EP1618173A1 - Lubricant compositions - Google Patents

Lubricant compositions

Info

Publication number
EP1618173A1
EP1618173A1 EP04729132A EP04729132A EP1618173A1 EP 1618173 A1 EP1618173 A1 EP 1618173A1 EP 04729132 A EP04729132 A EP 04729132A EP 04729132 A EP04729132 A EP 04729132A EP 1618173 A1 EP1618173 A1 EP 1618173A1
Authority
EP
European Patent Office
Prior art keywords
neutral
same
alkyl
phosphate
lubricant composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04729132A
Other languages
German (de)
French (fr)
Inventor
William David Phillips
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Switzerland GmbH
Original Assignee
Great Lakes Chemical Europe GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Great Lakes Chemical Europe GmbH filed Critical Great Lakes Chemical Europe GmbH
Publication of EP1618173A1 publication Critical patent/EP1618173A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—Gas-turbines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/247—Stainless steel

Definitions

  • This invention relates to novel lubricant compositions that are useful as lubricants in high load carrying oils, e.g. metal working fluids, gear oils, extreme pressure turbine oils and hydraulic oils.
  • the lubricant compositions of the invention are especially useful in metal working fluids.
  • the cutting of metal involves the expenditure of significant amounts of energy and the development of high temperatures as the cutting tool removes metal from the workpiece.
  • the lubricant used is able to operate efficiently under the conditions of operation. This means essentially that it is capable of working at very high loads and quickly removing the heat generated by the cutting process.
  • Mineral oil alone does not have sufficient lubricity to perform this function and it is necessary to incorporate additives to enhance this aspect of the oil's performance.
  • the most common extreme pressure additives have been those containing chlorine (for example C14-17 chlorinated paraffins), phosphorus containing additives in the form of neutral triaryl phosphates, alkyl or alkylaryl acid phosphates and alkylpolyalkoxy or alkylarylpolyalkoxy acid phosphates and sulphur carriers (for example sulphurised olefins, sulphurised esters, and sulphurised fats).
  • sulphur carriers for example sulphurised olefins, sulphurised esters, and sulphurised fats.
  • the level of performance offered by the different additives varies depending on the temperatures at which the active species are released to form a salt layer at the metal surface. This in turn depends on the speed and feed rate of the cutting tool, the type and hardness of the alloy being machined and the specific machining operation.
  • the severity of the application would largely determine the chemical nature of the selected extreme pressure additive, the level of use and whether a combination of additives might be preferable. For example, if the application was not too heavy duty it might use a low concentration of an extreme pressure additive (such as a chlorinated paraffin or a phosphate ester). While for heavier duty applications, higher concentrations of the different types of extreme pressure additives or mixtures of these additives are utilised by the formulator.
  • an extreme pressure additive such as a chlorinated paraffin or a phosphate ester
  • oil in water emulsions and water based solutions are also commonly used in applications which require less lubricity.
  • additives are required to improve the lubrication performance of the fluid.
  • the type of phosphorus-containing additives which are found in metal working fluids are typically alkyl or alkylaryl acid phosphates and alkylpolyalkoxy or alkylarylpolyalkoxy acid phosphates used either as the free acid or neutralised with basic materials such as alkanolamines and caustic soda e.g. products sold under the trade marks of Lubrhophos and Rhodafac; neutral triaryl phosphates e.g. synthetic isopropylated phenyl phosphates such as are available commercially under the Durad trademark.
  • One objective of the present invention is to provide a novel lubricant composition which improves the cutting performance of both neat oil and water based cutting fluids.
  • Another objective of the present invention is to replace acid phosphates as extreme pressure/anti wear additives in metal working applications. This objective has been achieved by the combination of certain neutral alkyl phosphorus compounds with certain sulphur carriers.
  • a lubricant composition for a high load carrying oil comprising:
  • R l5 R 2 and R 3 are the same or different and are alkyl groups with 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms.
  • R 4 , Re and Rs are -C ⁇ or C 3 H 8 and R 5 , R and R are the same or different and are alkyl groups with 1 to 8 carbon atoms and n is 1 to 6.
  • R 4 , R 5 , Re, R 7 , R 8 and R and n have the same meanings as in IV above.
  • R 4 , R 5 , Rg, R 7 , Rs and R and n have the same meanings as in IV above.
  • R 4 , R 5 , Re, R 7 and n have the same meanings as in IV above and R 10 is an alkyl group with 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms.
  • R 4 , R 5 and n have the same meanings as in IV above and R 10 and R ⁇ are the same or different and are alkyl groups with 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms.
  • R 7 and n have the same meanings as in IV above and R 12 and R 13 are the same or different and are alkyl groups with 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms.
  • R 12 is an alkyl group with 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms.
  • R 2 and R 3 are the same as in I above and R 4 and R 5 are the same as in IV above.
  • R 4 , R 5 Re, R 7 , Rs, R and n have the same meanings as in IV above.
  • the lubricant composition of the invention can comprise one or more of the compounds of general formulae I to XIII.
  • the neutral alkyl phosphorus compound and the sulphur carrier are utilised in a weight ratio of P to S content from 1:50 to 1:1, preferably a weight ratio of l:l to l:30.
  • Examples of compounds of the general formulae I to XIII are as follows:
  • Preferred sulphur carriers are selected from at least one of sulphurised synthetic esters, sulphurised hydrocarbons (e.g. sulphurised olefins), sulphurised vegetable oils and fats, metal sulphonates, metal dialkyldithiophosphates and triaryl phosphorothionates.
  • sulphurised synthetic esters e.g. sulphurised hydrocarbons (e.g. sulphurised olefins), sulphurised vegetable oils and fats, metal sulphonates, metal dialkyldithiophosphates and triaryl phosphorothionates.
  • the sulphur carriers serve to release sulphur at the cutting face of the workpiece where it reacts to form a lubricating film at relatively high temperatures.
  • the present invention is also a high load carrying oil which contains a lubricant composition as described above.
  • the high load carrying oil may be a metal working fluid, a gear oil, an extreme pressure turbine oil or a hydraulic oil.
  • the present invention is also a method for working metal comprising (a) contacting a metal workpiece with a lubricant composition as described above and (b) working the metal workpiece.
  • the lubricant composition of the invention can include other components conventional in the art, e.g. surfactants, non-ionic alcohols.
  • Lubrhophos LB400 ex Rhodia Chemicals which is based on oleyl alcohol reacted with ethylene oxide and then the product is reacted with phosphorus pentoxide. This product is oil soluble and recommended as an EP additive for cutting oils.
  • Durad is a registered trade mark of Great Lakes Chemical Corporation.
  • an automatic drilling machine is used to drill holes in metal discs 40mm thick.
  • the holes are 18mm deep while, for oil-based cutting fluids, the drill feeds and speeds were 0.13mm/rev (or 156mm/min) and 1200rpm respectively. Tests were carried out until the drill failed either due to breakage or to excessive wear. The average of at least duplicate test results are quoted.
  • the metal used was EN24T carbon steel; the drill feeds and speeds were as indicated below and the base stock was an ISO VG 22 paraffinic oil. In this case the S/P ratio was 13:1.
  • the formulation containing Durad TiBP is seen to be significantly more active than the chlorparaffin.
  • Stainless steel type 304 was used for this study.
  • the sulphur carriers used were a 4: 1 mix of a sulphurised fatty acid ester (26% total sulphur of which 15% is active) and a dialkyl polysulphide (40% total sulphur of which 36% is active).
  • the levels of sulphur and phosphorus used were 1.5% and 0.5% respectively giving an S/P ratio of 3:1.
  • the oil used was an ISO VG 22 Group 1 base.
  • This emulsion concentrate was then diluted to 4% to produce the working fluid. Tap water with a hardness of 160ppm calcium carbonate was used throughout. In this test, the concentration of the sulphur and phosphorus in the final emulsion were 0.36% sulphur and 0.012% phosphorus (a 30:1 ratio). The table below gives the approximate formulation of the concentrate before dilution.
  • the sulphur carriers used RC2526 and RC2540 were the same as used in the previous Examples.
  • the drill feed rate was 150mm/min and the speed was 1500 rpm.
  • the depth of hole was 18mm.
  • a major benefit of the present invention is that neutral alkyl phosphorus compounds provide a synergistic performance with sulphur carriers in both neat oil and aqueous cutting fluids on both mild steel and stainless steel. Such a synergistic combination enables the formulation of cutting fluids with the following properties:
  • neutral alkyl phosphorus compounds also allows higher levels of phosphorus to be used when necessary. Where acid phosphates are used, the acidity effectively limits the level of phosphorus that can be used because the acid can become corrosive at high levels. This allows for more flexibility in formulating mixtures of P/S and higher levels where necessary depending on the severity of the working process.

Abstract

A lubricant composition for a high load carrying oil comprises a synergistic mixture of a neutral alkyl phosphorus compound and a sulphur carrier. The neutral alkyl phosphorus compound is selected from neutral alkyl and alkoxyalkyl phosphates, phosphonates, phosphinates and phosphites. Preferred neutral alkyl phosphorus compounds are triisobutyl phosphate, tributoxyethyl phosphate and dioctyl octyl phosphonate. Preferred sulphur carriers are sulphurised fatty acid esters and dialkyl polysulphides. High load carrying oils containing the lubricant composition of the invention include metal working fluids, gear oils, extreme pressure turbine oils and hydraulic oils.

Description

LUBRICANT COMPOSITIONS
This invention relates to novel lubricant compositions that are useful as lubricants in high load carrying oils, e.g. metal working fluids, gear oils, extreme pressure turbine oils and hydraulic oils. The lubricant compositions of the invention are especially useful in metal working fluids.
The cutting of metal involves the expenditure of significant amounts of energy and the development of high temperatures as the cutting tool removes metal from the workpiece. In order to reduce the energy consumed, obtain a long life for the cutting tool and a high surface finish on the workpiece, it is essential that the lubricant used is able to operate efficiently under the conditions of operation. This means essentially that it is capable of working at very high loads and quickly removing the heat generated by the cutting process. Mineral oil alone does not have sufficient lubricity to perform this function and it is necessary to incorporate additives to enhance this aspect of the oil's performance.
In the past the most common extreme pressure additives have been those containing chlorine (for example C14-17 chlorinated paraffins), phosphorus containing additives in the form of neutral triaryl phosphates, alkyl or alkylaryl acid phosphates and alkylpolyalkoxy or alkylarylpolyalkoxy acid phosphates and sulphur carriers (for example sulphurised olefins, sulphurised esters, and sulphurised fats). The level of performance offered by the different additives varies depending on the temperatures at which the active species are released to form a salt layer at the metal surface. This in turn depends on the speed and feed rate of the cutting tool, the type and hardness of the alloy being machined and the specific machining operation.
The severity of the application would largely determine the chemical nature of the selected extreme pressure additive, the level of use and whether a combination of additives might be preferable. For example, if the application was not too heavy duty it might use a low concentration of an extreme pressure additive (such as a chlorinated paraffin or a phosphate ester). While for heavier duty applications, higher concentrations of the different types of extreme pressure additives or mixtures of these additives are utilised by the formulator.
None of the commonly used extreme pressure additives is without its disadvantages. Sulphur can produce staining of workpieces derived from non-ferrous alloys at high concentrations and also an unattractive odour as the carrier decomposes to release the sulphur. Problems associated with the usage of chlorine stem from concerns about disposal of the cutting fluid. These compounds can also produce hydrochloric acid on decomposition which can cause corrosion of the workpiece and equipment in the environment of the machining operation.
In addition to mineral oil as the "carrier" for the extreme pressure/antiwear additives, and usually for applications which are more severe, oil in water emulsions and water based solutions are also commonly used in applications which require less lubricity. However in all these fluids, additives are required to improve the lubrication performance of the fluid.
The type of phosphorus-containing additives which are found in metal working fluids are typically alkyl or alkylaryl acid phosphates and alkylpolyalkoxy or alkylarylpolyalkoxy acid phosphates used either as the free acid or neutralised with basic materials such as alkanolamines and caustic soda e.g. products sold under the trade marks of Lubrhophos and Rhodafac; neutral triaryl phosphates e.g. synthetic isopropylated phenyl phosphates such as are available commercially under the Durad trademark.
Concern has been expressed regarding the use of neutral or acid aryl and acid alkylaryl phosphates lest the used fluid containing phenolic compounds (arising largely from the hydrolysis of the phosphates) should escape into the environment, and contaminate water courses. Acid phosphate esters can also become less effective as extreme pressure additives when neutralised and are also unstable when subjected to hard water.
One objective of the present invention is to provide a novel lubricant composition which improves the cutting performance of both neat oil and water based cutting fluids. Another objective of the present invention is to replace acid phosphates as extreme pressure/anti wear additives in metal working applications. This objective has been achieved by the combination of certain neutral alkyl phosphorus compounds with certain sulphur carriers.
According to the present invention, there is provided a lubricant composition for a high load carrying oil said lubricating composition comprising:
(a) a neutral alkyl phosphorus compound selected from those corresponding to the following general formulae:
(i) neutral alkyl phosphates
O
II
wherein Rl5 R2 and R3 are the same or different and are alkyl groups with 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms.
(iϊ) neutral alkyl phosphonates
O
II
R2O — P — OR! II
I Rs wherein Rl5 R and R3 have the same meaning as in I above.
(Hi) neutral alkyl phosphinates
O
II
wherein Rl3 R2 and R3 have the same meaning as in I above. (iv) neutral alkoxyalkyl phosphates
O
II
R7(OR6)nO — P — OCR4θ)JR5
I IV
O(RsO)nR9
wherein R4, Re and Rs are -C^ or C3H8 and R5, R and R are the same or different and are alkyl groups with 1 to 8 carbon atoms and n is 1 to 6.
(v) neutral alkoxyalkyl phosphonates
O
II
R7(OR6)αO — P — (XEUO Hs V
(R*O)nR9
wherein R4, R5, Re, R7, R8 and R and n have the same meanings as in IV above.
(vi) neutral alkoxyalkyl phosphinates
O
II 7(O 6)n — P — O(R4θ)nR5 VI
(RsO)nR9
wherein R4, R5, Rg, R7, Rs and R and nhave the same meanings as in IV above.
(vii) neutral alkyldialkoxyalkyl phosphonates
O
II
wherein R4, R5, Re, R7 and n have the same meanings as in IV above and R10 is an alkyl group with 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms.
(viii) neutral dialkylalkoxyalkyl phosphinates
O
II
wherein R4, R5 and n have the same meanings as in IV above and R10 and Rπ are the same or different and are alkyl groups with 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms.
(ix) neutral alkoxyalkyl dialkyl phosphonates
O
II
R7(ORe)n— P — OR12 IX
O
Rl3
wherein Re, R7 and n have the same meanings as in IV above and R12 and R13 are the same or different and are alkyl groups with 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms.
(x) neutral dialkoxyalkylalkyl phosphinates
O
II
R7(ORe)n— P — OR12 X
(RsO)nR9
wherein Re, R7, Rg, R9 and n have the same meanings as in IV above and R12 is an alkyl group with 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms. (xi) neutral dialkylalkoxyalkyl phosphates
O
II
R2O— P— O(R4O)nR5 XI
O R3
wherein R2 and R3 are the same as in I above and R4 and R5 are the same as in IV above.
(xiϊ) neutral alkyl phosphites
R20— P — OR!
I XII OR3
wherein Ri, R2R3 have the same meaning as in I above.
(xiiϊ) neutral alkoxyalkyl phosphites
R7(ORe)nO— P — O(R4O)nR5
XIII
O
(RsO)nR9
wherein R4, R5 Re, R7, Rs, R and n have the same meanings as in IV above.
and (b) a sulphur carrier containing active or inactive sulphur.
The lubricant composition of the invention can comprise one or more of the compounds of general formulae I to XIII.
Advantageously, the neutral alkyl phosphorus compound and the sulphur carrier are utilised in a weight ratio of P to S content from 1:50 to 1:1, preferably a weight ratio of l:l to l:30. Examples of compounds of the general formulae I to XIII are as follows:
I - triisobutyl phosphate, tributyl phosphate, triisopropyl phosphate, trioctyl phosphate and tri-2-ethylhexyl phosphate
II - butyl dibutyl phosphonate and octyl dioctyl phosphonate
III - dioctyl octyl phosphinate
IV - tributoxyethyl phosphate
V - butoxyethyl dibutoxyethyl phosphonate
VI - dibutoxyethyl butoxyethyl phosphinate
VII - octyl dibutoxyethyl phosphonate
VIII - dioctyl butoxyethyl phosphinate
IX - butoxyethyl dioctyl phosphonate
X - dibutoxyethyl octyl phosphinate
XI - butoxyethyl dioctyl phosphate
XII - trilauryl phosphite, trioleyl phosphite, trioctyl phosphite and tributyl phosphite
XIII - tributoxyethyl phosphite
Preferred sulphur carriers are selected from at least one of sulphurised synthetic esters, sulphurised hydrocarbons (e.g. sulphurised olefins), sulphurised vegetable oils and fats, metal sulphonates, metal dialkyldithiophosphates and triaryl phosphorothionates.
The sulphur carriers serve to release sulphur at the cutting face of the workpiece where it reacts to form a lubricating film at relatively high temperatures.
The present invention is also a high load carrying oil which contains a lubricant composition as described above.
The high load carrying oil may be a metal working fluid, a gear oil, an extreme pressure turbine oil or a hydraulic oil. From another aspect, the present invention is also a method for working metal comprising (a) contacting a metal workpiece with a lubricant composition as described above and (b) working the metal workpiece.
The lubricant composition of the invention can include other components conventional in the art, e.g. surfactants, non-ionic alcohols.
Embodiments of the invention will now be described simply by way of example:
1) As sulphur carriers, Rhein Chemie products RC 2526 (a sulphurised fatty acid ester with 26% total sulphur of which 15% is active) and RC 2540 (a dialkylpentasulphide with 40% total sulphur of which 36% is active).
2) As an alkylpolyalkoxy acid phosphate, (mixed mono- and di-), Lubrhophos LB400 ex Rhodia Chemicals which is based on oleyl alcohol reacted with ethylene oxide and then the product is reacted with phosphorus pentoxide. This product is oil soluble and recommended as an EP additive for cutting oils.
3) Durad TiBP which is tri-isobutyl phosphate
4) Durad TBEP which is tributoxyethyl phosphate
Durad is a registered trade mark of Great Lakes Chemical Corporation.
In the following tests, an automatic drilling machine is used to drill holes in metal discs 40mm thick. The holes are 18mm deep while, for oil-based cutting fluids, the drill feeds and speeds were 0.13mm/rev (or 156mm/min) and 1200rpm respectively. Tests were carried out until the drill failed either due to breakage or to excessive wear. The average of at least duplicate test results are quoted.
(A) Drill Life Test Data on Mild Steel using Neat Oil: Durad TiBP/Sulphur Carriers as Replacements for Chlorparaffins
The metal used was EN24T carbon steel; the drill feeds and speeds were as indicated below and the base stock was an ISO VG 22 paraffinic oil. In this case the S/P ratio was 13:1. The formulation containing Durad TiBP is seen to be significantly more active than the chlorparaffin.
(B) Drill Life Tests on Stainless Steel using Neat Oil: A Comparison with Acid Phosphates
Stainless steel type 304 was used for this study. The sulphur carriers used were a 4: 1 mix of a sulphurised fatty acid ester (26% total sulphur of which 15% is active) and a dialkyl polysulphide (40% total sulphur of which 36% is active). The levels of sulphur and phosphorus used were 1.5% and 0.5% respectively giving an S/P ratio of 3:1. As for previous tests the oil used was an ISO VG 22 Group 1 base.
The quality of swarf associated with Durad TBEP in the above test was regarded as excellent throughout. In fact no drill failures occurred with this formulation. 10
(C) Performance of S/P Combinations on Stainless Steel using Macro- Εmulsions
The conditions for this test were somewhat different. In order to satisfactorily machine the stainless steel with the emulsion the conditions were modified to a feed rate of 70 mm/min and a speed of 700 rpm-slightly more severe conditions than were recommended by the drill manufacturers. The same sulphur carriers were used as in the previous test on stainless. A concentrate of the phosphate and sulphur carriers with emulsifiers, corrosion inhibitors, antifoams etc was first prepared in aqueous solution with the part addition of the triethanolamine base. This concentrate was subsequently added to a 60 solvent pale oil (naphthenic type) containing a further small amount of emulsifϊer and triethanolamine to produce an emulsion concentrate. This emulsion concentrate was then diluted to 4% to produce the working fluid. Tap water with a hardness of 160ppm calcium carbonate was used throughout. In this test, the concentration of the sulphur and phosphorus in the final emulsion were 0.36% sulphur and 0.012% phosphorus (a 30:1 ratio). The table below gives the approximate formulation of the concentrate before dilution.
In this test Durad TiBP is seen to be a most effective additive which in combination with the sulphur carriers shows a significant improvement over the sulphur carriers alone. (D) Drill Life Test Data on Stainless Steel using Neat Oil: A Comparison of Tributoxyethyl phosphate (TBEP) with Dioctyl octyl phosphonate
The sulphur carriers used RC2526 and RC2540 were the same as used in the previous Examples.
Concentrations used were 1.5% sulphur and 0.5% phosphorus in an ISO VG 22 paraffinic type neat oil (i.e. the same as before).
Stainless steel type 304 was used for this study.
The drill feed rate was 150mm/min and the speed was 1500 rpm. The depth of hole was 18mm.
The above results show that although both phosphorus additives showed enhanced activity, TBEP was the higher of the two.
N.B. In the above tests, an automatic drilling machine is used to drill holes in metal discs 40mm thick. The holes are 18mm deep, while drill feeds and speeds are normally 0.13mm/rev (or 156 mm/min) and 1200 rpm respectively. Tests were carried out until the drill failed either due to breakage or to excessive wear. The average of at least duplicate test results are quoted.
Although lubricity additives such as fatty oils and long chain esters can be used in cutting fluids, these were not included in the formulations shown above. CONCLUSIONS
A major benefit of the present invention is that neutral alkyl phosphorus compounds provide a synergistic performance with sulphur carriers in both neat oil and aqueous cutting fluids on both mild steel and stainless steel. Such a synergistic combination enables the formulation of cutting fluids with the following properties:
(a) no chlorine present;
(b) the elimination of the production of phenolic degradation products;
(c) a possible reduction in the level of sulphur in the oil;
(d) improved lubrication performance; and
(e) extended drill life in metal cutting applications.
The use of neutral alkyl phosphorus compounds also allows higher levels of phosphorus to be used when necessary. Where acid phosphates are used, the acidity effectively limits the level of phosphorus that can be used because the acid can become corrosive at high levels. This allows for more flexibility in formulating mixtures of P/S and higher levels where necessary depending on the severity of the working process.
Benefits from the use of the synergistic combination of the invention in applications other than metal cutting processes include:
(i) An increase in the level of performance without substantially increasing the level of the sulphur carriers. These can adversely affect the oxidation stability and corrosive tendencies of the formulation.
(iϊ) Alternatively, for the same level of performance, it is possible to lower the sulphur carrier level thereby favourably impacting the stability/corrosivity of the formulation.

Claims

1. A lubricant composition for a high load carrying oil said lubricating composition comprising:
(a) a neutral alkyl phosphorus compound selected from those corresponding to the following general formulae:
(i) neutral alkyl phosphates
O
II
wherein Ri, R2 and R3 are the same or different and are alkyl groups with 1 to 18 carbon atoms.
(ii) neutral alkyl phosphonates
O
II
wherein Rls Ri and R3 have the same meaning as in I above.
(iii) neutral alkyl phosphinates
O
II
R2 — P — OR! Ill
Rs
wherein Ri, R2 and R3 have the same meaning as in I above. (iv) neutral alkoxyalkyl phosphates
O
II
R7(ORe)nO —
wherein R , Re and R8 are - LLj or C3Hs and R5, R7 and R9 are the same or different and are alkyl groups with 1 to 8 carbon atoms and n is 1 to 6.
(v) neutral alkoxyalkyl phosphonates
O 11
R7(ORe)nO — P — O(R4O)nR5 V
(R8O)nR9
wherein R4., R5, Re, R7, R8 and R9 and n have the same meamngs as in IV above.
(vi) neutral alkoxyalkyl phosphinates
O 11
(R8O)nR9
wherein R4, R5, Re, R7, Rs and R9 and nhave the same meanings as in IV above. (vii) neutral alkyldialkoxyalkyl phosphonates
O
II
R7(ORe)πO— P — O(R4O)nR5 VII
R 10
wherein R4, R5, Re, R7 and n have the same meanings as in IV above and R10 is an alkyl group with 1 to 18 carbon atoms.
(viii) neutral dialkylalkoxyalkyl phosphinates
O
II
wherein R4, R5 and n have the same meanings as in IV above and R10 and Ri i are the same or different and are alkyl groups with 1 to 18 carbon atoms.
(ix) neutral alkoxyalkyl dialkyl phosphonates
O
II
R7(ORe)n— P — OR12 IX
O
wherein Re, R7 and n have the same meamngs as in IV above and R12 and R13 are the same or different and are alkyl groups with 1 to 18 carbon atoms. (x) neutral dialkoxyalkylalkyl phosphinates
O
II
R7(ORe)n— P OR12 X I
(RsO)nR9
wherein Re, R7, Rs, R9 and n have the same meanings as in IV above and R12 is an alkyl group with 1 to 18 carbon atoms.
(xi) neutral dialkylalkoxyalkyl phosphates
O
II
Rs
wherein R2 and R3 are the same as in I above and R4 and R5 are the same as in IV above.
(yάϊ) neutral alkyl phosphites
R2O— P — ORi
XII OR3
wherein Rls R2 R3 have the same meaning as in I above.
(xiiϊ) neutral alkoxyalkyl phosphites
R7(ORe)nO— P — O(R4O)nR5
XIII
O
(R8O)nR9 wherein R4, R5 Re, R , Rs, R9 and n have the same meanings as in IV above,
and (b) a sulphur carrier containing active or inactive sulphur.
2. A lubricant composition in accordance with claim 1 wherein the neutral alkyl phosphorus compound and the sulphur carrier are utilised in a weight ratio of P to S content from 1 : 50 to 1 : 1.
3. A lubricant composition as claimed in claim 2 wherein the neutral alkyl phosphosphorus compound and the sulphur carrier are utilised in a weight ratio of P to S content from 1:1 to 1:30.
4. A lubricant composition according to any one of claims 1 to 3 wherein the phosphorus compound selected from at least one of triisobutyl phosphate, tri- n-butyl phosphate, triisopropyl phosphate, trioctyl phosphate, tri-2-ethylhexyl phosphate, butyl dibutyl phosphonate, octyl dioctyl phosphonate, dioctyl octyl phosphinate, tributoxyethyl phosphate, butoxyethyl dibutoxyethyl phosphonate, dibutoxyethyl butoxyethyl phosphinate, octyl dibutoxyethyl phosphonate, dioctyl butoxyethyl phosphinate, butoxyethyl dioctyl phosphonate, dibutoxyethyl octyl phosphinate, butoxyethyl dioctyl phosphate, trilauryl phosphite, trioleyl phosphite, trioctyl phosphite, tributyl phosphite and tributoxyethyl phosphite.
5. A lubricant composition according to any one of the preceding claims wherein the sulphur carrier is selected from at least one of sulphurised synthetic esters, sulphurised hydrocarbons, sulphurised vegetable oils and fats, metal sulphonates, metal dialkyldithiophosphates and triaryl phosphorothionates.
6. A high load carrying oil which contains a lubricant composition as claimed in any one of claims 1 to 5.
7. A high load carrying oil according to claim 6 which is a metal working fluid, a gear oil, an extreme pressure turbine oil or a hydraulic oil.
A method for working metal comprising (a) contacting a metal workpiece with a metal working fluid comprising an effective amount of a lubricant composition as claimed in any one of claims 1 to 5 and (b) working the metal workpiece.
EP04729132A 2003-04-28 2004-04-23 Lubricant compositions Withdrawn EP1618173A1 (en)

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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0420256D0 (en) 2004-09-13 2004-10-13 Cassells John M Method and apparatus for sampling and analysis of fluids
EP1690920A1 (en) 2005-02-11 2006-08-16 JohnsonDiversey, Inc. Lubricant concentrate containing a phosphate triester
JP4979244B2 (en) * 2006-02-28 2012-07-18 Ｊｘ日鉱日石エネルギー株式会社 Metalworking oil composition
JP5232372B2 (en) * 2006-09-26 2013-07-10 株式会社ネオス Water-soluble metalworking fluid composition
US20090036338A1 (en) * 2007-07-31 2009-02-05 Chevron U.S.A. Inc. Metalworking Fluid Compositions and Preparation Thereof
US20090036333A1 (en) * 2007-07-31 2009-02-05 Chevron U.S.A. Inc. Metalworking Fluid Compositions and Preparation Thereof
EP2147968A1 (en) 2008-06-05 2010-01-27 Castrol Limited Compositions and methods
US9771540B2 (en) 2009-01-20 2017-09-26 Exxonmobil Research And Engineering Company Hydraulic oil compositions with improved hydraulic motor efficiency
PT2419491T (en) * 2009-04-15 2019-12-30 Dorf Ketal Chemicals I Private Ltd Method of using an effective non - polymeric and non - fouling additive for inhibiting high - temperature naphthenic acid corrosion
US20170002251A1 (en) 2015-06-30 2017-01-05 Exxonmobil Chemical Patents Inc. Glycerol Carbamate Based Lubricant Compositions and Methods of Making and Using Same
US10844264B2 (en) 2015-06-30 2020-11-24 Exxonmobil Chemical Patents Inc. Lubricant compositions comprising diol functional groups and methods of making and using same
JP2017132875A (en) 2016-01-27 2017-08-03 東燃ゼネラル石油株式会社 Lubricant composition
JP6730122B2 (en) * 2016-07-28 2020-07-29 Ｅｍｇルブリカンツ合同会社 Lubricating oil composition
JP7099876B2 (en) * 2018-05-30 2022-07-12 出光興産株式会社 Lubricating oil composition and its manufacturing method, lubrication method of drive system equipment, and drive system equipment
IT201800010416A1 (en) * 2018-11-19 2020-05-19 Lamberti Spa LUBRICANT ADDITIVES FOR METAL WORKING
CN111662773B (en) * 2019-03-07 2022-02-08 东莞市鹏润压铸材料科技有限公司 Long-acting total-synthesis magnesium alloy cutting fluid and processing method

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB749678A (en) * 1952-07-24 1956-05-30 Res And Engineering Company Lubricating oil composition
GB1205177A (en) * 1968-05-22 1970-09-16 Castrol Ltd Improvements in or relating to lubricating compositions
JPS4925406B1 (en) * 1969-11-26 1974-06-29
GB1365943A (en) * 1970-09-16 1974-09-04 Gaf Corp Metalworking additive and composition and process for making the same
US3843542A (en) * 1972-07-31 1974-10-22 Chevron Res Hydraulic oil
US4137187A (en) * 1977-08-10 1979-01-30 Chevron Research Company Antiwear additive and lubricating oil composition containing same
EP0135932B1 (en) * 1983-09-28 1990-05-02 Hitachi, Ltd. Lubricant for metal forming and process for metal forming
JPH0229714B2 (en) * 1984-08-31 1990-07-02 Hitachi Ltd SOSEIKAKOYOJUNKATSUZAIOYOBISOREOMOCHIITASOSEIKAKOHOHO
JPS61211398A (en) * 1985-03-18 1986-09-19 Hitachi Ltd Lubricant for plastic working and method of using same
JPS62207396A (en) * 1986-03-07 1987-09-11 Hitachi Ltd Lubricating oil for use in plastic working and plastic worked articles manufactured by use of the same
JPH0747754B2 (en) * 1989-05-16 1995-05-24 ユシロ化学工業株式会社 Cutting fluid for water-insoluble metal processing
US5308654A (en) * 1990-05-30 1994-05-03 Henkel Corporation Method for lubricating steel tubing prior to cold drawing
GB2272000B (en) * 1992-10-30 1997-03-26 Castrol Ltd A method of inhibiting corrosion
EP0653479B1 (en) * 1993-05-27 2004-06-30 Tonen Corporation Refrigerator oil
JP3422869B2 (en) * 1995-01-27 2003-06-30 新日本石油株式会社 Refrigeration oil composition that can be used for HCFC refrigerant and HFC refrigerant
JP3425020B2 (en) * 1995-11-06 2003-07-07 新日本石油株式会社 Cutting oil composition
JPH11209776A (en) * 1998-01-28 1999-08-03 Idemitsu Kosan Co Ltd Lubricating oil composition
WO1999038939A1 (en) * 1998-01-29 1999-08-05 Idemitsu Kosan Co., Ltd. Novel additive compositions
US6255260B1 (en) * 1998-03-26 2001-07-03 David J. Stork Metal forming lubricant with differential solid lubricants
US6254799B1 (en) * 1998-11-10 2001-07-03 Exxonmobil Research And Engineering Company Phosphate ester base stocks comprising mixed n-butyl/isobutyl phosphate esters and aircraft hydraulic fluids comprising the same
JP4464477B2 (en) * 1999-02-24 2010-05-19 協同油脂株式会社 Hot rolling oil and hot rolling method
JP2000290676A (en) * 1999-04-05 2000-10-17 Idemitsu Kosan Co Ltd Metalworking oil composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004096959A1 *

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