CN105018189A

CN105018189A - Lubricating oil compound

Info

Publication number: CN105018189A
Application number: CN201410181383.7A
Authority: CN
Inventors: 菅原常年
Original assignee: JX Nippon Oil and Energy Corp
Current assignee: Eneos Corp
Priority date: 2014-04-30
Filing date: 2014-04-30
Publication date: 2015-11-04

Abstract

The invention provides a lubricating oil compound which can well achieve oily sludge inhibition performance, abrasion resistance and the friction characteristic through high-level balance and is excellent in water separation performance. According to the lubricating oil compound, mineral oil and/or synthetic oil serve/serves as base oil. With the total amount of the compound being reference, the compound comprises, by mass, 0.01-2% of a chalcogenide extreme pressure agent (A), 0.01-5% of a phosphate ester extreme pressure agent (B) and 0.01-3% of an antioxidant (C). The kinematic viscosity of the compound at the temperature of 40 DEG C ranges from 22 mm<2>/s to 4600 mm<2>/s.

Description

Lubricating oil composition

Technical field

The present invention relates to lubricating oil composition.In particular to the lubricating oil composition being suitable as gear grease.

Background technology

Seek as social demand in recent years to save the energy, gear grease is also required to make great efforts to reduce frictionloss and improves mechanical efficiency.As the method for tackling this demand, can list: seek the method for the lowering viscousity of lubricating oil, use (patent documentations 1) such as the methods of excellent low friction compound.

But the tendency having the load putting on face of gear caused by high-efficiency homework, running to increase further in recent years, becomes and is difficult to further for lubricating oil lowering viscousity.

Summary of the invention

the problem that invention will solve

The present invention makes in view of the above circumstances, and object is to provide a kind of lubricating oil composition, by developing excellent low friction compound and need not lowering viscousity, reduces friction effect high and can realize saving the energy.

for the scheme of dealing with problems

The present inventor etc. further investigate to solve the problem, and result completes the present invention.

Namely, the present invention is a kind of lubricating oil composition, oil based on mineral oil and/or synthetic oil, in total composition benchmark containing (A) sulphur system extreme pressure agent 0.01 ~ 2 quality %, in total composition benchmark containing (B) phosphoric acid ester system extreme pressure agent 0.01 ~ 5 quality %, in total composition benchmark containing (C) antioxidant 0.01 ~ 3 quality %, kinematic viscosity during 40 DEG C of composition is 22 ~ 4600mm ²/ s.

the effect of invention

The reduction friction effect of lubricating oil composition of the present invention high and can realize save the energy, can tackle in recent years machinery high-efficiency homework.Particularly be suitable as the lubricating oil of gear.

Accompanying drawing explanation

Fig. 1 is for illustrating disk in SRV (reciprocal fine motion friction) test and the configuration of ball and the figure of action.

Embodiment

Below, describe the present invention.

Lubricating oil composition of the present invention contains oil based on mineral oil and/or synthetic oil.

As mineral oil, can enumerate: for the lubricating oil distillate that crude oil atmospheric distillation and underpressure distillation are obtained, utilize the one kind or two or more refining means such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrofining, sulfuric acid scrubbing, clay treatment and the mineral oil such as the paraffin series obtained or cycloalkanes hydrocarbon system by appropriately combined.

As synthetic oil, can exemplify such as: poly-alpha olefins (ethylene-propylene copolymer, polybutene, 1-octene oligomers, 1-decene oligopolymer and their hydride etc.); Alkylbenzene, alkylnaphthalene, monoesters (butyl stearate, octyl laurate); Diester (pentanedioic acid double tridecyl ester, hexanodioic acid two (2-ethylhexyl) ester, diisodecyl adipate, hexanodioic acid two (tridecyl) ester, sebacic acid two (2-ethylhexyl) ester etc.); Polyester (trimellitate etc.); Polyol ester (trimethylolpropane caprylate, TriMethylolPropane(TMP) pelargonate, tetramethylolmethane-2-ethylhexanoate, tetramethylolmethane pelargonate etc.); Polyether polyols; Polyphenylene ether; Dialkyl diphenyl ether; Phosphoric acid ester (tricresyl phosphate etc.); Fluorochemicals (PFPE, fluorinated polyolefin etc.); Silicone oil, synthetic wax FT to be reacted etc. and/or by the wax obtained in petroleum refinement operation (preferably by the slack wax obtained in solvent dewaxing operation) isomerization, hydrogenation and the high-performance hydrocarbon base oil obtained, hydrocarbon base wet goods that the unsaturated hydrocarbons hydrogenation of natural origin such for terpene is obtained.

As the base oil of lubricating oil composition of the present invention, can be used alone above-mentioned base oil, also can combinationally use two or more.

For the kinematic viscosity of base oil of the present invention, there is no particular limitation, excellent and by stirring the viewpoints such as frictionloss that resistance causes is few from rubbing characteristics, cooling (heat abstraction), kinematic viscosity when 40 DEG C is generally 5 ~ 1,000mm ²/ s, is preferably 7 ~ 500mm ²/ s, is more preferably 10 ~ 200mm ²/ s.

For the viscosity index of base oil of the present invention, have no particular limits, from viewpoints such as oil film minimizings during suppression high temperature, be preferably 80 ~ 500, be more preferably 100 ~ 300.

Pour point also can be arbitrary, but from the viewpoint such as startability of pump in winter, pour point is generally less than-5 DEG C, is preferably less than-15 DEG C.

Lubricating oil composition of the present invention contains sulphur system extreme pressure agent as (A) composition.

(A) sulphur system extreme pressure agent preferably uses such as: thiazolium compounds, thiadiazole compound, sulfide, sulfide aliphatic acid, sulfuration ester, sulfurized mineral oil, phosphorodithioic acid zn cpds, zinc dithiocarbamate compound, phosphorodithioic acid molybdenum compound, molybdenum dithiocarbamate compound, alkylthio carbamoyl compounds, thiocarbamate compound, sulfo-terpene compound, dialkyl thiodipropionate compound.

As thiazolium compounds, preferably use following general formula (1), compound represented by (2).

In formula (1), (2), R ¹and R ²represent alkyl or the amino of hydrogen atom, carbonatoms 1 ~ 30 respectively; R ³represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4; A and b represents the integer of 0 ~ 3.

Among them, the benzothiazole compound particularly preferably represented by above-mentioned general formula (2).Herein, the R in above-mentioned general formula (2) ²as previously mentioned, alkyl or the amino of hydrogen atom, carbonatoms 1 ~ 30 is represented; R ²be preferably the alkyl of hydrogen atom or carbonatoms 1 ~ 18, be more preferably the alkyl of hydrogen atom or carbonatoms 1 ~ 12.

In addition, the R in above-mentioned general formula (2) ³represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4 as previously mentioned; R ³be preferably the alkyl of hydrogen atom or carbonatoms 1 ~ 3, be more preferably the alkyl of hydrogen atom or carbonatoms 1 ~ 2.

And then the b in above-mentioned general formula (2) represents the integer of 0 ~ 3 as previously mentioned; B is preferably 0 ~ 2.

As the concrete example of such benzothiazole compound; can list: benzothiazole, 2-mercaptobenzothiazole, 2-(hexyl dithio) benzothiazole, 2-(octyl group dithio) benzothiazole, 2-(decyl dithio) benzothiazole, 2-(molybdenum didodecyl dithiophosphate) benzothiazole, 2-(N, N-diethyl-dithio formamyl) benzothiazole etc.

As thiadiazole compound, can list such as: represented by following general formula (3) 1,3,4-thiadiazoles, 1,2,4-thiadiazole compound represented by following general formula (4) and 1 represented by following general formula (5), 4,5-thiadiazole compound.

[in formula (3) ~ (5), R ⁴~ R ⁹optionally identical or different, represent the alkyl of hydrogen atom or carbonatoms 1 ~ 20 respectively; C, d, e, f, g and h are optionally identical or different, represent the integer of 0 ~ 8 respectively.]

As the concrete example of such thiadiazole compound, preferably can list: 2, two (the n-hexyl dithio)-1 of 5-, 3, 4-thiadiazoles, 2, two (the n-octyl dithio)-1 of 5-, 3, 4-thiadiazoles, 2, two (the n-nonyl dithio)-1 of 5-, 3, 4-thiadiazoles, 2, 5-two (1, 1, 3, 3-tetramethyl butyl dithio)-1, 3, 4-thiadiazoles, 3, two (the n-hexyl dithio)-1 of 5-, 2, 4-thiadiazoles, 3, two (the n-octyl dithio)-1 of 5-, 2, 4-thiadiazoles, 3, two (the n-nonyl dithio)-1 of 5-, 2, 4-thiadiazoles, 3, 5-two (1, 1, 3, 3-tetramethyl butyl dithio)-1, 2, 4-thiadiazoles, 4, two (the n-hexyl dithio)-1 of 5-, 2, 3-thiadiazoles, 4, two (the n-octyl dithio)-1 of 5-, 2, 3-thiadiazoles, 4, two (the n-nonyl dithio)-1 of 5-, 2, 3-thiadiazoles, 4, 5-two (1, 1, 3, 3-tetramethyl butyl dithio)-1, 2, 3-thiadiazoles and their mixture etc.

Sulfide specifically, refers to the compound represented by following general formula (6).

R ¹⁰-Sx-R ¹¹(6)

[in formula (6), R ¹⁰and R ¹¹optionally identical or different, represent alkyl respectively separately; X represents the integer of more than 1, be generally 1 ~ 8, the integer of preferably 2 ~ 6, more preferably 2 ~ 5]

Alkyl can list such as: the arylalkyl of the straight-chain of carbonatoms 3 ~ 20 or the alkyl of branched, the aryl of carbonatoms 6 ~ 20, the alkylaryl of carbonatoms 6 ~ 20 or carbonatoms 6 ~ 20.

More specifically, can list: the alkyl of the various straight-chain such as propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or branched;

The aryl such as phenyl, naphthyl;

Tolyl, ethylphenyl, xylyl, ethyl methyl phenyl, diethyl phenyl, linear propyl phenyl or branched chain propyl phenyl, straight chain butyl phenyl or branched butyl group phenyl, straight chain pentyl phenyl or branched pentyl phenyl, linear hexyl phenyl or branched hexyl phenyl, linear heptyl phenyl or branched heptyl phenyl, straight chain octyl phenyl or branched octyl phenyl, straight chain nonyl phenyl or branched nonyl phenyl, straight chain decyl phenyl or branched chain decyl phenyl, straight chain undecyl phenyl or side chain undecyl phenyl, linear dodecylbenzene base or side chain dodecyl benzen base, two (straight or branched) propyl group phenyl, two (straight or branched) butyl phenyl, methyl naphthyl, ethyl naphthyl, linear propyl naphthyl or branched chain propyl naphthyl, straight chain butyl naphthyl or branched butyl group naphthyl, dimethyl naphthyl, ethyl-methyl naphthyl, diethyl naphthyl, two (straight or branched) propyl group naphthyl, the alkylaryls such as two (straight or branched) butyl naphthyl, the aralkyl such as benzyl, phenylethyl, phenyl propyl, Deng,

Comprise whole isomer and the constitutional isomer of all compounds.

Wherein, as the R in general formula (6) ¹⁰and R ¹¹, the alkyl of the carbonatoms 3 ~ 18 preferably derived by propylene, 1-butylene or iso-butylene or the aryl of carbonatoms 6 ~ 8, alkylaryl or arylalkyl; It is particularly preferably the alkyl of the carbonatoms 3 ~ 18 derived by propylene, 1-butylene or iso-butylene.As these groups, can list such as: by sec.-propyl, the branched hexyl that propylene 2 aggressiveness is derivative, the branched nonyl derivative by propylene 3 aggressiveness, the branched dodecyl derivative by propylene 4 aggressiveness, the branched pentadecyl derivative by propylene 5 aggressiveness, the branched octadecyl derivative by propylene 6 aggressiveness, sec-butyl, the tertiary butyl, the branched octyl group derivative by 1-butylene 2 aggressiveness, the branched octyl group derivative by iso-butylene 2 aggressiveness, the branched dodecyl derivative by 1-butylene 3 aggressiveness, the branched dodecyl derivative by iso-butylene 3 aggressiveness, the branched hexadecyl derivative by 1-butylene 4 aggressiveness, the alkyl such as the branched hexadecyl derivative by iso-butylene 4 aggressiveness, any one includes all branched isomer.

And then, in above-mentioned alkyl, improve from the view point of wear resistant, be preferably alkyl.That is, in sulfide, most preferably dialkyl sulfide.

As abovementioned alkyl, more specifically, be more preferably by the branched-chain alkyl of the carbonatoms 3 ~ 18 of ethene or propylene derived, particularly preferably by the branched-chain alkyl of the carbonatoms 6 ~ 15 of ethene or propylene derived.

As the concrete example of sulfide, can list: dibutyl polysulfide, dihexyl polysulfide, dioctyl polysulfide, dinonyl polysulfide, didecyl polysulfide, two (dodecyl) polysulfide, two (tetradecyl) polysulfide, two (hexadecyl) polysulfide, two (octadecyl) polysulfide, two (eicosyl) polysulfide, diphenyl polysulfide, dibenzyl polysulfide, Diphenethyl polysulfide, polypropylene-base polysulfide, polybutylene-based polysulfide and their mixture etc.

For the manufacture method of sulfide, there is no particular limitation, can use known manufacture method.Such as, by carrying out sulfidizing to alkene, olefine sulfide sulfides can be obtained.

As olefine sulfide, can list such as: by the compound represented by following general formula (7).This compound reacts by making the alkene of carbonatoms 2 ~ 15 or its two ~ tetramer and the vulcanizing agent such as sulphur, sulfur subchloride and obtains, as this alkene, and preferred propylene, iso-butylene, diisobutylene etc.

R ¹²-Sy-R ¹³(7)

[in formula (7), R ¹²and R ¹³optionally identical or different, represent the alkyl or alkenyl of carbonatoms 2 ~ 15 separately respectively, y represents the integer of 1 ~ 8.]

As the example of sulfide aliphatic acid, sulfuration oleic acid etc. can be listed.

As sulfuration ester, can list such as: tallow, lard, fish tallow, rapeseed oil, soybean wet goods animal-plant oil; The unsaturated fatty acid ester that unsaturated fatty acids (fatty acid etc. comprising oleic acid, linolic acid or extracted by above-mentioned animal-plant oil) and various alcohol react and obtains; And by sulfuration ester that the sulfurations such as these mixture obtain by arbitrary method.More specifically, can list: sulfuration Witconol 2301, the misery ester of sulfuration rice bran fats and their mixture etc.

Material grease sulfuration obtained is such as: sulfurized lard, sulfuration rapeseed oil, sulfurized castor oil, sulfurized soybean oil, sulfuration rice bran wet goods are also referred to as sulfuration grease.

Sulfurized mineral oil instigates elemental sulfur to be dissolved in material in mineral oil., for being used as the mineral oil of sulfurized mineral oil described in the present invention, having no particular limits herein, the mineral oil in base oil of the present invention can be used as and the material enumerated.In addition, as elemental sulfur, the elemental sulfur of arbitrary forms such as bulk, Powdered, melting is aqueous can be used; If use Powdered or that melting is aqueous elemental sulfur, can efficiency carry out well dissolving in base oil, thus preferably.For the sulphur content in sulfurized mineral oil, have no particular limits, be usually preferably 0.05 ~ 1.0 quality % in sulfurized mineral oil total amount for benchmark, be more preferably 0.1 ~ 0.5 quality %.

Phosphorodithioic acid zn cpds, zinc dithiocarbamate compound, phosphorodithioic acid molybdenum compound and molybdenum dithiocarbamate compound refer to the compound represented by following general formula (8) ~ (11) respectively.

[in formula (8) ~ (11), R ¹⁴~ R ²⁹optionally identical or different, represent the alkyl of carbonatoms more than 1 respectively, X ¹and X ²represent Sauerstoffatom or sulphur atom respectively.]

Herein, if illustrate R ¹⁴~ R ²⁹the concrete example of represented alkyl, except methyl and ethyl, can list: the alkyl such as propyl group, butyl, amyl group, hexyl (comprising all branched chain isomers), heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, any one includes all branched chain isomers;

The cycloalkyl such as cyclopentyl, cyclohexyl, suberyl;

Methylcyclopentyl, ethylcyclopentyl, dimethylcyclopentyl, propyl group cyclopentyl, methylethyl cyclopentyl, trimethylammonium cyclopentyl, butyl cyclopentyl, methyl-propyl cyclopentyl, diethyl cyclopentyl, dimethyl ethyl cyclopentyl, methylcyclohexyl, ethylcyclohexyl, Dimethylcyclohexyl, propylcyclohexyl, methylethyl cyclohexyl, trimethylcyclohexyl, butylcyclohexyl, methyl-propyl cyclohexyl, diethyl cyclohexyl, dimethyl ethyl cyclohexyl, methylcycloheptyl, ethylcyclohexyl, dimethyl-cyclopentyl, propyl group suberyl, methylethyl suberyl, trimethylammonium suberyl, butyl suberyl, methyl-propyl suberyl, diethyl suberyl, the alkyl-cycloalkyls such as dimethyl ethyl suberyl, any one includes all replacement isomer and branched chain isomer,

The aryl such as phenyl, naphthyl;

The alkylaryls such as tolyl, xylyl, ethylphenyl, propyl group phenyl, methylethyl phenyl, trimethylphenyl, butyl phenyl, methyl-propyl phenyl, diethyl phenyl, dimethyl ethyl phenyl, amyl group phenyl, hexyl phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl, undecyl phenyl, dodecylphenyl, tridecyl phenyl, tetradecyl phenyl, pentadecylphenyl, hexadecyl phenyl, heptadecyl phenyl, octadecylphenyl, any one all comprises all replacement isomer and branched chain isomer;

The arylalkyls etc. such as benzyl, styroyl, phenyl propyl (comprising all branched chain isomers), phenyl butyl (comprising all branched chain isomers).

As alkylthio carbamoyl compounds, the compound such as represented by following general formula (12) can be listed.

[in formula (6), R ³⁰~ R ³³optionally identical or different, represent the alkyl of carbonatoms 1 ~ 20 respectively, i represents the integer of 1 ~ 8.]

As the concrete example of such alkylthio carbamoyl compounds, preferably can list: two (dimethylthiocarbamoyl) single sulfide, two (dibutyl thiocarbamoyl) single sulfide, two (dimethylthiocarbamoyl) disulphide, two (dibutyl thiocarbamoyl) disulphide, two (diamyl thiocarbamoyl) disulphide, two (dioctylthio formamyl) disulphide and their mixture etc.

As alkylthio carbamate compounds, the compound such as represented by following general formula (13) can be listed.

[in formula (13), R ³⁴~ R ³⁷optionally identical or different, represent the alkyl of carbonatoms 1 ~ 20 respectively, R ³⁸represent the alkylidene group of carbonatoms 1 ~ 10.]

As the concrete example of such alkylthio carbamate compounds, preferably can list: methylene-bis (Keywords dibutyl dithiocarbamate), methylene-bis [two (2-ethylhexyl) dithiocarbamate] etc.

And then, can list such as sulfo-terpene compound: the reaction product of thiophosphoric anhydride and firpene, can list such as dialkyl thiodipropionate compound: thiodipropionate dilauryl, distearylthiodi-propionate and their mixture etc.

In the present invention, in above-mentioned sulphur system extreme pressure agent, obtain the raising effect of abrasion performance characteristic, preferred sulfide from the view point of with more high level.Wherein, preferred dialkyl sulfide.The alkyl of dialkyl sulfide is preferably the alkyl of carbonatoms 2 ~ 5, particularly preferably isobutyl-.The alkene sulfurations such as iso-butylene also can obtain by dialkyl sulfide.

(A) content of sulphur system extreme pressure agent take total composition as benchmark, is more than 0.01 quality %, is preferably more than 0.05 quality %, is more preferably more than 0.1 quality %.On the other hand, content is below 2 quality %, is preferably below 1.5 quality %, is more preferably below 1 quality %.

If content is less than 0.01 quality %, wear resistant becomes insufficient, in addition, if more than 2 quality %, can not get the wear resistant corresponding to content and improves effect, not preferred from the viewpoint of economy.

Lubricating oil composition of the present invention contains phosphoric acid ester system extreme pressure agent as (B) composition.

(B) phosphoric acid ester system extreme pressure agent refers to (B1) neutral ortho-phosphoric acid ester, (B2) acid ortho-phosphoric acid ester, (B3) phosphorous acid ester or their mixture.

(B1) compound of neutral ortho-phosphoric acid ester represented by following general formula (14).

(in formula, R ³⁹~ R ⁴¹optionally identical or different, represent the saturated hydrocarbyl of carbonatoms 1 ~ 20 or the aryl of carbonatoms 6 ~ 15, be preferably saturated hydrocarbyl.)

The carbonatoms of saturated hydrocarbyl is 1 ~ 20, is preferably 4 ~ 12, is more preferably 8 ~ 12.As saturated hydrocarbyl, can list: alkyl, cycloalkyl, alkyl-cycloalkyl etc.As alkyl, cycloalkyl, alkyl-cycloalkyl, can list: methyl, ethyl, n-propyl, sec.-propyl, cyclopentyl, cyclohexyl, methylcyclopentyl etc.

The carbonatoms of aryl is 6 ~ 15, is preferably 6 ~ 9.Can list as aryl: phenyl, benzyl, tolyl (cresyl), xylyl etc.

As (B1) neutral ortho-phosphoric acid ester, can list such as: triphenyl, tricresyl phosphate, three (xylyl) phosphoric acid ester, cresyl diphenyl phosphate, xylyl diphenyl phosphoester, three (isopropyl phenyl) phosphoric acid ester, three (tert-butyl-phenyl) phosphoric acid ester, Tributyl phosphate ester (comprising straight chain and side chain), three pentyl (comprising straight chain and side chain), three hexyl phosphoric acid ester (comprising straight chain and side chain), three heptyl phosphoric acid ester (comprising straight chain and side chain), trioctyl phosphate (comprising straight chain and side chain), three nonyl phosphoric acid ester (comprising straight chain and side chain), three decylphosphonic acid esters (comprising straight chain and side chain), three (undecyl) phosphoric acid ester (comprising straight chain and side chain), three (dodecyl) phosphoric acid ester (comprising straight chain and side chain), three (tridecyl) phosphoric acid ester (comprising straight chain and side chain), three (tetradecyl) phosphoric acid ester (comprising straight chain and side chain), three (pentadecyl) phosphoric acid ester (comprising straight chain and side chain), three (hexadecyl) phosphoric acid ester (comprising straight chain and side chain), three (heptadecyl) phosphoric acid ester (comprising straight chain and side chain), three (octadecyl) phosphoric acid ester (comprising straight chain and side chain), three (oil base) phosphoric acid ester (comprising straight chain and side chain) etc.

Wherein, preferred triphenyl, tricresyl phosphate, three heptyl phosphoric acid ester (comprising straight chain and side chain), trioctyl phosphate (comprising straight chain and side chain), three nonyl phosphoric acid ester (comprising straight chain and side chain) and three decylphosphonic acid esters (comprising straight chain and side chain);

More preferably tricresyl phosphate and trioctyl phosphate (comprising straight chain and side chain);

And then preferred trioctyl phosphate (comprising straight chain and side chain);

Particularly preferably three (2-ethylhexyl) phosphoric acid ester.

(B2) compound of acid ortho-phosphoric acid ester represented by following general formula (15) or (16).

(in formula, R ⁴²~ R ⁴³optionally identical or different, represent the saturated hydrocarbyl of carbonatoms 4 ~ 20 or the aryl of carbonatoms 6 ~ 15, be preferably saturated hydrocarbyl.)

As saturated hydrocarbyl and aryl, the R as general formula (14) can be listed ³⁹~ R ⁴¹the group cited by concrete example.

(B2) acid ortho-phosphoric acid ester can list such as: monoalkyl acid ortho-phosphoric acid ester, dialkyl group acid ortho-phosphoric acid ester and their mixture.

The alkyl of these acid ortho-phosphoric acid alkyl esters is optionally the alkyl of straight-chain or branched, optionally saturated or unsaturated, but is preferably straight-chain.The carbonatoms of alkyl is 4 ~ 20, is preferably 6 ~ 16, is more preferably 6 ~ 10, most preferably is the straight-chain alkyl (n-octyl) of carbonatoms 8.In addition, the carbonatoms of 2 alkyl of dialkyl group acid ortho-phosphoric acid ester is optionally identical or different.

When carbonatoms is less than 4, solvability be deteriorated and not preferred.In addition, when carbonatoms is more than 20, the effect of per unit mass declines, thus not preferred.

As the alkyl of carbonatoms 4 ~ 20, specifically, can list: butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl; Saturated and undersaturated straight-chain group can be used respectively, or the group of saturated and undersaturated branched.

As (B2) acid ortho-phosphoric acid ester, can list such as: the positive butyl ester of acid phosphate list, acid phosphate list n-pentyl ester, the just own ester of acid phosphate list, the positive heptyl ester of acid phosphate list, acid phosphate list n-octyl, acid phosphate list ester in the positive ninth of the ten Heavenly Stems, acid phosphate list ester in the positive last of the ten Heavenly stems, acid phosphate list dodecyl ester, acid phosphate list Octadecane base ester, acid phosphate list isobutyl ester, acid phosphate list isopentyl ester, acid phosphate list dissident ester, acid phosphate list isocyanate, the different monooctyl ester of acid phosphate list, acid phosphate list ester in the different ninth of the ten Heavenly Stems, acid phosphate list isodecyl ester, acid phosphate list Permethyl 99A. base ester, acid phosphate list isocetyl ester, acid phosphate list isooctadecane base ester, acid phosphate di-n-butyl, acid phosphate two n-pentyl ester, the just own ester of acid phosphate two, the positive heptyl ester of acid phosphate two, acid phosphate di-n-octyl, acid phosphate two ester in the positive ninth of the ten Heavenly Stems, acid phosphate two ester in the positive last of the ten Heavenly stems, acid phosphate two dodecyl ester, acid phosphate two Octadecane base ester, acid phosphate diisobutyl ester, acid phosphate diisoamyl ester, acid phosphate two dissident ester, acid phosphate two isocyanate, acid phosphate diisooctyl ester, acid phosphate diisononyl esters, acid phosphate two isodecyl ester, acid phosphate two Permethyl 99A. base ester, acid phosphate two isocetyl ester, acid phosphate two isooctadecane base ester etc.

Wherein, the just own ester of preferred acid mono phosphoric acid ester, the positive heptyl ester of acid phosphate list, acid phosphate list n-octyl, acid phosphate list ester in the positive ninth of the ten Heavenly Stems, acid phosphate list ester in the positive last of the ten Heavenly stems, the just own ester of acid phosphate two, the positive heptyl ester of acid phosphate two, acid phosphate di-n-octyl, acid phosphate two ester in the positive ninth of the ten Heavenly Stems, acid phosphate two ester in the positive last of the ten Heavenly stems, acid phosphate two dissident ester, acid phosphate two isocyanate, acid phosphate di-isooctyl, acid phosphate dinonyl, acid phosphate two isodecyl ester;

More preferably acid phosphate list n-octyl, acid phosphate di-n-octyl, acid phosphate di-isooctyl and their mixture.

(B3) compound of phosphorous acid ester represented by following general formula (17) or (18).

(in formula, R ⁴⁴~ R ⁴⁶optionally identical or different, represent the saturated hydrocarbyl of carbonatoms 1 ~ 20 or the aryl of carbonatoms 6 ~ 15, be preferably saturated hydrocarbyl.)

As (B3) phosphorous acid ester, can list such as: the mixture etc. of dialkyl phosphites and trialkyl phosphite, wherein, the preferably mixture of two oil base phosphorous acid esters and three oil base phosphorous acid esters.

In the present invention, when containing (B1) phosphate compound as (B) composition, optional containing the arbitrary compound of (B1) ~ (B3), but from the view point of stability in storage, preferably (B1) neutral ortho-phosphoric acid ester, (B2) acid ortho-phosphoric acid ester or their mixture.

In total composition benchmark, the content of (B) phosphoric acid ester system extreme pressure agent is more than 0.01 quality %, is preferably more than 0.05 quality %, is more preferably more than 0.1 quality %.When content is less than 0.01 quality %, the raising effect of wear resistant and rubbing characteristics is had to become insufficient tendency.

On the other hand, content is below 5 quality %, is preferably below 3 quality %, is more preferably below 1 quality %.Even if also can not get the further raising effect of the wear resistant corresponding to content more than 5 quality %, the tendency also having oxidative stability and suppress greasy filth to reduce.

Lubricating oil composition of the present invention contains antioxidant as (C) composition.

For (C) antioxidant, have no particular limits, normally used antioxidant in lubricating oil can be used.Can list such as: (C1) phenol system antioxidant, (C2) amine system antioxidant.

As (C1) phenol system antioxidant, can be used as any phenol system compound that the antioxidant of lubricating oil is applied, there is no particular limitation, preferred following general formula (19) or the alkyl phenol compound represented by (20).

[in formula, R ⁴⁷represent the alkyl of carbonatoms 1 ~ 4, R ⁴⁸represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4, R ⁴⁹represent hydrogen atom, the alkyl of carbonatoms 1 ~ 4 or following general formula (i) or the group represented by (ii).

(in formula, R ⁵⁰represent the alkylidene group of carbonatoms 1 ~ 6, R ⁵¹represent the alkyl or alkenyl of carbonatoms 1 ~ 24.)

(in formula, R ⁵²represent the alkylidene group of carbonatoms 1 ~ 6, R ⁵³represent the alkyl of carbonatoms 1 ~ 4, R ⁵⁴represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4.)]

[in formula, R ⁵⁵and R ⁵⁷optionally identical or different, represent the alkyl of carbonatoms 1 ~ 4 respectively; R ⁵⁶and R ⁵⁸optionally identical or different, represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4 respectively; R ⁵⁹and R ⁶⁰optionally identical or different, represent the alkylidene group of carbonatoms 1 ~ 6 respectively; X represents the alkylidene group of carbonatoms 1 ~ 18 or the group represented by following general formula (iii).

-R ⁶¹-S-R ⁶²- (iii)

(in formula, R ⁶¹and R ⁶²optionally identical or different, represent the alkylidene group of carbonatoms 1 ~ 6 respectively.)]

As the R in general formula (19) ⁴⁷, specifically, can list: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc., from the view point of excellent oxidation stability, preferred tertiary butyl.

In addition, as R ⁴⁸, the alkyl of hydrogen atom or carbonatoms 1 ~ 4 described above can be listed, from the view point of excellent oxidation stability, preferable methyl or the tertiary butyl.

R in general formula (19) ⁴⁹when alkyl for carbonatoms 1 ~ 4, as R ⁴⁹can list: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc., from the view point of excellent oxidation stability, preferable methyl or ethyl.

In alkyl phenol compound represented by general formula (19), R ⁴⁹for the compound in the alkyl situation of carbonatoms 1 ~ 4, particularly preferably be 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenols and their mixture etc.

R in general formula (19) ⁴⁹when group represented by general formula (i), the R in general formula (i) ⁵⁰the optional straight-chain of alkylidene group of represented carbonatoms 1 ~ 6 or branched, specifically, can list such as: methylene radical, methylmethylene, ethylidene (dimethylene), ethyl methylene radical, propylidene (methyl ethylidene), the butylidene of trimethylene, straight or branched, the pentylidene of straight or branched, the hexylidene etc. of straight or branched.

From the view point of manufacturing the compound shown in general formula (19) with few reaction process, R ⁵⁰for the alkylidene group, specifically of carbonatoms 1 ~ 2, more preferably such as: methylene radical, methylmethylene, ethylidene (dimethylene) etc.

On the other hand, as the R of general formula (i) ⁵¹the alkyl or alkenyl of represented carbonatoms 1 ~ 24, optional straight-chain or branched, specifically, can to list such as: the alkyl (the optional straight-chain of these alkyl or branched) such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl; Thiazolinyl (the optional straight-chain of these thiazolinyls or the branched such as vinyl, propenyl, pseudoallyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base, vaccenic acid base, 18 carbon dialkylenes, 19 carbene bases, eicosylene base, heneicosene base, two dodecenyl succinic, tricosene base, tetracosa carbon thiazolinyl, in addition, the position of double bond is also arbitrary); Deng.

As R ⁵¹from the view point of the solvability excellence for base oil, the alkyl of preferred carbonatoms 4 ~ 18, specifically, preference is as alkyl (the optional straight-chain of these alkyl or branched) such as butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyls, more preferably the straight-chain of carbonatoms 6 ~ 12 or branched-chain alkyl, the particularly preferably branched-chain alkyl of carbonatoms 6 ~ 12.

In oxybenzene compound represented by general formula (19), R ⁴⁹compound when group represented by general formula (i), the R more preferably in general formula (i) ⁵⁰for alkylidene group, the R of carbonatoms 1 ~ 2 ⁵¹for straight-chain or the branched-chain alkyl of carbonatoms 6 ~ 12; R particularly preferably in general formula (i) ⁵⁰for alkylidene group, the R of carbonatoms 1 ~ 2 ⁵¹for the branched-chain alkyl of carbonatoms 6 ~ 12.

If more specifically illustrate preferred compound, can list: (3-methyl-5-tert-butyl-hydroxy phenyl) just own ester of acetic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid dissident ester, (3-methyl-5-tert-butyl-hydroxy phenyl) positive heptyl ester of acetic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid isocyanate, (3-methyl-5-tert-butyl-hydroxy phenyl) n-octyl acetate, (3-methyl-5-tert-butyl-hydroxy phenyl) isooctyl acetate, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid 2-ethylhexyl, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid ester in the positive ninth of the ten Heavenly Stems, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid ester in the different ninth of the ten Heavenly Stems, (3-methyl-5-tert-butyl-hydroxy phenyl) n-Decyl Acetate, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid isodecyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid n-undecane base ester, (3-methyl-5-tert-butyl-hydroxy phenyl) different undecyl ester of acetic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid dodecyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid Permethyl 99A. base ester, (3-methyl-5-tert-butyl-hydroxy phenyl) just own ester of propionic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid dissident ester, (3-methyl-5-tert-butyl-hydroxy phenyl) positive heptyl ester of propionic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid isocyanate, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid n-octyl, (3-methyl-5-tert-butyl-hydroxy phenyl) different monooctyl ester of propionic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid 2-ethylhexyl, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid ester in the positive ninth of the ten Heavenly Stems, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid ester in the different ninth of the ten Heavenly Stems, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid ester in the positive last of the ten Heavenly stems, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid isodecyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid n-undecane base ester, (3-methyl-5-tert-butyl-hydroxy phenyl) different undecyl ester of propionic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid dodecyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid Permethyl 99A. base ester, the just own ester of (3,5-di-tert-butyl-hydroxy phenyl) acetic acid, (3,5-di-tert-butyl-hydroxy phenyl) acetic acid dissident ester, the positive heptyl ester of (3,5-di-tert-butyl-hydroxy phenyl) acetic acid, (3,5-di-tert-butyl-hydroxy phenyl) acetic acid isocyanate, (3,5-di-tert-butyl-hydroxy phenyl) n-octyl acetate, (3,5-di-tert-butyl-hydroxy phenyl) isooctyl acetate, (3,5-di-tert-butyl-hydroxy phenyl) acetic acid 2-ethylhexyl, (3,5-di-tert-butyl-hydroxy phenyl) acetic acid ester in the positive ninth of the ten Heavenly Stems, (3,5-di-tert-butyl-hydroxy phenyl) acetic acid ester in the different ninth of the ten Heavenly Stems, (3,5-di-tert-butyl-hydroxy phenyl) n-Decyl Acetate, (3,5-di-tert-butyl-hydroxy phenyl) acetic acid isodecyl ester, (3,5-di-tert-butyl-hydroxy phenyl) acetic acid n-undecane base ester, the different undecyl ester of (3,5-di-tert-butyl-hydroxy phenyl) acetic acid, (3,5-di-tert-butyl-hydroxy phenyl) acetic acid dodecyl ester, (3,5-di-tert-butyl-hydroxy phenyl) acetic acid Permethyl 99A. base ester, the just own ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid dissident ester, the positive heptyl ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid isocyanate, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid n-octyl, the different monooctyl ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid 2-ethylhexyl, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid ester in the positive ninth of the ten Heavenly Stems, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid ester in the different ninth of the ten Heavenly Stems, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid ester in the positive last of the ten Heavenly stems, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid isodecyl ester, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid n-undecane base ester, the different undecyl ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid dodecyl ester, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid Permethyl 99A. base ester and their mixture etc.

R in general formula (19) ⁴⁹when group represented by general formula (ii), the R in general formula (ii) ⁵²represent the alkylidene group of carbonatoms 1 ~ 6.The optional straight-chain of this alkylidene group or branched, specifically, can list such as: above-mentioned R ⁵⁰explanation in illustrative various alkylidene group.From compound and its raw material viewpoint in hand that can manufacture general formula (19) with few reaction process, R ⁵²for the alkylidene group of carbonatoms 1 ~ 3, specifically, be more preferably such as: methylene radical, methylmethylene, ethylidene (dimethylene), ethyl methylene radical, propylidene (methyl ethylidene), trimethylene etc.In addition, as the R in general formula (ii) ⁵³, specifically, can list: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc., from the view point of excellent oxidation stability, preferred tertiary butyl.In addition, as R ⁵⁴, the alkyl of hydrogen atom or carbonatoms 1 ~ 4 described above can be listed, from the view point of excellent oxidation stability, preferable methyl or the tertiary butyl.

In alkyl phenol compound represented by general formula (19), R ⁴⁹compound when group represented by general formula (ii), if illustrate preferred compound particularly, can list: two (3, 5-di-tert-butyl-hydroxy phenyl) methane, 1, 1-two (3, 5-di-tert-butyl-hydroxy phenyl) ethane, 1, 2-two (3, 5-di-tert-butyl-hydroxy phenyl) ethane, 1, 1-two (3, 5-di-tert-butyl-hydroxy phenyl) propane, 1, 2-two (3, 5-di-tert-butyl-hydroxy phenyl) propane, 1, 3-two (3, 5-di-tert-butyl-hydroxy phenyl) propane, 2, 2-two (3, 5-di-tert-butyl-hydroxy phenyl) propane and their mixture etc.

On the other hand, in above-mentioned general formula (20), R ⁵⁵and R ⁵⁷optionally identical or different, be respectively the alkyl of carbonatoms 1 ~ 4, specifically, can exemplify: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc., from the view point of excellent oxidation stability, be preferably the tertiary butyl.

In addition, R ⁵⁶and R ⁵⁸optionally identical or different, the alkyl of hydrogen atom or carbonatoms 1 ~ 4 described above can be listed respectively, from the view point of excellent oxidation stability, be preferably methyl or the tertiary butyl respectively separately.

In addition, the expression R in general formula (20) ⁵⁹and R ⁶⁰the optional straight-chain of alkylidene group of carbonatoms 1 ~ 6 or branched, specifically, can R be listed respectively separately ⁵⁰explanation in illustrative various alkylidene group.From viewpoint and this raw material easy viewpoint in one's hands that can manufacture the compound represented by general formula (20) with few reaction process, R ⁵⁹and R ⁶⁰be respectively the alkylidene group of carbonatoms 1 ~ 2 separately, specifically, more preferably such as: methylene radical, methylmethylene, ethylidene (dimethylene) etc.

In addition, in general formula (20), as the alkylidene group of the carbonatoms 1 ~ 18 represented by X, specifically, can list such as: methylene radical, methylmethylene, ethylidene (dimethylene), ethyl methylene radical, propylidene (methyl ethylidene), trimethylene, butylidene, pentylidene, hexylidene, sub-heptyl, octylene, nonamethylene, sub-decyl, sub-undecyl, sub-dodecyl, sub-tridecyl, sub-tetradecyl, sub-pentadecyl, sub-hexadecyl, sub-heptadecyl, sub-octadecyl etc. (the optional straight-chain of these alkylidene groups or branched), from raw material easily grade in one's hands, more preferably the alkylidene group of carbonatoms 1 ~ 6, specifically such as: methylene radical, methylmethylene, ethylidene (dimethylene), ethyl methylene radical, propylidene (methyl ethylidene), trimethylene, butylidene, pentylidene, hexylidene etc. (the optional straight-chain of these alkylidene groups or branched), particularly preferably ethylidene (dimethylene), trimethylene, the straight chain butylidene (straight-chain alkyl-sub-of the carbonatoms 2 ~ 6 such as tetramethylene, straight chain pentylidene (pentamethylene), straight chain hexylidene (hexa-methylene).In alkyl phenol compound represented by general formula (20), X is the particularly preferably following compound of the compound in the alkylidene group situation of carbonatoms 1 ~ 18.

In addition, when the group of the X in general formula (20) represented by general formula (iii), the R in general formula (iii) ⁵⁸and R ⁵⁹the optional straight-chain of alkylidene group of represented carbonatoms 1 ~ 6 or branched, specifically, can list previously separately respectively for R ⁵⁰various alkylidene group described above.From raw material viewpoint in hand when manufacturing the compound of general formula (20), R ⁵⁸and R ⁵⁹more preferably the alkylidene group of carbonatoms 1 ~ 3 is respectively separately, specifically, such as: methylene radical, methylmethylene, ethylidene (dimethylene), ethyl methylene radical, propylidene (methyl ethylidene), trimethylene etc.In alkylphenol represented by general formula (20), the compound that the compound in the group situation of X represented by general formula (iii) is particularly preferably following.

These alkylphenol compounds can be used alone a kind of compound, also can use the mixture etc. of any blending ratio of two or more compound.In addition, also can containing other phenol system antioxidants except alkylphenol compound.

As (C2) amine system antioxidant, any amine compound that the antioxidant of lubricating oil is applied can be used as, there is no particular limitation, preferably can list such as: from the phenyl-a-naphthylamine represented by following general formula (21) or the p represented by following general formula (22), one or more the aromatic amine selected in p '-dialkyl group diphenylamine.

[in formula, R ⁶³represent the alkyl of hydrogen atom or carbonatoms 1 ~ 16.]

[in formula, R ⁶⁴and R ⁶⁵optionally identical or different, represent the alkyl of carbonatoms 1 ~ 16 respectively.]

Represent in the above-mentioned general formula (21) of phenyl-a-naphthylamine, R ⁶³represent hydrogen atom or the straight-chain of carbonatoms 1 ~ 16 or the alkyl of branched.R ⁶³carbonatoms more than 16 when, have functional group's ratio shared in the molecule to diminish, the worry that resistance of oxidation dies down.As R ⁶³alkyl, specifically, can list such as: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl etc. (the optional straight-chain of these alkyl or branched).

In compound represented by general formula (21), R ⁶³when for alkyl, from the view point of solvability excellence for base oil of himself oxidation products, the branched-chain alkyl of preferred carbonatoms 8 ~ 16, and then the branched-chain alkyl of the carbonatoms 8 ~ 16 more preferably derived by the olefin oligomer of carbonatoms 3 or 4.The alkene of carbonatoms 3 or 4 described herein, specifically, can list: propylene, 1-butylene, 2-butylene and iso-butylene, from the view point of solvability excellence for base oil of himself oxidation products, and preferred propylene or iso-butylene.

When using the phenyl-a-naphthylamine represented by general formula (21), as R ⁶³the side chain pentadecyl that preferred hydrogen molecule or the branched octyl derived by 2 aggressiveness of iso-butylene, the branched nonyl derived by 3 aggressiveness of propylene, the branched dodecyl derived by 3 aggressiveness of iso-butylene, the branched dodecyl derived by 4 aggressiveness of propylene or 5 aggressiveness by propylene derive, the branched dodecyl that branched octyl, the branched dodecyl derived by 3 aggressiveness of iso-butylene or 4 aggressiveness by propylene that particularly preferably hydrogen molecule or 2 aggressiveness by iso-butylene derive derive.

As the phenyl-a-naphthylamine represented by general formula (21), use R ⁶³for the N-of alkyl to alkyl phenyl-alpha-naphthylamine when, can use with the commercially available material of the form of this N-to alkyl phenyl-alpha-naphthylamine.In addition, the halogenated alkyl compound of phenyl-a-naphthylamine and carbonatoms 1 ~ 16, the olefine reaction of carbonatoms 2 ~ 16 can be made by using Friedel-Crafts catalyst, or make the olefin oligomer of carbonatoms 2 ~ 16 and phenyl-a-naphthylamine react and easily synthesize.As Friedel-Crafts catalyst now, specifically, can use such as: the metal halides such as aluminum chloride, zinc chloride, iron(ic) chloride; An acidic catalyst such as sulfuric acid, phosphoric acid, five phosphorus oxide, boron fluoride, acidic white earth, atlapulgite; Deng.

On the other hand, represent p, p '-dialkyl group diphenylamine above-mentioned general formula (22) in, R ⁶⁴and R ⁶⁵optionally identical or different, represent the alkyl of carbonatoms 1 ~ 16 respectively.R ⁶⁴and R ⁶⁵one or both when being hydrogen atom, have the worry himself passed through to be oxidized and become greasy filth and sedimentation; On the other hand, when carbonatoms is more than 16, there is the worry that ratio diminishes, resistance of oxidation dies down that functional group is shared in the molecule.

As R ⁶⁴and R ⁶⁵specifically, can list such as: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl etc. (the optional straight-chain of these alkyl or branched).Wherein, as R ⁶⁴and R ⁶⁵, from the view point of solvability excellence for base oil of himself oxidation products, the branched-chain alkyl of preferred carbonatoms 3 ~ 16, and then preferably by the alkene of carbonatoms 3 or 4 or the branched-chain alkyl of carbonatoms 3 ~ 16 that derived by its oligopolymer.The alkene of carbonatoms 3 or 4 described herein, specifically, can list: propylene, 1-butylene, 2-butylene, iso-butylene etc., from the view point of solvability excellence for lubricant base of himself oxidation products, and preferred propylene or iso-butylene.

Use the p represented by general formula (22), when p '-dialkyl group diphenylamine, as R ⁶⁴and R ⁶⁵, the side chain pentadecyl preferably derived by the sec.-propyl of propylene derived, the tertiary butyl derived by iso-butylene, the branched hexyl derived by 2 aggressiveness of propylene, the branched octyl derived by 2 aggressiveness of iso-butylene, the branched nonyl derived by 3 aggressiveness of propylene, the branched dodecyl derived by 3 aggressiveness of iso-butylene, the branched dodecyl derived by 4 aggressiveness of propylene or 5 aggressiveness by propylene; The branched dodecyl that the tertiary butyl particularly preferably derived by iso-butylene, the branched hexyl derived by 2 aggressiveness of propylene, the branched octyl derived by 2 aggressiveness of iso-butylene, the branched nonyl derived by 3 aggressiveness of propylene, the branched dodecyl derived by 3 aggressiveness of iso-butylene or 4 aggressiveness by propylene derive.

As the p represented by general formula (22), p '-dialkyl group diphenylamine, commercially available product can be used.In addition, in the same manner as the phenyl-a-naphthylamine represented by general formula (21), can by using Friedel-Crafts catalyst, make the halogenated alkyl compound of diphenylamine and carbonatoms 1 ~ 16, the olefine reaction of carbonatoms 2 ~ 16, or make the alkene of carbonatoms 2 ~ 16 or their oligopolymer and diphenylamine react and easily synthesize.As Friedel-Crafts catalyst now, specifically, can use such as: metal halide, an acidic catalyst etc. cited during phenyl-a-naphthylamine synthesis.

These aromatic amines can be used alone a kind of compound, also can use the mixture etc. of any blending ratio of two or more compound.In addition, also can containing other amine system antioxidants beyond aromatic amine.

(C1) phenol system antioxidant and (C2) amine system antioxidant can individually use, from the view point of taking into account antioxidant property and resistance to greasy filth performance, preferably combination uses (C1) phenol system antioxidant and (C2) amine system antioxidant.

In total composition benchmark, the content of (C) antioxidant is below 3 quality %, is preferably below 2 quality %, is more preferably below 1 quality %.Even if content is more than 3 quality %, also can not see the oxidative stability corresponding to content and suppress greasy filth generative nature to improve further, also have the tendency that the solvability for base oil reduces.

On the other hand, in total composition benchmark, be more than 0.01 quality %, be preferably the above % of 0.1 quality, be more preferably more than 0.2 quality %.When content is less than 0.01 quality %, exists and improved effect become insufficient tendency by its oxidative stability brought of interpolation, greasy filth generation inhibition.

Lubricating oil composition of the present invention is preferably and then containing fatty amine as (D) composition.

In the present invention, (D) fatty amine refers to that having 1 ~ 3 carbonatoms is the alkyl of 12 ~ 18 and/or the amine of thiazolinyl.If carbonatoms be less than 12 and carbonatoms more than 18, then due to positioning performance be deteriorated and not preferred.

(D) fatty amine can be any person of primary amine, secondary amine and tertiary amine, from the view point of oiliness effect, is preferably primary amine or secondary amine, most preferably is primary amine.

In addition, be optionally monoamine or polyamines, from the view point of stability in storage, be preferably monoamine.

As the alkyl or alkenyl of above-mentioned carbonatoms 12 ~ 18, specifically, can list: dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl; The thiazolinyl such as laurylene base, tridecylene base, tetradecene base, ten pentaene bases, hexadecylene base, 17 thiazolinyls, octadecylene base (position of the double bond of these thiazolinyls is arbitrary) etc.These alkyl or alkenyls can be straight-chain also can be branched.

Also can not contain (D) fatty amine, and when containing, in total composition benchmark, its content is preferably more than 0.01 quality %, is more preferably more than 0.03 quality %, and then is preferably more than 0.05 quality %.On the other hand, in total composition benchmark, content is preferably below 2 quality %, is more preferably below 1 quality %, and then is preferably below 0.5 quality %.

Respectively, if be less than 0.01 quality %, the improvement effect of positioning precision is little thus not preferred; If it is not more than 2 quality %, then due to foul smell, bring baneful influence for solvability and flash-point, thus preferred.

Lubricating oil composition of the present invention preferably containing benzotriazole and/or thiadiazoles as (E) composition.

As benzotriazole cpd, specifically, can list: two (2-the ethylhexyl)-4-methyl isophthalic acid H-benzotriazole-1-methylamine of N, N-, two (2-the ethylhexyl)-5-methyl isophthalic acid H-benzotriazole-1-methylamine of N, N-etc.

As thiadiazole compound, thiadiazoles illustrated in the explanation of (A) sulphur system extreme pressure agent can be listed.

Also can not contain (E) composition, and when containing, in total composition benchmark, its content is preferably more than 0.0001 quality %, is more preferably more than 0.0005 quality %, and then is preferably more than 0.001 quality %.On the other hand, in total composition benchmark, content is preferably below 1 quality %, is more preferably below 0.8 quality %, and then is preferably below 0.5 quality %.

(E) content of composition is less than 0.0001 quality % and then can not shows effective performance, more than 1 quality % then resistance to greasy filth be deteriorated, thus not preferred respectively.

Lubricating oil composition of the present invention is preferably containing phosphorodithioic acid molybdenum compound (MoDTP) and/or molybdenum dithiocarbamate compound (MoDTC) conduct (F) composition.

The general formula (10) recorded in the explanation of MoDTP and MoDTC is respectively (A) sulphur system extreme pressure agent, the compound represented by (11).

[in formula (10) ~ (11), R ²²~ R ²⁹optionally identical or different, represent the alkyl of carbonatoms more than 1 respectively, X ¹and X ²represent Sauerstoffatom or sulphur atom respectively.]

As the preferred concrete example of MoDTC, can list: moly-sulfide diethyldithiocarbamate, moly-sulfide dipropyl disulfide is for carbamate, moly-sulfide Keywords dibutyl dithiocarbamate, moly-sulfide diamyl dithiocarbamate ester, moly-sulfide dihexyl dithiocarbamate, moly-sulfide dioctyl dithiocarbamate, moly-sulfide didecyl dithiocarbamate, moly-sulfide two (dodecyl) dithiocarbamate, moly-sulfide two (tridecyl) dithiocarbamate, moly-sulfide two (butyl phenyl) dithiocarbamate, moly-sulfide two (nonyl phenyl) dithiocarbamate, sulfuration oxo molybdenum diethyldithiocarbamate, sulfuration oxo molybdenum dipropyl disulfide is for carbamate, sulfuration oxo molybdenum Keywords dibutyl dithiocarbamate, sulfuration oxo molybdenum diamyl dithiocarbamate ester, sulfuration oxo molybdenum dihexyl dithiocarbamate, sulfuration oxo molybdenum dioctyl dithiocarbamate, sulfuration oxo molybdenum didecyl dithiocarbamate, sulfuration oxo molybdenum two (dodecyl) dithiocarbamate, sulfuration oxo molybdenum two (tridecyl) dithiocarbamate, sulfuration oxo molybdenum two (butyl phenyl) dithiocarbamate, sulfuration oxo molybdenum two (nonyl phenyl) dithiocarbamate etc.

Also can not contain (F) composition, and when containing, in total composition benchmark, its content is preferably more than 0.01 quality %, is more preferably more than 0.05 quality %, and then is preferably more than 0.1 quality %.On the other hand, content is preferably below 2 quality %, is more preferably below 1.5 quality %, and then is preferably below 1 quality %.

(F), when the content of composition is less than 0.01 quality %, can not get reducing friction effect fully; In addition, above-mentioned more than 2 quality % when, can not get the reduction friction effect corresponding to use level, thus respectively not preferred.

Lubricating oil composition of the present invention preferably contains viscosity index improver as (G) composition.As (G) viscosity index improver, can list: (G1) Dispersant viscosity index improver, (G2) non-dispersive type viscosity index improver.

For (G1) Dispersant viscosity index improver, have no particular limits, any compound of usually application can be used, preference as: containing the multipolymer of nitrogen containing monomer as copolymer composition with ethylenic unsaturated bond.More specifically, preferably be selected from following general formula (23), (24) or the compound represented by (25) one or more monomer (following, be called " monomer (G1a) ") with the multipolymer of one or more monomer (hereinafter referred to as " monomer (G1b) ") being selected from following general formula (26) or the compound represented by (27).

[in formula, R ⁶⁶represent hydrogen atom or methyl, R ⁶⁷represent the alkyl of carbonatoms 1 ~ 18.]

[in formula, R ⁶⁸represent hydrogen atom or methyl, R ⁶⁹represent the alkyl of carbonatoms 1 ~ 12.]

[in formula, Y ¹and Y ²optionally identical or different, represent the alkoxyl group of hydrogen atom, carbonatoms 1 ~ 18 or the alkyl monosubstituted amino of carbonatoms 1 ~ 18 respectively.]

[in formula, R ⁷⁰represent hydrogen atom or methyl, R ⁷¹represent the alkylidene group of carbonatoms 2 ~ 18, j represents 0 or 1, Y ³represent the organic group of the carbonatoms 1 ~ 30 containing nitrogen-atoms.]

[in formula, R ⁷²represent hydrogen atom or methyl, Y ⁴represent the organic group of the carbonatoms 1 ~ 30 containing nitrogen-atoms.]

As the R in general formula (23) ⁶⁷the alkyl of represented carbonatoms 1 ~ 18.Specifically, can list: the alkyl (the optional straight-chain of these alkyl or branched) such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.

As the R in general formula (24) ⁶⁹the alkyl of represented carbonatoms 1 ~ 12, specifically, can list: the alkyl (the optional straight-chain of these alkyl or branched) such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl; The thiazolinyls (the optional straight-chain of these thiazolinyls or branched) such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic; The cycloalkyl of the carbonatomss 5 ~ 7 such as cyclopentyl, cyclohexyl, suberyl; The alkyl-cycloalkyl of the carbonatomss 6 ~ 11 such as methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl, diethyl cyclohexyl, methylcycloheptyl, dimethyl-cyclopentyl, methylethyl suberyl, diethyl suberyl (the optional straight-chain of alkyl or branched, the bonding position of itself and cycloalkyl is also arbitrary in addition); The aryl such as phenyl, naphthyl; Each alkylaryl of the carbonatomss 7 ~ 12 such as tolyl, xylyl, ethylphenyl, propyl group phenyl, butyl phenyl, amyl group phenyl, own phenyl (the optional straight-chain of alkyl or branched, the bonding position of itself and aryl is also arbitrary in addition); The arylalkyl (the optional straight-chain of alkyl or branched, the in addition bonding position of aryl and alkyl are also arbitrary) etc. of the carbonatomss such as benzyl, phenylethyl, phenyl propyl, phenyl butyl, phenylpentyl, Phenylhexyl 7 ~ 12.

Y in general formula (25) ¹and Y ²the alkoxyl group of represented carbonatoms 1 ~ 18 is the residue (-OR of hydrogen atom by the removing hydroxyl removal of the alkyl alcohol of carbonatoms 1 ~ 18 ⁷³; R ⁷³alkyl for carbonatoms 1 ~ 18).R ⁷³the alkyl of represented carbonatoms 1 ~ 18, can list the R in general formula (23) ⁶⁷alkyl illustrated in the explanation of the alkyl of represented carbonatoms 1 ~ 18.

Y in general formula (25) ¹and Y ²the alkyl monosubstituted amino of represented carbonatoms 1 ~ 18 is the residue (-NHR being eliminated hydrogen atom by the amino of the monoalkylamine of carbonatoms 1 ~ 18 ⁷⁴; R ⁷⁴alkyl for carbonatoms 1 ~ 18).R ⁷⁴the alkyl of represented carbonatoms 1 ~ 18, can list the R in general formula (23) ⁶⁷alkyl illustrated in the explanation of the alkyl of represented carbonatoms 1 ~ 18.

In general formula (26), as R ⁷¹the alkylidene group of represented carbonatoms 2 ~ 18, specifically, can list: the alkylidene group such as ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, octylene, nonamethylene, sub-decyl, sub-undecyl, sub-dodecyl, sub-tridecyl, sub-tetradecyl, sub-pentadecyl, sub-hexadecyl, sub-heptadecyl, sub-octadecyl (the optional straight-chain of these alkylidene groups or branched) etc.

As Y ³and Y ⁴represented organic group, is preferably and then contains the group of Sauerstoffatom, preferably have the group of ring in addition.Particularly, from the view point of suppression greasy filth, wear resistant and rubbing characteristics, Y ³and Y ⁴represented organic group preferably has the ring comprising Sauerstoffatom.In addition, Y ³and Y ⁴when represented organic group is the group with ring, this ring be optionally any one of aliphatics ring or aromatic ring, preferably aliphatics ring.And then, from the view point of suppression greasy filth, wear resistant and rubbing characteristics, Y ³and Y ⁴the ring that represented organic group has is preferably 6 Yuans rings.

As Y ³and Y ⁴represented organic group, specifically, can list: dimethylamino, diethylamino, dipropylamino, dibutylamino, anilino, toluene amido, dimethylbenzene amido, kharophen, benzamido, morpholino base, pyrryl, pyrrolinyl, pyridyl, picolyl, pyrrolidyl, piperidyl, quinonyl, pyrrolidone-base, pyrrolidone are for base, imidazolinyl, pyrazinyl etc.; Wherein particularly preferably morpholino base.

When monomer (G1a) is polymerized with monomer (G1b), monomer (G1a) and monomer (G1b) to be polymerized than (mol ratio) be arbitrary, but in the scope of preferred 80:20 ~ 95:5.In addition, the reaction method of copolymerization is also arbitrary, under the existence of the polymerization starters such as benzoyl peroxide, usually make monomer (G1a) and monomer (G1b) carry out free radical solution polymerization and easily and exactly can obtain the multipolymer of target.The number-average molecular weight of the multipolymer obtained is also for arbitrary but be preferably 1,000 ~ 1,500,000, be more preferably 10,000 ~ 200,000.

In compound represented by above-mentioned general formula (23) ~ (25), from the view point of low-temperature performance, monomer (G1a) is preferably the compound represented by general formula (23).On the other hand, from the view point of suppression greasy filth, wear resistant and rubbing characteristics, monomer (G1b) is preferably the compound represented by general formula (26).

As the preferred example of compound represented by above-mentioned general formula (23) ~ (25), can list: the alkene of the alkyl acrylate of carbonatoms 1 ~ 18, the alkyl methacrylate of carbonatoms 1 ~ 18, carbonatoms 2 ~ 20, vinylbenzene, vinyl toluene, maleic anhydride ester, maleic anhydride acid amides and their mixture etc.Wherein, the alkyl methacrylate of preferred carbonatoms 1 ~ 18, particularly preferably methyl methacrylate.

In addition, as the preferred example of compound represented by above-mentioned general formula (26) or (27), can list: dimethylamine methyl esters, methacrylic acid diethylamino methyl esters, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate, 2-methyl-5-vinylpyrine, morpholinomethyl methyl acrylate, morpholinomethyl ethyl propenoate, NVP and their mixture etc.

The compound obtained as making monomer (G1a) and monomer (G1b) copolymerization, from the view point of resistance to greasy filth, most preferably decentralized polymethacrylate.

As (G2) non-dispersive type viscosity index improver, can list: be selected from the multipolymer of one or more monomers of various methacrylic ester or the non-dispersive type polymethacrylate etc. of its hydrogenated products.

In total composition benchmark, the content of (G) viscosity index improver is preferably below 2 quality %, is more preferably below 1 quality %, and then is preferably below 0.5 quality %.Even if content is more than 2 quality %, also can not see the further raising of suppression greasy filth, wear resistant and the rubbing characteristics corresponding to content, also have the tendency that resistance to emulsion reduces.

On the other hand, in total composition benchmark, content is preferably more than 0.01 quality %, is more preferably more than 0.05 quality %, and then is preferably more than 0.2 quality %.When content is discontented with 0.01 quality %, there is the tendency suppressing greasy filth, wear resistant or rubbing characteristics to reduce.

In addition, in the present invention, polymethacrylate can be used as pour point depressant.

In the present invention, most preferably combinationally use three kinds of polymethacrylate of the non-dispersive type polymethacrylate as viscosity index improver, the polymethacrylate as pour point depressant together with decentralized polymethacrylate.

Also the polymethacrylate of pour point depressant can not be used as, but when using, in total composition benchmark, its content is preferably below 15 quality %, be more preferably below 10 quality %, and be preferably more than 5 quality %, be more preferably more than 3 quality %.By content is located at above-mentioned scope, can balances and meet thickening effectiveness and viscosity index improvement effect and shear stability well.

Lubricating oil composition of the present invention and then can contain ester oiliness improver as (H) composition.By containing (H) ester oiliness improver, can improve further and prevent barrel scratch (preventing stick-slip).

(H) ester oiliness improver can obtain by making alcohol and carboxylic acid react.As alcohol, both can be that monohydroxy-alcohol also can for polyvalent alcohol.In addition, as carboxylic acid, both can be that monoprotic acid also can for polyprotonic acid.

Form the monohydroxy-alcohol of (H) ester oiliness improver, usually use carbonatoms 1 ~ 24, be preferably the monohydroxy-alcohol that 1 ~ 12 is more preferably 1 ~ 8; As such alcohol, optional straight or branched is in addition, optionally saturated or unsaturated.As the alcohol of carbonatoms 1 ~ 24, specifically, can list such as: methyl alcohol, ethanol, the propyl alcohol of straight-chain or branched, the butanols of straight-chain or branched, the amylalcohol of straight-chain or branched, the hexanol of straight-chain or branched, the enanthol of straight-chain or branched, the octanol of straight-chain or branched, the nonyl alcohol of straight-chain or branched, the decyl alcohol of straight-chain or branched, the hendecanol of straight-chain or branched, the dodecanol of straight-chain or branched, the tridecyl alcohol of straight-chain or branched, the tetradecanol of straight-chain or branched, the pentadecylic alcohol of straight-chain or branched, the cetyl alcohol of straight-chain or branched, the heptadecanol of straight-chain or branched, the Stearyl alcohol of straight-chain or branched, the nonadecanol of straight-chain or branched, the eicosanol of straight-chain or branched, the heneicosane alcohol of straight-chain or branched, the tricosanol of straight-chain or branched, the Tetracosyl alcohol of straight-chain or branched and their mixture etc.

In addition, as the polyvalent alcohol forming (H) ester oiliness improver, usually can use 2 ~ 10 yuan of alcohol, be preferably the alcohol of 2 ~ 6 yuan.As the polyvalent alcohol of 2 ~ 10, specifically, can list such as: ethylene glycol, Diethylene Glycol, polyoxyethylene glycol (3 ~ 15 aggressiveness of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (3 ~ 15 aggressiveness of propylene glycol), 1, ammediol, 1,2-propylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2-methyl isophthalic acid, 2-propylene glycol, 2-methyl isophthalic acid, ammediol, 1,2-pentanediol, 1,3-pentanediol, 1,2 yuan of alcohol such as 4-pentanediol, 1,5-PD, neopentyl glycol; Glycerine, Polyglycerine (2 ~ 8 aggressiveness of glycerine such as: two glycerine, triglycerin, four glycerine etc.); Trimethylolalkane (trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane etc.) and their 2 ~ 8 aggressiveness; Tetramethylolmethane and their 2 ~ 4 aggressiveness, BT, 1,3,5-penta triol, 1,2,6-hexanetriol, 1, the polyvalent alcohols such as 2,3,4-butantetraol, Sorbitol Powder, anhydrosorbitol, Sorbitol Powder glycerol condensate, ribitol, arabitol, Xylitol, mannitol; Carbohydrate and their mixtures etc. such as wood sugar, pectinose, ribose, rhamnosyl, glucose, fructose, semi-lactosi, seminose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose.

In these polyvalent alcohols, preferred ethylene glycol, Diethylene Glycol, polyoxyethylene glycol (3 ~ 10 aggressiveness of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (3 ~ 10 aggressiveness of propylene glycol), 1, ammediol, 2-methyl isophthalic acid, 2-propylene glycol, 2-methyl isophthalic acid, ammediol, neopentyl glycol, glycerine, two glycerine, triglycerin, trimethylolalkane (trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane etc.) and their 2 ~ 4 aggressiveness, tetramethylolmethane, Dipentaerythritol, 1, 2, 4-trihydroxybutane, 1, 3, 5-penta triol, 1, 2, 6-hexanetriol, 1, 2, 3, 4-butantetraol, Sorbitol Powder, anhydrosorbitol, Sorbitol Powder glycerol condensate, ribose, arabitol, Xylitol, the polyvalent alcohol that mannitol etc. are 2 ~ 6 yuan and their mixture etc.And then barrel scratch is more excellent from the view point of preventing, more preferably ethylene glycol, propylene glycol, neopentyl glycol, glycerine, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, anhydrosorbitol and their mixture etc.

Forming the alcohol of (H) ester oiliness improver as above-mentioned, is optionally monohydroxy-alcohol or polyvalent alcohol, from the viewpoint etc. preventing barrel scratch more excellent, is preferably polyvalent alcohol.

In addition, form in the acid of (H) ester oiliness improver, usually use the lipid acid of carbonatoms 1 ~ 24 as monoprotic acid, this lipid acid is optionally straight or branched, optionally saturated or unsaturated in addition.Specifically, can list such as: formic acid, acetic acid, propionic acid, the butyric acid of straight-chain or branched, the valeric acid of straight-chain or branched, the caproic acid of straight-chain or branched, the enanthic acid of straight-chain or branched, straight-chain or branched sad, the n-nonanoic acid of straight-chain or branched, the capric acid of straight-chain or branched, the undecanoic acid of straight-chain or branched, the dodecylic acid of straight-chain or branched, the tridecanoic acid of straight-chain or branched, the tetradecanoic acid of straight-chain or branched, the pentadecylic acid of straight-chain or branched, the hexadecanoic acid of straight-chain or branched, the margaric acid of straight-chain or branched, the octadecanoic acid of straight-chain or branched, the hydroxyoctadecanoic acid of straight-chain or branched, the nondecylic acid of straight-chain or branched, the arachic acid of straight-chain or branched, the heneicosanoic acid acid of straight-chain or branched, the docosoic acid of straight-chain or branched, the tricosanic acid of straight-chain or branched, the saturated fatty acids such as the Lignoceric acid of straight-chain or branched, vinylformic acid, the butenoic acid of straight-chain or branched, the pentenoic acid of straight-chain or branched, the hexenoic acid of straight-chain or branched, the heptenoic acid of straight-chain or branched, the octylenic acid of straight-chain or branched, the nonenoic acid of straight-chain or branched, the decylenic acid of straight-chain or branched, the undecylenic acid of straight-chain or branched, the dodecenoic acid of straight-chain or branched, the tridecylenic acid of straight-chain or branched, the tetradecenoic acid of straight-chain or branched, the pentadecylenic acid of straight-chain or branched, the hexadecylenic acid of straight-chain or branched, the heptadecenoic acid of straight-chain or branched, the octadecenoic acid of straight-chain or branched, the isorpcinoleic acid of straight-chain or branched, the jecoleic acid of straight-chain or branched, the eicosenoic acid of straight-chain or branched, the heneicosene acid of straight-chain or branched, the Decosahedaenoic acid of straight-chain or branched, the tricosenoic acid of straight-chain or branched, unsaturated fatty acids and their mixtures etc. such as the tetracosenoic acid of straight-chain or branched.

As polyprotonic acid, can list: diprotic acid, trimellitic acid etc., preferred diprotic acid.Diprotic acid be optionally chain diprotic acid, ring-type diprotic acid any one.In addition, when for chain diprotic acid, be optionally straight-chain, branched any one, in addition, be optionally saturated, undersaturated any one.Chain diprotic acid is preferably the chain diprotic acid of carbonatoms 2 ~ 16, specifically, can list such as: oxalic acid, propanedioic acid, the succinic acid of straight-chain or branched, the pentanedioic acid of straight-chain or branched, the hexanodioic acid of straight-chain or branched, the pimelic acid of straight-chain or branched, the suberic acid of straight-chain or branched, the nonane diacid of straight-chain or branched, the sebacic acid of straight-chain or branched, the undecane diacid of straight-chain or branched, the dodecanedioic acid of straight-chain or branched, the undecane dicarboxylic acid of straight-chain or branched, the tetradecane diacid of straight-chain or branched, the pentadecane dicarboxylic acid of straight-chain or branched, the Thapsic acid of straight-chain or branched, the hexene diacid of straight-chain or branched, the pentene dicarboxylic acid of straight-chain or branched, the octene diacid of straight-chain or branched, the nonene diacid of straight-chain or branched, the octene dicarboxylic acid of straight-chain or branched, the nonene dicarboxylic acid of straight-chain or branched, the laurylene diacid of straight-chain or branched, the tridecylendioic acid of straight-chain or branched, the tetradecene diacid of straight-chain or branched, the heptadecene diacid of straight-chain or branched, the hexadecylene diacid of straight-chain or branched and their mixture etc.In addition, as ring-type diprotic acid, can list: 1,2-cyclohexane dicarboxylic acid, 4-tetrahydrobenzene-1,2-dicarboxylic acid, aromatic dicarboxylic acid etc.Wherein, from the view point of stability, preferred chain diprotic acid.

As the acid forming (H) ester oiliness improver, as mentioned above, being optionally monoprotic acid or polyprotonic acid, from the view point of preventing barrel scratch, being preferably monoprotic acid.

(H) alcohol in ester oiliness improver is arbitrary with being combined as of acid, has no particular limits, can list such as: the ester that the combination in following (Ha) ~ (Hg) is formed.

(Ha) monohydroxy-alcohol and monacid ester

(Hb) polyvalent alcohol and monacid ester

(Hc) monohydroxy-alcohol and polybasic ester

(Hd) polyvalent alcohol and polybasic ester

(He) mixture of monohydroxy-alcohol, polyvalent alcohol and the mixed ester of polyprotonic acid

(Hf) mixed ester of the mixture of polyvalent alcohol and monoprotic acid, polyprotonic acid

(Hg) mixed ester of the mixture of monohydroxy-alcohol, polyvalent alcohol and monoprotic acid, polyprotonic acid

The ester of above-mentioned (Hb) ~ (Hg) is optionally the hydroxyl of polyvalent alcohol or all esterified complete ester of the carboxyl of polyprotonic acid respectively, or remains the part ester of a part of hydroxyl or carboxyl.

In the ester of above-mentioned (Ha) ~ (Hg), preferably (Hb) polyvalent alcohol and monacid ester.Described ester prevent the raising effect of barrel scratch high in the extreme.

The ester of above-mentioned (Hb) is optionally the complete ester that the hydroxyl of polyvalent alcohol is all esterified, or remains the part ester of a part of hydroxyl.From the view point of preventing the property separated out, be preferably complete ester; In addition, from the view point of rubbing characteristics, be preferably part ester.

And then when the ester of above-mentioned (Hb) comprises part ester, from the view point of preventing the property separated out, rubbing characteristics, wear resistant and rust-preventing characteristic, this part ester is preferably the mixture of the different two or more part esters of gamma value; Be more preferably gamma value be 1 part ester and gamma value be the mixture of the part ester of more than 2.It should be noted that, gamma value described herein is the number of the ester bond in a part.Such as: when the polyvalent alcohol forming above-mentioned (Hb) ester is anhydrosorbitol, gamma value is the part ester of 1 is sorbitan mono; On the other hand, gamma value be more than 2 part ester comprise anhydrosorbitol diester and anhydrosorbitol three ester.

In addition, and then the ester of above-mentioned (Hb) is when comprising part ester that gamma value is 1 and the part ester that gamma value is more than 2, in both total meterings for benchmark, gamma value is that the ratio of the part ester of 1 is preferably 10 ~ 70 % by mole, is more preferably 20 ~ 50 % by mole.In addition, always measure as benchmark in both, gamma value is that the ratio of the part ester of more than 2 is preferably 30 ~ 70 % by mole, is more preferably 50 ~ 80 % by mole.

In addition, the monoprotic acid forming the ester of above-mentioned (Hb) is optionally any person of straight chain fatty acid or branched chain fatty acid, from the view point of rubbing characteristics, and preferred straight chain fatty acid; In addition, from the view point of preventing the property separated out, branched chain fatty acid is preferably.

In addition, the monoprotic acid forming the ester of above-mentioned (Hb) is optionally any person of saturated fatty acid or unsaturated fatty acids, from the view point of rubbing characteristics and wear resistant, is preferably saturated fatty acid; In addition, from the view point of preventing the property separated out, unsaturated fatty acids is preferably.And then, when monoprotic acid contains saturated fatty acid and unsaturated fatty acids, from the view point of rubbing characteristics (particularly frictional coefficient reduction), the ratio of saturated fatty acid shared by both totals is preferably more than 60 % by mole, be more preferably more than 75 % by mole, and then be preferably more than 90 % by mole, be more preferably more than 95 % by mole.

In addition, for the monacid carbonatoms forming above-mentioned (Hb) ester, have no particular limits, from the view point of preventing the property separated out, the longer chain fatty acid of the short chain fatty acid of preferably combination carbonatoms 1 ~ 4, more preferably carbonatoms 2 and carbonatoms 10 ~ 24 more preferably carbonatoms 12 ~ 18.And then when combining above-mentioned short chain fatty acid and longer chain fatty acid, the ratio of short chain fatty acid shared by both totals is preferably 50 ~ 80 % by mole, is more preferably 60 ~ 75 % by mole and then preferably 65 ~ 70 % by mole.

In the ester of above-mentioned (Hb), realize rubbing characteristics well from the view point of balance, prevent the various characteristics such as the property separated out, preferably use the ester represented by following (Hb-1) ~ (Hb-4).

(Hb-1) monoesters of polyvalent alcohol and unsaturated fatty acids

(Hb-2) ester of polyvalent alcohol and unsaturated fatty acids, for comprising the ester of part ester that gamma value is 1 and the part ester that gamma value is more than 2

(Hb-3) the complete ester of polyvalent alcohol and lipid acid, comprises the ester of the short chain fatty acid of carbonatoms 1 ~ 4 and the longer chain fatty acid of carbonatoms 10 ~ 24 for forming lipid acid

(Hb-4) ester of polyvalent alcohol and chain saturated fatty acid, for comprising the ester of part ester that gamma value is 1 and the part ester that gamma value is more than 2

The ester of above-mentioned (Hb-1) is preferred from taking into account rubbing characteristics with high level and prevent the viewpoint of the property separated out.From the view point of preventing barrel scratch from improving further, the carbonatoms forming the unsaturated fatty acids of the ester of above-mentioned (Hb-1) is preferably more than 10, is more preferably more than 12, and then is preferably more than 14.In addition, from the view point of preventing the property separated out, the carbonatoms of unsaturated fatty acids is preferably less than 28, is more preferably less than 26, and then is preferably less than 24.As such ester, can list: glyceryl monooleate, dehydrating sorbitol monooleate etc.

In addition, the ester of above-mentioned (Hb-2) from realizing rubbing characteristics (particularly preventing barrel scratch) well with high level balance, prevent the property separated out, whole viewpoint of wear resistant and rust-preventing characteristic and preferably.It should be noted that, the polyvalent alcohol forming (Hb-2) ester is optionally one or more mixture, when this polyvalent alcohol comprises 2 yuan of alcohol, needs the polyvalent alcohol comprising more than 3 yuan further.

In the ester of above-mentioned (Hb-2), in gamma value be 1 part ester and gamma value be total metering of the part ester of more than 2 for benchmark, gamma value is that the ratio of the part ester of 1 is preferably 10 ~ 70 % by mole, is more preferably 20 ~ 50 % by mole.In addition, in gamma value be 1 part ester and gamma value be total metering of the part ester of more than 2 for benchmark, gamma value is that the ratio of the part ester of more than 2 is preferably 30 ~ 70 % by mole, is more preferably 50 ~ 80 % by mole.It should be noted that, the ester of above-mentioned (Hb-2) can contain complete ester further, but realize rubbing characteristics (particularly preventing barrel scratch) well from the view point of with high level balance, prevent the whole of the property separated out, wear resistant and rust-preventing characteristic, in the ester total amount of (Hb-2) for benchmark, complete ester containing proportional be preferably less than 10 % by mole, be more preferably less than 5 % by mole, particularly preferably the ester of (Hb-2) is not containing complete ester.

In addition, above-mentioned (Hb-3) ester from realize well with high level balance rubbing characteristics (particularly frictional coefficient reduction and save the energy), prevent the property separated out and wear resistant whole viewpoints and preferably.The property separated out is prevented from the view point of improving further, in the ester of above-mentioned (Hb-3), the short chain fatty acid of preferably combination carbonatoms 2 and the longer chain fatty acid of carbonatoms 12 ~ 18.In addition, the ratio of short chain fatty acid shared by the total amount forming lipid acid is preferably 60 ~ 80 % by mole, is more preferably 60 ~ 75 % by mole, and then is preferably 65 ~ 70 % by mole.And then, from the view point of improving rubbing characteristics (particularly the reduction of frictional coefficient) further, the ratio of saturated fatty acid shared by the total amount forming lipid acid is preferably more than 60 % by mole, be more preferably more than 75 % by mole, and then be preferably more than 90 % by mole, be more preferably more than 95 % by mole.

In addition, the part ester of above-mentioned (Hb-4) from realizing rubbing characteristics well with high level balance, prevent the property separated out, whole viewpoint of wear resistant and rust-preventing characteristic and preferably.It should be noted that, the polyvalent alcohol forming (Hb-4) ester is optionally one or more mixture, when this polyvalent alcohol comprises 2 yuan of alcohol, needs the polyvalent alcohol comprising more than 3 yuan further.

In the part ester of above-mentioned (Hb-4), in gamma value be 1 part ester and gamma value be total metering of the part ester of more than 2 for benchmark, gamma value is that the ratio of the part ester of 1 is preferably 10 ~ 70 % by mole, is more preferably 20 ~ 50 % by mole.In addition, in gamma value be 1 part ester and gamma value be total metering of the part ester of more than 2 for benchmark, gamma value is that the ratio of the part ester of more than 2 is preferably 30 ~ 70 % by mole, is more preferably 50 ~ 80 % by mole.It should be noted that, the ester of above-mentioned (Hb-4) can contain complete ester further, but realize rubbing characteristics (particularly preventing barrel scratch) well from the view point of with high level balance, prevent the whole of the property separated out, wear resistant and rust-preventing characteristic, in the ester total amount of (Hb-4) for benchmark, complete ester containing proportional be preferably less than 10 % by mole, be more preferably less than 5 % by mole, particularly preferably the ester of (Hb-4) is not containing complete ester.

In the ester of above-mentioned (Hb-1) ~ (Hb-4), from the view point of rubbing characteristics, prevent the balance of the property separated out and wear resistant the best and rust-preventing characteristic also excellence, the particularly preferably ester of (Hb-2).

(H) content of ester oiliness improver can be arbitrary, but improve excellent effect from the view point of preventing barrel scratch, be that benchmark is preferably more than 0.01 quality % in total composition, be more preferably more than 0.05 quality %, and then be preferably more than 0.1 quality %.In addition, from the view point of preventing the property separated out, take total composition as benchmark, the content of (H) ester oiliness improver is preferably below 10 quality %, is more preferably below 7.5 quality %, and then is preferably below 5 quality %.

Lubricating oil composition of the present invention and then the polyalkylene glycol that also can contain represented by following general formula (28).By making it, containing these polyalkylene glycols, the raising of water separable performance can be sought.

R ⁷⁵O-(EO) _l-(R ⁷⁷O) _m-(EO) _n-R ⁷⁶(28)

[in formula (28), R ⁷⁵and R ⁷⁶optionally identical or different, represent the alkyl of hydrogen atom or carbonatoms 1 ~ 6 respectively; EO represents oxygen ethylidene, R ⁷⁷o represents the oxyalkylene of carbonatoms 3 ~ 6, and l, m and n are optionally identical or different, represents the integer of 1 ~ 50 respectively]

In general formula (28), as R ⁷⁵, R ⁷⁶alkyl, can be straight-chain, branched, ring-type any one.As the concrete example of described alkyl, can list: methyl, ethyl, n-propyl, sec.-propyl, various butyl, various amyl group, various hexyl, cyclopentyl, cyclohexyl etc.

In addition, the R in general formula (28) ⁷⁷o is the oxyalkylene of carbonatoms 3 ~ 6, as the oxyalkylene of repeating unit, can list: oxygen propylidene (PO), oxygen butylidene, oxygen pentylidene, oxygen hexylidene etc.Wherein, from the view point of more excellent with the separation property of water-soluble metalworking liquid, preferred oxygen propylidene.

According to expression EO, R ⁷⁷l, m, n of the repeat number of O, EO be respectively 1 ~ 50 integer known, polyalkylene glycol derivative of the present invention is oxyalkylene chain-(R ⁷⁷o) two ends of m-are in conjunction with aerobic ethylidene chain (EO) _l(EO) _nsegmented copolymer.When being the polyalkylene glycol derivative of 0 any one of use l, m, n, become insufficient with the separation property of water-soluble metalworking liquid.In addition, l, m, n preferably make the molecular-weight average of the polyalkylene glycol derivative represented by above-mentioned general formula (28) become 500 ~ 5, the value of 000 respectively.

Further, l, n and relative to l, m, n summation shared by ratio (l+n)/(l+m+n) be preferably 0.05 ~ 0.8, be more preferably 0.08 ~ 0.7, so be preferably 0.09 ~ 0.5.If (l+n)/(l+m+n) is in above-mentioned scope, then there is the tendency further improved with the separation property of water-soluble metalworking liquid.

It should be noted that, when m is more than 2, m R ⁷⁷o is optionally identical or different.In addition, oxyalkylene chain (R ⁷⁷o) _mby two or more R ⁷⁷when O is formed, this oxyalkylene chain can be any person of block copolymerization chain, random copolymerization chain.

In the present invention, above-mentioned polyalkylene glycol can be used alone one, also can combinationally use two or more.In addition, its content take total composition as benchmark, is preferably 0.0001 ~ 1 quality %, is more preferably 0.001 ~ 0.1 quality %.

Lubricating oil composition of the present invention and then count 0.1 ~ 10 quality % with total composition benchmark and contain olefin copolymer.By adding olefin copolymer, can shear stability be maintained and seek the thickening of high-performance base oil.

Olefin copolymer can use any olefin copolymer without particular limitation, is preferably ethylene-propylene copolymer, polybutene.

The number-average molecular weight of olefin copolymer is 50, less than 000, is preferably 20, less than 000, is more preferably 10, less than 000, most preferably is 6, less than 000.

In addition, in order to further high viscosity, preferably pitch is added.Pitch is had no particular limits, normally used pitch can be used.

Lubricating oil composition of the present invention, except above-claimed cpd, also can add various additive according to its purposes further.As such additive, can list: epoxy compounds, rust-preventive agent, corrosion inhibitor, pour point depressant, defoamer etc.

As epoxy compounds, can list: phenylglycidyl ether type epoxy compounds, alkyl glycidyl base ether type epoxy compounds, glycidyl ester type epoxy compounds, allyloxy silane compound, alkyl oxosilane compound, cycloaliphatic epoxy, epoxidized fat acid monoester, epoxidised vegetable wet goods.

As rust-preventive agent, specifically, can exemplify: the metal soaps such as fatty acid metal salt, lanolin fatty acid metal salt, oxidized petroleum waves metal-salt; The polyol moiety ester classes such as sorbitan fatty(acid)ester; The ester classes such as lanolin fatty acid esters; The Sulfonates such as calcium sulphonate, barium sulfonate; Oxidized petroleum waves; Amine; Phosphoric acid; Phosphoric acid salt etc.In the present invention, can to measure containing one or more compound optional from these rust-preventive agent arbitrarily; Usually, in total composition benchmark, its content is preferably 0.01 ~ 1 quality %.

As corrosion inhibitor, specifically, can arrange and illustrate: benzotriazole system, thiadiazoles system, imidazole compound etc.In the present invention, can to measure containing one or more compound optional from these metal passivators arbitrarily; Usually, in total composition benchmark, its content is preferably 0.001 ~ 1 quality %.

As pour point depressant, specifically, can exemplify: the multipolymer of one or more monomers selected from various acrylate, methacrylic ester or its hydrogenated products etc.In the present invention, can to measure containing one or more compound optional from these pour point depressants arbitrarily; Usually, in total composition benchmark, its content is preferably 0.01 ~ 5 quality %.

As defoamer, specifically, can exemplify: dimethyl silscone, fluorosilicone etc. are silicone based.In the present invention, can to measure containing one or more compound optional from these defoamers arbitrarily; Usually, in total composition benchmark, its content is preferably 0.001 ~ 0.05 quality %.

Kinematic viscosity during 40 DEG C of lubricating oil composition of the present invention is 22mm ²/ more than s, is preferably 60mm ²/ more than s, is more preferably 100mm ²/ more than s.On the other hand, be 4600mm ²/ below s, is preferably 2000mm ²/ below s, is more preferably 700mm ²/ below s.By kinematic viscosity when 40 DEG C is located at above-mentioned scope, rubbing characteristics, cooling (heat abstraction) are excellent and can reduce by the frictionloss of stirring resistance and causing.

For the viscosity index of lubricating oil composition of the present invention, have no particular limits, reduce from the view point of the oil film suppressed under high temperature, be preferably 80 ~ 500, be more preferably 100 ~ 300.

Pour point also can be arbitrary, but from the viewpoint such as startability of pump in winter, is generally less than-5 DEG C, is preferably less than-15 DEG C.

Lubricating oil composition of the present invention can be used as such as: hydraulic efficiency oil (hydraulic oil), turbine oil, compressor oil, gear oil, sliding guidance face oil, bearing wet goods.In these purposes, during as the purposes applied in the lubrication of gear, more excellent effect can be played.

Embodiment

Below, enumerate embodiment and specifically describe the present invention, but the present invention is not by any restriction of these embodiments.

The base oil used in embodiment and additive as follows.

[base oil]

Base oil 1: paraffin series height solvent treatment base oil (kinematic viscosity when 40 DEG C: 96mm ²/ s, viscosity index 95) and paraffin series height solvent treatment base oil (kinematic viscosity when 40 DEG C: 490mm ²/ s, viscosity index 96) mix with mass ratio 45:55

Base oil 2:PAO (kinematic viscosity when 40 DEG C: 412mm ²/ s, viscosity index 186) mix with mass ratio 91:9 with polybutene (number-average molecular weight=5,000)

[(A) composition: sulphur system extreme pressure agent]

A-1: olefine sulfide (diisobutyl polysulfide)

[(B) composition: phosphoric acid ester system extreme pressure agent]

B-1: dioctylphosphoric acid ester

[(C) composition: antioxidant]

C-1:2,6-di-t-butyl-p-cresol

C-2: dioctyl phenyl amine

[(D) composition]

D-1: oil base amine

[(E) composition]

E-1: benzotriazole

[(F) composition]

F-1: the MoDTC (Mo concentration 4.8 quality %) represented by following formula

(in formula, R represents the alkyl of carbonatoms 8 or 13, X represent Sauerstoffatom or sulphur atom)

[(G) composition: viscosity index improver]

G-1: the homopolymer (number-average molecular weight: 150,000) of the alkyl methacrylate of carbonatoms 1 ~ 18

[other additive]

X-1: organosilicon polymer

(embodiment 1 ~ 5 and comparative example 1)

Of the present invention each lubricating oil composition shown in the embodiment 1 ~ 5 of modulometer 1.The content of base oil and additive is all take total composition as benchmark.Use commercially available Zn system working oil (Exxon Mobil Corporation system; Trade(brand)name: DTE Oil25) as comparative example 1.For these lubricating oil compositions, carry out following evaluation test, be the results are shown in table 1.

[abrasion resistance test]

According to JPI-5S-32-90, in load: 392N, rotating speed: 1800rpm, test period: carry out four-ball test under the condition of 30 minutes, the mill mark diameter after determination test.

[SRV (reciprocal fine motion friction) test]

Carry out the SRV test of following detailed description, evaluate rubbing characteristics.More specifically, as shown in Figure 1, the point cantact region of the ball 2 that disk 1 with its upper surface configure is coated with sample oil, while make ball 2 relatively to-and-fro movement on the direction (arrow B in figure) of the upper surface along disk 1 in (arrow A in figure) applied load limit vertically downward to ball 2.By being installed on load sensor (not having to illustrate) the mensuration frictional coefficient now of disk 1 holding device (not having to illustrate).

Use the disk of the SPCC material of diameter 25mm, thickness 8mm as disk 1, use the ball of the SPCC material of diameter 10mm as ball 2 in addition.In addition, the load applied for ball 2 is 1200N, the amplitude of ball 2 is 1mm, frequency is 50Hz, temperature is 80 DEG C.

[table 1]

description of reference numerals

1 ... disk, 2 ... ball.

Claims

1. a lubricating oil composition, oil based on mineral oil and/or synthetic oil, in total composition benchmark containing (A) sulphur system extreme pressure agent 0.01 ~ 2 quality %, in total composition benchmark containing (B) phosphoric acid ester system extreme pressure agent 0.01 ~ 5 quality %, in total composition benchmark containing (C) antioxidant 0.01 ~ 3 quality %, kinematic viscosity during 40 DEG C of composition is 22 ~ 4600mm ²/ s.

2. lubricating oil composition according to claim 1, itself so that in total composition benchmark containing (D) aliphatic amine compound 0.01 ~ 2 quality %.

3. lubricating oil composition according to claim 1 and 2, itself so that in total composition benchmark containing (E) triazole compounds and/or thiadiazole compound 0.0001 ~ 1 quality %.

4. the lubricating oil composition according to any one of claims 1 to 3, itself so that in total composition benchmark containing (F) MoDTC and/or MoDTP0.01 ~ 2 quality %.

5. the lubricating oil composition according to any one of Claims 1 to 4, for the lubrication of gear.