EP0629235B1 - Surface-active base for non-soap lubricants - Google Patents
Surface-active base for non-soap lubricants Download PDFInfo
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- EP0629235B1 EP0629235B1 EP93904004A EP93904004A EP0629235B1 EP 0629235 B1 EP0629235 B1 EP 0629235B1 EP 93904004 A EP93904004 A EP 93904004A EP 93904004 A EP93904004 A EP 93904004A EP 0629235 B1 EP0629235 B1 EP 0629235B1
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- European Patent Office
- Prior art keywords
- carbon atoms
- lubricants
- group containing
- alkyl group
- contain
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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
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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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/30—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms containing a nitrogen-to-oxygen bond
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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
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/40—Polysaccharides, e.g. cellulose
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
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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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- 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
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
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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
- C10M2209/12—Polysaccharides, e.g. cellulose, biopolymers
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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
- C10M2215/20—Containing nitrogen-to-oxygen bonds
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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
- C10M2215/20—Containing nitrogen-to-oxygen bonds
- C10M2215/204—Containing nitrogen-to-oxygen bonds containing nitroso 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/32—Wires, ropes or cables lubricants
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/34—Lubricating-sealants
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/36—Release agents or mold release agents
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/38—Conveyors or chain belts
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/40—Generators or electric motors in oil or gas winning field
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/42—Flashing oils or marking oils
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/44—Super vacuum or supercritical use
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/50—Medical uses
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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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
Definitions
- the present invention relates to a new surfactant base for soap-free lubricants known per se, containing alkylamines and / or amphoteric compounds, optionally water and further additives and / or auxiliaries.
- the invention further relates to the use of the lubricant as a chain lubricant in the food industry.
- the lubricants according to the invention are used here for the lubrication, cleaning and disinfection of automatic chain and belt lubrication systems which are used when filling foodstuffs, preferably beverages, in glass and plastic bottles, cans, glasses, barrels, beverage containers (KEG), paper and cardboard containers and the like can be used.
- the chain lubricants previously used as lubricants are based on the one hand on fatty acids in the form of their water-soluble alkali or alkanolamine salts or on fatty amines in the form of their organic or inorganic salts.
- DE-A-23 13 330 describes soap-based lubricants which contain aqueous mixtures of C16-C18 fatty acid salts and surface-active substances.
- DE-A-36 31 953 describes a method for lubricating chain-shaped bottle conveyor belts in beverage filling plants, in particular in breweries, and for cleaning the belts by means of a liquid detergent, which is characterized in that the chain-shaped bottle conveyor belts are lubricated with belt lubricants based on neutralized primary fatty amines, which preferably have 12 to 18 C atoms and contain an unsaturated fraction of more than 10%, and the bottle conveyor belts are lubricated with cationic detergents, namely quaternary ammonium compounds such as alkyltrimethylammonium, dialkyldimethylammonium and alkyldimethylbenzylammonium chlorides or organic acids.
- cationic detergents namely quaternary ammonium compounds such as alkyltrimethylammonium, dialkyldimethylammonium and alkyldimethylbenzylammonium chlorides or organic acids.
- EP-A-0 044 458 describes lubricant preparations which are practically free from fatty acid soaps and which also contain a carboxylated nonionic surfactant and an acyl sarcosinate.
- the pH of these products is 7 to 11 and is therefore preferably in the neutral to alkaline range.
- DE-A-38 31 448 relates to aqueous, clear water-soluble, soap-free lubricant preparations, a process for their preparation and the use of the lubricant preparations according to the invention, in particular as a lubricant for the transport of glass bottles or polyethylene terephthalate bottles.
- the essentially neutral aqueous lubricant preparations (pH in the range from 6 to 8) contain alkylbenzenesulfonates, alkoxylated alkanol phosphates and alkane carboxylic acids, if appropriate in addition to customary solubilizers, solvents, defoamers and disinfectants.
- DE-A-39 05 548 describes lubricants which contain at least one secondary and / or tertiary amine and / or salts of such amines.
- PET polyethylene terephthalate
- Reusable PET bottles have proven particularly useful in this area for carbonated beverages such as mineral water and lemonades. While the bottles are being transported to the bottling plants, these bottles come into contact with chain conveyor lubricants. A more or less large part of the chain conveyor belt lubricant remains on the bottles, dries and sometimes damages these bottles. In particular, cracks in the PET material, so-called stress cracks, have been found in application technology. In extreme cases, this leads to the bottle bursting.
- the object of the present invention was therefore to provide a chain conveyor belt lubricant which meets the needs of the application side in that the So-called coefficient of friction is equal to or less than 0.1 to 0.12, the product simultaneously cleans, lubricates and disinfects, the product can be used in the lowest possible concentrations, the product does not damage the PET bottles, the product can be used regardless of the water hardness and the product is particularly suitable for mixed PET glass.
- the object of the present invention was achieved by the use of certain nonionic surfactants which meet all the requirements for chain conveyor belt lubricants, as listed above.
- the lubricant combinations according to the invention show a very good coefficient of friction, a low foaming behavior, a good cleaning effect and good skin tolerance.
- Moderate foaming behavior improves the lubricating effect in problem areas, such as Turntables, changers, etc., high substantivity and thus high lubricating performance even under unfavorable operating conditions (e.g. belt lubrication), generally applicable even with equipment shortcomings, good cleaning effect, high capillary activity and film formation on surfaces, also effective in the presence of organic loads and acids or alkalis and not corrosive even as a concentrate.
- the lubricant combinations according to the invention are both independent of the water quality and low-foaming, stable in storage at low temperatures, not corrosive and particularly environmentally and skin-friendly.
- the compounds of the general formula (I) are known in principle, as is the process for their preparation from "fatty amines and secondary products", company lettering from Hoechst AG.
- the lubricants according to the invention contain the compounds of the general formulas (I) to (IV) in amounts of 1 to 99% by weight, preferably in amounts of 5 to 15% by weight, based on the overall formulation.
- such lubricant combinations in the sense of the invention can consist exclusively of the amphoteric compounds mentioned and the associated surfactant base.
- the invention also includes those lubricant formulations which contain the compounds of the general formulas (I) to (IV) only to a lesser extent, preferably in amounts of 5 to 15% by weight and in particular 10 to 12% by weight , contain.
- the rest of the lubricant formulations preferably consist of water and additionally, if appropriate, of additives and / or auxiliaries and the surfactant base mentioned.
- Suitable as lubricant constituents are primary, secondary and / or tertiary amines and / or salts of such amines, as are described - among other things - in the above-cited German patent application DE-A-39 05 548.
- Examples of secondary amines of the general formulas (IIa) and (IIb) are: Di-coco-amine, di-stearyl-amine, di-tallow-amine and corresponding salts, preferably the acetates.
- the lubricants according to the invention can be secondary diamines of the general formulas (IIIa), (IIIb) or (IIIc) R4-NH- (CH2) 3NH2 (IIIa) R4-NH- (CH2) 3N+H3 X ⁇ (IIIb) R4-N+H2- (CH2) 3-N+H3 2X ⁇ (IIIc) contain, where the radicals R4 and X ⁇ each have the meanings given above for the general formulas (IIa) and (IIb).
- Examples of secondary diamines of the general formulas (IIIa), (IIIb) and (IIIc) are: N-lauryl-propylenediamine and N-tallow-propylenediamine, each in the form of the free amines and in the form of the acetate salts.
- tertiary amines of the general formulas (IVa) and (IVb) are: N, N-dipropyl-N-laurylamine, N, N-dimethyl-N-laurylamine, N, N-dimethyl-N-hexadecylamine, N, N-dimethyl-N-cocosamine, N, N-dimethyl-N-cetylamine and the corresponding acetate salts.
- Primary, secondary and tertiary amines which correspond to the general formulas (II), (III) and (IV) given above can be prepared by processes known from the literature and are in some cases offered as commercial products, for example from Hoechst AG, Frankfurt am Main, Germany, under the name GENAMIN R or from Lonza AG, Basel, Switzerland, under the name LONZABAC R 12.
- the weight ratio of the compounds of the general formula (I) to the amines of the general formulas (II), (III) and / or (IV) is not critical. However, a weight ratio of compounds of the general formula (I) to the compounds of the general formulas (II), (III) and / or (IV) in the range from 10: 1 to 1:10, in particular a ratio of 5: 1, is preferred up to 1: 1.
- the weight ratio mentioned above is based on the sum of the compounds (II), (III) and (IV) which may be used individually.
- the lubricants according to the invention can contain, as auxiliaries, solubilizers for obtaining a homogeneous, clear water-soluble application solution.
- solubilizers for obtaining a homogeneous, clear water-soluble application solution.
- examples include: alcohols, polyalcohols, ethers or polyethers, in particular isopropanol, butyl glycol, butyl diglycol or ethylene glycol ether.
- the amount of the solubilizer to be used depends in each case on the betaine or amine used, the person skilled in the art will determine the required amount of solubilizer by trial and error in the individual case. In general, additions to solubilizers in the range from 1 to 20% by weight, based on the overall formulation, are sufficient.
- the alkyldimetylamine oxides to be used have a chain length of 10 to 18, in particular 12 to 14, carbon atoms in the alkyl radical.
- the alkyl chains can be linear or branched, saturated, mono- or polyunsaturated.
- Alkyl oligoglycosides which are derived from aldoses or ketoses and, in particular, from glucose because of their ready availability are preferred.
- the preferred alkyl oligoglycosides are thus the alkyl oligoglucosides.
- the alkyl radical R 1 can be derived from primary alcohols having 4 to 22, preferably 8 to 16, in particular 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachyl alcohol, behenyl alcohol and their technical mixtures based on natural fats and oils, for example palm oil, palm kernel oil, coconut oil or beef tallow.
- Alkyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry.
- EP-A-0 301 298 As a representative of the extensive literature regarding its structure and synthesis, reference is made to the European patent application EP-A-0 301 298.
- the surfactants mentioned in the range from 1 to 10% by weight, based on the total formulation, are sufficient for wetting the chains and plate conveyor belts.
- the amine oxides as well as the alkyl oligoglycosides can each be used alone or in a mixture.
- auxiliaries from the prior art are, for example, alkoxylated fatty amines, fatty alcohols or alkoxylated fatty alcohols.
- these surfactants have the disadvantage of increased stress corrosion cracking in PET bottles. Such surfactants are therefore preferably not used in the sense of the present invention. If, however, this is desired, their share should be kept as low as possible.
- the lubricants according to the invention preferably have a pH in the range from 4 to 11, in particular in the range from 6 to 9. If the pH of the lubricant is not already in this range, it can be added by adding an acid, preferably one Acid with the anion X ⁇ defined above, for example with acetic acid to the desired value.
- the lubricants have a dynamic viscosity of less than 300 mPa.s, in particular less than 150 mPa.s and particularly preferably in the range from 5 to 100 mPa.s - in each case at 20 ° C - have.
- a separate adjustment of the viscosity to the values mentioned is generally not necessary or is optionally carried out by adding suitable amounts of the preferred diluent water or a solubilizer.
- the lubricants according to the invention can be prepared by simply mixing the components with water, optionally with the addition of the additives and / or auxiliaries mentioned.
- the present invention relates to the use of lubricants of the type described above as chain lubricants in the food industry, in particular for automatic chain and belt lubrication systems.
- the lubricants according to the invention are generally diluted with water.
- Such aqueous application solutions generally contain 0.01% by weight of compounds of the general formulas (I) to (IV), preferably 0.01 to 0.2% by weight and in particular 0.02 to 0.04% by weight. % of such compounds and 0.1 to 1% by weight of the surfactants according to the invention mentioned.
- the products according to the invention do not cause stress corrosion cracking and can therefore be used without problems for PET and PC containers.
- PET polyethylene terephthalate
- PC polycarbonate
- Neutral pH values are particularly preferred for clear water-soluble concentrates.
- the lubricants according to the invention are namely suitable in the concentration required for chain and belt lubrication also for cleaning empties as well as machines and machine parts.
- central foam systems in the food industry are partially equipped with permanently installed, automatic systems that automatically clean the outside of fillers, cylindroconical fermentation and storage tanks, conveyor belts and other machines and systems after production or during breaks.
- the lubricants according to the invention can be used with great advantage.
- the present invention further relates to the use of lubricants of the type described above for disinfecting and cleaning empties, machines and systems in the food and beverage industry.
- Examples 1 and 2 according to the invention show the frictional resistance and the foaming behavior of lubricant formulations according to the invention.
- the PET bottles are filled with carbonated water of 4.5 vol% CO2 and sealed accordingly.
- the bottles are immersed in the substance to be tested in the bottom area (see Table 1) and stored at 38 ° C for 72 hours. Then the bottle is sampled (from no stress cracks to destroyed bottle).
- the coefficient of friction " ⁇ " given below is the quotient of the measured tensile stress for a bottle to the weight of the bottle in grams.
- the coefficient of friction should be 0.10 to 0.12 or less. If the value exceeds 0.15, the lubricating effect and thus the perfect transport will decrease significantly.
- the clear water solubility of the application solutions should also be guaranteed over a longer test period in order to avoid deposits in ball valve filters, nozzles, spray and distribution systems, conveyor belts and transport goods.
- the foam development should be low, since excessive foam not only interferes with the workflow (automatic bottle inspector) and occupational safety (risk of slipping), but also can soften the label and penetrate into the not yet sealed container. In addition, the coefficient of friction deteriorates due to excessive foaming tendency.
- Anionic surfactants such as alkylbenzenesulfonate cannot be incorporated into the cationically reacting chain lubricants based on alkylamines, so that only amine oxides and alkyl polyglucosides remain for use in corresponding chain lubricants.
Abstract
Description
Die vorliegende Erfindung betrifft eine neue Tensidbasis für an sich bekannte seifenfreie Schmiermittel, enthaltend Alkylamine und/oder amphotere Verbindungen, gegebenenfalls Wasser sowie weitere Zusatz- und/oder Hilfsstoffe.The present invention relates to a new surfactant base for soap-free lubricants known per se, containing alkylamines and / or amphoteric compounds, optionally water and further additives and / or auxiliaries.
Die Erfindung betrifft weiterhin die Verwendung der Schmiermittel als Kettenschmiermittel in der Lebensmittelindustrie. Insbesondere finden die erfindungsgemäßen Schmiermittel hier Verwendung zum Schmieren, Reinigen und Desinfizieren von automatischen Ketten- und Bandschmieranlagen, die beim Abfüllen von Lebensmitteln, vorzugsweise Getränken, in Glas- und Kunststoffflaschen, Dosen, Gläser, Fässer, Getränkecontainer (KEG), Papier- und Pappbehälter und dergleichen eingesetzt werden.The invention further relates to the use of the lubricant as a chain lubricant in the food industry. In particular, the lubricants according to the invention are used here for the lubrication, cleaning and disinfection of automatic chain and belt lubrication systems which are used when filling foodstuffs, preferably beverages, in glass and plastic bottles, cans, glasses, barrels, beverage containers (KEG), paper and cardboard containers and the like can be used.
Die bisher als Schmiermittel eingesetzten Kettengleitmittel basieren einerseits auf Fettsäuren in Form ihrer wasserlöslichen Alkali- oder Alkanolaminsalze oder auf Fettaminen in Form ihrer organischen oder anorganischen Salze.The chain lubricants previously used as lubricants are based on the one hand on fatty acids in the form of their water-soluble alkali or alkanolamine salts or on fatty amines in the form of their organic or inorganic salts.
Die DE-A-23 13 330 beschreibt Schmiermittel auf Seifenbasis, die wäßrige Mischungen von C₁₆-C₁₈-Fettsäuresalzen und oberflächenaktiven Substanzen enthalten.DE-A-23 13 330 describes soap-based lubricants which contain aqueous mixtures of C₁₆-C₁₈ fatty acid salts and surface-active substances.
Neben diesen Schmiermitteln auf Seifenbasis werden ansonsten hauptsächlich solche auf Basis von primären Fettaminen verwendet. So beschreibt die DE-A-36 31 953 ein Verfahren zum Schmieren von kettenförmigen Flaschentransportbändern in Getränkeabfüllbetrieben, insbesondere in Brauereien, sowie zum Reinigen der Bänder mittels eines flüssigen Reinigungsmittels, das dadurch gekennzeichnet ist, daß man die kettenförmigen Flaschentransportbänder mit Bandschmiermitteln auf Basis neutralisierter primärer Fettamine, die vorzugsweise 12 bis 18 C-Atome aufweisen und einen ungesättigten Anteil von mehr als 10 % enthalten, schmiert und die Flaschentransportbänder mit kationischen Reinigungsmitteln, nämlich quaternären Ammoniumverbindungen wie Alkyltrimethylammonium-, Dialkyldimethylammonium- und Alkyldimethylbenzylammoniumchloriden oder organischen Säuren reinigt.In addition to these soap-based lubricants, mainly those based on primary fatty amines are used. For example, DE-A-36 31 953 describes a method for lubricating chain-shaped bottle conveyor belts in beverage filling plants, in particular in breweries, and for cleaning the belts by means of a liquid detergent, which is characterized in that the chain-shaped bottle conveyor belts are lubricated with belt lubricants based on neutralized primary fatty amines, which preferably have 12 to 18 C atoms and contain an unsaturated fraction of more than 10%, and the bottle conveyor belts are lubricated with cationic detergents, namely quaternary ammonium compounds such as alkyltrimethylammonium, dialkyldimethylammonium and alkyldimethylbenzylammonium chlorides or organic acids.
Schließlich sind im Stand der Technik weitere Kettenschmiermittel bekannt; so beschreibt die EP-A-0 044 458 Schmiermittelzubereitungen, die praktisch frei von Fettsäureseifen sind und die weiterhin ein carboxyliertes nichtionisches Tensid und ein Acylsarcosinat enthalten. Der pH-Wert dieser Produkte beträgt 7 bis 11 und liegt somit vorzugsweise im neutralen bis alkalischen Bereich.Finally, further chain lubricants are known in the prior art; this is how EP-A-0 044 458 describes lubricant preparations which are practically free from fatty acid soaps and which also contain a carboxylated nonionic surfactant and an acyl sarcosinate. The pH of these products is 7 to 11 and is therefore preferably in the neutral to alkaline range.
Die DE-A-38 31 448 betrifft schließlich wäßrige, klarwasserlösliche, seifenfreie Schmiermittelzubereitungen, ein Verfahren zu ihrer Herstellung und die Verwendung der erfindungsgemäßen Schmiermittelzubereitungen, insbesondere als Schmiermittel zum Transport von Glasflaschen oder Polyethylenterephthalat-Flaschen. Die im wesentlichen neutralen wäßrigen Schmiermittelzubereitungen (pH im Bereich von 6 bis 8) enthalten Alkylbenzolsulfonate, alkoxylierte Alkanolphosphate und Alkancarbonsäuren, gegebenenfalls neben üblichen Lösungsvermittlern, Lösungsmitteln, Entschäumungsmitteln und Desinfektionsmitteln.Finally, DE-A-38 31 448 relates to aqueous, clear water-soluble, soap-free lubricant preparations, a process for their preparation and the use of the lubricant preparations according to the invention, in particular as a lubricant for the transport of glass bottles or polyethylene terephthalate bottles. The essentially neutral aqueous lubricant preparations (pH in the range from 6 to 8) contain alkylbenzenesulfonates, alkoxylated alkanol phosphates and alkane carboxylic acids, if appropriate in addition to customary solubilizers, solvents, defoamers and disinfectants.
Allerdings zeigen auch diese beiden oben beschriebenen Produkte noch folgende drei Nachteile:
- 1. Sie sind mikrobiologisch ungünstig, da sie hervorragende Wachstumsbedingungen für Mikroorganismen schaffen.
- 2. Weiterhin zeigen sie nur eine geringe Reinigungskraft.
- 3. Schließlich weisen sie ein schwer zu kontrollierendes Schaumverhalten auf.
- 1. They are microbiologically unfavorable because they create excellent growth conditions for microorganisms.
- 2. Furthermore, they show only a low cleaning power.
- 3. Finally, they have a foam behavior that is difficult to control.
In der DE-A-39 05 548 werden Schmiermittel beschrieben, die mindestens ein sekundäres und/oder tertiäres Amin und/oder Salze derartiger Amine enthalten.DE-A-39 05 548 describes lubricants which contain at least one secondary and / or tertiary amine and / or salts of such amines.
In jüngster Zeit werden häufig Getränke in Polyethylenterephthalat (PET)-Flaschen abgefüllt. Insbesondere für kohlensäurehaltige Getränke wie Mineralwasser und Limonaden haben sich in diesem Bereich PET-Mehrwegflaschen bewährt. Während des Transportes der Flaschen in den Abfüllbetrieben kommen diese Flaschen mit Kettentransportband-Schmiermitteln in Kontakt. Ein mehr oder weniger großer Teil des Kettentransportband-Schmiermittels verbleibt an den Flaschen, trocknet an und führt teilweise zu Schädigungen dieser Flaschen. Insbesondere sind in der Anwendungstechnik Risse im PET-Material, sogenannte Spannungsrisse, festgestellt worden. Dies führt im Extremfall zum Platzen der Flasche.Recently, beverages have often been filled into polyethylene terephthalate (PET) bottles. Reusable PET bottles have proven particularly useful in this area for carbonated beverages such as mineral water and lemonades. While the bottles are being transported to the bottling plants, these bottles come into contact with chain conveyor lubricants. A more or less large part of the chain conveyor belt lubricant remains on the bottles, dries and sometimes damages these bottles. In particular, cracks in the PET material, so-called stress cracks, have been found in application technology. In extreme cases, this leads to the bottle bursting.
Aus diesem Grunde wurden bisher zur Schmierung der Flaschen praktisch ausschließlich seifenhaltige Kettentransport-Schmiermittel eingesetzt, die von den Herstellern jeweils auf ihre spezielle Eignung untersucht und freigegeben wurden. Allgemein im Stand der Technik bekannte Kettentransportband-Schmiermittel auf Alkylaminbasis, die wie oben aufgeführt, eine breite Verwendung im Stand der Technik für den Transport von anderen Getränkegebinden finden, führten scheinbar zu einer Schädigung der Flaschen.For this reason, so far only soap-containing chain transport lubricants have been used to lubricate the bottles, which have been examined and approved by the manufacturers for their particular suitability. Generally known in the art chain conveyor belt lubricants based on alkylamine, which, as stated above, are widely used in the prior art for the transportation of other beverage containers, apparently caused damage to the bottles.
Die Aufgabe der vorliegenden Erfindung bestand somit darin, ein Kettentransportband-Schmiermittel zur Verfügung zu stellen, das den Bedürfnissen der Anwendungsseite dahingehend gerecht wird, daß der sogenannte Reibbeiwert gleich oder weniger 0,1 bis 0,12 beträgt, das Produkt gleichzeitig reinigt, schmiert und desinfiziert, das Produkt in möglichst geringen Konzentrationen einsetzbar ist, das Produkt die PET-Flaschen nicht schädigt, das Produkt unabhängig von der Wasserhärte einsetzbar ist und das Produkt insbesondere für den Mischbetrieb PET-Glas geeignet ist.The object of the present invention was therefore to provide a chain conveyor belt lubricant which meets the needs of the application side in that the So-called coefficient of friction is equal to or less than 0.1 to 0.12, the product simultaneously cleans, lubricates and disinfects, the product can be used in the lowest possible concentrations, the product does not damage the PET bottles, the product can be used regardless of the water hardness and the product is particularly suitable for mixed PET glass.
Überraschenderweise wurde gefunden, daß nicht die Alkylamine selbst, sondern die üblicherweise eingesetzten Hilfsstoffe wie nichtionische Tenside, insbesondere alkoxilierte Fettamine, Fettalkohole, alkoxilierte Fettalkohole, zu einer mehr oder weniger großen Schädigung der PET-Mehrwegflaschen führten.Surprisingly, it was found that not the alkylamines themselves, but rather the auxiliaries usually used, such as nonionic surfactants, in particular alkoxylated fatty amines, fatty alcohols, alkoxylated fatty alcohols, caused more or less great damage to the returnable PET bottles.
Die Aufgabe der vorliegenden Erfindung wurde gelöst durch die Verwendung bestimmter nichtionogener Tenside, die sämtliche Anforderungen an Kettentransportband-Schmiermittel, wie oben aufgeführt, erfüllen.The object of the present invention was achieved by the use of certain nonionic surfactants which meet all the requirements for chain conveyor belt lubricants, as listed above.
Die vorliegende Erfindung betrifft seifenfreie Schmiermittel auf der Basis von amphoteren Verbindungen, primären, sekundären und/oder tertiären Aminen und/oder Salzen derartiger Amine der allgemeinen Formel (I), (IIa), (IIb), (IIIa), (IIIb), (IIIb), (IIIc), (IVa) und (IVb)
R⁴-NH-R⁵ (IIa)
R⁴-N⁺H₂-R⁵ X⁻ (IIb)
R⁴-NH-(CH₂)₃NH₂ (IIIa)
R⁴-NH-(CH₂)₃N⁺H₃ X⁻ (IIIb)
R⁴-N⁺H₂-(CH₂)₃-N⁺H₃ 2X⁻ (IIIc)
R⁴-NR⁷R⁸ (IVa)
und/oder
R⁴-N⁺HR⁷R⁸ X⁻ (IVb)
wobei
- R
- für einen gesättigten oder einfach oder mehrfach ungesättigten, linearen oder verzweigten Alkylrest mit 6 bis 22 C-Atomen, der gegebenenfalls durch -OH, -NH₂, -NH-, -CO-, -(CH₂CH₂O)l- oder -(CH₂CH₂CH₂O)l- substituiert sein kann,
- R¹
- für Wasserstoff, einen Alkylrest mit 1 bis 4 C-Atomen, einen Hydroxyalkylrest mit 1 bis 4 C-Atomen oder einen Rest -R³COOM
- R²
- nur für den Fall, daß M eine negative Ladung darstellt für Wasserstoff, einen Alkylrest mit 1 bis 4 C-Atomen, oder einen Hydroxyalkylrest mit 1 bis 4 C-Atomen,
- R³
- für einen gesättigten oder einfach oder mehrfach ungesättigten, linearen oder verzweigten Alkylrest mit 1 bis 12 C-Atomen, der gegebenenfalls durch -OH, -NH₂, -NH-, -CO-, -(CH₂CH₂O)l- oder -(CH₂CH₂CH₂O)l- substituiert sein kann,
- R⁴
- für einen substituierten oder unsubstituierten, linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen, der als Substituenten mindestens einen Amin-, Imin-, Hydroxy-, Halogen- und/oder Carboxyrest aufweisen kann,
einen substituierten oder unsubstituierten Phenylrest, der als Substituenten mindestens einen Amin-, Imin-, Hydroxy-, Halogen-, Carboxy- und/oder einen linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen aufweisen kann, - R⁵
- für Wasserstoff oder - unabhängig von R⁴ - für einen Rest R⁴,
- X⁻
- für ein Anion aus der Gruppe Amidosulfonat, Nitrat, Halogenid, Sulfat, Hydrogencarbonat, Carbonat, Phosphat oder R⁶-COO⁻ steht, wobei
- R⁶
- für Wasserstoff, einen substituierten oder unsubstituierten, linearen oder verzweigten Alkylrest mit 1 bis 20 C-Atomen oder Alkenylrest mit 2 bis 20 C-Atomen, die als Substituenten mindestens einen Hydroxy-, Amin- oder Iminrest aufweisen können, oder einen substituierten oder unsubstituierten Phenylrest, der als Substituenten einen Alkylrest mit 1 bis 20 C-Atomen aufweisen kann, steht, und
- R⁷ und R⁸
- jeweils unabhängig voneinander für einen substituierten oder unsubstituierten, linearen oder verzweigten Alkylrest mit 1 bis 20 C-Atomen oder Alkenylrest mit 2 bis 20 C-Atomen, die als Substituenten mindestens einen Hydroxy-, Amin- oder Iminrest aufweisen können, oder einen substituierten oder unsubstituierten Phenylrest, der als Substituenten einen Alkylrest mit 1 bis 20 C-Atomen aufweisen kann,
- M
- für Wasserstoff, Alkalimetall, Ammonium, einen Alkylrest mit 1 bis 4 C-Atomen, einen Benzylrest oder eine negative Ladung,
- n
- für eine ganze Zahl im Bereich von 1 bis 12,
- m
- für eine ganze Zahl im Bereich von 0 bis 5 und
- l
- für eine Zahl im Bereich von 0 bis 5 steht,
R⁴-NH-R⁵ (IIa)
R⁴-N⁺H₂-R⁵ X⁻ (IIb)
R⁴-NH- (CH₂) ₃NH₂ (IIIa)
R⁴-NH- (CH₂) ₃N⁺H₃ X⁻ (IIIb)
R⁴-N⁺H₂- (CH₂) ₃-N⁺H₃ 2X⁻ (IIIc)
R⁴-NR⁷R⁸ (IVa)
and or
R⁴-N⁺HR⁷R⁸ X⁻ (IVb)
in which
- R
- for a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, which may be replaced by -OH, -NH₂, -NH-, -CO-, - (CH₂CH₂O) l - or - (CH₂CH₂CH₂O) l - can be substituted,
- R¹
- for hydrogen, an alkyl radical with 1 to 4 carbon atoms, a hydroxyalkyl radical with 1 to 4 carbon atoms or a radical -R³COOM
- R²
- only in the case that 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,
- R³
- for a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 1 to 12 carbon atoms, which may be replaced by -OH, -NH₂, -NH-, -CO-, - (CH₂CH₂O) l - or - (CH₂CH₂CH₂O) l - can be substituted,
- R⁴
- for 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 a 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, - R⁵
- for hydrogen or - independently of R⁴ - for a radical R⁴,
- X⁻
- represents an anion from the group amidosulfonate, nitrate, halide, sulfate, hydrogen carbonate, carbonate, phosphate or R⁶-COO⁻, where
- R⁶
- for 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 substituents, or a substituted or unsubstituted phenyl radical , which can have an alkyl radical with 1 to 20 C atoms as a substituent, and
- R⁷ and R⁸
- each independently for 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 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
- l
- represents a number in the range from 0 to 5,
Im Sinne der vorliegenden Erfindung sind solche Verbindungen der allgemeinen Formel (I) bevorzugt, für welche gilt:
- R
- = gesättigter oder einfach oder mehrfach ungesättigter, linearer Alkylrest mit 10 bis 18 C-Atomen, der gegebenenfalls durch -CO- substituiert sein kann, insbesondere unsubstituierter, gesättigter linearer Alkylrest mit 12 bis 14 C-Atomen,
- R¹
- = Wasserstoff, Alkylrest mit 1 bis 3 C-Atomen oder ein Rest -CH₂CH₂OH, insbesondere Wasserstoff oder Alkylrest mit 1 bis 3 C-Atomen,
- R²
- = Wasserstoff oder Alkylrest mit 1 bis 3 C-Atomen,
- R³
- = Methylen- oder Di-methylen-rest, insbesondere Methylenrest,
- M
- = Wasserstoff oder eine negative Ladung,
- n
- = 2 oder 3, insbesondere 2
- m
- = 0, 1 oder 2, insbesondere 0.
- R
- = saturated or mono- or polyunsaturated, linear alkyl radical with 10 to 18 C atoms, which can optionally be substituted by -CO-, in particular unsubstituted, saturated linear alkyl radical with 12 to 14 C atoms,
- R¹
- = Hydrogen, alkyl radical with 1 to 3 C atoms or a radical -CH₂CH₂OH, in particular hydrogen or alkyl radical with 1 to 3 C atoms,
- R²
- = Hydrogen or alkyl radical with 1 to 3 carbon atoms,
- R³
- = Methylene or dimethylene residue, in particular methylene residue,
- M
- = Hydrogen or a negative charge,
- n
- = 2 or 3, especially 2
- m
- = 0, 1 or 2, especially 0.
Hinsichtlich ihrer Anwendungseigenschaften zeigen die erfindungsgemäßen Schmiermittelkombinationen einen sehr guten Reibbeiwert, ein geringes Schaumverhalten, eine gute Reinigungswirkung sowie gute Hautverträglichkeit. Zusätzlich zu den genannten positiven Eigenschaften werden folgende Randbedingungen erfüllt: Mäßiges Schaumverhalten verbessert die Schmierwirkung an Problemzonen, wie Drehtellern, Wechslern usw., hohe Substantivität und damit hohe Schmierleistung auch bei ungünstigen Betriebsbedingungen (z.B. Unterbandschmierung), allgemein einsetzbar auch bei apparativen Unzulänglichkeiten, guter Reinigungseffekt, hohe Kapillaraktivität und Filmbildung an Oberflächen, auch in Gegenwart von organischen Belastungen und Säuren oder Alkalien wirksam und auch als Konzentrat nicht korrosiv.With regard to their application properties, the lubricant combinations according to the invention show a very good coefficient of friction, a low foaming behavior, a good cleaning effect and good skin tolerance. In addition to the positive properties mentioned, the following boundary conditions are met: Moderate foaming behavior improves the lubricating effect in problem areas, such as Turntables, changers, etc., high substantivity and thus high lubricating performance even under unfavorable operating conditions (e.g. belt lubrication), generally applicable even with equipment shortcomings, good cleaning effect, high capillary activity and film formation on surfaces, also effective in the presence of organic loads and acids or alkalis and not corrosive even as a concentrate.
Die erfindungsgemäßen Schmiermittelkombinationen sind beim Einsatz in der Getränkeindustrie im Gegensatz zu den bislang eingesetzten Kettenschmiermitteln sowohl unabhängig von der Wasserqualität als auch schaumarm, lagerstabil bei tiefen Temperaturen, nicht korrosiv und besonders umwelt- und hautvertäglich.When used in the beverage industry, the lubricant combinations according to the invention, in contrast to the chain lubricants used hitherto, are both independent of the water quality and low-foaming, stable in storage at low temperatures, not corrosive and particularly environmentally and skin-friendly.
Die Verbindungen der allgemeinen Formel (I) sind prinzipiell ebenso wie das Verfahren zu ihrer Herstellung aus "Fettamine und Folgeprodukte", Firmenschrift der Hoechst AG, bekannt.The compounds of the general formula (I) are known in principle, as is the process for their preparation from "fatty amines and secondary products", company lettering from Hoechst AG.
Beispiele für amphotere Verbindungen der allgemeinen Formel (I), die im Sinne der Erfindung auch bevorzugt eingesetzt werden, sind nachstehend genannt: Dodecyl-aminopropyl-glycin, Dodecyl-di(aminoethyl)-glycin, N-Dodecyl-N,N-dipropyl-glycin, N-Cocos-N,N-dimethyl-glycin (Cocos = Fettalkylreste mit vorzugsweise 12 bzw. 14 C-Atomen), N-Hexadecyl-N,N-dimethyl-glycin, N-Soja-N,N-dimethyl-glycin (Soja = ein- und zweifach ungesättigte Fettalkylreste mit vorzugsweise 18 C-Atomen), N-Decyl-N,N-dimethylglycin, Dodecyl-di(aminopropyl)-glycin, C₁₀₋₁₈-Fettsäureamidoethyl-N-hydroxyethyl-glycin.Examples of amphoteric compounds of the general formula (I) which are also preferably used in the context of the invention are mentioned below: dodecylaminopropylglycine, dodecyldi (aminoethyl) glycine, N-dodecyl-N, N-dipropyl- glycine, N-coco-N, N-dimethyl-glycine (coco = fatty alkyl residues with preferably 12 or 14 carbon atoms), N-hexadecyl-N, N-dimethyl-glycine, N-soybean-N, N-dimethyl- glycine (soy = mono- and di-unsaturated fatty alkyl residues with preferably 18 carbon atoms), N-decyl-N, N-dimethylglycine, dodecyl-di (aminopropyl) -glycine, C₁₀₋₁₈ fatty acid amidoethyl-N-hydroxyethyl-glycine.
Die erfindungsgemäßen Schmiermittel enthalten die Verbindungen der allgemeinen Formeln (I) bis (IV) in Mengen von 1 bis 99 Gew.-%, vorzugsweise in Mengen von 5 bis 15 Gew-%, bezogen auf die Gesamtformulierung.The lubricants according to the invention contain the compounds of the general formulas (I) to (IV) in amounts of 1 to 99% by weight, preferably in amounts of 5 to 15% by weight, based on the overall formulation.
Mithin können derartige Schmiermittelkombinationen im Sinne der Erfindung ausschließlich aus den genannten amphoteren Verbindungen bestehen und der dazugehörigen Tensidbasis. Ferner umfaßt die Erfindung auch solche Schmiermittel-Formulierungen, die die Verbindungen der allgemeinen Formeln (I) bis (IV) nur zu einem geringeren Anteil, vorzugsweise in Mengen von 5 bis 15 Gew.-% und insbesondere von 10 bis 12 Gew.-%, enthalten. Der Rest der Schmiermittel-Formulierungen besteht in diesem Falle vorzugsweise aus Wasser und zusätzlich gegebenenfalls aus Zusatz- und/oder Hilfsstoffen sowie der genannten Tensidbasis.Accordingly, such lubricant combinations in the sense of the invention can consist exclusively of the amphoteric compounds mentioned and the associated surfactant base. Furthermore, the invention also includes those lubricant formulations which contain the compounds of the general formulas (I) to (IV) only to a lesser extent, preferably in amounts of 5 to 15% by weight and in particular 10 to 12% by weight , contain. In this case, the rest of the lubricant formulations preferably consist of water and additionally, if appropriate, of additives and / or auxiliaries and the surfactant base mentioned.
Als Schmiermittelbestandteile kommen ferner primäre, sekundäre und/oder tertiäre Amine und/oder Salze derartiger Amine in Betracht, wie sie - unter anderem - in der vorstehend zitierten deutschen Patentanmeldung DE-A-39 05 548 beschrieben sind.Also suitable as lubricant constituents are primary, secondary and / or tertiary amines and / or salts of such amines, as are described - among other things - in the above-cited German patent application DE-A-39 05 548.
Somit können die erfindungsgemäßen Schmiermittel primäre oder sekundäre Amine der allgemeinen Formeln (IIa) oder (IIb)
R⁴-NH-R⁵ (IIa)
R⁴-N⁺H₂-R⁵ X⁻ (IIb)
enthalten,
wobei der Rest R⁴ bedeutet:
- einen substituierten oder unsubstituierten, linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen, der als Substituenten mindestens einen Amin-, Imin-, Hydroxy-, Halogen- und/oder Carboxyrest aufweisen kann,
- einen substituierten oder unsubstituierten Phenylrest, der als Substituenten mindestens einen Amin-, Imin-, Hydroxy-, Halogen-, Carboxy- und/oder einen linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen aufweisen kann,
R⁵ für einen Rest R⁴ oder Wasserstoff.The lubricants according to the invention can thus primary or secondary amines of the general formulas (IIa) or (IIb)
R⁴-NH-R⁵ (IIa)
R⁴-N⁺H₂-R⁵ X⁻ (IIb)
contain,
where the rest R⁴ means:
- a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical with 6 to 22 carbon atoms, which may have at least one amine, imine, hydroxyl, halogen and / or carboxy radical as a substituent,
- a substituted or unsubstituted phenyl radical which has at least one amine, imine, hydroxyl, halogen, May have carboxy and / or a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms,
R⁵ for a radical R⁴ or hydrogen.
Als Beispiele für sekundäre Amine der allgemeinen Formel (IIa) und (IIb) seien genannt:
Di-cocos-amin, Di-stearyl-amin, Di-talg-amin sowie entsprechende Salze, vorzugsweise die Acetate.Examples of secondary amines of the general formulas (IIa) and (IIb) are:
Di-coco-amine, di-stearyl-amine, di-tallow-amine and corresponding salts, preferably the acetates.
Die erfindungsgemäßen Schmiermittel können sekundäre Diamine der allgemeinen Formeln (IIIa), (IIIb) oder (IIIc)
R⁴-NH-(CH₂)₃NH₂ (IIIa)
R⁴-NH-(CH₂)₃N⁺H₃ X⁻ (IIIb)
R⁴-N⁺H₂-(CH₂)₃-N⁺H₃ 2X⁻ (IIIc)
enthalten, wobei die Reste R⁴ und X⁻ jeweils die vorstehend für die allgemeinen Formeln (IIa) und (IIb) angegebenen Bedeutungen haben.The lubricants according to the invention can be secondary diamines of the general formulas (IIIa), (IIIb) or (IIIc)
R⁴-NH- (CH₂) ₃NH₂ (IIIa)
R⁴-NH- (CH₂) ₃N⁺H₃ X⁻ (IIIb)
R⁴-N⁺H₂- (CH₂) ₃-N⁺H₃ 2X⁻ (IIIc)
contain, where the radicals R⁴ and X⁻ each have the meanings given above for the general formulas (IIa) and (IIb).
Als Beispiele für sekundäre Diamine der allgemeinen Formeln (IIIa), (IIIb) und (IIIc) seien genannt:
N-Lauryl-propylendiamin und N-Talg-propylendiamin, jeweils in Form der freien Amine sowie in Form der Acetat-Salze.Examples of secondary diamines of the general formulas (IIIa), (IIIb) and (IIIc) are:
N-lauryl-propylenediamine and N-tallow-propylenediamine, each in the form of the free amines and in the form of the acetate salts.
Schließlich können die erfindungsgemäßen Schmiermittel tertiäre Amine der allgemeinen Formeln (IVa) oder (IVb)
R⁴-NR⁷R⁸ (IVa)
R⁴-N⁺HR⁷R⁸ X⁻ (IVb)
enthalten, wobei die Reste R⁴ und X⁻ jeweils die für die allgemeinen Formeln (IIa) und (IIb) angegebenen Bedeutungen haben und die Reste R⁷ und R⁸ jeweils unabhängig voneinander bedeuten:
- einen substituierten oder unsubstituierten, linearen oder verzweigten Alkylrest mit 1 bis 20 C-Atomen oder Alkenylrest mit 2 bis 20 C-Atomen, die als Substituenten mindestens einen Hydroxy-, Amin- oder Iminrest aufweisen können, oder
- einen substituierten oder unsubstituierten Phenylrest, der als Substituenten eine Alkylrest mit 1 bis 20 C-Atomen aufweisen kann.
R⁴-NR⁷R⁸ (IVa)
R⁴-N⁺HR⁷R⁸ X⁻ (IVb)
contain, where the radicals R⁴ and X⁻ each have the meanings given for the general formulas (IIa) and (IIb) and the radicals R⁷ and R⁸ each independently:
- 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
- a substituted or unsubstituted phenyl radical, which may have an alkyl radical having 1 to 20 C atoms as a substituent.
Als Beispiele für tertiäre Amine der allgemeinen Formeln (IVa) und (IVb) seien genannt: N,N-Dipropyl-N-laurylamin, N,N-Dimethyl-N-laurylamin, N,N-Dimethyl-N-hexadecylamin, N,N-Dimethyl-N-cocosamin, N,N-Dimethyl-N-cetylamin sowie die entsprechenden Acetat-Salze.Examples of tertiary amines of the general formulas (IVa) and (IVb) are: N, N-dipropyl-N-laurylamine, N, N-dimethyl-N-laurylamine, N, N-dimethyl-N-hexadecylamine, N, N-dimethyl-N-cocosamine, N, N-dimethyl-N-cetylamine and the corresponding acetate salts.
Im Sinne der Erfindung ist es bevorzugt, zusätzlich zu den Verbindungen der allgemeinen Formel (I) Gemische von sekundären Diaminen der allgemeinen Formeln (III) und tertiären Aminen der allgemeinen Formeln (IV) einzusetzen, beispielsweise ein Gemisch aus N-Laurylpropylen-diammoniumacetat und N,N-Dimethyl-N-lauryl-ammoniumacetat im Gewichsverhältnis 1 : 2 bis 3 : 1, vorzugsweise 2 : 1.For the purposes of the invention, it is preferred to use, in addition to the compounds of the general formula (I), mixtures of secondary diamines of the general formulas (III) and tertiary amines of the general formulas (IV), for example a mixture of N-laurylpropylene diammonium acetate and N, N-dimethyl-N-laurylammonium acetate in a weight ratio of 1: 2 to 3: 1, preferably 2: 1.
Primäre, sekundäre und tertiäre Amine, die den vorstehend angegebenen allgemeinen Formeln (II), (III) und (IV) entsprechen, können nach literaturbekannten Verfahren hergestellt werden und werden zum Teil als Handelsprodukte angeboten, beispielsweise von der Hoechst AG, Frankfurt am Main, Deutschland, unter der Bezeichnung GENAMINR oder von der Lonza AG, Basel, Schweiz, unter der Bezeichnung LONZABACR 12.Primary, secondary and tertiary amines which correspond to the general formulas (II), (III) and (IV) given above can be prepared by processes known from the literature and are in some cases offered as commercial products, for example from Hoechst AG, Frankfurt am Main, Germany, under the name GENAMIN R or from Lonza AG, Basel, Switzerland, under the name LONZABAC R 12.
Das Gewichtsverhältnis der Verbindungen der allgemeinen Formel (I) zu den Aminen der allgemeinen Formeln (II), (III) und/oder (IV) ist nicht kritisch. Bevorzugt wird jedoch ein Gewichtsverhältnis von Verbindungen der allgemeinen Formel (I) zu den Verbindungen der allgemeinen Formeln (II), (III) und/oder (IV) im Bereich von 10 : 1 bis 1 : 10, insbesondere ein Verhältnis von 5 : 1 bis 1 : 1, eingestellt. Das oben genannte Gewichtsverhältnis ist auf die Summe der gegebenenfalls einzeln eingesetzten Verbindungen (II), (III) und (IV) bezogen.The weight ratio of the compounds of the general formula (I) to the amines of the general formulas (II), (III) and / or (IV) is not critical. However, a weight ratio of compounds of the general formula (I) to the compounds of the general formulas (II), (III) and / or (IV) in the range from 10: 1 to 1:10, in particular a ratio of 5: 1, is preferred up to 1: 1. The weight ratio mentioned above is based on the sum of the compounds (II), (III) and (IV) which may be used individually.
Weiterhin können die erfindungsgemäßen Schmiermittel als Hilfsstoffe Lösungsvermittler zum Erhalt einer homogenen, klarwasserlöslichen Anwendungslösung enthalten. Als solche kommen beispielsweise in Betracht: Alkohole, Polyalkohole, Ether oder Polyether, insbesondere Isopropanol, Butylglykol, Butyldiglykol oder Ethylenglykolether. Die Menge des zu verwendenden Lösungsvermittlers richtet sich im Einzelfall nach dem eingesetzten Betain bzw. Amin, der Fachmann wird im Einzelfall die erforderliche Menge an Lösungsvermittler durch Ausprobieren ermitteln. Im allgemeinen sind Zusätze an Lösungsvermittler im Bereich von 1 bis 20 Gew.-%, bezogen auf die Gesamtformulierung, hinreichend.Furthermore, the lubricants according to the invention can contain, as auxiliaries, solubilizers for obtaining a homogeneous, clear water-soluble application solution. Examples include: alcohols, polyalcohols, ethers or polyethers, in particular isopropanol, butyl glycol, butyl diglycol or ethylene glycol ether. The amount of the solubilizer to be used depends in each case on the betaine or amine used, the person skilled in the art will determine the required amount of solubilizer by trial and error in the individual case. In general, additions to solubilizers in the range from 1 to 20% by weight, based on the overall formulation, are sufficient.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung sind die einzusetzenden Alkyldimetylaminoxide mit einer Kettenlänge von 10 bis 18, insbesondere 12 bis 14 C-Atomen, im Alkylrest ausgestattet. Hierbei können die Alkylketten linear oder verzweigt, gesättigt, einfach oder mehrfach ungesättigt sein.In a preferred embodiment of the present invention, the alkyldimetylamine oxides to be used have a chain length of 10 to 18, in particular 12 to 14, carbon atoms in the alkyl radical. The alkyl chains can be linear or branched, saturated, mono- or polyunsaturated.
Alkyloligoglykoside im Sinne der vorliegenden Erfindung umfassen vorzugsweise Verbindungen der Formel (V),
R¹-O-[G]p (V)
in der
- R¹
- für einen Alkylrest mit 4 bis 22 Kohlenstoffatomen,
- [G]
- für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und
- p
- für Zahlen von 1 bis 10
R¹-O- [G] p (V)
in the
- R¹
- for an alkyl radical with 4 to 22 carbon atoms,
- [G]
- for a sugar residue with 5 or 6 carbon atoms and
- p
- for numbers from 1 to 10
Bevorzugt sind Alkyloligoglykoside, die sich von Aldosen bzw. Ketosen und wegen ihrer leichten Verfügbarkeit insbesondere von der Glucose ableiten. Die bevorzugten Alkyloligoglykoside sind somit die Alkyloligoglucoside.Alkyl oligoglycosides which are derived from aldoses or ketoses and, in particular, from glucose because of their ready availability are preferred. The preferred alkyl oligoglycosides are thus the alkyl oligoglucosides.
Die Indexzahl p in der allgemeinen Formel (V) gibt den Oligomerisierungsgrad (DP-Grad), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Bevorzugt sind Alkyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0; besonders bevorzugt sind solche Alkyloligoglykoside, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt.The index number p in the general formula (V) indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and here can assume the values p = 1 to 6 in particular, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl oligoglycosides with an average degree of oligomerization p of from 1.1 to 3.0 are preferred; those alkyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are particularly preferred.
Der Alkyrest R¹ kann sich von primären Alkoholen mit 4 bis 22, vorzugsweise 8 bis 16, insbesondere 8 bis 10, Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol, Laurylalkhohol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Arachylalkohol, Behenylalkohol sowie deren technische Mischungen auf Basis von natürlichen Fetten und Ölen, beispielsweise Palmöl, Palmkernöl, Kokosöl oder Rindertalg.The alkyl radical R 1 can be derived from primary alcohols having 4 to 22, preferably 8 to 16, in particular 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachyl alcohol, behenyl alcohol and their technical mixtures based on natural fats and oils, for example palm oil, palm kernel oil, coconut oil or beef tallow.
Alkyloligoglykoside stellen bekannte Stoffe dar, die nach den einschlägigen Methoden der präparativen organischen Chemie erhalten werden können. Stellvertretend für das umfangreiche Schrifttum hinsichtlich ihrer Struktur und Synthese sei auf die Europäische Patentanmeldung EP-A-0 301 298 verwiesen.Alkyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. As a representative of the extensive literature regarding its structure and synthesis, reference is made to the European patent application EP-A-0 301 298.
Im allgemeinen sind die genannten Tenside im Bereich von 1 bis 10 Gew.%, bezogen auf die Gesamtformulierung für die Benetzung der Ketten und Plattentransportbänder ausreichend. Die Aminoxide ebenso wie die Alkyloligoglykoside können jeweils allein oder im Gemisch eingesetzt werden.In general, the surfactants mentioned in the range from 1 to 10% by weight, based on the total formulation, are sufficient for wetting the chains and plate conveyor belts. The amine oxides as well as the alkyl oligoglycosides can each be used alone or in a mixture.
Bekannte Hilfsstoffe des Standes der Technik sind beispielsweise alkoxylierte Fettamine, Fettalkohole oder alkoxylierte Fettalkohole. Diese Tenside haben jedoch den Nachteil einer erhöhten Spannungsrißkorrosionsbildung bei PET-Flaschen. Daher werden derartige Tenside im Sinne der vorliegenden Erfindung bevorzugt nicht eingesetzt. Sofern dies jedoch trotzdem erwünscht ist, so sollte jedoch ihr Anteil möglichst gering gehalten werden.Known auxiliaries from the prior art are, for example, alkoxylated fatty amines, fatty alcohols or alkoxylated fatty alcohols. However, these surfactants have the disadvantage of increased stress corrosion cracking in PET bottles. Such surfactants are therefore preferably not used in the sense of the present invention. If, however, this is desired, their share should be kept as low as possible.
Die erfindungsgemäßen Schmiermittel weisen vorzugsweise einen pH-Wert im Bereich von 4 bis 11, insbesondere im Bereich von 6 bis 9, auf. Sofern der pH-Wert des Schmiermittels nicht bereits in diesem Bereich liegt, kann er durch Zugabe einer Säure, vorzugsweise einer Säure mit dem vorstehend definierten Anion X⁻, beispielsweise mit Essigsäure auf den gewünschten Wert eingestellt werden.The lubricants according to the invention preferably have a pH in the range from 4 to 11, in particular in the range from 6 to 9. If the pH of the lubricant is not already in this range, it can be added by adding an acid, preferably one Acid with the anion X⁻ defined above, for example with acetic acid to the desired value.
Im Hinblick auf eine optimale Dosiermöglichkeit ist es ferner von Vorteil, daß die Schmiermittel eine dynamische Viskosität von weniger als 300 mPa.s, insbesondere von weniger als 150 mPa.s und besonders bevorzugt im Bereich von 5 bis 100 mPa.s - jeweils bei 20 °C - aufweisen. Eine gesonderte Einstellung der Viskosität auf die genannten Werte ist im allgemeinen nicht erforderlich bzw. erfolgt gegebenenfalls durch Zusatz geeigneter Mengen des bevorzugten Verdünnungsmittels Wasser oder eines Lösungsvermittlers.With regard to an optimal metering option, it is also advantageous that the lubricants have a dynamic viscosity of less than 300 mPa.s, in particular less than 150 mPa.s and particularly preferably in the range from 5 to 100 mPa.s - in each case at 20 ° C - have. A separate adjustment of the viscosity to the values mentioned is generally not necessary or is optionally carried out by adding suitable amounts of the preferred diluent water or a solubilizer.
Die erfindungsgemäßen Schmiermittel lassen sie sich durch einfaches Vermischen der Komponenten mit Wasser, gegebenenfalls unter Zusatz der genannten Zusatz- und/oder Hilfsstoffe, herstellen.The lubricants according to the invention can be prepared by simply mixing the components with water, optionally with the addition of the additives and / or auxiliaries mentioned.
Die vorliegende Erfindung betrifft schließlich die Verwendung von Schmiermitteln der vorstehend beschriebenen Art als Kettenschmiermittel in der Lebensmittelindustrie, insbesondere für automatische Ketten- und Bandschmieranlagen. Für diesen Anwendungszweck werden die erfindungsgemäßen Schmiermittel im allgemeinen noch mit Wasser verdünnt. Derartige wäßrige Anwendungslösungen enthalten in der Regel 0,01 Gew.-% Verbindungen der allgemeinen Formeln (I) bis (IV), vorzugsweise 0,01 bis 0,2 Gew.-% und insbesondere 0,02 bis 0,04 Gew.-% derartiger Verbindungen, sowie 0,1 bis 1 Gew.-% der genannten, erfindungsgemäßen Tenside.Finally, the present invention relates to the use of lubricants of the type described above as chain lubricants in the food industry, in particular for automatic chain and belt lubrication systems. For this purpose, the lubricants according to the invention are generally diluted with water. Such aqueous application solutions generally contain 0.01% by weight of compounds of the general formulas (I) to (IV), preferably 0.01 to 0.2% by weight and in particular 0.02 to 0.04% by weight. % of such compounds and 0.1 to 1% by weight of the surfactants according to the invention mentioned.
Die erfindungsgemäßen Produkte verursachen im Gegensatz zu Standard-Seifenprodukten keine Spannungsrißkorrosion und können daher für PET und PC-Gebinde problemlos eingesetzt werden. (PET = Polyethylenterephthalat, PC= Polycarbonat). Besonders bevorzugt für klarwasserlösliche Konzentrate sind neutrale pH-Werte.In contrast to standard soap products, the products according to the invention do not cause stress corrosion cracking and can therefore be used without problems for PET and PC containers. (PET = polyethylene terephthalate, PC = polycarbonate). Neutral pH values are particularly preferred for clear water-soluble concentrates.
Die erfindungsgemäßen Schmiermittel eignen sich nämlich in der für die Ketten- und Bandschmierung erforderlichen Konzentration auch zum Reinigen von Leergut sowie Maschinen und Maschinenteilen.The lubricants according to the invention are namely suitable in the concentration required for chain and belt lubrication also for cleaning empties as well as machines and machine parts.
Ferner sind die zentralen Schaumsysteme in der Lebensmittelindustrie teilweise mit fest installierten, automatischen Systemen ausgestattet, die nach produktionsablauf oder in Pausen automatisch die Außenreinigung von Füllern, zylindrokonischen Gär- und Lagertanks, Transportunterbändern und anderen Maschinen und Anlagen bewirken.Furthermore, the central foam systems in the food industry are partially equipped with permanently installed, automatic systems that automatically clean the outside of fillers, cylindroconical fermentation and storage tanks, conveyor belts and other machines and systems after production or during breaks.
Auch hier können die erfindungsgemäßen Schmiermittel mit großem Vorteil Verwendung finden.Here too, the lubricants according to the invention can be used with great advantage.
Somit betrifft die vorliegende Erfindung ferner die Verwendung von Schmiermitteln der vorstehend beschriebenen Art zum Desinfizieren und Reinigen von Leergut, Maschinen und Anlagen in der Lebensmittel- und Getränkeindustrie.Thus, the present invention further relates to the use of lubricants of the type described above for disinfecting and cleaning empties, machines and systems in the food and beverage industry.
Die vorliegende Erfindung wird durch die nachfolgenden Beispiele näher erläutert. In den erfindungsgemäßen Beispielen 1 und 2 werden der Reibungswiderstand und das Schaumverhalten von erfindungsgemäßen Schmiermittelformulierungen aufgezeigt. Zum Vergleich dienen die Vergleichsbeispiele 1 bis 3, die Produkte des Standes der Technik betreffen.The present invention is illustrated by the following examples. Examples 1 and 2 according to the invention show the frictional resistance and the foaming behavior of lubricant formulations according to the invention. Comparative examples 1 to 3, which relate to products of the prior art, serve for comparison.
Alle Prozentangaben in den nachstehenden Formulierungs-Beispielen beziehen sich auf Gewichtsprozente.All percentages in the formulation examples below relate to percentages by weight.
Die PET-Flaschen werden mit kohlensäurehaltigem Wasser von 4,5 Vol% CO2 gefüllt und entsprechend verschlossen. Die Flaschen werden im Bodenbereich in die zu prüfende Substanz (siehe Tabelle 1) getaucht und bei 38° C für 72 Studen gelagert. Danach wird die Flasche bemustert (von keine Spannungsrisse bis zerstörte Flasche).The PET bottles are filled with carbonated water of 4.5 vol% CO2 and sealed accordingly. The bottles are immersed in the substance to be tested in the bottom area (see Table 1) and stored at 38 ° C for 72 hours. Then the bottle is sampled (from no stress cracks to destroyed bottle).
Die Versuche zur Messung des Reibungswiderstandes, im folgenden kurz "Reibbeiwert" genannt, sind auf einem Technikums-Flaschentransportband unter folgenden Bedingungen durchgeführt worden:
Messung des Reibwiderstandes von 20 mit Wasser gefüllten 0,5 l Euro-Bierflaschen als Zugspannung mit einem Dynamometer.
Flaschentransportgeschwindigkeit: ca. 1 m/s
Besprühen des Flaschentransportbandes mit 0,4 %iger Bandschmiermittellösung, wie in den Beispielen genannt.
Sprühleistung der Düsen: 4 l/h, 1 Düse pro Band.The tests for measuring the frictional resistance, hereinafter referred to as "coefficient of friction", were carried out on a pilot bottle conveyor belt under the following conditions:
Measurement of the frictional resistance of 20 0.5 l Euro beer bottles filled with water as tension using a dynamometer.
Bottle transport speed: approx. 1 m / s
Spray the bottle conveyor belt with 0.4% tape lubricant solution, as mentioned in the examples.
Spraying performance of the nozzles: 4 l / h, 1 nozzle per belt.
Der im folgenden angegebene Reibbeiwert "µ" ergibt sich als der Quotient der gemessenen Zugspannung für eine Flasche zum Gewicht der Flasche in Gramm.The coefficient of friction "µ" given below is the quotient of the measured tensile stress for a bottle to the weight of the bottle in grams.
Weiterhin wurden die Produkte mit Hartwasser (16 °d) nach den Bestimmungen der DIN 53 902 getestet.Furthermore, the products were tested with hard water (16 ° d) according to the provisions of DIN 53 902.
Das Schaumverhalten wird nach folgenden Klassen beurteilt:
- 0 = schaumfrei
- 1 = vereinzelte Schaumblasen
- 2 = geringes Schäumen, nicht störend
- 3 = Schäumen, störend
- 4 = starkes Schäumen, nicht akzeptabel, Schaum unter dem Band
- 0 = foam-free
- 1 = isolated foam bubbles
- 2 = low foaming, not disturbing
- 3 = foaming, disturbing
- 4 = strong foaming, not acceptable, foam under the tape
Der Reibbeiwert sollte zur ausreichenden Schmierung bei oder kleiner gleich 0,10 bis 0,12 liegen. Bei Überschreiten von 0,15 läßt die Schmierwirkung und somit der einwandfreie Transport deutlich nach.For sufficient lubrication, the coefficient of friction should be 0.10 to 0.12 or less. If the value exceeds 0.15, the lubricating effect and thus the perfect transport will decrease significantly.
Die Klarwasserlöslichkeit der Anwendungslösungen sollte auch über einen längeren Versuchszeitraum gewährleistet sein, um Ablagerungen in Kugelventilfiltern, Düsen, Sprüh- und Verteilsystem, Band und Transportgut zu vermeiden.The clear water solubility of the application solutions should also be guaranteed over a longer test period in order to avoid deposits in ball valve filters, nozzles, spray and distribution systems, conveyor belts and transport goods.
Die Schaumentwicklung sollte gering sein, da übermäßiger Schaum nicht nur den Arbeitsablauf (automatischer bottle inspector) und die Arbeitssicherheit (Rutschgefahr) stört, sondern darüber hinaus auch das Etikett aufweichen und in das noch nicht verschlossene Gefäß dringen kann. Zusätzlich wird durch übermäßige Schaumneigung der Reibbeiwert verschlechtert.
Anionische Tenside wie das Alkylbenzolsulfonat lassen sich nicht in die kationisch reagierenden Kettengleitmittel auf Alkylaminbasis einarbeiten, so daß nur noch Aminoxide und Alkylpolyglucoside für den Einsatz in entsprechenden Kettengleitmitteln verbleiben.Anionic surfactants such as alkylbenzenesulfonate cannot be incorporated into the cationically reacting chain lubricants based on alkylamines, so that only amine oxides and alkyl polyglucosides remain for use in corresponding chain lubricants.
6 % Cocospropylendiammoniumacetat
6 % Cocosdipropylentriammoniumacetat
3 % Cocosalkyldimethylaminoxid
85 % Wasser
Reibbeiwert: 0,14 Schaumverhalten: schäumend
Eignung: wenig Risse Klarwasserlöslichkeit: absolut klar6% coconut propylene diammonium acetate
6% coconut dipropylene triammonium acetate
3% coco alkyl dimethyl amine oxide
85% water
Friction coefficient: 0.14 Foam behavior: foaming
Suitability: few cracks Clear water solubility: absolutely clear
6 % Cocospropylendiammoniumacetat
6 % Cocosdipropylentriammoniumacetat
3 % C₈₋₁₀ Glycosidn=1,4 (60 % Aktivsubstanz)
85 % Wasser
Reibbeiwert: 0,10 Schaumverhalten: mäßig schäumend
Eignung: keine Rißbildung Klarwasserlöslichkeit: absolut klar6% coconut propylene diammonium acetate
6% coconut dipropylene triammonium acetate
3% C₈₋₁₀ glycoside n = 1.4 (60% active substance)
85% water
Friction coefficient: 0.10 Foam behavior: moderately foaming
Suitability: no cracking Clear water solubility: absolutely clear
8 % Laurylpropylendiammoniumacetat
4 % N,N-Dimethyl-N-laurylammoniumacetat
88 % Wasser
Reibbeiwert: 0,10 Schaumverhalten: nicht schäumend
PET-Eignung: wenig Risse Klarwasserlöslichkeit: opak8% lauryl propylene diammonium acetate
4% N, N-dimethyl-N-laurylammonium acetate
88% water
Friction coefficient: 0.10 Foam behavior: not foaming
PET suitability: few cracks. Clear water solubility: opaque
6 % Cocospropylendiammoniumacetat
6 % Cocosdipropylentriammoniumacetat
88 % Wasser
Reibbeiwert: 0,10 Schaumverhalten: schwach schäumend
PET-Eignung: keine Risse Klarwasserlöslichkeit: schwach opak6% coconut propylene diammonium acetate
6% coconut dipropylene triammonium acetate
88% water
Friction coefficient: 0.10 Foam behavior: slightly foaming
PET suitability: no cracks. Clear water solubility: slightly opaque
6 % Cocospropylendiammoniumacetat
6 % Cocosdipropylentriammoniumacetat
3 % Cocosfettamin + 12EO
85 % Wasser
Reibbeiwert: 0,11 Schaumverhalten: schwach schäumend
PET-Eignung: starke Risse Klarwasserlöslichkeit: absolut klar6% coconut propylene diammonium acetate
6% coconut dipropylene triammonium acetate
3% coconut fatty amine + 12EO
85% water
Friction coefficient: 0.11 Foam behavior: slightly foaming
PET suitability: strong cracks Clear water solubility: absolutely clear
Claims (16)
- Soapless lubricants based on amphoteric compounds, primary, secondary and/or tertiary amines and/or salts of such amines corresponding to general formulae (I), (IIa), (IIb), (IIIa), (IIIb), (IIIc), (IVa) and (IVb):
R⁴-NH-R⁵ (IIa)
R⁴-N⁺H₂-R⁵ X⁻ (IIb)
R⁴-NH-(CH₂)₃NH₂ (IIIa)
R⁴-NH-(CH₂)₃N⁺H₃ X⁻ (IIIb)
R⁴-N⁺H₂-(CH₂)₃-N⁺H₃ 2X⁻ (IIIc)
R⁴-NR⁷R⁸ (IVa)
and/or
R⁴-N⁺HR⁷R⁸ X⁻ (IVb)
in whichR represents a saturated or mono- or polyunsaturated, linear or branched alkyl group containing 6 to 22 carbon atoms which may optionally be substituted by -OH, -NH₂, -NH-, -CO-, -(CH₂CH₂O)l- or -(CH₂CH₂CH₂O)l-,R¹ represents hydrogen, an alkyl group containing 1 to 4 carbon atoms, a hydroxyalkyl group containing 1 to 4 carbon atoms or a group -R³COOM,R² - only for the case where M is a negative charge - represents hydrogen, an alkyl group containing 1 to 4 carbon atoms or a hydroxyalkyl group containing 1 to 4 carbon atoms,R³ is a saturated or mono- or polyunsaturated, linear or branched alkyl group containing 1 to 12 carbon atoms which may optionally be substituted by -OH, -NH₂, -NH-, -CO-, -(CH₂CH₂O)l- or -(CH₂CH₂CH₂O)l-,R⁴ is a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl group containing 6 to 22 carbon atoms which may contain at least one amine, imine, hydroxy, halogen and/or carboxy group as substituent, a substituted or unsubstituted phenyl group which may contain at least one amine, imine, hydroxy, halogen, carboxy group and/or a linear or branched saturated or mono- or polyunsaturated alkyl group containing 6 to 22 carbon atoms as substituent(s),R⁵ is hydrogen or - independently of R⁴ - has the same meaning as R⁴,X⁻ is an anion from the group consisting of amidosulfonate, nitrate, halide, sulfate, hydrogen carbonate, carbonate, phosphate or R⁶-COO⁻, whereR⁶ is hydrogen, a substituted or unsubstituted, linear or branched alkyl group containing 1 to 20 carbon atoms or alkenyl group containing 2 to 20 carbon atoms, which may contain a hydroxy, amine or imine group as substituent, or a substituted or unsubstituted phenyl group which may contain an alkyl group with 1 to 20 carbon atoms as substituent, andR⁷ and R⁸ independently of one another represent a substituted or unsubstituted, linear or branched alkyl group containing 1 to 20 carbon atoms or alkenyl group containing 2 to 20 carbon atoms, which may contain at least one hydroxy, amine or imine group as substituent, or a substituted or unsubstituted phenyl group which may contain an alkyl group with 1 to 20 carbon atoms as substituent,M is hydrogen, alkali metal, ammonium, an alkyl group containing 1 to 4 carbon atoms, a benzyl group or a negative charge,n is an integer of 1 to 12,m is an integer of 0 to 5 andl is a number of 0 to 5,containing alkyl dimethylamine oxides and/or alkyl oligoglycosides as nonionic surfactants. - Lubricants as claimed in claim 1, characterized in that, in general formula (I),R is a saturated or mono- or polyunsaturated linear alkyl group containing 10 to 18 carbon atoms, which may optionally be substituted by -CO-, more particularly an unsubstituted, saturated linear alkyl group containing 12 to 14 carbon atoms,R¹ is hydrogen, an alkyl group containing 1 to 3 carbon atoms or a group -CH₂CH₂OH, more particularly hydrogen or an alkyl group containing 1 to 3 carbon atoms,R² is hydrogen or an alkyl group containing 1 to 3 carbon atoms,R³ is a methylene or dimethylene group, more particularly a methylene group,M is hydrogen or a negative charge,n = 2 or 3, more particularly 2,m = 0, 1 or 2, more particularly 0.
- Lubricants as claimed in claim 1 or 2, characterized in that they contain the compounds corresponding to general formulae (I) to (IV) in a quantity of 1 to 99% by weight, based on the formulation as a whole.
- Lubricants as claimed in claim 3, characterized in that they contain the compounds corresponding to general formulae (I) to (IV) in a quantity of 5 to 15% by weight and more particularly in a quantity of 10 to 12% by weight, based on the formulation as a whole.
- Lubricants as claimed in claims 1 to 4, characterized in that they additionally contain water and optionally additives and/or auxiliaries.
- Lubricants as claimed in one or more of claims 1 to 5, characterized in that the ratio by weight of compounds corresponding to general formula (I) to compounds corresponding to formulae (II), (III) and/or (IV) is in the range from 10:1 to 1:10 and more particularly in the range from 5:1 to 1:1.
- Lubricants as claimed in one or more of claims 1 to 6, characterized in that they contain solubilizers and/or pH regulators as auxiliaries.
- Lubricants as claimed in one or more of claims 1 to 7, characterized in that they have a pH value in the range from 4 to 11 and more particularly in the range from 6 to 9.
- Lubricants as claimed in one or more of claims 1 to 8, characterized in that they have a dynamic viscosity of less than 300 mPa.s and more particularly in the range from 5 to 100 mPa.s.
- Lubricants as claimed in one or more of claims 1 to 9, characterized in that the alkyl dimethylamine oxides have a linear or branched, saturated, mono- or polyunsaturated alkyl group containing 10 to 18 and more particularly 12 to 14 carbon atoms.
- Lubricants as claimed in one or more of claims 1 to 10, characterized in that the alkyl oligoglycosides are compounds corresponding to formula (V):
R¹-O-[G]p (V)
in whichR¹ is an alkyl group containing 4 to 22 carbon atoms, preferably 8 to 16 carbon atoms,[G] is a sugar unit containing 5 or 6 carbon atoms andp is a number of 1 to 10. - Lubricants as claimed in claim 11, characterized in that the alkyl oligoglycosides are derived from aldoses and/or ketoses, more particularly from glucose.
- Lubricants as claimed in one or more of claims 1 to 12, characterized in that they contain alkyl oligoglucosides.
- Lubricants as claimed in one or more of claims 1 to 13, characterized in that they contain 1 to 10% by weight of alkyl oligoglycosides and/or amine oxides.
- The use of the lubricants claimed in any of claims 1 to 14 as chain lubricants in the food industry, more particularly for automatic chain and belt lubrication systems.
- The use of the lubricants claimed in any of claims 1 to 14 for cleaning empties, machines and installations in the food and beverage industry.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4206506 | 1992-03-02 | ||
DE4206506A DE4206506A1 (en) | 1992-03-02 | 1992-03-02 | TENSID BASIS FOR SOAP-FREE LUBRICANTS |
PCT/EP1993/000413 WO1993018121A1 (en) | 1992-03-02 | 1993-02-22 | Surface-active base for non-soap lubricants |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0629235A1 EP0629235A1 (en) | 1994-12-21 |
EP0629235B1 true EP0629235B1 (en) | 1995-11-15 |
Family
ID=6453016
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93904004A Expired - Lifetime EP0629235B1 (en) | 1992-03-02 | 1993-02-22 | Surface-active base for non-soap lubricants |
Country Status (8)
Country | Link |
---|---|
US (1) | US5565127A (en) |
EP (1) | EP0629235B1 (en) |
AT (1) | ATE130361T1 (en) |
CA (1) | CA2131312A1 (en) |
DE (2) | DE4206506A1 (en) |
DK (1) | DK0629235T3 (en) |
ES (1) | ES2079966T3 (en) |
WO (1) | WO1993018121A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US8973803B2 (en) | 2008-02-14 | 2015-03-10 | Ethicon Endo-Surgery, Inc. | Surgical stapling apparatus with control features operable with one hand |
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DE19721602A1 (en) * | 1997-05-23 | 1998-11-26 | Henkel Ecolab Gmbh & Co Ohg | Paste or gel-like high concentrate for amine-containing lubricant solutions in the food industry |
GB2329644B (en) * | 1997-06-12 | 2002-03-27 | Laporte Industries Ltd | Aqueous lubricant composition comprising a monoamine |
US20040055965A1 (en) * | 1997-06-13 | 2004-03-25 | Hubig Stephan M. | Recreational water treatment employing singlet oxygen |
US20030194433A1 (en) * | 2002-03-12 | 2003-10-16 | Ecolab | Antimicrobial compositions, methods and articles employing singlet oxygen- generating agent |
DE19921709A1 (en) | 1999-05-12 | 2000-11-16 | Henkel Ecolab Gmbh & Co Ohg | Lubricating, cleaning or disinfecting of machinery used for filling containers with drinks or foodstuffs using a product concentrate diluted with water as lubricant and further diluted for cleaning |
ES2386297T3 (en) | 1999-07-22 | 2012-08-16 | Diversey, Inc. | Use of lubricant composition to lubricate a conveyor belt |
US6495494B1 (en) | 2000-06-16 | 2002-12-17 | Ecolab Inc. | Conveyor lubricant and method for transporting articles on a conveyor system |
US7384895B2 (en) * | 1999-08-16 | 2008-06-10 | Ecolab Inc. | Conveyor lubricant, passivation of a thermoplastic container to stress cracking and thermoplastic stress crack inhibitor |
US6207622B1 (en) * | 2000-06-16 | 2001-03-27 | Ecolab | Water-resistant conveyor lubricant and method for transporting articles on a conveyor system |
EP1308394B1 (en) | 1999-08-16 | 2011-11-30 | Ecolab Inc. | Method for Lubricating the Passage of a Container along a Conveyor |
US6427826B1 (en) | 1999-11-17 | 2002-08-06 | Ecolab Inc. | Container, such as a food or beverage container, lubrication method |
DE19942536A1 (en) | 1999-09-07 | 2001-03-08 | Henkel Ecolab Gmbh & Co Ohg | Use of polysiloxane-based lubricants |
DE19942534A1 (en) | 1999-09-07 | 2001-03-08 | Henkel Ecolab Gmbh & Co Ohg | Lubricants containing fluorine |
US7527745B1 (en) * | 1999-09-24 | 2009-05-05 | Ecolab Inc. | Product stability enhancement with phosphonium salts |
US7364033B2 (en) * | 1999-11-17 | 2008-04-29 | Ecolab Inc. | Container, such as a food or beverage container, lubrication method |
DE19959315A1 (en) | 1999-12-09 | 2001-06-21 | Henkel Ecolab Gmbh & Co Ohg | Improvement of the transport of containers on transport systems |
AU2001249216A1 (en) * | 2000-05-12 | 2001-11-26 | Ecolab Inc. | Product stability enhancement with phosphonium salts |
US6806240B1 (en) | 2000-08-14 | 2004-10-19 | Ecolab Inc. | Conveyor lubricant, passivation of a thermoplastic container to stress cracking, and thermoplastics stress crack inhibitor |
US6576298B2 (en) | 2000-09-07 | 2003-06-10 | Ecolab Inc. | Lubricant qualified for contact with a composition suitable for human consumption including a food, a conveyor lubrication method and an apparatus using droplets or a spray of liquid lubricant |
US6591970B2 (en) | 2000-12-13 | 2003-07-15 | Ecolab Inc. | Water-activatable conveyor lubricant and method for transporting articles on a conveyor system |
US6509302B2 (en) | 2000-12-20 | 2003-01-21 | Ecolab Inc. | Stable dispersion of liquid hydrophilic and oleophilic phases in a conveyor lubricant |
DE10106954A1 (en) | 2001-02-15 | 2002-09-05 | Ecolab Gmbh & Co Ohg | Alcohol-based lubricant concentrates |
DE10146264A1 (en) | 2001-09-20 | 2003-04-17 | Ecolab Gmbh & Co Ohg | Use of O / W emulsions for chain lubrication |
US6656886B1 (en) * | 2001-12-31 | 2003-12-02 | Philip Thoralf Johnson | Lubricant for smoothing caulking joints and method of use |
US6855676B2 (en) | 2002-02-11 | 2005-02-15 | Ecolab., Inc. | Lubricant for conveyor system |
US20070020300A1 (en) * | 2002-03-12 | 2007-01-25 | Ecolab Inc. | Recreational water treatment employing singlet oxygen |
US20040235680A1 (en) * | 2002-09-18 | 2004-11-25 | Ecolab Inc. | Conveyor lubricant with corrosion inhibition |
US6967189B2 (en) | 2002-11-27 | 2005-11-22 | Ecolab Inc. | Buffered lubricant for conveyor system |
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US7820603B2 (en) * | 2005-03-15 | 2010-10-26 | Ecolab Usa Inc. | Low foaming conveyor lubricant composition and methods |
US7741257B2 (en) | 2005-03-15 | 2010-06-22 | Ecolab Inc. | Dry lubricant for conveying containers |
US7745381B2 (en) | 2005-03-15 | 2010-06-29 | Ecolab Inc. | Lubricant for conveying containers |
US7727941B2 (en) | 2005-09-22 | 2010-06-01 | Ecolab Inc. | Silicone conveyor lubricant with stoichiometric amount of an acid |
US7915206B2 (en) | 2005-09-22 | 2011-03-29 | Ecolab | Silicone lubricant with good wetting on PET surfaces |
US7741255B2 (en) | 2006-06-23 | 2010-06-22 | Ecolab Inc. | Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with pet |
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-
1992
- 1992-03-02 DE DE4206506A patent/DE4206506A1/en not_active Withdrawn
-
1993
- 1993-02-22 CA CA002131312A patent/CA2131312A1/en not_active Abandoned
- 1993-02-22 AT AT93904004T patent/ATE130361T1/en not_active IP Right Cessation
- 1993-02-22 US US08/295,804 patent/US5565127A/en not_active Expired - Fee Related
- 1993-02-22 DE DE59300967T patent/DE59300967D1/en not_active Expired - Fee Related
- 1993-02-22 DK DK93904004.4T patent/DK0629235T3/en active
- 1993-02-22 ES ES93904004T patent/ES2079966T3/en not_active Expired - Lifetime
- 1993-02-22 EP EP93904004A patent/EP0629235B1/en not_active Expired - Lifetime
- 1993-02-22 WO PCT/EP1993/000413 patent/WO1993018121A1/en active IP Right Grant
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8973803B2 (en) | 2008-02-14 | 2015-03-10 | Ethicon Endo-Surgery, Inc. | Surgical stapling apparatus with control features operable with one hand |
Also Published As
Publication number | Publication date |
---|---|
ATE130361T1 (en) | 1995-12-15 |
CA2131312A1 (en) | 1993-09-16 |
DE4206506A1 (en) | 1993-09-09 |
ES2079966T3 (en) | 1996-01-16 |
DE59300967D1 (en) | 1995-12-21 |
EP0629235A1 (en) | 1994-12-21 |
WO1993018121A1 (en) | 1993-09-16 |
US5565127A (en) | 1996-10-15 |
DK0629235T3 (en) | 1996-03-25 |
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