EP1427801A1 - Verwendung von o/w-emulsionen zur kettenschmierung - Google Patents
Verwendung von o/w-emulsionen zur kettenschmierungInfo
- Publication number
- EP1427801A1 EP1427801A1 EP02799361A EP02799361A EP1427801A1 EP 1427801 A1 EP1427801 A1 EP 1427801A1 EP 02799361 A EP02799361 A EP 02799361A EP 02799361 A EP02799361 A EP 02799361A EP 1427801 A1 EP1427801 A1 EP 1427801A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- emulsion
- use according
- radical
- weight
- carbon atoms
- 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
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Classifications
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- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/34—Esters of monocarboxylic acids
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- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/18—Ethers, e.g. epoxides
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- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/40—Esters containing free hydroxy or carboxyl groups
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- 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
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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- 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
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/30—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
- C10M173/025—Lubricating compositions containing more than 10% water not containing mineral or fatty oils for lubricating conveyor belts
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- 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
- C10M2205/18—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras
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- 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
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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- 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
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
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- 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
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
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- 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
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- 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
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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- 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
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
- C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids used as base material
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- 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
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- 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
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- 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
- C10M2207/40—Fatty vegetable or animal oils
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- 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
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
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- 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
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- 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
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- 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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/046—Siloxanes with specific structure containing silicon-oxygen-carbon bonds
- C10M2229/0465—Siloxanes with specific structure containing silicon-oxygen-carbon bonds used as base material
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- 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
- C10N2040/38—Conveyors or chain belts
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- 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
- C10N2050/01—Emulsions, colloids, or micelles
- C10N2050/013—Water-in-oil
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- 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
- C10N2060/06—Chemical after-treatment of the constituents of the lubricating composition by epoxydes or oxyalkylation reactions
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- 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
- C10N2070/02—Concentrating of additives
Definitions
- the present invention relates to the use of an O / W emulsion, in particular a PIT emulsion, for the lubrication of conveyor belt systems in food processing plants and a lubricant concentrate based on wax ester.
- the containers to be filled in the filling plants are transported by means of conveyors of various designs and materials, for example by means of plate conveyor belts or chain-like arrangements, which are generally referred to below as transport chains.
- the transporters establish the connection between the various optional treatment stages of the filling process, such as B. Unpacker, bottle washer, filler, capper, labeler, packer, etc.
- the containers can be of various shapes, in particular glass and plastic bottles, cans, glasses, barrels, beverage containers (KEG), paper and cardboard containers.
- KEG beverage containers
- the transport chains must be lubricated in a suitable manner so that excessive friction against the containers is avoided. Diluted aqueous solutions containing suitable friction-reducing agents are usually used for lubrication.
- the transport chains are brought into contact with the aqueous solutions, for example by immersion or spraying, in which case one speaks of splash lubrication systems or automatic belt lubrication systems or central chain lubrication systems.
- the chain lubricants previously used as lubricants are mostly based on fatty acids in the form of their water-soluble alkali or alkanolamine salts or on fatty amines, preferably in the form of their organic or inorganic salts. While both substance classes can be used without problems in splash lubrication, they show a number of disadvantages in the central chain lubrication systems that are common today. For example, DE-A-23 13 330 describes soap-based lubricants, the aqueous mixtures of and contain surface-active substances. Such soap-based lubricants have the following disadvantages:
- Soap-based lubricant preparations continue to be dependent on water temperature.
- Soap-based lubricants only have a low storage stability, especially at low temperatures.
- the EDTA ethylenediaminetetraacetate contained in many products is known to be poorly biodegradable. 12. Such soap-based lubricant preparations are not suitable for all transport goods made of plastic, since in many cases stress corrosion cracking on the transport goods occurs when these agents are used.
- DE-A-36 31 953 describes a method for lubricating chain-shaped bottle conveyor belts in beverage filling companies, in particular in breweries, and for cleaning the belts using a liquid cleaning agent, which is characterized in that the chain-shaped bottle conveyor belts are based on belt lubricants neutralized primary fatty amines, which preferably have 12 to 18 carbon atoms and contain an unsaturated fraction of more than 10%.
- R1 is a saturated or unsaturated, branched or linear alkyl group with 8 to 22 C atoms
- R 2 is hydrogen, an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms or
- A is a linear or branched alkylene group with 1 to 8 carbon atoms
- a ⁇ is a linear or branched alkylene group having 2 to 4 carbon atoms.
- DE-A-39 05 548 discloses lubricants based on N-alkylated fatty amine derivatives which contain at least one secondary and / or tertiary amine.
- R is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, which may be replaced by -OH, - NH 2 , -NH-, -CO-, - (CH 2 CH 2 O) r or - (CH 2 CH 2 CH 2 O) r may be substituted,
- R 2 only if M represents a negative charge for hydrogen, an alkyl radical with 1 to 4 C atoms, or a hydroxyalkyl radical with 1 to 4 C atoms,
- R 3 is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 1 to 12 carbon atoms, which may be replaced by -OH, - NH 2 , -NH-, -CO-, - (CH 2 CH 2 O) r or - (CH 2 CH 2 CH 2 O) may be substituted,
- R 4 represents a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, which may have at least one amine, imine, hydroxyl, halogen and / or carboxy radical as substituent, a substituted or unsubstituted phenyl radical which may have at least one amine, imine, hydroxyl, halogen, carboxy and / or a linear or branched, saturated or mono- or polyunsaturated alkyl radical with 6 to 22 C atoms as substituents,
- R 5 for hydrogen or - independently of R 4 - for a radical R 4 ,
- X stands for an anion from the group amidosulfonate, nitrate, halide, sulfate, hydrogen carbonate, carbonate, phosphate or R 6 -COO " ,
- R 8 represents hydrogen, a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 carbon atoms or alkenyl radical having 2 to 20 carbon atoms, which may have at least one hydroxyl, amine or imine radical as a substituent, or one substituted or unsubstituted Phe- nyl radical, which may have an alkyl radical with 1 to 20 C atoms as a substituent, and
- R 7 and R 8 each independently of one another represent a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 C atoms or alkenyl radical having 2 to 20 C atoms, which may have at least one hydroxyl, amine or imine radical as substituents, or a substituted or unsubstituted phenyl radical, which may have an alkyl radical with 1 to 20 C atoms as substituents,
- M for hydrogen, alkali metal, ammonium, an alkyl radical with 1 to 4 carbon atoms, a benzyl radical or a negative charge
- n for an integer in the range from 1 to 12
- m for an integer in the range from 0 to 5 and
- I stands for a number in the range from 0 to 5, containing alkyldimethylamine oxides and / or alkyl oligoglycosides as nonionic
- EP-B-629 234 discloses a lubricant combination consisting of a) one or more compounds of the formula
- R1 is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, which can optionally be substituted by -OH, -NH 2 , -NH-, -CO-, halogen or a carboxyl radical
- R 2 represents a carboxyl radical with 2 to 7 C atoms
- M for hydrogen, alkali metal, ammonium, an alkyl radical with 1 to 4 C-
- Atoms or a benzyl radical and n is an integer in the range from 1 to 6, b) at least one organic carboxylic acid selected from monobasic or polybasic, saturated or mono- or polyunsaturated carboxylic acids having 2 to 22 carbon atoms, c) optionally water and Additives and / or auxiliaries.
- WO 94/03562 describes a lubricant concentrate based on fatty amines and, if appropriate, customary diluents or auxiliaries or additives, characterized in that it contains at least one polyamine derivative of a fatty amine and / or a salt of such an amine, the proportion of which is mentioned Polyamine derivatives of fatty amines on the total formulation is 1 to 100% by weight.
- this lubricant concentrate contains at least one polyamine derivative of a fatty amine of the general formula
- R is a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, the substituents being selected from amino, imino, hydroxy, halogen and carboxy, or a substituted or unsubstituted phenyl radical, where the Substituents are selected from amino, imino, hydroxyl, halogen, carboxy and a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms;
- the application DE 199 42 535.3 provides lubricants based on polyhydroxy compounds which are hydrophilic due to their molecular structure and at the same time improve the lubricating performance compared to the amines usually used as lubricants.
- Polyhydroxy compounds selected from alkanediols or alkanetriols, very particularly preferably glycerol, or their polymers and their esters and ethers are mentioned as particularly preferred.
- the present invention relates to the use of an O / W emulsion in concentrated form or after dilution with water for lubricating conveyor belts in food factories.
- phase inversion oil-in-water emulsions, henceforth called O / W emulsions, which are produced and stabilized with nonionic emulsifiers, undergo phase inversion when heated.
- This process of phase inversion means that the outer, aqueous phase becomes the inner phase at higher temperatures.
- This process is usually reversible, which means that the original emulsion type regresses when it cools down.
- position of the phase inversion temperature depends on many factors, for example the type and phase volume of the oil component, the hydrophilicity and the structure of the emulsifier or the composition of the emulsifier system, compare, for example, K. Shinoda and H.
- German patent application DE-OS-38 19 193 describes a process for producing low-viscosity O / W emulsions of polar oil components, which is based on the phase inversion temperature (PIT) method.
- phase inversion temperatures below 100 ° C. are achieved in that, in addition to nonionic emulsifiers, further co-emulsifiers are present. It has been found, however, that only oils with a dipole moment above 1.96 D can be obtained using this process in the form of coarse dispersions. This is in line with the publication by T Förster, F. Schambil and H.
- WO 93/11865 presents an improved process for producing finely dispersed and long-term stable O / W emulsions based on oil mixtures with a high proportion of polar oil components.
- a method was provided with which finely dispersed and storage-stable O / W emulsions based on oils with a dipole moment above 1.96 D can be produced.
- O / W emulsions based on polar oil bodies and nonionic emulsifiers are particularly fine and long-term stable if a mixture of polar oil, nonionic emulsifier and a special interface moderator is heated to a temperature within or above the phase inversion temperature range heated - or produces the emulsion at this temperature - and then cools the emulsion to a temperature below the phase inversion temperature range and, if necessary, further dilutes it with water.
- WO 93/11865 then claims a process for the preparation of oil-in-water emulsions of polar oil bodies (A), in which
- (D) 0.01 to 50 wt .-% of an interface moderator, which is selected from the group of tocopherols, Guerbet coal with 16 to 20 carbon atoms or a steroid with 1 to 3 OH groups in the presence of 8 to Emulsified 85% by weight of water at a temperature above the melting point of the mixture of components (A) to (D) and heated the emulsion to a temperature within or above the phase inversion temperature range - or produced the emulsion at this temperature - and then the emulsion to a temperature below the phase inversion sions temperature range cools and optionally further diluted with water.
- an interface moderator which is selected from the group of tocopherols, Guerbet coal with 16 to 20 carbon atoms or a steroid with 1 to 3 OH groups in the presence of 8 to Emulsified 85% by weight of water at a temperature above the melting point of the mixture of components (A) to (D) and heated the emulsion to a
- the oil-in-water emulsions produced by the PIT process are used e.g. as skin and body care products, as cooling lubricants or as textile and fiber auxiliaries. They are particularly preferred in processes for the preparation of emulsion-like preparations for skin and hair treatment.
- the O / W emulsion contains at least one wax ester.
- Wax esters are to be understood as esters of long-chain carboxylic acids with long-chain alcohols, which preferably follow the formula (1)
- R 1 CO represents a saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms and R 2 represents an alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms.
- Type- ical examples are esters of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid as well as their technical mixtures with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselyl alcohol, oleolol alcohol alcohol,
- cetyl palmitate, cetyl stearate, Cetylisostearat are cetyl oleate, cetyl behenate, Cetylerucat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate, Stearylerucat, Isosteraylpalmitat, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearylerucat, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbe- henate, olerlerucate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl oleate and mixtures
- the O / W emulsion to be used according to the invention preferably contains at least one further component selected from the groups of a) triglycerides, b) partial glycerides, or c) fatty alcohol polyglycol ethers, or any mixture of the components a) to c) mentioned.
- Triglycerides are substances of the formula (2)
- R 3 CO, R 4 CO and R 5 CO independently of one another for linear or branched, saturated and / or unsaturated, optionally hydroxyl and / or epoxy-substituted acyl radicals having 6 to 22, preferably 12 to 18 carbon atoms and the sum (m + n + p) stands for 0 or numbers from 1 to 100, preferably 20 to 80.
- the triglycerides can be of natural origin or can be produced synthetically.
- hydroxy- and / or epoxy-functionalized substances such as castor oil or hardened castor oil, epoxidized castor oil, ring opening products of epoxidized castor oils of different epoxy numbers with water and addition products of on average 1 to 100, preferably 20 to 80 and in particular 40 to 60 mol these called triglycerides.
- Partial glycerides are monoglycerides, diglycerides and their technical mixtures, which may still contain small amounts of triglycerides due to the manufacturing process.
- the partial glycerides preferably follow the formula (3),
- R 6 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms
- R 7 and R 8 independently of one another for R 6 CO or OH and the sum (m + n + p ) stands for 0 or numbers from 1 to 100, preferably 5 to 25, with the proviso that at least one of the two radicals R 7 and R 8 is OH.
- Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, Linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
- Technical lauric acid glycerides, palmitic acid glycerides, stearic acid glycerides, isostearic acid glycerides, oleic acid glycerides are preferably used.
- Behenic acid glycerides and / or erucic acid glycerides are used which have a monoglyceride content in the range from 50 to 95, preferably 60 to 90% by weight.
- the fatty alcohol polyglycol ethers relevant to the invention correspond to the formula (4),
- R 9 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and q represents numbers from 1 to 50.
- Typical examples are addition products of an average of 1 to 50, preferably 5 to 25, of capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, elaolylyl alcohol, elaolylyl alcohol , Elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures.
- the surfactants can have both a conventionally broad and a narrow homolog distribution. Addition products of an average of 10 or 20 moles of ethylene oxide with ceteary
- co-emulsifiers such as non-ionic surfactants from at least one of the following groups:
- polyglycerol esters such as e.g. Polyglycerol polyricinoleate or polyglycerol poly-12-hydroxystearate. Mixtures of compounds from several of these classes of substances are also suitable;
- partial esters based on linear, branched, unsaturated or saturated C 6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, Butyl glucoside, lauryl glucoside) and polyglucosides (eg cellulose); (6) trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;
- adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters as well as sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are mixtures of homologs, whose average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
- Ca alkyl mono- and oligoglycosides, their preparation and their use as surface-active substances are, for example, from US 3,839,318, US 3,707,535, US 3,547,828, DE-OS 19 43 689, DE-OS 20 36 472 and DE-A1 30 01 064 and EP -A 0 077 167 known. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
- the glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to approximately 8 are suitable.
- the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
- Zwitterionic surfactants can also be used as emulsifiers.
- Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
- Suitable emulsifiers are ampholytic surfactants.
- Ampholytic surfactants are surface-active compounds which, in addition to a Cs alkyl or acyl group, contain at least one free amino group and at least one COOH or SO 3 H group in the molecule and are capable of forming internal salts.
- ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each about 8 to 18 carbon atoms in the alkyl group.
- Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Ci 2 / i 8 -acylsarcosine.
- quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
- Substances such as lanolin and lecithin as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as further additives, the latter simultaneously serving as foam stabilizers.
- fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides are considered as consistency agents.
- a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred.
- suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and di-esters of fatty acids, polyacrylates, (for example Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides and electrolytes such as sodium chloride.
- polysaccharides in particular xanthan gum, guar guar, agar agar, alginates and ty
- suitable cationic polymers can also be added. These are selected, for example, from cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available from Amerchol under the name Polymer JR 400®, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as, for example, Luviquat® (BASF ), Condensation products of polyglycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxy-propyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as amidomethicones, copolymers of adipic acid and dimethyl aminohydroximine (s), quaternized silicone polymers such as amidomethicones, copolymers of
- hydrotropes such as, for example, ethanol, isopropyl alcohol or polyols can also be used.
- Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are
- Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;
- Methyl compounds such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; • Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside;
- Sugar alcohols having 5 to 12 carbon atoms such as, for example, sorbitol or mannitol,
- Aminosugars such as glucamine.
- O / W emulsions containing are used
- the O / W emulsions to be used according to the invention preferably contain at least one alcoholic component selected from monohydroxy, dihydroxy and trihydroxy compounds, in combination with at least one further component selected from d) nitrogenous, aliphatic, organic compounds with less than 10 ° C. -Atoms in the molecule, preferably less than 7 carbon atoms in the molecule, which particularly preferably contains an additional OH group, and / or e) an organic carboxylic acid with 1 to 10 carbon atoms in the molecule, preferably acetic acid and / or caproic acid ,
- the proportion of the alcoholic component mentioned, based on the total O / W emulsion to be used according to the invention, is greater than 20% by weight, particularly preferably greater than 50% by weight, but not greater than 61 , 8% by weight.
- the alcohol component mentioned to be used in the O / W emulsion to be used according to the invention is preferably essentially glycerol.
- An O / W emulsion to be used according to the invention is furthermore considered to be preferred, in which, as the nitrogenous compound (d) mentioned, a compound of the formula (5) R 1 -N- R 2 (5)
- organic carboxylic acid (s) mentioned is present in the O / W emulsion to be used according to the invention, its proportion, based on the total concentrate, is 0.1 to 20% by weight.
- the proportion of the aqueous phase in the O / W emulsion to be used according to the invention is greater than 95% by weight, based on the total O / W emulsion.
- an aqueous phase is to be understood as meaning at least 10% by weight of water together with all the components contained therein, with the proviso that together they form a single phase without phase boundaries.
- (c) contains 1 to 20% by weight of fatty alcohol polyglycol ether, with the proviso that the quantities given add up to 100% by weight with water and, if appropriate, other conventional auxiliaries and additives.
- the O / W emulsion to be used according to the invention additionally has at least one antimicrobial component selected from the groups of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives , Oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl contains carbamate, iodine, iodophores, peroxides, peracids, the components mentioned being different from the components mentioned hitherto in the O / W emulsion to be used according to the invention
- the O / W emulsion to be used according to the invention is produced immediately before application to the belts of the conveyor belt system mentioned, it being particularly preferred if the production of the O / W emulsion mentioned is specific for the production of O / W emulsions suitable mixing nozzles.
- the O / W emulsion or its diluted solution to be used according to the invention is preferably used for the transport of plastic, cardboard, metal or glass containers, in the case of plastic containers this particularly preferably at least one polymer selected from the groups of Contain polyethylene terephthalate (PET), polyethylene naphtenate (PEN), polycarbonate (PC), PVC and PET beverage bottles are very particularly preferred.
- PET polyethylene terephthalate
- PEN polyethylene naphtenate
- PC polycarbonate
- PET beverage bottles are very particularly preferred.
- additional antimicrobial active substances in particular organic peracids, chlorine dioxide or ozone, are used separately when used.
- the O / W emulsion to be used according to the invention it is further preferred to apply the O / W emulsion directly to the belts of the transport system without prior dilution using an application device.
- the O / W emulsion to be used according to the invention it is preferred to dilute the O / W emulsion with water in the transport installation, particularly preferably by a dilution factor which is between 20,000 and 100, before it is applied via an application device the conveyor belts is applied.
- the application device is in direct contact with the surfaces to be lubricated during the application.
- the application takes place, for example, using a brush, sponge, rag, wiper, which are in direct contact with the chain.
- a spray device as the application device.
- Another object of the present invention is a lubricant concentrate present as an O / W emulsion containing a wax ester for the lubrication of conveyor belt systems in food businesses.
- the lubricant concentrate according to the invention preferably contains at least one further component selected from the groups of a) triglycerides, b) partial glycerides, or c) fatty alcohol polyglycol ether.
- Chain lubricant concentrates were formulated as O / W emulsions in different compositions and examined for their properties.
- the viscosity of preparations E1 and E2 was determined using the Brookfield method in an RVF viscometer (spindle 1, 10 revolutions per minute (rpm)) once immediately after production (20 ° C.) and again after a storage period of 4 weeks measured at 45 ° C.
- the stability of the formulations was determined optically after storage (4 w, 45 ° C.). "+" Means stable and "-" phase separation.
- Lubrication tests were carried out with the formulations E1 and E3 and E4.
- the product was diluted with water of different quality to determine whether the lubrication behavior was dependent on the water quality.
- PET bottles were tested in lubrication tests on test carriers. The tests were carried out in the manner described in accordance with the prior art.
- the formulation E1 has excellent lubrication values, especially for salty, hard water.
- Formulations E3 and E4 show very good values even with deionized water.
- R is a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, the substituents being selected from amino, imino, hydroxy, halogen and carboxy, or a substituted or unsubstituted phenyl radical, where the Substituents are selected from amino, imino, hydroxyl, halogen, carboxy and a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms;
- A stands for -O-
- X represents an anion of an inorganic or organic acid, k, I independently of one another is an integer in the range from 1 to 6; y is O, 1, 2, 3, 4 or 5, n is an integer from 0 to 6 ,
- the present invention also enriches the choice of formulation resources for the application engineer.
- the lubricant concentrates combined with amine-containing chain lubricants are generally sufficiently antimicrobial to prevent germ growth or even kill germs in practice. If these combination active ingredients are missing or their concentration is not high enough, additional antimicrobial active ingredients can of course be added if necessary.
- the TNO method was used to determine the material compatibility.
- the recipe E1 was used without dilution and as a solution with 1%.
- PET bottles are filled with water and conditioned with carbon dioxide so that there is a pressure of around 7 bar inside the bottle.
- the bottom cups of the bottles are then immersed in the formulation of the comparative example or the example to be used according to the invention and placed in a Petri dish over a period of 24 hours. After the 24 hours, the bottles are opened, emptied and the floor cups rinsed with water.
- the floor cups are visually evaluated, it can be seen that in the experiment with the example to be used according to the invention, it can be ascertained that there are only a few stress cracks with a shallow depth, rating A, in the floor area.
- the pauses between dosing times can be increased by increasing the water hardness.
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP19152794.4A EP3508563A1 (de) | 2001-09-20 | 2002-09-11 | Verwendung von o/w-emulsionen zur kettenschmierung |
Applications Claiming Priority (3)
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DE10146264 | 2001-09-20 | ||
DE10146264A DE10146264A1 (de) | 2001-09-20 | 2001-09-20 | Verwendung von O/W-Emulsionen zur Kettenschmierung |
PCT/EP2002/010157 WO2003027217A1 (de) | 2001-09-20 | 2002-09-11 | Verwendung von o/w-emulsionen zur kettenschmierung |
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EP19152794.4A Division-Into EP3508563A1 (de) | 2001-09-20 | 2002-09-11 | Verwendung von o/w-emulsionen zur kettenschmierung |
EP19152794.4A Division EP3508563A1 (de) | 2001-09-20 | 2002-09-11 | Verwendung von o/w-emulsionen zur kettenschmierung |
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EP1427801A1 true EP1427801A1 (de) | 2004-06-16 |
EP1427801B1 EP1427801B1 (de) | 2019-03-20 |
EP1427801B8 EP1427801B8 (de) | 2019-04-24 |
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EP19152794.4A Pending EP3508563A1 (de) | 2001-09-20 | 2002-09-11 | Verwendung von o/w-emulsionen zur kettenschmierung |
EP02799361.7A Expired - Lifetime EP1427801B8 (de) | 2001-09-20 | 2002-09-11 | Verwendung von o/w-emulsionen zur kettenschmierung |
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US (5) | US7297666B2 (de) |
EP (2) | EP3508563A1 (de) |
DE (1) | DE10146264A1 (de) |
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WO (1) | WO2003027217A1 (de) |
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2001
- 2001-09-20 DE DE10146264A patent/DE10146264A1/de not_active Withdrawn
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2002
- 2002-09-11 WO PCT/EP2002/010157 patent/WO2003027217A1/de not_active Application Discontinuation
- 2002-09-11 EP EP19152794.4A patent/EP3508563A1/de active Pending
- 2002-09-11 US US10/490,569 patent/US7297666B2/en not_active Expired - Lifetime
- 2002-09-11 EP EP02799361.7A patent/EP1427801B8/de not_active Expired - Lifetime
- 2002-09-11 PL PL02369523A patent/PL369523A1/xx unknown
-
2007
- 2007-10-10 US US11/870,266 patent/US8759263B2/en active Active
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2014
- 2014-05-14 US US14/277,259 patent/US9249370B2/en not_active Expired - Fee Related
-
2015
- 2015-12-21 US US14/976,623 patent/US9758742B2/en not_active Expired - Lifetime
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2017
- 2017-08-07 US US15/670,657 patent/US10400190B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO03027217A1 * |
Also Published As
Publication number | Publication date |
---|---|
US10400190B2 (en) | 2019-09-03 |
EP1427801B8 (de) | 2019-04-24 |
PL369523A1 (en) | 2005-05-02 |
EP1427801B1 (de) | 2019-03-20 |
US20170335219A1 (en) | 2017-11-23 |
DE10146264A1 (de) | 2003-04-17 |
EP3508563A1 (de) | 2019-07-10 |
US8759263B2 (en) | 2014-06-24 |
WO2003027217A1 (de) | 2003-04-03 |
US20080108532A1 (en) | 2008-05-08 |
US20050070448A1 (en) | 2005-03-31 |
US20160108334A1 (en) | 2016-04-21 |
US9249370B2 (en) | 2016-02-02 |
US20140336091A1 (en) | 2014-11-13 |
US9758742B2 (en) | 2017-09-12 |
US7297666B2 (en) | 2007-11-20 |
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