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
  • 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
  • C10M169/06—Mixtures of thickeners 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
  • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/125—Carboxylix 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
  • C10M2207/127—Carboxylix 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 polycarboxylic
• • 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
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2213/006—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions used as thickening agents
• • 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
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2213/06—Perfluoro polymers
  • C10M2213/0606—Perfluoro polymers 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
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2213/06—Perfluoro polymers
  • C10M2213/0613—Perfluoro polymers used as thickening agents
• • 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
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2213/06—Perfluoro polymers
  • C10M2213/062—Polytetrafluoroethylene [PTFE]
  • C10M2213/0626—Polytetrafluoroethylene [PTFE] used as thickening agents
• • 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
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/223—Five-membered rings containing nitrogen and carbon only
• • 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
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • 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
  • C10N2030/08—Resistance to extreme temperature
• • 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
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
• • 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
  • C10N2040/02—Bearings
• • 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
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

• the present invention relates to a lubricant composition, and more particularly to a lubricant composition with a distinguished rust inhibition, particularly even after having been subjected to heat hysteresis.
• Lubricants such as grease, etc. are widely used in lubrication of various machines including automobiles, construction machines, industrial machines, machine tools, etc., and also various parts as members of the machines.
• the machines have a possibility of water intrusion, depending on the locations where they are used, and thus requirements for the rust inhibition thereof are more and more strict.
• recent trends towards higher speed much more size reduction, higher performance, lighter weight, etc. have made service temperatures of these peripheral equipment higher and higher, so the rust inhibition after having been subjected to such heat hysteresis has been also an important requirement.
• a grease composition for ball-and-roller bearings which comprises a grease composition containing silicone oil- or fluorocarbon oilbased lubricating oil as a base oil, and a rust inhibitor comprising a magnesium compound and a volatile rust inhibitor as essential components has been so far proposed, where triazole-based compound such as benzotriazole, methylbenzotriazole, etc., or dicyclohexyl ammonium nitrite have been recommended as preferable volatile rust inhibitors.
• Patent Literature 1 JP-A-9-59664
• the proposed grease composition for ball-and-roller bearings is said to have a distinguished rust inhibitive action in addition to a high durability at elevated temperatures, but it contains a volatile rust inhibitor as one of rust inhibitor components, so a long term rust inhibition at elevated temperatures is not satisfactory, and as to the alkaline component such as magnesium oxide, etc., their influence on the environments must be taken into consideration.
• a heat-resistant grease composition which comprises fluorosilicone oil, a fluororesin-based thickener, and an additive such as calcium alkylsulfonate, etc., and which can also contain other well known thickeners such as calcium stearate, etc. has been also proposed, where it is shown by evaporation tests or engine tests that the heat resistance is distinguished and also stable for a long time, but no mention is made of the rust inhibition, particularly even after having been subjected to heat resistance tests.
• Patent Literature 2 JP-A-8-143883
• a lubricating grease composition which comprises perfluoropolyether base oil, and a metal salt of aliphatic dicarboxylic acid as a thickener, where the applicant shows that the composition can further contain a powdery fluororesin to attain improvements of abrasion resistance of mating material, leakage resistance, detergency, etc.
• Patent Literature 3 JP-A-2001-354986
• a mixing proportion of the metal salt of aliphatic dicarboxylic acid used as a thickener is about 1 to about 50% by weight, preferably 3 to 35% by weight, on the basis of the composition.
• the thickener is used in such preferable mixing proportions.
• the powdery fluororesin as an admixable component it is recommended that the admixing proportion is not more than about 50% by weight, preferably about 3 to about 35% by weight, on the basis of the composition.
• the admixing proportion of powdery fluororesin is 5% by weight, whereas that of metal salt of aliphatic dicarboxylic acid as a thickener is 15-25% by weight.
• an increase in the admixing proportion of metal salt of aliphatic dicarboxylic acid as a thickener will inhibit any increase the admixing proportion of powdery fluororesin.
• An object of the present invention is to provide a lubricant composition with a distinguished rust inhibition, particularly even after having been subjected to heat hysteresis, which comprises a fluoro-oil and an appropriate admixing proportion of powdery fluororesin as a thickener.
• the object of the present invention can be attained by a lubricant composition, which comprises a fluoro-oil, a powdery fluororesin thickener, and a Ca salt or a Na salt of aromatic sulfonic acid or saturated aliphatic dicarboxylic acid as a rust-inhibitive additive, where the proportion of the thickener is 10-40% by weight, and that of the additive is 0.3-10% by weight, on the basis of the total weight of the composition, the balance being the fluoro-oil.
• perfluoropolyether oils are used as a fluoro-oil.
• the present lubricant composition has a distinguished rust inhibition, particularly even after having been subjected to heat hysteresis, and thus can be used widely in lubrication of machines and their parts to be used particularly outdoors, and specifically used in effective lubrication of bearings requiring substantial rust inhibition, heat resistance, low-temperature characteristics, load-carrying capacity, etc. in automobile auxil-iary equipment such electric fan motors, fuel injector equipments, alternators, etc. of automobiles. Furthermore, the present lubricant composition can be used for lubrication of solid-solid contacts such as sliding parts of ball-and-roller bearings, slide bearings, sintered bearings, gears, valve, cocks, oil seals, rolls, electric contacts, etc.
• Fluoro-oil for use as a base oil generally includes perfluoropolyether oil.
• Perfluoropolyether represented by the following general formula can be used for this purpose : RfO(CF 2 O) x (C 2 F 4 O) y (C 3 F 6 O) z Rf Specifically, those represented, for example, by the following formulae (1)-(3) can be used, and in addition, the one represented by the following general formula (4) can be also used, where Rf is a perfluoro lower alkyl groups having 1-5 carbon atoms, preferably 1-3 carbon atoms, such as a perfluoromethyl group, a perfluoroethyl group, perfluoropropyl group, etc.
• the perfluoropolyether (1) can be obtained by complete fluorination of a precursor formed by photo-oxidation polymerization of tetra-fluoroethylene.
• the perfluoropolyether (2) can be obtained by complete fluorination of a precursor formed by photo-oxidation polymerization of hexafluoropropene and tetra-fluoroethylene.
• the perfluoropolyether (4) can be obtained by anionic polymerization of 2,2,3,3-tetrafluorooxetane in the presence of a cesium fluoride catalyst, followed by treatment of the resulting fluorine -containing polyether (CH 2 CF 2 CF 2 O) n under ultraviolet irradiation at about 160° to about 300°C with a fluorine gas.
• perfluoropolyether base oils can be used alone or in a mixture thereof, and when used as a lubricating oil the viscosity (40°C) is desirably about 5 to about 2,000mm 2 /sec, preferably about 10 to about 1,500mm 2 /sec.
• the evaporation rate When the viscosity is less than about 5mm 2 /sec., the evaporation rate will be increased, and will fail to satisfy the requirements for evaporation rate of 1.5% or less set forth in JIS ball-and-roller bearing grease, class 3 as a heat-resistant grease, whereas when the viscosity is more than about 2, 000mm 2 /sec, the pour point (JIS K-2283) will be more than 10 °C , and bearings, gears, chains, etc. fail to start at low temperatures in the ordinary manner, resulting in necessary heating for starting, that is, a failure to meet the admissible limit to use as the ordinary grease.
• Fluororesin for use herein as a thickener includes polytetrafluoroethylene [PTFE], tetrafluoroethylene-hexafluoropropene copolymer [FEP], perfluoroalkylene resin, etc., so far used as a lubricant.
• PTFE polytetrafluoroethylene
• FEP tetrafluoroethylene-hexafluoropropene copolymer
• perfluoroalkylene resin etc.
• PTFE having a melting point of 300°C or higher which is suitable for use in the present invention, it is desirable that Mn is about 10,000 or more.
• Control of molecular weight can be also carried out by using a chain transfer agent during the copolymerization reaction.
• the resulting powdery fluororesin having, among others, an average primary particle size of generally about 500 ⁇ m, preferably about 0.1 to about 30 ⁇ m, can be used.
• the powdery fluororesin can be used in a proportion of 10-40% by weight, preferably 15-35% by weight, on the basis of total weight with base oil and rust-inhibitive additive.
• the fluororesin thickener is used in a proportion of above 40% by weight, the composition will be too hard, whereas in a proportion below 10% by weight, no satisfactory thickening capacity of fluororesin etc. can be obtained, resulting in deterioration such as oil separation, and any increase in scattering prevention and leakage prevention can be no more expected.
• the powdery fluororesin can be used together with other thickeners, which include metal soaps such as Li soap, etc., urea resin, minerals such as bentonite, silica, clay, graphite, carbon, zinc oxide, etc., organic pigments, polyethylene, polypropylene, and polyamide. From the viewpoints of heat resistance and lubricability, it is preferable to use monoamide monocarboxylic acid metal salts, monoester carboxylic acid metal salts, diurea, triurea, tetraurea, etc. These other thickeners having a melting point of 300°C or higher can be preferably used.
• Aromatic sulfonic acid salts for use herein as a rust-inhibitive additive include, for example, Ca salts or Na salts of petroleum sulfonic acid, alkylbenzene sulfonic acid, dialkylnaphtharene sulfonic acid, etc.
• the sulfonic acid salts having an aromatic ring are distinguished in both heat resistance and rust inhibition.
• Saturated aliphatic dicarboxylic acids for use herein as a rust-inhibitive additive include, for example, Ca salts or Na salts of oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid, undecamethylenedicarboxylic acid, dodecamethylenedicarboxylic acid, tridecamethylnenedicarboxylic acid, tetradecamethylenedicarboxylic acid, pentadecamethylenedicarboxylic acid, hexadecamethylenedicarboxylic acid, heptadecamethylenedicarboxylic acid, octadecamethylenedicarboxylic acid, etc.
• These with an aliphatic group having 6-12 carbon atoms are preferably used particularly in respect to the distinguished rust inhibition.
• rust-inhibitive additives can be used in a proportion of 0.3-10% by weight, preferably 0.3-5% by weight, on the basis of total weight with base oil and powdery fluororesin thickener. In a proportion below 0.3% by weight no desired rust-inhibitive effect can be obtained, whereas in a proportion above 10% by weight no desired proportion of the thickener can be admixed, and no thickening effect can be expected.
• the lubricant composition can further contain other additives so far used in the conventional lubricant, such as an antioxidant, other rust-inhibitors, a corrosion inhibitor, an extreme pressure additive, an oiliness agent, a solid lubricant, etc., when required.
• the antioxidant includes, for example phenol-based antioxidants such as 2,6-di-t-butyl-4-methylphenol, 4,4' -methylenebis(2,6-di-t-butylphenol), etc.
• antioxidants such as alkyldiphenylamine, triphenylamine, phenyl- ⁇ -naphthylamine, phenothiazine, alkylated phenyl- ⁇ -naphtylamine, phenithiazine, alkylated phenithiazine, etc.
• rust inhibitors include, for example, fatty acids, fatty acid amines, alkylsulfonic acid metal salts, alkylsulfonic acid amine salts, oxidiged paraffin, polyoxyalkylethers, etc.
• the corrosion inhibitors include, for example, benzotriazole, benzoimidazole, thiadiazole, etc.
• the extreme pressure agent includes, for example, phosphorus-based compounds such as phosphoric acid esters, phosphorous acid esters, phosphoric acid ester amine salts, etc., sulfur-based compounds such as sulfides, disulfides, etc., and sulfur-based compound metal salts, such as dialkyldithiophosphoric acid metal salts, dialkyldithiocarbamic acid metal salts, etc.
• phosphorus-based compounds such as phosphoric acid esters, phosphorous acid esters, phosphoric acid ester amine salts, etc.
• sulfur-based compounds such as sulfides, disulfides, etc.
• sulfur-based compound metal salts such as dialkyldithiophosphoric acid metal salts, dialkyldithiocarbamic acid metal salts, etc.
• the oiliness agent includes, for example, fatty acids, or their esters, higher alcohols, polyhydric alcohols, or their esters, aliphatic amines, fatty acid monoglycerides, etc.
• the other solid lubricant includes, for example, molybdenum disulfide, graphite, boron nitride, silane nitride, etc.
• the composition can be prepared by adding predetermined amounts of a powdery fluororesin thickener, a rust-inhibitive additive and other necessary additives to perfluoropolyether base oil, followed by through stirring in a stirring kettle, etc. and then by homogenization treatment through three-rolls, or in a high pressure homogenizer.
• the resulting lubricant compositions were subjected to MKO test (corrosion degree).
• the test included, in addition to the test under the following ordinary conditions, comparison of corrosion degrees after having been subjected to heat hysteresis at 180°C for 500 hours as to heating grease-sealed test bearings, followed by similar test to the above.
• Lubricant composition of Comparative Example 7 had a consistency number (JIS K2220 7 ; corresponding to DIN ISO 2137) of No. 4 and therefore too hard impossible to test and to use as a practical grease.
• the lubricating oil composition of all the Examples had consistency numbers of Nos. 1-3, and could form greases successfully.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)

Applications Claiming Priority (2)

Publications (4)

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Cited By (3)

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• 2005
  • 2005-03-07 JP JP2005061811A patent/JP4810842B2/ja not_active Expired - Lifetime
• 2006
  • 2006-03-03 WO PCT/JP2006/304051 patent/WO2006095644A1/fr not_active Ceased
  • 2006-03-03 EP EP06715134.0A patent/EP1764407B1/fr not_active Expired - Lifetime
  • 2006-03-03 US US11/885,892 patent/US20090270292A1/en not_active Abandoned

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