Low-friction sliding mechanism

[0001] The present invention relates to a sliding mechanism having excellent low-friction characteristics, particularly of the kind for use in an internal combustion engine, a drive train or a hard disk drive.

[0002] Global environmental problems such as global warming and ozone layer destruction are coming to the fore. As it is said that the global warming is significantly effected by CO₂ emission, the reduction of CO₂ emission, notably the setting of CO₂ emission standards, has become a big concern to each country.

[0003] One of challenges to reduce CO₂ emission is to improve vehicle fuel efficiency that depends on the performance of engine sliding members and a lubricant applied thereto. There are the following approaches to improving vehicle fuel efficiency: (1) to provide higher abrasion resistance and a lower friction coefficient for the sliding members, which are generally made of steel materials in the earlier technology, even under extreme conditions of abrasion and friction; (2) to lower the viscosity of the lubricant, thereby reducing viscous resistance in hydrodynamic lubrication regions and agitation resistance in the engine; and (3) to mix a suitable friction modifier and other additives into the lubricant so as to reduce friction losses under the conditions of mixed lubrication and boundary lubrication.

[0004] In view of the foregoing, many studies have been made on various friction modifiers including organomolybdenum compounds, such as molybdenum dithiocarbamate (MoDTC) and molybdenum dithiophosphate (MoDTP). As a result of the studies, it is found that the lubricant containing an organomolybdenum compound successfully produces a friction reducing effect on the steel sliding members in the early stages of use.

[0005] Heretofore, the application of hard coating materials to the engine sliding members has been also examined so that the sliding members can attain high abrasion resistance and a low friction coefficient. Above all, a diamond-like carbon (DLC) material is known for its low-friction performance in the air and therefore expected to be useful as a coating material for the sliding members.

[0006] However, the DLC material does not provide a low friction coefficient in the presence of a lubricant (as disclosed in Japan Tribology Congress 1999. 5, Tokyo, Proceeding Page 11-12, KANO et.al.). Even when used in combination with the lubricant containing an organomolybdenum compound, the DLC material cannot provide a sufficiently low friction coefficient (as disclosed in World Tribology Congress 2001. 9, Vienna, Proceeding Page 342, KANO et.al.).

[0007] It is therefore an object of the present invention to provide a sliding mechanism having stably excellent low-friction characteristics and high abrasion resistance so as to attain, when used in an automotive engine, more improvement in vehicle fuel efficiency than that attained by the earlier technology.

[0008] According to an aspect of the present invention, there is provided a low-friction sliding mechanism, comprising: a first sliding member having a sliding surface, at least the sliding surface of the first sliding member being made of a diamond-like carbon material; a second sliding member having a sliding surface slidable relative to the sliding surface of the first sliding member, at least the sliding surface of the second sliding member being made of either one of an aluminum-based alloy material, a magnesium-based alloy material and a diamond-like carbon material; and a lubricant applied to the sliding surfaces of the first and second sliding members, the lubricant comprising at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier.

[0009] The other objects and features of the invention will also become understood from the following description.

[0011] The present invention will be described below in detail. In the following description, all percentages (%) are by mass unless otherwise specified.

[0012] A sliding mechanism according to an exemplary embodiment of the present invention includes a first sliding member having a sliding surface, a second sliding member having a sliding surface slidable relative to the sliding surface of the first sliding member, and a lubricant applied to the sliding surfaces of the first and second sliding members.

[0013] The first sliding member has at least its sliding surface made of a diamond-like carbon (DLC) material, and generally includes a base made of e.g. an iron-based material, an aluminum-based alloy material or a resinous material and a coating of DLC material (hereinafter just referred to as a “DLC coating) applied to the base so as to define the sliding surface. The first sliding member may alternatively be formed in one piece of DLC material. Herein, the DLC material is defined as an amorphous form of carbon in which carbon exists in both sp² and sp³ hybridizations so as to have a composite structure of graphite and diamond. Specific examples of the DLC material usable in the present invention include hydrogen-free amorphous carbon (a-C) that consists of carbon, hydrogen-containing amorphous carbon (a-C:H) and metal carbide (MeC) that contains a metal element of titanium (Ti) or Molybdenum (Mo). For a significant reduction in friction, hydrogen-free amorphous carbon (a-C) is preferably used.

[0014] The second sliding member has at least its sliding surface made of either an aluminum-based alloy material, a magnesium-based alloy material or a DLC material.

[0015] The aluminum-based material for the second sliding member is preferably a hypoeutectic or hypereutectic aluminum-based alloy containing 4 to 20% silicon (Si) and 1.0 to 5.0% copper (Cu). Specific examples of the aluminum-based alloy include AC2A, AC8A, ADC12 and ADC14 in compliance with JIS H5205.

[0016] The magnesium-based alloy material for the sliding member is selected for the group consisting of magnesium-aluminum-zinc (Mg—Al—Zn) alloys, magnesium-aluminum-rare earth metal (Mg—Al-REM) alloys, magnesium-aluminum-calcium (Mg—Al—Ca) alloys, magnesium-zinc-aluminum-calcium (Mg—Zn—Al—Ca) alloys, magnesium-aluminum-calcium-rare earth metal (Mg—Al—Ca-REM) alloys, magnesium-aluminum-strontium (Mg—Al—Sr) alloys, magnesium-aluminum-silicon (Mg—Al—Si) alloys, magnesium-rare earth metal-zinc (Mg-REM-Zn) alloys, magnesium-silver-rare earth metal (Mg—Ag-REM) alloys, magnesium-yttrium-rare earth metal (Mg—Y-REM) alloys and combinations thereof. Specific examples of the magnesium-based alloy include AZ91, AE42, AX51, AXJ, ZAX85, AXE522, AJ52, AS21, QE22 and WE43 in compliance with ASTM.

[0017] The DLC material usable for the second sliding member can be exemplified by hydrogen-free amorphous carbon (a-C) that consists of carbon, hydrogen-containing amorphous carbon (a-C:H) and metal carbide (MeC) that contains a metal element of titanium (Ti) or molybdenum (Mo), as in the case with the DLC material usable for the first sliding member. Among these DLC materials, hydrogen-free amorphous carbon (a-C) is preferably used. In a case where at least the sliding surface of the second sliding member is of DLC material, the second sliding member generally has a base made of e.g. an iron-based material, an aluminum-based alloy material or a resinous material and a coating of DLC material (hereinafter referred to as a “DLC coating”) applied to the base so as to define the sliding surface. Alternatively, the second sliding member may be formed in one piece of DLC material. Further, it is preferable that at least one of the DLC materials of the first and second sliding members is hydrogen-free amorphous carbon (a-C).

[0018] Each of the sliding surfaces of the first and second sliding members preferably has an arithmetic mean roughness Ra of 0.1 μm or lower so as to attain a stable sliding between the first and second sliding members. When the surface roughness Ra exceeds 0.1 μm, the sliding surfaces of the first and second sliding members are locally subjected to scuffing to cause a great deterioration in friction coefficient.

[0019] Further, the DLC coating of the first sliding member preferably has a thickness of 0.3 to 2.0 μm and a micro Vickers hardness H_V of 1000 to 3500 as measured by the application of a 10 g load. When the thickness is less than 0.3 μm and the micro Vickers hardness H_V is less than 1000, the DLC coating is prone to wear. On the other hand, the DLC coating tends to be separated from the base when the thickness exceeds 2.0 μm and the micro Vickers hardness exceeds 3500.

[0020] The sliding surface of the second sliding member, when the second sliding member is made of the above aluminum-based alloy material, preferably has a Brinell hardness H_B of 80 to 130. If the Brinell hardness H_B is less than 80, the sliding surface of the second sliding surface is prone to wear.

[0021] The sliding surface of the second sliding member, when the second sliding member is made of the above magnesium-based alloy material, preferably has a Brinell hardness H_B of 45 to 95. If the Brinell hardness H_B is less than 45, the sliding surface of the second sliding surface is also prone to wear.

[0022] When the sliding surface of the second sliding member is made of the above DLC material, the DLC coating of the second sliding member preferably has a thickness of 0.3 to 2.0 μm and a micro Vickers hardness H_V of 1000 to 3500 as measured by the application of a 10 g load. When the thickness is less than 0.3 μm and the micro Vickers hardness H_V is less than 1000, the DLC coating is prone to wear. On the other hand, the DLC coating tends to be separated from the base when the thickness exceeds 2.0 μm and the micro Vickers hardness exceeds 3500.

[0023] The lubricant includes a base oil and at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier.

[0024] The base oil is not particularly limited and can be any base oil compound or compounds commonly used for a lubricant, such as a mineral oil or a synthetic oil.

[0025] Specific examples of the mineral oil include oil compounds prepared by extracting a lubricant fraction from petroleum by atmospheric or reduced-pressure distillation, and then, purifying the obtained lubricant fraction by at least one of the following treatments: solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydrotreating and wax isomerization. In the present invention, the mineral oil prepared through hydrocracking, hydrotreating and/or wax isomerization is preferably used.

[0026] Specific examples of the synthetic oil include: alkylbenzenes, alkylnaphthalenes, polybutenes and hydrides thereof; poly-α-olefins, such as 1-octene oligomer and 1-decene oligomer, and hydrides thereof; diesters, such as ditridecyl glutarate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate and dioctyl sebacate; polyol esters, such as trimethylolpropane caprylate, trimetylolpropane pelargonate, pentaerythritol-2-ethyl hexanoate and pentaerythritol pelargonate; and mixtures thereof. Among these synthetic oil compounds, preferred are poly-α-olefins, such as 1-octene oligomer and 1-decene oligomer and hydrides thereof.

[0027] The above-mentioned mineral and synthetic oil compounds may be used alone, or in the form of a mixture of any two or more thereof with no limitation on the mixture ratio.

[0028] The aromatic content of the base oil is not particularly restricted. Herein, the aromatic content is defined as the amount of aromatics fractions determined according to ASTM D2549 “Standard Test Method for Separation of Representative Aromatics and Nonaromatics Fractions of High-Boiling Oils by Elution Chromatography”. The aromatics fractions generally include alkylbenzenes, alkylnaphthalenes, anthracene, phenanthrene and alkylates thereof, condensed-ring compounds having four or more benzeoid rings fused together, and heteroaromatic compounds such as pyridines, quinolines, phenols and naphtols. In the present invention, the aromatic content of the base oil is preferably 15% or less, more preferably 10% or less, and most preferably 8% or less. When the aromatic content exceeds 15%, the base oil undesirably deteriorates in oxidation stability. It is noted that the lubricant may be able to produce a high friction reducing effect, even if the aromatic content of the base oil is 2% or less (inclusive of 0%). In such a case, however, there arise a possibility that the lubricant deteriorates in storage stability, e.g., when the fatty-ester friction modifier and/or aliphatic-amine friction modifier is contained in an amount of more than 1%. The aromatic content of the base oil is thus preferably controlled to e.g. 2% or more by adding solvent refining mineral oil, alkylbenzene or the like as needed.

[0029] The kinematic viscosity of the base oil is not particularly restricted. When the lubricant is used for an internal combustion engine, the kinematic viscosity of the base oil is preferably 2 mm²/s or higher, more preferably 3 mm²/s and, at the same time, is preferably 20 mm²/s or lower, more preferably 10 mm²/s or lower, most preferably 8 mm²/s or lower, as measured at 100° C. When the kinematic viscosity is 2 mm²/s or higher at 100° C., the lubricant is able to form a sufficient lubricant film so as to attain a high lubricity and is able to minimize its boil-off under high-pressure conditions. When the kinematic viscosity is 20 mm²/s or lower at 100° C., the lubricant is able to decrease its fluid resistance and minimize friction resistance in lubrication regions.

[0030] The viscosity index of the base oil is not particularly restricted, and is preferably 80 or higher, more preferably 100 or higher, most preferably 120 or higher, when the lubricant is used for an internal combustion engine. When the base oil has a higher viscosity index, the lubricant can attain excellent low-temperature viscosity properties and produce a good friction reducing effect.

[0031] The fatty-ester friction modifier and the aliphatic-amine friction modifier are an fatty acid ester and an aliphatic amine each having C₆-C₃₀ straight or branched hydrocarbon chains, preferably C₈-C₂₄ straight or branched hydrocarbon chains, more preferably C₁₀-C₂₀ straight or branched hydrocarbon chains. When the carbon number of the hydrocarbon chain is not within the range of 6 to 30, there arises a possibility that the lubricant may not produce a sufficient friction reducing effect as expected.

[0032] Specific examples of the C₆-C₃₀ straight or branched hydrocarbon chain include: alkyl groups, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triacontyl; and alkenyl groups, such as hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl and triacontenyl. The above alkyl and alkenyl groups include all possible isomers.

[0033] The fatty acid ester can be exemplified by esters of fatty acids having the above hydrocarbon groups and monofunctional aliphatic alcohols or aliphatic polyols. Specific examples of such fatty acid esters include glycerol monolate, glycerol diolate, sorbitan monolate and sorbitan diolate.

[0034] The aliphatic amine can be exemplified by aliphatic monoamines and alkylene oxide adducts thereof, aliphatic polyamines, imidazoline compounds, and derivatives thereof. Specific examples of such aliphatic amines include: aliphatic amine compounds, such as laurylamine, lauryldiethylamine, lauryldiethanolamine, dodecyldipropanolamine, palmitylamine, stearylamine, stearyltetraethylenepentamine, oleylamine, oleylpropylenediamine, oleyldiethanolamine and N-hydroxyethyloleylimidazolyne; adducts of the above aliphatic amines (C₆-C₂₈ alkyl or alkenyl amines) with alkylene oxides, such as N,N-dipolyoxyalkylene-N-alkylamines; and acid-modified compounds prepared by reacting the above aliphatic amines with C₂-C₃₀ monocarboxylic acids (such as fatty acids) or C₂-C₃₀ polycarboxylic acids (such as oxalic acid, phthalic acid, trimellitic acid and pyromellitic acid) so as to neutralize or amidate the whole or part of the remaining amino and/or imino groups. In the present invention, N,N-dipolyoxyethylene-N-oleylamine is preferably used.

[0035] The amount of the fatty-ester friction modifier and/or the aliphatic-amine friction modifier added in the lubricant is not particularly restricted, and is preferably 0.05 to 3.0%, more preferably 0.1 to 2.0%, and most preferably 0.5 to 1.4%, based on the total mass of the lubricant. When the amount of the fatty-ester friction modifier and/or the aliphatic-amine friction modifier is less than 0.05%, there arises a possibility that the lubricant may not produce a sufficient friction reducing effect. When the amount of the fatty-ester friction modifier and/or the aliphatic-amine friction modifier exceeds 3.0%, the lubricant produce a good friction reducing effect but undesirably deteriorates in storage stability and compatibility to cause precipitations.

[0036] Further, the lubricant desirably includes polybutenyl succinimide and/or a derivative thereof as an ashless dispersant. Specific examples of the polybutenyl succinimide usable in the present invention include compounds represented by the following general formulas (1) and (2).
In each of the formulas (1) and (2), n represents an integer of 1 to 5, preferably 2 to 4, so as to attain a good detergent effect. Further, PIB represents a polybutenyl group derived from polybutene. The polybutene can be prepared by polymerizing high-purity isobutene or a mixture of 1-butene and isobutene in the presence of a boron fluoride catalyst or an aluminum chloride catalyst in such a manner that the polybutene attains a number-average molecular weight of 900 to 3,500, preferably 1,000 to 2,000. When the number-average molecular weight of the polybutene is less than 900, there is a possibility of failing to attain a sufficient detergent effect. When the number-average molecular weight of the polybutene exceeds 3,500, the polybutene may undesirably deteriorate in low-temperature fluidity. In the production of the polybutenyl succinimide, the polybutene may be used after purified by removing trace amounts of fluorine and chlorine residues, which result from the above polybutene production catalyst, by any suitable treatment (such as adsorption process or washing process). The amount of the fluorine and chlorine residues is preferably controlled to 50 ppm or less, more preferably 10 ppm or less, most preferably 1 ppm or less.

[0037] The production method of the polybutenyl succinimide is not particularly restricted. For example, the polybutenyl succinimide can be prepared by reacting an chloride of the above-mentioned polybutene, or the polybutene from which fluorine and chlorine residues are removed, with maleic anhydride at 100 to 200° C. to form butenyl succinate, and then, reacting the thus-formed butenyl succinate with polyamine (such as diethylene triamine, triethylene tetramine, tetraethylene pentamine or pentaethylene hexamine).

[0038] The polybutenyl succinimide derivative can be exemplified by boron- and acid-modified compounds obtained by reacting the polybutenyl succinimide of the formulas (1) and (2) with boron compounds or oxygen-containing organic compounds so as to neutralize or amidate the whole or part of the remaining amino and/or imide groups. In the present invention, boron-containing polybutenyl succinimide, especially boron-containing bis(polybutenyl)succinimide, is preferably used. Herein, the content ratio of nitrogen to boron (B/N) by mass in the boron-containing polybutenyl succinimide is usually 0.1 to 3, preferably 0.2 to 1.

[0039] The above boron compound can be a boric acid, a borate or a boric acid ester. Specific examples of the boric acid include orthoboric acid, metaboric acid and paraboric acid. Specific examples of the borate include: ammonium salts including ammonium borates, such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate and ammonium octaborate. Specific examples of the boric acid ester include: esters of boric acids and alkylalcohols (preferably C₁-C₆ alkylalcohols), such as monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate and tributyl borate.

[0040] The above oxygen-containing organic compound can be exemplified by: C₁-C₃₀ monocarboxylic acids, such as formic acid, acetic acid, glycolic acid, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, nonadecanoic acid and eicosanoic acid; C₂-C₃₀ polycarboxylic acids, such as oxalic acid, phthalic acid, trimellitic acid and pyromellitic acid, and anhydrides and esters thereof; C₂-C₆ alkylene oxides; and hydroxy(poly)oxyalkylene carbonates.

[0041] The amount of the polybutenyl succinimide and/or the derivative thereof added in the lubricant is not particularly restricted, and is preferably 0.1 to 15%, more preferably 1.0 to 12%, based on the total mass of the lubricant. When the amount of the polybutenyl succineimide and/or the derivative thereof is less than 0.1%, there arises a possibility of failing to attain a sufficient detergent effect. It becomes uneconomical when the amount of the polybutenyl succineimide and/or the derivative thereof exceeds 15%. In addition, such a large amount of the polybutenyl succineimide and/or the derivative thereof tends to cause a deterioration in demulsification ability.

[0042] Furthermore, the lubricant desirably includes zinc dithiophosphate represented by the following general formula (3) as an antioxidant and as an anti-wear agent.
In the general formula (3), R⁴, R⁵, R⁶ and R⁷ each represent C₁-C₂₄ hydrocarbon groups. The C₁-C₂₄ hydrocarbon group is preferably a C₁-C₂₄ straight-chain or branched-chain alkyl group, a C₃-C₂₄ straight-chain or branched-chain alkenyl group, a C₅-C₁₃ cycloalkyl or straight-chain or branched-chain alkylcycloalkyl group, a C₆-C₁₈ aryl or straight-chain or branched-chain alkylaryl group, or a C₇-C₁₉ arylalkyl group. The above alkyl group or alkenyl group can be primary, secondary or tertiary. Specific examples of R⁴, R⁵, R⁶ and R⁷ include: alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl, docosyl, tricosyl and tetracosyl; alkenyl groups, such as propenyl, isopropenyl, butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl (oleyl), nonadecenyl, icosenyl, heneicosenyl, docosenyl, tricosenyl and tetracosenyl; cycloalkyl groups, such as cyclopentyl, cyclohexyl and cycloheptyl; alkylcycloalkyl groups, such as methylcyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, ethylmethylcyclopentyl, trimethylcyclopentyl, diethylcyclopentyl, ethyldimethylcyclopentyl, propylmethylcyclopentyl, propylethylcyclopentyl, di-propylcyclopentyl, propylethylmethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, ethylmethylcyclohexyl, trimethylcyclohexyl, diethylcyclohexyl, ethyldimethylcyclohexyl, propylmethylcyclohexyl, propylethylcyclohexyl, di-propylcyclohexyl, propylethylmethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, ethylcycloheptyl, propylcycloheptyl, ethylmethylcycloheptyl, trimethylcycloheptyl, diethylcycloheptyl, ethyldimethylcycloheptyl, propylmethylcycloheptyl, propylethylcycloheptyl, di-propylcycloheptyl and propylethylmethylcycloheptyl; aryl groups, such as phenyl and naphthyl; alkylaryl groups, such as tolyl, xylyl, ethylphenyl, propylphenyl, ethylmethylphenyl, trimethylphenyl, butylphenyl, propylmethylphenyl, diethylphenyl, ethyldimethylphenyl, tetramethylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl and dodecylphenyl; and arylalkyl groups, such as benzyl, methylbenzyl, dimethylbenzyl, phenethyl, methylphenethyl and dimethylphenethyl. The above hydrocarbon groups include all possible isomers.

[0043] Specific examples of the zinc dithiophosphate usable in the present invention include zinc diisopropyldithiophosphate, zinc diisobutyldithiophosphate, zinc di-sec-butyldithiophosphate, zinc di-sec-pentyldithiophosphate, zinc di-n-hexyldithiophosphate, zinc di-sec-hexyldithiophosphate, zinc di-octyldithiophosphate, zinc di-2-ethylhexyldithiophosphate, zinc di-n-decyldithiophosphate, zinc di-n-dodecyldithiophosphate, zinc diisotridecyldithiophosphate and mixtures thereof.

[0044] The amount of the zinc dithiophosphate added in the lubricant is not particularly restricted. The zinc dithiophosphate is preferably contained in an amount of 0.1% or less, more preferably in an amount of 0.06% or less, most preferably in a minimum effective amount, in terms of the phosphorus element based on the total mass of the lubricant in order to produce a higher friction reducing effect. When the amount of the zinc dithiophosphate exceeds 0.1%, there arises a possibility of inhibiting the effect of the ashless fatty-ester friction modifier and/or the ashless aliphatic-amine friction modifier.

[0045] The zinc dithiophosphate can be prepared by any known method. For example, the zinc dithiophosphate may be prepared by reacting alcohols or phenols having the above R⁴, R⁵, R⁶ and R⁷ hydrocarbon groups with phosphorous pentasulfide to form dithiophosphoric acid, and then, neutralizing the thus-formed dithiophosphoric acid with zinc oxide. Herein, the molecular structure of zinc dithiophosphate differs according to the alcohols or phenols used as a raw material for the zinc dithiophosphate production.

[0046] The lubricant may further include any other additive or additives, such as a metallic detergent, an antioxidant, a viscosity index improver, a friction modifier other than the above-mentioned fatty-ester friction modifier and/or the aliphatic-amine friction modifier, an ashless dispersant other than the above-mentioned polybutenyl succinimide and/or the derivative thereof, an anti-wear agent or extreme-pressure additive, a rust inhibitor, a nonionic surfactant, a demulsifier, a metal deactivator and/or an anti-foaming agent, when used in an internal combustion engine. These additives may be used alone or in the form of a mixture of two or more thereof so as to meet the lubricant performance required.

[0047] The metallic detergent can be any metallic-detergent compound commonly used for a lubricant. Specific examples of the metallic detergent usable in the present invention include sulfonates, phenates and salicylates of alkali metals or alkali-earth metals; and mixtures of two or more thereof. Examples of the alkali metals include sodium (Na) and potassium (K), and examples of the alkali-earth metals include calcium (Ca) and magnesium (Mg). In the present invention, sodium and calcium sulfonates, sodium and calcium phenates, and sodium and calcium salicylates are suitably used. The total base number and amount of the metallic detergent can be selected in accordance with the lubricant performance required. The total base number of the metallic detergent is usually 0 to 500 mgKOH/g, preferably 150 to 400 mgKOH/g, as measured by perchloric acid method according to ISO 3771 “Determination of base number—Perchloric acid potentiometric titration method”. The amount of the metallic detergent is usually 0.1 to 10% based on the total mass of the lubricant.

[0048] The antioxidant can be any antioxidant compound commonly used for a lubricant. Specific examples of the antioxidant usable in the present invention include: phenolic antioxidants, such as 4,4′-methylenebis(2,6-di-tert-butylphenol) and octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; amino antioxidants, such as phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine and alkyldiphenylamine; and mixtures of two or more thereof. The amount of the antioxidant is usually 0.01 to 5% based on the total mass of the lubricant.

[0049] The viscosity index improver can be exemplified by: non-dispersion type viscosity index improvers, such as methacrylic acids, copolymers of methacrylic acids and hydrides thereof; and dispersion type viscosity index improvers, such as copolymers of methacrylates (including nitrogen compounds). There may be also used, as the viscosity index improver, copolymers of ethylene and α-olefins (such as propylene, 1-butene and 1-pentene) and hydrides thereof, polyisobutylenes and hydrides thereof, a hydrogenated copolymer of styrene and diene, a copolymer of styrene and maleic anhydride and polyalkylstyrenes. The molecular weight of the viscosity index improver needs to be selected in view of shear stability. For example, the number-average molecular weight of the viscosity index improver is desirably in a range of 5,000 to 1,000,000, more desirably 100,000 to 800,000, for dispersion or non-dispersion type polymethacrylates; in a range of 800 to 5,000 for polyisobutylenes and hydrides thereof; and in a range of 800 to 300,000, more desirably 10,000 to 200,000 for ethylene/α-olefin copolymers and hydrides thereof. The above viscosity index improving compounds can be used alone or in the form of a mixture of two or more thereof. The amount of the viscosity index improver is preferably 0.1 to 40.0% based on the total mass of the lubricant.

[0050] The friction modifier other than the above-mentioned fatty-ester friction modifier and/or the aliphatic-amine friction modifier can be exemplified by ashless friction modifiers, such as boric acid esters, higher alcohols and aliphatic ethers, and metallic friction modifiers, such as molybdenum dithiophosphate, molybdenum dithiocarbamate and molybdenum disulfide.

[0051] The ashless dispersant other than the above-mentioned polybutenyl succinimide and/or the derivative thereof can be exemplified by polybutenylbenzylamines and polybutenylamines each having polybutenyl groups of number-average molecular weight of 900 to 3,500, polybutenyl succinimides having polybutenyl groups of number-average molecular weight of less than 900 and derivatives thereof.

[0052] The anti-friction agent or extreme-pressure additive can be exemplified by disulfides, sulfurized fats and oils, olefin sulfides, phosphate esters having one to three C₂-C₂₀ hydrocarbon groups, thiophosphate esters, phosphite esters, thiophosphite esters and amine salts of these esters.

[0053] The rust inhibitor can be exemplified by alkylbenzene sulfonates, dinonylnaphthalene sulfonates, esters of alkenylsuccinic acids and esters of polyalcohols.

[0054] The nonionic surfactant and the demulsifier can be exemplified by noionic polyalkylene glycol surfactants, such as polyoxyethylene alkylethers, polyoxyethylene alkylphenyleters and polyoxyethylene alkylnaphthyleters.

[0055] The metal deactivator can be exemplified by imidazoline compounds, pyrimidine derivatives, thiazole and benzotriazole.

[0056] The anti-foaming agent can be exemplified by silicones, fluorosilicones and fluoroalkylethers.

[0057] Each of the friction modifier other than the fatty-ester friction modifier and/or the aliphatic-amine friction modifier, the ashless dispersant other than the polybutenyl succinimide and/or the derivative thereof, the anti-wear agent or extreme-pressure additive, the rust inhibitor and the demulsifier is usually contained in an amount of 0.01 to 5% based on the total mass of the lubricant, and the metal deactivator is contained in an amount of 0.0005 to 1% based on the total mass of the lubricant.

[0058] With the above-described structure, the sliding mechanism is capable of attaining excellent low-friction characteristics and high abrasion resistance to be fit for a variety of uses, especially useful for an internal combustion engine, a hard disk drive and a drive train. The sliding mechanism can be also used as a sliding gear of an industrial machine.

[0059] The present invention will be described in more detail by reference to the following examples. However, it should be noted that the following examples are only illustrative and not intended to limit the invention thereto.

[0060] In Examples 1 to 27 and Comparative Examples 1 to 12, abrasion test units were assembled from varying combinations of pins, discs and lubricants. Each test unit had three pins and one disc as shown in FIGURE. The pins, discs and lubricants used were prepared as follows, and the detailed specifications of the test units are indicated in TABLES 1 to 3.

[0061] A high-carbon chromium material “SUJ2” (i.e. an iron-based material in compliance with JIS G4805) was formed into pin bases by grinding and subjected to spheroidizing at 780° C., water quenching at 30° C. and tempering at 150° C. The heat-treated pin bases were lapped with lapping tapes in such a manner as to form their respective base surfaces with different surface roughness (Ra=0.2 μm). Then, coatings were applied to the surfaces of the pin bases. The coatings were formed with different thickness by chemical vapor deposition (CVD) or physical vapor deposition (PVD) using the following coating material together with graphite targets.

[0062] [Coating Materials]

• • [0063] DLC: a-C (treated by PVD), a-C:H (treated by CVD)
  • [0064] TiN (treated by PVD)
  • [0065] CrN (treated by PVD)
    Finally, the coatings were lapped with lapping tapes in such a manner as to form their sliding surfaces with different surface thickness (Ra=0.1 μm). Each of the pins had a diameter of 5 mm and a length of 5 mm.

[0066] Discs of aluminum-based alloys, such as AC2A, AC8A, ADC12 and ADC14, were heat-treated under the following conditions.

[0067] [Heat Treatment]

• • [0068] AC2A: subjected to age hardening at 510° C. for 8 hours, water quenching at 160° C. for 9 hours and air cooling.
  • [0069] AC8A: subjected to age hardening at 200° C. for 4 hours and air cooling.
  • [0070] ADC12, ADC14: no heat treatment.
    Then, the aluminum-alloy discs were subjected to lapping to form their respective sliding surfaces with different surface roughness.

[0071] Discs of magnesium-based alloys, such as AZ91D, AE42, AS21, AX51, AJ52, QE22-T6 and WE43-T6, were heat-treated under the following conditions.

[0072] [Heat Treatment]

• • [0073] QE22-T6: subjected to age hardening at 525° C. for 4 hours, water quenching at 200° C. for 8 hours and air cooling.
  • [0074] WE43-T6: subjected to age hardening at 525° C. for 4 hours, water quenching at 250° C. for 16 hours and air cooling.
  • [0075] AZ91D, AE42, AS21, AX51, AJ52: no heat treatment.
    Then, the magnesium-alloy discs were subjected to lapping to form their respective sliding surfaces with different surface roughness.

[0076] A high-carbon chromium material “SUJ2” (i.e. an iron-based material in compliance with JIS G4805) was formed into disc bases by grinding and subjected to spheroidizing at 780° C., water quenching at 30° C., and tempering at 150° C. The heat-treated disc bases were lapped in such a manner as to form their respective base surfaces with different surface roughness. Then, DLC coatings were applied to the surfaces of the disc bases. The DLC coatings were formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD) using the following DLC coating material together with graphite targets.

[0077] [Coating Materials]

• • [0078] DLC: a-C (treated by PVD), a-C:H (treated by CVD)
    The DLC coatings were lapped with lapping tapes in such a manner as to form their sliding surfaces with different surface roughness (Ra=0.1 μm).

[0079] Each of lubricants A to I was prepared by mixing a base oil with a friction modifier or modifiers, an ashless dispersant, zinc dialkyldithiophospate, a metallic detergent and other additives. The compositions and properties of the thus-prepared lubricants A to I are shown in TABLE 4. In TABLE 4, the amount of each oil compound is indicated based on the total mass of the base oil, and the amount of each additive is indicated based on the total mass of the lubricant.

[0080] The test units of Examples 1 to 27 and Comparative Examples 1 to 12 were subjected to abrasion test under the following test conditions. The test results are shown in TABLES 1 to 3.

[0081] [Test Condition]

• • [0082] Maximum Hertz's pressure: 80 MPa
  • [0083] Disc rotation speed: 30 rpm
  • [0084] Lubrication method: Oil bath
  • [0085] Lubricant temperature: 80° C.
  • [0086] Test time: 60 minutes

[0087]

	TABLE 1
	Pin
	Coating	Disc
				Surface	Surface		Surface	Surface
	Base		Thickness	roughness	hardness		roughness	hardness		Friction
	Material	Material	(μm)	(μm)	(Hv)	Material	(μm)	(HB)	Lubricant	coefficient
Example 1	SUJ2	a-C	1.1	0.03	1850	AC2A	0.05	80	A	0.055
Example 2	SUJ2	a-C	15	0.03	1850	AC8A	0.05	120	B	0.057
Example 3	SUJ2	a-C	1.4	0.03	1850	ADC12	0.05	110	C	0.061
Example 4	SUJ2	a-C	0.8	0.03	1850	ADC14	0.05	130	D	0.066
Example 5	SUJ2	a-C:H	0.7	0.02	1250	AC8A	0.04	120	A	0.083
Example 6	SUJ2	a-C	2.0	0.02	1000	AC2A	0.03	80	B	0.060
Example 7	SUJ2	a-C	1.1	0.03	1850	AC8A	0.10	120	E	0.068
Example 8	SUJ2	a-C	0.9	0.10	1850	AC8A	0.05	120	F	0.066
Example 9	SUJ2	a-C	0.3	0.04	3500	ADC14	0.05	130	G	0.070
Comparative	SUJ2	none	—	0.03	1850	AC2A	0.10	80	H	0.14
Example 1
Comparative	SUJ2	none	—	0.03	1850	AC8A	0.05	120	E	0.12
Example 2
Comparative	SUJ2	a-C	1.2	0.03	1850	ADC14	0.05	130	I	0.10
Example 3
Comparative	SUJ2	TiN	2.5	0.04	2300	AC2A	0.05	80	E	0.11
Example 4
Comparative	SUJ2	CrN	2.6	0.03	1700	AC8A	0.05	120	E	0.11
Example 5

[0088]

	TABLE 2
	Pin
	Coating	Disc
				Surface	Surface		Surface	Surface
	Base		Thickness	roughness	hardness		roughness	hardness		Friction
	Material	Material	(μm)	(μm)	(Hv)	Material	(μm)	(HB)	Lubricant	coefficient
Example 10	SUJ2	a-C	1.2	0.03	1850	AZ91D	0.04	65	A	0.056
Example 11	SUJ2	a-C	1.4	0.04	1850	AE42	0.06	60	B	0.049
Example 12	SUJ2	a-C	1.3	0.04	1850	AS21	0.05	55	C	0.062
Example 13	SUJ2	a-C	0.9	0.03	1850	AS21	0.04	55	D	0.069
Example 14	SUJ2	a-C:H	0.7	0.03	1250	AE42	0.05	60	A	0.086
Example 15	SUJ2	a-C	1.9	0.02	1000	AX51	0.05	57	B	0.058
Example 16	SUJ2	a-C	1.0	0.02	1850	AJ52	0.08	63	E	0.060
Example 17	SUJ2	a-C	0.8	0.09	1850	QE22-T6	0.06	65	F	0.071
Example 18	SUJ2	a-C	0.4	0.03	3500	WE43-T6	0.06	75	G	0.066
Comparative	SUJ2	none	—	0.04	750	AZ91D	0.10	65	H	0.13
Example 6
Comparative	SUJ2	none	—	0.03	750	AE42	0.04	60	E	0.12
Example 7
Comparative	SUJ2	a-C	1.2	0.04	1850	AS21	0.04	55	I	0.096
Example 8
Comparative	SUJ2	TiN	2.4	0.04	2300	AZ91D	0.06	65	E	0.11
Example 9
Comparative	SUJ2	CrN	2.7	0.03	1700	AE42	0.05	60	E	0.10
Example 10

[0089]

	TABLE 3
	Pin	Disc
	Coating		Coating
				Surface	Surface				Surface	Surface
	Base		Thickness	roughness	hardness	Base		Thickness	roughness	hardness		Friction
	Material	Material	(μm)	(μm)	(Hv)	Material	Material	(μm)	(μm)	(Hv)	Lubricant	coefficient
Example 19	SUJ2	a-C	1.1	0.03	1850	SUJ2	a-C	1.1	0.04	1800	A	0.031
Example 20	SUJ2	a-C	1.5	0.03	1850	SUJ2	a-C:H	1.1	0.03	1800	B	0.046
Example 21	SUJ2	a-C:H	1.4	0.03	1250	SUJ2	a-C	1.9	0.05	1550	C	0.045
Example 22	SUJ2	a-C	0.8	0.03	1850	SUJ2	a-C	0.8	0.05	1800	D	0.033
Example 23	SUJ2	a-C:H	1.8	0.02	1250	SUJ2	a-C:H	1.9	0.04	1200	A	0.060
Example 24	SUJ2	a-C	2.0	0.02	1000	SUJ2	a-C	2.0	0.03	1200	B	0.032
Example 25	SUJ2	a-C	1.1	0.03	1850	SUJ2	a-C	1.1	0.10	1800	E	0.037
Example 26	SUJ2	a-C	0.9	0.10	1850	SUJ2	a-C	0.8	0.05	1800	F	0.035
Example 27	SUJ2	a-C	0.3	0.04	3500	SUJ2	a-C	0.3	0.05	2500	G	0.041
Comparative	SUJ2	none	—	0.03	750	AC2A	none	—	0.10	80	H	0.140
Example 11
Comparative	SUJ2	a-C	0.8	0.03	1850	SUJ2	a-C	0.8	0.05	1800	I	0.080
Example 12

[0090]

TABLE 4
Lubricant	A	B	C	D	E	F	G	H	I
Base oil
Mineral oil1)	mass %	100	100	—	100	100	100	100	100	100
Synthetic oil2)	mass %	—	—	100	—	—	—	—	—	—
Additives
Fatty-ester friction modifier3)	mass %	1.0	1.0	1.0	—	1.0	1.0	0.2	—	—
Aliphatic-amine friction modifier4)	mass %	—	—	—	1.0	—	0.5	—	—	—
Organomolybdenum compound5)	mass %	—	—	—	—	—	—	—	—	1.1
Ashless dispersant6)	mass %	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
ZDTP7)	mass %	—	0.047	0.047	0.047	0.094	0.094	0.047	0.094	0.094
(in terms of phosphorus element)
Metallic detergent	mass %	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15
(in terms of metal element)
Calcium sulfonate8)	mass %	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Calcium phenate9)	mass %	0.9	0.9	0.9	0.9	0.9	0.9	0.9	0.9	0.9
Others10)	mass %	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0
Properties
Kinematic viscosity at 100° C.	mm2/s	10.3	10.2	10.0	10.2	10.3	10.3	10.3	10.3	10.2
Total base number	mgKOH/g	6.2	6.2	6.2	6.2	6.5	6.5	6.5	6.5	7.5
according to perchloric acid method
Total base number	mgKOH/g	4.5	4.5	4.5	4.5	5.2	5.2	5.2	5.2	6.0
according to hydrochloric method
[Remarks]
1)Hydrocracked mineral oil (kinematic viscosity at 100° C.: 5.0 mm2/s, viscosity index: 120, aromatic content: 5.5 mass %)
2)1-Decene oligomer hydride (kinematic viscosity at 100° C.: 3.9 mm2/s, viscosity index: 124, aromatic content: 0.0 mass %)
3)Glycerol monolate
4)N,N-dipolyoxyethylene-N-oleylamine
5)Molybdenum dithiocarbamate (molybdenum content: 4.1 mass %)
6)Polybutenyl succinimide (nitrogen content: 1.2 mass %)
7)Zinc dialkyldithiophosphate (zinc content: 9.3 mass %, phosphrous content: 8.5 mass %, alkyl group: secondary butyl or hexyl group)
8)Calcium sulfonate (total base number: 300 mgKOH/g, calcium content: 12.0 mass %)
9)Calcium phenate (total base number: 255 mgKOH/g, calcium content: 9.2 mass %)
10)Including viscosity index improver, antioxidant, rust inhibitor, demulsifier, nonionic surfactanct, metal deactivator and anti-foaming agent

[0091] As seen in TABLES 1 to 3, the test units of Examples 1 to 27 showed more excellent low-friction characteristics and higher abrasion resistance than those of Comparative Examples 1 to 12.

[0092] The test units of Examples 1 to 9 were comprised of the DLC-coated pins, the aluminum-alloy discs and any of the lubricants A to G containing at least one of the ashless fatty-ester friction modifier and/or the ashless aliphatic-amine friction modifier, respectively. In comparison to the test unit of Comparative Example 1, the friction coefficients of the test units of Examples 1 to 9 were reduced by about 40 to 60%. Similarly, the test units of Examples 10 to 18 were comprised of the DLC-coated pins, the magnesium-alloy discs and any of the lubricants A to G, respectively. The friction coefficients of the test units of Examples 10 to 18 were also reduced by about 40 to 60% in comparison to the test unit of Comparative Example 6. The test units of Examples 19 to 27 were comprised of the DLC-coated pins, the DLC-coated discs and any of the lubricants A to G, respectively. The friction coefficients of the test units of Examples 19 to 17 were reduced by about 50 to 70% in comparison to the test unit of Comparative Example 11. In addition, any deterioration in surface appearance was not seen in the sliding members of Examples 1 to 27 even after the abrasion test.

[0093] Furthermore, the friction reducing effect became more pronounced as the amount of zinc dithiophosphate contained in the lubricant was decreased.

[0094] Among the DLC coatings, the a-C coating on the sliding surface was more effective in reducing friction than the a-C:H coating. In the case of both the discs and the pins being DLC coated as shown in Examples 19 to 27, the combination of the a-C coatings on the sliding surfaces was more effective than the combination of the a-C coating and the a-C:H coating, and the combination of the a-C coating, and the a-C:H coating was more effective than the combination of the a-C:H coatings.

[0095] On the other hand, the test unit of Comparative Example 1 was comprised of the pins with no DLC coatings, the aluminum-alloy disc and the lubricant H containing neither of the ashless fatty-ester and aliphatic amine friction modifiers. The test unit of Comparative Example 6 was comprised of the pins with no DLC coatings, the magnesium-alloy disc and the lubricant H. Further, the test unit of Comparative Examples 11 was assembled from the pins with no DLC coatings, the aluminum-alloy disc with no DLC coating and the lubricant H. The friction coefficients of the test units of Comparative Examples 1, 6 and 11 exceeded 0.1 to be much higher than those of Examples 1 to 27. The test units of Comparative Examples 2 and 7 were structurally similar to that of Comparative Examples 1 and 6, and had the pins with no DLC coatings, the SUJ2 discs with no DLC coatings and the lubricant E containing the ashless fatty-ester friction modifier, respectively. The friction coefficients of Comparative Examples 2 and 7 were slightly lower than those of Comparative Examples 1 and 6 but still exceeded 0.1. It is estimated that, in the test units of Comparative Examples 1, 2, 6, 7 and 11, reaction films were formed predominantly of zinc dithiophosphate (ZnDTP) on the sliding surfaces of the pins and discs to thereby cause increases in the friction coefficients. The test unit of Comparative Example 3 was comprised of the pins with the DLC coatings, the aluminum-alloy disc and the lubricant I. The test unit of Comparative Example 8 was comprised of the pins with the DLC coatings, the magnesium-alloy disc and the lubricant I. The test unit of Comparative Example 12 was comprised of the pins with the DLC coatings, the disc with the DLC coating and the lubricant I. In the lubricant I, the organomolybdenum compound was added in place of the ashless fatty-ester and/or aliphatic-amine friction modifier. The friction coefficients of the test units of Comparative Examples 3, 8 and 12 were thus nearly 0.1. It is thought that molybdenum disulfide films were not formed from the lubricant I in the test units of Comparative Examples 3, 8 and 12, thereby failing to obtain a sufficient friction reducing effect. The test units of Comparative Examples 4 and 9 had the pins with the TiN coatings, and the test units of Comparative Examples 5 and 10 had the pins with the CrN coatings. The friction coefficients of the test units of Comparative Examples 4, 5, 9 and 10 were slightly lowered by the use of the lubricant E, but stood at nearly 0.1. There was little difference between the friction coefficients of the test units Comparative Examples 4 and 5 and between the friction coefficients of the test units of Comparative Examples 9 and 10.

[0096] As described above, the sliding mechanism according to one exemplary embodiment of the present invention can attain world-class low-friction characteristics and high abrasion resistance and is therefore industrially useful. When the sliding mechanism is used in an internal combustion engine, it becomes possible to reduce friction loss dramatically so as to provide more improvement in vehicle fuel efficiency than ever before.

[0097] The entire contents of Japanese Patent Application No. 2002-322322 (filed on Nov. 6, 2002), No. 2003-207056 (filed on Aug. 11, 2003) and No. 2003-208193 (filed on Aug. 21, 2003) are herein incorporated by reference.

[0098] Although the present invention has been described with reference to a specific embodiment of the invention, the invention is not limited to the above-described embodiment. Various modifications and variations of the embodiment described above will occur to those skilled in the art in light of the above teaching. The scope of the invention is defined with reference to the following claims.