US20040242435A1 - Hard-carbon coated machine tool and cutting oil composition therefor - Google Patents

Hard-carbon coated machine tool and cutting oil composition therefor Download PDF

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US20040242435A1
US20040242435A1 US10/855,501 US85550104A US2004242435A1 US 20040242435 A1 US20040242435 A1 US 20040242435A1 US 85550104 A US85550104 A US 85550104A US 2004242435 A1 US2004242435 A1 US 2004242435A1
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oil composition
cutting oil
machine tool
friction modifier
ashless
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Kimio Nishimura
Yutaka Mabuchi
Tomohiro Kondo
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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Assigned to NISSAN MOTOR CO. LTD. reassignment NISSAN MOTOR CO. LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MABUCHI, YUTAKA, KONDO, TOMOHIRO, NISHIMURA, KIMIO
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00Lubricating compositions containing more than 10% water
    • C10M173/02Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68Esters
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56Amides; Imides
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    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/062Oxides; Hydroxides; Carbonates or bicarbonates
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08Inorganic acids or salts thereof
    • C10M2201/084Inorganic acids or salts thereof containing sulfur, selenium or tellurium
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085Phosphorus oxides, acids or salts
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087Boron oxides, acids or salts
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/223Five-membered rings containing nitrogen and carbon only
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/09Heterocyclic compounds containing no sulfur, selenium or tellurium compounds in the ring
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/02Groups 1 or 11
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/243Cold working
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015Dispersions of solid lubricants
    • C10N2050/02Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/06Chemical after-treatment of the constituents of the lubricating composition by epoxydes or oxyalkylation reactions

Definitions

  • the prevent invention relates to a hard-carbon coated machine tool and a cutting oil composition therefor.
  • a machine tool such as a drill or an end mill
  • a machine tool be able to machine a workpiece with high precision, to reduce cutting resistance for improvement in machining efficiency and to maintain a high-precision high-efficiency machining capability over an extended time period.
  • Japanese Laid-Open Patent Publication No. 2003-25117 and No. 2001-62605 propose forming a high-hardness, wear-resistant coating on the machine tool by chemical vapor deposition (CVD) or physical vapor deposition (PVD).
  • a cutting oil composition for a hard-carbon coated machine tool comprising: a base oil and at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier.
  • a machine tool for machining a workpiece in the presence of a cutting oil composition comprising: a tool base; and a hard carbon coating formed on the tool base, the hard carbon coating having 1 atomic % or less of hydrogen.
  • a machine tool unit comprising: a machine tool having a tool base and a hard carbon coating formed on the tool base, the hard carbon coating having 1 atomic % or less of hydrogen; and a cutting oil composition to lubricate the machine tool, the cutting oil composition containing at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier.
  • FIG. 1A is an end view of a machine tool according to a first embodiment of the present invention.
  • FIG. 1B is a side view of the machine tool of FIG. 1A.
  • FIG. 2A is an end view of a machine tool according to a second embodiment of the present invention.
  • FIG. 2B is a side view of the machine tool of FIG. 2A.
  • FIG. 3A is an end view of a machine tool according to a third embodiment of the present invention.
  • FIG. 3B is a side view of the machine tool of FIG. 3A.
  • FIG. 4 is a schematic view showing a unit for friction test.
  • FIG. 5 is a graph showing a comparison of the tool life of a machine tool according to an exemplary embodiment of the present invention to that of a machine tool according to the earlier technology.
  • FIG. 6 is a graph showing a comparison of the machining accuracy and efficiency of a machine tool according to an exemplary embodiment of the present invention to those of a machine tool according to the earlier technology.
  • a hard-carbon coated machine tool is used for machining a workpiece under a condition that the machine tool and workpiece are lubricated with the cutting oil composition.
  • the hard-carbon coated machine tool of the present invention is not particularly restricted, and can be formed into a drill (such as a gun drill), a reamer or an end mill.
  • the hard-carbon coated machine tool may be embodied as a drill 1 , as shown in FIGS. 1A and 1B, and be used for creating a hole in the workpiece in the presence of the cutting oil composition.
  • the drill 1 has a tool base made of a steel or carbide material and a hard carbon coating 3 formed on the tool base to cover the whole of the drill 1 including a cutting edge 2 (although it may seem as if the hard carbon coating 3 covers only the shaded areas in FIGS. 1A and 1B).
  • the hard-carbon coated machine tool may be embodied as another type of drill (called a gun drill) 21 and be used for creating a deeper hole in the workpiece in the presence of the cutting oil composition.
  • the gun drill 21 has a tool base made of a steel or carbide material and a hard carbon coating 23 formed on the tool base to cover a body portion 24 of the gun drill 21 including a cutting edge 22 , a groove 26 and a core 27 (although it may seem as if the hard carbon coating 23 covers only the shaded areas in FIGS. 2A and 2B).
  • An oil hole 25 is formed through the drill body portion 24 for supplying the cutting oil composition.
  • the hard-carbon coated machine tool may be embodied as a reamer 31 and be used for enlarging, shaping, smoothing, or otherwise fining a hole in the workpiece in the presence of the cutting oil composition.
  • the reamer 31 has a tool base made of a steel or carbide material and a hard carbon coating 33 formed on the tool base to cover a body portion 34 of the reamer 31 including a cutting edge 32 (although it may seem as if the hard carbon coating 33 covers only the shaded areas in FIGS. 3A and 3B).
  • the hard carbon coatings 3 , 23 and 33 can be formed by various physical vapor deposition (PVD) processes, and each of the hard carbon coatings 3 , 23 and 33 is preferably a diamond-like carbon (DLC) coating formed by arc ion plating.
  • the DLC coating is a coating of amorphous carbon, such as hydrogen-free amorphous carbon (a-C), hydrogen-containing amorphous carbon (a-C:H) and metal-containing carbon or metal carbide (MeC) that contains metal elements of e.g. titanium (Ti) or molybdenum (Mo).
  • a-C hydrogen-free amorphous carbon
  • a-C:H hydrogen-containing amorphous carbon
  • MeC metal-containing carbon or metal carbide
  • the amount of hydrogen in the DLC coating is preferably 1 atomic % or less, more preferably 0.5 atomic % or less, still more preferably substantially zero.
  • the hard carbon coatings 3 , 23 and 33 reflect the surface roughness of the tool bases, respectively.
  • the tool bases of the drill 1 , the gun drill 2 and the reamer 3 have an arithmetic mean surface roughness Ra exceeding 0.3 ⁇ m
  • the hard carbon coatings 3 , 23 and 33 become susceptible to cracking due to increased local contact of their surface roughness peaks with the workpieces. It is thus preferable to control the surface roughness Ra of the tool bases to be covered with the respective hard carbon coatings 3 , 23 and 33 to 0.03 ⁇ m or lower.
  • the cutting oil composition of the present invention contains a base oil and at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier, and may be supplied in mist form to limit the amount of the cutting oil composition supplied effectively.
  • the base oil is not particularly limited, and can be selected from any base oil compounds commonly used for cutting oils, such as mineral oils, synthetic oils, and fats.
  • mineral oils include normal paraffins and paraffin or naphthene oils each prepared by extracting cutting oil fractions from petroleum by atmospheric or reduced-pressure distillation, and then, purifying the obtained cutting oil fractions with at least one of the following treatments: solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydro-refining, wax isomerization, surfuric acid treatment and clay refining.
  • solvent deasphalting solvent extraction
  • hydrocracking solvent dewaxing
  • hydro-refining hydro-refining
  • wax isomerization surfuric acid treatment and clay refining.
  • GTL Gas-To-Liquids
  • synthetic oils include: poly- ⁇ -olefins, such as 1-octene oligomer, 1-decene oligomer and ethylene-propylene oligomer, and hydrides thereof; isobutene oligomer and a hydride thereof; isoparaffines; alkylbenzenes; alkylnaphthalenes; diesters, such as ditridecyl glutarate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate and dioctyl sebacate; polyol esters, such as trimethylolpropane esters (e.g.
  • poly- ⁇ -olefins such as 1-octene oligomer and 1-decene oligomer, and hydrides thereof.
  • the above-mentioned base oil compounds may be used alone or in combination thereof. It the case of using as the base oil a mixture of two or more of the above base oil compounds, there is no particular limitation to the mixing ratio of the base oil compounds.
  • the sulfur content of the base oil is not particularly restricted, and is preferably 0.2% or less, more preferably 0.1% or less, still more preferably 0.05% or lower, based on the total mass of the base oil. It is desirable to use the hydro-refined mineral oil or the synthetic oil because the hydro-refined mineral oil and the synthetic oil have a sulfur content of not more than 0.005% or substantially zero (lower than a detection limit of e.g. 5 ppm).
  • the aromatics content of the base oil is also not particularly restricted.
  • the aromatics content is defined as the amount of an aromatics fraction determined according to ASTM D2549.
  • the aromatics content of the base oil is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less, based on the total mass of the base oil.
  • the cutting oil composition undesirably deteriorates in oxidation stability when the aromatics content of the base oil exceeds 15%.
  • the kinematic viscosity of the base oil is not particularly restricted.
  • the kinematic viscosity of the base oil is preferably 2 mm 2 /s or higher, more preferably 3 mm 2 /S, as measured at 100° C.
  • the kinematic viscosity of the base oil is preferably 20 mm 2 /s or lower, more preferably 10 mm 2 /s or lower, most preferably 8 mm 2 /s or lower, as measured at 100° C.
  • the kinematic viscosity of the base oil is less than 2 mm 2 /s at 100° C., there is a possibility that the cutting oil composition fails to provide sufficient wear resistance and causes a considerable evaporation loss.
  • the cutting oil composition fails to exhibit low-friction characteristics and deteriorates in low-temperature performance.
  • 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, in order for the cutting oil composition to attain improved oil-consumption performance and low-temperature viscosity characteristics.
  • fatty-ester friction modifier and the aliphatic-amine friction modifier there may be used a fatty acid ester and an aliphatic amine having C 6 -C 30 straight or branched hydrocarbon chains, preferably C 8 -C 24 straight or branched hydrocarbon chains, more preferably C 10 -C 20 straight or branched hydrocarbon chains, respectively.
  • a fatty acid ester and an aliphatic amine having C 6 -C 30 straight or branched hydrocarbon chains, preferably C 8 -C 24 straight or branched hydrocarbon chains, more preferably C 10 -C 20 straight or branched hydrocarbon chains, respectively.
  • the carbon number of the hydrocarbon chain of the friction modifier is not within the range of 6 to 30, there arises a possibility of failing to obtain a sufficient friction reducing effect.
  • C 6 -C 30 straight or branched hydrocarbon chain examples 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, tetrade
  • the fatty acid ester is 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 is exemplified by aliphatic monoamines and alkylene oxide adducts thereof, aliphatic polyamines, imidazolines and derivatives thereof each having the above hydrocarbon groups.
  • 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; alkylene oxide adducts of the above aliphatic amine compounds (C 6 -C 28 alkyl or alkenyl amines), such as N,N-dipolyoxyalkylene-N-alkyl (or alkenyl) amines; and acid
  • the amount of the fatty-ester friction modifier and/or the aliphatic-amine friction modifier contained in the cutting oil composition 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 cutting oil composition.
  • the amount of the fatty-ester friction modifier and/or the aliphatic-amine friction modifier in the cutting oil composition is less than 0.05%, there arises a possibility of failing to obtain a sufficient friction reducing effect.
  • the solubility of the friction modifier or modifiers in the base oil becomes so low that the cutting oil composition deteriorates in storage stability to cause precipitations.
  • the cutting oil composition preferably includes polybutenyl succinimide and/or a derivative thereof as an ashless dispersant.
  • polybutenyl succinimide there may be used compounds represented by the following general formulas (1) and (2).
  • PIB represents a polybutenyl group derived from polybutene having a number-average molecular weight of 900 to 3500, preferably 1000 to 2000, that 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 aluminum chloride catalyst.
  • the number-average molecular weight of the polybutene is less than 900, there is a possibility of failing to obtain a sufficient detergent effect.
  • the number-average molecular weight of the polybutene exceeds 3500, the polybutenyl succinimide tends to deteriorate in low-temperature fluidity.
  • the polybutene may be purified, before used for the production of the polybutenyl succinimide, by removing trace amounts of fluorine and chlorine residues resulting from the above polybutene production catalyst with any suitable treatment (such as an adsorption or washing process) in such a way as to control the amount of the fluorine and chlorine residues in the polybutene to 50 ppm or less, desirably 10 ppm or less, more desirably 1 ppm or less.
  • any suitable treatment such as an adsorption or washing process
  • n represents an integer of 1 to 5, preferably 2 to 4, in the formulas (1) and (2) in view of the detergent effect.
  • the production method of the polybutenyl succinimide is not particularly restricted.
  • the polybutenyl succinimide may be prepared by reacting a chlorinated product of the polybutene, or the polybutene from which fluorine and chlorine residues are sufficiently removed, with maleic anhydride at 100 to 200° C. to form polybutenyl succinate, and then, reacting the thus-formed polybutenyl succinate with polyamine (such as diethylene triamine, triethylene tetramine, tetraethylene pentamine or pentaethylene hexamine).
  • polyamine such as diethylene triamine, triethylene tetramine, tetraethylene pentamine or pentaethylene hexamine.
  • polybutenyl succinimide derivative there may be used boron- or acid-modified compounds obtained by reacting the polybutenyl succinimides of the formula (1) or (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.
  • boron-containing polybutenyl succinimides especially boron-containing bis(polybutenyl)succinimide, are preferably used.
  • 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 boron compound used for producing the polybutenyl succinimide derivative can be a boric acid, a borate or a boric acid ester.
  • the boric acid include orthoboric acid, metaboric acid and tetraboric acid.
  • Specific examples of the borate include: ammonium salts such as ammonium borates (e.g. ammonium metaborate, ammonium tetraborate, ammonium pentaborate and ammonium octaborate).
  • boric acid ester examples include: esters of boric acids and alkylalcohols (preferably C 1 -C 6 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.
  • alkylalcohols preferably C 1 -C 6 alkylalcohols
  • the oxygen-containing organic compound used for producing the polybutenyl succinimide derivative can be any of C 1 -C 30 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; C 2 -C 30 polycarboxylic acids, such as oxalic acid, phthalic acid, trimellitic acid and pyromellitic acid, and anhydrides and esters thereof; C 2 -C 6 alkylene oxides; and hydroxy(poly)oxyalkylene carbonates.
  • monocarboxylic acids such as
  • the amount of the polybutenyl succinimide and/or the derivative thereof added in the cutting oil composition is not particularly restricted, and is preferably 0.1 to 15%, more preferably 1.0 to 12%, based on the total mass of the cutting oil composition.
  • the amount of the polybutenyl succineimide and/or the derivative thereof in the cutting oil composition is less than 0.1%, there is a possibility of failing to attain a sufficient detergent effect.
  • the amount of the polybutenyl succineimide and/or the derivative thereof in the cutting oil composition exceeds 15%, the cutting oil composition may deteriorate in demulsification ability.
  • the cutting oil composition preferably includes zinc dithiophosphate of the following general formula (3) as an antioxidant and as an anti-wear agent.
  • R 4 , R 5 , R 6 and R 7 each represent C 1 -C 24 hydrocarbon groups.
  • the C 1 -C 24 hydrocarbon group is preferably a C 1 -C 24 straight-chain or branched-chain alkyl group, a C 3 -C 24 straight-chain or branched-chain alkenyl group, a C 5 -C 13 cycloalkyl or straight- or branched-chain alkylcycloalkyl group, a C 6 -C 18 aryl or straight- or branched-chain alkylaryl group, or a C 7 -C 19 arylalkyl group.
  • alkyl group or alkenyl group can be primary, secondary or tertiary.
  • R 4 , R 5 , R 6 and R 7 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,
  • the zinc dithiophosphate is exemplified by 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 and zinc diisotridecyldithiophosphate.
  • the amount of the zinc dithiophosphate contained in the cutting oil composition is not particularly restricted.
  • the amount of the zinc dithiophosphate in the cutting oil composition is preferably 0.1% or less, more preferably 0.06% or less, still more preferably a minimum effective amount, in terms of the phosphorus element, based on the total mass of the cutting oil composition.
  • the amount of the zinc dithiophosphate in the cutting oil composition exceeds 0.1%, there is a possibility of inhibiting the effect of the ashless fatty-ester friction modifier and/or the ashless aliphatic-amine friction modifier.
  • the production method of the zinc dithiophosphate is not particularly restricted, and the zinc dithiophosphate can be prepared by any known method.
  • the zinc dithiophosphate may be prepared by reacting alcohols or phenols having the above R 4 , R 5 , R 6 and R 7 hydrocarbon groups with phosphorous pentasulfide to form dithiophosphoric acid, and then, neutralizing the thus-formed dithiophosphoric acid with zinc oxide.
  • the molecular structure of zinc dithiophosphate differs according to the alcohols or phenols used as raw materials for the zinc dithiophosphate production.
  • the above-mentioned zinc dithiophosphate compounds may be used alone or in the form of a mixture of two or more thereof.
  • the cutting oil composition 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 the aliphatic-amine friction modifier, an ashless dispersant other than the above-mentioned polybutenyl succinimide and the derivative thereof, an anti-wear agent or extreme-pressure agent, a rust inhibitor, a nonionic surfactant, a demulsifier, a metal deactivator and/or an anti-foaming agent, so as to meet the performance required of the cutting oil composition.
  • a metallic detergent such as a metallic detergent, an antioxidant, a viscosity index improver, a friction modifier other than the above-mentioned fatty-ester friction modifier and the aliphatic-amine friction modifier, an ashless dispersant other than the above-mentioned polybutenyl succinimide and the derivative thereof, an anti-wear agent or extreme-
  • the metallic detergent can be selected from any metallic detergent compounds commonly used for cutting oils.
  • the metallic detergent include sulfonates, phenates and salicylates of alkali metals, such as sodium (Na) and potassium (K), or alkali-earth metals, such as calcium (Ca) and magnesium (Mg); and a mixture of two or more thereof.
  • 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 determined in accordance with the performance required of the cutting oil composition.
  • 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.
  • the amount of the metallic detergent is usually 0.1 to 10% based on the total mass of the cutting oil composition.
  • the antioxidant can be selected from any antioxidant compounds commonly used for cutting oils.
  • Specific examples of the antioxidant include: phenolic antioxidants, such as 4,4′-methylenebis(2,6-di-tert-butylphenol) and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; amino antioxidants, such as phenyl- ⁇ -naphthylamine, alkylphenyl- ⁇ -naphthylamine and alkyldiphenylamine; and a mixture of two or more thereof.
  • the amount of the antioxidant is usually 0.01 to 5% based on the total mass of the cutting oil composition.
  • non-dispersion type polymethacrylate viscosity index improvers such as copolymers of one or more kinds of methacrylates and hydrogenated products thereof
  • dispersion type polymethacrylate viscosity index improvers such as copolymers of metacrylates further containing nitrogen compounds
  • other viscosity index improvers such as copolymers of ethylene and ⁇ -olefin (e.g.
  • the molecular weight of the viscosity index improver needs to be determined in view of the shear stability.
  • the number-average molecular weight of the viscosity index improver is desirably in the range of 5000 to 1000000, more desirably 100000 to 800000, for the dispersion or non-dispersion type polymethacrylate; in the range of 800 to 5000 for the polyisobutylene or hydrogenated product thereof; and in the range of 800 to 300,000, more desirably 10,000 to 200,000 for the ethylene/ ⁇ -olefin copolymer or hydrogenated product 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 cutting oil composition.
  • the friction modifier other than the above-mentioned fatty-ester and aliphatic-amine friction modifiers can be any of ashless friction modifiers, such as boric acid esters, higher alcohols or 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 derivative thereof can be any of polybutenylbenzylamines and polybutenylamines each having polybutenyl groups of which the number-average molecular weight is 900 to 3500, polybutenyl succinimides having polybutenyl groups of which the number-average molecular weight is less than 900, and derivatives thereof.
  • the anti-friction agent or extreme-pressure agent there may be used: disulfides, sulfurized fats, olefin sulfides, phosphate esters having one to three C 2 -C 20 hydrocarbon groups, thiophosphate esters, phosphite esters, thiophosphite esters and amine salts of these esters.
  • rust inhibitor there may be used: alkylbenzene sulfonates, dinonylnaphthalene sulfonates, esters of alkenylsuccinic acids and esters of polyalcohols.
  • noisy polyalkylene glycol surfactants such as polyoxyethylene alkylethers, polyoxyethylene alkylphenylethers and polyoxyethylene alkylnaphthylethers.
  • the metal deactivator can be any of imidazolines, pyrimidine derivatives, thiazole and benzotriazole.
  • the anti-foaming agent can be any of silicones, fluorosilicones and fluoroalkylethers.
  • Each of the friction modifier other than the fatty-ester and aliphatic-amine friction modifiers, the ashless dispersant other than the polybutenyl succinimide and derivative thereof, the anti-wear agent or extreme-pressure agent, the rust inhibitor and the demulsifier is usually contained in an amount of 0.01 to 5% based on the total mass of the cutting oil composition
  • the metal deactivator is usually contained in an amount of 0.005 to 1% based on the total mass of the cutting oil composition
  • the anti-foaming agent is usually contained in an amount of 0.0005 to 1% based on the total mass of the cutting oil composition.
  • the hard-carbon coated machine tool shows a considerably low friction coefficient in combination with the cutting oil composition containing the ashless fatty-ester friction modifier and/or the ashless aliphatic-amine friction modifier so that the adhesion of the workpiece or swarf to the machine tool does not occur.
  • This makes it possible to increase machining precision and efficiency and to avoid tool breakage.
  • the machine tool is thus able to machine a workpiece with high precision and efficiency while attaining a longer tool life.
  • a test unit was set up with a sliding member 10 (as a test sample) and a counterpart member 11 as shown in FIG. 4.
  • the sliding member 10 was prepared by cutting a semi-cylindrical base piece from S45C steel (compliant with JIS G4051), and then, forming a DLC coating on the base piece by PVD arc ion plating to cover a curved portion 10 a of the sliding member 10 .
  • the sliding member 10 had a size of 8 ⁇ 10 ⁇ 40 mm, and the DLC coating had a hydrogen content of 0.5 atomic % or less, a Knoop hardness Hk of 2170 kg/mm 2 , a surface roughness Ry of 0.03 ⁇ m and a thickness of 0.5 ⁇ m.
  • the counterpart member 11 was formed into a plate of ADC12 alloy (compliant with JIS H5302) having a size of 40 ⁇ 60 ⁇ 7 mm.
  • the sliding member 10 and the counterpart member 11 were lubricated with a cutting oil composition A.
  • the chemical makeup of the cutting oil composition A is shown in TABLE 1. In TABLE, the amount of each component in the cutting oil composition A is indicated with respect to the total mass of the cutting oil composition A.
  • the coefficient of friction of the sliding member 10 was measured by sliding the curved portion 10 a of the sliding member 10 over the counterpart member 11 in such a manner as to cause a reciprocating motion of the sliding surface 10 in the direction of arrows Q and R within a range A of the counterpart member 11 while pressing the sliding member 10 against the counterpart member 11 under a load P.
  • the test was conducted under the following test conditions. The test result is shown in TABLE 2.
  • Test unit Reciprocating type friction/wear tester
  • Sliding member 8 ⁇ 10 ⁇ 40 mm (JIS S45C base with DLC coating)
  • Counterpart member 40 ⁇ 60 ⁇ 7 mm (JIS ADC12 plate)
  • Test temperature 25° C.
  • Measuring time 60 min. after the test start.
  • Example 2 The same test unit as used in Example 1 was set up, except that the sliding member 10 and the counterpart member 11 were lubricated with a cutting oil composition B.
  • the chemical makeup of the cutting oil composition B is also indicated in TABLE 1.
  • TABLE 1 the amount of each component in the cutting oil composition B is indicated with respect to the total mass of the cutting oil composition B.
  • the coefficient of friction of the sliding member 10 was measured under the same conditions as used in Example 1. The test result is shown in TABLE 2.
  • the same type of drill as shown in FIG. 1 was produced by preparing a tool base of K10 carbide (compliant with ISO 513) and forming a DLC coating on the tool base.
  • the DLC coating had a hydrogen content of 0.5 atomic % or less, a Knoop hardness Hk of 2170 kg/mm 2 , a surface roughness Ry of 0.03 ⁇ m and a thickness of 0.5 ⁇ m.
  • the thus-produced drill was set to a main shaft of a machining center, thereby machining a workpiece while supplying the above cutting oil composition A in mist form. The machining conditions are indicated below. In the process of machining, the drill was tested for cutting resistance (i.e., a cutting force applied to the main shaft). The test result is shown in FIG. 5.
  • Feed rate 0.2 mm/rev.
  • Oil mist discharge rate 5 cc/hr.
  • Example 2 The same drill as used in Example 2 was produced, except that no DLC coating was formed on the drill.
  • the produced drill was set to a machining center, thereby machining a workpiece while supplying the above cutting oil composition B in mist form.
  • the machining conditions were the same as in Example 2.
  • the drill was tested for cutting resistance. The test result is shown in FIG. 5.
  • the same type of reamer as shown in FIG. 3 was produced by preparing a tool base of K10 carbide (compliant with ISO 513) and forming a DLC coating on the tool base.
  • the DLC coating had a hydrogen content of 0.5 atomic % or less, a Knoop hardness Hk of 2170 kg/mm 2 , a surface roughness Ry of 0.03 ⁇ m and a thickness of 0.5 ⁇ m.
  • the thus-produced reamer was set to a machining center, thereby finishing holes in a workpiece while supplying the cutting oil composition A in mist form. The machining conditions are indicated below.
  • the finished holes were tested for surface roughness Ra.
  • the test result is shown in FIG. 6.
  • the degree of machining represents the number of holes finished by the reamer.
  • Feed rate 0.24 mm/rev.
  • Oil mist discharge rate 5 cc/hr.
  • Example 3 The same reamer as used in Example 3 was produced, except that no DLC coating was formed on the reamer.
  • the produced reamer was set to a machining center, thereby finishing holes in a workpiece while supplying the above cutting oil composition B in mist form.
  • the machining conditions were the same as in Example 3.
  • the finished holes were tested for surface roughness Ra. The test result is shown in FIG. 6.

Abstract

A machine tool is used for machining a workpiece in the presence of a cutting oil composition. The machine tool includes a tool base and a hard carbon coating formed on the tool base. The hard carbon coating has 1 atomic % or less of hydrogen. The cutting oil composition 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 prevent invention relates to a hard-carbon coated machine tool and a cutting oil composition therefor. [0001]
  • It is desired that a machine tool (such as a drill or an end mill) be able to machine a workpiece with high precision, to reduce cutting resistance for improvement in machining efficiency and to maintain a high-precision high-efficiency machining capability over an extended time period. In order to respond to these desires, Japanese Laid-Open Patent Publication No. 2003-25117 and No. 2001-62605 propose forming a high-hardness, wear-resistant coating on the machine tool by chemical vapor deposition (CVD) or physical vapor deposition (PVD). [0002]
  • SUMMARY OF THE INVENTION
  • With the recent awareness of environmental issues, the use of a cutting oil in the machining process has become limited. In such a semi-dry machining process, however, the cutting point where the machine tool cuts a workpiece is not cooled sufficiently. As a result, there arises a problem that, in the case of the machine tool having a carbide base and a ceramic coating formed thereon, the machine tool is susceptible to adhesion with the workpiece. In addition, it is difficult to remove swarf from the cutting point. In the case of another diamond machine tool, there arises a problem that the machine tool is susceptible to chipping. The tool life of the machine tool is then shortened due to these problems. [0003]
  • It is therefore an object of the present invention to provide a hard-carbon coated machine tool and a cutting oil composition therefor, wherein the machine tool is, when lubricated with the cutting oil composition, capable of machining a workpiece with high accuracy and efficiency while attaining a long tool life even in a semi-dry machining process. [0004]
  • As a result of extensive researches, it was found by the present inventors that a hard-carbon coated machine tool shows excellent low-friction characteristics in the presence of a cutting oil composition that contains a specific ashless friction modifier or modifiers. The present invention has been accomplished based on the above finding. [0005]
  • According to a first aspect of the invention, there is provided a cutting oil composition for a hard-carbon coated machine tool, comprising: a base oil and at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier. [0006]
  • According to a second aspect of the invention, there is provided a machine tool for machining a workpiece in the presence of a cutting oil composition, the cutting oil composition containing at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier, the machine tool comprising: a tool base; and a hard carbon coating formed on the tool base, the hard carbon coating having 1 atomic % or less of hydrogen. [0007]
  • According to a third aspect of the invention, there is provided a machine tool unit, comprising: a machine tool having a tool base and a hard carbon coating formed on the tool base, the hard carbon coating having 1 atomic % or less of hydrogen; and a cutting oil composition to lubricate the machine tool, the cutting oil composition containing at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier. [0008]
  • The other objects and features of the invention will also become understood from the following description.[0009]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1A is an end view of a machine tool according to a first embodiment of the present invention. [0010]
  • FIG. 1B is a side view of the machine tool of FIG. 1A. [0011]
  • FIG. 2A is an end view of a machine tool according to a second embodiment of the present invention. [0012]
  • FIG. 2B is a side view of the machine tool of FIG. 2A. [0013]
  • FIG. 3A is an end view of a machine tool according to a third embodiment of the present invention. [0014]
  • FIG. 3B is a side view of the machine tool of FIG. 3A. [0015]
  • FIG. 4 is a schematic view showing a unit for friction test. [0016]
  • FIG. 5 is a graph showing a comparison of the tool life of a machine tool according to an exemplary embodiment of the present invention to that of a machine tool according to the earlier technology. [0017]
  • FIG. 6 is a graph showing a comparison of the machining accuracy and efficiency of a machine tool according to an exemplary embodiment of the present invention to those of a machine tool according to the earlier technology.[0018]
  • 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. [0019]
  • In the present invention, a hard-carbon coated machine tool is used for machining a workpiece under a condition that the machine tool and workpiece are lubricated with the cutting oil composition. [0020]
  • The hard-carbon coated machine tool of the present invention is not particularly restricted, and can be formed into a drill (such as a gun drill), a reamer or an end mill. [0021]
  • For example, the hard-carbon coated machine tool may be embodied as a [0022] drill 1, as shown in FIGS. 1A and 1B, and be used for creating a hole in the workpiece in the presence of the cutting oil composition. The drill 1 has a tool base made of a steel or carbide material and a hard carbon coating 3 formed on the tool base to cover the whole of the drill 1 including a cutting edge 2 (although it may seem as if the hard carbon coating 3 covers only the shaded areas in FIGS. 1A and 1B).
  • As shown in FIGS. 2A and 2B, the hard-carbon coated machine tool may be embodied as another type of drill (called a gun drill) [0023] 21 and be used for creating a deeper hole in the workpiece in the presence of the cutting oil composition. The gun drill 21 has a tool base made of a steel or carbide material and a hard carbon coating 23 formed on the tool base to cover a body portion 24 of the gun drill 21 including a cutting edge 22, a groove 26 and a core 27 (although it may seem as if the hard carbon coating 23 covers only the shaded areas in FIGS. 2A and 2B). An oil hole 25 is formed through the drill body portion 24 for supplying the cutting oil composition.
  • As shown in FIGS. 3A and 3B, the hard-carbon coated machine tool may be embodied as a [0024] reamer 31 and be used for enlarging, shaping, smoothing, or otherwise fining a hole in the workpiece in the presence of the cutting oil composition. The reamer 31 has a tool base made of a steel or carbide material and a hard carbon coating 33 formed on the tool base to cover a body portion 34 of the reamer 31 including a cutting edge 32 (although it may seem as if the hard carbon coating 33 covers only the shaded areas in FIGS. 3A and 3B).
  • The [0025] hard carbon coatings 3, 23 and 33 can be formed by various physical vapor deposition (PVD) processes, and each of the hard carbon coatings 3, 23 and 33 is preferably a diamond-like carbon (DLC) coating formed by arc ion plating. The DLC coating is a coating of amorphous carbon, such as hydrogen-free amorphous carbon (a-C), hydrogen-containing amorphous carbon (a-C:H) and metal-containing carbon or metal carbide (MeC) that contains metal elements of e.g. titanium (Ti) or molybdenum (Mo). In order to obtain a larger friction reducing effect, it is desirable to minimize the amount of hydrogen in the DLC coating. The amount of hydrogen in the DLC coating is preferably 1 atomic % or less, more preferably 0.5 atomic % or less, still more preferably substantially zero.
  • Further, the [0026] hard carbon coatings 3, 23 and 33 reflect the surface roughness of the tool bases, respectively. When the tool bases of the drill 1, the gun drill 2 and the reamer 3 have an arithmetic mean surface roughness Ra exceeding 0.3 μm, the hard carbon coatings 3, 23 and 33 become susceptible to cracking due to increased local contact of their surface roughness peaks with the workpieces. It is thus preferable to control the surface roughness Ra of the tool bases to be covered with the respective hard carbon coatings 3, 23 and 33 to 0.03 μm or lower.
  • The cutting oil composition of the present invention contains a base oil and at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier, and may be supplied in mist form to limit the amount of the cutting oil composition supplied effectively. [0027]
  • The base oil is not particularly limited, and can be selected from any base oil compounds commonly used for cutting oils, such as mineral oils, synthetic oils, and fats. [0028]
  • Specific examples of the mineral oils include normal paraffins and paraffin or naphthene oils each prepared by extracting cutting oil fractions from petroleum by atmospheric or reduced-pressure distillation, and then, purifying the obtained cutting oil fractions with at least one of the following treatments: solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydro-refining, wax isomerization, surfuric acid treatment and clay refining. Although a solvent-refined or hydro-refined mineral oil is often used as the base oil, it is more desirable to use a mineral oil prepared by Gas-To-Liquids (GTL) wax isomerization or by deep hydrocraking for reduction of an aromatics content in the oil. [0029]
  • Specific examples of the synthetic oils include: poly-α-olefins, such as 1-octene oligomer, 1-decene oligomer and ethylene-propylene oligomer, and hydrides thereof; isobutene oligomer and a hydride thereof; isoparaffines; alkylbenzenes; alkylnaphthalenes; diesters, such as ditridecyl glutarate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate and dioctyl sebacate; polyol esters, such as trimethylolpropane esters (e.g. trimethylolpropane caprylate, trimetylolpropane pelargonate and trimethylolpropane isostearate) and pentaerythritol esters (e.g. pentaerythritol-2-ethyl hexanoate and pentaerythritol pelargonate); polyoxyalkylene glycols; dialkyl diphenyl ethers; and polyphenyl ethers. Among others, preferred are poly-α-olefins, such as 1-octene oligomer and 1-decene oligomer, and hydrides thereof. [0030]
  • The above-mentioned base oil compounds may be used alone or in combination thereof. It the case of using as the base oil a mixture of two or more of the above base oil compounds, there is no particular limitation to the mixing ratio of the base oil compounds. [0031]
  • The sulfur content of the base oil is not particularly restricted, and is preferably 0.2% or less, more preferably 0.1% or less, still more preferably 0.05% or lower, based on the total mass of the base oil. It is desirable to use the hydro-refined mineral oil or the synthetic oil because the hydro-refined mineral oil and the synthetic oil have a sulfur content of not more than 0.005% or substantially zero (lower than a detection limit of e.g. 5 ppm). [0032]
  • The aromatics content of the base oil is also not particularly restricted. Herein, the aromatics content is defined as the amount of an aromatics fraction determined according to ASTM D2549. In order for the cutting oil composition to maintain its low-friction characteristics over time, the aromatics content of the base oil is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less, based on the total mass of the base oil. The cutting oil composition undesirably deteriorates in oxidation stability when the aromatics content of the base oil exceeds 15%. [0033]
  • The kinematic viscosity of the base oil is not particularly restricted. The kinematic viscosity of the base oil is preferably 2 mm[0034] 2/s or higher, more preferably 3 mm2/S, as measured at 100° C. At the same time, the kinematic viscosity of the base oil 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 of the base oil is less than 2 mm2/s at 100° C., there is a possibility that the cutting oil composition fails to provide sufficient wear resistance and causes a considerable evaporation loss. When the kinematic viscosity of the base oil exceeds 20 mm2/s at 100° C., there is a possibility that the cutting oil composition fails to exhibit low-friction characteristics and deteriorates in low-temperature performance. In the case of using two or more of the above-mentioned base oil compounds in combination, it is not necessary to limit the kinematic viscosity of each base oil compound to within such a specific range so long as the kinematic viscosity of the mixture of the base oil compounds at 100° C. is in the specified range.
  • 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, in order for the cutting oil composition to attain improved oil-consumption performance and low-temperature viscosity characteristics. [0035]
  • As the fatty-ester friction modifier and the aliphatic-amine friction modifier, there may be used a fatty acid ester and an aliphatic amine having C[0036] 6-C30 straight or branched hydrocarbon chains, preferably C8-C24 straight or branched hydrocarbon chains, more preferably C10-C20 straight or branched hydrocarbon chains, respectively. When the carbon number of the hydrocarbon chain of the friction modifier is not within the range of 6 to 30, there arises a possibility of failing to obtain a sufficient friction reducing effect. 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 is 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. [0037]
  • The aliphatic amine is exemplified by aliphatic monoamines and alkylene oxide adducts thereof, aliphatic polyamines, imidazolines and derivatives thereof each having the above hydrocarbon groups. 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; alkylene oxide adducts of the above aliphatic amine compounds (C[0038] 6-C28 alkyl or alkenyl amines), such as N,N-dipolyoxyalkylene-N-alkyl (or alkenyl) amines; and acid-modified compounds prepared by reacting the above aliphatic amine compounds 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. Above all, N,N-dipolyoxyethylene-N-oleylamine is preferably used.
  • The amount of the fatty-ester friction modifier and/or the aliphatic-amine friction modifier contained in the cutting oil composition 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 cutting oil composition. When the amount of the fatty-ester friction modifier and/or the aliphatic-amine friction modifier in the cutting oil composition is less than 0.05%, there arises a possibility of failing to obtain a sufficient friction reducing effect. When the amount of the fatty-ester friction modifier and/or the aliphatic-amine friction modifier in the cutting oil composition exceeds 3.0%, the solubility of the friction modifier or modifiers in the base oil becomes so low that the cutting oil composition deteriorates in storage stability to cause precipitations. [0039]
  • The cutting oil composition preferably includes polybutenyl succinimide and/or a derivative thereof as an ashless dispersant. [0040]
  • As the polybutenyl succinimide, there may be used compounds represented by the following general formulas (1) and (2). [0041]
    Figure US20040242435A1-20041202-C00001
  • In the formulas (1) and (2), PIB represents a polybutenyl group derived from polybutene having a number-average molecular weight of 900 to 3500, preferably 1000 to 2000, that 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 aluminum chloride catalyst. When the number-average molecular weight of the polybutene is less than 900, there is a possibility of failing to obtain a sufficient detergent effect. When the number-average molecular weight of the polybutene exceeds 3500, the polybutenyl succinimide tends to deteriorate in low-temperature fluidity. The polybutene may be purified, before used for the production of the polybutenyl succinimide, by removing trace amounts of fluorine and chlorine residues resulting from the above polybutene production catalyst with any suitable treatment (such as an adsorption or washing process) in such a way as to control the amount of the fluorine and chlorine residues in the polybutene to 50 ppm or less, desirably 10 ppm or less, more desirably 1 ppm or less. [0042]
  • Further, n represents an integer of 1 to 5, preferably 2 to 4, in the formulas (1) and (2) in view of the detergent effect. [0043]
  • The production method of the polybutenyl succinimide is not particularly restricted. For example, the polybutenyl succinimide may be prepared by reacting a chlorinated product of the polybutene, or the polybutene from which fluorine and chlorine residues are sufficiently removed, with maleic anhydride at 100 to 200° C. to form polybutenyl succinate, and then, reacting the thus-formed polybutenyl succinate with polyamine (such as diethylene triamine, triethylene tetramine, tetraethylene pentamine or pentaethylene hexamine). [0044]
  • As the polybutenyl succinimide derivative, there may be used boron- or acid-modified compounds obtained by reacting the polybutenyl succinimides of the formula (1) or (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. Among others, boron-containing polybutenyl succinimides, especially boron-containing bis(polybutenyl)succinimide, are preferably used. 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. [0045]
  • The boron compound used for producing the polybutenyl succinimide derivative can be a boric acid, a borate or a boric acid ester. Specific examples of the boric acid include orthoboric acid, metaboric acid and tetraboric acid. Specific examples of the borate include: ammonium salts such as ammonium borates (e.g. ammonium metaborate, ammonium tetraborate, ammonium pentaborate and ammonium octaborate). Specific examples of the boric acid ester include: esters of boric acids and alkylalcohols (preferably C[0046] 1-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 oxygen-containing organic compound used for producing the polybutenyl succinimide derivative can be any of C[0047] 1-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 cutting oil composition is not particularly restricted, and is preferably 0.1 to 15%, more preferably 1.0 to 12%, based on the total mass of the cutting oil composition. When the amount of the polybutenyl succineimide and/or the derivative thereof in the cutting oil composition is less than 0.1%, there is a possibility of failing to attain a sufficient detergent effect. When the amount of the polybutenyl succineimide and/or the derivative thereof in the cutting oil composition exceeds 15%, the cutting oil composition may deteriorate in demulsification ability. In addition, there is a possibility of failing to obtain a detergent effect commensurate with the amount of the polybutenyl succineimide and/or the derivative thereof added. [0048]
  • Furthermore, the cutting oil composition preferably includes zinc dithiophosphate of the following general formula (3) as an antioxidant and as an anti-wear agent. [0049]
    Figure US20040242435A1-20041202-C00002
  • In the general formula (3), R[0050] 4, 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- or branched-chain alkylcycloalkyl group, a C6-C18 aryl or straight- 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. Above all, preferred are C1-C18 straight- or branched-chain alkyl groups and C6-C18 aryl or straight- or branched-chain alkylaryl groups.
  • The zinc dithiophosphate is exemplified by 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 and zinc diisotridecyldithiophosphate. [0051]
  • The amount of the zinc dithiophosphate contained in the cutting oil composition is not particularly restricted. In order to obtain a larger friction reducing effect, the amount of the zinc dithiophosphate in the cutting oil composition is preferably 0.1% or less, more preferably 0.06% or less, still more preferably a minimum effective amount, in terms of the phosphorus element, based on the total mass of the cutting oil composition. When the amount of the zinc dithiophosphate in the cutting oil composition exceeds 0.1%, there is a possibility of inhibiting the effect of the ashless fatty-ester friction modifier and/or the ashless aliphatic-amine friction modifier. [0052]
  • The production method of the zinc dithiophosphate is not particularly restricted, and 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 R[0053] 4, R5, R6 and R7 hydrocarbon groups with phosphorous pentasulfide to form dithiophosphoric acid, and then, neutralizing the thus-formed dithiophosphoric acid with zinc oxide. It is noted that the molecular structure of zinc dithiophosphate differs according to the alcohols or phenols used as raw materials for the zinc dithiophosphate production.
  • The above-mentioned zinc dithiophosphate compounds may be used alone or in the form of a mixture of two or more thereof. In the case of using two or more of the above zinc dithiophosphate compounds in combination, there is no particular limitation to the mixing ratio of the zinc dithiophosphate compounds. [0054]
  • The cutting oil composition 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 the aliphatic-amine friction modifier, an ashless dispersant other than the above-mentioned polybutenyl succinimide and the derivative thereof, an anti-wear agent or extreme-pressure agent, a rust inhibitor, a nonionic surfactant, a demulsifier, a metal deactivator and/or an anti-foaming agent, so as to meet the performance required of the cutting oil composition. [0055]
  • The metallic detergent can be selected from any metallic detergent compounds commonly used for cutting oils. Specific examples of the metallic detergent include sulfonates, phenates and salicylates of alkali metals, such as sodium (Na) and potassium (K), or alkali-earth metals, such as calcium (Ca) and magnesium (Mg); and a mixture of two or more thereof. Among others, 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 determined in accordance with the performance required of the cutting oil composition. 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. The amount of the metallic detergent is usually 0.1 to 10% based on the total mass of the cutting oil composition. [0056]
  • The antioxidant can be selected from any antioxidant compounds commonly used for cutting oils. Specific examples of the antioxidant include: phenolic antioxidants, such as 4,4′-methylenebis(2,6-di-tert-butylphenol) and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; amino antioxidants, such as phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine and alkyldiphenylamine; and a mixture of two or more thereof. The amount of the antioxidant is usually 0.01 to 5% based on the total mass of the cutting oil composition. [0057]
  • As the viscosity index improver, there may be used: non-dispersion type polymethacrylate viscosity index improvers, such as copolymers of one or more kinds of methacrylates and hydrogenated products thereof; dispersion type polymethacrylate viscosity index improvers, such as copolymers of metacrylates further containing nitrogen compounds; and other viscosity index improvers, such as copolymers of ethylene and α-olefin (e.g. propylene, 1-butene or 1-pentene) and hydrogenated products thereof, polyisobutylenes and hydrogenated products thereof, styrene-diene hydrogenated copolymers, styrene-maleate anhydride copolymers, and polyalkylstyrenes. The molecular weight of the viscosity index improver needs to be determined in view of the shear stability. For example, the number-average molecular weight of the viscosity index improver is desirably in the range of 5000 to 1000000, more desirably 100000 to 800000, for the dispersion or non-dispersion type polymethacrylate; in the range of 800 to 5000 for the polyisobutylene or hydrogenated product thereof; and in the range of 800 to 300,000, more desirably 10,000 to 200,000 for the ethylene/α-olefin copolymer or hydrogenated product 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 cutting oil composition. [0058]
  • The friction modifier other than the above-mentioned fatty-ester and aliphatic-amine friction modifiers can be any of ashless friction modifiers, such as boric acid esters, higher alcohols or aliphatic ethers, and metallic friction modifiers, such as molybdenum dithiophosphate, molybdenum dithiocarbamate and molybdenum disulfide. [0059]
  • The ashless dispersant other than the above-mentioned polybutenyl succinimide and derivative thereof can be any of polybutenylbenzylamines and polybutenylamines each having polybutenyl groups of which the number-average molecular weight is 900 to 3500, polybutenyl succinimides having polybutenyl groups of which the number-average molecular weight is less than 900, and derivatives thereof. [0060]
  • As the anti-friction agent or extreme-pressure agent, there may be used: disulfides, sulfurized fats, olefin sulfides, phosphate esters having one to three C[0061] 2-C20 hydrocarbon groups, thiophosphate esters, phosphite esters, thiophosphite esters and amine salts of these esters.
  • As the rust inhibitor, there may be used: alkylbenzene sulfonates, dinonylnaphthalene sulfonates, esters of alkenylsuccinic acids and esters of polyalcohols. [0062]
  • As the nonionic surfactant and demulsifier, there may be used: noionic polyalkylene glycol surfactants, such as polyoxyethylene alkylethers, polyoxyethylene alkylphenylethers and polyoxyethylene alkylnaphthylethers. [0063]
  • The metal deactivator can be any of imidazolines, pyrimidine derivatives, thiazole and benzotriazole. [0064]
  • The anti-foaming agent can be any of silicones, fluorosilicones and fluoroalkylethers. [0065]
  • Each of the friction modifier other than the fatty-ester and aliphatic-amine friction modifiers, the ashless dispersant other than the polybutenyl succinimide and derivative thereof, the anti-wear agent or extreme-pressure agent, the rust inhibitor and the demulsifier is usually contained in an amount of 0.01 to 5% based on the total mass of the cutting oil composition, the metal deactivator is usually contained in an amount of 0.005 to 1% based on the total mass of the cutting oil composition, and the anti-foaming agent is usually contained in an amount of 0.0005 to 1% based on the total mass of the cutting oil composition. [0066]
  • As described above, the hard-carbon coated machine tool shows a considerably low friction coefficient in combination with the cutting oil composition containing the ashless fatty-ester friction modifier and/or the ashless aliphatic-amine friction modifier so that the adhesion of the workpiece or swarf to the machine tool does not occur. This makes it possible to increase machining precision and efficiency and to avoid tool breakage. The machine tool is thus able to machine a workpiece with high precision and efficiency while attaining a longer tool life. [0067]
  • The present invention will be described in more detail by reference to the following examples. It should be however noted that the following examples are only illustrative and not intended to limit the invention thereto. [0068]
  • EXAMPLE 1
  • A test unit was set up with a sliding member [0069] 10 (as a test sample) and a counterpart member 11 as shown in FIG. 4. The sliding member 10 was prepared by cutting a semi-cylindrical base piece from S45C steel (compliant with JIS G4051), and then, forming a DLC coating on the base piece by PVD arc ion plating to cover a curved portion 10 a of the sliding member 10. The sliding member 10 had a size of 8×10×40 mm, and the DLC coating had a hydrogen content of 0.5 atomic % or less, a Knoop hardness Hk of 2170 kg/mm2, a surface roughness Ry of 0.03 μm and a thickness of 0.5 μm. On the other hand, the counterpart member 11 was formed into a plate of ADC12 alloy (compliant with JIS H5302) having a size of 40×60×7 mm. The sliding member 10 and the counterpart member 11 were lubricated with a cutting oil composition A. The chemical makeup of the cutting oil composition A is shown in TABLE 1. In TABLE, the amount of each component in the cutting oil composition A is indicated with respect to the total mass of the cutting oil composition A.
  • The coefficient of friction of the sliding [0070] member 10 was measured by sliding the curved portion 10 a of the sliding member 10 over the counterpart member 11 in such a manner as to cause a reciprocating motion of the sliding surface 10 in the direction of arrows Q and R within a range A of the counterpart member 11 while pressing the sliding member 10 against the counterpart member 11 under a load P. The test was conducted under the following test conditions. The test result is shown in TABLE 2.
  • [Test Conditions][0071]
  • Test unit: Reciprocating type friction/wear tester [0072]
  • Sliding member: 8×10×40 mm (JIS S45C base with DLC coating) [0073]
  • Counterpart member: 40×60×7 mm (JIS ADC12 plate) [0074]
  • Reciprocating speed: 600 cpm (counts per minute) [0075]
  • Test temperature: 25° C. [0076]
  • Load (P) applied: 10 kgf [0077]
  • Measuring time: 60 min. after the test start. [0078]
  • COMPARATIVE EXAMPLE 1
  • The same test unit as used in Example 1 was set up, except that the sliding [0079] member 10 and the counterpart member 11 were lubricated with a cutting oil composition B. The chemical makeup of the cutting oil composition B is also indicated in TABLE 1. In TABLE 1, the amount of each component in the cutting oil composition B is indicated with respect to the total mass of the cutting oil composition B. The coefficient of friction of the sliding member 10 was measured under the same conditions as used in Example 1. The test result is shown in TABLE 2.
  • COMPARATIVE EXAMPLE 2
  • The same test unit as used in Comparative Example 1 was set up, except that the sliding [0080] member 10 was made of K10 carbide (compliant with ISO 513) with no DLC coating. The coefficient of friction of the sliding member 10 was measured under the same conditions as used in Example 1 and Comparative Example 1. The test result is shown in TABLE 2.
    TABLE 1
    Oil composition (mass %) A B
    Base oil 87 100
    (mineral oil)
    Fatty-ester friction modifier 1.0
    (glycerol monolate)
    Aliphatic-amine friction modifier
    Ashless dispersant 5.0
    (polybutenyl succinimide)
    Other additives (including an 7.0
    antioxidant and a rust inhibitor)
  • [0081]
    TABLE 2
    Friction coefficient
    Example 1 0.05
    Comparative Example 1 0.08
    Comparative Example 2 0.11
  • As is apparent from TABLE 2, the sliding [0082] member 10 of Example 1 had a much lower friction coefficient than those of Comparative Examples 1 and 2.
  • EXAMPLE 2
  • The same type of drill as shown in FIG. 1 was produced by preparing a tool base of K10 carbide (compliant with ISO 513) and forming a DLC coating on the tool base. The DLC coating had a hydrogen content of 0.5 atomic % or less, a Knoop hardness Hk of 2170 kg/mm[0083] 2, a surface roughness Ry of 0.03 μm and a thickness of 0.5 μm. The thus-produced drill was set to a main shaft of a machining center, thereby machining a workpiece while supplying the above cutting oil composition A in mist form. The machining conditions are indicated below. In the process of machining, the drill was tested for cutting resistance (i.e., a cutting force applied to the main shaft). The test result is shown in FIG. 5.
  • [Machining Conditions][0084]
  • Workpiece: ADC [0085] 12/AC2A alloy (JIS H53 02/H5202)
  • Cutting speed: 213.52 m/min. [0086]
  • Shaft rotation speed: 10000 rpm [0087]
  • Feed rate: 0.2 mm/rev. [0088]
  • Oil mist discharge rate: 5 cc/hr. [0089]
  • COMPARATIVE EXAMPLE 3
  • The same drill as used in Example 2 was produced, except that no DLC coating was formed on the drill. The produced drill was set to a machining center, thereby machining a workpiece while supplying the above cutting oil composition B in mist form. The machining conditions were the same as in Example 2. In the process of machining, the drill was tested for cutting resistance. The test result is shown in FIG. 5. [0090]
  • As is apparent from FIG. 5, the drill of Example 2 had much lower cutting resistance than that of Comparative Example 3. [0091]
  • EXAMPLE 3
  • The same type of reamer as shown in FIG. 3 was produced by preparing a tool base of K10 carbide (compliant with ISO 513) and forming a DLC coating on the tool base. The DLC coating had a hydrogen content of 0.5 atomic % or less, a Knoop hardness Hk of 2170 kg/mm[0092] 2, a surface roughness Ry of 0.03 μm and a thickness of 0.5 μm. The thus-produced reamer was set to a machining center, thereby finishing holes in a workpiece while supplying the cutting oil composition A in mist form. The machining conditions are indicated below. The finished holes were tested for surface roughness Ra. The test result is shown in FIG. 6. In FIG. 6, the degree of machining represents the number of holes finished by the reamer.
  • [Test Conditions][0093]
  • Workpiece: ADC [0094] 12/AC2A alloy (JIS H5302/H5202)
  • Cutting speed: 339.12 m/min. [0095]
  • Rotation speed: 6000 rpm [0096]
  • Feed rate: 0.24 mm/rev. [0097]
  • Oil mist discharge rate: 5 cc/hr. [0098]
  • COMPARATIVE EXAMPLE 4
  • The same reamer as used in Example 3 was produced, except that no DLC coating was formed on the reamer. The produced reamer was set to a machining center, thereby finishing holes in a workpiece while supplying the above cutting oil composition B in mist form. The machining conditions were the same as in Example 3. The finished holes were tested for surface roughness Ra. The test result is shown in FIG. 6. [0099]
  • As is apparent from FIG. 6, the surface roughness Ra of the holes finished by the reamer of Example 3 was much lower than that of Comparative Example 4. [0100]
  • It is thus proved by the test results of TABLE 2 and FIGS. 5 and 6 that the machine tool of the present invention has the advantages of not only a longer tool life but also higher machining precision and efficiency over the machine tool of the earlier technology. [0101]
  • The entire contents of Japanese Patent Application Nos. 2003-151855 (filed on May 29, 2003) and 2003-409856 (filed on Dec. 9, 2003) are herein incorporated by reference. [0102]
  • 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. [0103]

Claims (19)

What is claimed is:
1. A cutting oil composition for a hard-carbon coated machine tool, comprising: a base oil and at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier.
2. A cutting oil composition according to claim 1, wherein said at lease one of the ashless fatty-ester friction modifier and the ashless aliphatic-amine friction modifier has a C6-C30 hydrocarbon group, and is contained in an amount of 0.05 to 3.0% by mass based on the total mass of the cutting oil composition.
3. A cutting oil composition according to claim 1, further comprising a polybutenyl succinimide and/or a derivative thereof.
4. A cutting oil composition according to claim 3, wherein the polybutenyl succinimide and/or the derivative thereof is contained in an amount of 0.1 to 15% by mass based on the total mass of the cutting oil composition.
5. A cutting oil composition according to claim 1, further comprising 0.1% or less by mass of zinc dithiophosphate in terms of phosphorus based on the total mass of the cutting oil composition.
6. A cutting oil composition according to claim 1, wherein the oil is supplied in mist form.
7. A machine tool for machining a workpiece in the presence of a cutting oil composition, the cutting oil composition containing at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier, the machine tool comprising:
a tool base; and
a hard carbon coating formed on the tool base, the hard carbon coating having 1 atomic % or less of hydrogen.
8. A machine tool according to claim 7, wherein the hard carbon coating has 0.5 atomic % or less of hydrogen.
9. A machine tool according to claim 7, wherein the hard carbon coating is formed by physical vapor deposition.
10. A machine tool according to claim 7, wherein the tool base has a surface roughness Ra of 0.03 μm or lower.
11. A machine tool unit, comprising:
a machine tool including a tool base and a hard carbon coating formed on the tool base, the hard carbon coating having 1 atomic % or less of hydrogen; and
a cutting oil composition to lubricate the machine tool, the cutting oil composition containing at least one of an ashless fatty-ester friction modifier and an ashless aliphatic-amine friction modifier.
12. A machine tool unit according to claim 11, wherein the hard carbon coating has 0.5 atomic % or less of hydrogen.
13. A machine tool unit according to claim 11, wherein the hard carbon coating is formed by physical vapor deposition.
14. A machine tool unit according to claim 11, wherein the tool base has a surface roughness Ra of 0.03 μm or lower.
15. A machine tool unit according to claim 11, wherein said at lease one of the ashless fatty-ester friction modifier and the ashless aliphatic-amine friction modifier has a C6-C30 hydrocarbon group, and is contained in an amount of 0.05 to 3.0% by mass based on the total mass of the cutting oil composition.
16. A machine tool unit according to claim 11, wherein the cutting oil composition further contains a polybutenyl succinimide and/or a derivative thereof.
17. A machine tool unit according to claim 16, wherein the polybutenyl succinimide and/or the derivative thereof is contained in an amount of 0.1 to 15% by mass based on the total mass of the cutting oil composition.
18. A machine tool unit according to claim 11, wherein the cutting oil composition further contains 0.1% or less by mass of zinc dithiophosphate in terms of phosphorus based on the total mass of the cutting oil composition.
19. A machine tool unit according to claim 11, wherein the cutting oil composition is supplied in mist form.
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Publication number Priority date Publication date Assignee Title
US20050244236A1 (en) * 2002-12-19 2005-11-03 Joerg Guehring Deep hole drill
US7273655B2 (en) 1999-04-09 2007-09-25 Shojiro Miyake Slidably movable member and method of producing same
EP2003190A2 (en) * 2006-03-30 2008-12-17 Kyodo Yushi Co., Ltd. Oil composition for metal working, method for metal working, and metal work
US7650976B2 (en) 2003-08-22 2010-01-26 Nissan Motor Co., Ltd. Low-friction sliding member in transmission, and transmission oil therefor
US7771821B2 (en) 2003-08-21 2010-08-10 Nissan Motor Co., Ltd. Low-friction sliding member and low-friction sliding mechanism using same
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US8152377B2 (en) 2002-11-06 2012-04-10 Nissan Motor Co., Ltd. Low-friction sliding mechanism
US8206035B2 (en) 2003-08-06 2012-06-26 Nissan Motor Co., Ltd. Low-friction sliding mechanism, low-friction agent composition and method of friction reduction
US8575076B2 (en) 2003-08-08 2013-11-05 Nissan Motor Co., Ltd. Sliding member and production process thereof
US20140271002A1 (en) * 2013-03-15 2014-09-18 Fanuc Corporation Cutting fluid control device for machine tool
US9885004B2 (en) 2013-12-23 2018-02-06 Exxonmobil Research And Engineering Company Method for improving engine fuel efficiency
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Citations (83)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3790315A (en) * 1970-10-01 1974-02-05 Atlas Copco Ab Rotary piston compressors with liquid injection
US3932228A (en) * 1973-11-01 1976-01-13 Suzuki Jidosha Kogyo Kabushiki Kaisha Metal material for sliding surfaces
US4367130A (en) * 1970-11-30 1983-01-04 Lemelson Jerome H Chemical reaction
US4645610A (en) * 1984-04-20 1987-02-24 Institut Francais Du Petrole Method for the preparation of olefin polysulfides, the products obtained and their utilization as lubricant additives
US4919974A (en) * 1989-01-12 1990-04-24 Ford Motor Company Making diamond composite coated cutting tools
US4981717A (en) * 1989-02-24 1991-01-01 Mcdonnell Douglas Corporation Diamond like coating and method of forming
US4988421A (en) * 1989-01-12 1991-01-29 Ford Motor Company Method of toughening diamond coated tools
US4992082A (en) * 1989-01-12 1991-02-12 Ford Motor Company Method of toughening diamond coated tools
US5000541A (en) * 1987-09-18 1991-03-19 At&T Bell Laboratories Hermetically sealed optical fibers
US5077990A (en) * 1988-05-06 1992-01-07 Sipra Patententwicklungs- Und Beteiligungsgesellschaft Mbh Knitting machine and parts having diamond-like carbon coated surfaces
US5078848A (en) * 1988-01-18 1992-01-07 Asko Anttila Procedure and apparatus for the coating of materials by means of a pulsating plasma beam
US5087608A (en) * 1989-12-28 1992-02-11 Bell Communications Research, Inc. Environmental protection and patterning of superconducting perovskites
US5096352A (en) * 1987-03-31 1992-03-17 Lemelson Jerome H Diamond coated fasteners
US5187021A (en) * 1989-02-08 1993-02-16 Diamond Fiber Composites, Inc. Coated and whiskered fibers for use in composite materials
US5190807A (en) * 1990-10-18 1993-03-02 Diamonex, Incorporated Abrasion wear resistant polymeric substrate product
US5190824A (en) * 1988-03-07 1993-03-02 Semiconductor Energy Laboratory Co., Ltd. Electrostatic-erasing abrasion-proof coating
US5202156A (en) * 1988-08-16 1993-04-13 Canon Kabushiki Kaisha Method of making an optical element mold with a hard carbon film
US5205188A (en) * 1990-11-05 1993-04-27 Detlef Repenning Friction pairing and process for its production
US5284394A (en) * 1987-03-31 1994-02-08 Jerome Lemelson Ball and roller bearings and bearing components
US5288556A (en) * 1987-03-31 1994-02-22 Lemelson Jerome H Gears and gear assemblies
US5295305A (en) * 1992-02-13 1994-03-22 The Gillette Company Razor blade technology
US5380196A (en) * 1993-05-13 1995-01-10 Minnesota Mining And Manufacturing Company Orthodontic bracket with archwire slot liner
US5401543A (en) * 1993-11-09 1995-03-28 Minnesota Mining And Manufacturing Company Method for forming macroparticle-free DLC films by cathodic arc discharge
US5482602A (en) * 1993-11-04 1996-01-09 United Technologies Corporation Broad-beam ion deposition coating methods for depositing diamond-like-carbon coatings on dynamic surfaces
US5491028A (en) * 1993-05-21 1996-02-13 Trustees Of Boston University Enhanced adherence of diamond coatings
US5497550A (en) * 1991-11-15 1996-03-12 The Gillette Company Shaving system
US5593719A (en) * 1994-03-29 1997-01-14 Southwest Research Institute Treatments to reduce frictional wear between components made of ultra-high molecular weight polyethylene and metal alloys
US5707409A (en) * 1994-08-24 1998-01-13 Minnesota Mining And Manufacturing Company Abrasive article having a diamond-like coating layer and method for making same
US5714202A (en) * 1995-06-07 1998-02-03 Lemelson; Jerome H. Synthetic diamond overlays for gas turbine engine parts having thermal barrier coatings
US5719109A (en) * 1993-12-30 1998-02-17 Exxon Chemical Patents Inc Lubricating oil composition
US5723207A (en) * 1988-01-21 1998-03-03 The National Research Development Corporation Infra-red transparant materials
US5731046A (en) * 1994-01-18 1998-03-24 Qqc, Inc. Fabrication of diamond and diamond-like carbon coatings
US5866195A (en) * 1988-03-31 1999-02-02 Lemelson; Jerome H. Methods for forming diamond-coated superconductor wire
US5871805A (en) * 1996-04-08 1999-02-16 Lemelson; Jerome Computer controlled vapor deposition processes
US5881444A (en) * 1997-12-12 1999-03-16 Aluminum Company Of America Techniques for transferring holograms into metal surfaces
US6016000A (en) * 1998-04-22 2000-01-18 Cvc, Inc. Ultra high-speed chip semiconductor integrated circuit interconnect structure and fabrication method using free-space dielectrics
US6015597A (en) * 1997-11-26 2000-01-18 3M Innovative Properties Company Method for coating diamond-like networks onto particles
US6023979A (en) * 1997-07-21 2000-02-15 Helix Technology Apparatus and methods for heat loss pressure measurement
US6028393A (en) * 1998-01-22 2000-02-22 Energy Conversion Devices, Inc. E-beam/microwave gas jet PECVD method and apparatus for depositing and/or surface modification of thin film materials
US6170156B1 (en) * 1999-03-24 2001-01-09 General Motors Corporation Gear tooth smoothing and shaping process
US6173913B1 (en) * 1999-08-25 2001-01-16 Caterpillar Inc. Ceramic check for a fuel injector
US6190514B1 (en) * 1997-12-30 2001-02-20 Premark Rwp Holdings, Inc. Method for high scan sputter coating to produce coated, abrasion resistant press plates with reduced built-in thermal stress
US6193906B1 (en) * 1997-02-27 2001-02-27 Idemitsu Kosan Co., Ltd. Refrigerating oil composition containing a polyether additive
US6197428B1 (en) * 1994-08-26 2001-03-06 Deposition Sciences, Inc. Gemstones and decorative objects comprising a substrate and an optical interference film
US6205291B1 (en) * 1999-08-25 2001-03-20 A. O. Smith Corporation Scale-inhibiting heating element and method of making same
US6203651B1 (en) * 1995-09-20 2001-03-20 Uponor Innovation Ab Method and apparatus for making an extrusion product, and an extrusion product
US6207625B1 (en) * 1998-12-21 2001-03-27 Tonen Corporation Lubricant oil composition for diesel engines (LAW913)
US6338881B1 (en) * 1996-09-03 2002-01-15 Saxonia Umformtechnik Gmbh Diamond-like coating and method of making same
US6340245B1 (en) * 1997-09-16 2002-01-22 Skf Engineering & Research Centre B.V. Coated rolling element bearing
US20020026889A1 (en) * 2000-08-08 2002-03-07 Doyle Robert E. Pivoting battens
US20020031987A1 (en) * 1998-09-23 2002-03-14 Seagate Technology Llc Apparatus and method for reducing disc surface asperities to sub-microinch height
US20020034632A1 (en) * 2000-09-20 2002-03-21 Griffin Nigel Dennis Polycrystalline diamond partially depleted of catalyzing material
US20030012234A1 (en) * 2000-06-19 2003-01-16 Watson Tom A. Six to ten KHz, or greater gas discharge laser system
US20030019111A1 (en) * 2001-07-26 2003-01-30 Korb William B. Composite utility knife blade, and method of making such a blade
US20030036341A1 (en) * 1999-10-12 2003-02-20 Hunatech Co., Ltd. Conditioner for polishing pad and method for manufacturing the same
US6524212B2 (en) * 2000-03-23 2003-02-25 Nissan Motor Co., Ltd. Toroidal-type continuously variable transmission for automobiles
US6523456B1 (en) * 1999-07-05 2003-02-25 Honda Giken Kogyo Kabushiki Kaisha Sliding members and piston for internal combustion engine
US6534141B1 (en) * 1998-10-27 2003-03-18 Raymond J. Hull, Jr. Method of forming an improved support member for a fabric and film forming device
US6537310B1 (en) * 1999-11-19 2003-03-25 Advanced Bio Prosthetic Surfaces, Ltd. Endoluminal implantable devices and method of making same
US6537429B2 (en) * 2000-12-29 2003-03-25 Lam Research Corporation Diamond coatings on reactor wall and method of manufacturing thereof
US20040003638A1 (en) * 1997-12-12 2004-01-08 Schaefer Mark W. Transfer of holographic images into metal sporting and fitness products
US20040010068A1 (en) * 2002-07-09 2004-01-15 Signature Control Systems Process and apparatus for improving and controlling the vulcanization of natural and synthetic rubber compounds
US20040008406A1 (en) * 2000-10-27 2004-01-15 Blitstein Jeffrey L. Wavelength specific coating for mirrored optics and method for reducing reflection of white light
US20040011900A1 (en) * 2002-05-22 2004-01-22 Jens Gebhardt Fuel injector assembly
US6684513B1 (en) * 2000-02-29 2004-02-03 The Gillette Company Razor blade technology
US6684759B1 (en) * 1999-11-19 2004-02-03 Vladimir Gorokhovsky Temperature regulator for a substrate in vapor deposition processes
US20040027018A1 (en) * 2002-08-06 2004-02-12 Leblanc Jeffry Arnold Hydraulic compensation for magnetically biased fluid dynamic bearing motor
US6695865B2 (en) * 2000-03-20 2004-02-24 Advanced Bio Prosthetic Surfaces, Ltd. Embolic protection device
US20050001201A1 (en) * 2003-07-03 2005-01-06 Bocko Peter L. Glass product for use in ultra-thin glass display applications
US20050005892A1 (en) * 2003-05-23 2005-01-13 Nissan Motor Co., Ltd. Piston for internal combustion engine
US6844068B1 (en) * 1999-04-09 2005-01-18 Nissan Motor Co., Ltd. Slidably movable member and method of producing same
US6849085B2 (en) * 1999-11-19 2005-02-01 Advanced Bio Prosthetic Surfaces, Ltd. Self-supporting laminated films, structural materials and medical devices manufactured therefrom and method of making same
US20050025975A1 (en) * 2003-07-31 2005-02-03 Nissan Motor Co., Ltd. Gear
US6855237B2 (en) * 2001-02-01 2005-02-15 International Technology Exchange, Inc. Pulsed carbon plasma apparatus
US20050035222A1 (en) * 2003-04-15 2005-02-17 Nissan Motor Co., Ltd. Fuel injection valve
US20050037879A1 (en) * 2003-08-13 2005-02-17 Nissan Motor Co., Ltd. Chain drive system
US6865952B2 (en) * 2002-10-16 2005-03-15 Helix Technology Corporation Apparatus and methods for heat loss pressure measurement
US20050056241A1 (en) * 2003-08-08 2005-03-17 Nissan Motor Co., Ltd. Valve train for internal combustion engine
US20050064196A1 (en) * 2003-08-21 2005-03-24 Jean Martin Low-friction sliding member and low-friction sliding mechanism using same
US20050061636A1 (en) * 2002-03-08 2005-03-24 Frost Charles C. Conveyor chain
US20050061291A1 (en) * 2003-08-13 2005-03-24 Nissan Motor Co., Ltd. Structure for connecting piston to crankshaft
US6871700B2 (en) * 2000-11-17 2005-03-29 G & H Technologies Llc Thermal flux regulator
US7324945B2 (en) * 2001-06-28 2008-01-29 Sri International Method of dynamically altering grammars in a memory efficient speech recognition system

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL137370C (en) * 1963-08-02
US3846162A (en) * 1968-10-21 1974-11-05 Texas Instruments Inc Metal carbonitride coatings
JP2599383B2 (en) * 1987-04-11 1997-04-09 出光興産 株式会社 Lubricating oil composition
CA2060823C (en) * 1991-02-08 2002-09-10 Naoya Omori Diamond-or diamond-like carbon-coated hard materials
WO1993021288A1 (en) * 1992-04-15 1993-10-28 Exxon Chemical Patents Inc. Lubricant composition containing mixed friction modifiers
RU2114210C1 (en) * 1997-05-30 1998-06-27 Валерий Павлович Гончаренко Process of formation of carbon diamond-like coat in vacuum
JP2003147508A (en) * 2001-11-07 2003-05-21 Sumitomo Electric Ind Ltd Carbon film, method of depositing carbon film, and carbon film-coated member

Patent Citations (100)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3790315A (en) * 1970-10-01 1974-02-05 Atlas Copco Ab Rotary piston compressors with liquid injection
US4367130A (en) * 1970-11-30 1983-01-04 Lemelson Jerome H Chemical reaction
US3932228A (en) * 1973-11-01 1976-01-13 Suzuki Jidosha Kogyo Kabushiki Kaisha Metal material for sliding surfaces
US4645610A (en) * 1984-04-20 1987-02-24 Institut Francais Du Petrole Method for the preparation of olefin polysulfides, the products obtained and their utilization as lubricant additives
US5288556A (en) * 1987-03-31 1994-02-22 Lemelson Jerome H Gears and gear assemblies
US5284394A (en) * 1987-03-31 1994-02-08 Jerome Lemelson Ball and roller bearings and bearing components
US5096352A (en) * 1987-03-31 1992-03-17 Lemelson Jerome H Diamond coated fasteners
US5000541A (en) * 1987-09-18 1991-03-19 At&T Bell Laboratories Hermetically sealed optical fibers
US5078848A (en) * 1988-01-18 1992-01-07 Asko Anttila Procedure and apparatus for the coating of materials by means of a pulsating plasma beam
US5723207A (en) * 1988-01-21 1998-03-03 The National Research Development Corporation Infra-red transparant materials
US5190824A (en) * 1988-03-07 1993-03-02 Semiconductor Energy Laboratory Co., Ltd. Electrostatic-erasing abrasion-proof coating
US5866195A (en) * 1988-03-31 1999-02-02 Lemelson; Jerome H. Methods for forming diamond-coated superconductor wire
US5077990A (en) * 1988-05-06 1992-01-07 Sipra Patententwicklungs- Und Beteiligungsgesellschaft Mbh Knitting machine and parts having diamond-like carbon coated surfaces
US5202156A (en) * 1988-08-16 1993-04-13 Canon Kabushiki Kaisha Method of making an optical element mold with a hard carbon film
US4992082A (en) * 1989-01-12 1991-02-12 Ford Motor Company Method of toughening diamond coated tools
US4988421A (en) * 1989-01-12 1991-01-29 Ford Motor Company Method of toughening diamond coated tools
US4919974A (en) * 1989-01-12 1990-04-24 Ford Motor Company Making diamond composite coated cutting tools
US5187021A (en) * 1989-02-08 1993-02-16 Diamond Fiber Composites, Inc. Coated and whiskered fibers for use in composite materials
US4981717A (en) * 1989-02-24 1991-01-01 Mcdonnell Douglas Corporation Diamond like coating and method of forming
US5087608A (en) * 1989-12-28 1992-02-11 Bell Communications Research, Inc. Environmental protection and patterning of superconducting perovskites
US5190807A (en) * 1990-10-18 1993-03-02 Diamonex, Incorporated Abrasion wear resistant polymeric substrate product
US5205188A (en) * 1990-11-05 1993-04-27 Detlef Repenning Friction pairing and process for its production
US5497550A (en) * 1991-11-15 1996-03-12 The Gillette Company Shaving system
US5295305A (en) * 1992-02-13 1994-03-22 The Gillette Company Razor blade technology
US5295305B1 (en) * 1992-02-13 1996-08-13 Gillette Co Razor blade technology
US5380196A (en) * 1993-05-13 1995-01-10 Minnesota Mining And Manufacturing Company Orthodontic bracket with archwire slot liner
US5491028A (en) * 1993-05-21 1996-02-13 Trustees Of Boston University Enhanced adherence of diamond coatings
US5482602A (en) * 1993-11-04 1996-01-09 United Technologies Corporation Broad-beam ion deposition coating methods for depositing diamond-like-carbon coatings on dynamic surfaces
US5401543A (en) * 1993-11-09 1995-03-28 Minnesota Mining And Manufacturing Company Method for forming macroparticle-free DLC films by cathodic arc discharge
US5719109A (en) * 1993-12-30 1998-02-17 Exxon Chemical Patents Inc Lubricating oil composition
US5731046A (en) * 1994-01-18 1998-03-24 Qqc, Inc. Fabrication of diamond and diamond-like carbon coatings
US5593719A (en) * 1994-03-29 1997-01-14 Southwest Research Institute Treatments to reduce frictional wear between components made of ultra-high molecular weight polyethylene and metal alloys
US6171343B1 (en) * 1994-03-29 2001-01-09 Southwest Research Institute Ultra high molecular weight polyethylene components treated to resist shearing and frictional wear
US5707409A (en) * 1994-08-24 1998-01-13 Minnesota Mining And Manufacturing Company Abrasive article having a diamond-like coating layer and method for making same
US6197428B1 (en) * 1994-08-26 2001-03-06 Deposition Sciences, Inc. Gemstones and decorative objects comprising a substrate and an optical interference film
US5714202A (en) * 1995-06-07 1998-02-03 Lemelson; Jerome H. Synthetic diamond overlays for gas turbine engine parts having thermal barrier coatings
US6203651B1 (en) * 1995-09-20 2001-03-20 Uponor Innovation Ab Method and apparatus for making an extrusion product, and an extrusion product
US5871805A (en) * 1996-04-08 1999-02-16 Lemelson; Jerome Computer controlled vapor deposition processes
US6338881B1 (en) * 1996-09-03 2002-01-15 Saxonia Umformtechnik Gmbh Diamond-like coating and method of making same
US6193906B1 (en) * 1997-02-27 2001-02-27 Idemitsu Kosan Co., Ltd. Refrigerating oil composition containing a polyether additive
US6023979A (en) * 1997-07-21 2000-02-15 Helix Technology Apparatus and methods for heat loss pressure measurement
US6340245B1 (en) * 1997-09-16 2002-01-22 Skf Engineering & Research Centre B.V. Coated rolling element bearing
US6015597A (en) * 1997-11-26 2000-01-18 3M Innovative Properties Company Method for coating diamond-like networks onto particles
US6197120B1 (en) * 1997-11-26 2001-03-06 3M Innovative Properties Company Apparatus for coating diamond-like networks onto particles
US20040003638A1 (en) * 1997-12-12 2004-01-08 Schaefer Mark W. Transfer of holographic images into metal sporting and fitness products
US5881444A (en) * 1997-12-12 1999-03-16 Aluminum Company Of America Techniques for transferring holograms into metal surfaces
US6190514B1 (en) * 1997-12-30 2001-02-20 Premark Rwp Holdings, Inc. Method for high scan sputter coating to produce coated, abrasion resistant press plates with reduced built-in thermal stress
US6028393A (en) * 1998-01-22 2000-02-22 Energy Conversion Devices, Inc. E-beam/microwave gas jet PECVD method and apparatus for depositing and/or surface modification of thin film materials
US6016000A (en) * 1998-04-22 2000-01-18 Cvc, Inc. Ultra high-speed chip semiconductor integrated circuit interconnect structure and fabrication method using free-space dielectrics
US20020031987A1 (en) * 1998-09-23 2002-03-14 Seagate Technology Llc Apparatus and method for reducing disc surface asperities to sub-microinch height
US6358123B1 (en) * 1998-09-23 2002-03-19 Seagate Technology Llc Apparatus and method for reducing disc surface asperities to sub-microinch height
US6534141B1 (en) * 1998-10-27 2003-03-18 Raymond J. Hull, Jr. Method of forming an improved support member for a fabric and film forming device
US6207625B1 (en) * 1998-12-21 2001-03-27 Tonen Corporation Lubricant oil composition for diesel engines (LAW913)
US6170156B1 (en) * 1999-03-24 2001-01-09 General Motors Corporation Gear tooth smoothing and shaping process
US6844068B1 (en) * 1999-04-09 2005-01-18 Nissan Motor Co., Ltd. Slidably movable member and method of producing same
US6523456B1 (en) * 1999-07-05 2003-02-25 Honda Giken Kogyo Kabushiki Kaisha Sliding members and piston for internal combustion engine
US6205291B1 (en) * 1999-08-25 2001-03-20 A. O. Smith Corporation Scale-inhibiting heating element and method of making same
US6173913B1 (en) * 1999-08-25 2001-01-16 Caterpillar Inc. Ceramic check for a fuel injector
US20030036341A1 (en) * 1999-10-12 2003-02-20 Hunatech Co., Ltd. Conditioner for polishing pad and method for manufacturing the same
US6699106B2 (en) * 1999-10-12 2004-03-02 Hunatech Co., Ltd. Conditioner for polishing pad and method for manufacturing the same
US6849085B2 (en) * 1999-11-19 2005-02-01 Advanced Bio Prosthetic Surfaces, Ltd. Self-supporting laminated films, structural materials and medical devices manufactured therefrom and method of making same
US6684759B1 (en) * 1999-11-19 2004-02-03 Vladimir Gorokhovsky Temperature regulator for a substrate in vapor deposition processes
US6537310B1 (en) * 1999-11-19 2003-03-25 Advanced Bio Prosthetic Surfaces, Ltd. Endoluminal implantable devices and method of making same
US6866894B2 (en) * 2000-02-29 2005-03-15 The Gillette Company Razor blade technology
US6684513B1 (en) * 2000-02-29 2004-02-03 The Gillette Company Razor blade technology
US6695865B2 (en) * 2000-03-20 2004-02-24 Advanced Bio Prosthetic Surfaces, Ltd. Embolic protection device
US6524212B2 (en) * 2000-03-23 2003-02-25 Nissan Motor Co., Ltd. Toroidal-type continuously variable transmission for automobiles
US20030012234A1 (en) * 2000-06-19 2003-01-16 Watson Tom A. Six to ten KHz, or greater gas discharge laser system
US20020026889A1 (en) * 2000-08-08 2002-03-07 Doyle Robert E. Pivoting battens
US20030035957A1 (en) * 2000-09-20 2003-02-20 Griffin Nigel Dennis Polycrystalline diamond partially depleted of catalyzing material
US20030021995A1 (en) * 2000-09-20 2003-01-30 Griffin Nigel Dennis Method of making polycrystalline diamond with working surfaces depleted of catalyzing material
US20020034632A1 (en) * 2000-09-20 2002-03-21 Griffin Nigel Dennis Polycrystalline diamond partially depleted of catalyzing material
US20030034182A1 (en) * 2000-09-20 2003-02-20 Griffin Nigel Dennis Polycrystalline diamond partially depleted of catalyzing material
US6861137B2 (en) * 2000-09-20 2005-03-01 Reedhycalog Uk Ltd High volume density polycrystalline diamond with working surfaces depleted of catalyzing material
US20030037640A1 (en) * 2000-09-20 2003-02-27 Griffin Nigel Dennis Polycrystalline diamond partially depleted of catalyzing material
US6861098B2 (en) * 2000-09-20 2005-03-01 Reedhycalog Uk Ltd Polycrystalline diamond partially depleted of catalyzing material
US20030035958A1 (en) * 2000-09-20 2003-02-20 Griffin Nigel Dennis Polycrystalline diamond partially depleted of catalyzing material
US20020034631A1 (en) * 2000-09-20 2002-03-21 Griffin Nigel Dennis High volume density polycrystalline diamond with working surfaces depleted of catalyzing material
US20040008406A1 (en) * 2000-10-27 2004-01-15 Blitstein Jeffrey L. Wavelength specific coating for mirrored optics and method for reducing reflection of white light
US6871700B2 (en) * 2000-11-17 2005-03-29 G & H Technologies Llc Thermal flux regulator
US6537429B2 (en) * 2000-12-29 2003-03-25 Lam Research Corporation Diamond coatings on reactor wall and method of manufacturing thereof
US6855237B2 (en) * 2001-02-01 2005-02-15 International Technology Exchange, Inc. Pulsed carbon plasma apparatus
US7324945B2 (en) * 2001-06-28 2008-01-29 Sri International Method of dynamically altering grammars in a memory efficient speech recognition system
US20030019332A1 (en) * 2001-07-26 2003-01-30 Korb William B. Composite utility knife blade, and method of making such a blade
US6701627B2 (en) * 2001-07-26 2004-03-09 American Saw & Mfg. Company, Inc. Composite utility knife blade
US20030019111A1 (en) * 2001-07-26 2003-01-30 Korb William B. Composite utility knife blade, and method of making such a blade
US20050061636A1 (en) * 2002-03-08 2005-03-24 Frost Charles C. Conveyor chain
US20040011900A1 (en) * 2002-05-22 2004-01-22 Jens Gebhardt Fuel injector assembly
US6855791B2 (en) * 2002-07-09 2005-02-15 Signature Control Systems Process and apparatus for improving and controlling the vulcanization of natural and synthetic rubber compounds
US20040010068A1 (en) * 2002-07-09 2004-01-15 Signature Control Systems Process and apparatus for improving and controlling the vulcanization of natural and synthetic rubber compounds
US20040027018A1 (en) * 2002-08-06 2004-02-12 Leblanc Jeffry Arnold Hydraulic compensation for magnetically biased fluid dynamic bearing motor
US6865952B2 (en) * 2002-10-16 2005-03-15 Helix Technology Corporation Apparatus and methods for heat loss pressure measurement
US20050035222A1 (en) * 2003-04-15 2005-02-17 Nissan Motor Co., Ltd. Fuel injection valve
US20050005892A1 (en) * 2003-05-23 2005-01-13 Nissan Motor Co., Ltd. Piston for internal combustion engine
US20050001201A1 (en) * 2003-07-03 2005-01-06 Bocko Peter L. Glass product for use in ultra-thin glass display applications
US20050025975A1 (en) * 2003-07-31 2005-02-03 Nissan Motor Co., Ltd. Gear
US20050056241A1 (en) * 2003-08-08 2005-03-17 Nissan Motor Co., Ltd. Valve train for internal combustion engine
US20050061291A1 (en) * 2003-08-13 2005-03-24 Nissan Motor Co., Ltd. Structure for connecting piston to crankshaft
US20050037879A1 (en) * 2003-08-13 2005-02-17 Nissan Motor Co., Ltd. Chain drive system
US20050064196A1 (en) * 2003-08-21 2005-03-24 Jean Martin Low-friction sliding member and low-friction sliding mechanism using same

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7273655B2 (en) 1999-04-09 2007-09-25 Shojiro Miyake Slidably movable member and method of producing same
US8152377B2 (en) 2002-11-06 2012-04-10 Nissan Motor Co., Ltd. Low-friction sliding mechanism
US20070065243A1 (en) * 2002-12-19 2007-03-22 Joerg Guehring Deep hole drill
US20050244236A1 (en) * 2002-12-19 2005-11-03 Joerg Guehring Deep hole drill
US8096205B2 (en) 2003-07-31 2012-01-17 Nissan Motor Co., Ltd. Gear
US8206035B2 (en) 2003-08-06 2012-06-26 Nissan Motor Co., Ltd. Low-friction sliding mechanism, low-friction agent composition and method of friction reduction
US8575076B2 (en) 2003-08-08 2013-11-05 Nissan Motor Co., Ltd. Sliding member and production process thereof
US7771821B2 (en) 2003-08-21 2010-08-10 Nissan Motor Co., Ltd. Low-friction sliding member and low-friction sliding mechanism using same
US7650976B2 (en) 2003-08-22 2010-01-26 Nissan Motor Co., Ltd. Low-friction sliding member in transmission, and transmission oil therefor
EP2003190A4 (en) * 2006-03-30 2011-03-16 Kyodo Yushi Oil composition for metal working, method for metal working, and metal work
US20090018039A1 (en) * 2006-03-30 2009-01-15 Koichi Goto Metal working oil composition, metal working method and metal work
US8236742B2 (en) 2006-03-30 2012-08-07 Kyodo Yushi Co., Ltd. Metal working oil composition, metal working method and metal work
EP2003190A2 (en) * 2006-03-30 2008-12-17 Kyodo Yushi Co., Ltd. Oil composition for metal working, method for metal working, and metal work
US20140271002A1 (en) * 2013-03-15 2014-09-18 Fanuc Corporation Cutting fluid control device for machine tool
US9399273B2 (en) * 2013-03-15 2016-07-26 Fanuc Corporation Cutting fluid control device for machine tool
US9885004B2 (en) 2013-12-23 2018-02-06 Exxonmobil Research And Engineering Company Method for improving engine fuel efficiency
US10190072B2 (en) 2013-12-23 2019-01-29 Exxonmobil Research And Engineering Company Method for improving engine fuel efficiency

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Owner name: NISSAN MOTOR CO. LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NISHIMURA, KIMIO;MABUCHI, YUTAKA;KONDO, TOMOHIRO;REEL/FRAME:015419/0512;SIGNING DATES FROM 20040512 TO 20040513

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION