JP2002338983A - Lubricating oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ashless lubricating oil composition which does not contain a metal and exhibits excellent extreme-pressure properties and corrosion- proofing properties even under severe lubricating conditions from both the viewpoints of lubricating properties and rust-preventing properties of a lubricating oil. SOLUTION: This lubricating oil composition is prepared by compounding (I) 100 pts.wt. lube base oil with (II) 0.001-0.5 pt.wt. carboxylic acid-base or carboxylic ester-base rust-preventive and (III)0.001-0.2 pt.wt. at least one amine selected from the group consisting of alkylamines represented by the formula (1): (R<1> )n NH3-n and N-alkyl-polyalkylenediamines represented by formula (2): R<2> NH(CH2 )m NH2 .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent rust-preventive properties under severe use environment where water or seawater is mixed,
The present invention relates to a lubricating oil composition exhibiting excellent characteristics in both corrosion resistance and lubricity for various devices.

[0002]

2. Description of the Related Art Rust inhibitors are added to lubricating oil to protect mechanical parts from rust when water or seawater is mixed. In general, a rust preventive has a strong adsorptivity to a metal surface in order to form a rust preventive film on a metal surface and prevent direct contact between the metal and water to suppress rust generation. On the other hand, as the speed of the mechanical device is increased, the load is increased, and the efficiency is increased, the friction surface of the device is exposed to severe conditions, and seizure of the friction surface due to breakage of the lubricating oil film is likely to occur. For this reason, an appropriate amount of an extreme pressure agent that maintains lubricity by reacting with the metal surface on the friction surface to prevent adhesion between the friction surfaces is added to the lubricating oil used under severe conditions. However, it is known that the addition of a rust preventive inhibits the reaction between the extreme pressure agent and the metal surface on the friction surface, greatly impairing the effect of the extreme pressure additive.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to maintain excellent extreme pressure performance even under severe lubricating conditions and to provide excellent rust prevention from both the lubricating performance and rust prevention performance of a lubricating oil. An object of the present invention is to provide an ashless lubricating oil composition containing no metal having properties.

[0004]

Means for Solving the Problems The present inventor has conducted intensive studies to solve the drawback of reducing the effect of the extreme pressure agent by the conventional rust preventive agent, and as a result, has combined the rust preventive agent with a specific alkylamine. As a result, it has been found that the amount of the rust preventive added can be greatly reduced, and as a result, the decrease in the extreme pressure performance due to the rust preventive can be suppressed to a minimum, and the present invention has been completed.

[0005] The summary of the present invention is that (I) a lubricating base oil containing a mineral oil and / or a synthetic hydrocarbon, (II) a carboxylic acid-based rust inhibitor or a carboxylic ester-based rust inhibitor, and (II)
I) A lubricating oil composition comprising a specific alkylamine, wherein the alkylamine of (III) is composed of a primary or secondary alkylamine or an N-alkylpolyalkylenediamine. A composition.

That is, the first aspect of the present invention is as follows: (I) 0.001 to 0.5 parts by weight of a carboxylic acid type or carboxylic acid ester type rust inhibitor per 100 parts by weight of a lubricating base oil; ) (A) The following general formula (1)

(R ¹ ) _n NH _{3 -n} (1) (wherein, R ¹ is a straight-chain saturated or unsaturated alkyl group having 12 to 30 carbon atoms, and n is an integer of 1 or 2) Alkylamines represented by the following general formula (2):

Embedded image R ² NH (CH ₂ ) _m NH ₂ (2) (wherein, R ² is a straight-chain saturated or unsaturated alkyl group having 12 to 30 carbon atoms, and m is an integer of 2 to 5) Is.)
At least one amine selected from the group consisting of N-alkyl polyalkylene diamines represented by
To 0.2 parts by weight of a lubricating oil composition. A second aspect of the present invention is that an extreme pressure agent is represented by the following general formula (3):

S = P (—O—R ³ ) ₂ SCH ₂ CH (R ⁴ ) COOH (3) (wherein, R ³ is a branched alkyl group having 3 to 8 carbon atoms, R ⁴ is a hydrogen atom and a carbon atom A group selected from the group consisting of linear or branched alkyl groups of formulas 1 to 4.)
The lubricating oil composition according to claim 1, further comprising 0.001 to 0.5 parts by weight of dithiophosphorylpropionic acid. A third aspect of the present invention is that an extreme pressure agent is represented by the following general formula (4):

Embedded image S = P (O-ph-R ⁵ ) ₃ (4) (where ph is a phenyl group, R ⁵ is hydrogen or carbon atom 1)
To 9 linear or branched alkyl groups. The lubricating oil composition according to claim 1 or 2, further comprising 0.05 to 5 parts by weight of a triarylphosphothioate represented by the formula (1). A fourth aspect of the present invention is that an extreme pressure agent is represented by the following general formula (5):

Embedded image O = P (OR ⁶ ) _3-r (OH) _r (5) (wherein, R ⁶ is a linear or branched alkyl group having 3 to 13 carbon atoms, and r is 1 or 2 4. The lubricating oil composition according to any one of claims 1 to 3, wherein the composition contains 0.01 to 0.5 parts by weight of an acidic phosphate represented by the following formula: A fifth aspect of the present invention is that the lubricating base oil has a kinematic viscosity of 2-6.
^{80mm 2 / s (40 ℃)} , total sulfur content from 0 to 1 wt%, one of claims 1 to 4, a total nitrogen content 0 to 100 ppm, petroleum and / or synthetic hydrocarbon-based showing the aniline point 80 to 130 ° C. Or a lubricating oil composition as described above.

The lubricating base oil component constituting the lubricating oil composition of the present invention is not particularly limited as long as it contains a petroleum-based and / or synthetic hydrocarbon-based component, but the kinematic viscosity is 2 to 680 mm. ² / s (40 ° C.), preferably 5 to 3
20 mm ² / s (40 ° C.), particularly preferably 8 to 22
0 mm ² / s (40 ° C.), total sulfur content (% by weight) is 0 to 1
%, Preferably 0 to 0.3%, total nitrogen (ppm by weight)
Is 0 to 100 ppm, preferably 0 to 30 ppm, and the aniline point is 80 to 130 ° C, preferably 100 to 125 ° C.
Those exhibiting physical properties of are preferred.

[0008] The petroleum-based lubricating base oil used in the present invention comprises:
Solvent-refined base oil, hydrorefined base oil, highly hydrocracked base oil, etc., alone or as a mixture. Highly hydrocracked base oil is a raw wax (slack wax) separated by solvent dewaxing, which isomerizes linear paraffins into branched paraffins by hydrocracking (catalytic cracking) under the catalyst. 130 or more (typically 14)
5-155), or heavy linear paraffin obtained by Fischer-Tropsch polymerization using hydrogen and carbon monoxide obtained by gasification process (partial oxidation) of natural gas (such as methane) as raw materials. ,
This is a lubricating base oil having a viscosity index of 130 or more (typically 145 to 155) obtained by subjecting this to the same catalytic cracking isomerization as described above.

[0009] The synthetic hydrocarbon base oil used in the present invention comprises a monomer selected from linear or branched olefinic hydrocarbons having 3 to 15 carbon atoms, preferably 4 to 12 carbon atoms. It can be an olefin oligomer obtained by homopolymerization or copolymerization.

In the present invention, the petroleum-based lubricating base oil and the synthetic hydrocarbon-based base oil can be used alone or in combination.

The carboxylic acid type or carboxylic acid ester type rust preventive used in the present invention has a carboxylic acid or carboxylic acid ester group in the rust preventive molecule, and is a known rust preventive generally used widely in lubricating oils. Things. Specifically, monocarboxylic acids having 8 to 30 carbon atoms, alkyl or alkenyl succinic acids and their partial esters, hydroxy fatty acids having 12 to 30 carbon atoms and derivatives thereof,
Sarcosine having 8 to 24 carbon atoms and its derivatives, amino acids and its derivatives, naphthenic acid and its derivatives, lanolin fatty acids, mercapto fatty acids, oxidized paraffins and the like. More specific compound names are shown below.

Examples of monocarboxylic acids (C8-30): caprylic acid, pelagonic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachiic acid, behenic acid, serotinic acid, montanic acid,
Melicic acid, oleic acid, docosanoic acid, erucic acid, eicosenoic acid, tallow fatty acid, soybean oil fatty acid, coconut oil fatty acid,
Linoleic acid, linoleic acid, tall oil fatty acid, 12 hydroxystearic acid, lauryl sarcosine acid, myristyl sarcosine acid, palmityl sarcosine acid, stearyl sarcosine acid, oleyl sarcosine, alkylation (C8
-20) phenoxyacetic acid, lanolin fatty acid, C8-24
Mercapto fatty acids and the like.

Examples of polyvalent carboxylic acids: alkenyl (C20-100) succinic acid represented by CAS No. 27859-58-1 and its partial ester;
Dimer acid, N-acyl-N-alkoxyalkyl aspartates having the following structure (USP 5
27549), the compound of CAS No. 68906-34-3, and the like.

Embedded image (Wherein, R ⁷ and R ⁸ are hydrogen, a C1-30 alkyl group,
A group independently selected from the group consisting of a C1-30 acyl group and an alkyl oxide group, and R ⁹ -R ¹³
Is a group independently selected from the group consisting of hydrogen and a C1-30 alkyl group. )

Among the alkylamines represented by the general formula (1), examples of the primary amines include laurylamine, coconutamine, n-tridecylamine, myristylamine, n-pentadecylamine, and palladium. Mytylamine, n-heptadecylamine, stearylamine, n-
Examples include nonadecylamine, n-eicosylamine, n-heneicosylamine, n-docosylamine, n-tricosylamine, n-pentacosylamine, oleylamine, tallowamine, hydrogenated tallowamine, and soyamine. Examples of the secondary amines include dilaurylamine, dicoconutamine, di-n-tridecylamine, dimyristylamine, di-n-pentadecylamine, dipalmitylamine, di-n-heptadecylamine, and di-n-heptadecylamine. Stearylamine, di-n-nonadecylamine, di-n-eicosylamine, di-n-heneicosylamine, di-n-docosylamine, di-n-tricosylamine, di-n-pentacosylamine, dioleylamine, di-tallowamine, dihydrogen Beef tallow amine, di-soy amine, and the like.

Examples of the N-alkylpolyalkylenediamine represented by the general formula (2) include lauryl ethylenediamine, coconut ethylenediamine, n-tridecylethylenediamine, myristylethylenediamine,
n-pentadecylethylenediamine, palmitylethylenediamine, n-heptadecylethylenediamine, stearylethylenediamine, n-nonadecylethylenediamine, n-eicosylethylenediamine, n-heneicosylethylenediamine, n-docosylethylenediamine, n-tricosylethylenediamine, ethylenediamines such as n-pentacosylethylenediamine, oleylethylenediamine, tallowethylenediamine, hydrogenated tallowethylenediamine, soybean ethylenediamine; laurylpropylenediamine, coconut propylenediamine, n
-Tridecyl propylene diamine, myristyl propylene diamine, n-pentadecyl propylene diamine, palmityl propylene diamine, n-heptadecyl propylene diamine, stearyl propylene diamine, n-nonadecyl propylene diamine, n-eicosyl propylene diamine, n-hen Eicosyl propylene diamine,
Propylene diamines such as n-docosyl propylene diamine, n-tricosyl propylene diamine, n-pentacosyl propylene diamine, oleyl propylene diamine, tallow propylene diamine, hydrogenated tallow propylene diamine, soy propylene dimine; lauryl butylene diamine, coco Nut butylene diamine, n-tridecyl butylene diamine, myristyl butylene diamine, n-
Pentadecyl butylene diamine, palmityl butylene diamine, n-heptadecyl butylene diamine, stearyl butylene diamine, n-nonadecyl butylene diamine, n-eicosyl butylene diamine, n-hen eicosyl butylene diamine, n-docosyl butylene diamine, Butylene diamines such as n-tricosyl butylene diamine, n-pentacosyl butylene diamine, oleyl butylene diamine, tallow butylene diamine, hydrogenated tallow butylene diamine, and soy butylene diamine; lauryl pentylene diamine, coconut pentylene diamine, myristyl Pentylenediamine, palmitylpentylenediamine, stearylpentylenediamine, oleylpentylenediamine, tallow pentylenediamine, hydrogenated tallow pentylenediamine, Pliers diamine such as beans pentylene diamine and the like.

In the present invention, in addition to the above-mentioned essential components, in order to further improve the performance, various additional additives usually used can be appropriately used as needed. These include known lubricating oil additives such as antioxidants, metal deactivators, extreme pressure agents, defoamers, viscosity index improvers, pour point depressants, cleaning dispersants, rust inhibitors, demulsifiers and the like. Can be added.

As the amine-based antioxidant, p, p'-
Dioctyl-diphenylamine (Nonflex OD-3 manufactured by Seiko Chemical Co., Ltd.), p, p'-di-α-methylbenzyl-diphenylamine, Np-butylphenyl-N-
dialkyl-diphenylamines such as p'-octylphenylamine;mono-t-butyldiphenylamine;
Monoalkyldiphenylamines such as monooctyldiphenylamine; bis (dialkylphenyl) amines such as di (2,4-diethylphenyl) amine and di (2-ethyl-4-nonylphenyl) amine; octylphenyl-1-naphthylamine; Alkylphenyl-1-naphthylamines such as Nt-dodecylphenyl-1-naphthylamine; 1-naphthylamine, phenyl-1-
Naphthylamine, phenyl-2-naphthylamine, N-
Aryl-naphthylamines such as hexylphenyl-2-naphthylamine and N-octylphenyl-2-naphthylamine; phenylenediamines such as N, N'-diisopropyl-p-phenylenediamine and N, N'-diphenyl-p-phenylenediamine Phenothiazine (Phenothiazine, manufactured by Hodogaya Chemical Co., Ltd.);
And phenothiazines such as 3,7-dioctylphenothiazine.

Examples of sulfur-based antioxidants include dialkyl sulfides such as didodecyl sulfide and dioctadecyl sulfide; didodecyl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, dodecyl octadecyl thiodipropionate. Thiodipropionates such as acrylates;
2-mercaptobenzimidazole and the like.

The phenolic antioxidants include 2-t
-Butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 2,
4-di-t-butylphenol, 2,4-dimethyl-6
-T-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone (Antage DBH, manufactured by Kawaguchi Chemical Co., Ltd.), 2,6 2,6-di-t-butyl-4- such as di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4-ethylphenol Alkylphenols; 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-ethoxyphenol, and other 2,6-di-tert-butyl-4-alkoxyphenols; 3,5-di-t-butyl-4-hydroxybenzylmercapto-octyl acetate, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propione Doo (Yoshitomi Pharmaceutical Co., Ltd. Yoshinox SS), n-dodecyl-3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate, 2'
Ethylhexyl-3- (3,5-di-t-butyl-4-
Alkyl- such as (hydroxyphenyl) propionate
3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionates; 2,6-di-tert-butyl-α-
Dimethylamino-p-cresol, 2,2'-methylenebis (4-methyl-6-t-butylphenol) (manufactured by Kawaguchi Chemical Co .: Antage W-400), 2,2'-methylenebis (4-ethyl-6-t) 2,2'- such as -butylphenol) (Antage W-500, manufactured by Kawaguchi Chemical Co., Ltd.)
Methylenebis (4-alkyl-6-t-butylphenol); 4,4'-butylidenebis (3-methyl-6-
t-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd .: Antage W)
-300), 4,4'-methylenebis (2,6-di-t
-Butylphenol) (Shell Japan: Ion
ox 220AH), 4,4'-bis (2,6-di-t)
-Butylphenol), 2,2- (di-p-hydroxyphenyl) propane (Bisphenol A, manufactured by Shell Japan), 2,2-bis (3,5-di-t-butyl-)
4-hydroxyphenyl) propane, 4,4'-cyclohexylidenebis (2,6-t-butylphenol),
Hexamethylene glycol bis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
(Ciba Specialty Chemicals: Irgan
ox L109), triethylene glycol bis [3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionate] (Tominox manufactured by Yoshitomi Pharmaceutical Co., Ltd.)
917), 2,2'-thio- [diethyl-3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals: I
rganox L115), 3,9-bis {1,1-dimethyl-2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl}.
2,4,8,10-tetraoxaspiro [5,5] undecane (Sumitomo Chemical: Sumilizer GA80), 4,4 '
-Thiobis (3-methyl-6-t-butylphenol)
Bisphenols such as (Antage RC, manufactured by Kawaguchi Chemical Co., Ltd.) and 2,2′-thiobis (4,6-di-t-butyl-resorcinol); tetrakis [methylene-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate] methane (manufactured by Ciba Specialty Chemicals: Irganox L101), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) Butane (Yoshinox 930, manufactured by Yoshitomi Pharmaceutical Co., Ltd.),
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene (Ionox 330, manufactured by Shell Japan), bis- [3,3'-bis- (4'-hydroxy-3'-t-)
Butylphenyl) butyric acid] glycol ester, 2- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) methyl-4- (2 ", 4" -di-tert-butyl-3 "- (Hydroxyphenyl) methyl-6-t-butylphenol, 2,6-bis (2'-hydroxy-
Polyphenols such as 3'-t-butyl-5'-methyl-benzyl) -4-methylphenol; phenol aldehyde condensation such as a condensate of pt-butylphenol and formaldehyde and a condensate of pt-butylphenol and acetaldehyde Body and the like.

As the phosphorus-based antioxidant, triaryl phosphites such as triphenyl phosphite and tricresyl phosphite, trialkyl phosphites such as trioctadecyl phosphite and tridecyl phosphite, and tridodecyl trithiophosphite And the like.

These antioxidants can be used alone or in combination in a range of 0.01 to 2.0 parts by weight based on 100 parts by weight of the base oil.

The metal deactivator which can be used in combination with the composition of the present invention includes benzotriazole, 4-methyl-benzotriazole, 4-ethyl-benzotriazole and the like.
-Alkyl-benzotriazoles; 5-alkyl-benzotriazoles such as 5-methyl-benzotriazole, 5-ethyl-benzotriazole and 1- such as 1-dioctylaminomethyl-2,3-benzotriazole.
Alkyl-benzotriazoles; benzotriazole derivatives such as 1-alkyl-tolutriazoles such as 1-dioctylaminomethyl-2,3-tolutriazole; benzimidazole, 2- (octyldithio) -benzimidazole, 2- (decyldithio) ) -Benzimidazole, 2- (alkyldithio) -benzimidazoles such as 2- (dodecyldithio) -benzimidazole; 2- (octyldithio) -toluimidazole, 2-
Benzimidazole derivatives such as 2- (alkyldithio) -toluimidazoles such as (decyldithio) -toluimidazole and 2- (dodecyldithio) -toluimidazole; indazole, 4-alkyl-indazole, 5-
Indazole derivatives such as toluindazoles such as alkyl-indazole; benzothiazole, 2-mercaptobenzothiazole derivative (manufactured by Chiyoda Chemical Co .: Thiolite B-3100), 2- (hexyldithio) benzothiazole, 2- (octyldithio) benzo 2- (alkyldithio) benzothiazoles such as thiazole;
2- (alkyldithio) toltiazoles such as (hexyldithio) toltiazole and 2- (octyldithio) toltiazole; 2- (N, N-diethyldithiocarbamyl) benzothiazole, 2- (N, N-dibutyl) Dithiocarbamyl) -benzothiazole, 2- (N, N-dihexyldithiocarbamyl) -benzothiazole, etc.
-(N, N-dialkyldithiocarbamyl) benzothiazoles; 2- (N, N-diethyldithiocarbamyl)
2- (N, N-dialkyldithiocarbamyl) -torzothiazole such as toltiazole, 2- (N, N-dibutyldithiocarbamyl) toltiazole, 2- (N, N-dihexyldithiocarbamyl) toltiazole 2- (octyldithio) benzoxazole, 2- (decyldithio) benzoxazole, 2- (alkyldithio) -benzoxazoles such as 2- (dodecyldithio) benzoxazole; 2
Benzoxazole derivatives such as 2- (alkyldithio) toluoxazoles such as-(octyldithio) toluoxazole, 2- (decyldithio) toluoxazole, 2- (dodecyldithio) toluoxazole; 2,5-bis (heptyldithio)- 1,3,4-thiadiazole,
2,5-bis (nonyldithio) -1,3,4-thiadiazole, 2,5-bis (dodecyldithio) -1,3,4
2,5-bis (alkyldithio) -1,3,4-thiadiazoles such as thiadiazole and 2,5-bis (octadecyldithio) -1,3,4-thiadiazole;
2,5-bis (N, N-diethyldithiocarbamyl)-
1,3,4-thiadiazole, 2,5-bis (N, N-
2,5-bis (N, N-dialkyl) such as dibutyldithiocarbamyl) -1,3,4-thiadiazole and 2,5-bis (N, N-dioctyldithiocarbamyl) -1,3,4-thiadiazole Dithiocarbamyl) -1,3,3
4-thiadiazoles; 2-N, N-dibutyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole, 2-N, N-dioctyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole 2-N, such as
N-dialkyldithiocarbamyl-5-mercapto-
Thiadiazole derivatives such as 1,3,4-thiadiazoles; and triazole derivatives such as 1-alkyl-2,4-triazoles such as 1-di-octylaminomethyl-2,4-triazole.

These metal deactivators can be used alone or in combination in a range of 0.01 to 0.5 part by weight based on 100 parts by weight of the base oil.

Examples of the antifoaming agent include organosilicates such as dimethylpolysiloxane, diethylsilicate and fluorosilicone, and non-silicone antifoaming agents such as polyalkyl acrylate. The amount of addition is 0.0 parts with respect to 100 parts by weight of the base oil.
It can be used alone or in combination of two or more in the range of 001 to 0.1 parts by weight.

Examples of the viscosity index improver include non-dispersible viscosity index improvers such as polymethacrylates, olefin copolymers such as ethylene-propylene copolymer and styrene-diene copolymer, and nitrogen-containing monomers. And copolymerized dispersion type viscosity index improvers. The addition amount is 0.05 to 2 parts by weight based on 100 parts by weight of the base oil.
It can be used alone or in combination of two or more in the range of 0 parts by weight.

Examples of the pour point depressant include polymethacrylate polymers. The addition amount can be used in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the base oil.

Examples of the detergent and dispersant include metal-based detergents such as neutral or basic alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates; alkenyl succinimides and alkenyl succinates. Alternatively, an ashless dispersant such as a product modified with a boron compound, a sulfur compound, or the like may be used. The addition amount can be used alone or in combination in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of the base oil.

Examples of extreme pressure agents include sulfur extreme pressure agents such as dialkyl sulfide, dibenzyl sulfide, dialkyl polysulfide, dibenzyl disulfide, alkyl mercaptan, dibenzothiophene, and 2,2'-dithiobis (benzothiazole); Phosphorus extreme pressure agents such as phosphate, triarylphosphate, trialkylphosphonate, trialkylphosphite, triarylphosphite, dialkylhydrozenphosphite; zinc dialkyldithiophosphate, dialkyldithiophosphate, trialkyl Phosphorus-sulfur extreme pressure agents such as dithiophosphates, acidic thiophosphates, and trialkyltrithiophosphites can be used. These extreme pressure agents can be used alone or in combination in a range of 0.1 to 2 parts by weight with respect to 100 parts by weight of the base oil.

As the demulsifier, there may be mentioned known ones usually used as lubricating oil additives. The amount added
It can be used in the range of 0.0005 to 0.5 part by weight based on 100 parts by weight of the base oil.

[0030]

EXAMPLES The present invention will be described in detail below, but the present invention is not limited to these examples. As a base oil, a hydrorefined base oil having a kinematic viscosity at 40 ° C. of 31 mm ² / s, a viscosity index of 107, a sulfur content of 5 ppm or less, a nitrogen content of 1 ppm or less, and an aniline point of 112 ° C. A pressure agent and a carboxylic acid-based, carboxylic acid ester-based rust inhibitor, which is an essential component of the present invention, and an amine are mixed at various concentrations to prepare a sample oil, and the effect of the present invention is evaluated as rust inhibitor performance and extreme pressure performance. From both sides. Various performance test methods in Examples and Comparative Examples are as shown below.

Rust Prevention Test ASTM D665 was used to evaluate the rust prevention performance of the sample oil.
A rust prevention test was performed at 60 ° C. for 24 hours in the presence of artificial seawater in accordance with the standards described in Example 1, and it was examined whether or not rust occurred on the steel test piece after the test.

FZG Gear Test In order to evaluate the lubrication performance of the sample oil on the gear device,
In accordance with SO / WD14635-1, the test gear A was operated for 15 minutes at each load stage under the conditions of an initial oil temperature of 90 ° C. and a motor rotation speed of 1450 rpm, and the test gear was increased while increasing the load stages. The load stage until the seizure occurred on the tooth surface of each was measured.

Examples 1 to 9 and Comparative Examples 1 to 9 The compositions and test results are shown in Tables 1 to 3.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3] Note) (1) Lubrizol 859 manufactured by Lubrizol Co., Ltd. (2) Sarkosyl O manufactured by Ciba Specialty Chemicals Co., Ltd. (3) Irgacore NPA manufactured by Ciba Specialty Chemicals Co., Ltd. (4) Collacoa 93 CAS No. manufactured by Colonial Chemical Co. 68906-34-3, 27136-7
3-8 (5) K-CORR 10 manufactured by King Industries
0 Rust inhibitor described in UP5277549 (Jan. 4.1994)

Comparative Examples 1 and 8 show good extreme pressure performance in a gear test when only an extreme pressure agent is blended, but generate rust in the rust prevention test because no rust inhibitor and amine are added. However, in Comparative Examples 3 to 8, since the carboxylic acid or carboxylic acid ester-based rust preventive was added in the minimum necessary amount, no rust was generated in the rust preventive test. It can be seen that a marked decrease in load carrying capacity occurs. In Comparative Examples 2 and 9, only the amine was added, and there was no compounding of the carboxylic acid or carboxylic acid ester-based rust preventive agent, so that a sufficient rust preventive effect was not obtained. Example 1
In Nos. To 9, the required amount of the carboxylic acid or the carboxylic acid ester-based rust inhibitor can be greatly reduced by the synergistic effect of the carboxylic acid or the carboxylic acid ester-based rust inhibitor, which is an essential component of the present invention, and the rust inhibitor. Can significantly reduce extreme pressure performance.

[0038]

(1) The lubricating oil composition of the present invention contains little or no harmful metals from the viewpoint of environment and safety, and is capable of increasing the speed, pressure, and compactness of industrial machines in recent years. It is possible to provide a lubricating oil composition that maintains excellent rust-preventing performance and still has extreme pressure performance in response to improvement in durability. Further, since the amount of the rust inhibitor added can be reduced by the present invention, a lubricating oil composition having excellent performance can be provided at low cost. (2) The lubricating oil composition of the present invention comprises a hydraulic oil, a gear oil,
It is useful as a lubricating oil composition that requires rustproofing performance and extreme pressure performance for use as compressor oil, turbine oil, and bearing oil.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C10M 129/44 C10M 129/44 129/58 129/58 129/93 129/93 129/95 129/95 133 / 06 133/06 135/26 135/26 137/02 137/02 137/10 137/10 Z // C10N 20:00 C10N 20:00 A Z 20:02 20:02 30:06 30:06 30: 12 30:12 40:00 40:00 A 40:02 40:02 40:04 40:04 40:08 40:08 40:12 40:12 40:30 40:30 F term (reference) 4H104 BA02A BA07A BB17C BB19C BC05C BC09C BE02C BG14C BH02C BH06C CA01A CA16C DA02A EA02A EA04A EA21A LA03 LA06 PA01 PA02 PA05 PA07 PA09 PA20

Claims (5)

[Claims] (1) 100% by weight of a lubricating base oil, (II) 0.001 to 0.5 part by weight of a carboxylic acid type or carboxylic acid ester type rust inhibitor, and (III) (A) Formula (1): (R ¹ ) _n NH _{3 -n} (1) (wherein, R ¹ is a straight-chain saturated or unsaturated alkyl group having 12 to 30 carbon atoms, and n is 1 or And an alkylamine represented by the following general formula (2): R ² NH (CH ₂ ) _m NH ₂ (2) (wherein R ² has 12 carbon atoms) -30 straight-chain saturated or unsaturated alkyl groups, and m is an integer of 2-5.)
At least one amine selected from the group consisting of N-alkyl polyalkylene diamines represented by
A lubricating oil composition characterized by containing 0.2 to 0.2 parts by weight. 2. An extreme pressure agent represented by the following general formula (3): S = P (—O—R ³ ) ₂ SCH ₂ CH (R ⁴ ) COOH (3) (wherein R ³ represents a carbon number) A branched alkyl group having 3 to 8 atoms, and R ⁴ is a group selected from the group consisting of a hydrogen atom and a linear or branched alkyl group having 1 to 4 carbon atoms.)
The lubricating oil composition according to claim 1, further comprising 0.001 to 0.5 parts by weight of dithiophosphorylpropionic acid. 3. An extreme pressure agent represented by the following general formula (4): S = P (O-ph-R ⁵ ) ₃ (4) (where ph is a phenyl group, R ⁵ is hydrogen or carbon number) 1
To 9 linear or branched alkyl groups. The lubricating oil composition according to claim 1 or 2, further comprising 0.05 to 5 parts by weight of a triarylphosphorothioate represented by the formula (1). 4. An extreme pressure agent represented by the following general formula (5): O = P (OR ⁶ ) _3-r (OH) _r (5) (wherein, R ⁶ is a straight-chain having 3 to 13 carbon atoms) The lubricating composition according to any one of claims 1 to 3, wherein the acidic phosphoric acid ester represented by the formula (1) is a chain or branched alkyl group, and r is an integer of 1 or 2. Oil composition. 5. The lubricating base oil has a kinematic viscosity of 2 to 680 m.
Petroleum-based and / or synthetic hydrocarbon-based compounds exhibiting m ² / s (40 ° C.), total sulfur content of 0 to 1% by weight, total nitrogen content of 0 to 100 ppm, and aniline point of 80 to 130 ° C.
The lubricating oil composition according to any of the above.