Low-friction sliding mechanism

Information

  • Patent Grant
  • 8152377
  • Patent Number
    8,152,377
  • Date Filed
    Tuesday, July 13, 2010
    14 years ago
  • Date Issued
    Tuesday, April 10, 2012
    12 years ago
Abstract
A low-friction sliding mechanism includes first and second sliding members having respective sliding surfaces slidable relative to each other and a lubricant applied to the sliding surfaces of the first and second sliding members. At least the sliding surface of the first sliding member is made of a diamond-like carbon material, and at least the sliding surface of the second sliding member is made of either an aluminum-based alloy material, a magnesium-based alloy material or a diamond-like carbon material. The lubricant contains a base oil and at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier.
Description
BACKGROUND OF THE INVENTION

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.


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.


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.


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.


SUMMARY OF THE INVENTION

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.


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.).


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.


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.


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





BRIEF DESCRIPTION OF THE DRAWINGS

FIGURE is a schematic illustration of an abrasion test unit.





DESCRIPTION OF THE EMBODIMENTS

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


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.


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.


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.


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.


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.


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).


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.


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 HV 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 HV 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.


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 HB of 80 to 130. If the Brinell hardness HB is less than 80, the sliding surface of the second sliding surface is prone to wear.


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 HB of 45 to 95. If the Brinell hardness HB is less than 45, the sliding surface of the second sliding surface is also prone to wear.


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 HV 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 HV 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.


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


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.


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.


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, trimethylolpropane 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.


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.


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.


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.


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.


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.


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.


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.


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.


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.


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).




embedded image



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.


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).


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.


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.


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.


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.


Furthermore, the lubricant desirably includes zinc dithiophosphate represented by the following general formula (3) as an antioxidant and as an anti-wear agent.




embedded image



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.


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.


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.


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.


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.


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.


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.


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.


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.


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.


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.


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


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


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


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


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.


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.


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.


(1) Assembling of Test Units

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.


(1-1) Preparation of Pins

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.


[Coating Materials]


DLC: a-C (treated by PVD), a-C:H (treated by CVD)


TiN (treated by PVD)


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.


(1-2) Preparation of Aluminum-alloy Discs

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


[Heat Treatment]

    • AC2A: subjected to age hardening at 510° C. for 8 hours, water quenching at 160° C. for 9 hours and air cooling.
    • AC8A: subjected to age hardening at 200° C. for 4 hours and air cooling.
    • ADC12, ADC14: no heat treatment.


      Then, the aluminum-alloy discs were subjected to lapping to form their respective sliding surfaces with different surface roughness.


(1-3) Preparation of Magnesium-alloy Discs

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


[Heat Treatment]

    • QE22-T6: subjected to age hardening at 525° C. for 4 hours, water quenching at 200° C. for 8 hours and air cooling.
    • WE43-T6: subjected to age hardening at 525° C. for 4 hours, water quenching at 250° C. for 16 hours and air cooling.
    • 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.


(1-4) Preparation of DLC Discs

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.


[Coating Materials]


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).


(1-5) Preparation of Lubricants

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.


(2) Abrasion Test

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.


[Test Condition]


Maximum Hertz's pressure: 80 MPa


Disc rotation speed: 30 rpm


Lubrication method: Oil bath


Lubricant temperature: 80° C.


Test time: 60 minutes












TABLE 1









Pin












Coating
Disc






















Surface
Surface

Surface
Surface





Base

Thickness
roughness
hardness

roughness
hardness
Lubri-
Friction



Material
Material
(μm)
(μm)
(Hv)
Material
(μm)
(HB)
cant
coefficient





















Example 1
SUJ2
a-C
1.1
0.03
1850
AC2A
0.05
80
A
0.055


Example 2
SUJ2
a-C
1.5
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



















TABLE 2









Pin












Coating
Disc






















Surface
Surface

Surface
Surface





Base

Thickness
roughness
hardness

roughness
hardness
Lubri-
Friction



Material
Material
(μm)
(μm)
(Hv)
Material
(μm)
(HB)
cant
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




















TABLE 3









Pin
Disc













Coating

Coating
























Surface
Surface



Surface
Surface





Base

Thickness
roughness
hardness
Base

Thickness
roughness
hardness
Lubri-
Friction



Material
Material
(μm)
(μm)
(Hv)
Material
Material
(μm)
(μm)
(Hv)
cant
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


























TABLE 4





Lubricant

A
B
C
D
E
F
G
H
I


























Base oil
Mineral oil 1)
mass %
100
100

100
100
100
100
100
100



Synthetic oil 2)
mass %


100








Additives
Fatty-ester friction modifier 3)
mass %
1.0
1.0
1.0

1.0
1.0
0.2





Aliphatic-amine friction modifier 4)
mass %



1.0

0.5






Organomolybdenum compound 5)
mass %








1.1



Ashless dispersant 6)
mass %
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0



ZDTP 7)
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 sulfonate 8)
mass %
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5



Calcium phenate 9)
mass %
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9



Others 10)
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







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.


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.


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


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.


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.


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.


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.

Claims
  • 1. A low-friction sliding mechanism, comprising: a first sliding member having a sliding surface, at least the sliding surface of the first sliding member comprising a diamond-like carbon material;a second sliding member having a sliding surface slidable relative to the sliding surface of the first sliding member, the second sliding member being formed in one piece of diamond-like carbon material; anda 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.
  • 2. A low-friction sliding mechanism according to claim 1, wherein the diamond-like carbon material of the first sliding member is hydrogen-free amorphous carbon.
  • 3. A low-friction sliding mechanism according to claim 1, wherein the aluminum-based alloy material of the second sliding member is a hypoeutectic or hypereutectic aluminum alloy containing 4 to 20% by mass silicon and 1.0 to 5.0% by mass copper.
  • 4. A low-friction sliding mechanism according to claim 1, wherein the magnesium-based alloy material of the second sliding member comprises at least one alloy selected from the group consisting of magnesium-aluminum- zinc alloys, magnesium-aluminum-rare earth metal alloys, magnesium- aluminum-calcium alloys, magnesium-zinc-aluminum-calcium alloys, magnesium-aluminum-calcium-rare earth metal alloys, magnesium-aluminum- strontium alloys, magnesium-aluminum-silicon alloys, magnesium-rare earth metal-zinc alloys, magnesium-silver-rare earth metal alloys and magnesium-yttrium-rare earth metal alloys.
  • 5. A low-friction sliding mechanism according to claim 1, wherein each of the sliding surfaces of the first and second sliding member has an arithmetic mean roughness of 0.1 μm or less.
  • 6. A low-friction sliding mechanism according to claim 1, wherein the first sliding member comprises a base and a coating of the diamond-like carbon material applied to the base to define the sliding surface, the coating has a thickness of 0.3 to 2.0 μm and a micro Vickers hardness HV of 1000 to 3500 as measured by application of a 10 g load, the second sliding member is made of the aluminum-based alloy material, and the sliding surface of the second sliding member has a Brinell hardness HB of 80 to 130.
  • 7. A low-friction sliding mechanism according to claim 1, wherein the first sliding member comprises a base and a coating of the diamond-like carbon material applied to the base to define the sliding surface, the coating has a thickness of 0.3 to 2.0 μm and a micro Vickers hardness HV of 1000 to 3500 as measured by application of a 10 g load, the second sliding member comprises an magnesium-based alloy material, and the sliding surface of the second sliding member has a Brinell hardness HB of 45 to 95.
  • 8. An internal combustion engine comprising a low-friction sliding mechanism according to claim 1.
  • 9. A low-friction sliding mechanism according to claim 1, wherein the fatty-ester friction modifier and the aliphatic-amine friction modifier comprise C6-C30 straight or branched hydrocarbon chains, respectively, and the lubricant comprises 0.05 to 3.0% by mass based on the total mass of the lubricant of the at least one of the fatty-ester friction modifier and the aliphatic-amine friction modifier.
  • 10. A low-friction sliding mechanism according to claim 1, wherein the lubricant further comprises polybutenyl succinimide and/or a derivative thereof.
  • 11. A low-friction sliding mechanism according to claim 10, wherein the lubricant comprises 0.1 to 15% by mass based on the total mass of the lubricant of the polybutenyl succinimide and/or the derivative.
  • 12. A low-friction sliding mechanism according to claim 1, wherein the lubricant further comprises zinc dithiophosphate in an amount of 0.1% or less by mass in terms of an phosphorus element based on a total mass of the lubricant.
  • 13. A low-friction sliding mechanism, comprising: a first sliding member having a sliding surface, at least the sliding surface of the first sliding member comprising a diamond-like carbon material wherein the diamond-like carbon material of the first sliding member is hydrogen-free amorphous carbon;a second sliding member having a sliding surface slidable relative to the sliding surface of the first sliding member, the second sliding member consisting essentially of a diamond-like carbon material; anda lubricant applied to the sliding surfaces of the first and second sliding members, the lubricant comprising friction modifier.
Priority Claims (3)
Number Date Country Kind
2002-322322 Nov 2002 JP national
2003-207056 Aug 2003 JP national
2003-208193 Aug 2003 JP national
Parent Case Info

The present application is a continuation of U.S. application Ser. No. 11/955,949, filed Dec. 13, 2007 now abandoned, which is a continuation of U.S. application Ser. No. 11/123,016, filed May 6, 2005 now U.S. Pat. No. 7,322,749, which is a divisional of U.S. application Ser. No. 10/692,853, filed Oct. 27, 2003 now U.S. Pat. No. 6,969,198, which claims priority from Japanese Patent Application No. 2002-322322 filed on Nov. 6, 2002; Japanese Patent Application No. 2003-207056 filed on Aug. 11, 2003; and Japanese Patent Application No. 2003-208193 filed on Aug. 21, 2003 the entire contents of which are incorporated herein by reference.

US Referenced Citations (372)
Number Name Date Kind
1461 Day Dec 1839 A
2716972 Farny et al. Sep 1955 A
2982733 Wright et al. May 1961 A
3211647 O'Halloran et al. Oct 1965 A
3790315 Emanuelsson et al. Feb 1974 A
3846162 Bloom Nov 1974 A
3932228 Sugiyama et al. Jan 1976 A
4031023 Musser et al. Jun 1977 A
4367130 Lemelson Jan 1983 A
4385880 Lemelson May 1983 A
4538929 Ehrentraut et al. Sep 1985 A
4554208 MacIver et al. Nov 1985 A
4645610 Born et al. Feb 1987 A
4702808 Lemelson Oct 1987 A
4712982 Inagaki et al. Dec 1987 A
4755237 Lemelson Jul 1988 A
4755426 Kokai et al. Jul 1988 A
4783368 Yamamoto et al. Nov 1988 A
4834400 Lebeck May 1989 A
4842755 Dunn Jun 1989 A
4859493 Lemelson Aug 1989 A
4874596 Lemelson Oct 1989 A
4919974 McCune et al. Apr 1990 A
4933058 Bache et al. Jun 1990 A
4943345 Asmussen et al. Jul 1990 A
4960643 Lemelson Oct 1990 A
4974498 Lemelson Dec 1990 A
4980021 Kitamura et al. Dec 1990 A
4980610 Varga Dec 1990 A
4981717 Thaler Jan 1991 A
4988421 Drawl et al. Jan 1991 A
4992082 Drawl et al. Feb 1991 A
5000541 DiMarcello et al. Mar 1991 A
5021628 Lemelson Jun 1991 A
5032243 Bache et al. Jul 1991 A
5036211 Scott Jul 1991 A
5040501 Lemelson Aug 1991 A
5067826 Lemelson Nov 1991 A
5077990 Plath Jan 1992 A
5078848 Anttila et al. Jan 1992 A
5087608 Chan et al. Feb 1992 A
5096352 Lemelson Mar 1992 A
5110435 Haberland May 1992 A
5112025 Nakayama et al. May 1992 A
5127314 Swain Jul 1992 A
5131941 Lemelson Jul 1992 A
5132587 Lemelson Jul 1992 A
5142785 Grewal et al. Sep 1992 A
5143634 Quinga et al. Sep 1992 A
5148780 Urano et al. Sep 1992 A
5187021 Vydra et al. Feb 1993 A
5190807 Kimock et al. Mar 1993 A
5190824 Itoh Mar 1993 A
5202156 Yamamoto et al. Apr 1993 A
5205188 Repenning et al. Apr 1993 A
5205305 Yamakita Apr 1993 A
H1210 Jansen Jul 1993 H
5232568 Parent et al. Aug 1993 A
5237967 Willermet et al. Aug 1993 A
5249554 Tamor et al. Oct 1993 A
5255783 Goodman et al. Oct 1993 A
5255929 Lemelson Oct 1993 A
5284394 Lemelson Feb 1994 A
5288556 Lemelson Feb 1994 A
5295305 Hahn et al. Mar 1994 A
5299937 Gow Apr 1994 A
5317938 de Juan, Jr. et al. Jun 1994 A
5326488 Minokami et al. Jul 1994 A
5332348 Lemelson Jul 1994 A
5334306 Dautremont-Smith et al. Aug 1994 A
5349265 Lemelson Sep 1994 A
5358402 Reed et al. Oct 1994 A
5359170 Chen et al. Oct 1994 A
5360227 Lemelson Nov 1994 A
5380196 Kelly et al. Jan 1995 A
5401543 O'Neill et al. Mar 1995 A
H1461 DiVita et al. Jul 1995 H
5432539 Anderson Jul 1995 A
5433977 Sarin et al. Jul 1995 A
H1471 Braun et al. Aug 1995 H
5443032 Vichr et al. Aug 1995 A
5447208 Lund et al. Sep 1995 A
5456406 Lemelson Oct 1995 A
5458754 Sathrum et al. Oct 1995 A
5461648 Nauflett et al. Oct 1995 A
5462772 Lemelson Oct 1995 A
5464667 Köhler et al. Nov 1995 A
5466431 Dorfman et al. Nov 1995 A
5479069 Winsor Dec 1995 A
5482602 Cooper et al. Jan 1996 A
5491028 Sarin et al. Feb 1996 A
5497550 Trotta et al. Mar 1996 A
5509841 Winsor Apr 1996 A
5516729 Dawson et al. May 1996 A
5529815 Lemelson Jun 1996 A
5531878 Vadgama et al. Jul 1996 A
5541566 Deeney Jul 1996 A
5547716 Thaler Aug 1996 A
5551959 Martin et al. Sep 1996 A
5552675 Lemelson Sep 1996 A
5568391 Mckee Oct 1996 A
5593719 Dearnaley et al. Jan 1997 A
5616372 Conley et al. Apr 1997 A
5619889 Jones et al. Apr 1997 A
5628881 Lemelson May 1997 A
5630275 Wexler May 1997 A
5630953 Klink May 1997 A
5653300 Lund et al. Aug 1997 A
5669144 Hahn et al. Sep 1997 A
5672054 Cooper et al. Sep 1997 A
5688557 Lemelson et al. Nov 1997 A
5707409 Martin et al. Jan 1998 A
5714202 Lemelson et al. Feb 1998 A
5719109 Tokashiki et al. Feb 1998 A
5723207 Lettington et al. Mar 1998 A
5731046 Mistry et al. Mar 1998 A
5735769 Takemura et al. Apr 1998 A
5740941 Lemelson Apr 1998 A
5775817 Gottemoller et al. Jul 1998 A
5786038 Conley et al. Jul 1998 A
5790146 Anderson Aug 1998 A
5793390 Claflin et al. Aug 1998 A
5794801 Lemelson Aug 1998 A
5799549 Decker et al. Sep 1998 A
5806557 Helge Sep 1998 A
5824387 Boutaghou et al. Oct 1998 A
5834708 Svetal et al. Nov 1998 A
5840662 Nibert et al. Nov 1998 A
5843571 Sho Dec 1998 A
5851962 Kaga Dec 1998 A
5866195 Lemelson Feb 1999 A
5871805 Lemelson Feb 1999 A
5881444 Schaefer et al. Mar 1999 A
5901021 Hirano et al. May 1999 A
5910940 Guerra Jun 1999 A
5927897 Attar Jul 1999 A
5937812 Reedy et al. Aug 1999 A
5940975 Decker et al. Aug 1999 A
5945214 Ma et al. Aug 1999 A
5947710 Cooper et al. Sep 1999 A
5952102 Cutler Sep 1999 A
5958261 Offer et al. Sep 1999 A
5960762 Imai Oct 1999 A
5967250 Lund et al. Oct 1999 A
5968596 Ma et al. Oct 1999 A
5975686 Hauck et al. Nov 1999 A
5976707 Grab Nov 1999 A
5992268 Decker et al. Nov 1999 A
5993938 Tsukuda et al. Nov 1999 A
6006415 Schaefer et al. Dec 1999 A
6015597 David Jan 2000 A
6016000 Moslehi Jan 2000 A
6023979 Bills et al. Feb 2000 A
6028393 Izu et al. Feb 2000 A
6051298 Ko et al. Apr 2000 A
6056443 Koike et al. May 2000 A
6059460 Ono et al. May 2000 A
6059830 Lippincott, III et al. May 2000 A
6071597 Yang et al. Jun 2000 A
6083313 Venkatraman et al. Jul 2000 A
6083570 Lemelson et al. Jul 2000 A
6095690 Niegel et al. Aug 2000 A
6099541 Klopotek Aug 2000 A
6099976 Lemelson et al. Aug 2000 A
6106919 Lee et al. Aug 2000 A
6124198 Moslehi Sep 2000 A
6139964 Sathrum et al. Oct 2000 A
6142481 Iwashita et al. Nov 2000 A
6145608 Lund et al. Nov 2000 A
6156439 Coffinberry Dec 2000 A
6159558 Wolfe et al. Dec 2000 A
6160683 Boutaghou Dec 2000 A
6165616 Lemelson et al. Dec 2000 A
6170156 Lev et al. Jan 2001 B1
6171343 Dearnaley et al. Jan 2001 B1
6173913 Shafer et al. Jan 2001 B1
6190514 Ma et al. Feb 2001 B1
6193906 Kaneko et al. Feb 2001 B1
6197120 David Mar 2001 B1
6197428 Rogers Mar 2001 B1
6203651 Järvenkylä et al. Mar 2001 B1
6205291 Hughes et al. Mar 2001 B1
6207625 Ogano et al. Mar 2001 B1
6227056 Bills et al. May 2001 B1
6237441 Nishioka et al. May 2001 B1
6237852 Svetal et al. May 2001 B1
6238839 Tomita et al. May 2001 B1
6255262 Keenan et al. Jul 2001 B1
6261424 Goncharenko et al. Jul 2001 B1
6273793 Liners et al. Aug 2001 B1
6274220 Tsukuda et al. Aug 2001 B1
6289593 Decker et al. Sep 2001 B1
6293648 Anderson Sep 2001 B1
6296552 Boutaghou et al. Oct 2001 B1
6299425 Hirano et al. Oct 2001 B1
6305416 Snel et al. Oct 2001 B1
6309283 Liners et al. Oct 2001 B1
6311524 Brennan, III et al. Nov 2001 B1
6316734 Yang Nov 2001 B1
6322431 Schaenzer et al. Nov 2001 B1
6322719 Kaneko et al. Nov 2001 B2
6324060 Hsu Nov 2001 B1
6325385 Iwashita et al. Dec 2001 B1
6329328 Koganei et al. Dec 2001 B1
6333298 Waddoups et al. Dec 2001 B1
6338881 Sellschopp et al. Jan 2002 B1
6340245 Horton et al. Jan 2002 B1
6358123 Liners et al. Mar 2002 B1
6367705 Lee et al. Apr 2002 B1
6368676 Gaudreau et al. Apr 2002 B1
6377422 Boutaghou et al. Apr 2002 B1
6379383 Palmaz et al. Apr 2002 B1
6385987 Schlom et al. May 2002 B2
6386468 Neuberger et al. May 2002 B1
6399215 Zhu et al. Jun 2002 B1
6401058 Akalin et al. Jun 2002 B1
6439845 Veres Aug 2002 B1
6439986 Myoung et al. Aug 2002 B1
6452752 Boutaghou Sep 2002 B1
6468642 Bray et al. Oct 2002 B1
6471979 New et al. Oct 2002 B2
6494881 Bales et al. Dec 2002 B1
6523456 Kobayashi et al. Feb 2003 B1
6524212 Ushijima et al. Feb 2003 B2
6534141 Hull, Jr. et al. Mar 2003 B1
6537310 Palmaz et al. Mar 2003 B1
6537429 O'Donnell et al. Mar 2003 B2
6543394 Tinney Apr 2003 B2
6544308 Griffin et al. Apr 2003 B2
6553957 Ishikawa et al. Apr 2003 B1
6557968 Lee et al. May 2003 B2
6562445 Iwamura May 2003 B2
6562462 Griffin et al. May 2003 B2
6570172 Kim et al. May 2003 B2
6572651 De Scheerder et al. Jun 2003 B1
6572935 He et al. Jun 2003 B1
6572937 Hakovirta et al. Jun 2003 B2
6585064 Griffin et al. Jul 2003 B2
6586069 Dykes et al. Jul 2003 B2
6589640 Griffin et al. Jul 2003 B2
6592519 Martinez Jul 2003 B1
6592985 Griffin et al. Jul 2003 B2
6601662 Matthias et al. Aug 2003 B2
6626949 Townley Sep 2003 B1
6629906 Chiba et al. Oct 2003 B1
6637528 Nishiyama et al. Oct 2003 B2
6638569 McLaughlin et al. Oct 2003 B2
6645354 Gorokhovsky Nov 2003 B1
6656329 Ma et al. Dec 2003 B1
6658941 Bills et al. Dec 2003 B1
6666328 Sykora Dec 2003 B2
6666671 Olver et al. Dec 2003 B1
6684513 Clipstone et al. Feb 2004 B1
6684759 Gorokhovsky Feb 2004 B1
6695865 Boyle et al. Feb 2004 B2
6699106 Myoung et al. Mar 2004 B2
6701627 Korb et al. Mar 2004 B2
6715693 Dam et al. Apr 2004 B1
6726993 Teer et al. Apr 2004 B2
6729350 Schick May 2004 B2
6729527 Sonnenreich et al. May 2004 B2
6733513 Boyle et al. May 2004 B2
6739214 Griffin et al. May 2004 B2
6739238 Ushijima et al. May 2004 B2
6740393 Massler et al. May 2004 B1
6745742 Meyer Jun 2004 B2
6749033 Griffin et al. Jun 2004 B2
6753042 Bakounine et al. Jun 2004 B1
6753635 Kuhlmann-Wilsdorf Jun 2004 B2
6761532 Capone et al. Jul 2004 B2
6761736 Woo et al. Jul 2004 B1
6780177 Shafirstein et al. Aug 2004 B2
6797326 Griffin et al. Sep 2004 B2
6799468 Borenstein Oct 2004 B2
6806242 Shirahama et al. Oct 2004 B2
6818029 Myoung et al. Nov 2004 B2
6820676 Palmaz et al. Nov 2004 B2
6821189 Coad et al. Nov 2004 B1
6821624 Utsumi et al. Nov 2004 B2
6822788 Blitstein Nov 2004 B2
6844068 Miyake et al. Jan 2005 B1
6849085 Marton Feb 2005 B2
6855237 Kolpakov et al. Feb 2005 B2
6855791 Van Doren et al. Feb 2005 B2
6861098 Griffin et al. Mar 2005 B2
6861137 Griffin et al. Mar 2005 B2
6865952 Bills et al. Mar 2005 B2
6866894 Trankiem et al. Mar 2005 B2
6871700 Gorokhovsky Mar 2005 B2
6872203 Shafirstein et al. Mar 2005 B2
6878447 Griffin et al. Apr 2005 B2
6880469 Frost Apr 2005 B2
6882094 Dimitrijevic et al. Apr 2005 B2
6883476 Nohara et al. Apr 2005 B1
6885521 Kikuchi Apr 2005 B2
6886521 Hamada et al. May 2005 B2
6887585 Herbst-Dederichs May 2005 B2
6890700 Tomita et al. May 2005 B2
6893720 Nakahigashi et al. May 2005 B1
6969198 Konishi et al. Nov 2005 B2
7322749 Konishi et al. Jan 2008 B2
20010036800 Liners et al. Nov 2001 A1
20020026899 McLaughlin et al. Mar 2002 A1
20020031987 Liners et al. Mar 2002 A1
20020034631 Griffin et al. Mar 2002 A1
20020034632 Griffin et al. Mar 2002 A1
20020051286 Blitstein May 2002 A1
20020070357 Kim et al. Jun 2002 A1
20020074168 Matthias et al. Jun 2002 A1
20020089571 Lee et al. Jul 2002 A1
20020090155 Ushijima et al. Jul 2002 A1
20020090578 Schaefera et al. Jul 2002 A1
20020130219 Parseghian et al. Sep 2002 A1
20020148430 Kano et al. Oct 2002 A1
20020155015 Esumi et al. Oct 2002 A1
20020175476 Chinou et al. Nov 2002 A1
20030012234 Watson et al. Jan 2003 A1
20030019111 Korb et al. Jan 2003 A1
20030019332 Korb et al. Jan 2003 A1
20030021995 Griffin et al. Jan 2003 A1
20030034182 Griffin et al. Feb 2003 A1
20030035957 Griffin et al. Feb 2003 A1
20030035958 Griffin et al. Feb 2003 A1
20030036341 Myoung et al. Feb 2003 A1
20030037640 Griffin et al. Feb 2003 A1
20030069632 De Scheerder et al. Apr 2003 A1
20030108777 Gunsel et al. Jun 2003 A1
20030114094 Myoung et al. Jun 2003 A1
20030128903 Yasuda et al. Jul 2003 A1
20030159919 Fairbairn et al. Aug 2003 A1
20030162672 Shirahama et al. Aug 2003 A1
20030168323 Frost Sep 2003 A1
20030180565 Herbst-Dederichs Sep 2003 A1
20030199741 Martinez Oct 2003 A1
20030234371 Ziegler Dec 2003 A1
20030235691 Griffin et al. Dec 2003 A1
20040003638 Schaefer et al. Jan 2004 A1
20040008406 Blitstein Jan 2004 A1
20040010068 Doren et al. Jan 2004 A1
20040011900 Gebhardt et al. Jan 2004 A1
20040027018 LeBlanc et al. Feb 2004 A1
20040035375 Gibisch et al. Feb 2004 A1
20040074467 Hamada et al. Apr 2004 A1
20040092405 Konishi et al. May 2004 A1
20040105806 Griffin et al. Jun 2004 A1
20040109621 Frost Jun 2004 A1
20040115435 Griffin et al. Jun 2004 A1
20040133301 Van Doren et al. Jul 2004 A1
20040154570 Mabuchi et al. Aug 2004 A1
20040168326 Korb et al. Sep 2004 A1
20040184687 Morales et al. Sep 2004 A1
20040223256 Feng et al. Nov 2004 A1
20040241448 Kano et al. Dec 2004 A1
20040242435 Nishimura et al. Dec 2004 A1
20040244539 Korb et al. Dec 2004 A1
20040261614 Hamada et al. Dec 2004 A1
20050001201 Bocko et al. Jan 2005 A1
20050005892 Nishimura et al. Jan 2005 A1
20050025975 Okamoto et al. Feb 2005 A1
20050035222 Hamada et al. Feb 2005 A1
20050037879 Murata et al. Feb 2005 A1
20050056241 Nomura et al. Mar 2005 A1
20050061291 Nishimura et al. Mar 2005 A1
20050061636 Frost et al. Mar 2005 A1
20050064196 Martin et al. Mar 2005 A1
20050082139 Ishikawa et al. Apr 2005 A1
20050084390 Ueno et al. Apr 2005 A1
20050089685 Hamada et al. Apr 2005 A1
20050098134 Nishimura et al. May 2005 A1
20050100701 Hamada et al. May 2005 A1
20050115744 Griffin et al. Jun 2005 A1
20050188942 Hamada et al. Sep 2005 A1
Foreign Referenced Citations (300)
Number Date Country
2009582 Aug 1990 CA
643 034 Mar 1937 DE
19507086 Sep 1996 DE
19507086 Sep 1996 DE
197 04 224 Aug 1997 DE
198 15 989 Oct 1999 DE
19825860 Dec 1999 DE
100 17 459 Oct 2000 DE
100 61 697 May 2002 DE
101 58 683 Jun 2003 DE
103 18 135 Nov 2003 DE
10337559 Mar 2005 DE
0 286 996 Oct 1988 EP
0 291 006 Nov 1988 EP
0 299 785 Jan 1989 EP
0308143 Mar 1989 EP
0 333 416 Sep 1989 EP
0378378 Jul 1990 EP
0384772 Aug 1990 EP
0388800 Sep 1990 EP
0392125 Oct 1990 EP
0398985 Nov 1990 EP
407977 Jan 1991 EP
0 435 312 Jul 1991 EP
0474369 Mar 1992 EP
0 500 253 Aug 1992 EP
0511153 Oct 1992 EP
0 529 327 Mar 1993 EP
0392125 Mar 1993 EP
0546824 Jun 1993 EP
0308143 Nov 1993 EP
0573943 Dec 1993 EP
0619504 Oct 1994 EP
0621136 Oct 1994 EP
0624353 Nov 1994 EP
0624354 Nov 1994 EP
0378378 Jan 1995 EP
0651069 May 1995 EP
0652301 May 1995 EP
0656458 Jun 1995 EP
0 661 470 Jul 1995 EP
0396603 Jun 1996 EP
0 731 190 Sep 1996 EP
0388800 Dec 1996 EP
0 759 519 Feb 1997 EP
0474369 Mar 1997 EP
0 818 622 Jan 1998 EP
0652301 Jan 1998 EP
0826790 Mar 1998 EP
0842754 May 1998 EP
0 870 820 Oct 1998 EP
0816112 Oct 1998 EP
0882759 Dec 1998 EP
0893677 Jan 1999 EP
0624353 Feb 1999 EP
0656458 Feb 1999 EP
0 905 221 Mar 1999 EP
0 905 419 Mar 1999 EP
0647318 Mar 1999 EP
0651069 Mar 1999 EP
0949200 Oct 1999 EP
0845154 Nov 1999 EP
0624354 Dec 1999 EP
0582676 Mar 2000 EP
1063085 Dec 2000 EP
1 067 211 Jan 2001 EP
0850126 Jan 2001 EP
1076087 Feb 2001 EP
1078736 Feb 2001 EP
1109196 Jun 2001 EP
0778902 Sep 2001 EP
1 154 012 Nov 2001 EP
0826790 Nov 2001 EP
1034320 Dec 2001 EP
0893677 Jan 2002 EP
0850133 Feb 2002 EP
1184480 Mar 2002 EP
1190791 Apr 2002 EP
1219464 Jul 2002 EP
1 233 054 Aug 2002 EP
0971812 Oct 2002 EP
1018291 Oct 2002 EP
1281513 Feb 2003 EP
1 300 608 Apr 2003 EP
0950123 May 2003 EP
0882759 Jun 2003 EP
1 338 641 Aug 2003 EP
1340605 Sep 2003 EP
1365141 Nov 2003 EP
1083946 Dec 2003 EP
1078736 Jan 2004 EP
1378271 Jan 2004 EP
0757615 Mar 2004 EP
0842754 Mar 2004 EP
1 411 145 Apr 2004 EP
0862395 Apr 2004 EP
1 418 353 May 2004 EP
1440775 Jul 2004 EP
1445119 Aug 2004 EP
1475557 Nov 2004 EP
1481699 Dec 2004 EP
1482190 Dec 2004 EP
1498597 Jan 2005 EP
1 510 594 Mar 2005 EP
1311885 Mar 2005 EP
1512781 Mar 2005 EP
1183470 Apr 2005 EP
2 669 689 May 1992 FR
768226 Feb 1957 GB
1005638 Oct 1988 GB
2338716 Dec 1999 GB
0990532 Mar 2001 IE
62-111106 May 1987 JP
63-21209 Jan 1988 JP
63-288994 Nov 1988 JP
5-70879 Mar 1993 JP
5-36004 May 1993 JP
5-42616 Jun 1993 JP
6-264993 Sep 1994 JP
6-294307 Oct 1994 JP
7-63135 Mar 1995 JP
07-090553 Apr 1995 JP
7-103238 Apr 1995 JP
07-118832 May 1995 JP
7-41386 Oct 1995 JP
7-286696 Oct 1995 JP
8-14014 Jan 1996 JP
8-61499 Mar 1996 JP
9-20981 Jan 1997 JP
52006318 Jan 1997 JP
253770 Sep 1997 JP
10-088369 Apr 1998 JP
10-265790 Oct 1998 JP
10-298440 Nov 1998 JP
11-22423 Jan 1999 JP
11-190406 Jul 1999 JP
11-292629 Oct 1999 JP
11-294118 Oct 1999 JP
11-333773 Dec 1999 JP
2000-88104 Mar 2000 JP
2000-119843 Apr 2000 JP
2000-504089 Apr 2000 JP
2000-297373 Oct 2000 JP
2000-327484 Nov 2000 JP
2000-339083 Dec 2000 JP
2001-62605 Mar 2001 JP
2001-64005 Mar 2001 JP
2001-93141 Apr 2001 JP
2001-172766 Jun 2001 JP
2001-172766 Jun 2001 JP
2001-192864 Jul 2001 JP
2001-269938 Oct 2001 JP
2001-280236 Oct 2001 JP
2002-265968 Sep 2002 JP
2002-309912 Oct 2002 JP
2002-332571 Nov 2002 JP
2003-13163 Jan 2003 JP
2003-13799 Jan 2003 JP
2003-25117 Jan 2003 JP
2003-28174 Jan 2003 JP
2003-88939 Mar 2003 JP
2003-113941 Apr 2003 JP
2003-147508 May 2003 JP
2004-36788 Feb 2004 JP
2005-68529 Mar 2005 JP
2004586 Dec 1993 RU
2153782 Jul 2000 RU
1770350 Oct 1992 SU
WO 8906707 Jul 1989 WO
WO 8906708 Jul 1989 WO
WO 8906338 Jul 1989 WO
WO 9202602 Feb 1992 WO
WO 9206843 Apr 1992 WO
WO 9219425 Nov 1992 WO
WO 9321288 Oct 1993 WO
WO 9321289 Oct 1993 WO
WO 9324828 Dec 1993 WO
WO 9520253 Jul 1995 WO
WO 9529044 Nov 1995 WO
WO 9529273 Nov 1995 WO
WO 9531584 Nov 1995 WO
WO 9604485 Feb 1996 WO
WO 9605333 Feb 1996 WO
WO 9605942 Feb 1996 WO
WO 9606961 Mar 1996 WO
WO 9612389 Apr 1996 WO
WO 9624488 Aug 1996 WO
WO 9640446 Dec 1996 WO
WO 9707531 Feb 1997 WO
WO 9710093 Mar 1997 WO
WO 9710940 Mar 1997 WO
WO 9714555 Apr 1997 WO
WO 9716138 May 1997 WO
WO 9802715 Jan 1998 WO
WO 9812994 Apr 1998 WO
WO 9813528 Apr 1998 WO
WO 9847141 Oct 1998 WO
WO 9909547 Feb 1999 WO
WO 9912404 Mar 1999 WO
WO 9914512 Mar 1999 WO
WO 9916371 Apr 1999 WO
WO 9922694 May 1999 WO
WO 9927157 Jun 1999 WO
WO 9929477 Jun 1999 WO
WO 9931557 Jun 1999 WO
WO 9934385 Jul 1999 WO
WO 9946847 Sep 1999 WO
WO 9954520 Oct 1999 WO
WO 9954934 Oct 1999 WO
WO 9957743 Nov 1999 WO
WO 9962077 Dec 1999 WO
WO 9962572 Dec 1999 WO
WO 0022613 Apr 2000 WO
WO 0024554 May 2000 WO
WO 0025410 May 2000 WO
WO 0028142 May 2000 WO
WO 0033051 Jun 2000 WO
WO 0035000 Jun 2000 WO
WO 0044032 Jul 2000 WO
WO 0047402 Aug 2000 WO
WO 0055385 Sep 2000 WO
WO 0056127 Sep 2000 WO
WO 0056393 Sep 2000 WO
WO 0062327 Oct 2000 WO
WO 0068451 Nov 2000 WO
WO 0075517 Dec 2000 WO
WO 0078504 Dec 2000 WO
WO 0105917 Jan 2001 WO
WO 01006033 Feb 2001 WO
WO 0114736 Mar 2001 WO
WO 0114745 Mar 2001 WO
WO 0126862 Apr 2001 WO
WO 0137631 May 2001 WO
WO 0140537 Jun 2001 WO
WO 0147451 Jul 2001 WO
WO 0159544 Aug 2001 WO
WO 0161182 Aug 2001 WO
WO 0161719 Aug 2001 WO
WO 0162372 Aug 2001 WO
WO 0163639 Aug 2001 WO
WO 0167834 Sep 2001 WO
WO 0179583 Oct 2001 WO
WO 0180224 Oct 2001 WO
WO 02006875 Jan 2002 WO
WO 0213188 Feb 2002 WO
WO 0224601 Mar 2002 WO
WO 0224603 Mar 2002 WO
WO 0224970 Mar 2002 WO
WO 0232625 Apr 2002 WO
WO 0244440 Jun 2002 WO
WO 02054454 Jul 2002 WO
WO 02062714 Aug 2002 WO
WO 02073021 Sep 2002 WO
WO 02080996 Oct 2002 WO
WO 02085237 Oct 2002 WO
WO 02090461 Nov 2002 WO
WO 02097289 Dec 2002 WO
WO 03009978 Feb 2003 WO
WO 03013990 Feb 2003 WO
WO 03020329 Mar 2003 WO
WO 03021731 Mar 2003 WO
WO 03031543 Apr 2003 WO
WO 2003046508 Jun 2003 WO
WO 03054876 Jul 2003 WO
WO 03076309 Sep 2003 WO
WO 03078679 Sep 2003 WO
WO 03091758 Nov 2003 WO
WO 2003095009 Nov 2003 WO
WO 03105134 Dec 2003 WO
WO 2004001804 Dec 2003 WO
WO 2004004998 Jan 2004 WO
WO 2004019809 Mar 2004 WO
WO 2004024206 Mar 2004 WO
WO 2004026359 Apr 2004 WO
WO 2004026500 Apr 2004 WO
WO 2004036169 Apr 2004 WO
WO 2004036292 Apr 2004 WO
WO 2004038701 May 2004 WO
WO 2004043631 May 2004 WO
WO 2004048126 Jun 2004 WO
WO 2004067466 Aug 2004 WO
WO 2004068530 Aug 2004 WO
WO 2004071670 Aug 2004 WO
WO 2004072959 Aug 2004 WO
WO 2004078424 Sep 2004 WO
WO 2004084773 Oct 2004 WO
WO 2004088113 Oct 2004 WO
WO 2005010596 Feb 2005 WO
WO 2005011744 Feb 2005 WO
WO 2005014760 Feb 2005 WO
WO 2005014882 Feb 2005 WO
WO 2005016620 Feb 2005 WO
WO 2005021851 Mar 2005 WO
WO 2005025844 Mar 2005 WO
WO 2005034791 Apr 2005 WO
WO 2005037144 Apr 2005 WO
WO 2005037985 Apr 2005 WO
WO 2005040451 May 2005 WO
WO 2005042064 May 2005 WO
WO 2005047737 May 2005 WO
Related Publications (1)
Number Date Country
20110028361 A1 Feb 2011 US
Divisions (1)
Number Date Country
Parent 10692853 Oct 2003 US
Child 11123016 US
Continuations (2)
Number Date Country
Parent 11955949 Dec 2007 US
Child 12835705 US
Parent 11123016 May 2005 US
Child 11955949 US