiment, the proterties and the performance of the lubricating oil composition in the comparative example can be tried to achieve through following method.

(1) kinematic viscosity

Measure according to JIS K 2283.

(2) phosphorus content

Measure according to JPI-5S-38-92.

(3) sulphur content

Measure according to JIS K2541.

(4) boron content

Measure according to JPI-5S-38-92.

(5) sulphated ash

Measure according to JIS K 2272.

(6) reciprocating type kinetic friction test

On reciprocating type kinetic friction trier, use following test board and test ball, under following condition, make an experiment, obtain frictional coefficient.

Test board: SUJ-2 making sheet

Test ball: through DLC (hydrogen richness: 1/2 inch ball of SUJ-2 system of 20%) handling

(test conditions)

Test temperature: 100 ℃

Load: 200g

Amplitude: 10mm

Sliding velocity: 1.0mm/sec

(7) friction-wear test

On reciprocating type kinetic friction trier, use following test board and test ball, under following condition, make an experiment, obtain the polishing scratch width of test board.

Test board: SUJ-2 making sheet

Test ball: SUJ-2 system ball (diameter 10mm)

(test conditions)

Test temperature: 100 ℃

Load: 200N

Amplitude: 10mm

Vibration number: 10Hz

Test period: 30 minutes

Embodiment 1～7, comparative example 1～9

According to base oil and the additive shown in the 1st table of mixed shown in the 1st table, preparation lubricating oil composition.The proterties of said composition, composition and performance are seen the 1st table.

[table 1]

The 1st table

[table 2]

The 2nd table

[notes]

Base oil: hydrofinishing base oil, 40 ℃ of kinematic viscosity 21mm ²/ s, 100 ℃ of kinematic viscosity 4.5mm ²/ s, viscosity index 127, %CA0.0, sulphur content less than 20 quality ppm, NOACK steam output 13.3 quality %

Sulfocompound A:1, two (carbonyl octyloxy methyl) disulfides of 1-

Sulfocompound B: the own ester of dithio oxysuccinic acid four-1-

Polar functionalities compd A: glyceryl monooleate

Polar functionalities compd B: oleoyl diethylolamine

Polar functionalities Compound C: glycerine list oleyl alcohol ether

Polar functionalities Compound D: N, N-two polyoxies ethene-N-oleyl alcohol amine

Polar functionalities compd E: the reactant of glyceryl monooleate and boric acid

Polar functionalities compound F 17-hydroxy-corticosterone: the reactant of oleoyl diethylolamine and boric acid

Viscosity index improver: Rohm tech inc, weight-average molecular weight 420000, amount of resin 39 quality %

Pour point depressor: gather alkylmethacrylate, weight-average molecular weight is 6000

Polybutylene-based succinimide: polybutylene-based number-average molecular weight 1000, nitrogen content 1.76 quality %, boron content are 1.9 quality %

Phenol is inhibitor: octadecyl-3-(3,5-di-t-butyl-4-phenylor) propionic ester

Amine is inhibitor: dialkyl group p-diaminodiphenyl, nitrogen content 4.62 quality %

Zinc dialkyl dithiophosphate: Zn content 9.0 quality %, phosphorus content 8.2 quality %, sulphur content 17.1 quality %, alkyl (mixture of sec.-butyl and Sec-Hexyl)

Other: skimmer, metal passivator

Shown in the 1st table, the 2nd table, the lubricating oil composition of embodiment 1～7 based on and with the synergy of sulfocompound and polar functionalities compound, demonstrate low-friction coefficient and low polishing scratch directly is worth.

Promptly; Although not having the frictional coefficient of the comparative example 1 of polar functionalities compound is 0.140; The frictional coefficient that does not have the comparative example 2～7 of sulfocompound is 0.124～0.128, but through with they combinations, can frictional coefficient be reduced to 0.110～0.117 (embodiment 1～7).In addition; Although not having the polishing scratch of the comparative example 1 of polar functionalities compound directly to be worth is 0.52; Not having the polishing scratch of the comparative example 2～7 of sulfocompound directly to be worth is 0.60～0.65, but through with they combinations, can polishing scratch directly be worth to be reduced to 0.42～0.46 (embodiment 1～7).

In addition, can know with the contrast of comparative example 8 from embodiment 1～7, the application's invention and with the effect that additive embodied, the effect when having surpassed independent mixing zinc dialkyl dithiophosphate.In addition, shown in comparative example 9, use zinc dialkyl dithiophosphate to replace the application to invent employed sulfocompound and polar functionalities compound and usefulness, can not obtain the low-friction coefficient shown in the embodiment 1～7 and low polishing scratch directly is worth.

As stated; Through and with specific sulfocompound and specific polar functionalities compound; Can have the wear resistance of bringing above zinc dialkyl dithiophosphate; Consequently, even can obtain low-phosphorous branch, low sulphur content, low sulfuric acid ash content, also have superior abrasion resistance, embody the lubricating oil composition that excellent friction reduces effect.

Utilizability on the industry

Even can provide low-phosphorous branch, low sulphur content, low sulfuric acid ash content also to have superior abrasion resistance according to the present invention, and also can embody the lubricating oil composition that excellent friction reduces effect when promptly being used in the slide unit of handling through DLC.Therefore, lubricating oil composition of the present invention especially can be used as lubricant composition for internal combustion engine such as petrol engine, diesel engine, gas engine aptly.

Claims

1. lubricating oil composition; It is characterized in that; In base oil, mix (A) and be selected from formula (I) and the sulfocompound of (II) representing at least a kind; The polar functionalities compound that (B) has an alkyl of at least a kind of polar group being selected from amino, carboxamido-group and hydroxyl and carbonatoms 3～24 forms

[changing 1]

R ¹-Y-(CH ₂) _n-S _x-(CH ₂) _n-Y-R ² (1)

R ¹～R ¹²Represent Wasserstoffatoms respectively independently; Be selected from the alkyl of alkyl, naphthenic base, thiazolinyl, cycloalkenyl group and aryl; Or comprise the heteroatom group that contains that the atom that is selected from Sauerstoffatom, nitrogen-atoms and sulphur atom forms in these alkyl, Y respectively independently expression be selected from-O-,-S-,-SO-,-SO ₂-,-(C=O) O-,-(C=O) NH-,-O (C=O) NH-,-C (=O)-,-N (H)-,-NHCONH-,-N=N-,-NH-C (=NH)-NH-,-S-C (=O)-,-NH-C (=S)-with-NH-C (=S)-divalent group of NH-; X is 1～3 integer, and n is respectively 1～5 integer independently.

2. according to the lubricating oil composition of putting down in writing in the claim 1; It is characterized in that the polar functionalities compound that above-mentioned (B) has an alkyl of at least a kind of polar group being selected from amino, carboxamido-group and hydroxyl and carbonatoms 3～24 is at least a kind of compound that is selected from the group that glycerine partial fatty acid ester, glycerol monoethers compound, amine compound and amide compound form.

3. according to the lubricating oil composition of putting down in writing in the claim 1; It is characterized in that; The polar functionalities compound that above-mentioned (B) has an alkyl of at least a kind of polar group being selected from amino, carboxamido-group and hydroxyl and carbonatoms 3～24 is the formula (III) or (IV) monoglyceride of expression; Formula (V) or (VI) expression the glycerol monoethers compound

[changing 2]

R ¹³And R ¹⁴The alkyl of representing carbonatoms 3～24 respectively independently.

4. according to the lubricating oil composition of putting down in writing in the claim 1; It is characterized in that; The polar functionalities compound that above-mentioned (B) has the alkyl of at least a kind of polar group being selected from amino, carboxamido-group and hydroxyl and carbonatoms 3～24 is the amine compound of formula (VII) expression or the amide compound of formula (VIII) expression

[changing 3]

R ¹⁵And R ¹⁷The alkyl of representing carbonatoms 3～24 respectively independently, R ¹⁶And R ¹⁸The terminal Wasserstoffatoms of representing the straight chained alkyl of Wasserstoffatoms or carbonatoms 2～4 is respectively independently replaced the group that forms by hydroxyl.

5. according to the lubricating oil composition of any record of claim 1～4, it is characterized in that, is benchmark with the lubricating oil composition total amount, and phosphorus content is below 0.5 quality %, and sulphated ash is below 0.6 quality %.

6. according to the lubricating oil composition of any record of claim 1～5, it is characterized in that, is benchmark with the lubricating oil composition total amount, and phosphorus content is 0 quality %, and sulphated ash is below 0.1 quality %.

7. according to the lubricating oil composition of any record of claim 1～6, it is characterized in that said lubricating oil composition is to implement the slide unit that quasi-diamond DLC handles to use lubricating oil composition.