Patent Grant
9803155
This application is a national stage entry of PCT/JP2013/057749 dated Mar. 18, 2013 which claims priority of Japanese Patent Application No. JP2012/060624, filed Mar. 16, 2012, which is incorporated by reference in its entirety.
The present invention relates to a lubricating oil composition and a sliding mechanism using the lubricating oil composition, and more precisely relates to a lubricating oil composition that exhibits an extremely low friction coefficient when used as a lubricating oil for low-friction sliding materials, and to a sliding mechanism that uses the lubricating oil composition and exhibits a low friction coefficient.
In recent years, it is important to cope with environmental problems in various fields. Technical development on energy saving and reduction of a discharge amount of carbon dioxide is thus being promoted. For example, it is an important subject to improve the fuel efficiency for vehicles, and for attaining the subject, technological development of lubricating oils and sliding materials is carried out.
As regards development of lubricating oil compositions, various base oils and additives have so far been developed for the purpose of improving various performances. As performances required to engine oils, there may be mentioned, for example, appropriate viscosity characteristics, oxidation stability, detergent dispersibility, abrasion resistance and antifoaming property. These performances are attempted to be improved by combination of various base oils and additives. In particular, zinc dialkyldithiophosphate (ZnDTP) is excellent as an abrasion resistant additive and, therefore, is often used as an additive for engine oils.
As regards development of sliding materials, on the other hand, materials having a hard film such as a TiN film or a CrN film which contributes to an improvement in an abrasion resistance are known as materials for use in parts which are exposed to severe frictional and abrasive environments (for example, a sliding part of an engine). Further, it is known that a friction coefficient can be reduced in the air in the absence of a lubricating oil by utilizing a diamond-like carbon (DLC) film. Thus, a material having a DLC film (hereinafter referred to as a DLC material) is expected as a low-friction sliding material.
However, the friction reducing effect of a DLC material is occasionally small in the presence of a lubricating oil composition, and, in this case, a fuel consumption saving effect is less liable to be obtained. Accordingly, development of a lubricating oil composition for low-friction sliding materials such as DLC materials or the like has heretofore been carried out.
For example, a lubricating oil composition for a low-friction sliding member which contains an ether-based ashless friction reducing agent is disclosed in PTL 1. Disclosed in PTL 2 and 3 are techniques in which lubricating oil compositions containing fatty acid ester-based ashless friction controlling agents and aliphatic amine-based ashless friction controlling agents are used for a sliding face between a DLC member and an iron base member and a sliding face between a DLC member and an aluminum alloy member. Disclosed in PTL 4 is a technique in which a low-friction agent composition containing an oxygen-containing organic compound and an aliphatic amine-based compound is used in a low-friction sliding mechanism having a DLC coating sliding member.
As in the above, lubricating oil compositions for low-friction sliding materials have been developed; however, even though these techniques are applied, the friction coefficient may increase when ZnDTP is incorporated for further improving abrasion resistance, and there is recognized a phenomenon that could not attain friction reduction.
Accordingly, even such a lubricating oil composition that contains, for example, ZnDTP for maintaining and improving various performances required for lubricating oil compositions, there is still required a lubricating oil composition that shows an extremely low friction coefficient when used as a lubricating oil composition for low-friction sliding materials.
There is also desired a sliding mechanism excellent in low-friction performance, which uses a lubricating oil composition capable of exhibiting excellent low-friction performance while maintaining various characteristics as such lubricating oil compositions, as combined with a sliding member that uses the above-mentioned DLC film on the sliding surface thereof.
PTL 1: Japanese Patent Application Publication No. JP2006-036850A
PTL 2: Japanese Patent Application Publication No. JP2003-238982A
PTL 3: Japanese Patent Application Publication No. JP2004-155891A
PTL 4: Japanese Patent Application Publication No. JP2005-098495A
The present invention has been made in consideration of the above-mentioned situation, and its object is to provide a lubricating oil composition which, even though containing a zinc dialkyldithiophosphate, can still exhibit an extremely low friction coefficient when used as a lubricating oil composition for low-friction sliding materials. Another object is to provide a sliding mechanism which, even though using a lubricating oil composition containing ZnDTP, is still excellent in low-friction performance when combined with a sliding member having a film of a specific low-friction sliding material on the sliding surface thereof.
The present inventors have assiduously studied and, as a result, have found that the above-mentioned problems can be solved by a lubricating oil composition incorporated with a specific additive. The present inventors have further found that the above-mentioned problems can be solved by constructing a sliding mechanism from the lubricating oil composition and a sliding member having, as formed thereon, a film of a specific low-friction sliding material. The present invention has been completed based on the above findings.
Thus, the present invention provides:
According to the present invention, there is provided a lubricating oil composition which, even though the lubricating oil therein contains a zinc dialkyldithiophosphate, can still exhibit an extremely low friction coefficient when used as a lubricating oil composition for low-friction sliding materials. The present invention also provides a sliding mechanism which, even though using a lubricating oil composition containing a zinc dialkyldithiophosphate, is still excellent in low-friction performance when combined with a sliding member having a film of a specific low-friction sliding material on the sliding surface thereof.
The present invention relates to a lubricating oil composition, and a sliding mechanism using the lubricating oil composition. These are described in detail hereinunder.
1. Lubricating Oil Composition
[Lubricant Base Oil]
The lubricating oil composition of the present invention generally contains a lubricant base oil and a specific additive, and is used as a lubricating oil for use for sliding surfaces of low-friction sliding materials.
The lubricant base oil used in the present invention is not specifically limited, and may be suitably selected from publicly known mineral base oils (hereinafter this may be referred to as “mineral oils”) and synthetic base oils (hereinafter this may be referred to as “synthetic oils”) which have so far been used.
Here, the mineral base oils include, for example, distillate oils obtained through atmospheric distillation of paraffin-base crude oils, intermediate-base crude oils or naphthene-base crude oils, or those obtained through reduced-pressure distillation of the residual oils in atmospheric distillation, as well as purified oils obtained through purification of those distillate oils and others according to an ordinary method, for example, solvent-purified oils, hydrocracked oils, hydrogenation-refined oils, dewaxed oils, clay-treated oils, and further wax-isomerized oils, etc.
On the other hand, the synthetic oils include, for example, poly-α-olefins that are oligomers of α-olefins having from 8 to 14 carbon atoms, polybutene, polyol esters, alkylbenzenes, etc.
In the present invention, the above mineral oils may be used singly or in combination of two or more thereof as the lubricant base oil. Also, the above synthetic oils may be used singly or in combination of two or more thereof. Further, one or more mineral oils may be used in combination with one or more synthetic oils.
Advantageously, the lubricant base oil has a kinematic viscosity at 100° C. of generally from 2 mm2/s to 50 mm2/s, preferably from 3 mm2/s to 30 mm2/s, more preferably from 3 mm2/s to 15 mm2/s. When the kinematic viscosity at 100° C. is 2 mm2/s or more, an evaporation loss is small, and when 50 mm2/s or less, a power loss by viscosity resistance is less liable to become large so that a favorable fuel consumption improving effect is obtainable.
Preferably, the lubricant base oil has a viscosity index of 60 or more, more preferably 70 or more, even more preferably 80 or more. When the viscosity index is 60 or more, then the viscosity change depending on the base oil temperature is small and therefore stable lubrication performance can be exhibited.
Further, the lubricant base oil preferably has a sulfur content of 1000 ppm by mass or less, more preferably 500 ppm by mass or less, even more preferably 100 ppm by mass or less. The sulfur content of 1000 ppm by mass or less is effective for improving oxidation stability.
Also preferably, the composition contains the lubricant base oil in an amount of 70% by mass or more, more preferably 80% by mass or more, based on the total amount of the composition.
[Lubricating Oil Additives]
In the lubricating oil composition of the present invention, an organic zinc dithiophosphate is used as the component (A) of the lubricating oil additive. As the organic zinc dithiophosphate, in general, a zinc dithiophosphate represented by the following general formula (I):
can be used.
In the general formula (I), R1, R2, R3 and R4 each independently represent a hydrocarbon group having from 1 to 24 carbon atoms. Such a hydrocarbon group is any of a straight-chained or branched alkyl group having from 1 to 24 carbon atoms, a straight-chained or branched alkenyl group having from 3 to 24 carbon atoms, a cycloalkyl group or a straight-chained or branched alkylcycloalkyl group having from 5 to 13 carbon atoms, an aryl group or a straight-chained or branched alkylaryl group having from 6 to 18 carbon atoms, or an arylalkyl group having from 7 to 19 carbon atoms.
The content of the zinc dithiophosphate of the component (A) must be, based on the total amount of the composition and in terms of the phosphorus concentration therein, from 0.005% by mass to 0.12% by mass. The content of less than 0.005% by mass could not provide a sufficient friction-reducing effect and abrasion-reducing effect; when the content is more than 0.12% by mass, any remarkable result of improving the effect corresponding thereto could not be expected. From these, the content of the component (A) is preferably from 0.01% by mass to 0.11% by mass, based on the total amount of the composition and in terms of the phosphorus concentration therein, more preferably from 0.02% by mass to 0.10% by mass.
In the present invention, preferably, the zinc dithiophosphate of the component (A) must contain a zinc primary dialkyldithiophosphate in an amount of from 0.005% by mass to 0.05% by mass, based on the total amount of the composition and in terms of the phosphorus concentration therein. Preferably, the zinc primary dialkyldithiophosphate is contained in an amount of from 0.007% by mass to 0.05% by mass, more preferably from 0.01% by mass to 0.05% by mass, based on the total amount of the composition and in terms of the phosphorus concentration therein.
Existence of the zinc dithiophosphate that contains the specific amount of the zinc primary dialkyldithiophosphate as above as the component (A) in the lubricating oil can noticeably increase the friction-reducing effect on the sliding surface having a low-friction sliding material, in the presence of the amine-based friction-reducing agent of the component (B) to be mentioned below. Further, at the same time, even the abrasion resistance on the sliding surface not having a low-friction sliding material can also be increased.
In the present invention, an amine-based friction-reducing agent is used as the component (B).
As the amine-based friction-reducing agent, there are exemplified aliphatic monoamines or alkylene oxide adducts thereof, alkanolamines, aliphatic polyamines, imidazoline compounds, etc.
As the aliphatic monoamines, herein used are aliphatic monoamines having from 6 to 30 carbon atoms, preferably from 12 to 24 carbon atoms, more preferably from 16 to 22 carbon atoms. Those aliphatic monoamines may be straight-chained ones or branched ones, and may be saturated or unsaturated ones. Specific examples of such aliphatic monoamines include, for example, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, stearylamine, isostearylamine, nonadecylamine, eicosylamine, heneicosylamine, docosylamine, tricosylamine, tetracosylamine, 11-ethyltricosylamine, pentacosylamine, hexacosylamine, heptacosylamine, octacosylamine, nonacosylamine, triacontylamine, hexenylamine, heptenylamine, octenylamine, nonenylamine, decenylamine, undecenylamine, dodecenylamine, tridecenylamine, tetradecenylamine, pentadecenylamine, hexadecenylamine, heptadecenylamine, octadecenylamine, nonadecenylamine, eicosenylamine, heneicosenylamine, docosenylamine, tricosenylamine, tetracosenylamine, pentacosenylamine, hexacosenylamine, heptacosenylamine, octacosenylamine, nonacosenylamine, triacontenylamine, etc.
The aliphatic monoamine alkylene oxide adducts are preferably adducts of the above-mentioned aliphatic monoamines with alkylene oxide(s) having 2 or 3 carbon atoms Specific examples of such aliphatic monoamine alkylene oxide adducts include aliphatic monoethanolamines such as hexylmonoethanolamine, heptylmonoethanolamine, octylmonoethanolamine, 2-ethylhexylmonoethanolamine, nonylmonoethanolamine, decylmonoethanolamine, undecylmonoethanolamine, dodecylmonoethanolamine, tridecylmonoethanolamine, tetradecylmonoethanolamine, pentadecylmonoethanolamine, hexadecylmonoethanolamine, heptadecylmonoethanolamine, octadecylmonoethanolamine, 2-heptylundecylmonoethanolamine, nonadecylmonoethanolamine, eicosylmonoethanolamine, heneicosylmonoethanolamine, docosylmonoethanolamine, tricosylmonoethanolamine, tetracosylmonoethanolamine, 11-ethyltricosylmonoethanolamine, pentacosylmonoethanolamine, hexacosylmonoethanolamine, heptacosylmonoethanolamine, octacosylmonoethanolamine, nonacosylmonoethanolamine, triacontylmonoethanolamine, hexenylmonoethanolamine, heptenylmonoethanolamine, octenylmonoethanolamine, nonenylmonoethanolamine, decenylmonoethanolamine, undecenylmonoethanolamine, dodecenylmonoethanolamine, tridecenylmonoethanolamine, tetradecenylmonoethanolamine, pentadecenylmonoethanolamine, hexadecenylmonoethanolamine, heptadecenylmonoethanolamine, octadecenylmonoethanolamine, nonadecenylmonoethanolamine, eicosenylmonoethanolamine, heneicosenylmonoethanolamine, docosenylmonoethanolamine, tricosenylmonoethanolamine, tetracosenylmonoethanolamine, pentacosenylmonoethanolamine, hexacosenylmonoethanolamine, heptacosenylmonoethanolamine, octacosenylmonoethanolamine, nonacosenylmonoethanolamine, triacontenylmonoethanolamine, etc.;
aliphatic diethanolamines such as hexyldiethanolamine, heptyldiethanolamine, octyldiethanolamine, 2-ethylhexyldiethanolamine, nonyldiethanolamine, decyldiethanolamine, undecyldiethanolamine, dodecyldiethanolamine, tridecyldiethanolamine, tetradecyldiethanolamine, pentadecyldiethanolamine, hexadecyldiethanolamine, heptadecyldiethanolamine, octadecyldiethanolamine, octadecenyldiethanolamine, 2-heptylundecyldiethanolamine, nonadecyldiethanolamine, eicosyldiethanolamine, heneicosyldiethanolamine, docosyldiethanolamine, docosenyldiethanolamine, tricosyldiethanolamine, tetracosyldiethanolamine, 11-ethyltricosyldiethanolamine, pentacosyldiethanolamine, hexacosyldiethanolamine, heptacosyldiethanolamine, octacosyldiethanolamine, nonacosyldiethanolamine, triacontyldiethanolamine, hexenyldiethanolamine, heptenyldiethanolamine, octenyldiethanolamine, nonenyldiethanolamine, decenyldiethanolamine, undecenyldiethanolamine, dodecenyldiethanolamine, tridecenyldiethanolamine, tetradecenyldiethanolamine, pentadecenyldiethanolamine, hexadecenyldiethanolamine, heptadecenyldiethanolamine, octadecenyldiethanolamine such as cis-9-octadecenyldiethanolamine, nonadecenyldiethanolamine, eicosenyldiethanolamine, heneicosenyldiethanolamine, docosenyldiethanolamine such as cis-13-docosenyldiethanolamine, tricosenyldiethanolamine, tetracosenyldiethanolamine, pentacosenyldiethanolamine, hexacosenyldiethanolamine, heptacosenyldiethanolamine, octacosenyldiethanolamine, nonacosenyldiethanolamine, triacontenyldiethanolamine, etc.;
aliphatic monopropanolamines such as hexylmonopropanolamine, heptylmonopropanolamine, octylmonopropanolamine, 2-ethylhexylmonopropanolamine, nonylmonopropanolamine, decylmonopropanolamine, undecylmonopropanolamine, dodecylmonopropanolamine, tridecylmonopropanolamine, tetradecylmonopropanolamine, pentadecylmonopropanolamine, hexadecylmonopropanolamine, heptadecylmonopropanolamine, octadecylmonopropanolamine, 2-heptylundecylmonopropanolamine, nonadecylmonopropanolamine, eicosylmonopropanolamine, heneicosylmonopropanolamine, docosylmonopropanolamine, tricosylmonopropanolamine, tetracosylmonopropanolamine, 11-ethyltricosylmonopropanolamine, pentacosylmonopropanolamine, hexacosylmonopropanolamine, heptacosylmonopropanolamine, octacosylmonopropanolamine, nonacosylmonopropanolamine, triacontylmonopropanolamine, hexenylmonopropanolamine, heptenylmonopropanolamine, octenylmonopropanolamine, nonenylmonopropanolamine, decenylmonopropanolamine, undecenylmonopropanolamine, dodecenylmonopropanolamine, tridecenylmonopropanolamine, tetradecenylmonopropanolamine, pentadecenylmonopropanolamine, hexadecenylmonopropanolamine, heptadecenylmonopropanolamine, octadecenylmonopropanolamine, nonadecenylmonopropanolamine, eicosenylmonopropanolamine, heneicosenylmonopropanolamine, docosenylmonopropanolamine, tricosenylmonopropanolamine, tetracosenylmonopropanolamine, pentacosenylmonopropanolamine, hexacosenylmonopropanolamine, heptacosenylmonopropanolamine, octacosenylmonopropanolamine, nonacosenylmonopropanolamine, triacontenylmonopropanolamine, etc.;
aliphatic dipropanolamines such as hexyldipropanolamine, heptyldipropanolamine, octyldipropanolamine, 2-ethylhexyldipropanolamine, nonyldipropanolamine, decyldipropanolamine, undecyldipropanolamine, dodecyldipropanolamine, tridecyldipropanolamine, tetradecyldipropanolamine, pentadecyldipropanolamine, hexadecyldipropanolamine, heptadecyldipropanolamine, octadecyldipropanolamine, 2-heptylundecyldipropanolamine, nonadecyldipropanolamine, eicosyldipropanolamine, heneicosyldipropanolamine, docosyldipropanolamine, tricosyldipropanolamine, tetracosyldipropanolamine, 11-ethyltricosyldipropanolamine, pentacosyldipropanolamine, hexacosyldipropanolamine, heptacosyldipropanolamine, octacosyldipropanolamine, nonacosyldipropanolamine, triacontyldipropanolamine, hexenyldipropanolamine, heptenyldipropanolamine, octenyldipropanolamine, nonenyldipropanolamine, decenyldipropanolamine, undecenyldipropanolamine, dodecenyldipropanolamine, tridecenyldipropanolamine, tetradecenyldipropanolamine, pentadecenyldipropanolamine, hexadecenyldipropanolamine, heptadecenyldipropanolamine, octadecenyldipropanolamine, nonadecenyldipropanolamine, eicosenyldipropanolamine, heneicosenyldipropanolamine, docosenyldipropanolamine, tricosenyldipropanolamine, tetracosenyldipropanolamine, pentacosenyldipropanolamine, hexacosenyldipropanolamine, heptacosenyldipropanolamine, octacosenyldipropanolamine, nonacosenyldipropanolamine, triacontenyldipropanolamine, etc.
The alkanolamines are preferably 2-hydroxy-aliphatic monoamines (in which the aliphatic monoamine is an aliphatic monoamine having from 6 to 30 carbon atoms, preferably from 12 to 24 carbon atoms, more preferably from 16 to 22 carbon atoms). Specific examples of such alkanolamines include 2-hydroxyhexylamine, 2-hydroxyheptylamine, 2-hydroxyoctylamine, 2-hydroxynonylamine, 2-hydroxydecylamine, 2-hydroxyundecylamine, 2-hydroxydodecylamine, 2-hydroxytridecylamine, 2-hydroxytetradecylamine, 2-hydroxypentadecylamine, 2-hydroxyhexadecylamine, 2-hydroxyheptadecylamine, 2-hydroxyoctadecylamine, 2-hydroxyheptylundecylamine, 2-hydroxynonadecylamine, 2-hydroxyeicosylamine, 2-hydroxyheneicosylamine, 2-hydroxydocosylamine, 2-hydroxytricosylamine, 2-tetracosylamine, 11-ethyl-2-hydroxytricosylamine, 2-hydroxypentacosylamine, 2-hydroxyhexacosylamine, 2-hydroxyheptacosylamine, 2-hydroxyoctacosylamine, 2-hydroxynonacosylamine, 2-hydroxytriacontylamine, 2-hydroxyhexenylamine, 2-hydroxyheptenylamine, 2-hydroxyoctenylamine, 2-hydroxynonenylamine, 2-hydroxydecenylamine, 2-hydroxyundecenylamine, 2-hydroxydodecenylamine, 2-hydroxytridecenylamine, 2-hydroxytetradecenylamine, 2-hydroxypentadecenylamine, 2-hydroxyhexadecenylamine, 2-hydroxyheptadecenylamine, 2-hydroxyoctadecenylamine, 2-hydroxynonadecenylamine, 2-hydroxyeicosenylamine, 2-hydroxyheneicosenylamine, 2-hydroxydocosenylamine, 2-hydroxytricosenylamine, 2-hydroxytetracosenylamine, 2-hydroxypentacosenylamine, 2-hydroxyhexacosenylamine, 2-hydroxyheptacosenylamine, 2-hydroxyoctacosenylamine, 2-hydroxynonacosenylamine, 2-hydroxytriacontenylamine, etc.
The aliphatic polyamines include aliphatic polyamines having from 6 to 30 carbon atoms in total, preferably from 12 to 24 carbon atoms, more preferably from 16 to 20 carbon atoms. Specific examples of such aliphatic polyamines include hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 1,21-diaminoheneicosane, 1,22-diaminodocosane, 1,23-diaminotricosane, 1,24-diaminotetracosane, 1,25-diaminopentacosane, 1,26-diaminohexacosane, 1,27-diaminoheptacosane, 1,28-diaminooctacosane, 1,29-diaminononacosane, 1,30-diaminotriacontane, hexenyldiamine, heptenyldiamine, octenyldiamine, nonenyldiamine, decenyldiamine, undecenyldiamine, dodecenyldiamine, tridecenyldiamine, tetradecenyldiamine, pentadecenyldiamine, hexadecenyldiamine, heptadecenyldiamine, octadecenyldiamine, nonadecenyldiamine, eicosenyldiamine, heneicosenyldiamine, docosenyldiamine, tricosenyldiamine, tetracosenyldiamine, pentacosenyldiamine, hexacosenyldiamine, heptacosenyldiamine, octacosenyldiamine, nonacosenyldiamine, triacontenyldiamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine, pentapentylenehexamine, tris(2-aminoethyl)amine, etc.
Of the above-mentioned amine-based friction reducing agents, preferred are adducts of primary amines having a saturated or unsaturated, straight-chained or branched aliphatic hydrocarbon group having from 12 to 24 carbon atoms, preferably from 16 to 20 carbon atoms, with alkylene oxide (s) having 2 or 3 carbon atoms, from the viewpoint of the friction-reducing effect thereof.
One alone or two or more different types of those amine-based friction-reducing agents may be used as the component (B), either singly or as combined.
In the present invention, the content of the component (B) is from 0.05% by mass to 5% by mass based on the total amount of the composition, more preferably from 0.1% by mass to 3% by mass. The content of the component (B) of less than 0.05% by mass could not provide a sufficient friction-reducing effect; when the content is more than 5% by mass, any remarkable result of improving the effect corresponding to the increase in the content could not be expected.
In the present invention, the composition contains, as the component (C), an alkaline earth metal salicylate-based detergent and/or an alkaline earth metal sulfonate-based detergent.
The alkaline earth metal salicylate is an alkaline earth metal salt of an alkyl (generally alkyl group with from 4 to 30 carbon atoms) salicylic acid, in which the alkaline earth metal salt is preferably a calcium salt or a magnesium salt, especially preferably a calcium salt.
The alkaline earth metal sulfonate is preferably an alkaline earth metal salt of an alkyl-aromatic sulfonic acid that is obtained through sulfonation of an alkyl-aromatic compound having a molecular weight of from 300 to 1,500, preferably from 400 to 700.
The metallic detergent may be any of neutral salts, basic salts and overbased salts, and in general, herein usable are one or more selected from metallic detergents having a total base number of from 10 mg KOH/g to 500 mg KOH/g, preferably from 15 mg KOH/g to 450 mg KOH/g, more preferably from 15 mg KOH/g to 400 mg KOH/g, either singly or as combined.
In particular, combined use of one or more overbased alkylsalicylates and one or more of neutral sulfonates enhances both the detergency and the abrasion resistance. For example, preferred is combined use of an alkylsalicylate having a total base number of from 150 mg KOH/g to 400 mg KOH/g, more preferably from 180 mg KOH/g to 350 mg KOH/g, and a sulfonate having a total base number of from 0 mg KOH/g to 100 mg KOH/g, more preferably from 10 mg KOH/g to 70 mg KOH/g. In this case, the blend ratio of the overbased alkylsalicylate and the neutral sulfonate (metal amount-equivalent ratio by mass) is preferably 1/(0.02 to 0.5), more preferably 1/(0.05 to 0.3).
The term “total base number” as used herein means the value as measured by a potentiometric titration method (base number/perchlorate method) according to the Item 7 of JIS K 2501 “Petroleum Products and Lubricants-Neutralization Number Testing Method.”
The metallic detergent is, in general, commercially sold and available in a state diluted with a light lubricant base oil or the like. In general, it is desirable that a commercial product having a metal content of from 1.0% by mass to 20% by mass, preferably from 2.0% by mass to 16% by mass, be used.
The content of the metallic detergent of the component (C) is from 0.05% by mass to 0.5% by mass, based on the total amount of the lubricating oil composition and in terms of the alkaline earth metal concentration therein, preferably from 0.1% by mass to 0.3% by mass, more preferably from 0.15% by mass to less than 0.25% by mass.
The content of the component (C) of less than 0.05% by mass would provide insufficient detergency, but the content of more than 0.5% by mass may provide, as the case may be, an insufficient effect of reducing the friction coefficient.
The lubricating oil composition of the present invention may contain, as incorporated therein without detracting from the advantageous effects of the present invention, any other known conventional additive than the components (A), (B) and (C), and for example, there are mentioned a metallic detergent, an ashless dispersant, a friction-reducing agent, a viscosity index improver, a pour-point depressant, an antioxidant, a rust inhibitor, etc.
The metallic detergent includes alkaline earth metal phenates.
The ashless dispersant includes, for example, succinic acid imides, boron-containing succinic acid imides, benzylamines, boron-containing benzylamines, succinates, amides of mono- or di-carboxylic acids such as typically fatty acids or succinic acid, etc. Of those, preferred are boron-free succinic acid imides from the viewpoint of reducing friction.
The friction-reducing agent includes ashless friction-reducing agents such as fatty acid ester-based, aliphatic amine-based, higher alcohol-based ones or the like ashless friction-reducing agents.
As the viscosity index improver, concretely, there are exemplified so-called non-dispersive viscosity index improvers such as various methacrylates as well as copolymers thereof in any desired combination and their hydrides, etc.; and so-called dispersive viscosity index improvers prepared by further copolymerization with various nitrogen compound-containing methacrylates, etc. Further exemplified are non-dispersive or dispersive ethylene-α-olefin copolymers (in which α-olefin is, for example, propylene, 1-butene, 1-pentene, etc.) and hydrides thereof, polyisobutylene and hydrides thereof, styrene-diene copolymer hydrides, styrene-maleic anhydride ester copolymers, as well as polyalkylstyrenes, etc. The molecular weight of those viscosity index improvers must be defined in consideration of shear stability. Concretely, the number-average molecular weight of the viscosity index improver of, for example, dispersive or non-dispersive polymethacrylate is from 5000 to 1000000, preferably from 100000 to 800000; that of polyisobutylene or its hydride is from 800 to 5000; that of ethylene-α-olefin copolymer or its hydride is from 800 to 300000, preferably from 10000 to 200000. One alone or plural types of those viscosity index improvers may be incorporated either singly or as combined, but in general, the content of the improver is from 0.1% by mass to 40.0% by mass or so based on the total amount of the lubricating oil composition.
The pour-point depressant includes, for example, polymethacrylates, etc.
The antioxidant includes phenolic antioxidants and amine-based antioxidants. The phenolic antioxidants include, for example, 4,4′-methylenebis(2,6-di-t-butylphenol); 4,4′-bis(2,6-di-t-butylphenol); 4,4′-bis(2-methyl-6-t-butylphenol); 2,2′-methylenebis(4-ethyl-6-t-butylphenol); 2,2′-methylenebis(4-methyl-6-t-butylphenol); 4,4′-butylidenebis(3-methyl-6-t-butylphenol); 4,4′-isopropylidenebis(2,6-di-t-butylphenol); 2,2′-methylenebis(4-methyl-6-nonylphenol); 2,2′-isobutylidenebis(4,6-dimethylphenol); 2,2′-methylenebis(4-methyl-6-cyclohexylphenol); 2,6-di-t-butyl-4-methylphenol; 2,6-di-t-butyl-4-ethylphenol; 2,4-dimethyl-6-t-butylphenol; 2,6-di-t-amyl-p-cresol; 2,6-di-t-butyl-4-(N,N′-dimethylaminomethylphenol; 4,4′-thiobis(2-methyl-6-t-butylphenol); 4,4′-thiobis(3-methyl-6-t-butylphenol); 2,2′-thiobis(4-methyl-6-t-butylphenol); bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide; bis(3,5-di-t-butyl-4-hydroxybenzyl) sulfide; n-octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl) propionate; 2,2′-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. Among them, bisphenolic and ester group-containing phenolic antioxidants are particularly preferred.
The amine-based antioxidants include, for example, monoalkyldiphenylamines such as monooctyldiphenylamine, monononyldiphenylamine and the like; dialkyldiphenylamines such as 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine, 4,4′-diheptyldiphenylamine, 4,4′-diocyldiphenylamine, 4,4′-dinonyldiphenylamine and the like; polyalkyldiphenylamines such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenylamine and the like; naphthylamines, to be specific, α-naphthylamine, phenyl-α-naphthylamine and alkyl-substituted phenyl-α-naphthylamines such as butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine, nonylphenyl-α-naphthylamine and the like. Among them, dialkyldiphenylamines-based and naphthylamine-based antioxidants are preferred.
As the rust inhibitor, there may be mentioned alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenylsuccinates, polyalcohol esters, etc.
The lubricating oil composition of the present invention may be applied to a sliding face having a low-friction sliding material and can impart excellent low-friction property and excellent abrasion resistance thereto. Especially when applied to internal combustion engines, the lubricating oil composition can achieve a fuel consumption-saving effect.
The sliding face having a low-friction sliding material described above is preferably a sliding face which has a DLC material as the low-friction sliding material and which constitutes at least one of the sliding faces. In this case, a material of the other sliding face may be, for example, a DLC material, an iron base material and an aluminum alloy material. That is, examples of the combination of two sliding faces are a constitution in which both of the two sliding faces are the DLC materials, a constitution in which one sliding face is the DLC material and the other sliding face is the iron base material, and a constitution in which one sliding face is the DLC material and the other sliding face is the aluminum alloy material.
Here, the above-mentioned DLC material has a DLC film on the surface thereof. DLC that constitutes the film is made of an amorphous material constituted mainly of carbon elements, in which the bonding form of carbons includes a diamond structure (SP3 bond) and a graphite bond (SP2 bond).
To be specific, DLC may include a-C (amorphous carbon) composed only of carbon elements, a-C:H (hydrogenated amorphous carbon) containing hydrogen and MeDLC (metal doped DLC) partially containing metal elements such as silicon (Si), titanium (Ti), molybdenum (Mo) and the like.
Among them, a-C:H (hydrogenated amorphous carbon), specifically a-C:H containing from 5 atom % to 50 atom % of hydrogen is preferred.
Further, DLC is preferably DLC showing a graphite crystal peak in the X-ray scattering spectrum thereof.
DLC having such a graphite crystal peak may be formed by a cathode PIG (Penning Ionization Gauge) plasma CVD method in a high density plasma atmosphere.
As the iron base material, on the other hand, there may be mentioned, for example, carburized steel SCM420 and SCr420 (JIS). As the aluminum alloy material, it is preferable to use a hypoeutectic aluminum alloy or a hypereutectic aluminum alloy containing from 4% by mass to 20% by mass of silicon and from 1.0% by mass to 5.0% by mass of copper. To be more specific, there may be mentioned, for example, AC2A, AC8A, ADC12, ADC14 (JIS).
It is also preferred that the DLC material and the iron base material, or the DLC material and the aluminum alloy material each have a surface roughness of 0.1 μm or less in terms of an arithmetic average roughness Ra from the viewpoint of stable sliding. When the roughness is 0.1 μm or less, local scuffing is less liable to be formed, and an increase of friction coefficient can be inhibited. It is further preferred that the DLC material described above has a surface hardness Hv of from 1,000 to 3,500 in terms of micro-Vickers hardness (98 mN load) and a thickness of from 0.3 μm to 2.0 μm.
On the other hand, the iron base material described above has preferably a surface hardness HRC of from 45 to 60 in terms of Rockwell hardness (C scale). This is effective because, the durability of the film can be maintained even exposed to a sliding condition, which is under a high face pressure of about 700 MPa, as is the case with a cam follower.
Also, the aluminum alloy material described above preferably has a surface hardness HB of from 80 to 130 in terms of Brinell hardness.
When the surface hardness and thickness of the DLC material fall within the ranges described above, abrasion and peeling may be inhibited. Further, when the surface hardness of the iron base material is HRC 45 or more, it is possible to inhibit buckling and peeling under a high face pressure. On the other hand, when the surface hardness of the aluminum alloy material falls within the range described above, the aluminum alloy material is inhibited from being abraded.
The sliding part to which the lubricating oil composition of the present invention is applied shall not specifically be restricted as long as it has a surface in which two metal surfaces are brought into contact with each other and in which at least one of them has a low-friction sliding material. A sliding part of an internal combustion engine may be mentioned as a preferred example thereof. In this case, more excellent low-friction property as compared with conventional technique is obtained. And this is effective because the fuel consumption saving effect is also exerted. As the DLC member, for example, there are mentioned disc like shims and lifter crestal planes each having a coating of DLC on a base plate of a steel material. Examples of the iron base material include cam lobes formed of low alloy chilled cast iron, carburized steel or thermally refined carbon steel, or any combination thereof.
2. Sliding Mechanism
The sliding mechanism of the present invention is a sliding mechanism having, as sandwiched between the sliding surfaces of two sliding materials that slide to each other, the above-mentioned lubricating oil composition, in which a DLC film containing hydrogen in an amount of from 5 atom % to 50 atom % is formed on at least one sliding surface of the two sliding materials.
More preferably, the DLC film is a DLC film having graphite crystal peaks in the X-ray scattering spectrum thereof.
A case in which the DLC film described above is a DLC film having graphite crystal peaks in its X-ray scattering spectrum will be explained below with reference to the drawings.
Referring to
A primer layer 21 may be provided, as shown in
The above DLC film having a peak of a graphite crystal may be formed by a cathode PIG (Penning Ionization Gauge) plasma CVD method in a high density plasma atmosphere.
To be specific, a plasma generated, for example, in a cathode PIG is shut in a magnetic field formed by a coil, whereby the plasma is densified. Thus, a raw material gas is decomposed into active atoms, molecules and ions at a high efficiency. Further, a direct current pulse is applied onto the substrate while piling up the highly active raw material gas components, whereby high energy ions can be radiated. This makes it possible to efficiently form a DLC film which is excellent in a sliding characteristic. In respect to the details of the forming method, the method described in Japanese Patent Application No. 2008-335718 is preferred.
In
The DLC film can be formed in the following manner by using the device described above.
First, the substrate 41 which is supported by the holder 42 is disposed in the chamber 40. Next, Ar gas is injected from the gas introducing port 47, and the plasma 50 is generated and stabilized by using the plasma source 43, the electrode 44 and the coil 45. The Ar gas decomposed in the plasma is attracted to the substrate 41 by the bias electric source 49 to carry out surface etching. Then, a metal layer which is a primer layer is formed by using the cathode 46 comprising metal and the Ar gas. Further, a raw material gas injected from the gas introducing port 47 is decomposed and reacted in a high density plasma atmosphere to thereby form graphite crystal in the DLC film. This is maintained as is until the DLC film having a prescribed thickness is obtained. In this case, a crystal diameter of the graphite crystal is controlled so that the diameter becomes from 15 nm to 100 nm.
In the cathode PIG plasma CVD device described above, the characteristics of the DLC film obtained may be changed by changing the plasma characteristics and the kind of gases, and the sliding property and the durability may be improved by optimizing an amount of the graphite crystal and a hardness, a surface roughness and the like of the DLC film in addition to a crystal diameter of the graphite crystal described above.
The presence of the graphite crystal in the DLC film formed and the crystal diameter are preferably confirmed by using X-ray diffraction measurement shown below.
Generally, a plural number of sharp diffraction peaks corresponding to the respective lattice planes are present in an X-ray diffraction spectrum of a crystal material, and a crystal structure thereof is usually determined by checking the above peaks. In contrast to this, in a case of the preferred DLC film of the present invention, the diffraction peaks of the graphite crystal are present among scattered broad peaks which are inherent to an amorphous material and called halo patterns.
Measurement Conditions
X-ray source: radiant light source
X-ray energy: 15 KeV
Incident slit width: 0.1 mm
Detector: scintillation counter (solar slit is placed in the front stage)
Measuring range of scattering angle 2θ: 5 to 100°
Measuring step: 0.1°
Integration time: 30 seconds/step
The DLC film sample was peeled off from the base plate, and it was filled into a narrow glass tube (capillary) and measured.
As shown in
In the embodiment of the present invention, largest 10 peaks are selected among peaks that are present in the derivative spectrum. When there are at least 3 peaks which coincide with the peak positions of the graphite crystal, then the DLC film is judged to contain the graphite crystal. The above method is based on a Hanawalt method used in X-ray diffraction of ordinary crystal materials, that is, a method for characterizing diffraction patterns by using three most intense peaks in the pattern.
Further, the crystal diameter of the graphite crystal may be estimated from broadening of the diffraction peaks shown above. To be more specific, the crystal diameter may be determined by deducting halo patterns attributed to amorphous components as a background from the X-ray scattering spectrum to extract graphite crystal peaks, followed by applying a Scherrer equation shown by Equation 1. The result obtained by extracting the graphite crystal peaks of the same DLC film sample as used in
D=(0.9×λ)/(β×cos θ) Equation 1
The DLC film obtained has, as described above, an amorphous structure comprising carbon as the main component. The bonding form of carbons comprises both of a diamond structure (SP3 structure) and a graphite structure (SP2 structure). The film contains from 10 atom % to 35 atom % of hydrogen.
In general, it is difficult to form the above DLC film on an iron base material, an aluminum alloy and the like with a good adhesive force. Therefore, the intermediate layer as an adhesive layer is provided as described above. More specifically, the intermediate layer preferably comprises any one or more layers of a metal layer, a metal nitride layer or a metal carbide layer containing any metal selected from, for example, Ti, Cr, W and Si. The total thickness of the intermediate layer is preferably from 0.1 μm to 3.5 μm. The thickness of 0.1 μm or more can secure the function of the intermediate layer. On the other hand, the thickness of 3.5 μm or less may prevent the impact resistance and the adhesiveness of the DLC film from being lowered owing to the low hardness of the intermediate layer. The primer layer includes, to be specific, a film of metal selected from, for example, Ti, Cr, W and Si.
The sliding mechanism according to the present invention is constituted from the above-described lubricating oil and the sliding member. Because both of the lubricating oil and the sliding member have an excellent low-friction property, as described above, a sufficiently low friction coefficient can be obtained.
In the sliding member, the DLC film described above is formed on at least one of two sliding faces which slidably move relative to each other. The sliding face of the opposite member is not specifically limited, i.e. a DLC film may be formed similarly thereon or may not be formed. As the material of the opposite member on which a DLC film is not formed, there may be mentioned an iron base material, an aluminum alloy material, etc. which are described above.
Next, the present invention will be described in further detail with reference to examples, but the present invention shall by no means be restricted to these examples.
The lubricating oil compositions comprising the components shown in Table 1 were prepared and subjected to a frictional property test shown below to determine the friction coefficient between the DLC-coated plate and steel (SUJ-2). Further, the compositions were subjected to an abrasion resistance test of steel-to-steel abrasion-resistance experiments to determine the abrasion (wear track size). The results are shown in Table 1.
<Frictional Property Test>
The DLC-coated disc used here is as follows.
DLC containing 20 atom % hydrogen (graphite crystal size 20 nm)
The intermediate layer of the DLC coating is comprised of a Ti layer, and the total thickness thereof is 3.0 μm.
<Abrasion Resistance Test>
The components in Table 1 used in the preparation of the lubricating oil compositions are as follows.
From the results in Table 1, it is known that the compositions of Examples 1 to 4, which are the lubricating oil compositions of the present invention, have a low friction coefficient between DLC (DLC-coated plate) and steel and a small wear track size in steel-to-steel friction, and have good steel-to-steel abrasion resistance.
On the other hand, the composition of Comparative Example 1 not containing a friction-reducing agent has a high friction coefficient between DLC (DLC-coated plate) and steel and a large steel-to-steel wear track size.
Further, the compositions of Comparative Examples 2 and 3 containing a molybdenum-based friction-reducing agent or an ester-based friction-reducing agent have a high DLC-to-steel friction coefficient, and therefore could not attain the object of the present invention.
In addition, the composition of Comparative Example 4 containing an amine-based friction-reducing agent but not containing a zinc primary dialkyldithiophosphate also has a high DLC-to-steel friction coefficient.
The lubricating oil composition of the present invention is applicable to a sliding face formed of a low-friction sliding material such as a DLC material and is capable of imparting excellent low-frictional property thereto. In particular, when applied to internal combustion engines, the lubricating oil composition can give a fuel consumption-saving effect. Further, the sliding mechanism of the present invention in which the lubricating oil composition is allowed to be present is excellent in low-friction property.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2012-060624 | Mar 2012 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2013/057749 | 3/18/2013 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2013/137477 | 9/19/2013 | WO | A |
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