CN100587045C - Low-friction sliding mechanism, low-friction agent composition and method of reducing friction - Google Patents

Low-friction sliding mechanism, low-friction agent composition and method of reducing friction Download PDF

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CN100587045C
CN100587045C CN200480022605A CN200480022605A CN100587045C CN 100587045 C CN100587045 C CN 100587045C CN 200480022605 A CN200480022605 A CN 200480022605A CN 200480022605 A CN200480022605 A CN 200480022605A CN 100587045 C CN100587045 C CN 100587045C
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low
friction
acid
sliding
agent composition
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CN1833018A (en
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琼·米歇尔·马丁
竹岛茂树
小西正三郎
加纳真
马渕丰
石川贵朗
上野贵文
中村清隆
浜田孝浩
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Nissan Motor Co Ltd
Eneos Corp
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Nissan Motor Co Ltd
Nippon Oil Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
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    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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Abstract

The invention provides a low-friction sliding mechanism, a low-friction agent composition, a friction reduction method, a manual transmission and a final reduction gear unit that can exert very excellent low friction characteristics to sliding surfaces present under various applications, and, in particular, that have more excellent low friction characteristics than that of a combination of an existing steel material and an organic Mo compound. Thelow-frictionsliding mechanism has an oxygen-containing organic compound or an aliphatic amine compound interposed between sliding surfaces that a DLCcoated sliding member and a sliding member form. The low-friction agent composition contains an oxygen-containing organic compound or an aliphatic amine compound. The friction reduction method includes supplying the low-friction agent composition between sliding surfaces that a DLC coated sliding member and a sliding member form. The manual transmission includes, as at least one of sliding members, a DLC coated sliding section. The final reduction gear unit includes, as at least one of sliding members, a DLC coated sliding section.

Description

Low-friction sliding mechanism, low-friction agent composition and the method that reduces to rub
Technical field
The present invention relates to low-friction sliding mechanism, low-friction agent composition, the method that reduces to rub, manual transmission and final reduction gear device.More specifically, the present invention relates to low-friction sliding mechanism, it can improve the frictional behaviour of the different sliding surfaces in the drive disk assembly of for example oil engine and drive system; The method that relates to low-friction agent composition and reduce to rub; The manual transmission that is provided by slide unit is provided, and it is good that this slide unit has little frictional coefficient and seizure resistance and wearability, and demonstrated good fuel cost for a long time; And relating to final reduction gear device, these parts can reduce the frictional coefficient of slide unit and improve seizure resistance and wearability, and reduce friction resistance, thereby improve the fuel efficiency of automobile.
Background technology
Global environment problem such as Global warming and depletion of the ozone layer is very remarkable.Especially, reduce CO 2Quantity discharged, it is said has very large influence to Global warming, it has caused how each country to determining the very big concern of adjusted value.
For reducing CO 2, reduce because the energy consumption that the frictional dissipation of machine and equipment brings, especially reducing the automobile fuel cost is a big problem.Correspondingly, the effect of sliding material and lubricant is extremely important in this regard.
The effect of sliding material is to have good wear resistance, and makes that the abominable parts of friction and wear environment have good wear resistance in the slide unit of engine.Recently, various hard thin film materials are advanced in application.The frictional coefficient of DLC material commonly used in air and when the lacking lubricating oil wear-resisting hard coating material more such than TiN and CrN is low; Therefore, these are supposed to as low Frictional Slipping material.
In addition, power-economizing method as lubricating oil, the method of fuel efficiency for engine for example, propose: 1) reduce the reduction of the stirring resistance of the viscous resistance in the hydrostatic lubrication district that causes and engine by lubricating oil viscosity, with 2) owing to sneaked into best friction modifiers and various additive, thus reduce to mix, the lubricated and boundary lubrication frictional dissipation under regional.Mainly, carried out big quantity research as friction modifiers as MoDTC and MoDTP for organic-molybdenum (Mo) compound.On the sliding surface that is made by existing steel, lubricating oil composition wherein using the organic Mo compound that demonstrates good low-friction coefficient in early days, is used expediently.
On the other hand, in air, have the conventional DLC material of good low rubbing characteristics, it is reported in the presence of lubricating oil its effect that reduces to rub low (for example, non-patent literature 1).Be applied on the sliding material even have been found that the lubricating oil composition that will contain organic molybdenum in addition, can not fully show the effect (for example, non-patent literature 2) that reduces to rub.
Non-patent literature 1:Kano et al., Proceedings of JapaneseTribology Society, p.11-12, May, 1999 (Tokyo)
Non-patent literature 2:Kano et al., Proceeding of World TribologyCongress Sep., 2001, p.342, (Vienna)
Therefore, for the fuel efficiency technology of manual gear of vehicle, avoid stirring lubricating oil, or make it very little to prevent to weaken the motion (for example, patent documentation 1) of power transmission efficiency owing to the stirring resistance by power transmission.
Patent documentation 1:JP-A-10-166877
On the other hand, for the lubricating oil that is used for this class transmission, the lubricating oil composition of ashless dispersant, alkaline-earth metal-based dispersion agent and the sulfenyl additive of mixing boracic is by motion (patent documentation 2) in lubricating base oil.In addition, contain zinc dithiophosphate, alkaline-earth metal dispersion agent, have the gear oil of the polybutylene-based alkenyl succinimide of predetermined molecular weight, its derivative, phosphate amine salt and sulphur compound having low sulphur content and have in the base oil of predetermined viscosity by motion (patent documentation 3).
Patent documentation 2:JP-A-2003-82377
Patent documentation 3:JP-A-11-181463
In addition, fuel efficiency technology about the automobile final reduction gear device, intention improves the transmission efficiency of differential gearing, the lubricating oil composition that is used for final reduction gear device is by motion, and it comprises the phosphorus base extreme pressure agent that is selected from specified range, the sulfenyl extreme pressure agent (patent documentation 4) that has the organic acid of ad hoc structure and be selected from specified range in lubricating base oil.
Patent documentation 4:JP-A-6-200274
In addition, in order to reduce the sliding friction loss between roller end surface and the big shield cap of interior wheel, the conical centre of tapered roller external diameter surface is from the tapered roller bearing of the central shaft of interior wheel skew, and this class tapered roller bearing in the application of automobile mixing box by motion (patent documentation 5).
Patent documentation 5:JP-A-2000-192951
Summary of the invention
In aforesaid patent documentation 1 described manual transmission, studied the reduction that lubricating oil stirs resistance.Yet, the reduction that rubs owing to slide unit is not studied improvement, the especially slide unit of performance and fuel efficiency and the consistency between the lubricating oil.
In addition,, formed the lubricating oil of component described in patent documentation 2 and 3 embodiment, to improve wear resistance, fatigue lifetime and the frictional behaviour between clutch ring and the cone gear for lubricating oil itself.Yet, in its research, do not consider the characteristic of sliding component especially, to reduce frictional coefficient.
In addition, the lubricating oil composition of in patent documentation 4, describing that is used for final reduction gear device, the research prescription is to improve the transmission efficiency of geared parts.In addition, in patent documentation 5, the improvement of research tapered roller bearing arrangement is to reduce frictional dissipation.Yet, consistency between the friction that reduces sliding surface self and slide unit and the lubricating oil is not studied.
The present invention considers the existing problem of present technology; And the method that intention provides a kind of low-friction sliding mechanism, low-friction agent composition and reduces to rub, it can provide very good low friction performance to the sliding surface under the various application, and especially it has preferred low friction performance than existing steel and organic Mo combination of compounds.
In addition, the invention is intended to provide a kind of manual transmission that can reduce the frictional coefficient of the various slide units (as parts of bearings) in the manual transmission, improving seizure resistance and wear resistance, and the sliding resistance that reduces each parts is to improve the fuel efficiency of automobile.
In addition, the invention is intended to provide a kind of final reduction gear device, these parts can reduce the frictional coefficient of the various slide units in the final stage deceleration component, for example the side gear back side that contacts slidably by packing ring and the parts between the differential case internal surface, improving seizure resistance and wear resistance, and the sliding resistance that reduces each parts is to improve the fuel efficiency of automobile.
The inventor has overcome the problems referred to above through arduous research, the combination that discovery contains the slide unit of a kind of DLC material and specific compound at least demonstrates very excellent friction performance, to such an extent as to reach the degree that to recognize from existing lubrication theory, thereby finished the present invention.
In addition, the inventor finds, when providing the hard carbon thin film with low hydrogen content on one of the sliding surface of sliding contact to each other or two sides, in the presence of low-friction agent composition, frictional coefficient can reduce widely.In addition, the inventor finds, when covering slide unit with this class hard carbon thin film, for realizing low frictional coefficient and improve seizure resistance and wear resistance that the additive to affect that is used for low-friction agent composition is also not little.Thereby the present invention is accomplished.
That is, the present invention is as follows.
A kind of low-friction sliding mechanism wherein, is inserted with low-friction agent composition between the sliding surface of sliding component (A) that DLC applies and sliding component (B), it is characterized in that:
The sliding component (A) that described DL C applies forms by apply diamond-like carbon on base material;
Described sliding component (B) is selected from down the material in the group and forms with at least a: metallic substance, non-metallic material and coated film and the coating material that forms on the surface of metallic substance or non-metallic material; And
Described low-friction agent composition comprises oxygen-containing organic compound (C), described oxygen-containing organic compound (C) be selected from down the group at least a: alcohol, carboxylic acid, ester, ether, ketone, aldehyde, carbonic ether and derivative thereof.
A kind of method that reduces to rub is characterized in that,
Between sliding component (A) and the formed sliding surface of sliding component (B) that DLC applies, the low-friction agent composition that comprises oxygen-containing organic compound (C) is provided, being lubricated,
Described oxygen-containing organic compound (C) be selected from down the group at least a: alcohol, carboxylic acid, ester, ether, ketone, aldehyde, carbonic ether and derivative thereof,
The sliding component (A) that this DLC applies forms by applying diamond-like carbon, and this sliding component (B) uses at least a material that is selected from down in the group: metallic substance, non-metallic material, reach coated film on the surface of metallic substance or non-metallic material and the coating material that obtains.
A kind ofly it is characterized in that, comprise oxygen-containing organic compound (C) according to employed low-friction agent composition in the low-friction sliding mechanism of the present invention.
A kind ofly it is characterized in that, comprise oxygen-containing organic compound (C) according to employed low-friction agent composition in the method for reducing friction of the present invention.
A kind of manual transmission is characterized in that, uses low-friction sliding mechanism of the present invention.
A kind of final reduction gear device is characterized in that, uses low-friction sliding mechanism of the present invention.
In low-friction sliding mechanism of the present invention, when the sliding surface that forms when the sliding component that is applied by D LC contained oxygen-containing organic compound or fatty amine compound, it can obtain than the combination of present slide unit and low-friction agent composition excellent friction performance more.
In addition, manual transmission according to the present invention has reduced the frictional coefficient of various slide units such as interconnecting piece, has improved seizure resistance and wear resistance, thereby and has reduced the fuel efficiency that sliding resistance in each parts has improved automobile.
In addition, final reduction gear device of the present invention has reduced the frictional coefficient between the side gear back side and the differential case inner face, has improved seizure resistance and wear resistance, thereby and the sliding resistance that has reduced each parts improved the fuel efficiency of automobile.
Description of drawings
Fig. 1 is the sectional view that illustrates according to the sliding part that covers with hard carbon thin film in the manual transmission of the present invention;
Fig. 2 is the sectional view that illustrates according to the sliding part that covers with hard carbon thin film in the final reduction gear device of the present invention;
Fig. 3 illustrates the synoptic diagram that dish is gone up an example of roller rub(bing)test;
Fig. 4 illustrates in the rub(bing)test of embodiment according to the present invention the skeleton view of cylinder swing dynamic friction process of the test on the employed dish;
Fig. 5 illustrates the chart of comparison according to the frictional coefficient test result of roller rub(bing)test gained on the dish shown in Figure 3;
Fig. 6 illustrates the chart of comparison according to the frictional coefficient test result of cylinder swing dynamic friction test gained on the dish shown in Figure 3.
Embodiment
Below, will be described in detail low-friction sliding mechanism of the present invention and low-friction agent composition.In specification sheets, unless otherwise indicated, " % " refers to mass percent.
By comprising that between sliding surface low-friction agent composition forms this low-friction sliding mechanism, described sliding surface is to be formed by sliding component when the sliding component (A) of DLC coating and sliding component (B) slip.Employed low-friction agent composition, it comprises at least a compound that is selected from down in the group: oxygen containing organic compound (C) and fatty amine compound (D).Therefore, the sliding component of DLC coating and sliding component are each other to slide than much lower in the past frictional force.
Herein, DLC (diamond-like carbon) material that is used for the sliding component (A) of DLC coating is the amorphous material that is mainly formed by carbon, and the bonding state between the carbon comprises diamond lattic structure (SP 3Key) and graphite key (SP 2Key).That can mention particularly, is a-C (decolorizing carbon), the hydrogenous a-C:H (decolorizing carbon of hydrogenation) that are formed by carbon fully and the MeC of part containing metal element such as titanium (Ti) or molybdenum (Mo).In low-friction sliding mechanism according to the present invention, from bringing into play the angle of big reduction rubbing effect, the DLC material preferably makes by not wrapping hydrogenous a-C material.In addition, in the DLC material, along with the increase of hydrogen richness, frictional coefficient increases.Therefore, hydrogen richness preferably is less than or equal to 20 atom %.In addition, fully reduce frictional coefficient during for slip in low-friction agent composition, and in order to guarantee more stable sliding capability, its hydrogen richness preferably is less than or equal to 10 atom %, be more preferably less than or equal 5 atom %, and be more preferably less than or equal 0.5 atom %.DLC material with this low hydrogen content can obtain by utilizing PVD method deposition, and these class methods are not utilized hydrogen or hydrogen-containing compound such as sputtering process or ion plating basically.
In this case,, not only wish between depositional stage, to use and do not wrap hydrogenous gas, and wish before deposition, to cure on demand reaction vessel and base material fixer in order to reduce the hydrogen amount in the film, and thorough clean substrate material surface.
In addition, be used for the base material of the sliding component (A) of DLC coating, can use for example converted steel, hardened steel and non-ferrous metal such as aluminium.
About applying the surfaceness of DLC base material before, because the film thickness of hard carbon thin film is quite thin, therefore, the surfaceness of deposited film is had a significant impact, therefore, the surface roughness Ra of base material (center line average roughness) preferably is less than or equal to 0.1 μ m.That is to say, when the surface roughness Ra of base material surpasses 0.1 μ m, because the local contact pressure that the bossing that is caused by the film surfaceness has increased and matched assembly, thereby the possibility of initiation film breaks becomes higher.
In addition, there is no particular limitation to the composition material of sliding component (B).Particularly, can adopt metallic substance such as ferrous material, alumina-base material, mg-based material and titanium base material.Especially, preferred such ferrous material, alumina-base material and mg-based material, it can easily be applied to the slide unit of existing machinery and equipment and can be widely used in conservation measures in each field.
In addition, for the composition material of sliding component (B), also can use non-metallic material such as resin, plastics and carbon.
In addition, also can use by on metal and non-metallic material, applying the material that various film obtained.
Ferrous material is had no particular limits.Not only high purity iron can be used, but also various iron alloys (with nickel, copper, zinc, chromium, cobalt, molybdenum, lead, silicon or titanium, with and the alloy that forms of arbitrary combination) can be used.Particularly, for example can use converted steel SCM420 or SCr420 (JIS).
In addition, alumina-base material is had no particular limits.Not only rafifinal can be used, but also various aluminum base alloys can be used.Particularly, for example can use hypoeutectic aluminium alloy or the hypereutectic aluminium alloy that contains 4% to 20% silicon (Si) and 1.0% to 5.0% bronze medal ideally.The preferred embodiment of the aluminium alloy that can mention is for example AC2A, AC8A, ADC12 and ADC14 (JIS).
In sliding component (B), the metallic substance that is coated with various coatings is had no particular limits.Particularly, what can mention is various metallic substance, as by TiN, CrN or DLC material film are coated in the metal_based material that obtains on the surface of ferrous material, alumina-base material, mg-based material or titanium base material.Wherein, preferably be coated with the metallic substance of DLC material.In addition, the preferably not hydrogenous a-C diamond-like carbon of DLC material.
In addition, consider sliding stability, the surface roughness Ra of sliding component (A) that DLC applies and sliding component (B) (for example metallic substance or with the metallic substance of various thin film coated) is less than or equal to 0.1 μ m, preferably is less than or equal to 0.08 μ m.When surface roughness Ra surpasses 0.1 μ m, can cause local the scuffing in some cases, thereby cause frictional coefficient to increase greatly.
In addition, in the sliding component (A) that DLC applies, preferably its surface hardness is in the scope of micro-vickers hardness (micro-Vickers hardness) (under the 10g load) Hv1000 to 3500, and the DLC film thickness is in the scope of 0.3 to 2.0 μ m.The surface hardness of the sliding component (A) that applies as DLC and thickness not in above-mentioned scope so that surface hardness less than Hv1000 and thickness during less than 0.3 μ m, the sliding component that DLC applies is easy to wearing and tearing, otherwise, when they during respectively greater than Hv3500 and 2.0 μ m, then be easy to peel off, and when the surface hardness of irony member outside this scope so that when being lower than HRC45, then under high pressure, becoming in some cases is easy to wrinkling and peels off.
When ferrous material was used in the sliding component (B), the surface hardness of ferrous material was preferably in the scope of RHC HRC45 to 60.In this case, even under high surface pressure sliding condition, for example, also can keep the weather resistance of film effectively as under about 700MPa in cam follower.
In addition, when alumina-base material was used to sliding component (B), the surface hardness of alumina-base material was preferably at Brinell hardness (Brinell hardness) H BIn the scope of 80-130.When the surface hardness of alumina-base material outside above-mentioned scope so that be lower than H B80 o'clock, alumina-base material became and is easy to wearing and tearing.
In addition, in sliding component (B), use the situation of the metallic substance that is coated with film, especially use the situation of the metallic substance of DL C coating, preferably the surface hardness of this metallic substance is in the scope of micro-vickers hardness (under the 10g load) Hv1000 to 3500, and the DLC film thickness is in the scope of 0.3 to 2.0 μ m.When its surface hardness and thickness not in above-mentioned scope so that surface hardness during less than 0.3 μ m, is easy to cause wearing and tearing less than Hv1000 and thickness, otherwise, when they during greater than Hv3500 and 2.0 μ m, then in some cases, be easy to cause and peel off.
So long as two sliding surfaces contact by low-friction agent composition, the sliding surface that sliding component (A) that is applied by DLC and sliding component (B) form just has no particular limits.For example, to as if the sliding part of oil engine such as 4-two-stroke engine and 2-two-stroke engine (for example, valve operating system, piston, piston ring, piston skirt, cylinder liner, connecting rod, bent axle, bearing, roller bearing, sliding surface bearing, gear, chain, band, oil pump etc.), the sliding part of drive system transmission rig (for example gear) and hard drive, thereby and severe other various sliding surfaces that need low friction performance of friction condition.In sliding surface, only be selected from least a of oxygen containing organic compound and amine compound, just can obtain compared with prior art higher oilness and extremely excellent low friction performance effectively by at least one sliding component, applying DLC and providing.
For example, in the valve operating system of oil engine, embodiment preferred is to use the sliding surface that is made by disk-like pad, crown (lifter crown surface) on coating DLC on the steel base material, the cam of the material of use low-alloy chilled cast iron, converted steel or tempering carbon steel and arbitrary combination thereof.
On the other hand, just there is no particular limitation to the oxygen-containing organic compound (C) in the above-mentioned low-friction sliding mechanism of the present invention, can be any organic compound that contains aerobic in the molecule.It for example can be the oxygen-containing organic compound that constitutes by carbon, hydrogen and oxygen.This oxygen-containing organic compound can comprise other element, as nitrogen, sulphur, halogen (fluorine, chlorine etc.), phosphorus, boron, metal etc.Particularly from sliding component of further reduction (DLC apply sliding component) (A) and the friction of the sliding surface of other sliding component (B) consider, preferably constitute and comprise the oxygen-containing organic compound and the derivative thereof of hydroxyl, wherein more preferably contain two or more hydroxyls by carbon, hydrogen and oxygen.For the same reason, more preferably low sulfur content or the not oxygen-containing organic compound of sulfur-bearing.
Wherein employed " derivative " also has no particular limits, and it can be that the oxygen-containing organic compound and nitrogenous compound, P contained compound, sulphur or sulfocompound, boron-containing compound, halogen or halogen contained compound, metallic element, the containing metal compound compounds such as (inorganic or organic) that for example are made of carbon, hydrogen and oxygen react the compound that obtains.
Above-mentioned oxygen-containing organic compound (C) specifically can be hydroxyl, carboxyl, carbonyl, ester bond or the ehter bond compound of (also can comprise two or more such group or keys), preferably contain one or more group that is selected from hydroxyl, carboxyl, carbonyl and ester bond or keys, more preferably contain one or more and be selected from the group of hydroxyl, carboxyl and ester bond or the oxygen-containing organic compound of key, also more preferably contain the oxygen-containing organic compound that one or more are selected from the group of hydroxyl and carboxyl, especially preferably contain the oxygen-containing organic compound of one or more hydroxyls.
More specifically the example of oxygen-containing organic compound comprise alcohol (I), carboxylic acid (II), ester (III), ether (IV), ketone (V), aldehyde (VI), carbonic ether (these compounds can also further contain one or more group that is selected from hydroxyl, carboxyl, carbonyl, ester bond and ehter bond or keys) (VII), its derivative and mixture arbitrarily thereof.
Above-mentioned alcohol (I) is the oxygen-containing organic compound as following general formula (1) expression:
R-(OH) n (1)
The compound that for example contains one or more hydroxyls.
The example of the alcohol that can mention (I) is as follows:
Monohydroxy-alcohol (I-1);
Dibasic alcohol (I-2);
Ternary or high-grade polyvalent alcohol (I-3) more; And
Be selected from one or more the mixture (I-4) in above-mentioned three kinds of alcohol.
Monohydroxy-alcohol (I-1) has a hydroxyl in molecule, for example it comprises the monobasic alkyl alcohol (wherein alkyl can be a straight or branched) with 1-40 carbon atom, as methyl alcohol, ethanol, propyl alcohol (1-propyl alcohol, the 2-propyl alcohol), butanols (1-butanols, the 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propyl alcohol), amylalcohol (1-amylalcohol, the 2-amylalcohol, the 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 3-methyl-2-butanols, 2-methyl-2-butanols, 2,2-dimethyl-1-propyl alcohol), hexanol (1-hexanol, the 2-hexanol, the 3-hexanol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2,3-dimethyl-1-butanols, 2,3-dimethyl-2-butanols, 3,3-dimethyl-1-butanols, 3,3-dimethyl-2-butanols, 2-ethyl-1-butanols, 2, the 2-dimethyl butyrate alcohol), enanthol (1-enanthol, the 2-enanthol, the 3-enanthol, 2-methyl isophthalic acid-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 5-methyl-2-hexanol, 3-ethyl-3-amylalcohol, 2,2-dimethyl-3-amylalcohol, 2,3-dimethyl-3-amylalcohol, 2,4-dimethyl-3-amylalcohol, 4,4-dimethyl-2-amylalcohol, 3-methyl isophthalic acid-hexanol, 4-methyl isophthalic acid-hexanol, 5-methyl isophthalic acid-hexanol, the 2-ethylpentanol), octanol (1-octanol, sec-n-octyl alcohol, the 3-octanol, 4-methyl-3-enanthol, 6-methyl-2-enanthol, 2-ethyl-1-hexanol, 2-propyl group-1-amylalcohol, 2,4,4-trimethylammonium-1-amylalcohol, 3,5-dimethyl-1-hexanol, 2-methyl isophthalic acid-enanthol, 2,2-dimethyl-1-hexanol), nonyl alcohol (1 nonyl alcohol, the 2-nonyl alcohol, 3,5,5-trimethylammonium-1-hexanol, 2, the 6-2,6-dimethyl-4-heptanol, 3-ethyl-2,2-dimethyl-3-amylalcohol, 5-methyl octanol etc.), decyl alcohol (1-decanol, the 2-decyl alcohol, the 4-decyl alcohol, 3,7-dimethyl-1-octanol, 2,4,6-trimethylammonium enanthol etc.), hendecanol, dodecanol, tridecyl alcohol, tetradecanol, pentadecylic alcohol, cetyl alcohol, heptadecanol, Stearyl alcohol (stearyl alcohol etc.), nonadecanol, eicosanol, heneicosane alcohol, tricosanol, Tetracosyl alcohol; (wherein thiazolinyl can be a straight or branched to have the monohydroxy alkenyl alcohol of 2-40 carbon atom, two keys can be at any desired location place), as vinyl alcohol, vinylcarbinol, butenol, hexenol, octenol, decenol, lanolin alcohol, oleyl alcohol (oleyl alcohol etc.); (wherein alkyl can be a straight or branched to have monohydroxy (alkyl) cycloalkanol of 3-40 carbon atom, alkyl and hydroxyl can be at any desired location places), as cyclopentanol, hexalin, suberyl alcohol, the ring octanol, methylcyclopentanol, methyl-cyclohexanol, dimethyl cyclohexanol, ethyl cyclohexanol, the propyl group hexalin, the butyl hexalin, dimethyl cyclohexanol, cyclopentyl carbinol, cyclohexyl ethyl alcohol (1-cyclohexyl ethyl alcohol, 2-cyclohexyl ethyl alcohol etc.), cyclohexyl ethyl alcohol, cyclohexyl propyl alcohol (3-cyclohexyl propyl alcohol etc.), cyclohexyl butanols (4-cyclohexyl butanols etc.), the butyl hexalin, 3,3,5,5-tetramethyl-ring hexanol; (alkyl) is fragrant and mellow, and (wherein alkyl can be a straight or branched, alkyl and hydroxyl can be at any desired location places), as phenyl alcohol, aminomethyl phenyl alcohol (ortho-cresol, meta-cresol, p-cresol), methoxycresol, ethylphenyl alcohol, propyl group phenyl alcohol, butyl phenyl alcohol, butyl methyl phenyl alcohol (3-methyl-6-tert butyl phenyl alcohol etc.), 3,5-dimethylphenyl alcohol, diethyl phenyl alcohol, dibutyl phenyl alcohol (2,6-di-tert-butyl-phenyl alcohol, 2,4-di-tert-butyl-phenyl alcohol etc.), dibutylmethyl phenyl alcohol (2,6-di-t-butyl-4-aminomethyl phenyl alcohol etc.), dibutyl ethylphenyl alcohol (2,6-di-t-butyl-4-ethylphenyl alcohol etc.), tributyl phenyl alcohol (2,4,6-tri-tert phenyl alcohol etc.), naphthols (naphthyl alcohol, 2-Naphthol etc.), dibutyl naphthols (2,4-di-t-butyl-naphthyl alcohol etc.); 6-(4-hydroxyl-3,5-di-tert-butyl amido)-2, two (n-octyl the sulfo-)-1,3,5-triazines of 4-; And composition thereof.
The alcohol that wherein more preferably has the straight or branched alkyl or alkenyl of 12-18 carbon atom, as oleyl alcohol and stearyl alcohol, because they can more effectively reduce the friction between sliding component (A) that DLC applies and any other the sliding surface of sliding component (B) formation, and their volatility is low, even therefore under hot conditions (for example sliding condition in the oil engine), also have the effect that reduces to rub.
Dibasic alcohol (I-2) is the alcohol that two hydroxyls are arranged in the molecule, for example comprise that (wherein alkyl or alkenyl can be a straight or branched for the glycol of the alkyl or alkenyl with 2-40 carbon atom, two keys of thiazolinyl can be at any desired location place, hydroxyl also can be at any desired location place), as ethylene glycol, Diethylene Glycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 2-butyleneglycol, the 2-methyl isophthalic acid, ammediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 2-ethyl-2-methyl isophthalic acid, ammediol, 2-methyl-2, the 4-pentanediol, 1, the 7-heptanediol, 2-methyl-2-propyl group-1, ammediol, 2,2-diethyl-1, ammediol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 2-butyl-2-ethyl-1, ammediol, 1, the 10-decanediol, 1,11-undecane glycol, 1, the 12-dodecanediol, 1,13-tridecane glycol, 1,14-tetradecane glycol, 1,15-pentadecane glycol, 1,16-n-Hexadecane glycol, 1,17-heptadecane glycol, 1, the 18-octadecandiol, 1,19-nonadecane glycol, 1,20-eicosane glycol; (alkyl) naphthenic hydrocarbon glycol (wherein alkyl can be a straight or branched, alkyl and hydroxyl can at any desired location place) is as cyclohexanediol, methyl cyclohexane glycol; Having the binary (alkyl) of 2-40 carbon atom, fragrant and mellow (wherein alkyl can be a straight or branched, alkyl and hydroxyl can be at any desired location places), as Benzenediol (pyrocatechol etc.), the methylbenzene glycol, the ethylbenzene glycol, butylbenzene glycol (p-ten.-butylcatechol etc.), dibutyl Benzenediol (4,6-di-tert-butyl resorcin etc.), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,2 '-thiobis (4, the 6-di-tert-butyl resorcin), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 2,2 '-(3,5-di-t-butyl hydroxyl) propane, 4,4 '-cyclohexadiene two (2,6 di t butyl phenol); P-tert-butylphenol/formaldehyde condensation products, p-tert-butylphenol/acetaldehyde condensation thing; And composition thereof.
Wherein preferred ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butyleneglycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 2-methyl-2,4-pentanediol, 2-ethyl-2-methyl isophthalic acid, ammediol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane two pure and mild 1, the 12-dodecanediol is because they can more effectively reduce the friction that DLC applies the sliding surface of sliding component (A) and any sliding component (B).Also preferred molecular weight is at least 300, preferably is at least 400 high molecular hindered alcohols as 2 in addition, 6-di-t-butyl-4-(3,5-di-t-butyl-4-acrinyl) phenyl alcohol, even because they at high temperature (for example under the sliding condition in oil engine) also be difficult to the volatilization, has excellent heat resistance, and they can demonstrate the effect that reduces to rub well, can give the antioxidative stabilizer of lubricating oil excellence.
Ternary or more high-grade polyvalent alcohol (I-3) be alcohol with three or its above hydroxyl.3 to 10 yuan of alcohol of general use preferably use 3 to 6 yuan of alcohol.The example of these components is trimethylolalkane such as glycerine, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane; And erythritol, tetramethylolmethane, 1,2,4-trihydroxybutane, 1,3,5-penta triol, 1,2,6-hexanetriol, 1, Sorbitol Powder, ribitol, arabitol, Xylitol, mannitol; And polymkeric substance or condenses (as the glycerine dipolymer to octamer, as two glycerine, triglycerin, four glycerine; The TriMethylolPropane(TMP) dipolymer is to octamer, as two TriMethylolPropane(TMP)s; The tetramethylolmethane dipolymer is to tetramer such as Dipentaerythritol; Sorbitanic; Condenses such as Sorbitol Powder/glycerol condensate (comprise intramolecular condensation thing, intermolecular condensation thing and from condenses)).
Also can use carbohydrate such as wood sugar, arabitol, ribose, rhamnosyl, glucose, fructose, semi-lactosi, seminose, sorbose, cellobiose, seminose, isomaltose, trehalose and sucrose.
Wherein more preferably 3 to 6 yuan of alcohol such as glycerine, trimethylolalkane (as trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane), tetramethylolmethane, 1,2,4-trihydroxybutane, 1,3,5-penta triol, 1,2,6-hexanetriol, 1,2,3,4-butantetraol, Sorbitol Powder, sorbitanic, Sorbitol Powder/glycerol condensate, ribitol, arabitol, Xylitol, mannitol and composition thereof; More preferably glycerine, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, sorbitanic and composition thereof.Special preferred oxygen content is at least 20%, preferably be at least 30%, more preferably be at least 40% polyvalent alcohol.The polyvalent alcohol that is higher than hexavalent alcohol can increase oil body too much.
Above-mentioned carboxylic acid (II) is the compound of following general formula (2) expression:
R-(CO?OH) n (2)
The compound that for example contains one or more carboxyls.
The example of carboxylic acid (II) is as follows:
Aliphatics monocarboxylic acid (lipid acid) (II-1);
Aliphatics polycarboxylic acid (II-2);
Carbocyclic ring carboxylic acid (II-3);
Heterocyclic carboxylic acid (II-4); With
Be selected from two or more mixture (II-5) of above-mentioned four kinds of carboxylic acids.
Aliphatics monocarboxylic acid (lipid acid) is the carboxylic acid that a carboxyl is arranged in the molecule (II-1), for example it comprises the representative examples of saturated aliphatic monocarboxylic acid (wherein the representative examples of saturated aliphatic structure can be a straight or branched) with 1-40 carbon atom, as formic acid, acetate (acetic acid), propionic acid (n Propanoic acid), butyric acid (butanic acid, isopropylformic acid etc.), valeric acid (positive valeric acid, isovaleric acid, PIVALIC ACID CRUDE (25) etc.), caproic acid (n-caproic acid etc.), enanthic acid, sad (n-caprylic acid etc.), n-nonanoic acid (pelargonic acid etc.), capric acid, undecanoic acid, dodecylic acid (lauric acid etc.), tridecanoic acid, tetradecanoic acid (tetradecanoic acid etc.), pentadecylic acid, hexadecanoic acid (palmitinic acid etc.), margaric acid, octadecanoic acid (stearic acid etc.), nondecylic acid, arachic acid, heneicosanoic acid, docosoic acid, tricosanic acid, Lignoceric acid, pentacosoic acid, hexacosanoic acid, carboceric acid, octocosoic acid, montanic acid, triacontanoic acid; (wherein the unsaturated aliphatic structure can be a straight or branched to have the unsaturated aliphatic monocarboxylic acid of 1 to 40 carbon atom, unsaturated link(age) can be at any desired location place), as vinylformic acid (acrylic acid etc.), propynoic acid (propiolic acid etc.), butenoic acid (methacrylic acid, Ba Dousuan, iso-crotonic acid etc.), pentenoic acid, hexenoic acid, heptenoic acid, octylenic acid, nonenoic acid, decylenic acid, undecylenic acid, dodecenoic acid, tridecylenic acid, tetradecenoic acid, pentadecylenic acid, hexadecylenic acid, heptadecenoic acid, octadecenoic acid (oleic acid etc.), jecoleic acid, eicosenoic acid, heneicosene acid, Decosahedaenoic acid, tricosenoic acid, tetracosenoic acid, Timnodonic Acid, hexacosenoic acid, cerotene acid, two octadecenoic acids, two jecoleic acids, lumequeic acid.
Aliphatics polycarboxylic acid (II-2) comprises that (wherein saturated or unsaturated aliphatic structure can be a straight or branched to the saturated or unsaturated aliphatic di-carboxylic acid with 2 to 40 carbon atoms, unsaturated link(age) can be at any desired location place), as oxalic acid (oxalic acid), propanedioic acid (maleic acid etc.), Succinic Acid (succsinic acid, Methylpropanedioic acid etc.), pentanedioic acid (glue acid, ethyl malonic acid etc.), hexanodioic acid (adipic acid etc.), pimelic acid (jambulol etc.), suberic acid (cork acid etc.), nonane diacid (lepargylic acid etc.), sebacic acid (sebacic acid etc.), the propylene diacid, butene dioic acid (toxilic acid, fumaric acid etc.), propene dicarboxylic acid (citraconic acid, methylfumaric acid etc.), hexene diacid, pentene dicarboxylic acid, octene diacid, nonene diacid, octene dicarboxylic acid; (wherein saturated or unsaturated aliphatic structure can be a straight or branched to saturated or unsaturated tribasic carboxylic acid, unsaturated link(age) can be at any desired location place), as the third three acid, fourth three acid, penta 3 acid, oneself three acid, acid in heptan three, hot three acid, acid in the ninth of the ten Heavenly Stems three, acid in the last of the ten Heavenly stems three; Saturated or unsaturated quaternary carboxylic acid (wherein saturated or unsaturated aliphatic structure can be a straight or branched, unsaturated link(age) can at any desired location place).
Carbocyclic ring carboxylic acid (II-3) is the carboxylic acid that one or more carboxyls are arranged in the carbocyclic ring molecule, for example it comprises: carbonatoms 3 to 40 have one of a naphthenic ring, two, three or tetracarboxylic acid (if alkyl or alkenyl is wherein arranged, then alkyl or alkenyl can be a straight or branched, if two keys are arranged, then two keys can be at any desired location place, to substituent number and position without limits), hexanaphthene monocarboxylic acid for example, the methylcyclohexane monocarboxylic acid, the ethylcyclohexane monocarboxylic acid, the propyl cyclohexane monocarboxylic acid, the butyl cyclohexane monocarboxylic acid, amyl group hexanaphthene monocarboxylic acid, hexyl hexanaphthene monocarboxylic acid, heptyl hexanaphthene monocarboxylic acid, octyl group hexanaphthene monocarboxylic acid, the suberane monocarboxylic acid, the cyclooctane monocarboxylic acid, trimethyl cyclopentane dicarboxylic acid (dextrocamphoric acid etc.); The one dollar aromatic carboxylic acid of carbonatoms 7 to 40, as benzene carboxylic acid (phenylformic acid), methylbenzene carboxylic acid (toluic acid etc.), ethylbenzene carboxylic acid, propylbenzene carboxylic acid, benzene dicarboxylic acid (phthalic acid, m-phthalic acid, terephthalic acid etc.), benzene tricarbonic acid's (trimellitic acid etc.), benzene tertacarbonic acid's (pyromellitic acid etc.), naphthalene monocarboxylic acid (naphthoic acid etc.); One, two, three or the tetracarboxylic acid with aryl of carbonatoms 7 to 40 are (if wherein have alkyl or alkenyl as substituting group, then alkyl or alkenyl can be a straight or branched, if two keys are arranged, then two keys can be at any desired location place, to substituent number and position without limits), the alkyl salicylate with one or more alkyl of phenylpropionic acid (hydratropic acid), phenylacrylic acid (atropic acid, styracin etc.), Whitfield's ointment, carbonatoms 1 to 30 for example.
Heterocyclic carboxylic acid (II-4) is the carboxylic acid that one or more carboxyls are arranged in molecule, and it comprises the carboxylic acid that for example has 5 to 40 carbon atoms, as furancarboxylic acid, thiophene carboxylic acid, pyridine carboxylic acid (nicotinic acid, Yi Yansuan etc.).
Above-mentioned ester (III) is the compound of following general formula (3) expression:
R-(COO-R′) n (3)
The compound that for example contains one or more ester bonds,
The example of ester (III) is as follows:
The ester (III-1) of aliphatics monocarboxylic acid (lipid acid);
The ester of aliphatics polycarboxylic acid (III-2);
The ester of carbocyclic ring carboxylic acid (III-3);
The ester of heterocyclic carboxylic acid (III-4);
Be selected from the mixture (III-5) of any compound of above-mentioned 5 kinds of esters.
The ester of above-mentioned III-1 to III-5 can be all esterified complete ester of hydroxyl and carboxyl, also can be the part ester that part of hydroxyl or carboxyl are kept intact.
The ester (III-1) of aliphatics monocarboxylic acid (lipid acid) is that one or more are selected from above-mentioned aliphatics monocarboxylic acid (lipid acid) acid (II-1) and one or more and are selected from above-mentioned one, two, three or the ester of the alcohol of higher polyol (I-1 to I-3) more.Lipid acid refers to the aliphatics monocarboxylic acid herein.Specifically, the preferred example of ester is Rylo MG 19, glycerol dioleate, sorbitanic monooleate, sorbitanic dioleate etc.
The ester of aliphatics polycarboxylic acid (III-2) is that one or more are selected from the acid of above-mentioned aliphatics polycarboxylic acid (II-1) and one or more and are selected from above-mentioned one, two, three or the ester of the alcohol of higher polyol (I-1 to I-3) more.Preferred example is that one or more are selected from and have 2 to 40, preferred 4 to 18, more preferably the polycarboxylic acid of the di-carboxylic acid of 6 to 12 carbon atoms is selected from one or more and has 4 to 40, preferred 4 to 18, the more preferably diester of the alcohol of the monohydroxy-alcohol of 6 to 14 carbon atoms, for example dibutyl maleinate, L-glutamic acid two (tridecyl) ester, hexanodioic acid two (2-ethylhexyl) ester, diisodecyl adipate, hexanodioic acid two (tridecyl) ester, sebacic acid two (2-ethylhexyl) ester, and these diester (as dibutyl maleinate) and have the multipolymer of the poly-alpha-olefin of 4-16 carbon atom; The alpha-olefin adducts of diacetyl oxide etc. and ester with alcohol of 1 to 40 carbon atom.
The ester of carbocyclic ring carboxylic acid (III-3) is that one or more are selected from the acid of above-mentioned carbocyclic ring carboxylic acid (II-3) and one or more and are selected from above-mentioned one, two, three or the ester of the alcohol of higher polyol (I-1 to I-3) more.Preferred examples is an aromatic carboxylic acid ester, for example phthalic ester, trimellitate, pyromellitic ester, salicylate.
The ester of heterocyclic carboxylic acid (III-4) is that one or more are selected from the acid of above-mentioned heterocyclic carboxylic acid (II-4) and one or more and are selected from above-mentioned one, two, three or the ester of the alcohol of higher polyol (I-1 to I-3) more.
Above-mentioned ether (IV) is the compound of following general formula (4) expression:
R-(O-R′) n (3)
The compound that for example contains one or more ehter bonds.
The example of ether (IV) is as follows:
Saturated or unsaturated aliphatic ether (IV-1);
Aromatic oxide (IV-2);
Cyclic ethers (IV-3);
Polyalcohol ether (IV-4); With
Be selected from the mixture (IV-5) of two or more ethers of above-mentioned three kinds of ethers.
Specifically, saturated or unsaturated aliphatic ether (aliphatic monoethers) is to have the saturated of 1 to 40 carbon atom or unsaturated aliphatic ether (IV-1) (wherein saturated or unsaturated aliphatic structure can be a straight or branched, unsaturated link(age) can be at any desired location place), dimethyl ether for example, Anaesthetie Ether, di ether, Di Iso Propyl Ether, dibutyl ether, diisobutyl ether, two n-pentyl ethers, diisoamyl ether, hexyl ether, diheptyl ether, dicaprylyl ether, dinonyl ether, didecyl ether, two (undecyl) ether, two (dodecyl) ether, two (tridecyl) ether, two (tetradecyl) ether, two (pentadecyl) ether, two (hexadecyl) ether, two (heptadecyl) ether, two (octadecyl) ether, two (nonadecyl) ether, two (eicosyl) ether, methyl ethyl ether, the methyl n-propyl ether, methyl isopropyl ether, methyl-isobutyl ether, methyl tertiary butyl ether, methyl n-pentyl ether, the methyl isoamyl ether, the ethyl n-propyl ether, the ethyl isopropyl ether, the ethyl isobutyl ether, Ethyl Tertisry Butyl Ether, ethyl n-pentyl ether, the ethyl isoamyl ether, divinyl ether, diallyl ether, methylvinylether, methallyl ether, ethyl vinyl ether, ethyl allyl ether.
Specifically, aromatic oxide (IV-2) comprises for example methyl-phenoxide, phenyl ethyl ether, phenyl ether, dibenzyl ether, benzyl phenyl ether, Alpha-Naphthyl ether, betanaphthyl ether, polyphenylene ether, perfluoro-ether; These ethers can have saturated or unsaturated group (wherein saturated or unsaturated group can be a straight or branched, and unsaturated link(age) can be at any desired location place, to substituent number and position without limits).Preferably, these ethers particularly at room temperature are liquid under working conditions.
Specifically, cyclic ethers (IV-3) is the ether with 2 to 40 carbon atoms, and for example it comprises oxyethane, propylene oxide, trimethylene oxide, tetrahydrofuran (THF), tetrahydropyrans, dioxane, glycidyl ether; These ethers can have saturated or unsaturated group, carbocyclic ring or have the saturated or unsaturated aliphatic group of isocyclic (wherein saturated or unsaturated group can be a straight or branched, unsaturated link(age) can be at any desired location place, to substituent number and position without limits).
Polyalcohol ether (IV-4) comprises one or more ethers of one or more polyalcohols, and this polyalcohols is selected from above-mentioned glycol or triol (I-2 to I-3) or monohydroxy-alcohol.The ether of indication of the present invention can be all hydroxyls of polyalcohols all by the complete ether of etherificate, also can be the part ether that part of hydroxyl is kept intact, wherein therefore part ether be preferred owing to shown low friction performance.
Ketone (V) is the compound of following general formula (5) expression:
R-(CO-R′) n (5)
For example, oxygen-containing organic compound and contain the compound of one or more carbonyls.
The preferred example of above-mentioned ketone (V) comprising:
Saturated or unsaturated aliphatic ketone (V-1);
Carbocyclic ring ketone (V-2);
Heterocyclic ketone (V-3);
Keto-alcohol (V-4);
Ketone acid (V-5); With
Be selected from two or more mixture (V-6) of above-mentioned five class ketone.
Specifically, saturated or unsaturated aliphatic ketone (V-1) can be that the saturated or unsaturated aliphatic ketone with 1 to 40 carbon atom (can be straight or branched, locating at an arbitrary position to have unsaturated link(age)), for example acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl Ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), pinacoline, metacetone, 4-Heptanone, diisopropyl ketone, methyl vinyl ketone, mesityl oxide or Sulcatone.
Specifically, carbocyclic ring ketone (V-2) can be the carbocyclic ring ketone with 1 to 40 carbon atom equally, for example cyclobutanone, cyclopentanone, pimelinketone, methyl phenyl ketone, Propiophenone, n-butyrophenone, isobutyl phenenyl ketone, benzophenone, dibenzyl ketone or 2-acetonaphthone, they can have saturated or unsaturated aliphatic group (can be a straight or branched, can be in any position of unsaturated link(age), substituent position and number also are arbitrarily).
Specifically, heterocyclic ketone (V-3) can be the carbocyclic ring ketone with 1 to 40 carbon atom equally, for example thienylmethylketone or 2-acetofuran ketone, they can have saturated or unsaturated aliphatic group (can be a straight or branched, can be in any position of unsaturated link(age), substituent position and number also are arbitrarily).
Specifically, keto-alcohol (ketone alcohol) (ketol) (V-4) can be the keto-alcohol with 1-40 carbon atom equally, for example hydroxyacetone, acetoin, acetyl ethyl alcohol, diacetone alcohol, phenacyl alcohol or bitter almond oil camphor, they can have carbocyclic ring or heterocycle (heterocycle), can have also that (aliphatic group can be a straight or branched with the carbocyclic ring of saturated or unsaturated aliphatic group or heterocycle, can be in any position of unsaturated link(age), substituent position and number also are arbitrarily).
Specifically, ketone acid (V-5) can be the ketone acid with 1 to 40 carbon atom equally, for example alpha-ketoacid such as pyruvic acid, benzoyl formic acid or phenylpyruvic acid, beta-keto acid such as etheric acid, propionyl acetate or benzoyl acetic acid, perhaps γ-ketone acid such as levulinic acid or 6-benzoylamino propionic acid.
Aldehyde (VI) is the oxygen-containing organic compound of following general formula (6) expression:
R(CHO) n (6)
The compound that for example has one or two aldehyde radical.
The object lesson of above-mentioned aldehyde (VI) comprising:
Saturated or unsaturated aliphatic aldehyde (VI-1);
Carbocyclic ring aldehyde (VI-2);
Heterocyclic aldehydes (VI-3);
Be selected from two or more mixture (VI-4) of above-mentioned three kinds of aldehyde.
Specifically, saturated or unsaturated aliphatic aldehyde (VI-1) can be that (so saturated or unsaturated aliphatic structure can be a straight or branched to the saturated or unsaturated aliphatic aldehyde with 1 to 40 carbon atom, unsaturated link(age) can be located at an arbitrary position), formaldehyde for example, acetaldehyde, propionic aldehyde, butyraldehyde, isobutyric aldehyde, valeral, isovaleric aldehyde, pivalyl aldehyde, n-hexyl aldehyde, enanthaldehyde, octanal, aldehyde C-9, capraldehyde, hendecanal, lauryl aldehyde, tridecylic aldehyde, myristic aldehyde, pentadecane aldehyde, palm fibre paulownia aldehyde, heptadecylaldehyde, stearyl aldehyde, propenal, crotonic aldehyde, propionic aldehyde, oxalic dialdehyde or suceinic aldehyde.
Specifically, carbocyclic ring aldehyde (VI-2) can be the carbocyclic ring aldehyde with 1 to 40 carbon atom, for example phenyl aldehyde, o-toluylaldehyde, a toluic aldehyde, p-tolualdehyde, salicylic aldehyde, phenylacrolein, α-naphthaldehyde or β-naphthaldehyde, they can have saturated or unsaturated aliphatic group (can be a straight or branched, can be in any position of unsaturated link(age), substituent position and number also are arbitrarily).
Specifically, heterocyclic aldehydes (VI-3) can be the heterocyclic aldehydes with 1 to 40 carbon atom, furfural for example, and they can have saturated or unsaturated aliphatic group (can be a straight or branched, can be in any position of unsaturated link(age), substituent position and number also are arbitrarily).
Carbonic ether (VII) is the oxygen-containing organic compound of following general formula (7) expression:
R-(O-COO-R′) n (7)
The compound that for example has one or two carbonic acid ester bond.
Specifically, carbonic ether (VII) can be the carbonic ether with 1 to 40 carbon atom, it has saturated or unsaturated aliphatic group, carbon ring group, carbon ring group with saturated or unsaturated aliphatic group, or (so saturated or unsaturated aliphatic group can be a straight or branched to have the saturated or unsaturated aliphatic group of carbon ring group, the position of unsaturated link(age) is any, substituent position and number also are arbitrarily), methylcarbonate for example, diethyl carbonate, the carbonic acid di-n-propyl ester, the carbonic acid diisopropyl ester, n-butyl carbonate, the carbonic acid diisobutyl ester, the dimethyl dicarbonate butyl ester, diamyl carbonate, the carbonic acid dihexyl, carbonic acid two heptyl esters, the carbonic acid dioctyl ester, carbonic acid ester in two ninth of the ten Heavenly Stems, carbonic acid didecyl ester, carbonic acid two (undecane) ester, carbonic acid two (dodecane) ester, carbonic acid two (tridecane) ester, carbonic acid two (tetradecane) ester, carbonic acid two (pentadecane) ester, carbonic acid two (n-Hexadecane) ester, carbonic acid two (heptadecane) ester, carbonic acid two (octadecane) ester, or diphenyl carbonate, or the hydroxyl that the addition oxirane forms on these carbonic ethers (gathering) oxyalkylene carbonic ether.
On the other hand, R in general formula (1)-(7) and R ' represent that independently of one another (these alkyl can also further comprise one or more groups or the key that is selected from hydroxyl, carboxyl, carbonyl, ester bond and ehter bond, can also further comprise the element such as nitrogen or sulphur (as heterogeneous ring compound), halogen (as fluorine or chlorine), phosphorus, boron or the metal that are not carbon, hydrogen and oxygen for alkyl such as alkyl, thiazolinyl, alkylidene group, cycloalkyl, alkyl-cycloalkyl, aryl, alkylaryl or arylalkyl.
Carbon atom number to alkyl is not particularly limited, but preferred 1 to 40 carbon atom, more preferably 2 to 30 carbon atoms, preferred especially 3 to 20 carbon atoms.
The example of alkyl comprises the alkyl with 1 to 40 carbon atom, methyl for example, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, the straight or branched amyl group, the straight or branched hexyl, the straight or branched heptyl, the straight or branched octyl group, the straight or branched nonyl, the straight or branched decyl, the straight or branched undecyl, the straight or branched dodecyl, the straight or branched tridecyl, the straight or branched tetradecyl, the straight or branched pentadecyl, the straight or branched hexadecyl, the straight or branched heptadecyl, the straight or branched octadecyl, the straight or branched nonadecyl, the straight or branched eicosyl, the straight or branched heneicosyl, the straight or branched docosyl, straight or branched tricosyl or straight or branched tetracosyl, the alkyl that preferably has 2 to 30 carbon atoms especially preferably has the alkyl of 3 to 20 carbon atoms.
The example of thiazolinyl comprises the thiazolinyl with 2 to 40 carbon atoms, vinyl for example, the straight or branched propenyl, the straight or branched butenyl, the straight or branched pentenyl, the straight or branched hexenyl, the straight or branched heptenyl, the straight or branched octenyl, straight or branched nonene base, straight or branched decene base, the straight or branched undecenyl, the straight or branched dodecenyl succinic, straight or branched tridecylene base, straight or branched tetradecene base, straight or branched 15 carbene bases, straight or branched cetene base, straight or branched heptadecene base, straight or branched vaccenic acid base, straight or branched 19 carbene bases, straight or branched eicosylene base, straight or branched heneicosene base, straight or branched two dodecenyl succinic, straight or branched tricosene base or straight or branched tetracosa carbon thiazolinyl, the thiazolinyl that preferably has 2 to 30 carbon atoms especially preferably has the thiazolinyl of 3 to 20 carbon atoms.
The example of cycloalkyl comprises the cycloalkyl with 3 to 40 carbon atoms, and for example cyclopentyl, cyclohexyl, suberyl or ring octyl group preferably have the cycloalkyl of 3 to 20 carbon atoms, especially preferably have the cycloalkyl of 5 to 8 carbon atoms.
The example of alkyl-cycloalkyl is given and is comprised the alkyl-cycloalkyl with 4 to 40 carbon atoms, methylcyclopentyl for example, dimethylcyclopentyl (comprising all structure isomerides), methylethyl cyclopentyl (comprising all structure isomerides), diethyl cyclopentyl (comprising all structure isomerides), methylcyclohexyl, Dimethylcyclohexyl (comprising all structure isomerides), methylethyl cyclohexyl (comprising all structure isomerides), diethyl cyclohexyl (comprising all structure isomerides), the methyl suberyl, dimethyl suberyl (comprising all structure isomerides), methylethyl suberyl (comprising all structure isomerides) or diethyl suberyl (comprising all structure isomerides), the alkyl-cycloalkyl that preferably has 5 to 20 carbon atoms especially preferably has the alkyl-cycloalkyl of 6 to 12 carbon atoms.
The example of aryl comprises the aryl with 6 to 20 carbon atoms, and phenyl or naphthyl for example preferably has the aryl of 6 to 10 carbon atoms.
The example of alkylaryl comprises the alkylaryl with 7 to 40 carbon atoms, for example monosubstituted phenyl such as tolyl (comprising all structure isomerides), ethylbenzene base (comprising all structure isomerides), straight or branched propyl phenyl (comprising all structure isomerides), straight or branched butylbenzene base (comprising all structure isomerides), straight or branched penta phenyl (comprising all structure isomerides), the own phenyl of straight or branched (comprising all structure isomerides), straight or branched phenyl in heptan (comprising all structure isomerides), the hot phenyl (comprising all structure isomerides) of straight or branched, straight or branched nonyl phenyl (comprising all structure isomerides), straight or branched phenyl in the last of the ten Heavenly stems (comprising all structure isomerides), straight or branched undecyl phenyl (comprising all structure isomerides) or straight or branched dodecylphenyl (comprising all structure isomerides); Perhaps have the aryl of two or more identical or different straight or branched alkyl such as xylyl (comprising all structure isomerides), diethyl phenyl, two propyl phenyls, 2-methyl-6-tert butyl phenyl, 2,6-di-t-butyl-4-aminomethyl phenyl or 2,6-di-t-butyl-4-(3,5-di-t-butyl-4-phenmethyl) (alkyl can also comprise aryl, alkylaryl or arylalkyl to phenyl, comprise all structure isomerides), the alkylaryl that preferably has 7 to 20 carbon atoms especially preferably has the alkylaryl of 7 to 12 carbon atoms.
Equally, the example of arylalkyl comprises the arylalkyl with 7 to 40 carbon atoms, for example phenmethyl, styroyl, hydrocinnamyl (isomer that comprises propyl group), benzene butyl (isomer that comprises butyl), benzene amyl group (isomer that comprises amyl group) or benzene hexyl (isomer that comprises hexyl), the arylalkyl that preferably has 7 to 20 carbon atoms especially preferably has the arylalkyl of 7 to 12 carbon atoms.
The derivative of above-mentioned organic oxygen-containing organic compound (C) can equally with oxygen-containing organic compound use.The example of this analog derivative is nitrogenous compound, sulphur or sulfocompound, boron-containing compound, halogen or halogen contained compound, metallic element or containing metal compound (inorganic or organic) etc., and reacts the compound that obtains with oxirane; Yet this derivative is not limited to above-claimed cpd.Specifically, this derivative comprises the compound that for example will be selected from a kind of sulfuration in above-mentioned alcohol, carboxylic acid, ester and ether, ketone, aldehyde and the carbonic ether and prepare; With its halogenation (fluoridize, chlorination) and the compound of preparation; Itself and the reaction product of acid as sulfuric acid, nitric acid, boric acid, phosphoric acid or their ester or metal-salt; The reaction product of itself and metal, containing metal compound or amine compound.
Wherein be preferably selected from the reaction product (as Manny phase (Mannich) reaction product, acylate, acid amides) of one or more materials and the amine compound of alcohol, carboxylic acid and derivative thereof.
Preferred herein amine compound comprises ammonia, monoamine, diamines and polyamines.More specifically, their example is an ammonia; Has carbonatoms and is the alkylamine (wherein alkyl can be a straight or branched) of 1 to 30 alkyl, methylamine for example, ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecyl amine, lauryl amine, tridecyl amine, tetradecylamine, pentadecyl amine, hexadecylamine, heptadecyl amine, octadecylamine, stearylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, two heptyl amices, Di-Octyl amine, nonyl amine, didecylamine, two (undecyl) amine, two (dodecyl) amine, two (tridecyl) amine, two (tetradecyl) amine, two (pentadecyl) amine, two (hexadecyl) amine, two (heptadecyl) amine, two (octadecyl) amine, thyl methyl amine, the first propylamine, the first butylamine, the second propylamine, the second butylamine and third butylamine; Has carbonatoms and is the alkenyl amine (wherein thiazolinyl can be a straight or branched) of 2 to 30 thiazolinyl, for example vinyl amine, propenyl amine, butenyl amine, octenyl amine and oleyl amine; Has carbonatoms and is the alkanolamine (wherein silane alcohol base can be a straight or branched) of 1 to 30 triacontanol group, for example carbinolamine, thanomin, Propanolamine, butanolamine, amylalcohol amine, hexanol amine, enanthol amine, octanol amine, nonyl alcohol amine, methanol amine, methyl alcohol Propanolamine, methyl alcohol butanolamine, ethanol propanol amine, ethanol and butanol amine and propyl alcohol butanolamine; Has carbonatoms and is Alkylenediamine such as methylene diamine, ethylene diamine, trimethylene diamine and the butylene diamine of 1 to 30 alkylidene group; Polyamines such as diethylenetriamine, Triethylenetetramine (TETA), tetren, penten; Derived from above-mentioned monoamine, diamines or polyamines and also have the compound that carbonatoms is 8 to 20 alkyl or alkenyl, as undecyl diethylamine, undecyl diethanolamine, dodecyl dipropanolamine, oil base diethanolamine, oil base trimethylene diamine, stearyl tetren; Heterogeneous ring compound such as N-hydroxyethyl oil-based imidazoline; The oxirane adducts of these compounds; And composition thereof.
In these nitrogenous compounds, preferably has carbonatoms and is the fatty amine (these alkyl or alkenyls can be straight or brancheds) of 10 to 20 alkyl or alkenyl, for example decyl amine, lauryl amine, tridecyl amine, heptadecyl amine, octadecylamine, oleyl amine and stearylamine.
In the derivative of these oxygen-containing organic compounds, the acid amides such as the amine hydroxybenzene of preferred above-mentioned aliphatics monocarboxylic acid (lipid acid) carboxylic acid (II-1) with 8 to 20 carbon atoms.
Owing to reducing aspect the friction goodly, preferably having the above-mentioned oxygen-containing organic compound of hydroxyl.Directly link to each other with hydroxyl and to compare the preferred alcoholic hydroxyl of hydroxyl as carboxyl with carbonyl.In addition, although the hydroxyl value in the compound is not limited, because its good effect that reduces to rub preferably has a plurality of hydroxyls.Yet under situation about using with medium of discussing later such as lubricating oil, the limited amount of hydroxyl is fixed sometimes from deliquescent angle.
The example of the fatty amine compound (D) in the low-friction agent composition of the present invention is to have C separately 6-C 30, preferred C 8-C 24, more preferably C 10-C 20The hydrocarbon chain of straight or branched or the fatty amine compound of group.When the carbonatoms of hydrocarbon chain was not in 6 to 30 scope, what lubricating oil just might be able to not produce expection fully reduced the effect that rubs.If the straight or branched aliphatic alkyl in above-mentioned carbon number range, can certainly be other alkyl.
C 6-C 30The specific examples of straight or branched hydrocarbon chain comprises: alkyl, for example hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl, triacontyl; And thiazolinyl, for example hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base, vaccenic acid base, 19 carbene bases, eicosylene base, heneicosene base, two dodecenyl succinic, tricosene base, tetracosa carbon thiazolinyl, ppentacosene base, cerotene base, cerotene base, two vaccenic acid bases, 29 carbene bases and triacontylene base.
Abovementioned alkyl and thiazolinyl comprise all possible straight or branched structure.In addition, the position of double bond of thiazolinyl is arbitrarily.
The example of fatty amine compound (D) can be various amine compound and derivative thereof, the nitrogen-containing heterocycle compound of monoamine, polyamines, alkanolamine, imidazolinium compounds etc. for example, and they all have carbonatoms is 6 to 30 straight or branched aliphatic alkyl.
The object lesson of monoamine is: lauryl amine, lauryl dimethylamine, palmitamide, stearylamine, oleyl amine etc.
The object lesson of polyamines is: stearyl tetren, oil base trimethylene diamine etc.
The object lesson of alkanolamine is: lauryl diethanolamine, dodecyl dipropanolamine, oil base diethanolamine etc.
The object lesson of nitrogen-containing heterocycle compound is a N-hydroxyethyl oil-based imidazoline etc.
The example of derivative is oxirane adducts, sour modified compound etc.
The example of oxirane adducts is that oxirane is added to the compound that is obtained in the oxynitride of above-mentioned various amine compound, to have carbonatoms be the N that is obtained in the unary primary amine of 6 to 28 alkylidene group and thiazolinyl to object lesson in order oxirane is added to, N-two polyoxygenated ethylidene-N-alkyl (thiazolinyl) amine, more specifically be N, N-two polyoxygenated ethylidene-N-oleyl amine etc.
The example of acid modified compound is the compound that above-mentioned various amine compound and carboxylic acid (II) reaction make, preferred above-mentioned aliphatics monocarboxylic acid (II-1) (more preferably have carbonatoms be 2 to 30 monocarboxylic acid), (more preferably have carbonatoms is 2 to 30 to above-mentioned aliphatics polycarboxylic acid (II-2), or contain polycarboxylic acid of oxalic acid etc.), (more preferably have carbonatoms is 6 to 30 to above-mentioned carbocyclic ring carboxylic acid (II-3), or contain phthalic acid, trimellitic acid and pyromellitic acid etc.) so that neutralization or remaining amino of amidation all or part and/or imido grpup.
Above-mentioned oxygenatedchemicals (C) and fatty amine compound (D) separately (or with 100% amount) are used for the sliding component (A) that D LC applies and the sliding surface of sliding component (B) as low-friction agent composition, thereby demonstrate extremely good low friction performance.Yet, in low-friction agent composition of the present invention, can use other component to sneak in oxygen-containing organic compound (C) and/or the fatty amine compound (D), and offer sliding surface, thus lubricated sliding surface.As other component, the example is the medium as lubricant base, various additives etc.
The content of oxygen-containing organic compound (C) or fatty amine compound (D) is not done special restriction; Yet, from reducing the angle of rubbing effect, be generally 0.001% based on the content lower limit of low-friction agent composition total amount (total mass), preferred 0.05%, more preferably 0.1%, especially preferred 0.5%.Its upper content limit is aforesaid 100%.In other is formed, preferably sneak into medium, from concerning the angle of the solvability of medium and stability in storage, its upper limit based on the low-friction agent composition total amount is generally 50%, and is preferred 20%, and more preferably 10%, especially preferred 5%.In the present invention, even add a spot of about oxygen-containing organic compound of 0.1% to 2% (C) and/or fatty amine compound (D) also can demonstrate good low friction performance.In addition, if mainly consider solvability and the stability in storage of fatty amine compound (D) to medium, then preferably its upper limit is preferably 3.0%, and more preferably 2.0%, also more preferably 1.4%.
The object lesson of above-mentioned medium have mineral oil, synthetic oil, natural fats and oils, thinning oil, lubricating oil, wax, hydrocarbon, hydrocarbon solvent, the nonhydrocarbon organic solvent except that hydrocarbon solvent, water etc. with 3-40 carbon atom, and composition thereof, particularly be liquid, grease-like or waxy medium under sliding condition or under the normal temperature.
Above-mentioned medium especially preferably uses lubricant base (base oil of lubricating oil).This class lubricating oil base oil is not particularly limited, can uses any common base oil that can be used for lubricant compositions, mineral oil origin or synthesis type base oil all can.
The example of mineral oil origin lubricant base comprises the product of preparation with the following method: obtain the lubricant cut with distillation or vacuum distilling crude oil under the normal atmosphere, then the lubricant cut is carried out at least a treatment process in solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydrofining and the wax isomerization, particularly pass through the isomerized base oil of hydrocracking, hydrofining or wax.In these products, the preferred mineral oil that obtains by hydrofining or hydrocracking, or by GTL (gas is to liquid) wax isomerization that obtains by Fischer-Tropsch method (Fischer-Tropsche) or the resulting isoparaffin mineral oil of the wax isomerization of being rich in n-paraffin that in the lubricating oil dewaxing step, obtains.
The example of synthesis type lubricant base comprises: the described alkylnaphthalene of preamble, alkylbenzene, polybutene and hydrogenation product thereof; Poly-alpha-olefin is as 1-octene oligopolymer, 1-decene oligopolymer, ethylene, propylene oligopolymer or its hydrogenation product; Isobutylene oligomer and hydrogenated products thereof; Isoparaffin, alkylbenzene, alkylnaphthalene, diester (for example trimethyl propane ester such as trimethyl propane octanoate, trimethyl propane pelargonate, TriMethylolPropane(TMP) pelargonate, TriMethylolPropane(TMP) isostearate etc.; And pentaerythritol ester such as tetramethylolmethane-2-ethylhexanoate, tetramethylolmethane pelargonate), polyoxyalkylene glycol, dialkyl group phenyl ether, polyphenylene oxide etc.; And their mixture.The example of preferred synthetic lubricant base oil is a poly-alpha-olefin, as 1-octene oligopolymer, 1-decene oligopolymer etc., and their hydrogenation product.
Except using mineral oil origin lubricant base or the synthesis type lubricant base separately or as mixture, can also use the mixture of two or more mineral oil origin base oils or synthesis type base oil.Equally in these mixtures, the ratio of mixture of two or more base oils is not particularly limited, can select arbitrarily.
Aromatic hydrocarbons total content in the lubricant base also is not particularly limited, but preferably is less than or equal to 15%, be more preferably less than or equal 10%, further more preferably 8%.When the aromatic hydrocarbons total content in the lubricant base greater than 15% the time, will cause the oxidative stability variation, be worthless therefore.Even in lubricant base, for example in hydrogenated products, polyol ester or its mixture of grease lubrication oil base oil such as highly hydrogenated cracked mineral oil, wax isomerization mineral oil, poly-alpha-olefin or hydrogenated products, 1-decene oligopolymer, the aromatic hydrocarbons total content is less than or equal to 2%, or even 0%, also can access and have the high composition that reduces rubbing effect.Surpass under 2% the situation at organic oxygen-containing organic compound (C) (not comprising ester) content as lubricant base, because stability in storage may be damaged, so if desired, preferably mineral oil of purifying by mixed solvent or alkylbenzene are regulated the aromatic hydrocarbons total content (for example more than or equal to 2%) in the lubricant base, perhaps use ester to be used as lubricant base, thereby increase the solubleness of oxygenatedchemicals (C).The aromatic fraction content that " aromatic hydrocarbons total content " expression is measured according to ASTM D2549, these aromatic fractions contain alkylbenzene, alkylnaphthalene, anthracene, phenanthrene, its alkylation products usually, four or a plurality of phenyl ring condensed compound in the compound, and the compound such as pyrimidine, quinoline, phenol and the naphthols that contain the heteroaromatic structure.
In addition, the sulphur content in the lubricant base is not particularly limited.Sulphur content based on the base oil total amount is no more than 0.2%, more preferably no more than 0.1%, also more preferably no more than 0.05%.Especially, the mineral oil of hydrogenation purifying or the sulphur content of synthetic base oil are no more than 0.005% or in fact do not comprise sulphur (being no more than 5ppm), so it is preferably used as base oil.
Equally, the kinematic viscosity of lubricant base is not particularly limited, but under the situation as the lubricant compositions of oil engine, the kinematic viscosity under 100 ℃ is preferably greater than or equals 2mm 2/ s, more preferably greater than or equal 3mm 2/ s, and its upper limit preferably is less than or equal to 20mm 2/ s, more preferably less than or equal 10mm 2/ s especially preferably is less than or equal to 8mm 2/ s.When the kinematic viscosity of lubricant base under 100 ℃ more than or equal to 2mm 2/ s can obtain fully forming the composition of oil film, excellent lubricating property is arranged, and base oil also has less vaporization losses under hot conditions.And on the other hand, the kinematic viscosity under 100 ℃ is to be less than or equal to 20mm 2/ s can reduce fluid resistance, has the more composition of friction resistance thereby can access in lubricated position.If kinematic viscosity is lower than 2mm 2/ s may obtain enough friction resistance when the volatility difference, not preferred.If kinematic viscosity is higher than 20mm 2/ s then may be difficult to show its low friction performance when low-temperature performance is degenerated, not preferred.In the present invention, can use by two or more and be selected from the directly mixed mixture that gets of above-mentioned base oil, wherein also can use the base oil with kinematic viscosity (as single base oil) except that above-mentioned, if this base oil in the kinematic viscosity under 100 ℃ within above-mentioned preferable range.
In addition, the viscosity index of lubricant base is not particularly limited, but is preferably greater than or equals 80, and under the situation of the lubricant compositions that is used as oil engine, be preferably greater than or equal 100, more preferably greater than or equal 120, and can be in 140 to 250 scopes.The lubricant base of high viscosity index (HVI) can access low temperature viscosity excellent performance not only but also at the composition of the effect excellence that reduces oil consumption, fuel efficiency performance and reduce to rub.
In order to improve desired properties, low-friction agent composition can further include the independent or multiple ashless dispersant that is used in combination, anti-wear agent or extreme pressure agent, metal matrix sanitising agent, antioxidant, viscosity index improver, is different from (C) and friction modifiers (D), rust-preventive agent, nonionogenic tenside, emulsion splitter, metal passivator or defoamer.
As ashless dispersant, can use various known ashless dispersants.For example can advantageously use polybutylene-based succinimide or derivatives thereof.
Above-mentioned polybutylene-based succinimide comprises the compound of following chemical structural formula (1) and (2) expression.
Figure C20048002260500351
In this chemical structural formula, PIB represents polybutylene-based derived from polybutene.Can prepare polybutene with the following method: in the presence of boron fluoride catalyst or aluminum chloride catalyst,, make the number-average molecular weight of polybutene reach 900 to 3,500 with the polymerization of mixtures of high-purity isobutylene or 1-butylene and iso-butylene, preferred 1,000 to 2,000.When the number-average molecular weight of polybutene is lower than 900, might not have the effect of abundant cleaning.When the number-average molecular weight of polybutene is higher than at 3,500 o'clock, polybutene may destroy low-temperature fluidity.
In each chemical structural formula, n represents 1 to 5 integer, and is preferred 2 to 4, to reach good cleaning action.When producing polybutylene-based succinimide, can will remove from the trace fluorine and the cl residue of above-mentioned polybutene production catalyzer with the treatment process (as absorption method or washing method) of any appropriate, polybutene purification back is used.Preferably the content of fluorine and cl residue is controlled to be and is less than or equal to 50ppm, more preferably less than or equal 10ppm, most preferably be less than or equal to 1ppm.
Production method to polybutylene-based succinimide is not particularly limited.For example can prepare polybutylene-based succinimide with the following method: make the muriate of above-mentioned polybutene or remove fluorine and the muriate of the polybutene of cl residue and maleic anhydride reaction under 100 to 200 ℃, form polybutylene-based succinate, make the polybutylene-based succinate and polyamines (as diethylenetriamine, Triethylenetetramine (TETA), tetren or the penten) reaction of formation like this then.
The example of polybutylene-based succinimide derivatives is the polybutylene-based succinimide of formula (1) and (2) and boron compound or oxygen-containing organic compound reaction with boron and the sour modified compound that all or part of remaining amino and/or imido grpup neutralization or amidation are obtained.Wherein preferably use two (polybutylene-based) succinimides of boracic polybutylene-based succinimide, particularly boracic.
Above-mentioned boron compound can be boric acid, borate or boric acid ester.The object lesson of boric acid comprises ortho-boric acid, metaboric acid and to boric acid.Boratory object lesson comprises the ammonium salt of boric acid, as ammonium metaborate, tetraboric acid ammonium, ammonium pentaborate and eight ammonium borates.The object lesson of boric acid ester comprises: boric acid and alkanol (preferred C 1-C 6Alkanol) ester is as boric acid one methyl esters, trimethyl borate, trimethyl borate, boric acid one ethyl ester, boric acid diethyl ester, triethyl borate, boric acid one propyl ester, boric acid dipropyl, tripropoxy-boron, boric acid one butyl ester, boric acid dibutylester and tributyl borate.In the polybutylene-based succinimide of boracic of the present invention, the mass content of nitrogen and boron is than (B/N) normally 0.1 to 3, preferred 0.2 to 1.
The example of above-mentioned oxygen-containing organic compound has: C 1-C 30Monocarboxylic acid, as formic acid, acetate, oxyacetic acid, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, palmitinic acid, margaric acid, stearic acid, oleic acid, nondecylic acid and arachic acid; C 2-C 30Polycarboxylic acid, as oxalic acid, phthalic acid, trimellitic acid and pyromellitic acid, its acid anhydrides and ester; C 2-C 6Oxirane; And hydroxyl (gathering) oxyalkylene carbonic ether.
Add-on in low-friction agent composition is not particularly limited to polybutylene-based succinimide and/or its derivative, in the total amount of lubricating oil, and its add-on preferably 0.1% to 15%, more preferably 1.0% to 12%.When the add-on of polybutylene-based succinimide and/or its derivative is lower than 0.1%, possibly can't reach sufficient cleaning action.When the add-on of polybutylene-based succinimide and/or its derivative is higher than 15%, then very uneconomical.In addition, so a large amount of polybutylene-based succinimide and/or its derivative deterioration that can cause demulsification performance.
The example that is different from above-mentioned ashless dispersant has: have number-average molecular weight respectively and be 900 to 3500 polybutylene-based polybutylene-based benzene methanamine and polybutylene-based amine, have number-average molecular weight less than 900 polybutylene-based polybutylene-based succinimide and derivative thereof.
As antioxidant and anti-wear agent, can sneak into various known compounds.For example, as antioxidant and anti-wear agent, preferably comprise the zinc dithiophosphate of following formula (3) expression.
Figure C20048002260500371
In chemical formula (3), R 4, R 5, R 6And R 7Represent C separately 1-C 24Alkyl.C 1-C 24Alkyl is C preferably 1-C 24Straight or branched alkyl, C 3-C 24Straight or branched thiazolinyl, C 5-C 13Cycloalkyl or straight or branched alkyl-cycloalkyl, C 6-C 18Aryl or straight or branched alkylaryl or C 7-C 19Arylalkyl.Abovementioned alkyl or thiazolinyl can be primary, the second month in a season or tertiary alkyl or thiazolinyl.
R 4, R 5, R 6And R 7Object lesson comprise: alkyl, for example 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, and tetracosyl; Thiazolinyl, propenyl for example, pseudoallyl, butenyl, butadienyl, 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 (oil base), 19 carbene bases, eicosylene base, heneicosene base, two dodecenyl succinic, tricosene base, and tetracosa carbon thiazolinyl; Cycloalkyl, cyclopentyl for example, cyclohexyl and suberyl; Alkyl-cycloalkyl, methylcyclopentyl for example, dimethylcyclopentyl, the ethyl cyclopentyl, the propyl group cyclopentyl, the methylethyl cyclopentyl, the trimethylammonium cyclopentyl, the diethyl cyclopentyl, the dimethyl ethyl cyclopentyl, the methyl-propyl cyclopentyl, the ethyl propyl cyclopentyl, the dipropyl cyclopentyl, methylethyl propyl group cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, the ethyl cyclohexyl, the propyl group cyclohexyl, the methylethyl cyclohexyl, trimethylcyclohexyl, the diethyl cyclohexyl, the dimethyl ethyl cyclohexyl, the methyl-propyl cyclohexyl, the ethyl propyl cyclohexyl, the dipropyl cyclohexyl, methylethyl propyl group cyclohexyl, the methyl suberyl, the dimethyl suberyl, the ethyl suberyl, the propyl group suberyl, the methylethyl suberyl, the trimethylammonium suberyl, the diethyl suberyl, the dimethyl ethyl suberyl, the methyl-propyl suberyl, the ethyl propyl suberyl, the dipropyl suberyl, and methylethyl propyl group suberyl; Aryl, for example phenyl and naphthyl; Alkylaryl, for example tolyl, xylyl, ethylbenzene base, propyl phenyl, methylethyl phenyl, trimethylphenyl, butylbenzene base, methyl-propyl phenyl, diethyl phenyl, dimethyl ethyl phenyl, tetramethylphenyl, penta phenyl, own phenyl, heptan phenyl, hot phenyl, nonyl phenyl, the last of the ten Heavenly stems phenyl, undecyl phenyl, and dodecylphenyl; Arylalkyl, for example phenmethyl, methylbenzene methyl, dimethyl benzene methyl, styroyl, methylbenzene ethyl and dimethyl benzene ethyl.
Above-mentioned alkyl comprises all admissible straight or branched structures.The binding position of position, alkyl and the cycloalkyl of the two keys of thiazolinyl and the binding position of alkyl and aryl all are arbitrarily.
The object lesson of spendable zinc dithiophosphate comprises zinc diisopropyl dithiophosphate, the diisobutyl zinc dithiophosphate, two sec-butyl zinc dithiophosphates, the di-sec-amyl zinc dithiophosphate, the di-n-hexyl zinc dithiophosphate, two Sec-Hexyl zinc dithiophosphates, the dioctyl zinc dithiophosphate, two-(2-ethylhexyl) zinc dithiophosphates, two positive decyl zinc dithiophosphates, two dodecyl zinc dithiophosphates, two isotridecyl zinc dithiophosphates, and composition thereof.
The add-on of zinc dithiophosphate in lubricating oil is not particularly limited.In order to produce the higher effect that reduces to rub, based on the total amount of lubricating oil, zinc dithiophosphate content preferably is less than or equal to 0.1% according to phosphoric, and be more preferably less than or equal 0.06%, most preferably be its minimal effective dose.When zinc dithiophosphate content greater than 0.1% the time, may suppress the effect of the good reduction friction of oxygen-containing organic compound (C) on the sliding surface of DLC member and various metallic substance (especially iron).
Can prepare zinc dithiophosphate with any known method.For example can prepare zinc dithiophosphate with the following method: make the R that has in above-mentioned chemical general formula (3) 4, R 5, R 6And R 7The alcohol of alkyl or phenol and thiophosphoric anhydride reaction form phosphorodithioic acid, use in the zinc oxide then and the phosphorodithioic acid that so forms.In this application, the molecular structure of zinc dithiophosphate is with as the alcohol of zinc dithiophosphate raw materials for production etc. and different.
The example of other anti-wear agent or extreme-pressure additive has: disulphide, the sulfuration grease, alkene sulfide, have 1 to 3 C 2-C 20The amine salt of the phosphoric acid ester of alkyl, thiophosphatephosphorothioate, phosphorous acid ester, thiophosphite and these esters.
Metal detergent can be lubricating oil used any metal cleaning immunomodulator compounds usually, and the object lesson that can be used for metal detergent of the present invention comprises sulfonate, phenates and the salicylate of basic metal or alkaline-earth metal; And two or more mixture.Alkali-metal example comprises sodium (Na) and potassium (K), and the example of alkaline-earth metal comprises calcium (Ca) and magnesium (Mg).Can suitably use the salicylate of phenates, sodium and calcium of sulfonate, sodium and the calcium of sodium and calcium in the present invention.Can select the total basicnumber and the content of metal detergent according to the performance of lubricating oil needs.The total basicnumber of the metal detergent of measuring according to the perchloric acid method of ISO 3771 " the perchloric acid potentiometric titration is determined base number " is normally 0 to 500mgKOH/g, and preferred 150 to 400mgKOH/g.In the total mass of lubricating oil, the content of metal detergent normally 0.1% to 10%.
Antioxidant can be any antioxidant that is generally used for lubricating oil.The object lesson that can be used for antioxidant of the present invention comprises: phenol antioxidant, and as 4,4-methylene-bis (2,6 di t butyl phenol) and octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester; Amino antioxidant is as phenyl-a-naphthylamine, alkyl phenyl-alpha-naphthylamine and alkyl diphenylamine; And two or more mixture.In the total mass of lubricating oil, the content of antioxidant normally 0.01% to 5%.
Viscosity index improver can specifically be exemplified as: non-dispersive type viscosity index improver, as be selected from one or both the monomeric multipolymers of various methacrylic acids and the hydride of this multipolymer; The decentralized viscosity index improver is as the methacrylic ester multipolymer of (comprising nitrogenous compound).Following material also can be used as viscosity index improver: the multipolymer of hydride, vinylbenzene and the maleic anhydride of the multipolymer of ethene and alpha-olefin (as propylene, 1-butylene and 1-amylene) and the multipolymer of hydride, polyisobutene and hydride thereof, vinylbenzene and diene thereof, and polyoxyethylene alkylphenyl ethene.
The molecular weight of viscosity index improver will be selected according to shear stability.For example for decentralized or non-dispersive type polymethacrylate, the number-average molecular weight scope of viscosity index improver wishes it is 5,000 to 1,000,000, more preferably 100,000 to 800,000; For polyisobutene and hydride thereof, its scope is 800 to 5,000; For ethylene/alpha-olefin copolymer and hydride thereof, its scope is 800 to 300,000, more preferably 10,000 to 200,000.Above-mentioned viscosity index improver can use separately, also can use with two or more the form of mixture.In the total mass of lubricating oil, the amount of viscosity index improver is preferably 0.1% to 40.0%.
Except that above-mentioned (C) and the example of the friction improver (D) can be the metal friction improving agent, as boric acid ester, molybdenum dithiophosphate, molybdenum dithiocarbamate and molybdenumdisulphide etc.
The example of rust-preventive agent has: as alkylbenzene sulfonate, dinonylnaphthalene sulfonic acid salt, alkenyl succinic acid ester and polyol ester.
The example of nonionogenic tenside or emulsion splitter has: nonionic polyalkylene glycol tensio-active agent, and as poly-epoxy ethyl alkyl oxide, poly-epoxy ethyl alkyl phenyl ether, poly-epoxy ethyl alkyl naphthyl ether.
The example of metal passivator has: tetrahydroglyoxaline, pyrimidine derivatives, thiazole, benzotriazole, thiadiazole etc.
The example of defoamer has: silicone, fluorosilicone and fluoro-alkyl ether.
These additive-package are contained in when being used for low-friction agent composition of the present invention, and its content is as follows: except that (C) and the content of friction improver, rust-preventive agent or emulsion splitter (D) can in the scope of total composition 0.01% to 5%, select aptly; And the content of metal passivator can be selected in the scope of total composition 0.0005% to 1% aptly.
Below, will describe the method that reduces to rub of the present invention in detail.
In the method that this reduces to rub, between the sliding surface that forms by DLC coating sliding component (A) that applies with diamond-like carbon and sliding component (B), insert low-friction agent composition, described sliding component (B) uses metallic substance, non-metallic material or coating material and arbitrary combination thereof by obtaining at its surface-coated film, uses a kind of compound that is selected from oxygen-containing organic compound (C) and fatty amine compound (D) between sliding surface at least.Thereby, can improve the low friction performance of various sliding surfaces.
Below, will describe in detail according to manual transmission of the present invention.
Manual transmission according to the present invention utilizes above-mentioned low-friction sliding mechanism and comprise that described sliding component slides over each other by apply the sliding part that diamond-like carbon forms at least one sliding surface of sliding component in the presence of low-friction agent composition.Thereby, owing to reduced the frictional coefficient of sliding part, therefore improved seizure resistance and wear resistance, and, can improve the fuel consumption of automobile owing to the low sliding resistance in each one.
Fig. 1 is the sectional view that illustrates according to an example of the sliding part in the manual gear of vehicle of the present invention.Manual transmission 1 according to the present invention comprises: in clutch housing, and the input shaft 3 that supports by two spot contact bearing 2a and 2b with rotating freely; And the main shaft 5 that supports by roller bearing 4a and spot contact bearing 4b with rotating freely, respectively 3-speed input gear 3a and 4-speed input gear 3b are rotatably joined on the input shaft by needle bearing 2c and 2d, and 5-speed input gear 3c is installed on the input shaft.
On the other hand, to rotatably join on the main shaft 5 with the 1-speed master gear 5a of the gear 3d engagement of input shaft 3 with the 2-speed master gear 5b of the gear 3e engagement of input shaft 3 respectively by needle bearing 4c and needle bearing 4d, described needle bearing 4d installs by 2-speed axle sleeve 6a.In addition, the 5-speed master gear 5c that will mesh with the 5-speed input gear 3c of input shaft 3 by needle bearing 4e rotatably joins on the main shaft 5, and described needle bearing 4e installs by 5-speed axle sleeve 6b.
In manual transmission 1 according to the present invention, in the sliding part between the needle bearing 2c of input shaft 3 and 3-speed input gear 3a, and on the surface of input shaft 3 one sides in the sliding part between the needle bearing 2d of input shaft 3 and 4-speed input gear 3b, can apply hard carbon thin film.Much less, hard carbon thin film can be coated on the surface of needle bearing 2c and 2d, and can form hard carbon coating in its surface.
In addition, for main shaft 5, hard carbon thin film can be coated on the surface of the main shaft 5 in the sliding part between the needle bearing 4c of main shaft 5 and 1-speed master gear 5a; And on the surface of the axle sleeve 6a in the sliding part between the 2-that is coated at main shaft 5 speed axle sleeve 6a and the needle bearing 4d and on the surface of the axle sleeve 6b in the sliding part between 5-speed axle sleeve 6b and needle bearing 4e.Equally in this case, on the surface of needle bearing 4a, 4b or 4e, or on two sliding surfaces that contact with each other and slide, can form the hard carbon shallow layer.
Can be respectively on the interior perimeter surface of 3-speed input gear 3a, the 4-speed input gear 3b, 1-speed master gear 5a, 2-speed master gear 5b and the 5-speed master gear 5c that contact with each other and slide with each needle bearing 2c, 2d, 4c, 4d and 4e, form required hard carbon coating.
In the above, on 5 sliding parts altogether shown in the example, promptly the 3-of input shaft 3 speed input gear 3a and 4-speed input gear 3b on 1-speed master gear 5a, the 2-speed master gear 5b and 5-speed master gear 5c of main shaft 5, form hard carbon thin film.This hard carbon thin film can be formed on other sliding part, on each sliding part of spot contact bearing 2a, the 2b of for example rotatably mounted input shaft 3 and main shaft 5,4b and roller bearing 4a.
In addition, employed low-friction agent composition in this manual transmission, when be used in have as the sliding surface of hard carbon thin films such as D LC on the time, demonstrate extremely good low friction performance.Yet, especially, in order to improve the required performance of work oil as variator, add metal base sanitising agent, antioxidant, viscosity index improver, other ashless friction modifiers, other ashless dispersant, anti-wear agent or extreme pressure agent, rust-preventive agent, nonionogenic tenside, emulsion splitter, metal passivator and defoamer separately or in the mode of multiple combinations of substances, can improve desired properties.
Next, will describe in detail according to final reduction gear device of the present invention.
Use above-mentioned low-friction sliding mechanism according to final reduction gear device of the present invention, and be included in the sliding part that is formed by diamond coated class carbon at least one sliding surface of sliding component, described sliding component slides over each other in the presence of low-friction agent composition.Owing to can reduce the frictional coefficient of sliding part, therefore can improve seizure resistance and wearability, and the sliding resistance of each one be lower, can improve the fuel consumption of vehicle.
Fig. 2 is the sectional view that illustrates according to the example of sliding part in the automobile final reduction gear device of the present invention.Final reduction gear device 20 comprises: in differential box (reduction box) 22, the top is provided with the main drive shaft 23 of driver pinion 23a; Be equipped with and the gear ring 25a of driver pinion 23a engagement and the differential carrier 25 that rotatably supports by side bearing 24 by differential box 22; Two side gears 26 that in differential carrier 25, rotatably supported; And two pinion(gear)s 28 that in differential carrier 25, rotatably support by shaft pinion 27, and these two pinion(gear)s 28 mesh with side gear 26 respectively, differential box 22 rotatably supports main drive shaft 23 by two roller bearings 29, and this main drive shaft 23 links to each other with transmission shaft.
In final reduction gear device 20, when transmission shaft revolves spool, rotation is sent to differential carrier 25 by driver pinion 23a and gear ring 25.When vehicle was kept straight on, differential carrier 25 rotate integratedly with side gear 26 and pinion(gear) 28, thus with identical speed left and to the right live axle rotate.
On the other hand, when vehicle when turning round, because the increase of interior axle resistance, the rotation in differential carrier 25 respectively of side gear 26 and pinion(gear) 28, the speed of rotation of interior axle is slack-off thus, only by these, the speed of rotation of outer shaft accelerates, thereby can change the direction of vehicle reposefully.
Now, as the sliding component in the final reduction gear device 20, that can mention is the roller 24a of for example side bearing 24 and inner race 24b, differential carrier 25, side gear 26, shaft pinion 27, pinion(gear) 28 and inserts between differential carrier 25 and the side gear 26 packing ring 30 with the regulating tooth gap.Part between the rear surface of the outer surface of the rear surface of the internal surface of the internal surface of the end face of the roller 24a of side bearing 24 and inner race 24b, differential carrier 25 and side gear 26, differential carrier 25 and packing ring 30, side gear 26 and packing ring 30, shaft pinion 27 and pinion(gear) 28 and pinion(gear) 28 and the internal surface of differential carrier 25 becomes sliding part, and described sliding part slides over each other in the presence of the low-friction agent composition of final reduction gear device being used for.At a sliding surface of each sliding part for example on the rear surface of the outer surface of internal surface, the shaft pinion 27 of end surfaces, the differential carrier 25 of the roller 24a in the side bearing 24 and pinion(gear) 28, and on two surfaces of packing ring 30, can apply hard carbon thin film.Much less, hard carbon thin film can be applied to this sliding surface paired sliding surface on, or be coated on two sliding surfaces.
Hard carbon thin film can be applied on other sliding surface except that above-mentioned, for example is coated on one or two outer surface of the end face of the roller 29a in the roller bearing 29 that supports main drive shaft 23 and inner race 29b.
In addition, employed low-friction agent composition in this manual transmission in the time of on being used in the sliding surface with hard carbon thin film such as DLC, demonstrates extremely good low friction performance.Yet, especially, in order to improve the required performance of work oil as variator, add metal base sanitising agent, antioxidant, viscosity index improver, other ashless friction improver, other ashless dispersant, anti-wear agent or extreme pressure agent, rust-preventive agent, nonionogenic tenside, emulsion splitter, metal passivator and defoamer separately or in the mode of multiple combinations of substances, can improve desired properties.
Embodiment
Below, reference example and comparative example are described the present invention in more detail.Yet, the invention is not restricted to these embodiment.
1. low-friction sliding mechanism
Sliding component
As an example of sliding component, the preparation test specimen that is used for roller rub(bing)test on the monomer dish as shown in Figure 3.The monomer test specimen comprises three rollers and a disk, and this monomer test specimen is to utilize the sliding component that obtains according to following method to make.
■ roller material
To make predetermined roller shape by grinding through heat treated SUJ2 material, then with the abrasive belt polishing, the roller of gained is worn into various surfacenesses (Ra is less than or equal to 0.2 μ m).
The ■ disc material
Will be after the ageing treatment that the discoid raw material that heat treated SUJ2 material and AC2A material make is scheduled to, the sliding surface that will contact with roller grinds, and subsequently it is trimmed to various surfacenesses.
The ■ surface treatment
Utilize graphite as target body, on the surface of roller material that so makes and disc material, apply the following material (1) of different film thicknesses to material (3) with PVD method or CVD method.Further grind coated surface and coated surfacing is become various surfacenesses (Ra is less than or equal to 0.1 μ m) with abrasive belt.
(1) a-C ... (PVD processing)
(2) DLC (a-C:H) ... (CVD processing)
(3)CrN
Sliding component is as shown in table 1.
Figure C20048002260500461
The preparation low-friction agent composition
■ sample oil 1
Use the hydrogenant 1-decene oligopolymer (kinematic viscosity under 100 ℃: 3.9mm 2/ s, viscosity index: 124, and aromaticity content: 0.0%) as lubricant base.To wherein sneaking into 1.0% oleyl alcohol as oxygen-containing organic compound, 13.0% other additive (5.0% ashless dispersant: polybutylene-based succinimide (nitrogen content: 1.2%), metal base sanitising agent: 0.5% calcium sulphonate (total basicnumber: 300mgKOH/g, 12.0%) and 0.9% calcium phenylate (total basicnumber: 255mgKOH/g calcium contents:, calcium contents: 9.2%), viscosity index improver, antioxidant, extreme pressure agent, rust-preventive agent, emulsion splitter, nonionogenic tenside, metal passivator, defoamer etc.) be prepared.
■ sample oil 2
Except that not adding other additive of 13.0%, the same operation of repeat samples 1 is prepared.
■ sample oil 3
Except that oleic acid is used as the oxygen-containing organic compound, the same operation of repeat samples 1 is prepared.
■ sample oil 4
Except that with the oleic acid of 0.5% oleyl alcohol and 0.5% as the oxygen-containing organic compound, the same operation of repeat samples 1 is prepared.
■ sample oil 5
Remove the mineral oil (kinematic viscosity under 100 ℃: 5.0mm with hydrocracking 2/ s, viscosity index: 120, total aromaticity content: 5.5%) as lubricant base, the amine hydroxybenzene of adding 1.0% is as outside the oxygen-containing organic compound, and the same operation of repeat samples 1 is prepared.
■ sample oil 6
The machine oil that use is obtained commercially, the kinematic viscosity under its 100 ℃ is 10.2mm 2/ s.
■ sample oil 7
Replace the amine hydroxybenzene except that adding molybdenum dithiocarbamate, the same operation of repeat samples 5 is prepared.
■ sample oil 8
Independent use glycerine (anhydrous glycerol: 1,2, the 3-glycerol, Fluka is made by SigmaAldrich Japan Co.) (100%).
■ sample oil 9
Use separately TriMethylolPropane(TMP) (KAOLUBE KSL-268) and aliphatic acid different-three esters (100%) of the mixture of C8, just-C8, C10 and C11.
■ sample oil 10
Except that the single oleyl ether of the glycerol that adds 1.0% as the oxygen-containing organic compound, the same operation of repeat samples 5 is prepared.
■ sample oil 11
Use glycerol list-2-ethylhexyl ether separately.
The component and the sample characteristics of for example of low-friction agent composition are as shown in table 2.
Figure C20048002260500491
Embodiment 1 to 13
As shown in table 1, each sliding component is combined, further combined with each low-friction agent composition (sample oil 1 to 5 and 8 to 11) that is described in the lump in the table 1, preparation low-friction sliding mechanism, the roller rub(bing)test of coiling as described below subsequently.Its result is as shown in table 1 in the lump.
[roller rub(bing)test on the dish]
Maximum hertz pressure: 80MPa
Disc rotation speed: 30rpm
Fuel supply method: oil bath
The temperature of the oil that provides: 80 ℃
Test period: 60 minutes
Comparative example 1 to 4
Similar to embodiment, each sliding component is combined, further combined with each low-friction agent composition (sample oil 1,2,6 and 7) that is described in the lump in the table 1, preparation low-friction sliding mechanism, the roller rub(bing)test of coiling as described below subsequently.Its result is as shown in table 1 in the lump.
All base materials that discovery embodiment 1 to 13 is obtained from table 1 and the combination of sample oil demonstrate good low-friction coefficient.For example compare with the combination of sample oil 6, can obtain basically the effect of 50% to 70% reduction friction with the base material that comparative example 1 is used for the regular price gasoline engine.
In addition, the hydroxyl the low-friction agent composition of found that from embodiment 6 to 8 has the effect of good reduction friction.
In addition, the compound that has an alcoholic hydroxyl from found that of embodiment 10 and 11 has the effect of good reduction friction.
Each test specimen that is obtained in embodiment 1 to 11 is after test, and surface shape is without any problem, and it has extremely good wear resistance equally, and demonstrates stable low rubbing characteristics.
According to the combination of the test specimen base material of reference example 1 and low-friction agent composition is to be steel and the combined combination of handling through CrN of organic-molybdenum with one of them, and described organic-molybdenum it is said that the low-friction agent composition that conduct is used for the sliding surface between the steel is the most effective.As a result, its low-friction coefficient value is shown as 0.06 low value in fact.Can infer, similar to the mechanism of in different field, having studied up to now, obtained low friction thereby on sliding surface, formed the molybdenumdisulphide film.In the present invention, target is to obtain low friction, and finds that low in the above-described embodiments rubbing characteristics is extremely good.
In addition, be the bearing steel of routine and the combination of machine oil according to the test specimen base material of comparative example 1 and the combination of low-friction agent composition.As a result, its frictional coefficient surpasses 0.1, and rubbing characteristics is poor.Can infer that the mechanism that demonstrates low frictional properties in the present invention can not work fully.
On the other hand, comparative example 2 is to be combination through DLC steel of handling and the sample oil combination that is mixed with organic molybdenum with one of them.Its frictional coefficient does not promptly obtain to be similar to the favourable part of embodiment 2 basically up to 0.1.Can infer that it is the mechanism that is different from the sliding surface between the existing steel that this friction reduces mechanism.
In addition, comparative example 3 and 4 is to use CrN to handle steel that obtained and that be used for comparative example 2 and the combination that is used for the sample oil of embodiment on base material, promptly be the combination that can obtain the sample oil of low friction effect during through steel that DLC handles being applied to one of them.As a result, show that its frictional coefficient is high to surpassing 0.1.Can infer,, can not obtain lower frictional property owing to be different from the combination of metallic substance shown in the present and sample oil.
According to the combination of the test specimen base material of reference example 1 and low-friction agent composition is to be the combined combination of the steel of handling through CrN and the sample oil of sneaking into organic-molybdenum 7 with one of them, and wherein organic-molybdenum is the most effective at the low-friction agent composition that is used for existing the sliding surface between the steel.As a result, show that its frictional coefficient is low to moderate 0.05 basically.Can infer similarly, obtain low friction thereby on sliding surface, form the molybdenumdisulphide film to the mechanism studied up to now in the different field.
2. manual transmission
As shown in Figure 4, with cylindric test specimen 11 as the slipping plane test specimen, and with discoid test specimen 12 as the opposite test specimen, coil cylinder swing rub(bing)test, and under the condition below, measure frictional coefficient.
[1] rub(bing)test condition
Testing installation: cylinder swing frictional testing machines on the dish
Slipping plane test specimen: the cylindric test specimen of φ 15 * 22mm
Pairing interview part: the discoid test specimen of φ 24 * 7.9mm
Load: 400N (pressure load of slipping plane test specimen)
Amplitude: 3.0mm
Frequency: 50Hz
Test temperature: 80 ℃
Test duration: 30 minutes
[2] prepare cylindric test specimen (slipping plane)
The SUJ2 steel that will be defined as high-carbon-chromium bearing steel in JIS G4805 will be processed into above-mentioned size as the cylindric test specimen 11 of slipping plane test specimen as raw material, be finish-machined to subsequently to surface roughness Ra be 0.04 μ m.
[3] prepare discoid test specimen (slip pairing face)
Similarly, use the SUJ2 steel, to be processed into above-mentioned size as the discoid test specimen 12 of pairing interview part, be finish-machined to after surface roughness Ra is 0.05 μ m will going up sliding surface, utilize PVD arc ions type ion electroplating method, at its surface deposition film thickness is the DLC film of 0.5 μ m, and the amount of hydrogen atom is less than or equal to 0.5 atom % in this DLC film, and knoop hardness Hk is 2170kg/mm 2, and surfaceness Ry is 0.03 μ m.In reference example, use the test specimen of uncoated DLC film.
[4] preparation is used for the low-friction agent composition of manual transmission
As the low-friction agent composition that is used for manual transmission, poly-alpha-olefin (1-octene oligopolymer)), SP (having the sulfur-bearing of thiophosphoric acid amine salt of 0.5 quality % and the compound of phosphorus) or ZnDTP (zinc dithiophosphate) extreme pressure agent (as compound 1.5 quality %), anti-wear agent and aliphatic ester or fatty amine friction modifiers make up and prepared respectively will be as the mineral oil of base oil or synthetic oil (PAO:.
[5] test-results
Cylindric test specimen and discoid test specimen, and the low-friction agent composition combination as shown in table 3 that is used for manual transmission are measured frictional coefficient according to aforesaid method subsequently.
The result as shown in Figure 5.
Figure C20048002260500541
Can obviously find out from the result of Fig. 5, confirm to compare, use the frictional coefficient of the embodiment of the discoid test specimen of deposition DLC film on last sliding surface to greatly reduce with the comparative example that uses the discoid test specimen that does not deposit the DLC film thereon.
3. final reduction gear device
As shown in Figure 4, with cylindric test specimen 11 as the slipping plane test specimen, and with discoid test specimen 12 as pairing interview part, coil cylinder swing rub(bing)test, and under the condition below, the mensuration frictional coefficient.
[1] rub(bing)test condition
Testing installation: cylinder swing frictional testing machines on the dish
Slipping plane test specimen: the cylindric test specimen of φ 15 * 22mm
Pairing interview part: the discoid test specimen of φ 24 * 7.9mm
Load: 400N (pressure load of slipping plane test specimen)
Amplitude: 3.0mm
Frequency: 50Hz
Test temperature: 80 ℃
Test duration: 30 minutes
[2] prepare cylindric test specimen (slipping plane)
The SUJ2 steel that will be defined as high-carbon-chromium bearing steel in JIS G4805 will be processed into above-mentioned size as the cylindric test specimen 11 of slipping plane test specimen as raw material, and being refined to surface roughness Ra subsequently is 0.04 μ m.
[3] prepare discoid test specimen (slip pairing face)
Similarly, use the SUJ2 steel, to be processed into above-mentioned size as the discoid test specimen 12 of pairing interview part, be finish-machined to after surface roughness Ra is 0.05 μ m will going up sliding surface, utilize PVD arc ions type ion electroplating method, at its surface deposition film thickness is the DLC film of 0.5 μ m, and the amount of hydrogen atom is less than or equal to 0.5 atom % in this DLC film, and knoop hardness Hk is 2170kg/mm 2, and surfaceness Ry is 0.03 μ m.In reference example, use the test specimen of uncoated DLC film.
[4] preparation is used for the low-friction agent composition of final reduction gear device
Low-friction agent composition is used for final reduction gear device, poly-alpha-olefin (1-octene oligopolymer)), S-base (as compound 4 quality %), SP-base (as compound 1.5 quality %) or borate base extreme pressure agent (as compound 3 quality %), anti-wear agent and aliphatic ester friction modifiers make up and prepared respectively will be as the mineral oil of base oil or synthetic oil (PAO:.
[5] test-results
Cylindric test specimen and discoid test specimen, and the low-friction agent composition combination as shown in table 4 that is used for final reduction gear device are measured frictional coefficient according to aforesaid method subsequently.
The result as shown in Figure 6.
Figure C20048002260500571
Can obviously find out from the result of Fig. 6, confirm to compare, use the frictional coefficient of the embodiment of the discoid test specimen of deposition DLC film on last sliding surface to greatly reduce with the comparative example that uses the discoid test specimen that does not deposit the DLC film thereon.
As mentioned above, describe in detail according to embodiments of the invention and comparative example; Yet, the invention is not restricted to this, and in spirit of the present invention, can carry out multiple improvement.
For example, the present invention also can be applied to employed gear sliding component in the industrial machinery.

Claims (14)

1. low-friction sliding mechanism wherein, is inserted with low-friction agent composition between the sliding surface of sliding component (A) that DLC applies and sliding component (B), it is characterized in that:
The sliding component (A) that described DLC applies forms by apply diamond-like carbon on base material;
Described sliding component (B) is selected from down the material in the group and forms with at least a: metallic substance, non-metallic material and coated film and the coating material that forms on the surface of metallic substance or non-metallic material; And
Described low-friction agent composition comprises oxygen-containing organic compound (C), described oxygen-containing organic compound (C) be selected from down the group at least a: alcohol, carboxylic acid, ester, ether, ketone, aldehyde, carbonic ether and derivative thereof.
2. low-friction sliding mechanism according to claim 1 is characterized in that, in described sliding component (B), described metallic substance is at least a material that is selected from down in the group: ferrous material, aluminum alloy materials and magnesium alloy sill; Described coating material forms by the film that coating is selected from least a material of DLC, TiN and CrN.
3. low-friction sliding mechanism according to claim 1 and 2 is characterized in that, the hydrogen richness of the DLC of coating is less than or equal to 20 atom %.
4. low-friction sliding mechanism according to claim 1 and 2 is characterized in that, the hydrogen richness of the DLC of coating is less than or equal to 10 atom %.
5. low-friction sliding mechanism according to claim 1 and 2 is characterized in that, the hydrogen richness of the DLC of coating is less than or equal to 0.5 atom %.
6. low-friction sliding mechanism according to claim 1 and 2 is characterized in that, the DLC of coating is formed by not hydrogenous a-C diamond-like carbon.
7. low-friction sliding mechanism according to claim 1 is characterized in that, with respect to the total amount of low-friction agent composition, the content of described oxygen-containing organic compound (C) is in 0.05% to 3.0% scope.
8. low-friction sliding mechanism according to claim 1 is characterized in that, described low-friction agent composition also comprises fatty amine compound (D).
9. low-friction sliding mechanism according to claim 8 is characterized in that, described fatty amine compound (D) has the alkyl that carbonatoms is 6-30, and with respect to the total amount of low-friction agent composition, its content is in 0.05% to 3.0% scope.
10. a method that reduces to rub is characterized in that,
Between sliding component (A) and the formed sliding surface of sliding component (B) that DLC applies, the low-friction agent composition that comprises oxygen-containing organic compound (C) is provided, being lubricated,
Described oxygen-containing organic compound (C) be selected from down the group at least a: alcohol, carboxylic acid, ester, ether, ketone, aldehyde, carbonic ether and derivative thereof,
The sliding component (A) that this DLC applies forms by applying diamond-like carbon, and this sliding component (B) uses at least a material that is selected from down in the group: metallic substance, non-metallic material, reach coated film on the surface of metallic substance or non-metallic material and the coating material that obtains.
11. employed low-friction agent composition in the low-friction sliding mechanism according to claim 1 is characterized in that, comprises oxygen-containing organic compound (C).
12. employed low-friction agent composition in the method for reducing friction according to claim 10 is characterized in that, comprises oxygen-containing organic compound (C).
13. a manual transmission is characterized in that, uses low-friction sliding mechanism according to claim 1.
14. a final reduction gear device is characterized in that, uses low-friction sliding mechanism according to claim 1.
CN200480022605A 2003-08-06 2004-08-06 Low-friction sliding mechanism, low-friction agent composition and method of reducing friction Expired - Lifetime CN100587045C (en)

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