WO2008038701A1

WO2008038701A1 - Lubricating oil composition

Info

Publication number: WO2008038701A1
Application number: PCT/JP2007/068779
Authority: WO
Inventors: Tahei Okada
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2006-09-28
Filing date: 2007-09-27
Publication date: 2008-04-03
Also published as: EP2067846B1; JP2014012855A; JP5710720B2; US20100009880A1; JP5373400B2; IN2009CN01716A; JPWO2008038701A1; ES2384584T3; CN101517056B; EP2067846A4; EP2067846A1; US20140051618A1; CN101517056A

Abstract

A lubricating oil composition comprising: a base oil; (A) an acidic alkyl phosphate ester having a C6-C20 alkyl group; (B) a dialkylamine and/or a trialkylamine; and (C) (c-1) 0.2 to 0.6 mass% (in term of S) of a sulfur compound which does not contain a poly-sulfur bond equal to or higher than -S-S-S- in the molecule and has a S content of 15% by mass or more in the molecule and optionally (c-2) 0.1 to 1.0% by mass of a trihydrocarbyl thiophosphate ester represented by the general formula (I), wherein the composition has a P content of 150 to 500 ppm by mass: (R-O-)3P=S (I) wherein R represents a hydrocarbyl group having 6 to 20 carbon atoms. The lubricating oil composition is excellent in seizure resistance and fatigue resistance including FZG micropitting resistance, and can produce a reduced amount of sludge in an oxidation test.

Description

Specification

Lubricating oil composition

Technical field

TECHNICAL FIELD [0001] The present invention relates to a lubricating oil composition, and more specifically, a lubricating oil composition that has excellent seizure resistance and fatigue resistance and has sludge generation suppressed in an oxidation test, particularly for wind power generation. The present invention relates to a lubricating oil composition suitable as a speed increaser oil composition.

Background art

[0002] From the viewpoints of reducing environmental burden and fossil fuel depletion in recent years, wind power generation using renewable energy is expected to increase further in the future.

Wind power generation using wind power uses propellers and other rotors that rotate in response to wind to convert the kinetic energy of the wind into power, which is then used to drive the generator and convert it into electric energy.

In such wind power generation, since the rotor rotation speed is slow, a speed increaser is used in consideration of the power generation efficiency of the generator. Various gears are known as this speed increaser. Among them, planetary gear type power transmission devices are frequently used.

It has excellent seizure resistance, fatigue resistance such as FZG micropitting resistance, and oxidation stability for the speed increasing gear oil composition used for such planetary gear type power transmission devices. In the property test, the generation of sludge is required to be small.

Lubricating oil compositions used in wind power gearboxes include, for example, extreme pressure compounds containing ω sulfur compounds, (b) mixtures of hydrocarbylamine compounds and alkyl phosphorothioate compounds, (c) for friction adjustment A lubricating oil composition containing a compound and (d) a base oil has been proposed (see, for example, Patent Document 1).

However, this lubricating oil composition fully satisfies all of the required performance required for the wind power booster oil composition! /, But not!

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2005_126709

Disclosure of the invention

Problems to be solved by the invention [0004] Under such circumstances, the present invention is a lubricating oil composition that is excellent as seizure resistance and fatigue resistance, and is suitable as a step-up gear oil composition for wind power generation in which sludge generation is suppressed in an oxidation test. Is intended to provide.

Means for solving the problem

[0005] As a result of intensive studies to develop the lubricating oil composition having the above-mentioned excellent performance, the present inventors have found that the base oil contains a specific acidic alkyl phosphate ester, an alkyl amine, It has been found that a lubricating oil composition comprising a combination of specific sulfur compounds and containing P and S in a predetermined ratio can meet the purpose. The present invention has been completed based on such knowledge.

That is, the present invention

[1] base oil, (A) alkyl phosphate alkyl ester having 6 to 20 carbon atoms, (B) dialkylamine and / or trialkylamine, and (C) (cl) intramolecular The sulfur compound not containing polysulfur bonds of S—S—S or more and having an S content in the molecule of 15% by mass or more is defined as 0.2 to 0.6% by mass as S and optionally (c 2 ) —General formula (I) (RO-) P = S… (I)

(In the formula, R represents a hydrocarbyl group having 6 to 20 carbon atoms.)

Lubrication becomes ~ to 1 · 0 Weight ^_0/0 formulation, and the P content in the composition is characterized in that 150 to 500 mass ppm;! A Chiorin trihydrocarbyl ester represented 0 · in Oil composition,

[2] The above component (B) is blended so that the mass ratio of [P] in [(A) component] / [N in (B) component] is 1.7 to 2.1 [1] A lubricating oil composition according to claim 1,

[3] The lubricating oil composition according to the above [1] or [2], wherein the component (B) is a trialkylamine having 6 to 20 carbon atoms in the alkyl group,

[4] The lubricating oil composition according to any one of the above [1] to [3], further comprising (D) 5 to 20% by mass of a partial ester of polyol, and

[5] The lubricating oil composition according to [1] to [4] above, which is a gearbox oil composition for wind power generation,

Is to provide. The invention's effect

[0006] According to the present invention, it is excellent in seizure resistance and fatigue resistance such as FZG micropitting resistance, and is suitable as a speed increasing oil composition for wind power generation in which sludge generation is suppressed in an oxidation test. A lubricating oil composition can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0007] The lubricating oil composition of the present invention comprises a base oil, (A) an alkyl alkyl phosphate having 6 to 20 carbon atoms in an alkyl group, (B) a dialkylamine and / or a trialkylamine, In addition, (C) (c 1) a sulfur compound not containing polysulfur bonds of S—S—S or more in the molecule and having an S content of 15% by mass or more in the molecule is defined as 0.2 to 0.6% by weight and optionally (c 2) —general formula (I)

(R-O-) P = S… (I)

(In the formula, R represents a hydrocarbyl group having 6 to 20 carbon atoms.)

In the Chiorin trihydrocarbyl ester 0-represented;! It was ~ 1 · 0 Weight ^_0/0 compounded, and P content in the composition is characterized in that it is a 150 to 500 mass ppm.

As the base oil used in the lubricating oil composition of the present invention, those having a kinematic viscosity at 40 ° C. in the range of 30 to 800 mm ² / s and a viscosity index of 80 or more are preferable. If the kinematic viscosity at 40 ° C is 30 mm ² / s or more, the evaporation loss is small. On the other hand, if it is 800 mm ² / s or less, the power loss due to viscous resistance is not so large. More preferably 40 ° C kinematic viscosity is 32~680mm 2 / s, it is preferable in particular 100 to 500 mm ² / s. If the viscosity index is 80 or more, the change in viscosity due to a change in temperature is small. The viscosity index is more preferably 100 or more, and further preferably 130 or more.

The pour point is preferably -25 ° C or lower. When this pour point is −25 ° C. or lower, the resulting lubricating oil composition has sufficient fluidity even in a low temperature environment. This pour point is more preferably 30 ° C or lower, and further preferably 40 ° C or lower.

The kinematic viscosity and viscosity index are values measured according to JIS K 2283, and the pour point is a value measured according to JIS K 2265.

[0008] As the base oil, it is possible to use both mineral oils and synthetic oils that are not particularly limited in their types. Here, various conventionally known mineral oils are used. For example, paraffin-based mineral oils, intermediate-based mineral oils, naphthenic-based mineral oils, etc., and specific examples include light neutral oil, medium neutral oil, heavy neutral oil by solvent refining or hydrogen refining, or Bright stock etc. can be mentioned. As the synthetic oil, various conventionally known oils can also be used. For example, poly α-olefin, polybutene, polyol ester, dibasic acid ester, phosphoric ester ester, polyphenyl ether, alkylbenzene, alkyl Naphthalene, polyoxyanol glycolene, neopentino glycolol, silicone oil, trimethylol propane, pentaerythritol, hindered ester and the like can be used. These base oils can be used alone or in combination of two or more kinds, and mineral oil and synthetic oil may be used in combination.

In the lubricating oil composition of the present invention, the acidic phosphoric acid alkyl ester having an alkyl group having a carbon number of ˜20 used as the component (Α) has the general formula (式)

[0010] [Chemical 1]

[0011] A compound represented by the following can be used.

In the general formula (式), X ¹ represents a hydrogen atom or an alkyl group having 6 to 20 carbon atoms, and X ² represents an alkyl group having 6 to 20 carbon atoms.

Examples of the alkyl group having 6 to 20 carbon atoms may be linear, branched or cyclic. Examples thereof include various hexyl groups, octyl groups, decyl groups, dodecyl groups, tetradecyl groups, hexadecyl groups. Group, octadecyl group, icosyl group and the like. Among these, an alkyl group having 10 to 18 carbon atoms is preferable.

Examples of the acidic phosphoric acid alkyl esters represented by the general formula (Π) include monoota

Nomyristyl acid phosphate, monopalmityl acid phosphate, monostearinole Acid phosphate monoesters such as acid phosphate, dioctyl acid phosphate, sulfate, di (tridecyl) acid phosphate, dipalmityl acid phosphate, distearyl acid phosphate and the like.

In the present invention, as the component (A), the acidic phosphates may be used alone or in combination of two or more. Also, the blending amount requires that the total P content in the lubricating oil composition be 150 to 500 ppm by mass. If the P content is less than 150 ppm by mass, the seizure resistance is insufficient. On the other hand, if it exceeds 500 ppm by mass, the fatigue resistance (FZG micropitting resistance) decreases. More preferred! /, P content is 250 to 450 ppm by mass, more preferably 350 to 400 ppm by mass.

The test methods for seizure resistance and fatigue resistance are shown below.

(1) FZG seizure test

ASTM D 5182—91 ί compliant, 90. The test is displayed at 15 ° C, 15 minutes at C, and at the stage where the rolling load is generated.

(2) Timken test

In accordance with ASTM D 2782, test at 800 rpm for 10 minutes and display as seizure V and maximum load (lbs).

<Fatigue resistance> In the above FZG seizure test, display on the micropitting load stage.

[0013] In the lubricating oil composition of the present invention, the dialkylamines and / or trialkylamines used as the component (B) preferably have 6 to 20 carbon atoms in the alkyl group.

Examples of dialkylamines include dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, and examples of trialkylamines include trihexylamine, tricyclohexylamine, trioctylamine. Amamine, trilaurylamine, tristearylamine and the like can be mentioned. In the lubricating oil composition of the present invention, as the component (B), the dialkylamines or trialkylamines may be used alone or in combination of two or more thereof. Among them, trialkylamines are preferable from the viewpoint of performance. In addition, seizure resistance decreases with monoalkylamines.

The blending amount of the component (B) is preferably selected so that the mass ratio of [P in the component (A)] / [N in the component (B)] is 1.7 to 2.1. If the mass ratio is 1.7 or more, seizure resistance is good, and if it is 2.1 or less, the formation of sludge in the oxidation test is suppressed.

[0014] In the lubricating oil composition of the present invention, as the sulfur compound of component (C), (c 1) the molecule contains no S-S-S or higher polysulfur bond and the S content in the molecule A sulfur compound with a content of 15% by weight or more, and optionally (c 2) —the general formula (I)

(R-O-) P = S (I)

(In the formula, R represents a hydrocarbyl group having 6 to 20 carbon atoms.)

Thiophosphoric acid trihydrocarbyl esters represented by the formula:

When the sulfur compound of component (c 1) is a compound having a polysulfur bond greater than or equal to S—S—S in the molecule, in addition to the generation of sludge in the Indiana oxidation test, the FZG resistance against micropitting Decreases. In addition, if the S content in the molecule is less than 15% by mass, the effect of adding the sulfur compound may not be sufficiently exerted, and the seizure resistance may be insufficient. For example, the following compound can be cited by the force S.

(1) Mono or disulfide olefin

(2) Dihydrocarbyl mono or disulfide

(3) Thiadiazole compounds

(4) Dithiocarbamate compounds

(5) Ester compound having disulfide structure

(6) Other sulfur compounds

[0015] [mono or disulfide olefin]

As the olefin fin, for example, the following general formula (III) R ¹ — S -R ² ---(I)

a

(In the formula, R ¹ represents an alkenyl group having 2 to 15 carbon atoms, R ² represents an alkyl group or alkenyl group having 2 to 15 carbon atoms, and a represents 1 or 2.)

The compound etc. which are represented by these can be mentioned. This compound is obtained by reacting olefins having 2 to 15 carbon atoms or dimers or tetramers thereof with a sulfurizing agent such as sulfur or sulfur chloride. Examples of the olefins include propylene, isobutene and diisobutene. Is preferred.

[Dihydrocarbyl mono or disulfide]

As dihydrocarbyl mono or disulfide, the following general formula (IV)

R ³ — S -R ⁴ ---(IV)

b

(In the formula, R ³ and R ⁴ are each an alkyl group or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or 7 to 20 carbon atoms. And these may be the same or different from each other. B represents 1 or 2.)

It is a compound represented by these. Here, when R ³ and R ⁴ are alkyl groups, they are referred to as alkyl sulfides.

Examples of the dihydrocarbyl mono or disulfide represented by the general formula (IV) include dibenzyl mono or disulfide, various dinonyl mono or disulfide, various didodecyl mono or disulfide, various dibutyl mono or disulfide, various dioctyl mono or Preferred examples include disulfide, diphenyl mono or disulfide, dicyclohexyl mono or disulfide.

[Thiadiazole compounds]

Examples of the thiadiazole compound include 2,5 bis (n-hexyldithio) 1,3,4-chiasia zonole, 2,5 bis (n otachinoreschio) 1,3,4 thiodiazonore, 2,5-bis (n nonyldithio) ) 1, 3, 4-thiadiazole, 2,5-bis (1, 1, 3, 3, 3-tetramethinolevbutinoresitio) 1, 3, 4-thiadiazonore, 3,5-bis (n-hexinoresio) 1 , 2, 4—Thiadiazoles, 3, 6—Bis (n otachinoreschio) 1, 2, 4—Thiadiazoles, 3,5 Bis (n nonyldithio) 1, 2, 4 Thiadiazoles, 3, 5—Bis (1, 1, 3 , 3—Tetramethino Lebutino Resio) 1, 2, 4—Thiasia zonole, 4, 5 Bis (n-octyldithio) 1, 2, 3 thiadiazole, 4,5 Bis (n nonyldithio) 1, 2, 3-thiadiazonore, 4, 5-bis (1, 1, 3, 3, 3-tetramethinolebutinoresithio ) 1, 2, 3-thiadiazole and the like can be preferably mentioned.

[Dithiocarbamate compound]

Dithiocarnoite compounds include alkylene bisdialkyl dithiocarnomates. Among them, alkylene groups having 1 to 3 carbon atoms, linear or branched saturated or unsaturated alkyl groups having 3 to 20 carbon atoms, or A compound in which! / Is a cyclic alkyl group having 6 to 20 carbon atoms is preferably used. Specific examples of such a dithiocarbamate compound include one noite and methylenebistridecyl dithiocarnoite.

[Ester compound having disulfide structure]

Examples of ester compounds having a disulfide structure include general formula (V)

R ⁵ OOC-A ¹ -S-S-A-COOR ⁶ … (V)

And disulfide compounds represented by general formula (VI)

R ^U OOC-CR ¹³ R ¹⁴ -CR ¹⁵ (COOR ¹² ) S— S— R ²⁰ (COOR ¹⁷ ) — CR ¹⁸ R ¹⁹ — CO OR ¹⁶ ... (VI)

The disulfide compound represented by these is used.

In the general formula (V), R ⁵ and R ⁶ are each independently a hydrocarbyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 2 to 18 carbon atoms, particularly 3 carbon atoms. ~ 18 hydrocarbyl groups are preferred. The hydrocarbyl group may be linear, branched, or cyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom. R ⁵ and R ⁶ may be the same or different from each other, but they are preferably the same for reasons of manufacturing.

Next, A ¹ and A ² are each independently a group represented by CR ⁷ R ⁸ or CR ⁷ R ⁸ — CR ⁹ R ^1Q , and R ^{7 to} R ^1Q are each independently a hydrogen atom or a carbon number. 1-20 hydrocarbyl groups. The hydrocarbyl group preferably has 1 to 12 carbon atoms, and more preferably has 8 to 8 carbon atoms. A ¹ and A ² may be the same or different from each other, but are preferably the same for manufacturing reasons. On the other hand, in the general formula (VI), R ^u , R ¹² , R ^16, and R ¹⁷ are each independently a hydrocanolevinole group having 1 to 30 carbon atoms, preferably carbon number; Further, a hydrocarbyl group having 2 to 18 carbon atoms, particularly 3 to 18 carbon atoms is preferable. The hydrocarbyl group may be linear, branched, or cyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom. R ^u , R ¹² , R ¹⁶ and R ¹⁷ may be the same or different from each other, but are preferably the same for manufacturing reasons.

Next, R ^{13 to} R ¹⁵ and R ^{18 to} R ² ° are each independently a hydrogen atom or a hydrocarbyl group having 1 to 5 carbon atoms. A hydrogen atom is preferable because the raw material is easily available.

Specific examples of the disulfide compound represented by the general formula (V) include bis (methoxycarbonylmethyl) disulfide, bis (ethoxycarbonylmethyl) disulfide, bis (n-propoxycarbonylmethyl) disulfide, and bis (isopropoxy). Carbonylmethyl) ditoxoxycarbonylruthenole) disulfide, 1,1 bis (1-methoxycarbonolulu-n-propinole) disulfide, 1,1 bis (1-methoxycarbonolulubutynole) disulfide, 1,1-bis (1-methoxycarbox) 2-ruxhexyl) disulfide, 1,1-bis (1-methoxycarbonylnioctinole) disulfide, 2,2-bis (2-methoxycarbodilu-propinole) disulfide, α, a bis (α-methoxy) Carbonylbenzinore) disulfide, 1, 1 bis (2 —Methoxycarboletinole) disulfide, 1,1 bis (2-ethoxycarbonylethyl) disulfide, 1,1 bis (2-ηpropoxycarbonylethyl) disunorefido, 1,1 bis (2-isopropoxycarbonylruthenole) Disulfide, 1, 1 noreblonyl η-propinole) disulfide, 1,1 bis (2-methoxycarbonolu ηbutinole) disulfide, 1,1 bis (2-methoxycarboroyl ηhexyl) disulfide, 1,1 bis And (2 methoxycarbonoluene η-propinole) disulfide, 2,2 bis (3 methoxycarbonoluene η-pentinole) disulfide, 1,1 bis (2-methoxycarbonoluyl 1 phenylethyl) disulfide, and the like.

[0020] Specific examples of the disulfide compound represented by the general formula (VI) include tetramethyl dithiomalate, tetraethyl dithiomalate, tetra-1-propyl dithiomalate, dithio Tetra-2-propyl oleate, tetra-1-butyl dithiomalate, tetra-2-butyl dithiomalate, tetraisobutyl dithiomalate, tetra-1-dithiomalate, tetra-1-octyl dithiomalate, tetra-1-dithiomalate (2-ethyl) Hexyl, tetra-dithiomalate 1- (3,5,5-trimethyl) hexyl, tetra-decyl dithiomalate, tetra-1-didecyl malate, tetra-deciolate dithiomalate, 1-hexadecyl dithiomalate, tetra-octadecyl dithiomalate, tetrabenzil dithiomalate , Tetra-α- (methyl) benzyl dithiomalate, tetra-α-, α-dimethylbenzyl dithiomalate, tetra (2-methoxy) ethyl dithiomalate, tetra (1) (2-ethoxy) ethyl dithiomalate 1- (2-butoxy) ethyl dithiomalate, 1- (2-ethoxy) ethyl dithiomalate, 1- (2-butoxybutoxy) ethyl dithiomalate, tetra 1-dithiomalate (2-phenoxy) You can use the power S to raise your ethyl.

[Other sulfur compounds]

Other sulfur compounds include sulfurized lard, sulfurized rapeseed oil, sulfurized castor oil, sulfurized soybean oil, sulfurized rice bran oil, sulfurized fats and oils such as thioglycolic acid and sulfurized oleic acid, dilauryl thiodipropionate, disulfide. Examples include stearyl thiodipropi compounds and thioterpene compounds obtained by reacting phosphorus pentasulfide with pinene.

In the lubricating oil composition of the present invention, as the sulfur compound of component (c1), the above sulfur compounds may be used alone or in combination of two or more. Further, the blending amount of the component (c 1) requires that the lubricating oil composition contains 0.2 to 0.6 mass% as S. When the S content is less than 0.2% by mass, the seizure resistance is insufficient. On the other hand, when the S content exceeds 0.6% by mass, the fatigue resistance such as FZG micropitting resistance is inferior, and the Indiana oxidation test is performed. In this case, sludge generation increases. A preferable S content is 0.3 to 0.5% by mass.

The Indiana oxidation test is performed by the following method.

<Indiana oxidation test> In compliance with Standard's Indiana Oxidation Test Method, air was blown at a rate of 10 liters / hour into a 300 milliliter sample at 121 ° C for 312 hours. The amount is captured with a Millipore filter and weighed.

In the lubricating oil composition of the present invention, the component (c 2) is optionally represented by the general formula (I) (R-O-) P = S ··· (I)

Three

Thiophosphoric acid trihydrocarbyl esters represented by the formula:

R in the general formula (I) represents a hydrocarbyl group having 6 to 20 carbon atoms. The hydrocarbyl group is a linear, branched or cyclic alkyl group or alkenyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. In the above-mentioned aryl group and aralkyl group, one or more alkyl groups may be introduced on the aromatic ring. In addition, the three R 2 O groups may be the same or different.

Examples of the alkyl group and alkenyl group having 6 to 20 carbon atoms include various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, and cyclohexyl groups. Examples thereof include a xyl group, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, various octadecenyl groups, and cyclohexenyl groups.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, tolyl group, xylyl group, decylphenyl group, 2,4 didecylphenyl group, naphthyl group, etc., and aralkyl group having 7 to 20 carbon atoms. Examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a methylbenzyl group, a methylphenethyl group, and a methylnaphthylmethyl group. Specific examples of the trihydrocarbyl thiophosphate represented by the general formula (I) include trihexyl thiophosphate, tri-2-ethylhexyl thiophosphate, tris (decyl) thiophosphate, trilauryl thiophosphate, Trimyristyl thiophosphate, tripalmityl thiophosphate, tristearyl thiophosphate, trioleyl thiophosphate, tricresyl thiophosphate, trixylyl thiophosphate, tris (decylphenyleno) thiophosphate, tris [2,4 isoalkyl (C, C ) Hueninore] Choophoshue

9 10

And the like. These thiophosphate trihydrocarbyl phosphates are a single type. You can use it alone or in combination of two or more.

In the lubricating oil composition of the present invention, the thiophosphoric acid trihydrocarbyl ester of the component (c 2) is added as desired in order to further enhance the effect of adding the sulfur compound of the component (c 1). The amount added is preferably in the range of 0.;! To 1.0% by mass, more preferably 0.2 to 0.5% by mass, based on the total amount of the lubricating oil composition. However, the total P content in the lubricating oil composition must be 150 to 500 ppm by mass.

In the lubricating oil composition of the present invention, a partial ester of polyol can be further blended as component (D) if desired. This component (D) has an effect of further suppressing sludge formation in the Indiana oxidation test!

The polyol used as a raw material for the partial ester of the polyol is not particularly limited, and 1S aliphatic polyol is preferred, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, Dihydric alcohols such as neopentyl glycol, trihydric alcohols such as glycerin, trimethylol ethane, trimethylol propane, etc. Can you mention an ano rekorenore?

The number of ester bonds in the partial ester is not particularly limited as long as at least one hydroxyl group remains. The hydrocarbyl group constituting the ester bond is preferably an alkyl group or alkenyl group having 6 to 20 carbon atoms, such as various hexyl groups, octyl groups, decyl groups, dodecyl groups, tetradecyl groups, hexadecyl groups, Examples thereof include an otadecyl group, a hexenyl group, an otatur group, a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, and an octadecenyl group.

Specific examples of the partial ester of the polyol include neopentyl dallicol monolaurate, neopentinoreglycolole monomyristate, neopentinoreglycololemononoremitate, neopentinoreglycolole monostearate, neopentinorelate. Glycolol monoisostearate, trimethylolpropane mono or dilaurate, trimethylolpropane mono or dimyristate, trimethylolpropane mono or dipalmitate, trimethylolpropane mono or distearate, trimethylolpropane mono or diisostearate, glyceride Forces S that can include phosphorus mono or dilaurate, glycerin mono or distearate, glycerin mono or diisostearate, and the like are not limited thereto.

In the lubricating oil composition of the present invention, as the component (D), a partial ester of polyol may be used alone or in combination of two or more. The blending amount is usually about 5 to 20% by mass, preferably 7 to 15% by mass based on the total amount of the composition from the viewpoint of the effect of suppressing sludge generation in the Indiana oxidation test.

[0024] In the lubricating oil composition of the present invention, various additives such as an ashless detergent dispersant, an antioxidant, an antifungal agent, and a metal deactivator may be used as necessary without departing from the object of the present invention. It is possible to combine at least one selected from an agent, a viscosity index improver, a pour point depressant and an antifoaming agent.

Here, as the ashless detergent dispersant, for example, succinimides, boron-containing succinic acid imides, benzylamines, boron-containing benzylamines, succinic acid esters, fatty acids or succinic acid can be used. And carboxylic acid amides.

[0025] As the antioxidant, amine-based antioxidants, phenol-based antioxidants and sulfur-based antioxidants conventionally used in lubricating oils can be used. These antioxidants can be used singly or in combination of two or more. Examples of amine-based antioxidants include monoalkyldiphenylamine compounds such as monooctyldiphenylamine and monononyldiphenylamine, 4, 4 ′ dibutyldiphenylamine, 4, 4′- Dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, etc. Dialkyldiphenylamine compounds, tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, polyalkyldiphenylamine compounds such as tetranonyldiphenylamine, α-naphthylamine, phenyl-α Naphthylamine, butyl phenyl α naphthylamine, pentylphenyl α naphthylamine Hexyl phenyl chromatography α Nafuchiruamin, Hepuchirufu Eninore α Nafuchinoreamin, O lipped Honoré Hue Nino rate α Nafuchinoreamin include Nafuchiruamin based compounds such as Noninorefue two Honoré α Nafuchiruamin.

[0026] Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methyl. Monophenolic compounds such as phenol, 2, 6 di tert butyl-4-ethyl phenol, octadecyl 3- (3.5-di tert butyl 4-hydroxyphenol) propionate, 4, 4'-methylene bis (2, 6 di tert butyl phenol), Examples include diphenolic compounds such as 2,2, -methylenebis (4-ethyl-6-tert butylphenol).

Examples of sulfur-based antioxidants include 2, 6-di-tert-butyl 4- (4,6 bis (octylthio) -1,3,5 triazine-2-ylamino) phenol, and a reaction product of phosphorus pentasulfide and pinene. And dialkylthiodipropionates such as thioterpene compounds, dilauryl thiodipropionate, and distearyl thiodipropionate. Examples of antifungal agents include metal sulfonates and succinates, and examples of metal deactivators include benzotriazole and thiadiazole. Examples of viscosity index improvers include polymers. Tatalylate, dispersed polymetatalylate, olefinic copolymer (eg, ethylene propylene copolymer), dispersed olefinic copolymer, styrene copolymer (eg, styrene-hydrogenated copolymer) Etc.).

As the pour point depressant, use of polymetatalylate having a weight average molecular weight of about 50,000 to 150,000, etc., is performed with a force S.

As the antifoaming agent, a polymer silicone-based antifoaming agent or a polyacrylate-based antifoaming agent is preferred. Examples of the polymeric silicone antifoaming agent include organopolysiloxane, and fluorine-containing organopolysiloxane such as trifluoropropylmethyl silicone oil is particularly suitable.

The lubricating oil composition of the present invention is excellent in seizure resistance and fatigue resistance (FZG micropitting resistance, etc.) and generates less sludge in oxidation tests. For example, it is used as various lubricating oils such as gear oil and bearing oil. In particular, it is suitable as a lubricating oil used in a planetary gear type power transmission device used in a wind power generator. [0028] As described above, the present invention is a lubricating oil composition comprising a base oil, the components (A) to (C), and further these components and the component (D). , (A) to (C), and a lubricating oil composition containing these components and (D).

Example

[0029] Next, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

In addition, the properties of the use and the base oil in each example and the characteristics of the lubricating oil composition obtained in each example were determined according to the following methods.

(1) Kinematic viscosity, viscosity index

Measured according to JIS K 2283.

(2) Pour point

Measured according to JIS K 2265.

(3) FZG seizure test

The test was conducted according to the method described in the specification text. 13 stage pass is passed

(4) Timken test

The test was conducted according to the method described in the specification text. 451bs or more pass.

The test was conducted according to the method described in the specification text. 9 stage pass is passed.

(6) Indiana oxidation test

The test was conducted according to the method described in the specification text. Sludge amount of 10 or less by Millipore filter is acceptable.

Moreover, the kind of each component used for preparation of a lubricating oil composition is as follows.

(1) Base oil: PAO, a-olefin oligomer, 40 ° C kinematic viscosity 390mm ² / s, viscosity index 149, pour point 50 ° C or less

(2) Acidic phosphate ester 'Isodecyl: acid phosphoric acid (molybdenum) isodecyl ester (mixing ratio of mono and di = 1: 1)

'Tridecyl: acid phosphoric acid (molybdenum) tridecyl ester (mono, di mixed molar ratio = 1: 1

)

• Isoamyl: acid phosphoric acid (moly di) isoamyl ester (mixing ratio of mono and di = 1: 1). 2-ethyl hexyl: acid phosphoric acid (moly di) 2-ethyl hexyl ester (mono, di) Di mixing molar ratio = 1: 1)

'Oleil: acid phosphoric acid (molydi) oleyl ester (mixing molar ratio of molydi) = 1: 1)

(3) Amines

• Trioctylamine

'Dodecylamine

(4) Sulfur compounds

'Dithiocarbamate: Methylenebisdibutyldithiocarbamate: S content 30 mass

%

'Thiophosphate: Tris (2,4 diisoalkyl (C, C) phenyl) thiophosphie

9 10 g, S content 44% by mass

• Dibutyl dithioglycolate: S content 20% by mass

'Thiadiazole: 1,5,5-bis (1,1,3,3 tetramethylbutanedithio) 1,3,4-thiadiazole, S content 39 mass. / ₀

• Butene sulfide: containing trisulfide bond (mono, di, tri, tetrasulfide S: x average value

X

2.3), S content 40% by mass

(5) Polyol ester

Partial ester: ester of trimethylolpropane and isostearic acid (molar ratio 1: 2) Complete ester: ester of trimethylolpropane and isostearic acid (molar ratio 1: 3)

(6) Antioxidants

A: Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

Β: 4, 4'—Dioctyldiphenylamine (7) Antifungal agent: Dialkylaminomethylbenzotriazole

[0031] Examples;! To 8 and comparative examples;! To 7

A lubricating oil composition having the composition shown in Table 1 was prepared, and various properties of the composition were determined. The results are shown in Table 1.

[0032] [Table 1]

Table 1 1

[0033] [Table 2] Table 1 1

3] Table 1 1

As can be seen from Table 1, the examples;! To 5 are also passed in the Timken test, the FZG seizure test, the FZG microphone pitch test and the Indiana oxidation test. In Example 6, no polyol partial ester was added, and in Example 7, a complete polyol ester was added. In both cases, sludge generation was slightly higher in the Indiana oxidation test. In Example 8, acidic 2-ethylhexyl ester having an alkyl group having 8 carbon atoms is used as the acidic phosphate ester, and sludge generation is slightly increased in the Indiana oxidation test. In Comparative Examples 1 to 6, any one of the prescribed requirements in the present invention is removed, and therefore the performance is inferior to that of the Examples.

The commercially available product (Comparative Example 7) produces significantly more sludge in the Indiana oxidation test.

Yes

Industrial applicability

The lubricating oil composition of the present invention is excellent in seizure resistance and fatigue resistance such as FZG micropitting resistance, and various lubricating oils such as gear oils and bearing oils that generate less sludge in an oxidation test, especially wind power. It is suitable as a lubricating oil used in a speed increaser such as a planetary gear type power transmission device used in a generator.

Claims

The scope of the claims

[1] Base oil and (A) alkyl phosphate alkyl ester having 6 to 20 carbon atoms in alkyl group, (B) dialkylamine and / or trialkylamine, and (C) (c1) molecule A sulfur compound not containing a polysulfur bond of S—S—S or more and having an S content in the molecule of 15% by mass or more as S is 0.2 to 0.6% by mass and optionally ( c 2) —General formula (I)

(R-O-) P = S… (I)

(In the formula, R represents a hydrocarbyl group having 6 to 20 carbon atoms.)

Lubrication becomes ~ to 1 · 0 Weight ^_0/0 formulation, and the P content in the composition is characterized in that 150 to 500 mass ppm;! A Chiorin trihydrocarbyl ester represented 0 · in Oil composition.

[2] The component (B) is blended so that the mass ratio of [P in the component (A)] / [N in the component (B)] is 1.7 to 2.1. The lubricating oil composition described.

[3] The lubricating oil composition according to claim 1, wherein the component (B) is a trialkylamine having an alkyl group having 6 to 20 carbon atoms.

[4] The lubricating oil composition according to claim 1, further comprising (D) 5 to 20% by mass of a polyol partial ester.

[5] The lubricating oil composition according to any one of [1] to [4], wherein the lubricating oil composition is a gearbox oil composition for wind power generation.