CN101568626A

CN101568626A - Lubricating oil composition

Info

Publication number: CN101568626A
Application number: CNA2008800013339A
Authority: CN
Inventors: 永仮光洋; 金子弘; 马场善治
Original assignee: Showa Shell Sekiyu KK
Current assignee: Showa Shell Sekiyu KK; Shell Internationale Research Maatschappij BV
Priority date: 2007-02-07
Filing date: 2008-02-06
Publication date: 2009-10-28
Also published as: JP2008214618A; EP2109657A1; US20100105590A1; WO2008095966A1; JP5426829B2

Abstract

The present invention provides a lubricating oil composition comprising a base oil, an aspartic acid derivative and an aliphatic amine compound. The lubricating oil composition is ideal as an industrial lubricating oil such as for example for a hydraulic working oil in hydraulic equipment. Primary amine, secondary amine, diamine, and/or tertiary amines may be employed for the aliphatic amine compound.

Description

Lubricating oil composition

Technical field

The present invention relates to lubricating oil composition, in particular as the lubricating oil composition of industrial lubricant, in particular as for example lubricating oil composition of machinery oil, hydraulic efficiency oil, turbine oil, compressor oil, gear oil, slipping plane oil, bearing oil or demarcation oil.

Background technology

Be used for the necessary rust-preventing characteristic of the lubricating oil needs of mechanical means to keep its performance.Its reason comprises following aspect: the temperature according to the lubricating oil in the fuel tank in working conditions rising and the reduction mechanical means, may cause the lubricating oil in water of condensation and the fuel tank to mix thus; And the mixing of leaking contingent moisture because of water from water-cooled tube.In order to obtain this rust-preventing characteristic, adopt aspartate etc.Referring to Japanese kokai publication hei 6-200268 communique.

And in recent years, the industrial lubrication oil compositions need have excellent nature of friction.This be because, by low-friction coefficient (μ) is provided, that is, have low frictional properties matter by making lubricating oil, can effectively reduce the frictionloss in the mechanism, thereby realize high energy saving.In addition, although hydraulic efficiency installation generally is used in building machinery etc., if but the frictional coefficient of lubricating oil that is used for hydraulic efficiency oil is higher, little stick-slip effect then takes place in the sliding area of the to-and-fro movement module of hydro-cylinder, thereby cause such as phenomenons such as hydro-cylinder vibration, vibration, sharp sound or generation abnormal sounds, make and accurately to control hydraulic efficiency installation.Accurately and reposefully move in order to ensure hydro-cylinder, therefore need to reduce the friction of lubricating oil.

Summary of the invention

The problem that the invention is intended to solve is to obtain a kind of industrial lubricant, and it has excellent rust inhibiting property and low friction, realizes high energy saving thus.The lubricating oil composition that addresses this problem is during as the hydraulic efficiency oil in the hydraulic efficiency installation, can accurately control hydraulic efficiency installation and do not exist such as hydro-cylinder vibration, vibration, sharp sound or produce phenomenon such as abnormal sound.The present invention seeks to obtain a kind of lubricating oil composition, suppress thus to get rusty, and this lubricating oil composition has excellent energy-conservation character and operational efficiency.

According to the present invention, can obtain by being added in highly refined base oil and/or the synthetic base oil as the lubricating oil composition of hydraulic pressure wet goods industrial lubricant for example ideally as the aspartic acid derivate of additive and fatty amine compound.

Primary amine, secondary amine, diamines or tertiary amine etc. can be used as above mentioned fatty amine compound.

Adopt the present invention, can be suppressed the lubricating oil composition that gets rusty and have the excellence of low-friction coefficient thus.By reducing frictional coefficient, can effectively reduce the frictionloss that produces in various types of industrial equipmentss, thereby can realize energy-conservation.And when as hydraulic efficiency oil,, therefore can eliminate such as phenomenons such as hydro-cylinder vibration, vibration, sharp sound or generation abnormal sounds, and can accurately control hydraulic efficiency installation owing to reduced frictional coefficient.

Embodiment

Base oil as lubricating oil composition of the present invention, can use mineral oil (being called as highly refined base oil) or synthetic oil, particularly, can be separately or use the base oil that belongs to group I, group II, group III or group IV etc. in the classification of API (API) base oil with mixture.The content of the elementary sulfur of the base oil that herein uses can be preferably below the 500ppm as below the 700ppm.Its density can be 0.8～0.9.Aromatic fraction can be preferably less than 3% for less than 5%.

Group I base oil comprises, for example, uses the paraffinic mineral oil that the suitable combination as process for refining such as solvent treatment, hydrofining and dewaxings obtains by the lubricating oil distillate that the air distillation by crude oil is obtained.Viscosity index can be 80～120, is preferably 95～110 (ASTMD2270).Kinetic viscosity in the time of 40 ℃ is preferably 2mm ²/ s～680mm ²/ s, and then 8mm more preferably ²/ s～220mm ²/ s (ASTM D445).In addition, total sulfur content can be less than 700ppm, preferably less than 500ppm.Total nitrogen content can be less than 50ppm, preferably less than 25ppm.In addition, aniline point can be 80 ℃～150 ℃, is preferably 90 ℃～122 ℃.

Group II base oil comprises, for example, uses the paraffinic mineral oil that the suitable combination as process for refining such as hydrocracking and dewaxings obtains by the lubricating oil distillate that the air distillation by crude oil is obtained.By as Gulfinishing (Gulf Oil ' s hydrofining) method and purified group II base oil has less than the total sulfur content of 10ppm with less than 5% aromaticity content, therefore be suitable for the present invention.These basic oil viscosities are not subjected to particular restriction, and viscosity index can be 80～120, is preferably 100～120.Kinetic viscosity in the time of 40 ℃ is preferably 2mm ²/ s～680mm ²/ s, and then 8mm more preferably ²/ s～220mm ²/ s.In addition, total sulfur content can preferably less than 200ppm, and then be more preferably less than 10ppm less than 300ppm.Total nitrogen content can be less than 10ppm, preferably less than 1ppm.In addition, aniline point can be 80 ℃～150 ℃, is preferably 100 ℃～135 ℃.

As group III base oil and group II base oil, for example can suitably use and carry out the paraffinic mineral oil that height hydrofining is made by the lubricating oil distillate that the air distillation by crude oil is obtained, perhaps carry out the purified dewaxing base oil that operation was produced by relating to isomerization dewaxing (ISODEWAX) technology, wherein dewaxing is undertaken by wax being converted to isoparaffin, perhaps passes through Mobil wax isomerization process and the purified base oil.Comprise that also the judgement according to the NAD (National Advertising Division) that is responsible for U.S.'s advertisement explanation can be expressed as the product of " synthetic oil ".

These basic oil viscosities are not subjected to particular restriction, but viscosity index can be 95～145, preferred 100～140.Kinetic viscosity in the time of 40 ℃ is preferably 2mm ²/ s～680mm ²/ s, and then 8mm more preferably ²/ s～220mm ²/ s.Total sulfur content can be 0ppm～100ppm, preferably less than 10ppm.Total nitrogen content can be less than 10ppm, preferably less than 1ppm.In addition, aniline point can be 80 ℃～150 ℃, is preferably 100 ℃～135 ℃.

Can be used as base oil of the present invention ideally by the fischer-tropsch technologies synthetic GTL (Sweet natural gas system liquid) that Natural Gas Conversion is become liquid, this is to have extremely low sulphur content and aromaticity content because compare it with the mineral base oil that goes out from crude oil refining, and has high paraffinic hydrocarbons component ratio, also have excellent oxidative stability, and demonstrate minimum vaporization losses because of it.Although the viscosity of GTL base oil is not subjected to particular restriction, usually viscosity index is 130～180, more preferably 140～175.Kinetic viscosity in the time of 40 ℃ is preferably 2mm ²/ s～680mm ²/ s, and then 5mm more preferably ²/ s～120mm ²/ s.In addition, common total sulfur content is less than 10ppm, and total nitrogen content is less than 1ppm.An example of described GTL base oil product is SHELL XHVI (registered trademark).

The example of the synthetic oil that can be mentioned comprises: polyolefine, alkylbenzene, alkylnaphthalene, ester, polyoxyalkylene glycol, polyphenylene ether, dialkyl diphenyl ether, fluorochemicals (for example perfluoro polyether or fluoro polyolefine) or silicone oil.

Said polyolefins comprises the polymkeric substance and the hydride thereof of various alkene.Although can select alkene arbitrarily, the specific examples that can provide comprises that ethene, propylene, butylene or carbon number are the alpha-olefin more than 5.In polyolefinic manufacturing, can use a kind of in the above-mentioned alkene separately, also can be used in combination two or more.Particularly, the polyolefine that is called as poly-alpha olefins (PAO) is an ideal: the base oil of these formation groups IV.

Although the viscosity of these synthetic base oils is not subjected to particular restriction, the kinetic viscosity in the time of its 40 ℃ is preferably 2mm ²/ s～680mm ²/ s, and then 8mm more preferably ²/ s～220mm ²/ s.

Although the content of above-mentioned base oil in lubricating oil composition of the present invention is not subjected to particular restriction, but with respect to the total amount of lubricating oil composition, described content can be 60 weight %, is preferably at least 80 weight %, at least 90 weight % more preferably, and then at least 95 weight % more preferably.

Aspartic acid derivate is represented by following general formula (1):

In above-mentioned general formula 1, X ₁And X ₂Respectively do for oneself hydrogen or carbon number is 3～6 alkyl, thiazolinyl or hydroxyalkyl, X ₁And X ₂Can be identical or different, and be preferably the 2-methyl-propyl or the tertiary butyl separately.X ₃Can be that carbon number is 1～30 alkyl or alkenyl, the alkyl with ehter bond or hydroxyalkyl.For example, can be octadecyl, alkoxyl group propyl group, 3-(-oxyl of C6～C18) (alkyl of C3～C6), or cyclohexyl oxygen propyl group, 3-octyl group oxygen propyl group, 3-iso-octyl oxygen propyl group, 3-decyl oxygen propyl group, 3-isodecyl oxygen propyl group or 3-(the alkoxyl group propyl group of C12～C16) more preferably.X ₄Can be that carbon number is 1～30 saturated or unsaturated carboxylic acid base, or carbon number be 1～30 alkyl, thiazolinyl or hydroxyalkyl.The example is propionyloxy or propionyl acidic group (propionylic acid group).

The acid number of determining with JIS K2501 of above-mentioned aspartic acid derivate can be 10mgKOH/g～200mgKOH/g, is preferably 50mgKOH/g～150mgKOH/g.The consumption of the aspartic acid derivate in the lubricating oil composition can be about 0.01 weight %～5 weight %, is preferably about 0.05 weight %～2 weight %.Can use a kind of aspartic acid derivate, perhaps use the mixture of many kinds of derivatives.

This lubricating oil composition can with the fatty amine compound.The described fatty amine examples for compounds that can be mentioned comprises by the primary amine of general formula (2) expression, by the secondary amine of general formula (3) expression, by the diamines of general formula (4) expression and the tertiary amine of being represented by general formula (5).

H ₂N-X ₅ (2)

In this general formula 2, X ₅Be that carbon number is 1～30 alkyl or alkenyl.The example that can be mentioned comprises: lauryl amine, coconut amine, n-tridecane base amine, tetradecylamine, Pentadecane base amine, positive palmityl amine, n-heptadecane base amine, positive stearic amine, iso stearyl amine, NSC 77136 base amine, NSC 62789 base amine, heneicosane base amine, n-docosane base amine, n-tricosane base amine, pentacosane base amine, oleyl amine, tallow amine, tallow amine hydride and soybean amine.X preferably ₅The carbon number that has is 8～24, and the carbon number that more preferably has is 12～18.In addition, X ₅Can be straight chain aliphatic alkyl, side chain aliphatic alkyl or tertiary alkyl.

X ₆-NH-X ₇ (3)

In above general formula 3, X ₆And X ₇Be that carbon number is 1～30 alkyl or alkenyl.The example that can enumerate comprises: dilaurylamine, two coconut amines, two n-tridecane base amine, two (tetradecyl) amine, two Pentadecane base amine, two positive palmityl amines, two n-heptadecane base amine, two positive stearic amines, two iso stearyl amine, two NSC 77136 base amine, two NSC 62789 base amine, two heneicosane base amine, two n-docosane base amine, two n-tricosane base amine, two pentacosane base amine, two oleyl amines, two tallow amines, two tallow amine hydride and two soybean amine.X preferably ₆And X ₇The carbon number that has is 8～24, and the carbon number that more preferably has is 12～18.X ₆And X ₇Can be identical or different.

X ₈-NH-X ₉-NH ₂ (4)

In the general formula 4, X ₈Can be that carbon number is 1～30 alkyl or alkenyl.X preferably ₈The carbon number that has is 8～24, and the carbon number that more preferably has is 12～18.X ₉Be that carbon number is 1～12 alkylidene group.X preferably ₉The carbon number that has is 1～8, and the carbon number that more preferably has is 2～4.

The example that can enumerate comprises quadrol, for example: N-octyl group-1, the 2-quadrol, N-nonyl-1, the 2-quadrol, N-decyl-1, N-undecyl-1, N-lauryl-1, the 2-quadrol, N-tridecyl-1, the 2-quadrol, N-nutmeg base-1, N-tetradecyl-1, N-pentadecyl-1, the 2-quadrol, N-palmityl-1, the 2-quadrol, N-heptadecyl-1, N-oil base-1, N-stearyl-1, the 2-quadrol, N-iso stearyl-1, the 2-quadrol, N-nonadecyl-1, N-eicosyl-1, N-cocoyl-1, the 2-quadrol, N-tallow base-1, the 2-quadrol, N-tallow base-1 hydride and N-be soybean oil based-1.

In addition, adducible example comprises propylene diamine, for example: N-octyl group-1,3-propylene diamine, N-nonyl-1, the 3-propylene diamine, N-decyl-1, the 3-propylene diamine, N-undecyl-1, the 3-propylene diamine, N-lauryl-1, the 3-propylene diamine, N-tridecyl-1, the 3-propylene diamine, N-nutmeg base-1, the 3-propylene diamine, N-tetradecyl-1, the 3-propylene diamine, N-pentadecyl-1, the 3-propylene diamine, N-palmityl-1, the 3-propylene diamine, N-heptadecyl-1, the 3-propylene diamine, N-oil base-1, the 3-propylene diamine, N-stearyl-1, the 3-propylene diamine, N-iso stearyl-1, the 3-propylene diamine, N-nonadecyl-1, the 3-propylene diamine, N-eicosyl-1, the 3-propylene diamine, N-cocoyl-1, the 3-propylene diamine, N-tallow base-1, the 3-propylene diamine, N-tallow base-1,3-propylene diamine hydride and N-are soybean oil based-1, the 3-propylene diamine.

In addition, adducible example comprises butanediamine, for example: N-octyl group-1,4-butanediamine, N-nonyl-1, the 4-butanediamine, N-decyl-1, the 4-butanediamine, N-undecyl-1, the 4-butanediamine, N-bay alkyl-1, the 4-butanediamine, N-tridecyl-1, the 4-butanediamine, N-nutmeg base-1, the 4-butanediamine, N-tetradecyl-1, the 4-butanediamine, N-pentadecyl-1, the 4-butanediamine, N-palmityl-1, the 4-butanediamine, N-heptadecyl-1, the 4-butanediamine, N-oil base-1, the 4-butanediamine, N-stearyl-1, the 4-butanediamine, N-iso stearyl-1, the 4-butanediamine, N-nonadecyl-1, the 4-butanediamine, N-eicosyl-1, the 4-butanediamine, N-cocoyl-1, the 4-butanediamine, N-tallow base-1, the 4-butanediamine, N-tallow base-1,4-butanediamine hydride and N-are soybean oil based-1, the 4-butanediamine.

X ₁₀-N-(X ₁₁) ₂ (5)

In the general formula 5, X ₁₀Can be that carbon number is 1～30 alkyl or alkenyl.X preferably ₁₀The carbon number that has is 1～20, but the carbon number that more preferably has is 1～8 or 12～18.X ₁₁Be that carbon number is 1～20 alkyl, thiazolinyl or hydroxyalkyl, preferably X ₁₁Carbon number be 1～8, or 12～18.

X ₁₀The example that is the situation of methyl comprises the dialkyl group methylamine, for example: the dioctyl methylamine, the dinonyl methylamine, the didecyl methylamine, two (undecyl) methylamine, the dilauryl methylamine, two (tridecyl) methylamine, two nutmeg base methylamines, two (tetradecyl) methylamine, two (pentadecyl) methylamine, two palmityl methylamines, two (heptadecyl) methylamine, two oil base methylamines, the distearyl methylamine, two iso stearyl methylamines, two (nonadecyl) methylamine, two (eicosyl) methylamine, two cocoyl methylamines, two tallow base methylamines, two tallow base methylamine hydride and two soybean oil based methylamines.

In addition, X ₁₁The example that is the situation of methyl comprises alkyl dimethylamine, for example: octyl group dimethylamine, nonyl dimethylamine, decyl dimethylamine, undecyl dimethylamine, lauryl dimethylamine, tridecyl dimethylamine, nutmeg base dimethylamine, tetradecyl dimethylamine, pentadecyl dimethylamine, palmityl dimethylamine, heptadecyl dimethylamine, oil base dimethylamine, stearyl dimethylamine, iso stearyl dimethylamine, nonadecyl dimethylamine, eicosyl dimethylamine, cocoyl dimethylamine, tallow base dimethylamine, tallow base dimethylamine hydride and soybean oil based dimethylamine.

In addition, X ₁₁The example that is the situation of hydroxyalkyl comprises N-alkyl diethanolamine, for example: N-octyl group diethanolamine, N-nonyl diethanolamine, N-decyl diethanolamine, N-undecyl diethanolamine, N-lauryl diethanolamine, N-tridecyl diethanolamine, N-nutmeg base diethanolamine, N-tetradecyl diethanolamine, N-pentadecyl diethanolamine, N-palmityl diethanolamine, N-heptadecyl diethanolamine, N-oil base diethanolamine, N-stearyl diethanolamine, N-iso stearyl diethanolamine, N-nonadecyl diethanolamine, N-eicosyl diethanolamine, N-cocoyl diethanolamine, N-tallow base diethanolamine, N-tallow base diethanolamine hydride and the soybean oil based diethanolamine of N-; And N-alkyl dipropanolamine, for example: N-octyl group dipropanolamine, N-nonyl dipropanolamine, N-decyl dipropanolamine, N-undecyl dipropanolamine, N-lauryl dipropanolamine, N-tridecyl dipropanolamine, N-nutmeg base dipropanolamine, N-tetradecyl dipropanolamine, N-pentadecyl dipropanolamine, N-palmityl dipropanolamine, N-heptadecyl dipropanolamine, N-oil base dipropanolamine, N-stearyl dipropanolamine, N-iso stearyl dipropanolamine, N-nonadecyl dipropanolamine, N-eicosyl dipropanolamine, N-cocoyl dipropanolamine, N-tallow base dipropanolamine, N-tallow base dipropanolamine hydride and the soybean oil based dipropanolamine of N-.

The base number of determining with JIS K2501 of above-mentioned fatty amine can be 10mg KOH/g～800mg KOH/g, but preferred base number is 100mg KOH/g～500mg KOH/g.At least a this fatty amine consumption that is combined in the lubricating oil composition independent or that conduct suits that is selected from above group can be about 0.05 weight %～5 weight %, is preferably about 0.01 weight %～1 weight %.

In order further to improve performance, except mentioned component, can also suitably use various additives in case of necessity.The example of the additive that can enumerate comprises antioxidant, metal passivator, extreme pressure agent, oiliness improver, defoamer, viscosity index improver, pour point depressant, detergent dispersant, rust inhibitor, rust-preventive agent, emulsion splitter etc., or other known lubricating oil additive.

As can be used for antioxidant of the present invention, the antioxidant that uses in lubricating oil is preferred especially; The example that can enumerate comprises: phenol antioxidant, aromatic amine antioxidant, sulphur class antioxidant and Phosphorus antioxidant.With respect to the base oil of 100 weight %, these antioxidants a kind of or can be 0.01 weight %～5 weight % more than a kind of consumption of combination.

The example of the aromatic amine antioxidant that can enumerate comprises: dialkyl diphenylamine, p for example, p '-dioctyl-pentanoic (Non-flex OD-3, society makes by the Seiko chemistry), p, p '-two-α-Jia Jibianji-pentanoic or N-p-butyl phenyl-N-p '-octyl phenyl amine; The monoalkyl pentanoic, for example single tertiary butyl pentanoic or single octyl diphenylamine; Two (dialkyl phenyl organic) amine, for example two (2,4-diethyl phenyl) amine or two (2-ethyl-4-nonyl phenyl) amine; Alkyl phenyl-1-ALPHA-NAPHTHYL AMINE, for example octyl phenyl-1-ALPHA-NAPHTHYL AMINE or uncle's N-dodecylphenyl-1-ALPHA-NAPHTHYL AMINE; Aryl-ALPHA-NAPHTHYL AMINE, for example 1-ALPHA-NAPHTHYL AMINE, phenyl-1-naphthylamine, phenyl-2-ALPHA-NAPHTHYL AMINE, N-hexyl phenyl-2-ALPHA-NAPHTHYL AMINE or N-octyl phenyl-2-ALPHA-NAPHTHYL AMINE; Phenylenediamine is N for example, N '-di-isopropyl-Ursol D or N, N '-phenylbenzene-Ursol D; Or phenothiazines, thiodiphenylamine (Phenothiazine, by hodogaya chemical society make) or 3 for example, 7-dioctyl thiodiphenylamine.

The example of phenol antioxidant comprises 2-tert.-butyl phenol, the 2-tertiary butyl-4-methylphenol, the 2-tertiary butyl-5-methylphenol, 2,4-DI-tert-butylphenol compounds, 2,4-dimethyl-6-tert.-butyl phenol, the 2-tertiary butyl-4-methoxyphenol, the 3-tertiary butyl-4-methoxyphenol, 2,5-di-tert-butyl hydroquinone (AntageDBH, make by Kawaguchi chemistry society), 2, the 6-DI-tert-butylphenol compounds, 2,6-di-t-butyl-4-alkylphenol, for example 2,6-di-tert-butyl-4-methy phenol or 2,6-di-t-butyl-4-ethylphenol; Or 2,6-di-t-butyl-4-alkoxyl group phenols, for example 2,6-di-t-butyl-4-methoxyphenol or 2,6-di-t-butyl-4-thanatol.

Other examples comprise alkyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, for example 3,5-di-tert-butyl-4-hydroxyl benzyl sulfydryl-octyl group acetic ester, Octadecane base-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester (Yoshinox SS, make by Yoshitomi Seiyaku Inc.), dodecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 2 '-ethylhexyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester or phenylpropionic acid 3,5-two (1,1-dimethyl-ethyl)-4-hydroxyl-C7～C9 side chain alkyl ester (Irganox L135, make by Ciba Specialty Chemicals Inc.), or 2,2 '-methylene-bis (two 4-alkyl-6-tert.-butyl phenol), for example 2,6-di-t-butyl-alpha-alpha-dimethyl amino-p-cresol, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) (Antage W-400, make by chemistry society of Kawaguchi) or 2,2 '-methylene-bis (4-ethyl-6-tert-butyl phenol) (Antage W-500 is made by chemistry society of Kawaguchi).

Other examples also comprise bis-phenol, for example 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol) (Antage W-300, make by chemistry society of Kawaguchi), 4,4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds) (Ionox 220AH, make by Shell Japan Inc.), 4,4 '-two (2, the 6-DI-tert-butylphenol compounds), 2,2-(two p-hydroxybenzenes) propane (bisphenol A, make by Shell Japan Inc.), 2,2-two (3, the 5-di-tert-butyl-hydroxy phenyl) propane, 4,4 '-cyclohexylidene two (2, the 6-tert.-butyl phenol), hexamethylene glycol is two, and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (Irganox L109, make by Ciba SpecialtyChemicals Inc.), (Tominox 917 for triethylene glycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], make by Yoshitomi Chemical Inc.), 2,2 '-sulfo--[diethyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (Irganox L115, make by Ciba Specialty ChemicalsInc.), 3,9-pair 1,1-dimethyl-2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] and ethyl } 2,4,8,10-four oxaspiros [5,5] undecane (Sumilizer GA80, by the Sumitomo Chemical manufacturing) or 4,4 '-thiobis (3 methy 6 tert butyl phenol) (Antage RC is made by chemistry society of Kawaguchi), or 2,2 '-thiobis (4,6-di-t-butyl-Resorcinol).

Adducible other examples also comprise polyphenol, for example four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane (Irganox L101, make by Ciba Specialty Chemicals Inc.), 1,1, (Yoshinox 930 for butane for 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl), make by Yoshitomi Chemical Inc.), 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (Ionox 330, made by Shell Japan Inc.), two-[3,3 '-two-(4 '-hydroxyl-3 '-tert-butyl-phenyl) butyric acid] glycol ester, 2-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) methyl-4-(2 ", 4 " di-t-butyl-3 "-hydroxy phenyls) methyl-6-tert butyl phenol or 2,6-two (2 '-hydroxyl-3 '-tertiary butyl-5 '-methyl-benzyl)-the 4-methylphenol; perhaps phenol/aldehyde condensate, for example condenses of p-tert-butylphenol and formaldehyde or to the condenses of tert-butyl-phenyl ketone and acetaldehyde.

As sulphur class antioxidant, the example that can enumerate has: dialkyl sulfide, for example two (dodecyl) thioethers or two (octadecyl) thioether, thiodipropionate, for example thio-2 acid two (dodecyl) ester, thio-2 acid two (octadecyl) ester, thio-2 acid two (nutmeg base) ester or thio-2 acid dodecyl stearyl, perhaps 2-mercaptobenzimidazole.

As Phosphorus antioxidant, the example that can enumerate: triaryl phosphites, for example tricresyl phosphite phenylester or tricresyl phosphite tolyl ester, trialkyl phosphite, for example tricresyl phosphite (octadecyl) ester or tricresyl phosphite decyl ester, perhaps trithio tricresyl phosphite (dodecyl) ester.

Can comprise benzotriazole with the metal passivator that composition of the present invention uses, 4-alkyl-benzotriazole, for example 4-methyl-benzotriazole or 4-ethyl-benzotriazole, 5-alkyl-benzotriazole, for example 5-methyl-benzotriazole or 5-ethyl-benzotriazole, 1-alkyl-benzotriazole, 1-dioctyl aminomethyl-2 for example, the 3-benzotriazole, benzotriazole derivatives such as 1-alkyl-tolytriazole, 1-dioctyl aminomethyl-2 for example, the 3-tolytriazole, benzoglyoxaline, 2-(alkyl dithio)-benzoglyoxaline, 2-(octyl group dithio)-benzoglyoxaline for example, 2-(decyl dithio)-benzoglyoxaline or 2-(dodecyl dithio)-benzoglyoxaline, the perhaps derivative of benzoglyoxaline such as 2-(alkyl dithio) Vermox, for example 2-(octyl group dithio)-Vermox, 2-(decyl dithio)-Vermox or 2-(dodecyl dithio) Vermox.

Other examples comprise indazole or indazole derivatives such as toluene indazole; for example 4-alkyl-indazole or 5-alkyl-indazole; benzothiazole or benzothiazole derivant such as 2-mercaptobenzothiazole derivative (Thiolite B-3100; make by Chiyoda Chemicals Inc.); 2-(alkyl dithio) benzothiazole; 2-(hexyl dithio) benzothiazole for example; 2-(alkyl dithio) toluene thiazole such as 2-(octyl group dithio) benzothiazole; 2-(hexyl dithio) toluene thiazole; 2-(octyl group dithio) toluene thiazole; 2-(N; N-dialkyl dithio formamyl) benzothiazole; 2-(N for example; N-diethyl-dithio formamyl) benzothiazole; 2-(N; N-dibutyl Dithiocarbamyl) benzothiazole or 2-(N; N-dihexyl Dithiocarbamyl) benzothiazole; perhaps 2-(N; N-dialkyl dithio formamyl)-the toluene thiazole; 2-(N for example; N-diethyl-dithio formamyl) toluene thiazole; 2-(N; N-dibutyl Dithiocarbamyl) toluene thiazole or 2-(N, N-dihexyl Dithiocarbamyl) toluene thiazole.

In addition, other examples also comprise benzoxazole derivative such as 2-(alkyl dithio) benzoxazole, for example 2-(octyl group dithio) benzoxazole; 2-(decyl dithio) benzoxazole or 2-(dodecyl dithio) benzoxazole; perhaps 2-(alkyl dithio) Jia Ben oxazole, for example 2-(octyl group dithio) Jia Ben oxazole; 2-(decyl dithio) Jia Ben oxazole or 2-(dodecyl dithio) Jia Ben oxazole, thiadiazoles derivative is as 2; two (the alkyl dithio)-1,3 of 5-, the 4-thiadiazoles; for example 2; 5-pair of (diamyl disulfide generation)-1,3, the 4-thiadiazoles; 2; two (the nonyl dithio)-1 of 5-; 3, the 4-thiadiazoles; 2, two (the dodecyl dithio)-1 of 5-; 3; 4-thiadiazoles or 2, two (the octadecyl dithio)-1,3 of 5-; the 4-thiadiazoles; for example 2, two (N, the N-dialkyl dithio formamyls)-1 of 5-; 3; the 4-thiadiazoles, for example 2, the two (N of 5-; N-diethyl-dithio formamyl)-1; 3, the 4-thiadiazoles; 2, the two (N of 5-; N-dibutyl Dithiocarbamyl)-1; 3,4-thiadiazoles or 2, the two (N of 5-; N-dioctyl Dithiocarbamyl)-1; 3,4-thiadiazoles, perhaps 2-N; N-dialkyl dithio formamyl-5-sulfydryl-1; 3,4-thiadiazoles, for example 2-N; N-dibutyl Dithiocarbamyl-5-sulfydryl-1; 3,4-thiadiazoles or 2-N, N-dioctyl Dithiocarbamyl-5-sulfydryl-1; 3; the 4-thiadiazoles, perhaps triazole derivative such as 1-alkyl-2,4-triazole; 1-dioctyl aminomethyl-2 for example, the 4-triazole.

With respect to the base oil of 100 weight %, a kind of in these metal passivators, or can in the scope of 0.01 weight %～0.5 weight %, use more than a kind of combination.

Phosphorus compound can be added in the lubricating oil composition of the present invention, wear-resisting property and extreme pressure property can be further improved thus.The example of the of the present invention suitable phosphorus compound that can enumerate comprises: the amine salt of phosphoric acid ester, acid phosphoric acid ester, acid phosphoric acid ester, phosphorous acid ester, thiophosphatephosphorothioate, zinc dithiophosphate, phosphorated carboxylic acid and phosphorated carboxylicesters.With respect to the base oil of 100 weight %, a kind of in these phosphorus compounds, or can in the scope of 0.01 weight %～2 weight %, use more than a kind of combination.

The example of the above phosphoric acid ester that can enumerate comprises: the tricresyl phosphate butyl ester, tricresyl phosphate amyl group ester, the tricresyl phosphate polyhexamethylene, tricresyl phosphate heptyl ester, tricresyl phosphate octyl group ester, tricresyl phosphate nonyl ester, the tricresyl phosphate decyl ester, tricresyl phosphate (undecyl) ester, tricresyl phosphate (dodecyl) ester, tricresyl phosphate (tridecyl) ester, tricresyl phosphate (tetradecyl) ester, tricresyl phosphate (pentadecyl) ester, tricresyl phosphate (hexadecyl) ester, tricresyl phosphate (heptadecyl) ester, tricresyl phosphate (octadecyl) ester, trioleyl phosphate, or Triphenyl phosphate, tricresyl phosphate (isopropyl phenyl) ester, the tricresyl phosphate allyl ester, tricresyl phosphate (tolyl) ester, tricresyl phosphate (xylyl) ester, tricresyl phosphate base diphenyl or phosphoric acid (xylyl) diphenyl.

The specific examples of the above acid phosphoric acid ester that can enumerate comprises: acid phosphatase monobutyl ester, acid phosphatase list amyl group ester, acid phosphatase list polyhexamethylene, acid phosphatase list heptyl ester, acid phosphatase list octyl group ester, acid phosphatase list nonyl ester, acid phosphatase list decyl ester, acid phosphatase list undecyl ester, acid phosphatase list dodecyl ester, acid phosphatase list tridecyl ester, acid phosphatase list tetradecyl ester, acid phosphatase list pentadecyl ester, acid phosphatase list cetyl ester, acid phosphatase list heptadecyl ester, acid phosphatase list stearyl, acid phosphatase list oil base ester, acid phosphatase dibutyl ester, acid phosphatase diamyl ester, acid phosphatase dihexyl ester, acid phosphatase diheptyl ester, acid phosphatase dioctyl ester, acid phosphatase dinonyl ester, acid phosphatase didecyl ester, acid phosphatase two (undecyl) ester, acid phosphatase two (dodecyl) ester, acid phosphatase two (tridecyl) ester, acid phosphatase two (tetradecyl) ester, acid phosphatase two (pentadecyl) ester, acid phosphatase two (hexadecyl) ester, acid phosphatase two (heptadecyl) ester, acid phosphatase two (octadecyl) ester or acid phosphatase two oil base esters.

As the amine salt of acid phosphoric acid ester, can enumerate for example above-mentioned acid phosphoric acid ester and salts amine such as methylamine, ethylamine, propyl group amine, butylamine, amylamine, hexyl amine, heptyl amine, octyl amine, dimethylamine, diethylamide, dipropylamine, dibutylamine, diamyl amine, dihexyl amine, diheptyl amine, dioctylamine, Trimethylamine 99, triethylamine, tripropylamine, tributylamine, three amylamines, three hexyl amines, three heptyl amine and trioctylphosphine amine.

As phosphorous acid ester, can enumerate for example phosphorous acid dibutyl ester, phosphorous acid diamyl ester, phosphorous acid dihexyl ester, phosphorous acid diheptyl ester, phosphorous acid dioctyl ester, phosphorous acid dinonyl ester, phosphorous acid didecyl ester, phosphorous acid two (undecyl) ester, phosphorous acid two (dodecyl) ester, phosphorous acid two oil base esters, the phosphorous acid diphenyl, phosphorous acid two (tolyl) ester, the tricresyl phosphite butyl ester, tricresyl phosphite amyl group ester, the tricresyl phosphite polyhexamethylene, tricresyl phosphite heptyl ester, tricresyl phosphite octyl group ester, tricresyl phosphite nonyl ester, the tricresyl phosphite decyl ester, tricresyl phosphite (undecyl) ester, tricresyl phosphite (dodecyl) ester, tricresyl phosphite oil base ester, tricresyl phosphite phenylester or tricresyl phosphite (tolyl) ester.

The specific examples of the thiophosphatephosphorothioate that can enumerate comprises the tri o cresyl thiophosphate butyl ester, tri o cresyl thiophosphate amyl group ester, the tri o cresyl thiophosphate polyhexamethylene, tri o cresyl thiophosphate heptyl ester, thiophosphoric acid trioctylphosphine ester, tri o cresyl thiophosphate nonyl ester, the tri o cresyl thiophosphate decyl ester, tri o cresyl thiophosphate (undecyl) ester, tri o cresyl thiophosphate (dodecyl) ester, tri o cresyl thiophosphate (tridecyl) ester, tri o cresyl thiophosphate (tetradecyl) ester, tri o cresyl thiophosphate (pentadecyl) ester, tri o cresyl thiophosphate (hexadecyl) ester, tri o cresyl thiophosphate (heptadecyl) ester, tri o cresyl thiophosphate (octadecyl) ester, tri o cresyl thiophosphate oil base ester, the tri o cresyl thiophosphate phenylester, tri o cresyl thiophosphate (tolyl) ester, tri o cresyl thiophosphate (xylyl) ester, thiophosphoric acid tolyl diphenyl, thiophosphoric acid (xylyl) diphenyl, tri o cresyl thiophosphate (n-propyl phenyl) ester, tri o cresyl thiophosphate (isopropyl phenyl) ester, tri o cresyl thiophosphate (n-butylphenyl) ester, tri o cresyl thiophosphate (isobutyl phenenyl) ester, tri o cresyl thiophosphate (secondary butyl phenenyl) ester or tri o cresyl thiophosphate (tert-butyl-phenyl) ester.Can also use the mixture of these materials.

The specific examples of the zinc dithiophosphate that can enumerate generally comprises zinc dialkyl dithiophosphate, diaryl zinc dithiophosphate or arylalkyl zinc dithiophosphate.For example, can use following zinc dialkyl dithiophosphate, wherein the alkyl of zinc dialkyl dithiophosphate is that carbon number is 3～22 primary alkyl or secondary alkyl, or to have with carbon number be the primary alkyl or the secondary alkyl of the alkylaryl that replaces of 3～18 alkyl.The specific examples of the zinc dialkyl dithiophosphate that can enumerate comprises the dipropyl zinc dithiophosphate, zinc dibutyldithiophosphate, diamyl disulfide is for zinc phosphate, the dihexyl zinc dithiophosphate, the diisoamyl zinc dithiophosphate, two (ethylhexyl) zinc dithiophosphate, the dioctyl zinc dithiophosphate, the dinonyl zinc dithiophosphate, the didecyl zinc dithiophosphate, two (dodecyl) zinc dithiophosphate, two (propyl group phenyl) zinc dithiophosphate, two (amyl group phenyl) zinc dithiophosphate, two (propyl group aminomethyl phenyl) zinc dithiophosphate, two (nonyl phenyl) zinc dithiophosphate, two (dodecylphenyl) zinc dithiophosphates or two (dodecylphenyl) zinc dithiophosphate.

As phosphorated carboxylic acid or phosphorated carboxylic acid cpd such as its ester, its structure is not made particular restriction, as long as these materials comprise carboxyl and phosphorus atom simultaneously in same molecule; But, when extreme pressure property and heat/oxidative stability is considered, preferably phosphoric acid carboxylic acid or phosphorylation carboxylicesters.

About phosphorylation carboxylic acid and phosphorylation carboxylicesters, can exemplify out the compound of for example representing by following (6).

Wherein, in following formula 6, R4 and R5 can be identical or different, and represent that respectively hydrogen atom or carbon number are 1～30 alkyl, R6 represents that carbon number is 1～20 alkylidene group, R7 represents that hydrogen atom or carbon number are 1～30 alkyl, and X1, X2, X3 or X4 can be identical or different, and represent Sauerstoffatom or sulphur atom respectively.

As the R4 in the above general formula (6) and the carbon number among the R5 is 1～30 alkyl, and the example that can enumerate comprises alkyl, thiazolinyl, aryl, alkylaryl or arylalkyl.

In above phosphorylation carboxylic acid, available β-phosphorodithioic acid propionic acid has the structure of following general formula (7).

The specific examples of the described β-phosphorodithioic acid propionic acid that can enumerate comprises 3-(two-isobutoxy-thiophosphoryl base sulfenyl)-2-methyl-propionic acid.

The content of the phosphorus-containing carboxylic acid compound in the lubricating oil composition of the present invention is not subjected to particular restriction, but with respect to the base oil of 100 weight %, this content is preferably 0.001 weight %～1 weight %, more preferably 0.002 weight %～0.5 weight %.

If the content of phosphorus-containing carboxylic acid compound less than above-mentioned lower limit, then is difficult for obtaining competent lubricity.On the other hand, if addition, then is difficult for realization and the lubricated effect of improving that addition matches greater than the above-mentioned upper limit, in addition, also have the danger of infringement heat/oxidative stability and/or stability to hydrolysis, so this is unfavorable.

Should be noted that, in phosphorylation carboxylic acid by above general formula (6) expression, wherein R7 is that the content of the compound of hydrogen atom is 0.001 weight %～0.1 weight %, be preferably 0.002 weight %～0.08 weight %, 0.003 weight %～0.07 weight % more preferably, and then 0.004 weight %～0.06 weight % more preferably, further 0.005 weight %～0.05 weight % more preferably.

The polyhydroxy-alcohol fatty acid ester can mix to improve oiliness with lubricating oil composition of the present invention.For example can use carbon number is 1～24 saturated or unsaturated fatty acids and such as the partial ester of polyhydroxy-alcohols such as glycerine, Sorbitol Powder, alkylene glycol, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane or Xylitol or ester fully.As glyceryl ester, can exemplify out glyceryl monolaurate, glyceryl monostearate, monopalmitin, XU 61518.10, GLYCERYL DILAURATE, distearin, glycerol-1,3-dipalmitate or glyceryl dioleate.

As sorbitol ester, can exemplify out mono laurate sorbitol ester, single palmitinic acid sorbitol ester, Stearinsaeure sorbitol ester, single oleic acid sorbitol ester, two lauric acid sorbitol esters, two palmitinic acid sorbitol esters, distearyl acid sorbitol ester, two oleic acid sorbitol esters, three sorbitan monostearates, three lauric acid sorbitol esters, three oleic acid sorbitol esters or four oleic acid sorbitol esters.

As the alkylene glycol ester, can exemplify out mono laurate glycol ester, Tego-stearate, single oleic acid glycol ester, two lauric acid glycol esters, diglycol stearate, two oleic acid glycol esters, mono laurate propylene glycol ester, propylene glycolmonostearate, single oleic acid propylene glycol ester, two lauric acid propylene glycol esters, distearyl acid propylene glycol ester or two oleic acid propylene glycol esters.

As DOPCP, can exemplify out mono laurate DOPCP, Stearinsaeure DOPCP, single oleic acid DOPCP, two lauric acid DOPCP, distearyl acid DOPCP or two oleic acid DOPCP.

As trihydroxymethylpropanyl ester, can exemplify out TriMethylolPropane(TMP) mono-laurate, TriMethylolPropane(TMP) monostearate, TriMethylolPropane(TMP) monoleate, TriMethylolPropane(TMP) dilaurate, TriMethylolPropane(TMP) SUNSOFT Q-182S, TriMethylolPropane(TMP) dioleate or pentaerythritol monolaurate.

As pentaerythritol ester, can exemplify out pentaerythritol monostearate, pentaerythritol monooleate, tetramethylolmethane dilaurate, pentaerythritol stearic acid ester 2, tetramethylolmethane dioleate or pentaerythritol monooleate.As the fatty acid ester of these polyhydroxy-alcohols, preferably use the partial ester of polyhydroxy-alcohol and unsaturated fatty acids.

Low-temperature fluidity or viscosity performance in order to improve lubricating oil composition of the present invention can also add pour point depressant or viscosity index improver.As viscosity index improver, can exemplify out non-dispersive type viscosity index improver, for example polymethacrylate or ethylene-propylene copolymer, vinylbenzene-diene copolymers or such as olefin polymers such as polyisobutene or polystyrene, perhaps decentralized viscosity index improver by nitrogen containing monomer and these material copolymerizations are obtained.With respect to the base oil of 100 weight %, they can use in the scope of 0.05 weight %～20 weight %.As pour point depressant, can exemplify out polymethacrylate type polymkeric substance.With respect to the base oil of 100 weight %, they can use in the scope of 0.01 weight %～5 weight %.

In order to give lubricating oil composition of the present invention, can add defoamer with the froth breaking characteristic.As being suitable for defoamer of the present invention, can exemplify out the organosilicon acid esters, for example dimethyl polysiloxane, silicic acid diethyl ester or fluorosilicone, perhaps non-silicon type defoamer, for example polyalkyl acrylate.With respect to the base oil of 100 weight %, they can use separately or be used in combination in the scope of 0.0001 weight %～0.1 weight %.

As being suitable for emulsion splitter of the present invention, can exemplify out the known emulsion splitter that uses with additive as plain oil.With respect to the base oil of 100 weight %, they can use in the scope of 0.005 weight %～0.5 weight %.

Embodiment

Describe various embodiments of the present invention and comparative example below in detail, but, the present invention is not only limited in these embodiment.

When preparation embodiment and comparative example, preparation has the material of following composition.

1. base oil

(1-1) base oil 1: by the paraffinic mineral oil that lubricating oil distillate that the air distillation by crude oil is obtained is used as the suitable combination of means of purification such as hydrocracking and dewaxing obtains, classification is classified as and organizes II (Gp II) according to API (API) base oil.(characteristic: 100 ℃ kinetic viscosity: 1.35mm ²/ s; 40 ℃ kinetic viscosity: 31.4mm ²/ s; Viscosity index: 103; 15 ℃ density: 0.864; Sulphur content (being scaled the value of elementary sulfur): less than 10ppm; Nitrogen content (being scaled the value of elemental nitrogen): less than 1ppm; Aniline point, 110 ℃; Use the ring analysis paraffinic hydrocarbons part of the method for ASTM D3238: 62%; The naphthenic hydrocarbon part of ring analysis: 38%; The aromatic hydrocarbons part of ring analysis: less than 1%; Use the method for ASTM D5480 to distill the initial boiling point temperature that obtains by gas-chromatography: 312 ℃).

(1-2) base oil 2: by the paraffinic mineral oil that lubricating oil distillate that the air distillation by crude oil is obtained is used as the suitable combination of means of purification such as hydrocracking and dewaxing obtains, classification is classified as and organizes III (Gp III) according to API (API) base oil.(characteristic: 100 ℃ kinetic viscosity: 6.57mm ²/ s; 40 ℃ kinetic viscosity: 37.5mm ²/ s; Viscosity index: 130; 15 ℃ density: 0.823; Sulphur content (being scaled the value of elementary sulfur): less than 10ppm; Nitrogen content (being scaled the value of elemental nitrogen): less than 1ppm; Aniline point, 130 ℃; Use the ring analysis paraffinic hydrocarbons part of the method for ASTM D3238: 78%; The naphthenic hydrocarbon part of ring analysis: 22%; The aromatic hydrocarbons part of ring analysis: less than 1%; Use the polycyclic aromatic hydrocarbons part of the method for IP 346: 0.2%).

(1-3) base oil 3: use Fischer-Tropsch method synthetic GTL base oil, classification is classified as group III according to API (API) base oil.(characteristic: 100 ℃ kinetic viscosity: 5.10mm ²/ s; 40 ℃ kinetic viscosity: 23.5mm ²/ s; Viscosity index: 153; 15 ℃ density: 0.821; Sulphur content (being scaled the value of elementary sulfur): less than 10ppm; Nitrogen content (being scaled the value of elemental nitrogen): less than 1ppm; The aromatic hydrocarbons part of the ring analysis of the method for use ASTM D3238: less than 1%).

(1-4) base oil 4: generic name is the synthetic oil poly-alpha-olefin (PAO) of PAO6, and classification is classified as group IV according to API (API) base oil.(characteristic: 100 ℃ kinetic viscosity: 5.89mm ²/ s; 40 ℃ kinetic viscosity: 31.2mm ²/ s; Viscosity index: 135; 15 ℃ density: 0.827; Sulphur content (being scaled the value of elementary sulfur): less than 10ppm; Nitrogen content (being scaled the value of elemental nitrogen): less than 1ppm; Aniline point, 128 ℃; Use the ring analysis aromatic hydrocarbons part of the method for ASTM D3238: less than 1%; Use the method for ASTM D5480 to distill the initial boiling point temperature that obtains by gas-chromatography: 403 ℃).

(1-5) base oil 5: by the paraffinic mineral oil that lubricating oil distillate that the air distillation by crude oil is obtained is used as the suitable combination of means of purification such as dewaxing obtains, classification is classified as and organizes I (Gp I) according to API (API) base oil.(characteristic: 100 ℃ kinetic viscosity: 4.60mm ²/ s; 40 ℃ kinetic viscosity: 24.6mm ²/ s; Viscosity index: 101; 15 ℃ density, 0.866; Sulphur content (being scaled the value of elementary sulfur): 460ppm; Nitrogen content (being scaled the value of elemental nitrogen): 20ppm; Use the ring analysis paraffinic hydrocarbons part of the method for ASTM D3238: 66%; The naphthenic hydrocarbon part of ring analysis: 31%; The aromatic hydrocarbons part of ring analysis: 3%; Aniline point, 99 ℃; Use the polycyclic aromatic hydrocarbons part of the method for IP 346: 0.8%; Use the method for ASTM D5480 to distill the initial boiling point temperature that obtains by gas-chromatography: 331 ℃).

2. additive

(2-1) additive A 1: aspartic acid derivate: K-CORR 100, make (the acid number that obtains according to the method for JIS K2501: 100mgKOH/g) by King Inc

(2-2) additive A 2: aspartic acid derivate: COLACOR93, make (the acid number that obtains according to the method for JIS K2501: 75mgKOH/g) by ColonialChemicals Inc

(2-3) additive A 3: aspartic acid derivate: MONACOR39, make (the acid number that obtains according to the method for JIS K2501: 60mg KOH/g) by UnichemaInc

(2-4) additive B 1: coconut amine (main component is a lauryl amine): the primary alkyl primary amine (base number that obtains according to the method for JIS K2501: 390mg KOH/g)

(2-5) additive B 2: oleyl amine: the primary alkyl primary amine (base number that obtains according to the method for JIS K2501: 215mg KOH/g)

(2-6) additive B 3: tallow amine (main component: oleyl amine, stearylamine, palmitamide): the primary alkyl primary amine (base number that obtains according to the method for JIS K2501: 215mg KOH/g)

(2-7) primary amine of additive B 4:C18 tertiary alkyl: the primary t-alkyl-amine compound (base number that obtains according to the method for JISK2501: 155mg KOH/g)

(2-8) additive B 5: coconut secondary amine (main component is two (dodecyl) amine): the primary alkyl secondary amine compound (base number that obtains according to the method for JIS K2501: 160mg KOH/g)

(2-9) additive B 6: coconut diamines (main component is a N-dodecyl-1, the 3-the propylene diamine) (base number that obtains according to the method for JIS K2501: 440mg KOH/g)

(2-10) additive B 7: tallow diamines (main component is a N-oil base-1,3-propylene diamine, N-stearylamine-1,3-propylene diamine, N-palmityl-1,3-the propylene diamine) (base number that obtains according to the method for JIS K2501: 330mg KOH/g)

(2-11) additive B 8:N-alkyl diethanolamine (main component is the N-domiphen): the tertiary amine compound (base number that obtains according to the method for JIS K2501: 160mg KOH/g)

(2-12) additive B 9:N-alkyl diethanolamine (main component is a N-oil base diethanolamine): the tertiary amine compound (base number that obtains according to the method for JIS K2501: 160mg KOH/g)

(2-13) other additives: the compound shown in below can also adding: diphenylamine, phenyl naphthyl amines, phenylpropionic acid 3; 5-two (1; 1-dimethyl-ethyl)-4-hydroxyl-C7～C9 side chain alkyl ester, N, two (2-ethylhexyl)-(4 or the 5)-methyl isophthalic acid H-benzotriazoles of N--1-methylamine, tricresyl phosphate allyl ester, 3-(two isobutoxies-thiophosphoryl base sulfenyl)-2-methyl-propionic acid, pentaerythritol ester, polymethacrylate type pour point depressant, dimethyl polysiloxane type defoamer and polyoxyethylene and/polyoxypropylene type emulsion splitter.

Embodiment 1～19, comparative example 1～5

Use the material of above-mentioned composition, prepare the lubricating oil composition of embodiment 1～19 and comparative example 1～5 with the composition shown in table 1～table 5.

Test

For the performance of the lubricating oil composition of assessment embodiment 1～19 and comparative example 1～5, carry out the test of following rustless property, and use pendulum measurements determination frictional coefficient.

The rustless property test

According to JIS K2510, get 300ml sample oil and be placed in the container that is installed in the thermostatic bath, by stirring, when temperature reaches 60 ℃, iron testing plate is inserted in this sample oil with the 1000rpm rotation; And then the synthetic sea water of adding 30ml, temperature is remained on 60 ℃, continue to stir 24 hours.Subsequently testing plate is taken out, and whether have rust to occur on the visual inspection testing plate:, think that then sample passes through test if do not get rusty.

Pendulum test/frictional coefficient

Measure frictional coefficient with the Masuda type pendulum oiliness test equipment that Shinko Zoki Inc makes at 25 ℃.In this test, with the friction portion of sample supply of oil, make the pendulum vibration, and obtain frictional coefficient by the decay of vibration to the pendulum fulcrum.

The assessment of testing according to following standard.

Frictional coefficient is less than 0.135:@ (excellence)

Frictional coefficient is 0.135 to less than 0.150:O (satisfactory)

Frictional coefficient is more than 0.150: X (unsatisfactory)

Test result

Test result is presented in table 1～table 5.

Discuss

Shown in the embodiment 1～3 of table 1,, provide rust inhibiting property, and frictional coefficient can reduce by the rust inhibiting property test by using aspartic acid derivate and fatty amine and base oil 1.In addition, as can be seen, as shown in embodiment 1～3, aspartic acid derivate can use separately, perhaps as shown in Example 4, also can use its mixture.In addition, as shown in Example 5,, also obtained good result even use the mixture of aspartic acid derivate and fatty amine.

In addition, shown in the embodiment 6～9 of table 2, use high purifying base oil 2 to any lubricating oil composition in the base oil 5 also to obtain excellent rust inhibiting property and lower friction as base oil.And, shown in embodiment 10, as can be seen, as mentioned above by the friction effect of the rust inhibiting property of the excellence that combination produced of aspartic acid derivate and fatty amine and reduction with other additive and described to combine when using also be effective.

In the embodiment 11～18 of table 3 and table 4, as can be seen, (combination of additive B 2～B9) has obtained excellent rust inhibiting property and excellent low frictional properties matter by aspartic acid derivate (additive A 1) and various fatty amine compound.In addition, when wherein being mixed with fatty amine compound (embodiment 19), also obtained good result.Particularly, shown in embodiment 15～19,, can realize sizable reduction of frictional coefficient, and give the energy-conservation character of lubricating oil composition thus with excellence by using fatty amine compound additive B6～B9 and blended additive B 1 and B4.

On the contrary, high-visible by the test result in the table 5, in the situation of using base oil 1 separately (comparative example 1), by test, frictional coefficient is not unsatisfactory yet for its rust inhibiting property.In addition, although ((comparative example 2～4) rust inhibiting property has passed through test in the situation of the lubricating oil composition of additive A 1～A3), and these compositions are still unsatisfactory because of having very high frictional coefficient to be added with aspartic acid derivate therein in the base oil.It can also be seen that even be added with in the base oil therein in the situation of lubricating oil composition of fatty amine (additive B 1) (comparative example 5), rustless property is yet by test, and frictional coefficient is also very high, causes lubricating oil composition unsatisfactory.

Claims

1. lubricating oil composition, described lubricating oil composition comprises base oil, aspartic acid derivate and fatty amine compound.

2. lubricating oil composition as claimed in claim 1, wherein, the acid number of described aspartic acid derivate is 10mg KOH/g～200mg KOH/g.

3. lubricating oil composition as claimed in claim 1 or 2, wherein, the amount of described aspartic acid derivate is 0.01 weight %～5 weight %, the amount of described fatty amine compound is 0.005 weight %～5 weight %.

4. as each described lubricating oil composition in the claim 1～3, wherein, described fatty amine compound comprises the primary amine by following general formula (2) expression:

H ₂N-X ₅ (2)

Wherein, in the general formula (2), X ₅Be that carbon number is 1～30 alkyl or alkenyl.

5. as each described lubricating oil composition in the claim 1～4, wherein, described fatty amine compound comprises the secondary amine by following general formula (3) expression:

X ₆-NH-X ₇ (3)

Wherein, in the general formula (3), X ₆And X ₇Be that carbon number is 1～30 alkyl or alkenyl.

6. as each described lubricating oil composition in the claim 1～5, wherein, described fatty amine compound comprises the diamines by following general formula (4) expression:

X ₈-NH-X ₉-NH ₂ (4)

Wherein, in the general formula (4), X ₈Be that carbon number is 1～30 alkyl or alkenyl, X ₉Be that carbon number is 1～12 alkylidene group.

7. as each described lubricating oil composition in the claim 1～6, wherein, described fatty amine compound comprises the tertiary amine by following general formula (5) expression:

X ₁₀-NH-(X ₁₁) ₂ (5)

Wherein, in the general formula (5), X ₁₀Be that carbon number is 1～30 alkyl or alkenyl, X ₁₁Be that carbon number is 1～20 alkyl, thiazolinyl or hydroxyalkyl.

8. as each described lubricating oil composition in the claim 1～7, wherein, described lubricating oil composition also comprises aromatic amines compound and/or phenolic compound.

9. as each described lubricating oil composition in the claim 1～8, wherein, described base oil is a synthetic oil.

10. lubricating oil composition as claimed in claim 9, wherein, described synthetic oil is a poly-alpha-olefin.

11. lubricating oil composition as claimed in claim 9, wherein, described synthetic oil is GTL.

12. each described lubricating oil composition is used to improve the purposes of one or more kinds of rust inhibiting property, low frictional properties matter and high energy-efficient performance in the claim 1～11.

13. be lubricated the method for one or more kinds of improving rust inhibiting property, low frictional properties matter and high energy-efficient performance by each described lubricating oil composition in the use claim 1～11.