EP2373771B1 - Schmierfett für industrielle und kfz-anwendung sowie verfahren zu seiner herstellung - Google Patents
Schmierfett für industrielle und kfz-anwendung sowie verfahren zu seiner herstellung Download PDFInfo
- Publication number
- EP2373771B1 EP2373771B1 EP09830730.9A EP09830730A EP2373771B1 EP 2373771 B1 EP2373771 B1 EP 2373771B1 EP 09830730 A EP09830730 A EP 09830730A EP 2373771 B1 EP2373771 B1 EP 2373771B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- oil
- iso
- grease
- obtaining
- 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.)
- Not-in-force
Links
Images
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
-
- 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
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- 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
- 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
- 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
- C10M2203/108—Residual fractions, e.g. bright stocks
- C10M2203/1085—Residual fractions, e.g. bright stocks 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
-
- 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
- C10M2205/024—Propene
-
- 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
- C10M2205/026—Butene
-
- 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
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
-
- 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
- C10M2207/1276—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 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
-
- 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
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- 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
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/073—Star shaped polymers
-
- 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
- C10N2030/02—Pour-point; 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
- C10N2030/06—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
- C10N2030/08—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
- C10N2030/10—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
- C10N2030/26—Waterproofing or water resistance
-
- 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
-
- 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
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/02—Reduction, e.g. hydrogenation
-
- 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
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- This invention relates to a lubricating grease composition suitable for industrial and automotive uses, and a process for its manufacture.
- the invention relates to a premium multipurpose grease composition exhibiting favorable water resistant properties, high and low temperature performance, and which is suitable for use in both industrial and automotive applications.
- a lubricating grease In North America and other northern climates, it is desirable for a lubricating grease to exhibit good performance over a wide range of temperatures. In addition, industrial greases often require good performance in wet environments. Testing methods and performance criteria established by the National Lubricating Grease Institute (NLGI) have become industry-wide accepted standards. These standards include greases for use in automotive applications. It is therefore desirable for lubricating grease to meet NLGI grade classification. Preferably, such greases should be multipurpose, being suitable for industrial applications and meet NLGI grade classification for automotive application. For instance, WO 2005/090531 and EP 0 405 893 A2 disclose grease compositions having good water resistance.
- NLGI National Lubricating Grease Institute
- this invention relates to a premium multipurpose lubricating grease suitable for industrial and automotive uses, and a process for making the same.
- a lubricating grease composition comprising, based on the overall grease composition:
- a method for making a lubricating grease comprises: (a) obtaining at least one bright stock Group I oil, (b) obtaining at least one naphthenic Group V oil, (c) obtaining at least one ISO 68 Group I oil, (d) obtaining at least one ISO 100 Group II oil, (e) obtaining a hydrophilic copolymer containing a styrene and a carboxylic acid, an anhydride or an ester, (f) obtaining a soap thickener, (g) obtaining an antioxidant, and (h) mixing, based on the overall grease composition, 30 to 40 wt% of the at least one bright stock Group I oil (a), 5 to 15 wt% of the at least one naphthenic Group V oil (b), 5 to 10 wt% of the at least one ISO 68 Group I oil (c), 20 to 30 wt% of the least one ISO 100 Group II oil (d), 2 to 6 wt% of the polymer (e)
- Various lubricating oils can be employed in preparing the grease compositions of the present invention. Applicants have found that using oils of a certain type during the cooking phase of the grease preparation, and oils of a different type during the finishing phase achieved a grease with favorable properties. Another embodiment of the present invention is the inclusion of a polymer that imparts excellent water resistance properties without compromising the low temperature performance of the grease. Applicants have found that using a hydrophilic polymer provided favorable properties.
- Groups I, II, III, IV and V are broad categories of base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils.
- Group I base stocks generally have a viscosity index of between about 80 to 120 and contain greater than about 0.03% sulfur and/or less than about 90% saturates.
- Group II base stocks generally have a viscosity index of between about 80 to 120, and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates.
- Group III stock generally has a viscosity index greater than about 120 and contains less than or equal to about 0.03 % sulfur and greater than about 90% saturates.
- Group IV includes polyalphaolefins (PAO).
- Group V base stocks include base stocks not included in Groups I-IV. Table 1 summarizes properties of each of these five groups. Table 1: Base Stock Properties Saturates Sulfur Viscosity Index Group I ⁇ 90% and/or > 0.03% and ⁇ 80 and ⁇ 120 Group II ⁇ 90% and ⁇ 0.03% and ⁇ 80 and ⁇ 120 Group III ⁇ 90% and ⁇ 0.03% and ⁇ 120 Group IV Polyalphaolefins (PAO) Group V All other base oil stocks not included in Groups I, II, III, or IV
- the base stocks include at least one base stock of synthetic oils.
- Synthetic oil for purposes of this application shall include all oils that are not naturally occurring mineral oils.
- lubricating oils will typically comprise between 50 - 90 wt% of the overall grease composition. These oils will typically combine to provide an overall viscosity of the grease in the range of ISO 100 to ISO 320.
- the preferred viscosity for the present invention is between ISO 150 to ISO 275, with ISO 220 being the most preferred.
- the lubricating oils used as the base stock in the cooking phase of the manufacturing process are at least one bright stock Group I oil and at least one naphthenic Group V oils. These oils will have a preferred viscosity in the range of 200 to 1400 cSt at 40°C, with a range of 200 to 500 cSt at 40°C being most preferred.
- a combination of heavy naphthenic oil and a bright stock are used as the base stock during the cooking phase, with 5-15 wt% heavy naphthenic oil and 30 - 40 wt% bright stock.
- the use of Group II oils during the cooking phase should be limited or avoided altogether.
- a combination of 5 - 10 wt% of an ISO 68 Group I and 20 - 30 wt% of an ISO 100 Group II are used during the finishing phase.
- Various other oils in smaller amounts may also be incorporated during the finishing phase.
- the grease composition will also contain a soap thickener dispersed in the lubricating oil during the cooking phase to form a base grease.
- the soap thickener will comprise between 5% and 15% of the overall grease composition weight.
- the particular thickener employed is not critical and can vary broadly provided that it is effectively water insoluble.
- the thickener may be based on aluminum, barium, calcium or lithium soaps, or their complexes.
- Soap thickeners may be derived from a wide range of animal oils, vegetable oils and greases, as well as the fatty acids derived therefrom. Carbon black, silica, and clays may be used as well as dyes, polyureas and other organic thickeners. Pyrrolidone-based thickeners can also be used.
- Preferred thickeners are based on lithium soap, calcium soap, their complexes, or mixtures thereof. Particularly preferred is a lithium or lithium complex thickener derived from reacting a C-18 fatty acid (12-hydroxy stearic acid) and a C-9 dicarboxylic acid (azelaic acid) with lithium hydroxide monohydrate.
- Canadian Patent 996537 provides a process for making this preferred thickener.
- a mixture of Group I and Group V oils and a lithium soap of a C 12 to C 24 hydroxy fatty acid is first prepared. Then a C 2 to C 12 aliphatic carboxylic acid is added to that mixture and converted to its dilithium soap under conditions that are suitable for the formation of a complex between the lithium soap of the dicarboxylic acid and the lithium soap of the hydroxy fatty acid. While the lithium soap of the hydroxy fatty acid could be preformed and then dispersed in the lubricating oil medium, it is generally more expedient to prepare that soap in situ in the lubricating oil by neutralizing the hydroxy fatty acid with lithium base.
- the usual procedure during the cooking phase is to charge into the grease kettle the Group I and Group V oils and to then add the hydroxy fatty acid.
- the mixture of fatty acid and oil is heated sufficiently to bring about the dissolving action, e.g. at 82 to 93°C (180 to 200°F ) .
- a concentrated aqueous solution of the lithium base is added, usually in an amount slightly in excess of that required to neutralize the acid.
- the temperature at this stage of the cooking phase is usually between 93 to 99°C (200 and 210°F ) .
- the rate of addition of the lithium base may be varied.
- the temperature of the mixture of the Group I and Group V oils and lithium soap of the hydroxy fatty acid be raised to between 121 to 149°C (250 and 300°F ) . This is done in order to bring about a substantial dehydration of the mixture, such as, the removal of 70 to 100% of the water.
- the temperature of the grease mixture is once again raised in order to bring about dehydration. Preferably this will take place at 138 to 149°C (280 to 300°F ) .
- the temperature of the mixture should further be raised to preferably between 193 to 204°C (380 and 400°F ) .
- the soap stock is then cooled during the finishing phase of the grease preparation. Finishing oils, including Group II oils and various other lubricating oils, may be added into the mixture at this point. Mixing may continue until the grease has reached ambient temperatures. When the temperature has been lowered to about 65°C (150°F), other grease additives can be introduced as would be understood by persons skilled in the art.
- one embodiment contemplates the inclusion of a polymer.
- Various polymers may be used in greases, although the precise impact of any given polymer on a given grease cannot be predicted. Applicants have found that the use of a hydrophilic copolymer was important in achieving excellent water resistance properties.
- maleic anhydride styrene esterified copolymer is used, with the preferred amount being between 2 and 6 wt% of the overall grease.
- the polymer may be incorporated during either the cooking phase or finishing phase of the grease preparation.
- the preferred styrene maleic anhydride ester (SMAE) copolymer is unique from other polymer examples because it contains oxygen groups.
- the structure of the SMAE copolymer (shown below) has exposed hydroxyl and carbonyl groups that can act as hydrogen bond donors (former) and acceptors (latter).
- the SMAE copolymer is more hydrophilic than strictly hydrocarbon-based copolymers such as styrene isoprene and styrene isobutylene.
- Equation 1 shows the chemical structure of the SMA ester and the esterification of styrene maleic anhydride copolymer to form a SMA ester and the resulting chemical structure of the SMA ester.
- the grease structure is a type of soap. The ability of the soap to dissolve in waters varies. Preferably, the grease soap should not readily dissociate in contact with water.
- the grease soap structure is held together with a variety of bonds, including ionic bonds with the metal, hydrogen bonds within the oxygen-rich triglyceride and the ester function of 12-hydroxy stearic acid (once incorporated into the structure) and van der Waals interactions between the C-C side chains.
- bonds including ionic bonds with the metal, hydrogen bonds within the oxygen-rich triglyceride and the ester function of 12-hydroxy stearic acid (once incorporated into the structure) and van der Waals interactions between the C-C side chains.
- a polymer that incorporates or binds water molecules into its structure may enhance the water resistance performance of a grease.
- Hydrogen bonding capability present in certain copolymers can improve their ability to incorporate or bind water molecules into their respective structures.
- the water resistance performance of a grease may be improved where the copolymer provides preferential binding of the water, such as, the attraction of water to the copolymer, through hydrogen bonding, is stronger than the attraction of water to the grease structure.
- the grease may also contain small amounts of supplemental additives, which include antioxidants, anti-wear agents and other additives.
- supplemental additives include antioxidants, anti-wear agents and other additives.
- Specific antioxidants employed are not critical and can vary broadly to achieve favorable properties. A combination of a Group II oil and diphenylamine antioxidant was found to enhance the oxidation life of the grease, while achieving good high temperature performance.
- Antioxidants will typically comprise less than 5 wt% of the overall grease composition.
- the total amount of all additives, including the antioxidant will typically be between 2 - 10wt% of the overall grease.
- a person skilled in the art will recognize the benefits of adding specific additives to the grease disclosed herein to achieve favorable properties.
- the examples in table 2 below disclose various screening tests for the influence of the base oils and thickener on overall grease performance.
- the grease performance tests include water spray-off, low temperature torque, fretting wear and wheel bearing life.
- Table 3 below discloses screening test for the influence of the polymer selection and concentration on overall grease performance. These tests includes water spray-off, wet roll, water washout, low temperature torque, fretting wear, wheel bearing life and apparent viscosity.
- Table 4 discloses screening tests for the influence of various antioxidants on grease performance for wheel bearing life. The results of Table 4 demonstrate that a combination of an ISO 100 Group II base oil and a diphenylamine antioxidant achieved good high temperature performance and oxidation life.
- Table 4 EXAMPLE # 1 * 19 * 20 * 21 22 BATCH # Invention 12-52-07 GR1004-156-2 GR1004-156-3 GR1004-156-1 Batch 8 GR1004-152 BASE OILS ISO 100 Group II 24 24 24 24 24 0 Heavy Naphthenic 10.2 10.2 10.2 10.2 11.7 ISO 68 Group I 8.7 8.7 8.7 16.6 Bright Stock 35.6 35.6 35.6 35.6 47.5 ISO 22 Naphthenic 0 0 0 0 4.1 ADDITIVES Polymer A 3 3 3 3 3 3 3 3 3 Antioxidant (diphenylamine) 1.5 0.76 0.30 0 1.5 PERFORMANCE Wheel Bearing Life, D3527, hr (125 min.) 153 134 130 80 47 LEGEND Base Oil
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Claims (6)
- Schmierfettzusammensetzung, die, bezogen auf die gesamte Fettzusammensetzung:(a) 30 bis 40 Gew.-% mindestens eines Bright Stock - Gruppe I Öls;(b) 5 bis 15 Gew.-% mindestens eines naphthenischen Gruppe V Öls;(c) 5 bis 10 Gew.-% mindestens eines ISO 68 Gruppe I Öls,(d) 20 bis 30 Gew.% mindestens eines ISO 100 Gruppe II Öls;(e) 2 bis 6 Gew.-% hydrophiles Copolymer, das ein Styrol und Carbonsäure, Anhydrid oder Ester enthält;(f) 5 bis 15 Gew.-% Seifenverdicker und(g) Antioxidansumfasst;
wobei
der Seifenverdicker (f) in dem mindestens einen Bright Stock Gruppe I Öl (a) und dem mindestens einen naphthenischen Gruppe V Öl (b) während einer Kochphase dispergiert wird, und
das mindestens eine ISO 68 Gruppe I Öl (c) und das mindestens eine ISO 100 Gruppe II Öl (d) während einer Endbehandlungsphase eingeführt werden. - Fett nach Anspruch 1, bei dem das Copolymer Styrol/Maleinsäureanhydridester ist.
- Fett nach einem der vorhergehenden Ansprüche, bei dem der Verdicker sich von der Umsetzung einer Mischung einer C12-bis C24-Hydroxyfettsäure und einer C2- bis C12-Dicarbonsäure mit einer Lithiumbase ableitet.
- Fett nach Anspruch 1, bei dem das Antioxidans ein auf Amin basierendes Antioxidans ist.
- Fett nach Anspruch 1, bei dem das Antioxidans Diphenylamin ist.
- Verfahren zur Herstellung eines Schmierfetts, wobei das Verfahren umfasst:(a) Bereitstellen mindestens eines Brigth Stock Gruppe I Öls,(b) Bereitstellen mindestens eines naphthenischen Gruppe V Öls,(c) Bereitstellen mindestens eines ISO 68 Gruppe I Öls,(d) Bereitstellen mindestens eines ISO 100 Gruppe II Öls,(e) Bereitstellen eines hydrophilen Copolymers, das ein Styrol und Carbonsäure, Anhydrid oder Ester enthält,(f) Bereitstellen eines Seifenverdickers,(g) Bereitstellen eines Antioxidans und(h) Mischen, bezogen auf die Gesamtfettzusammensetzung, von 30 bis 40 Gew.-% des mindestens einen Brigth Stock (a), 5 bis 15 Gew.-% des mindestens einen naphthenischen Öls (b), 5 bis 10 Gew.-% des mindestens einen ISO 68 Gruppe I Öls (c), 20 bis 30 Gew.-% des mindestens einen ISO 100 Gruppe II Öls (d), 2 bis 6 Gew.-% des Polymers (e), 5 bis 15 Gew.-% des Seifenverdickers (f) und des Antioxidans (g) um ein Fett zu bilden, wobeider Verdicker (f) in dem mindestens einen Brigth Stock Gruppe I Öl (a) und dem mindestens einen naphthenischen Gruppe V Öl (b) während einer Kochphase dispergiert wird und
das mindestens eine ISO 68 Gruppe I Öl (c) und das mindestens eine ISO 100 Gruppe II Öl (d) während einer Endbehandlungsphase eingeführt werden.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US20096508P | 2008-12-05 | 2008-12-05 | |
PCT/US2009/006387 WO2010065130A1 (en) | 2008-12-05 | 2009-12-04 | Industrial and automotive grease and process for its manufacture |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2373771A1 EP2373771A1 (de) | 2011-10-12 |
EP2373771A4 EP2373771A4 (de) | 2012-07-04 |
EP2373771B1 true EP2373771B1 (de) | 2014-02-12 |
Family
ID=42233524
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09830730.9A Not-in-force EP2373771B1 (de) | 2008-12-05 | 2009-12-04 | Schmierfett für industrielle und kfz-anwendung sowie verfahren zu seiner herstellung |
Country Status (4)
Country | Link |
---|---|
US (1) | US20110059879A1 (de) |
EP (1) | EP2373771B1 (de) |
CA (1) | CA2743826C (de) |
WO (1) | WO2010065130A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106047458A (zh) * | 2016-05-31 | 2016-10-26 | 安徽潜山轴承制造有限公司 | 一种环保型轴承润滑脂组合物 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6841547B2 (ja) * | 2017-01-18 | 2021-03-10 | 出光興産株式会社 | グリース組成物及びその製造方法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3791973A (en) * | 1971-02-24 | 1974-02-12 | Exxon Research Engineering Co | Grease thickened with lithium soap of hydroxy fatty acid and lithium salt of aliphatic dicarboxylic acid |
JPS59204695A (ja) * | 1983-05-10 | 1984-11-20 | Idemitsu Kosan Co Ltd | リチウム系グリ−スおよびその製造方法 |
US5110490A (en) * | 1989-06-27 | 1992-05-05 | Exxon Research And Engineering Company | Water resistant grease composition |
US6300288B1 (en) * | 1994-03-31 | 2001-10-09 | The Lubrizol Corporation | Functionalized polymer as grease additive |
US5707943A (en) * | 1996-12-16 | 1998-01-13 | The Lubrizol Corporation | Mixtures of esterified carboxy-containing interpolymers and lubricants containing them |
US5880074A (en) * | 1997-01-09 | 1999-03-09 | Dishong; Dennis M. | Additive concentrates containing mixtures of organic diluents and esterified carboxy-containing interpolymers and lubricants containing them |
US20040018946A1 (en) * | 2002-07-26 | 2004-01-29 | Aoyagi Edward I. | Method of improving the frictional properties of functional fluids |
EP1546292B1 (de) * | 2002-10-01 | 2009-01-14 | The Lubrizol Corporation | Herstellung von Schmiermitteln aus Metallhydroxid enthaltenden entwässerten Emulsionen |
US7141157B2 (en) * | 2003-03-11 | 2006-11-28 | Chevron U.S.A. Inc. | Blending of low viscosity Fischer-Tropsch base oils and Fischer-Tropsch derived bottoms or bright stock |
US20050209114A1 (en) * | 2004-03-19 | 2005-09-22 | The Lubrizol Corporation, A Corporation Of The State Of Ohio | Functionalized polymer composition for grease |
BRPI0717456A2 (pt) * | 2006-10-19 | 2013-12-24 | Shell Int Research | Composição de óleo elétrico, e, uso da composição |
-
2009
- 2009-12-04 CA CA2743826A patent/CA2743826C/en not_active Expired - Fee Related
- 2009-12-04 US US12/592,922 patent/US20110059879A1/en not_active Abandoned
- 2009-12-04 WO PCT/US2009/006387 patent/WO2010065130A1/en active Application Filing
- 2009-12-04 EP EP09830730.9A patent/EP2373771B1/de not_active Not-in-force
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106047458A (zh) * | 2016-05-31 | 2016-10-26 | 安徽潜山轴承制造有限公司 | 一种环保型轴承润滑脂组合物 |
Also Published As
Publication number | Publication date |
---|---|
EP2373771A1 (de) | 2011-10-12 |
CA2743826C (en) | 2016-12-20 |
CA2743826A1 (en) | 2010-06-10 |
WO2010065130A1 (en) | 2010-06-10 |
EP2373771A4 (de) | 2012-07-04 |
US20110059879A1 (en) | 2011-03-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU673385B2 (en) | Lubricating grease compositions | |
CN105733753A (zh) | 一种润滑脂组合物、其制备方法及应用 | |
KR102263290B1 (ko) | 복합 칼슘 술포네이트 그리스의 제조 방법 | |
US20120004153A1 (en) | Lithium Complex Grease with Improved Thickener Yield | |
WO2007102266A1 (ja) | グリース組成物及び軸受 | |
EP2373771B1 (de) | Schmierfett für industrielle und kfz-anwendung sowie verfahren zu seiner herstellung | |
CN109266420A (zh) | 一种改性复合磺酸钙润滑脂的组合物及制备方法 | |
CN108531264B (zh) | 用于汽车车门玻璃升降器的润滑脂及其制备方法 | |
WO2012076638A9 (en) | Polymer thickened grease compositions with improved low friction properties | |
KR102118917B1 (ko) | 과염기성 설포네이트 개질된 리튬 카복실레이트 그리스의 조성물 및 과염기성 설포네이트 개질된 리튬 카복실레이트 그리스의 제조 방법 | |
CN103060059A (zh) | 一种抗氧剂组合物和润滑油组合物 | |
JPH0118120B2 (de) | ||
CN112608780B (zh) | 一种低气味汽车润滑脂组合物及其制备方法 | |
EP3060635B1 (de) | Verwendung von calcium salicylat zur verbesserung der rollstabilität in einer fettzusammensetzung | |
US11629307B2 (en) | Grease compositions and a method for making the same | |
KR20080049460A (ko) | 윤활 그리스 조성물 | |
CN117603751B (zh) | 一种长寿命环保型成型加工切削油及其制备方法 | |
CN115710525B (zh) | 一种中碱值复合磺酸钙润滑脂组合物及其制备方法 | |
RU2391386C1 (ru) | Пластичная смазка | |
CN104560277B (zh) | 一种环烷酸钙锆基润滑脂及其制备方法 | |
CN107916161A (zh) | 一种陶瓷抛光机传动轴承润滑脂组合物 | |
CN115806853B (zh) | 一种高质量环保型铝轧制油及其制备方法 | |
CN112795422B (zh) | 一种润滑脂及其制备方法 | |
CN112795421B (zh) | 一种钙基润滑脂及其制备方法 | |
EP4389858A1 (de) | Gemischte schmierfettzusammensetzung auf komplexbasis und verfahren zur herstellung davon |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20110704 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20120601 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C10N 30/02 20060101ALN20120525BHEP Ipc: C10M 169/06 20060101AFI20120525BHEP Ipc: C10N 30/08 20060101ALN20120525BHEP Ipc: C10M 177/00 20060101ALI20120525BHEP Ipc: C10N 50/10 20060101ALN20120525BHEP Ipc: C10N 30/06 20060101ALN20120525BHEP Ipc: C10M 169/00 20060101ALI20120525BHEP Ipc: C10N 30/10 20060101ALN20120525BHEP Ipc: C10N 20/02 20060101ALN20120525BHEP Ipc: C10N 10/02 20060101ALN20120525BHEP Ipc: C10N 70/00 20060101ALN20120525BHEP |
|
17Q | First examination report despatched |
Effective date: 20130109 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C10N 70/00 20060101ALN20130613BHEP Ipc: C10N 30/02 20060101ALN20130613BHEP Ipc: C10N 30/06 20060101ALN20130613BHEP Ipc: C10M 169/00 20060101ALI20130613BHEP Ipc: C10M 177/00 20060101ALI20130613BHEP Ipc: C10N 10/02 20060101ALN20130613BHEP Ipc: C10N 20/02 20060101ALN20130613BHEP Ipc: C10M 169/06 20060101AFI20130613BHEP Ipc: C10N 50/10 20060101ALN20130613BHEP Ipc: C10N 30/08 20060101ALN20130613BHEP Ipc: C10N 30/10 20060101ALN20130613BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20130723 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602009021868 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: C10M0111040000 Ipc: C10M0169060000 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C10N 70/00 20060101ALN20131031BHEP Ipc: C10N 30/10 20060101ALN20131031BHEP Ipc: C10N 30/06 20060101ALN20131031BHEP Ipc: C10N 50/10 20060101ALN20131031BHEP Ipc: C10M 169/00 20060101ALI20131031BHEP Ipc: C10M 177/00 20060101ALI20131031BHEP Ipc: C10M 169/06 20060101AFI20131031BHEP Ipc: C10N 30/02 20060101ALN20131031BHEP Ipc: C10N 30/08 20060101ALN20131031BHEP Ipc: C10N 20/02 20060101ALN20131031BHEP Ipc: C10N 10/02 20060101ALN20131031BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
INTG | Intention to grant announced |
Effective date: 20131212 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 652165 Country of ref document: AT Kind code of ref document: T Effective date: 20140215 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602009021868 Country of ref document: DE Effective date: 20140327 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20140212 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 652165 Country of ref document: AT Kind code of ref document: T Effective date: 20140212 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140512 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140612 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140612 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602009021868 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20141113 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602009021868 Country of ref document: DE Effective date: 20141113 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141204 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20150831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20141204 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20141231 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20141231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20141231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140513 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20091204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140212 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20181114 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20181129 Year of fee payment: 10 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602009021868 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20191204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191204 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200701 |