EP2935539A1 - Schmierfettzusammensetzung - Google Patents

Schmierfettzusammensetzung

Info

Publication number
EP2935539A1
EP2935539A1 EP13811953.2A EP13811953A EP2935539A1 EP 2935539 A1 EP2935539 A1 EP 2935539A1 EP 13811953 A EP13811953 A EP 13811953A EP 2935539 A1 EP2935539 A1 EP 2935539A1
Authority
EP
European Patent Office
Prior art keywords
acid
grease
fatty acid
grease composition
mass
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.)
Granted
Application number
EP13811953.2A
Other languages
English (en)
French (fr)
Other versions
EP2935539B1 (de
Inventor
Kazuya Watanabe
Keiji Tanaka
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.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP2935539A1 publication Critical patent/EP2935539A1/de
Application granted granted Critical
Publication of EP2935539B1 publication Critical patent/EP2935539B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
    • C10M123/02—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a non-macromolecular 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts 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
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
    • C10M2203/102—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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • 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
    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • C10M2207/1225—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic used as thickening agent
    • 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
    • C10M2207/126—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 monocarboxylic
    • C10M2207/1265—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 monocarboxylic used as thickening agent
    • 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
    • C10M2207/128—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 containing hydroxy groups; Ethers thereof
    • C10M2207/1285—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 containing hydroxy groups; Ethers thereof 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
    • C10M2207/1415—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic used as thickening agent
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/74—Noack Volatility
    • 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—Semi-solids; greasy

Definitions

  • JP-A-2008-231310 proposes diurea grease which can be used for a long period of time at a high temperature.
  • an amine compound such as aniline which is used as the starting material, is extremely toxic, extra care should be taken when handling for production, and therefore there is a safety problem.
  • JP-A-2009-249419 proposes a calcium complex grease having a high dropping point which uses as a thickener calcium soap comprising calcium salts of a dibasic acid and fatty acid.
  • a suitable consistency cannot be maintained if the added amount of thickener is small, and there is a restriction in the form of dibasic acid, especially terephthalic acid, which is used as a starting material, and the terephthalic acid has to be introduced at a high temperature of 120°C for production.
  • an objective of the present invention is to provide a heat-stable grease composition which comprises a grease that has a thermal resistance
  • monocarboxylic acid having a benzene ring and a C2-4 straight-chain saturated lower fatty acid are used as carboxylic acids constituting the calcium complex soap and lithium soap.
  • the grease composition may be obtained by blending 3 to 25 parts by mass of a straight-chain higher fatty acid, 0.5 to 3 parts by mass of an aromatic monocarboxylic acid and 1 to 5 parts by mass of a straight-chain saturated lower fatty acid as base starting materials, based on 100 parts by mass of the total blended amount for the grease composition.
  • the grease composition may include a straight-chain higher fatty acid which is at least one selected from stearic acid, oleic acid, 12-hydroxystearic acid and behenic acid, an aromatic monocarboxylic acid which is at least one selected from benzoic acid and p- toluic acid, and a straight-chain saturated lower fatty acid which is at least one selected from acetic acid and butyric acid.
  • a straight-chain higher fatty acid which is at least one selected from stearic acid, oleic acid, 12-hydroxystearic acid and behenic acid
  • an aromatic monocarboxylic acid which is at least one selected from benzoic acid and p- toluic acid
  • a straight-chain saturated lower fatty acid which is at least one selected from acetic acid and butyric acid.
  • the mass ratio (Li/Ca) of the lithium metal content to the calcium metal content in the thickener starting material may be 1 part per 100 to 5 parts per 100.
  • the method for producing a grease composition may be a method comprising the step of forming lithium- containing calcium complex soap by adding a straight- chain higher fatty acid, an aromatic monocarboxylic acid, a straight-chain saturated lower fatty acid, calcium hydroxide and lithium hydroxide to base oil.
  • the lithium-containing calcium complex grease composition according to the present invention has a high dropping point and maintains a suitable consistency, and in addition to the fact that the composition can be used under a high temperature environment, which was only possible with lithium-based grease or urea grease in the past, the composition exhibits safety, environmental and low-cost effects. Furthermore, the lithium-containing calcium complex grease composition according to the present invention has excellent shear stability, and exhibits thermal stability and long bearing life.
  • the grease composition of the present embodiment includes "base oil” and “thickener” as essential
  • the base oil for use in the grease composition of the present embodiment is not particularly restricted.
  • oil used in general grease compositions such as mineral oil, synthetic oil, animal and vegetable oils or mixed oil thereof may be appropriately selected.
  • base oils belonging to Group 1, Group 2, Group 3, Group 4 and the like in the API (American Petroleum Institute) base oil category may be used singly or as a mixture .
  • Examples of the Group 1 base oil include paraffin- based mineral oils which can be obtained by refining a lubricating oil distillate obtained from an atmospheric distillation of crude oil, by appropriately combining means of solvent refining, hydrotreating, dewaxing or the like.
  • Examples of the Group 2 base oil include paraffin- based mineral oils which can be obtained by refining a lubricating oil distillate obtained from an atmospheric distillation of crude oil, by appropriately combining means of hydrotreating, dewaxing or the like.
  • the Group 2 base oil refined by Gulf's hydrotreating or the like has less than 10 ppm sulphur content and at most 5% aroma content, and may be preferably used in the present invention.
  • Group 3 base oil and Group 2 plus base oil examples include paraffin-based mineral oils which can be manufactured by subjecting a lubricating oil distillate obtained from an atmospheric distillation of crude oil to high hydrogenation refinement, base oils refined by the ISODEWAX process according to which a wax produced by a dewaxing process is converted/dewaxed to isoparaffin, and base oils refined by the Mobil wax isomerisation process, and these oils may also be preferably used in the present embodiment.
  • Examples of synthetic oil include polyolefins, diesters of dibasic acid such as dioctyl sebacate, polyol esters, alkyl benzenes, alkyl naphthalenes, esters, polyoxyalkylene glycols, polyoxyalkylene glycol esters, polyoxyalkylene glycol ethers, polyphenyl ethers, dialkyl diphenyl ethers, fluorine-containing compounds
  • Any olefins may be used, and examples include ethylene, propylene, butene, a- olefins having 5 or more carbon atoms and the like.
  • Polyolefins may be produced by using one of the above- mentioned olefins or two or more of them in combination.
  • so-called poly-a-olefin (PAO) is
  • the oils can be preferably used as the base oil of the present
  • a thickener used in the present embodiment is lithium-containing calcium complex soap obtained by a plurality of carboxylic acids being reacted with a specific base (typical examples are calcium hydroxide and lithium hydroxide) .
  • the term "complex" in the lithium-containing calcium complex soap according to the present embodiment means that a plurality of carboxylic acids are employed.
  • carboxylic acids for the lithium-containing calcium complex soap according to the present embodiment which are (1) higher fatty acid, (2) aromatic monocarboxylic acid and (3) lower fatty acid.
  • carboxylic acid moieties (anion moieties) in the lithium-containing calcium complex soap will be described.
  • a higher fatty acid for use in the present embodiment is a C18-22 straight-chain higher fatty acid (monocarboxylic acid) .
  • the straight-chain higher fatty acid may be unsubstituted or substituted with one or more substituents (for example, a hydroxyl group or the like) .
  • the straight-chain higher fatty acid may be a saturated or unsaturated fatty acid, but is preferably a saturated fatty acid.
  • a saturated fatty acid examples include stearic acid ( octadecanoic acid, C18), tuberculostearic acid ( nonadecanoic acid, C19), arachidic acid (icosanoic acid, C20), henicosanoic acid (C21), behenic acid (docosanoic acid, C22) and hydroxystearic acid (C18, hydrogenated castor oil fatty acid), and examples of an unsaturated fatty acid include oleic acid, linoleic acid, linolenic acid (C18), gadoleic acid, eicosadienoic acid, mead acid (C20), erucic acid, docosadienoic acid (C22) and the like. These acids may be used alone or a number of them may be used in
  • a saturated fatty acid is preferably used in combination.
  • aromatic monocarboxylic acid may be any aromatic monocarboxylic acid.
  • aromatic monocarboxylic acid may be any aromatic monocarboxylic acid.
  • substituents for example, an o-, m- or p-alkyl group, a hydroxy group, an alkoxy group or the like.
  • substituents for example, an o-, m- or p-alkyl group, a hydroxy group, an alkoxy group or the like.
  • Specific examples include benzoic acid, methyl benzoic acid
  • ⁇ toluic acid p-, m-, o- ⁇ , dimethyl benzoic acid (xylyl acid, hemellitic acid, mesitylenic acid) , trimethyl benzoic acid ⁇ prehnitylic acid, durylic acid, isodurylic acid ( ⁇ -, ⁇ -, ⁇ -) ⁇ , 4-isopropylbenzoic acid (cuminic acid), hydroxybenzoic acid (salicylic acid),
  • a lower fatty acid (monocarboxylic acid) for use in the present embodiment is a C2-4 straight-chain saturated lower fatty acid. Specific examples include acetic acid (C2), propionic acid (C3) and butyric acid
  • polytetrafluoroethylene and the like. These may be used alone or in combination of two or more kinds . Apart from the listed examples, any substances capable of imparting thickening effects to a liquid substance may be used.
  • the grease composition of the present embodiment may also include optional additives such as an antioxidant, an anti-rust agent, an oiliness improver, an extreme pressure additive, an anti-wear agent, a solid lubricant, a metal deactivator, a polymer, a metal-based cleaner, a non-metallic cleaner, a colouring agent and a water repellent agent, where the total amount of optional components is about 0.1 to 20 parts by mass based on 100 parts by mass of the total grease composition.
  • optional additives such as an antioxidant, an anti-rust agent, an oiliness improver, an extreme pressure additive, an anti-wear agent, a solid lubricant, a metal deactivator, a polymer, a metal-based cleaner, a non-metallic cleaner, a colouring agent and a water repellent agent, where the total amount of optional components is about 0.1 to 20 parts by mass based on 100 parts by mass of the total grease composition.
  • Examples of an oiliness improver, extreme pressure additive and anti-wear agent include sulphurised zinc dialkyl dithiophosphate , sulphurised zinc diallyl dithiophosphate, sulphurised zinc dialkyl
  • dithiocarbamate an organic molybdenum complex
  • a sulphurised olefin a sulphurised olefin
  • triphenyl phosphate triphenyl phosphorothionate
  • tricresine phosphate other phosphate esters
  • sulphurised fats and oils and the like examples include molybdenum disulphide, graphite, boron nitride, melamine cyanurate, PTFE
  • tungsten disulphide graphite fluoride and the like.
  • metal deactivator examples include N, ' -disalicylidene-1 , 2-diaminopropane,
  • benzotriazole benzimidazole
  • benzothiazole thiadiazole and the like.
  • a polymer examples include polybutene, polyisobutene , polyisobutylene, polyisoprene,
  • Examples of a metal-based cleaner include metal sulphonate, metal salicylate, metal phenate and the like.
  • Examples of a non-metallic cleaner include succinic acid imide and the like.
  • the blended amount of base oil is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, even more preferably 70 to 85 parts by mass, with respect to 100 parts by mass of the total grease composition.
  • the lithium-containing calcium complex soap as the thickener may be blended in an amount of preferably 1 to 40 parts by mass, more preferably 3 to 25 parts by mass, even more preferably 5 to 20 parts by mass, particularly preferably 15 to 20 parts by mass in terms of a starting material base, with respect to 100 parts by mass of the total grease composition.
  • the higher fatty acid in the lithium-containing calcium complex soap may be blended in an amount of 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, even more preferably 5 to 20 parts by mass, with respect to 100 parts by mass of the entire grease composition.
  • the aromatic monocarboxylic acid in the lithium- containing calcium complex soap may be blended in an amount of 0.1 to 5 parts by mass, more preferably 0.5 to
  • the lower fatty acid in the lithium-containing calcium complex soap may be blended in an amount of 0.15 to 7 parts by mass, more preferably 0.5 to 6 parts by mass, even more preferably 1 to 5 parts by mass,
  • the calcium content in the lithium-containing calcium complex soap is 3 to 15 parts by mass, more preferably 5 to 14 parts by mass, even more preferably 8 to 12 parts by mass, with respect to 100 parts by mass of the total thickener starting materials .
  • the lithium content in the lithium-containing calcium complex soap is 0.05 to 1 parts by mass, more preferably 0.1 to 0.6 parts by mass, even more preferably 0.15 to 0.5 parts by mass, with respect to 100 parts by mass of the total thickener starting materials.
  • the mass ratio of the lithium-containing calcium complex soap to the base oil is preferably about 99:1 to 60:40, more preferably about 95:5 to 65:35, even more preferably about 90:10 to 70:30.
  • the mass ratio of the higher fatty acid to the total carboxylic acid amount is preferably about 50 to 90%, more preferably about 60 to 80%, even more preferably about 65 to 75%.
  • the mass ratio of the aromatic monocarboxylic acid to the total carboxylic acid amount is preferably about 1 to 30%, more preferably about 3 to 20%, even more preferably about 5 to 15%. It is thought that with an aromatic monocarboxylic acid ratio of greater than 30%, a grease form cannot be obtained, and with a ratio of less than 1%, thermal resistance cannot be provided.
  • the mass ratio of the lower fatty acid to the total carboxylic acid amount is preferably about 7 to 35%, more preferably about 10 to 30%, even more preferably about 15 to 25%. It is thought that with a lower fatty acid ratio of greater than 35%, a grease form cannot be obtained, and with a ratio of less than 7%, thermal resistance cannot be provided.
  • the mass ratio of the aromatic monocarboxylic acid to the higher fatty acid is preferably about 3:97 to 30:70, more preferably about 5:95 to 25:75, even more preferably about 7:93 to 16:84. It is thought that when the aromatic monocarboxylic acid ratio based on the sum amount of higher fatty acid and aromatic monocarboxylic acid is greater than 30%, a grease form cannot be obtained, and when the ratio is less than 3%, thermal resistance cannot be provided.
  • the mass ratio of the higher fatty acid to the lower fatty acid is preferably about 85:15 to 65:35, more preferably about 83:17 to 70:30, even more preferably about 81:19 to 76:24. It is thought that when the lower fatty acid ratio based on the sum amount of higher fatty acid and lower fatty acid is greater than 35%, a grease form cannot be obtained, and when the ratio is less than 15%, thermal resistance cannot be provided.
  • the mass ratio of the lower fatty acid to the aromatic monocarboxylic acid is preferably about 55:45 to 15:85, more preferably about 50:50 to 20:80, even more preferably about 45:55 to 23:77. It is thought that when the lower fatty acid ratio based on the sum amount of aromatic monocarboxylic acid and lower fatty acid is greater than 90 mass%, a weak thickening effect is produced and a grease form cannot be obtained.
  • the mass ratio (Li/Ca) of the lithium metal content to the calcium metal content in the thickening agent starting material is preferably about 0.3 parts per 100 to 10 parts per 100, more preferably about 0.5 parts per 100 to 7 parts per 100, even more preferably about 1 part per 100 to 5 parts per 100.
  • the numerical value is less than 0.3 parts per 100, there is no improvement in thermal resistance or shear stability, and extension of bearing life at high temperature cannot be expected, so is not preferable.
  • the numerical value is greater than 10 parts per 100, the grease softens and the feeling of body is lost, and then poor rolling stability (shear stability) is produced; it is therefore not preferable.
  • the grease composition of the present embodiment may be produced according to a method generally used for producing grease.
  • the production method is not
  • an example includes a method which involves mixing base oil, a higher fatty acid, a lower fatty acid and an aromatic monocarboxylic acid in a grease manufacturing vessel, and dissolving the contents at a temperature between 60 and 120°C.
  • a composition having a dropping point equal to or higher than 180°C is preferably used, a composition having a dropping point equal to or higher than 220°C is more preferably used, and a composition having a dropping point equal to or higher than 260°C is particularly preferably used.
  • the dropping point herein refers to the temperature at which viscous grease loses the thickener configuration with increase in temperature.
  • the dropping point is measured according to JIS K 2220 8.
  • the consistency of the grease of the present embodiment is preferably Nos . 1 to 4 (175 to 340), more preferably Nos. 2 to 3 (220 to 295) according to the consistency test.
  • the consistency indicates the apparent grease hardness.
  • the consistency is measured by carrying out worked penetration measurements according to JIS K 2220 7.
  • the grease composition of the present embodiment preferably shows an evaporation loss of less than 5% based on the thin film oven test (at 150°C for 24 hours) .
  • the thin film oven test method is described as follows.
  • Comparative Examples 1 to 4 based on 100 parts by mass of the total blended amount in the grease composition, and the test is carried out.
  • Evaporation amount (%) ⁇ (weight before the heat test in g - weight after the heat test in g) /weight before the heat test in g ⁇ ⁇ 100 Oxidation Stability
  • the oxygen pressure loss due to an oxidation reaction according to an oxidation stability test is preferably 40 kPa or less, more preferably
  • the oxidation stability of grease refers to the resistance to oxidation of grease caused by a reaction with oxygen in air.
  • the grease composition deterioration due to
  • a thickener The basic function of a thickener is to hold the base oil and maintain the physical hardness of the grease in order to allow the base oil to stay on the lubrication part of a machine, and at the same time, the thickener plays a role in appropriately supplying the base oil component held by the thickener to sliding faces.
  • this thickener is destroyed by oxidation, the hardness originally possessed by the grease cannot be maintained and the ability to hold the base oil is lost, which base oil then slides off the lubrication part, and a suitable lubrication status cannot be maintained. This occurrence is greatly
  • oxidative degradation accelerates with the increase in temperature.
  • an oxidation product forms, and an increase in viscosity of the base oil content, formation of sludge, destruction of network structure and the like occur, which cause hardening or softening of the grease and cause it to reach the end of its lubrication life.
  • Use of such grease in machines may finally develop into a reduction in the service life of the machines or loss of - In operative reliability. Therefore, the high oxidation stability of the grease composition is extremely
  • the oxidation stability is measured according to JIS2220 12.
  • the grease consistency of the grease composition of the present embodiment after the rolling stability test is preferably 340 or less, more preferably 330 or less, even more preferably 320 or less.
  • the rolling stability test is used to evaluate the shear stability of the grease by measuring the
  • the shear stability of the grease composition is an important element for maintaining the lubrication ability and physical behaviour of the grease. Poor shear stability causes grease to readily escape from the lubrication part of machine, and the required lubrication cannot be provided, which results in shortening of life, and also scattering of grease may occur which pollutes the surrounding area of the machine and impairs the working environment.
  • the rolling stability test which is used to evaluate the shear stability is carried out according to ASTMD 1831.
  • the life according to a grease bearing life test is preferably 200 hours or longer, more preferably 300 hours or longer, even more preferably 400 hours or longer.
  • a grease bearing life test For the bearing life test, 6.0 g of test grease is provided to a 6306 deep-groove radial ball bearing and the test grease-placed bearing is operated with a cycle of 20 hours operation and 4 hours rest at a temperature of 150 °C.
  • the device has a mechanism wherein it stops when the power current of the motor that drives the bearing exceeds a certain level due to the subsequent loss of lubrication function of the grease and the consequent occurrence of poor bearing rotation. The time at which the device stops is read and recorded as the life of the grease.
  • the lubrication life of grease has a great impact on the physical behaviour of grease and on chemical deterioration, and loss in either function has a great impact on the lubrication life. For example, when grease turns into a liquid at high temperature or softens a lot due to shear in the bearing, grease escapes and is lost from the bearing and the lubricating oil
  • the grease lubrication life is measured according to bearing life test ASTMDl 741.
  • the grease composition of the present embodiment can, of course, be used for generally used machines, bearings, gears and the like, and exhibits excellent performance under severe conditions, for example, under high temperature conditions.
  • the grease composition may be preferably used for lubrication of various components in automobiles such as engine
  • peripherals including the starter, alternator and various actuators, the powertrain including the propeller shaft, constant velocity joint (CVJ), wheel bearing and clutch, the electric power steering (EPS), brake unit, ball joint, door hinge, steering wheel, cooling fan motor, brake expander and the like.
  • the grease composition may also be preferably used in various high temperature/heavy duty parts in construction machinery such as a power shovel, bulldozer and crane truck, the steel industry, the papermaking industry, forestry machines, agricultural machines, chemical plants, power- generating facilities, drying furnaces, copying machines, railway vehicles, screw joints of seamless pipes and the like.
  • the composition may also be preferably used for hard disk bearings, plastic
  • the starting materials used in the present Examples and Comparative examples are as follows. Unless otherwise particularly mentioned, the quantities shown in Table 1A were used for Examples 1 to 6 and in Table IB for Comparative Examples 1 to 4.
  • the amount of starting materials shown in Table 1 ⁇ in particular, calcium hydroxide, lithium hydroxide and various carboxylic acids (higher fatty acid, aromatic monocarboxylic acid and lower fatty acid) ⁇ is the amount of reagent. Therefore, the actual component amount in the composition can be calculated on the basis of the numerical values in Tables 1A and IB and the purity described below.
  • Calcium hydroxide special grade reagent having a purity of 96.0%
  • Lithium hydroxide lithium hydroxide monohydrate of special grade reagent having a purity of 98.0%
  • Stearic acid C18 straight-chain alkyl saturated fatty acid, which was provided as a special grade reagent having a purity of 95.0%
  • Behenic acid C22 straight-chain alkyl saturated fatty acid, which was provided as a reagent having a purity of 99.0%
  • Benzoic acid special grade reagent having a purity of 99.5%
  • Para-toluic acid benzoic acid in which the hydrogen at p-position is substituted with a methyl group, which was provided as a special grade reagent having a purity of 98.0%
  • Acetic acid alkyl fatty acid having 2 carbon atoms, which was provided as a special grade reagent having a purity of 99.7%
  • Butyric acid alkyl fatty acid having 4 carbon atoms, which was provided as a special grade reagent having a purity of 98.0%
  • Formic acid alkyl fatty acid having 1 carbon atom, which was provided as a special grade reagent having a purity of 98.0%
  • Base oil A paraffin-based mineral oil obtained by dewaxing solvent refinement, belongs to Group 1, the kinetic viscosity at 100°C was 11.25 mm 2 /s, and the viscosity index was 97
  • Base oil B poly-a-olefin, belongs to Group 4, the kinetic viscosity at 100°C was 6.34 mm 2 /s, and the viscosity index was 136
  • Base oil C paraffin-based mineral oil manufactured by high hydrogenation refinement, belongs to Group 3, the kinetic viscosity at 100°C was 7.603 mm 2 /s, and the viscosity index was 128
  • Base oil D GTL (gas to liquid) oil synthesised by the Fischer-Tropsch process, belongs to Group 3, the kinetic viscosity at 100°C was 7.77 mm 2 /s, kinetic viscosity at 40°C was 43.88 mm 2 /s, and the viscosity index was 148
  • the commercially available all-purpose grease manufactured by Showa Shell Sekiyu K.K. was used.
  • the thickener was lithium 12-hydroxystearate soap, and the base oil was mineral oil-based lubricating oil.
  • the viscosity of the base oil at 100°C was 12.2 mm 2 /s.

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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)
EP13811953.2A 2012-12-21 2013-12-19 Schmierfettzusammensetzung Active EP2935539B1 (de)

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PCT/EP2013/077491 WO2014096258A1 (en) 2012-12-21 2013-12-19 Grease composition

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RU2780670C2 (ru) * 2017-10-02 2022-09-28 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Смазочная композиция

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CN106635348A (zh) * 2016-12-08 2017-05-10 新乡市恒星科技有限责任公司 一种船用螺旋桨润滑脂及其制备方法
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BR112015014520A2 (pt) 2017-07-11
US20150315509A1 (en) 2015-11-05
BR112015014520B1 (pt) 2020-12-15
JP6072532B2 (ja) 2017-02-01
KR20150099565A (ko) 2015-08-31
KR102127029B1 (ko) 2020-06-26
JP2014122282A (ja) 2014-07-03
CN104870620A (zh) 2015-08-26
WO2014096258A1 (en) 2014-06-26
CN104870620B (zh) 2017-11-24

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