EP1210400A2 - Lubricants containing fluorine - Google Patents

Lubricants containing fluorine

Info

Publication number
EP1210400A2
EP1210400A2 EP00967633A EP00967633A EP1210400A2 EP 1210400 A2 EP1210400 A2 EP 1210400A2 EP 00967633 A EP00967633 A EP 00967633A EP 00967633 A EP00967633 A EP 00967633A EP 1210400 A2 EP1210400 A2 EP 1210400A2
Authority
EP
European Patent Office
Prior art keywords
use according
formulations
transport
compounds
antimicrobial
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00967633A
Other languages
German (de)
French (fr)
Inventor
Stefan Küpper
Michael Schneider
Harald Kluschanzoff
Walter GROSSE BÖWING
Alfred Laufenberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab GmbH and Co OHG
Original Assignee
Henkel Ecolab GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Ecolab GmbH and Co KG filed Critical Henkel Ecolab GmbH and Co KG
Publication of EP1210400A2 publication Critical patent/EP1210400A2/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00Lubricating compositions containing more than 10% water
    • C10M173/02Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C10M173/025Lubricating compositions containing more than 10% water not containing mineral or fatty oils for lubricating conveyor belts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04Hydroxy compounds
    • C10M129/06Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/08Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least 2 hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M131/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen
    • C10M131/08Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen, halogen and oxygen
    • C10M131/10Alcohols; Ethers; Aldehydes; Ketones
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    • C10M131/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen
    • C10M131/08Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen, halogen and oxygen
    • C10M131/12Acids; Salts or esters thereof
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10Sulfonic acids or derivatives thereof
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/40Polysaccharides, e.g. cellulose
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M147/00Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
    • C10M147/04Monomer containing carbon, hydrogen, halogen and oxygen
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02Water
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/12Polysaccharides, e.g. cellulose, biopolymers
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    • C10M2211/00Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/042Alcohols; Ethers; Aldehydes; Ketones
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    • C10M2211/00Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/044Acids; Salts or esters thereof
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    • C10M2211/00Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06Perfluorinated compounds
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    • C10M2213/00Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
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    • C10M2213/00Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/04Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2213/00Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06Perfluoro polymers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/223Five-membered rings containing nitrogen and carbon only
    • C10M2215/224Imidazoles
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26Amines
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/30Refrigerators lubricants or compressors lubricants
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/32Wires, ropes or cables lubricants
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/34Lubricating-sealants
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/36Release agents or mold release agents
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/38Conveyors or chain belts
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/40Generators or electric motors in oil or gas winning field
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/42Flashing oils or marking oils
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    • C10N2040/44Super vacuum or supercritical use
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    • C10N2040/50Medical uses
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    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01Emulsions, colloids, or micelles

Definitions

  • the present invention relates to the use of formulations which contain at least one fluorinated component for reducing the friction between transport goods and transport systems.
  • the containers to be filled in the filling plants are transported by means of conveyors of various designs and materials, for example by means of plate conveyor belts or chain-like arrangements, which are generally referred to below as transport chains.
  • the transporters establish the connection between the various optional treatment stages of the filling process such as B. Unpacker, bottle washer, filler, capper, labeler, packer, etc.
  • the containers can be of various shapes, in particular glass and plastic bottles, cans, glasses, barrels, beverage containers (KEG), paper and cardboard containers.
  • KEG beverage containers
  • the transport chains must be lubricated in a suitable manner so that excessive friction against the containers is avoided. Diluted aqueous solutions containing suitable friction-reducing agents are usually used for lubrication.
  • the transport chains are brought into contact with the aqueous solutions, for example by immersion or spraying, in which case one speaks of splash lubrication systems or automatic belt lubrication systems or central chain lubrication systems.
  • the chain lubricants hitherto used as lubricants are mostly based on fatty acids in the form of their water-soluble alkali metal or alkanolamine salts or on fatty amines, preferably in the form of their organic or inorganic salts. While both substance classes can be used without problems in splash lubrication, they show a number of disadvantages in the central chain lubrication systems that are common today.
  • soap-based lubricants have the following disadvantages:
  • Soap-based lubricant preparations continue to be dependent on water temperature.
  • Soap-based lubricants only have a low storage stability, especially at low temperatures.
  • the EDTA ethylenediaminetetraacetate contained in many products is known to be poorly biodegradable. 12. Such soap-based lubricant preparations are not suitable for all transport goods made of plastic, since in many cases stress corrosion cracking on the transport goods occurs when these agents are used.
  • DE-A-36 31 953 describes a method for lubricating chain-shaped bottle conveyor belts in beverage bottling plants, particularly in breweries, and for cleaning the belts by means of a liquid cleaning agent, which is characterized in that the chain-shaped bottle conveyor belts are based on belt lubricants neutralized primary fatty amines, which preferably have 12 to 18 carbon atoms and contain an unsaturated fraction of more than 10%.
  • R 1 is a saturated or unsaturated, branched or linear alkyl group with 8 to 22 C atoms
  • R 2 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms or -A- NH 2 ;
  • A is a linear or branched alkylene group with 1 to 8 carbon atoms
  • a ⁇ is a linear or branched alkylene group having 2 to 4 carbon atoms.
  • DE-A-39 05 548 discloses lubricants based on N-alkylated fatty amine derivatives which contain at least one secondary and / or tertiary amine.
  • R is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, which may be replaced by -OH, - NH 2 , -NH-, -CO-, - (CH 2 CH 2 0) or - (CH 2 CH 2 CH 2 0) r can be substituted,
  • R 1 represents hydrogen, an alkyl radical having 1 to 4 carbon atoms, a hydroxyalkyl radical having 1 to 4 carbon atoms or a radical -R 3 COOM
  • R 2 only if M represents a negative charge for hydrogen, an alkyl radical with 1 to 4 C atoms, or a hydroxyalkyl radical with 1 to 4 C atoms,
  • R 3 is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 1 to 12 carbon atoms, which may be replaced by -OH, - NH 2 , -NH-, -CO-, - (CH 2 CH 2 0) r or - (CH 2 CH 2 CH 2 0)
  • - can be substituted,
  • R 4 represents a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, which may have at least one amine, imine, hydroxyl, halogen and / or carboxy radical as substituent, a substituted or unsubstituted phenyl radical which may have at least one amine, imine, hydroxyl, halogen, carboxy and / or a linear or branched, saturated or mono- or polyunsaturated alkyl radical with 6 to 22 C atoms as substituents,
  • R 5 for hydrogen or - independently of R 4 - for a radical R 4 ,
  • X stands for an anion from the group amidosulfonate, nitrate, halide, sulfate, hydrogen carbonate, carbonate, phosphate or R ⁇ -COO " ,
  • R ⁇ represents hydrogen, a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 carbon atoms or alkenyl radical having 2 to 20 carbon atoms, which may have at least one hydroxyl, amine or imine radical as a substituent, or a substituted or unsubstituted phenyl radical, which may have an alkyl radical with 1 to 20 C atoms as a substituent, and
  • R 7 and R 8 each independently of one another represent a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 C atoms or alkenyl radical having 2 to 20 C atoms, which may have at least one hydroxyl, amine or imine radical as substituents, or a substituted or unsubstituted phenyl radical, which may have an alkyl radical with 1 to 20 C atoms as substituents,
  • M for hydrogen, alkali metal, ammonium, an alkyl radical with 1 to 4 carbon atoms, a benzyl radical or a negative charge
  • n for an integer in the range from 1 to 12
  • m for an integer in the range from 0 to 5 and
  • I stands for a number in the range from 0 to 5, containing alkyldimethylamine oxides and / or alkyl oligoglycosides as nonionic
  • EP-B-629 234 discloses a lubricant combination consisting of a) one or more compounds of the formula
  • R 1 is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, which is optionally by -OH, -NH 2 , -NH-, -CO-, halogen or a carboxyl radical can be substituted,
  • R2 for a carboxyl radical with 2 to 7 carbon atoms
  • M represents hydrogen, alkali metal, ammonium, an alkyl radical having 1 to 4 carbon atoms or a benzyl radical and n represents an integer in the range from 1 to 6, b) at least one organic carboxylic acid selected from monobasic or polybasic, saturated or simple or polyunsaturated carboxylic acids with 2 to 22 carbon atoms, c) optionally water and additives and / or auxiliaries.
  • WO 94/03562 describes a lubricant concentrate based on fatty amines and, if appropriate, conventional diluents or auxiliaries or additives, characterized in that it contains at least one polyamine derivative of a fatty amine and / or a salt of such an amine, the proportion of the polyamine derivatives mentioned being Fatty amines in the total formulation is 1 to 100% by weight.
  • this lubricant concentrate contains at least one polyamine derivative of a fatty amine of the general formula
  • R is a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, the substituents being selected from amino, imino, hydroxy, halogen and carboxy, or is a substituted or unsubstituted phenyl radical, the substituents being selected from amino, imino, hydroxy, halogen, carboxy and a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms;
  • A represents either -NH- or -O-,
  • Lubricants based on polytetrafluoroethylene are used in some filling plants. These are in the form of dispersions and are not applied to the chains via nozzles, as is usually the practice, but with brushes. These agents have the advantage that they bring about a substantial reduction in the friction between the conveyor belts and the goods to be transported. In addition, the polytetrafluoroethylene adheres very strongly to the chains.
  • the object of the present invention is to provide lubricants based on organic fluorine compounds which, on the one hand, are stable in storage, on the other hand are well compatible with plastic containers and at the same time improve the lubricating performance compared to the amines usually used as lubricants.
  • the present invention relates to the use of formulations which contain at least one fluorinated component selected from the groups of a) per- or partially fluorinated monomeric organic compounds, b) pure and mixed di- and oligomers which are based on at least one per- or partially fluorinated organic monomer , c) pure and mixed polymers which are based on at least one per- or partially fluorinated organic monomer and in the polymer there is at least one monomer unit which is either less than 75% by weight of fluorine, based on the weight of the total monomer unit, or more than 2 ° C.
  • -Atoms contains, included, to reduce the friction between cargo and transportation equipment.
  • the present invention relates to the generally known characterization of polymers which are composed of so many identical or similar low molecular weight building blocks (monomers) that the physical properties of these substances, in particular the viscoelasticity, contribute to No longer noticeably change the increase or decrease in the number of blocks by one unit. This is generally the case when the average molecular weight of the "polymers" is 10,000 g / mol or more.
  • the term oligomers is used for the low molecular weight dimers, trimers and other lower members of the polymer homologous series.
  • group a) comprises at least per- and partially fluorinated surfactants, alkanes, ethers and amines, particularly preferably in the formulations used according to the invention ammonium perfluoroalkylsulfonates, lithium perfluoroalkylsulfonates, potassium perfluoroalkylsulfonates, amine perfluoroalkylsulfonates, sodium perfluoroalkylsulfonates, potassium fluoramate carboxylates, potassium fluoramate carboxylates, ammonium iodides, ammonium perfluoroalkyl carboxalates, fluorinated alkyl polyoxyethyl enethanols, fluorinated alkyl alkoxylates, fluorinated alkyl esters with concentrations of 0.001 to 10% are used.
  • the fluorinated components of group c) are preferably per- and / or partially fluorinated alkoxy polymers, which are particularly preferably obtainable from the copolymerization of tetrafluoroethylene and perfluoroalkoxy vinyl ethers.
  • the formulations from group c) to be used according to the invention contain at least per- and / or partially fluorinated polyethers.
  • formulations to be used according to the invention are in the form of solutions, gels, emulsions, pastes, dispersions.
  • the formulations to be used according to the invention additionally contain at least one antimicrobial component selected from the groups of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals , Benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinoline, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores, peroxides
  • the formulations to be used according to the invention have one or more antimicrobial components.
  • the formulations to be used according to the invention additionally have at least one component selected from the group of the polyhydroxy compounds, in particular from the groups of the polyalcohols and carbohydrates, and very particularly preferably one component selected from polyhydric alcohols, preferably alkane diols, alkane triols, particularly preferably glycerol and the polyethers derived therefrom, as well as glucose, arabinose, ribulose, fructose and the oligosaccharides and / or polysaccharides derived therefrom and their esters and ethers.
  • polyhydric alcohols preferably alkane diols, alkane triols, particularly preferably glycerol and the polyethers derived therefrom, as well as glucose, arabinose, ribulose, fructose and the oligosaccharides and / or polysaccharides derived therefrom and their esters and ethers.
  • the formulations to be used according to the invention contain further components selected from the groups of the surfactants and solubilizers, it being particularly preferred that at least one alkyl polyglycoside is contained as the surfactant.
  • Further preferred constituents are fatty alkyl amines and / or their alkoxylates, in particular coconut fatty amine ethoxylates and / or imidazoline compounds and / or amphoteric surfactants and / or nonionic surfactants and / or ether carboxylic acids and / or ether amine compounds.
  • paraffin compounds it is preferred to add paraffin compounds to the formulations to be used according to the invention.
  • the water content in the according to the invention Formulations using is preferably less than 20 wt .-%, very particularly preferably less than 10 wt .-%, based on the entire formulation, with the formulations not containing water in very specific embodiments, which means in the sense of the invention that the formulation does not water is added intentionally.
  • the formulations to be used according to the invention are applied to the transport chains, and in the best case it can be observed that no foam is produced when the transport goods are transported on the transport systems.
  • formulations to be used according to the invention are compared to conventional lubricants which are diluted with water in transport systems by a dilution factor of more than 100 and in the event that equal amounts of lubricating components are applied to the conveyor belt system within a defined period of time are, when using formulations to be used according to the invention, the frictional resistance between transport goods and conveyor belt system is reduced by more than 20%. This can be shown by example experiments.
  • a comparative formulation 1 which contains 5% by weight of coconut propylene diamine and is adjusted to pH 7 with acetic acid, is applied in a 0.2% aqueous concentration to the. Via a nozzle assembly with 5 nozzles, each of which has a spray rate of 5 liters per hour Transport chains applied. Over a period of 1 hour, 50 ml of the comparison formulation, or approximately 2.5 g of the coconut propylene diamine, thus reach the transport chains. This test is carried out over a period of 10 hours.
  • the coefficient of friction between the beverage bottle and stainless steel transport chains is defined as the ratio of the pulling weight which is exerted, for example, on a spring balance when one tries to hold a beverage bottle while the transport chains are running, to the weight of the bottle.
  • a further preferred embodiment of the present invention is the use of the formulations to be used according to the invention for the transport of plastic containers, the plastic containers particularly preferably at least one polymer selected from the groups of polyethylene terephthalate (PET), polyethylene naphthenate (PEN), polycarbonate (PC), PVC contain and are particularly preferred PET beverage bottles.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthenate
  • PC polycarbonate
  • PVC contain and are particularly preferred PET beverage bottles.
  • stress corrosion cracking is measured using a comparative example based on 5% polytetrafluoroethylene dispersion compared to a 5% perfluoropolyether solution in 95% glycerol.
  • PET bottles are filled with water and conditioned with carbon dioxide so that there is a pressure of about 7 bar in the interior of the bottles.
  • the bottom cups of the bottles are then immersed in the formulation of the comparative example or the example to be used according to the invention and placed in a Petri dish over a period of 24 hours. After the 24 hours, the bottles are opened, emptied and the floor cups rinsed with water.
  • a visual evaluation of the floor cups shows that there are many stress cracks with medium depth, rating C, in the test with the comparative example, while it is found in the test with the example to be used according to the invention that only a few stress cracks with low depth, rating A , are available.
  • the classification is based on the reference images contained in Chapter IV-22 of the book 'CODE OF PRACTICE - Guidelines for an Industrial Code of Practice for Refillable PET Bottles', Edition 1, 1993-1994.
  • Example 2 shows that the formulations to be used according to the invention have advantages over the transport of plastic bottles compared to polytetrafluoroethylene dispersions.
  • formulations to be used according to the invention are used for the transport of cardboard packaging.
  • Conveyor belt systems made of plastic, particularly preferably made of polyacetal and
  • the transport surfaces are
  • Transport conveyor system made of metal, particularly preferably made of stainless steel.
  • Add substances particularly preferably organic peracids, chlorine dioxide or ozone.
  • Formulations in automatic conveyor belt systems diluted with water and the application solution is applied to the conveyor belts via dosing devices, the dilution factor being between 10,000 and 100. It is further preferred that the formulations to be used according to the invention are selected and applied such that no further multiplication of microorganisms takes place on surfaces which are in contact with the formulations or solution, and very particularly preferably the number of microorganisms is reduced.
  • the formulations to be used according to the invention are preferably used for the transport of containers in the food industry, in which, in particularly preferred cases, dirt which is conditioned is repelled by the conveyor belts conditioned with the agent, the water consumption is reduced by at least 80% and no lubricants drip onto the floor, provided the lubricants are properly applied to the transport chains.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention relates to the use of formulations which contain selected organic fluorinated components, for reducing the friction between transported goods and transport installations.

Description

"Fluorhaltige Schmiermittel" "Fluorine-containing lubricants"
Die vorliegende Erfindung betrifft die Verwendung von Formulierungen, die mindestens eine fluorierte Komponente enthalten, zur Reduktion der Reibung zwischen Transportgütern und Transportanlagen.The present invention relates to the use of formulations which contain at least one fluorinated component for reducing the friction between transport goods and transport systems.
In der Lebensmittelindustrie, insbesondere in Getränkebetrieben werden die in den Abfüllanlagen zu befüllenden Behälter über Transporteure verschiedenster Ausgestaltung und Materialien, beispielsweise über Plattentransportbänder oder kettenartige Anordnungen, die im folgenden allgemein als Transportketten bezeichnet werden sollen, transportiert. Die Transporteure stellen die Verbindung her zwischen den verschiedenen optionalen Behandlungsstufen des Abfüllprozesses wie z. B. Auspacker, Flaschenreinigungsmaschine, Füller, Verschließer, Etikettierer, Einpacker u.a.. Bei den Behältern kann es sich um verschiedenste Formen handeln, insbesondere Glas- und Kunststoffflaschen, Dosen, Gläser, Fässer, Getränkecontainer (KEG), Papier- und Pappbehälter. Um den störungsfreien Betrieb zu gewährleisten, müssen die Transportketten in geeigneter Weise geschmiert werden, so daß eine zu starke Reibung zu den Behältern vermieden wird. Üblicherweise werden zur Schmierung verdünnte wäßrige Lösungen verwendet, die geeignete reibungsver- mindernde Wirkstoffe enthalten. Mit den wäßrigen Lösungen werden die Transportketten beispielsweise durch Eintauchen oder durch Besprühen in Kontakt gebracht, wobei man dann von Tauchschmieranlagen oder automatischen Bandschmiersystemen oder zentralen Kettenschmiersystemen spricht.In the food industry, in particular in beverage companies, the containers to be filled in the filling plants are transported by means of conveyors of various designs and materials, for example by means of plate conveyor belts or chain-like arrangements, which are generally referred to below as transport chains. The transporters establish the connection between the various optional treatment stages of the filling process such as B. Unpacker, bottle washer, filler, capper, labeler, packer, etc. The containers can be of various shapes, in particular glass and plastic bottles, cans, glasses, barrels, beverage containers (KEG), paper and cardboard containers. To ensure trouble-free operation, the transport chains must be lubricated in a suitable manner so that excessive friction against the containers is avoided. Diluted aqueous solutions containing suitable friction-reducing agents are usually used for lubrication. The transport chains are brought into contact with the aqueous solutions, for example by immersion or spraying, in which case one speaks of splash lubrication systems or automatic belt lubrication systems or central chain lubrication systems.
Die bisher als Schmiermittel eingesetzten Kettengleitmittel basieren meist auf Fettsäuren in Form ihrer wasserlöslichen Alkali- oder Alkanolaminsalze oder auf Fett- aminen, vorzugsweise in Form ihrer organischen oder anorganischen Salze. Während beide Substanzklassen in der Tauchschmierung problemlos anwendbar sind, zeigen sie in den heute üblichen zentralen Kettenschmiersystemen eine Reihe von Nachteilen. So beschreibt die DE-A- 23 13 330 Schmiermittel auf Seifenbasis, die wäßrige Mischungen von C-jg-C-is-Fettsäuresalzen und oberflächenaktivenThe chain lubricants hitherto used as lubricants are mostly based on fatty acids in the form of their water-soluble alkali metal or alkanolamine salts or on fatty amines, preferably in the form of their organic or inorganic salts. While both substance classes can be used without problems in splash lubrication, they show a number of disadvantages in the central chain lubrication systems that are common today. Thus, DE-A 23 13 330 soap-based lubricants, the aqueous mixtures of C- j gC-is-fatty acid salts and surfactants
Substanzen enthalten. Derartige Schmiermittel auf Seifenbasis weisen folgende Nachteile auf:Contain substances. Such soap-based lubricants have the following disadvantages:
1. Es kommt zu einer Reaktion mit der Wasserhärte, also den Erdalkali-Ionen, und anderen Wasserinhaltsstoffen unter Bildung schwerlöslicher Metallseifen, den sogenannten primären Erdalkaliseifen.1. There is a reaction with the water hardness, ie the alkaline earth ions, and other water constituents with the formation of poorly soluble metal soaps, the so-called primary alkaline earth soaps.
2. Es kommt zu einer Reaktion zwischen diesen Schmiermitteln auf Seifenbasis und in Wasser oder dem abzufüllenden Gut gelöstem Kohlendioxid.2. There is a reaction between these soap-based lubricants and carbon dioxide dissolved in water or the product to be filled.
3. Die so erzeugte Anwendungslösung ist stets keimfördernd.3. The application solution created in this way is always germ-promoting.
4. Bei Anwendung von hartem Wasser sind Ionenaustauscher zur Wasserenthärtung erforderlich, was eine zusätzliche Keimquelle bedeutet (und deshalb in der Praxis kaum anzutreffen ist), oder aber der Einsatz hoch komplexierungs- mittelhaitiger Produkte, was wiederum ökologisch bedenklich ist, ist nötig.4. When hard water is used, ion exchangers are required for water softening, which means an additional source of germs (and therefore can hardly be found in practice), or the use of highly complexing agent-containing products, which in turn is ecologically questionable, is necessary.
5. Es kommt zu vermehrter Schaumbildung, was insbesondere Probleme am Bottle-Inspector (automatische Flaschenkontrolle) hervorrufen kann und eine stärkere Benetzung der Transportbehältnisse zur Folge hat.5. There is increased foam formation, which can cause problems in particular with the bottle inspector (automatic bottle control) and result in greater wetting of the transport containers.
6. Die meisten dieser Produkte sind lösungsmittelhaltig.6. Most of these products contain solvents.
7. Die Reinigungswirkung dieser Produkte ist schlecht, so daß eine separate Reinigung notwendig ist.7. The cleaning effect of these products is poor, so that a separate cleaning is necessary.
8. Derartige Schmiermittelzubereitungen auf Seifenbasis zeigen ein pH-abhängiges Leistungsverhalten.8. Such soap-based lubricant preparations show pH-dependent performance.
9. Schmiermittelzubereitungen auf Seifenbasis zeigen weiterhin eine Wassertemperatur-Abhängigkeit.9. Soap-based lubricant preparations continue to be dependent on water temperature.
10. Schmiermittel auf Seifenbasis zeigen nur eine geringe Lagerstabilität, insbesondere bei niederen Temperaturen.10. Soap-based lubricants only have a low storage stability, especially at low temperatures.
11. Das in vielen Produkten enthaltene EDTA (Ethylendiamintetraacetat) ist bekanntermaßen nur schlecht biologisch abbaubar. 12. Derartige Schmiermittelzubereitungen auf Seifenbasis sind nicht für alle Transportgüter aus Kunststoff geeignet, da es bei Anwendung dieser Mittel in vielen Fällen zu Spannungsrißkorrosionen am Transportgut kommt.11. The EDTA (ethylenediaminetetraacetate) contained in many products is known to be poorly biodegradable. 12. Such soap-based lubricant preparations are not suitable for all transport goods made of plastic, since in many cases stress corrosion cracking on the transport goods occurs when these agents are used.
Neben Schmiermitteln auf Seifenbasis werden hauptsächlich solche auf Basis von Fettaminen verwendet. So beschreibt die DE-A-36 31 953 ein Verfahren zum Schmieren von kettenförmigen Flaschentransportbändern in Getränkeabfüllbetrie- ben, 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.In addition to soap-based lubricants, mainly those based on fatty amines are used. For example, DE-A-36 31 953 describes a method for lubricating chain-shaped bottle conveyor belts in beverage bottling plants, particularly in breweries, and for cleaning the belts by means of a liquid cleaning agent, which is characterized in that the chain-shaped bottle conveyor belts are based on belt lubricants neutralized primary fatty amines, which preferably have 12 to 18 carbon atoms and contain an unsaturated fraction of more than 10%.
Aus der EP-A-0 372 628 sind Fettaminderivate der FormelnFrom EP-A-0 372 628 are fatty amine derivatives of the formulas
N-A-NH2 und N-A1-C02HNA-NH 2 and NA 1 -C0 2 H
R2 R R2 R
als Schmiermittel bekannt, worinknown as a lubricant, wherein
R1 eine gesättigte oder ungesättigte, verzweigte oder lineare Alkylgruppe mit 8 bis 22 C-Atomen;R 1 is a saturated or unsaturated, branched or linear alkyl group with 8 to 22 C atoms;
R2 Wasserstoff, eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 4 C-Atomen oder -A- NH2;R 2 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms or -A- NH 2 ;
A eine lineare oder verzweigte Alkylengruppe mit 1 bis 8 C-Atomen; undA is a linear or branched alkylene group with 1 to 8 carbon atoms; and
A^ eine lineare oder verzweigte Alkylengruppe mit 2 bis 4 C-Atomen bedeutet. Darüber hinaus sind aus der DE-A-39 05 548 Schmiermittel auf Basis von N-alky- lierten Fettaminderivaten bekannt, die mindestens ein sekundäres und/oder tertiäres Amin enthalten.A ^ is a linear or branched alkylene group having 2 to 4 carbon atoms. In addition, DE-A-39 05 548 discloses lubricants based on N-alkylated fatty amine derivatives which contain at least one secondary and / or tertiary amine.
Aus der DE-A-42 06 506 sind bekannt:DE-A-42 06 506 discloses:
Seifenfreie Schmiermittel auf der Basis von amphoteren Verbindungen, primären, sekundären und/oder tertiären Aminen und/oder Salzen derartiger Amine der allgemeinen Formel (I), (lla), (Mb), (lila), (lllb), (lllc), (IVa) und (IVb)Soap-free lubricants based on amphoteric compounds, primary, secondary and / or tertiary amines and / or salts of such amines of the general formula (I), (lla), (Mb), (purple), (lllb), (lllc), (IVa) and (IVb)
R 1R 1
R-[NH-(CH2)n]m - N - R3 - COOM (I)R- [NH- (CH 2 ) n ] m - N - R 3 - COOM (I)
R2R2
R4-NH-R5 (lla)R 4 -NH-R 5 (lla)
R4-N+H2-R5 X- (Mb)R 4 -N + H 2 -R 5 X- (Mb)
R4-NH-(CH2)3NH2 (lila)R 4 -NH- (CH 2 ) 3 NH 2 (purple)
R4.NH-(CH2)3N+H3 x- (mb) R4.NH- (CH 2 ) 3 N + H 3 x- (mb)
R4_N+H2-(CH2)3-N+H3 2X" die) R 4_ N + H2 - (CH 2 ) 3 -N + H 3 2X " die)
R4-NR7R8 (IVa) und/oderR 4 -NR 7 R 8 (IVa) and / or
R4-N+HR7R8 X" (IVb) wobeiR 4 -N + HR 7 R 8 X " (IVb) in which
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-, -(CH2CH20) oder -(CH2CH2CH20)r substituiert sein kann,R is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, which may be replaced by -OH, - NH 2 , -NH-, -CO-, - (CH 2 CH 2 0) or - (CH 2 CH 2 CH 2 0) r can be substituted,
R1 für Wasserstoff, einen Alkylrest mit 1 bis 4 C-Atomen, einen Hydroxyalkylrest mit 1 bis 4 C-Atomen oder einen Rest -R3COOMR 1 represents hydrogen, an alkyl radical having 1 to 4 carbon atoms, a hydroxyalkyl radical having 1 to 4 carbon atoms or a radical -R 3 COOM
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,R 2 only if M represents a negative charge for hydrogen, an alkyl radical with 1 to 4 C atoms, or a hydroxyalkyl radical with 1 to 4 C atoms,
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-, -(CH2CH20)r oder -(CH2CH2CH20)|- substituiert sein kann,R 3 is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 1 to 12 carbon atoms, which may be replaced by -OH, - NH 2 , -NH-, -CO-, - (CH 2 CH 2 0) r or - (CH 2 CH 2 CH 2 0) | - can be substituted,
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,R 4 represents a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, which may have at least one amine, imine, hydroxyl, halogen and / or carboxy radical as substituent, a substituted or unsubstituted phenyl radical which may have at least one amine, imine, hydroxyl, halogen, carboxy and / or a linear or branched, saturated or mono- or polyunsaturated alkyl radical with 6 to 22 C atoms as substituents,
R5 für Wasserstoff oder - unabhängig von R4 - für einen Rest R4,R 5 for hydrogen or - independently of R 4 - for a radical R 4 ,
X" für ein Anion aus der Gruppe Amidosulfonat, Nitrat, Halogenid, Sulfat, Hydro- gencarbonat, Carbonat, Phosphat oder R^-COO" steht, wobeiX "stands for an anion from the group amidosulfonate, nitrate, halide, sulfate, hydrogen carbonate, carbonate, phosphate or R ^ -COO " ,
R^ 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, undR ^ represents hydrogen, a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 carbon atoms or alkenyl radical having 2 to 20 carbon atoms, which may have at least one hydroxyl, amine or imine radical as a substituent, or a substituted or unsubstituted phenyl radical, which may have an alkyl radical with 1 to 20 C atoms as a substituent, and
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,R 7 and R 8 each independently of one another represent a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 C atoms or alkenyl radical having 2 to 20 C atoms, which may have at least one hydroxyl, amine or imine radical as substituents, or a substituted or unsubstituted phenyl radical, which may have an alkyl radical with 1 to 20 C atoms as substituents,
M 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 undM for hydrogen, alkali metal, ammonium, an alkyl radical with 1 to 4 carbon atoms, a benzyl radical or a negative charge, n for an integer in the range from 1 to 12, m for an integer in the range from 0 to 5 and
I für eine Zahl im Bereich von 0 bis 5 steht, enthaltend Alkyldimethylaminoxide und/oder Alkyloligoglycoside als nichtionischeI stands for a number in the range from 0 to 5, containing alkyldimethylamine oxides and / or alkyl oligoglycosides as nonionic
Tenside.Surfactants.
Die EP-B-629 234 offenbart eine Schmiermittelkombination, bestehend aus a) einer oder mehrerer Verbindungen der FormelEP-B-629 234 discloses a lubricant combination consisting of a) one or more compounds of the formula
R1-N-(CH2)n-COOMR 1 -N- (CH 2 ) n -COOM
I R2 IR 2
wobeiin which
R1 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-, Halogen oder einen Carboxylrest substituiert sein kann,R 1 is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, which is optionally by -OH, -NH 2 , -NH-, -CO-, halogen or a carboxyl radical can be substituted,
R2 für einen Carboxylrest mit 2 bis 7 C-Atomen,R2 for a carboxyl radical with 2 to 7 carbon atoms,
M für Wasserstoff, Alkalimetall, Ammonium, einen Alkylrest mit 1 bis 4 C-Atomen oder einen Benzyirest und n für eine ganze Zahl im Bereich von 1 bis 6 steht, b) wenigstens eine organische Carbonsäure ausgewählt aus einbasigen oder mehrbasigen, gesättigten oder einfach oder mehrfach ungesättigten Carbonsäuren mit 2 bis 22 C-Atomen, c) gegebenenfalls Wasser und Zusatz- und/oder Hilfsstoffe.M represents hydrogen, alkali metal, ammonium, an alkyl radical having 1 to 4 carbon atoms or a benzyl radical and n represents an integer in the range from 1 to 6, b) at least one organic carboxylic acid selected from monobasic or polybasic, saturated or simple or polyunsaturated carboxylic acids with 2 to 22 carbon atoms, c) optionally water and additives and / or auxiliaries.
Die WO 94/03562 beschreibt ein Schmiermittelkonzentrat auf Basis von Fettaminen und gegebenenfalls üblichen Verdünnungsmitteln oder Hilfs- bzw. Zusatzstoffen, dadurch gekennzeichnet, daß es mindestens ein Poiyamindehvat eines Fettamins und/oder ein Salz eines derartigen Amins enthält, wobei der Anteil der genannten Polyaminderivate von Fettaminen an der Gesamtformulierung 1 bis 100 Gew.-% beträgt.WO 94/03562 describes a lubricant concentrate based on fatty amines and, if appropriate, conventional diluents or auxiliaries or additives, characterized in that it contains at least one polyamine derivative of a fatty amine and / or a salt of such an amine, the proportion of the polyamine derivatives mentioned being Fatty amines in the total formulation is 1 to 100% by weight.
Gemäß einer bevorzugten Ausführungsform der WO 94/03562 enthält dieses Schmiermittelkonzentrat mindestens ein Polyaminderivat eines Fettamins der allgemeinen FormelAccording to a preferred embodiment of WO 94/03562, this lubricant concentrate contains at least one polyamine derivative of a fatty amine of the general formula
R-A-(CH2)k-NH-[(CH2),-NH]y-(CH2)m-NH2 (H+X")n RA- (CH 2 ) k -NH - [(CH 2 ), - NH] y - (CH 2 ) m -NH 2 (H + X " ) n
wobeiin which
R ein substituierter oder unsubstituierter, linearer oder verzweigter, gesättigter oder einfach oder mehrfach ungesättigter Alkylrest mit 6 bis 22 C-Atomen, wobei die Substituenten ausgewählt sind aus Amino, Imino, Hydroxy, Halogen und Carboxy, oder ein substituierter oder unsubstituierter Phenylrest, wobei die Substituenten ausgewählt sind aus Amino, Imino, Hydroxy, Halogen, Carboxy und einem linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen, ist; A entweder für -NH- oder für -O- steht,R is a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, the substituents being selected from amino, imino, hydroxy, halogen and carboxy, or is a substituted or unsubstituted phenyl radical, the substituents being selected from amino, imino, hydroxy, halogen, carboxy and a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms; A represents either -NH- or -O-,
X" ein Anion einer anorganischen oder organischen Säure bedeutet, k, I, m unabhängig voneinander eine ganze Zahl im Bereich von 1 bis 6 ist; y im Falle A = -NH- 0, 1 , 2 oder 3 und im Falle A = -O- 1 , 2, 3 oder 4 ist, n eine ganze Zahl von 0 bis 6 ist.X "is an anion of an inorganic or organic acid, k, I, m is independently an integer in the range from 1 to 6; y in the case A = -NH- 0, 1, 2 or 3 and in the case A = - Is O- 1, 2, 3 or 4, n is an integer from 0 to 6.
In einigen Abfüllbetrieben werden Schmiermittel auf Basis von Polytetrafluorethylen eingesetzt. Diese liegen in Form von Dispersionen vor und werden nicht, wie üblicherweise praktiziert, über Düsen, sondern über Pinsel auf die Ketten aufgebracht. Diese Mittel haben den Vorteil, daß sie eine wesentliche Reduktion der Reibung zwischen Transportbändern und Transportgütern mit sich bringen. Darüber hinaus haftet das Polytetrafluorethylen sehr stark auf den Ketten.Lubricants based on polytetrafluoroethylene are used in some filling plants. These are in the form of dispersions and are not applied to the chains via nozzles, as is usually the practice, but with brushes. These agents have the advantage that they bring about a substantial reduction in the friction between the conveyor belts and the goods to be transported. In addition, the polytetrafluoroethylene adheres very strongly to the chains.
Von Nachteil stellte sich in der Praxis heraus, daß der gesamte hygienische Zustand bezüglich Verkeimung und Verschmutzung der Transportketten verschlechtert wurde. Dies führte sogar so weit, daß das Leistungsprofil des Schmiermittels aufgrund der Zunahme der Verschmutzung mit der Zeit nachließ.In practice, it turned out to be disadvantageous that the overall hygienic condition with regard to contamination and contamination of the transport chains deteriorated. This even went so far that the performance profile of the lubricant deteriorated over time due to the increase in contamination.
Als weiterer Nachteil wurde beobachtet, daß die Dispersionen von Polytetrafluorethylen nicht lagerstabil waren und mit der Zeit separierten. Dies hat zur Folge, daß über einen längeren Zeitraum beobachtet, nicht konstante Mengen an Wirkstoff auf die Transportketten kommen.Another disadvantage was that the dispersions of polytetrafluoroethylene were not stable in storage and separated over time. The consequence of this is that observed over a long period of time does not result in constant amounts of active ingredient on the transport chains.
Bei dem Versuch der Reinigung der Transportketten stellte sich heraus, daß die Schmiermittelschicht von den Transportketten sehr schwer zu entfernen war. Bei der Überprüfung der Verträglichkeit von Polytetrafluorethylendispersionen bezüglich ihrer Kunststoffverträglichkeit, wurde außerdem festgestellt, daß sie auf PET- Flaschen Spannungsrisse erzeugen.When trying to clean the transport chains, it was found that the lubricant layer was very difficult to remove from the transport chains. When checking the compatibility of polytetrafluoroethylene dispersions with regard to their plastic compatibility, it was also found that they produce stress cracks on PET bottles.
Die vorliegende Erfindung stellt sich die Aufgabe, Schmiermittel auf Basis von organischen Fluorverbindungen zur Verfügung zu stellen, die zum einen lagerstabil sind, zum anderen gut verträglich mit Kunststoff-Gebinden sind und gleichzeitig die Schmierleistung gegenüber den üblicherweise als Schmiermittel eingesetzten Ami- nen verbessern.The object of the present invention is to provide lubricants based on organic fluorine compounds which, on the one hand, are stable in storage, on the other hand are well compatible with plastic containers and at the same time improve the lubricating performance compared to the amines usually used as lubricants.
Die vorliegende Erfindung betrifft die Verwendung von Formulierungen, die mindestens eine fluorierte Komponente ausgewählt aus den Gruppen der a) per- oder teilfluorierten monomeren organischen Verbindungen, b) reinen und gemischten Di- und Oligomeren, die auf zumindest einem per- oder teilfluorierten organischen Monomer basieren, c) reinen und gemischten Polymeren, die auf zumindest einem per- oder teilfluorierten organischen Monomer basieren und im Polymer zumindest eine Mo- nomereneinheit vorliegt, die entweder weniger als 75 Gew.% Fluor bezogen auf das Gewicht der gesamten Monomereneinheit oder mehr als 2 C-Atome enthält, enthalten, zur Reduktion der Reibung zwischen Transportgütern und Transportanlagen.The present invention relates to the use of formulations which contain at least one fluorinated component selected from the groups of a) per- or partially fluorinated monomeric organic compounds, b) pure and mixed di- and oligomers which are based on at least one per- or partially fluorinated organic monomer , c) pure and mixed polymers which are based on at least one per- or partially fluorinated organic monomer and in the polymer there is at least one monomer unit which is either less than 75% by weight of fluorine, based on the weight of the total monomer unit, or more than 2 ° C. -Atoms contains, included, to reduce the friction between cargo and transportation equipment.
Bei der Definition der Grenze zwischen Oligomeren und Polymeren bezieht sich die vorliegende Erfindung auf die allgemein bekannte Charakterisierung von Polymeren, die aus so vielen gleichen oder ähnlichen niedermolekularen Bausteinen (Monomeren) aufgebaut sind, daß sich die physikalischen Eigenschaften dieser Substanzen, insbesondere die Viskoelastizität, bei Erhöhung oder Reduzierung der Anzahl der Bausteine um eine Einheit nicht mehr merklich ändern. Dies ist im allgemeinen dann der Fall, wenn die mittlere Molmasse der .Polymeren' 10.000 g/mol oder mehr beträgt. Für die niedermolekularen Dimere, Trimere und andere niedere Glieder der polymerhomologen Reihe verwendet man die Bezeichnung Oligomere. In einer bevorzugten Form umfaßt die Gruppe a) zumindest per- und teilfluorierte Tenside, Alkane, Ether und Amine, wobei besonders bevorzugt in den erfindungsgemäß verwendeten Formulierungen Ammoniumperfluoralkylsulfonate, Lithiumper- fluoralkylsuifonate, Kaliumperfluoralkylsulfonate, Aminperfluoralkylsulfonate, Natri- umperfluoralkylsulfonate, Kaliumfluoralkylcarboxylate, quatemäre fluorierte Alkyl- amomoniumiodide, Ammoniumperfluoralkylcarboxalate, fluorierte Alkylpoiyoxyethyl- enethanole, fluorierte Alkylalkoxylate, fluorierte Alyklester mit Konzentrationen von 0,001 bis 10% zum Einsatz kommen. Die fluorierten Komponenten der Gruppe c) sind vorzugsweise per- und/oder teilfluorierte Alkoxypolymere, die besondes bevorzugt aus der Copolymerisation von Tetrafluorethylen und Perfluoralkoxyvinylethern erhältlich sind.When defining the boundary between oligomers and polymers, the present invention relates to the generally known characterization of polymers which are composed of so many identical or similar low molecular weight building blocks (monomers) that the physical properties of these substances, in particular the viscoelasticity, contribute to No longer noticeably change the increase or decrease in the number of blocks by one unit. This is generally the case when the average molecular weight of the "polymers" is 10,000 g / mol or more. The term oligomers is used for the low molecular weight dimers, trimers and other lower members of the polymer homologous series. In a preferred form, group a) comprises at least per- and partially fluorinated surfactants, alkanes, ethers and amines, particularly preferably in the formulations used according to the invention ammonium perfluoroalkylsulfonates, lithium perfluoroalkylsulfonates, potassium perfluoroalkylsulfonates, amine perfluoroalkylsulfonates, sodium perfluoroalkylsulfonates, potassium fluoramate carboxylates, potassium fluoramate carboxylates, ammonium iodides, ammonium perfluoroalkyl carboxalates, fluorinated alkyl polyoxyethyl enethanols, fluorinated alkyl alkoxylates, fluorinated alkyl esters with concentrations of 0.001 to 10% are used. The fluorinated components of group c) are preferably per- and / or partially fluorinated alkoxy polymers, which are particularly preferably obtainable from the copolymerization of tetrafluoroethylene and perfluoroalkoxy vinyl ethers.
In einer weiterhin bevorzugten Ausführung sind in den erfindungsgemäß zu verwendenden Formulierungen aus der Gruppe c) zumindest per- und/oder teilfluorierte Polyether enthalten.In a further preferred embodiment, the formulations from group c) to be used according to the invention contain at least per- and / or partially fluorinated polyethers.
Es ist außerdem bevorzugt, daß die erfindungsgemäß zu verwendenden Formulierungen in Form von Lösungen, Gelen, Emulsionen, Pasten, Dispersionen vorliegen.It is also preferred that the formulations to be used according to the invention are in the form of solutions, gels, emulsions, pastes, dispersions.
Die erfindungsgemäß zu verwendenden Formulierungen enthalten in einer bevorzugten Ausführung zusätzlich mindestens eine antimikrobielle Komponente ausgewählt aus den Gruppen der Alkohole, Aldehyde, antimikrobiellen Säuren, Carbonsäureester, Säureamide, Phenole, Phenolderivate, Diphenyle, Diphenylalkane, Harnstoffderivate, Sauerstoff-, Stickstoff-Acetale sowie -Formale, Benzamidine, Isothiazoline, Phthalimidderivate, Pyridinderivate, antimikrobiellen oberflächenaktiven Verbindungen, Guanidine, antimikrobiellen amphoteren Verbindungen, Chino- line, 1 ,2-Dibrom-2,4-dicyanobutan, iodo-2-propynyl-butyl-carbamat, lod, lodophore, Peroxide, wobei in einer besonders bevorzugten Ausführung die erfindungsgemäß zu verwendenden Formulierungen als antimikrobielle Komponenten eine oder meh- rere Verbindungen ausgewählt aus Ethanol, n-Propanol, i-Propanol, 1 ,3-Butandiol, Phenoxyethanol, 1 ,2-Propylenglykol, Glycerin, Undecylensäure, Zitronensäure, 2- Benzyl-4-chlorphenol, 2,2'-Methylen-bis-(6-brom-4-chlorphenol), 2,4,4'-Trichlor-2'- hydroxydiphenylether, N-(4-Chlorphenyl)-N-(3,4-dichlorphenyl)-hamstoff, N,N'-(1 ,10- decandiyldi-1-pyridinyl-4-yliden)-bis-(1-octanamin)-dihydrochlorid, N,N'-Bis-(4-In a preferred embodiment, the formulations to be used according to the invention additionally contain at least one antimicrobial component selected from the groups of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals , Benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinoline, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores, peroxides In a particularly preferred embodiment, the formulations to be used according to the invention have one or more antimicrobial components. Other compounds selected from ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerol, undecylenic acid, citric acid, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis - (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N'- (1, 10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis- (4-
Chlorphenyl)-3,12-diimino-2,4,11 ,13-tetraaza-tetradecandiimidamid, quaternären Ammoniumverbindungen oder Alkyl-Aminen, Guanidinen, Amphoteren, enthalten.Chlorphenyl) -3,12-diimino-2,4,11, 13-tetraaza-tetradecanediimidamide, quaternary ammonium compounds or alkyl amines, guanidines, amphoterics.
Während stabile Formulierungen aus Polytetrafluorethylendispersionen und antimikrobiellen Komponenten nicht oder nur sehr schwer erhältlich sind, ergeben die erfindungsgemäß zu verwendenden Formulierungen mit antimikrobiellen Komponenten meist stabile Formulierungen.While stable formulations composed of polytetrafluoroethylene dispersions and antimicrobial components are not or only very difficult to obtain, the formulations to be used according to the invention with antimicrobial components usually result in stable formulations.
Es ist weiterhin bevorzugt, daß die erfindungsgemäß zu verwendenden Formulierungen zusätzlich mindestens eine Komponente ausgewählt aus der Gruppe der Polyhydroxyverbindungen, insbesondere aus den Gruppen der Polyalkohole und Kohlenhydrate, und ganz besonders bevorzugt eine Komponente ausgewählt aus mehrwertigen Alkoholen, vorzugsweise Alkandiole, Alkantriole, besonders bevorzugt Glycerin und den davon abgeleiteten Polyethern, sowie Glukose, Arabinose, Ribu- lose, Fructose und den davon abgeleiteten Oligo- und/oder Polysacchariden und deren Ester und Ether enthalten.It is further preferred that the formulations to be used according to the invention additionally have at least one component selected from the group of the polyhydroxy compounds, in particular from the groups of the polyalcohols and carbohydrates, and very particularly preferably one component selected from polyhydric alcohols, preferably alkane diols, alkane triols, particularly preferably glycerol and the polyethers derived therefrom, as well as glucose, arabinose, ribulose, fructose and the oligosaccharides and / or polysaccharides derived therefrom and their esters and ethers.
In einer ebenfalls bevorzugten Ausführung enthalten die erfindungsgemäß zu verwendenden Formulierungen weitere Komponenten ausgewählt aus den Gruppen der Tenside und Lösevermittler, wobei besonders bevorzugt ist, daß als Tensid zumindest ein Alkylpolyglykosid enthalten ist. Weitere bevorzugte Bestandteile sind Fettal- kylamine und/oder deren Alkoxylate, insbesondere Kokosfettaminethoxylate und/oder Imidazolinverbindungen und/oder amphotere Tenside und/oder nichtionische Tenside und/oder Ethercarbonsäuren und/oder Etheraminverbindungen. Darüber hinaus ist es bevorzugt, den erfindungsgemäß zu verwendenden Formulierungen Paraffinverbindungen zuzusetzen. Der Wasseranteil in den erfindungsgemäß zu verwendenden Formulierungen liegt vorzugsweise unter 20 Gew.-%, ganz besonders bevorzugt unter 10 Gew.-%, bezogen auf die gesamte Formulierung, wobei in ganz speziellen Ausführungen die Formulierungen rezepturgemäß kein Wasser enthalten, was im Sinne der Erfindung bedeutet, daß der Formulierung nicht absichtlich Wasser zugesetzt wird. Die erfindungsgemäß zu verwendenden Formulierungen werden in der Praxis auf die Transportketten aufgebracht, wobei im günstigsten Fall zu beobachten ist, daß beim Transport der Transportgüter auf den Transportanlagen kein Schaum entsteht. Es ist weiterhin bevorzugt, daß die erfindungsgemäß zu verwendenden Formulierungen im Vergleich zu üblichen Schmiermitteln, die in Transportanlagen mit Wasser um einen Verdünnungsfaktor von mehr als 100 verdünnt werden und für den Fall, daß innerhalb eines definierten Zeitraums gewichtsgleiche Mengen an schmieraktiven Komponenten auf die Transportbandanlage aufgetragen werden, bei Einsatz von erfindungsgemäß zu verwendenden Formulierungen der Reibwiderstand zwischen Transportgütern und Transportbandanlage um mehr als 20 % gesenkt wird. Dies kann durch Beispielversuche gezeigt werden.In a likewise preferred embodiment, the formulations to be used according to the invention contain further components selected from the groups of the surfactants and solubilizers, it being particularly preferred that at least one alkyl polyglycoside is contained as the surfactant. Further preferred constituents are fatty alkyl amines and / or their alkoxylates, in particular coconut fatty amine ethoxylates and / or imidazoline compounds and / or amphoteric surfactants and / or nonionic surfactants and / or ether carboxylic acids and / or ether amine compounds. In addition, it is preferred to add paraffin compounds to the formulations to be used according to the invention. The water content in the according to the invention Formulations using is preferably less than 20 wt .-%, very particularly preferably less than 10 wt .-%, based on the entire formulation, with the formulations not containing water in very specific embodiments, which means in the sense of the invention that the formulation does not water is added intentionally. In practice, the formulations to be used according to the invention are applied to the transport chains, and in the best case it can be observed that no foam is produced when the transport goods are transported on the transport systems. It is further preferred that the formulations to be used according to the invention are compared to conventional lubricants which are diluted with water in transport systems by a dilution factor of more than 100 and in the event that equal amounts of lubricating components are applied to the conveyor belt system within a defined period of time are, when using formulations to be used according to the invention, the frictional resistance between transport goods and conveyor belt system is reduced by more than 20%. This can be shown by example experiments.
Beispiel 1 :Example 1 :
Eine Vergleichsformulierung 1 , die 5 Gew.-% Kokospropylendiamin enthält und mit Essigsäure auf pH 7 eingestellt wird, wird über einen Düsenstock mit 5 Düsen, die je eine Sprühleistung von 5 I pro Stunde haben, in 0,2%iger wäßriger Konzentration auf die Transportketten aufgetragen. Über einen Zeitraum von 1 Stunde gelangen somit 50 ml der Vergleichsformulierung, bzw. ca. 2,5 g des Kokospropylendiamins auf die Transportketten. Dieser Versuch wird über einen Zeitraum von 10 Stunden durchgeführt. Der Reibkoeffizient zwischen Getränkeflasche und Edelstahltransportketten wird gemäß der vorliegenden Erfindung als Verhältnis des Zuggewichts, das beispielsweise auf eine Federwaage ausgeübt wird, wenn man versucht, bei laufenden Transportketten eine Getränkeflasche festzuhalten, zu dem Gewicht der Flasche definiert.A comparative formulation 1, which contains 5% by weight of coconut propylene diamine and is adjusted to pH 7 with acetic acid, is applied in a 0.2% aqueous concentration to the. Via a nozzle assembly with 5 nozzles, each of which has a spray rate of 5 liters per hour Transport chains applied. Over a period of 1 hour, 50 ml of the comparison formulation, or approximately 2.5 g of the coconut propylene diamine, thus reach the transport chains. This test is carried out over a period of 10 hours. According to the present invention, the coefficient of friction between the beverage bottle and stainless steel transport chains is defined as the ratio of the pulling weight which is exerted, for example, on a spring balance when one tries to hold a beverage bottle while the transport chains are running, to the weight of the bottle.
Der Reibkoeffizient bei Verwendung des oben beschriebenen Vergleichsbeispiels μ = 0,10. Sobald man den Dosiervorgang unterbricht, steigt der Reibkoeffizient schnell an und es kommt innerhalb weniger Minuten zum Umfallen der Transportgüter bzw. der Flaschen.The coefficient of friction when using the comparative example μ = 0.10 described above. As soon as you stop the dosing process, the coefficient of friction increases quickly arrives and the goods or bottles fall over within a few minutes.
Innerhalb des gesamten Versuchszeitraums von 10 Stunden gelangen bei dem Vergleichsbeispiel insgesamt 25 ml an schmieraktiven Kokospropylendiaminrohstoffen auf die Transportketten. In einem zweiten Versuch werden 25 ml einer erfindungsgemäß zu verwendenden Formulierung, bestehend aus 5 Gew.-% Perfluorpolyether und 95 Gew.-% Glycerin, mit einem Lappen auf den Transportketten verteilt. Danach wird unter identischen Bedingungen, wie im Versuch mit Vergleichsbeispiel 1 , der Reibkoeffizient zwischen Flaschen und Transportkette über einen Zeitraum von 10 Stunden gemessen. Über den gesamten Zeitraum von 10 Stunden liegt der Reibkoeffizient μ zwischen 0,04 und 0,05. Dieses Beispiel zeigt, daß der Reibwiderstand zwischen Transportgütern und Transportbandanlage um mehr als 20 % gesenkt werden kann, im vorliegenden Beispiel sogar um mehr als 40 %.In the comparative example, a total of 25 ml of lubricating-active coconut propylene diamine raw materials reach the transport chains over the entire test period of 10 hours. In a second experiment, 25 ml of a formulation to be used according to the invention, consisting of 5% by weight of perfluoropolyether and 95% by weight of glycerol, are distributed on the transport chains with a rag. The coefficient of friction between bottles and transport chain is then measured over a period of 10 hours under identical conditions, as in the experiment with comparative example 1. The coefficient of friction μ lies between 0.04 and 0.05 over the entire period of 10 hours. This example shows that the frictional resistance between goods to be transported and the conveyor belt system can be reduced by more than 20%, in the present example even by more than 40%.
Eine weitere bevorzugte Ausführung der vorliegenden Erfindung ist der Einsatz der erfindungsgemäß zu verwendenden Formulierungen für den Transport von Kunststoffgebinden, wobei die Kunststoffgebinde besonders bevorzugt mindestens ein Polymer ausgewählt aus den Gruppen der Polyethylenterephthalate (PET), Polyethylennaphthenate (PEN), Polycarbonate (PC), PVC enthalten und ganz besonders bevorzugt PET-Getränke-Flaschen sind. Im Laborversuch wird die Spannungsrißkorrosion von einem Vergleichsbeispiel auf Basis von 5 %iger Polytetrafluorethylendispersion im Vergleich zu einer 5 %igen Perfluorpolyetherlösung in 95 % Glycerin gemessen.A further preferred embodiment of the present invention is the use of the formulations to be used according to the invention for the transport of plastic containers, the plastic containers particularly preferably at least one polymer selected from the groups of polyethylene terephthalate (PET), polyethylene naphthenate (PEN), polycarbonate (PC), PVC contain and are particularly preferred PET beverage bottles. In a laboratory test, stress corrosion cracking is measured using a comparative example based on 5% polytetrafluoroethylene dispersion compared to a 5% perfluoropolyether solution in 95% glycerol.
Beispiel 2:Example 2:
Laut Versuchsbeschreibung werden PET-Flaschen mit Wasser gefüllt und mit Kohlendioxid so konditioniert, daß im Innenbereich der Flaschen ein Druck von etwa 7 bar vorliegt. Danach werden die Bodentassen der Flaschen in die Formulierung des Vergleichsbeispiels bzw. des erfindungsgemäß zu vewendenden Beispiels getaucht und über einen Zeitraum von 24 Stunden in eine Petri-Schale gestellt. Nach den 24 Stunden werden die Flaschen geöffnet, entleert und die Bodentassen mit Wasser abgespült. Bei visueller Auswertung der Bodentassen kann man feststellen, daß bei dem Versuch mit dem Vergleichsbeispiel viele Spannungsrisse mit mittlerer Tiefe, Einstufung C, vorliegen, während für den Versuch mit dem erfindungsgemäß zu verwendenden Beispiel festzustellen ist, daß nur wenige Spannungsrisse mit geringer Tiefe, Einstufung A, vorliegen. Die Einstufung erfolgt in Anlehnung an die Referenzbilder, die in Kapitel IV-22 des Buches 'CODE OF PRACTICE - Guidelines for an Industrial Code of Practice for Refillable PET Bottles', Edition 1 , 1993-1994, enthalten sind.According to the test description, PET bottles are filled with water and conditioned with carbon dioxide so that there is a pressure of about 7 bar in the interior of the bottles. The bottom cups of the bottles are then immersed in the formulation of the comparative example or the example to be used according to the invention and placed in a Petri dish over a period of 24 hours. After the 24 hours, the bottles are opened, emptied and the floor cups rinsed with water. A visual evaluation of the floor cups shows that there are many stress cracks with medium depth, rating C, in the test with the comparative example, while it is found in the test with the example to be used according to the invention that only a few stress cracks with low depth, rating A , are available. The classification is based on the reference images contained in Chapter IV-22 of the book 'CODE OF PRACTICE - Guidelines for an Industrial Code of Practice for Refillable PET Bottles', Edition 1, 1993-1994.
Beispiel 2 zeigt daß die erfindungsgemäß zu verwendenden Formulierungen gegenüber Polytetrafluorethylendispersionen Vorteile beim Transport von Kunststoffflaschen haben.Example 2 shows that the formulations to be used according to the invention have advantages over the transport of plastic bottles compared to polytetrafluoroethylene dispersions.
In einer weiteren bevorzugten Ausführung werden die erfindungsgemäß zu verwendenden Formulierungen für den Transport von Kartonverpackungen verwendet.In a further preferred embodiment, the formulations to be used according to the invention are used for the transport of cardboard packaging.
Weiterhin ist eine Verwendung bevorzugt, bei der die Transportflächen derFurthermore, use is preferred in which the transport surfaces of the
Transportbandanlagen aus Kunststoff, besonders bevorzugt aus Polyacetal undConveyor belt systems made of plastic, particularly preferably made of polyacetal and
Polyethylen sind.Are polyethylene.
In einer anderen bevorzugten Ausführung sind die Transportflächen derIn another preferred embodiment, the transport surfaces are
Transportbaπdanlage aus Metall, besonders bevorzugt aus Edelstahl.Transport conveyor system made of metal, particularly preferably made of stainless steel.
Es ist weiterhin bevorzugt, den erfindungsgemäß zu verwendenden Formulierungen vor oder nach der Applikation durch separate Zuführung zusätzliche antimikrobielleIt is further preferred to add additional antimicrobial to the formulations to be used according to the invention before or after application by separate addition
Stoffe, besonders bevorzugt organische Persäuren, Chlordioxid oder Ozon, zuzusetzen.Add substances, particularly preferably organic peracids, chlorine dioxide or ozone.
In einer bevorzugten Ausführung werden die erfindungsgemäß zu verwendendenIn a preferred embodiment, those to be used according to the invention
Formulierungen über ein Hilfsmittel, das ausgewählt sein kann aus Pinsel,Formulations using a tool that can be selected from a brush,
Schwamm, Rollen, Tücher, Lappen, Bürsten, Wischer, Gummi, Sprühvorrichtung auf die Transportbänder ohne vorherige Verdünnung mit Wasser aufgebracht. In einer anderen bevorzugten Ausführung werden die erfindungsgemäß zu verwendendenSponge, rollers, cloths, rags, brushes, wipers, rubber, spray device applied to the conveyor belts without prior dilution with water. In another preferred embodiment, those to be used according to the invention are used
Formulierungen in automatischen Transportbandanlagen mit Wasser verdünnt und die Anwendungslösung über Dosiervorrichtungen auf die Transportbänder aufgebracht, wobei der Verdünnungsfaktor zwischen 10.000 und 100 liegt. Es ist weiterhin bevorzugt, daß die erfindungsgemäß zu verwendenden Formulierungen so ausgewählt und angewandt werden, daß auf Oberflächen, die mit den Formulierungen oder Lösung in Kontakt stehen, keine weitere Vermehrung von Mikroorganismen erfolgt und ganz besonders bevorzugt, die Anzahl der Mikroorganismen reduziert wird.Formulations in automatic conveyor belt systems diluted with water and the application solution is applied to the conveyor belts via dosing devices, the dilution factor being between 10,000 and 100. It is further preferred that the formulations to be used according to the invention are selected and applied such that no further multiplication of microorganisms takes place on surfaces which are in contact with the formulations or solution, and very particularly preferably the number of microorganisms is reduced.
Vorzugsweise werden die erfindungsgemäß zu verwendenden Formulierungen für den Transport von Gebinden in der Lebensmittelindustrie verwendet, wobei in besonders bevorzugten Fällen aufkommender Schmutz von den mit dem Mittel konditionierten Transportbändern abgewiesen wird, der Wasserverbrauch um mindestens 80 % abgesenkt wird und keine Schmiermittel auf den Boden tropfen, sofern die Auftragung der Schmiermittel auf den Transportketten sachgemäß erfolgt. The formulations to be used according to the invention are preferably used for the transport of containers in the food industry, in which, in particularly preferred cases, dirt which is conditioned is repelled by the conveyor belts conditioned with the agent, the water consumption is reduced by at least 80% and no lubricants drip onto the floor, provided the lubricants are properly applied to the transport chains.

Claims

Patentansprüche Patent claims
1. Verwendung von Formulierungen, die mindestens eine fluorierte Komponente ausgewählt aus den Gruppen der a) per- oder teilfluorierten monomeren organischen Verbindungen, b) reinen und gemischten Di- und Oligomeren, die auf zumindest einem per- oder teilfluorierten organischen Monomer basieren, c) reinen und gemischten Polymeren, die auf zumindest einem per- oder teiifluorierten organischen Monomer basieren und im Polymer zumindest eine Monomereneinheit vorliegt, die entweder weniger als 75 Gew.% Fluor bezogen auf das Gewicht der gesamten Monomereneinheit oder mehr als 2 C-Atome enthält, enthalten, zur Reduktion der Reibung zwischen Transportgütern und Transportaniagen.1. Use of formulations which contain at least one fluorinated component selected from the groups of a) per- or partially fluorinated monomeric organic compounds, b) pure and mixed di- and oligomers which are based on at least one per- or partially fluorinated organic monomer, c) pure and mixed polymers which are based on at least one perfluorinated or partially fluorinated organic monomer and the polymer contains at least one monomer unit which contains either less than 75% by weight of fluorine based on the weight of the entire monomer unit or more than 2 carbon atoms , to reduce friction between transport goods and transport equipment.
2. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, daß die Gruppe a) zumindest per- und teilfluorierte Tenside, Alkane, Ether und Amine umfaßt.2. Use according to claim 1, characterized in that group a) comprises at least perfluorinated and partially fluorinated surfactants, alkanes, ethers and amines.
3. Verwendung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß aus der Gruppe c) zumindest per- und/oder teilfluorierte Alkoxy-Polymere enthalten sind.3. Use according to one of claims 1 or 2, characterized in that from group c) at least per- and / or partially fluorinated alkoxy polymers are included.
4. Verwendung nach Anspruch 3, dadurch gekennzeichnet, daß als Alkoxy- Polymere Verbindungen enthalten sind, die aus der Copolymerisation von Tetrafluorethylen und Perfluoralkoxyvinylethern erhältlich sind.4. Use according to claim 3, characterized in that the alkoxy polymers contained are compounds which are obtainable from the copolymerization of tetrafluoroethylene and perfluoroalkoxyvinyl ethers.
5. Verwendung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß aus der Gruppe c) zumindest per- und/oder teilfluorierte Polyether enthalten sind. 5. Use according to one of claims 1 or 2, characterized in that from group c) at least per- and / or partially fluorinated polyethers are included.
6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Formulierungen als Lösungen, Gel, Emulsion, Paste, Dispersion vorliegen.6. Use according to one of claims 1 to 5, characterized in that the formulations are present as solutions, gel, emulsion, paste, dispersion.
7. Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Formulierungen zusätzlich mindestens eine antimikrobielle Komponente ausgewählt aus den Gruppen der Alkohole, Aldehyde, antimikrobiellen Säuren, Carbonsäureester, Säureamide, Phenole, Phenolderivate, Diphenyle, Diphenylalkane, Harnstoffderivate, Sauerstoff-, Stickstoff-Acetale sowie - Formale, Beπzamidine, Isothiazoline, Phthalimidderivate, Pyridinderivate, antimikrobiellen oberflächenaktiven Verbindungen, Guanidine, antimikrobiellen amphoteren Verbindungen, Chinoline, 1 ,2-Dibrom-2,4-dicyanobutan, lodo-2- propynyl-butyl-carbamat, lod, lodophore, Peroxide enthalten.7. Use according to one of claims 1 to 6, characterized in that the formulations additionally contain at least one antimicrobial component selected from the groups of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen , nitrogen acetals and - formals, beπzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, lodo-2-propynyl-butyl-carbamate, Contain iodine, iodophors, peroxides.
8. Verwendung nach Anspruch 7, dadurch gekennzeichnet, daß die Formulierungen als antimikrobielle Komponenten eine oder mehrere Verbindungen ausgewählt aus Ethanol, n-Propanol, i-Propanol, 1 ,3-Butandiol, Phenoxyethanol, 1,2- Propylenglykol, Glycerin, Undecylensäure, Zitronensäure, 2-Benzyl-4- chlorphenol, 2,2'-Methylen-bis-(6-brom-4-chlorphenol), 2,4,4'-Trichlor-2'- hydroxydiphenylether, N-(4-Chlorphenyl)-N-(3,4-dichlorphenyl)-harnstoff, N,N'- (1 ,10-decandiyldi-1-pyridinyl-4-yliden)-bis-(1-octanamin)-dihydrochlorid, N,N'-Bis- (4-Chlorphenyl)-3,12-diimino-2,4,11 ,13-tetraaza-tetradecandiimidamid, quatemären Ammoniumverbindungen oder Alkyl-Aminen, Guanidinen, Amphoteren8. Use according to claim 7, characterized in that the formulations contain, as antimicrobial components, one or more compounds selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, Citric acid, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl) -N-(3,4-dichlorophenyl)-urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octanamine)-dihydrochloride, N,N'-Bis - (4-Chlorophenyl)-3,12-diimino-2,4,11,13-tetraaza-tetradecanediimidamide, quaternary ammonium compounds or alkyl amines, guanidines, amphoteres
9. Verwendung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Formulierungen zusätzlich mindestens eine fluorfreie Komponente ausgewählt aus der Gruppe der Polyhydroxyverbindungen enthalten.9. Use according to one of claims 1 to 8, characterized in that the formulations additionally contain at least one fluorine-free component selected from the group of polyhydroxy compounds.
10. Verwendung nach Anspruch 9, dadurch gekennzeichnet, daß die Polyhydroxyverbindungen ausgewählt sind aus den Gruppen der Polyalkohole und Kohlenhydrate. 10. Use according to claim 9, characterized in that the polyhydroxy compounds are selected from the groups of polyalcohols and carbohydrates.
1.Verwendung nach Anspruch 10, dadurch gekennzeichnet, daß als Polyhydroxyverbindungen mindestens eine Komponente ausgewählt aus mehrwertigen Alkoholen, vorzugsweise Alkandiole, Alkantriole, und den davon abgeleiteten Polyethem, sowie Glucose, Arabinose, Ribulose, Fructose und den davon abgeleiteten Oligo- und/oder Polysacchariden und deren Ester und Ether enthalten ist.1. Use according to claim 10, characterized in that as polyhydroxy compounds at least one component selected from polyhydric alcohols, preferably alkanediols, alkanetriols, and the polyethers derived therefrom, as well as glucose, arabinose, ribulose, fructose and the oligo- and/or polysaccharides derived therefrom and whose esters and ethers are included.
12. Verwendung nach einem der Ansprüche 1 bis 11 , dadurch gekennzeichnet, daß die Formulierungen weitere Komponenten ausgewählt aus den Gruppen der Tenside und Lösevermittler enthalten.12. Use according to one of claims 1 to 11, characterized in that the formulations contain further components selected from the groups of surfactants and solubilizers.
13. Verwendung nach Anspruch 12, dadurch gekennzeichnet, daß als Tensid zumindest ein Alkylpolyglycosid enthalten ist.13. Use according to claim 12, characterized in that at least one alkyl polyglycoside is contained as the surfactant.
14. Verwendung nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß der Wasseranteil in den Formulierungen unter 20 Gew.%, bezogen auf die gesamte Formulierung, liegt.14. Use according to one of claims 1 to 13, characterized in that the water content in the formulations is less than 20% by weight, based on the entire formulation.
15. Verwendung nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß der Wasseranteil unter 10 Gew.%, bezogen auf die gesamte Formulierung, liegt.15. Use according to one of claims 1 to 14, characterized in that the water content is less than 10% by weight, based on the entire formulation.
16. Verwendung von Formulierungen nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß beim Transport der Transportgüter auf den Transportanlagen kein Schaum entsteht.16. Use of formulations according to one of claims 1 to 15, characterized in that no foam is produced when the transport goods are transported on the transport systems.
17. Verwendung nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, daß im Vergleich zu üblichen Schmiermitteln, die in automatischen Transportbandanlagen mit Wasser um einen Verdünnungsfaktor von mehr als 100 verdünnt werden und für den Fall, daß innerhalb eines definierten Zeitraumes gewichtsgleiche Mengen an schmieraktiven Komponenten auf die Transportbandanlage aufgetragen werden, bei Einsatz von Formulierungen gemäß einem der Ansprüche 1 bis 16 der Reibwiderstand zwischen Transportgütern und Transportbandanlage um mehr als 20 % gesenkt wird.17. Use according to one of claims 1 to 16, characterized in that in comparison to conventional lubricants which are diluted with water in automatic conveyor belt systems by a dilution factor of more than 100 and in the event that equal amounts of lubricating active substances are used within a defined period of time components on the Conveyor belt system are applied, when using formulations according to one of claims 1 to 16 the frictional resistance between transport goods and conveyor belt system is reduced by more than 20%.
18. Verwendung nach einem der Ansprüche 1 bis 17 für den Transport von Kunststoff-Gebinden.18. Use according to one of claims 1 to 17 for the transport of plastic containers.
19. Verwendung nach Anspruch 18, dadurch gekennzeichnet, daß die Kunststoff- Gebinde mindestens ein Polymer ausgewählt aus den Gruppen der Polyethylenterephthalate (PET), Polyethylennaphtenate (PEN), Polycarbonate (PC), PVC enthalten.19. Use according to claim 18, characterized in that the plastic containers contain at least one polymer selected from the groups of polyethylene terephthalates (PET), polyethylene naphtenates (PEN), polycarbonates (PC), PVC.
20. Verwendung nach Anspruch 19, dadurch gekennzeichnet, daß die Kunststoff- Gebinde PET-Getränke-Flaschen sind.20. Use according to claim 19, characterized in that the plastic containers are PET beverage bottles.
21. Verwendung nach einem der Ansprüche 1 bis 19 für den Transport von Kartonverpackungen.21. Use according to one of claims 1 to 19 for the transport of cardboard packaging.
22. Verwendung nach einem der Ansprüche 1 bis 21 , dadurch gekennzeichnet, daß die Transportflächen der Transportbandanlage aus Kunststoff sind.22. Use according to one of claims 1 to 21, characterized in that the transport surfaces of the conveyor belt system are made of plastic.
23. Verwendung nach einem der Ansprüche 1 bis 21 , dadurch gekennzeichnet, daß die Transportflächen der Transportbandanlage aus Metall sind.23. Use according to one of claims 1 to 21, characterized in that the transport surfaces of the conveyor belt system are made of metal.
24. Verwendung nach einem der Ansprüche 1 bis 23, dadurch gekennzeichnet, daß bei der Applikation separat zusätzliche antimikrobielle Wirkstoffe zugesetzt werden.24. Use according to one of claims 1 to 23, characterized in that additional antimicrobial active ingredients are added separately during application.
25. Verwendung nach Anspruch 24, dadurch gekennzeichnet, daß als antimikrobielle Wirkstoffe organische Persäuren, Chlordioxid oder Ozon verwendet werden. 25. Use according to claim 24, characterized in that organic peracids, chlorine dioxide or ozone are used as antimicrobial active ingredients.
26. Verwendung nach einem der Ansprüche 1 bis 25, dadurch gekennzeichnet, daß die Formulierungen über ein Hilfsmittel, das ausgewählt ist aus Pinsel, Schwamm, Rollen, Tücher, Lappen, Bürsten, Wischer, Gummi, Sprühvorrichtung auf die Transportbänder ohne vorherige Verdünnung mit Wasser aufgebracht werden.26. Use according to one of claims 1 to 25, characterized in that the formulations are applied to the conveyor belts via an aid selected from brushes, sponges, rollers, cloths, rags, brushes, wipers, rubber, spray devices without prior dilution with water be applied.
27. Verwendung nach einem der Ansprüche 1 bis 25, dadurch gekennzeichnet, daß die Formulierungen in automatischen Transportbandanlagen mit Wasser verdünnt und die Anwendungslösung über Dosiervorrichtungen auf die Transportbänder aufgebracht werden.27. Use according to one of claims 1 to 25, characterized in that the formulations are diluted with water in automatic conveyor belt systems and the application solution is applied to the conveyor belts via metering devices.
28. Verwendung nach Anspruch 27, dadurch gekennzeichnet, daß der Verdünnungsfaktor zwischen 10000 und 100 liegt.28. Use according to claim 27, characterized in that the dilution factor is between 10,000 and 100.
29. Verwendung nach einem der Ansprüche 1 bis 28, dadurch gekennzeichnet, daß auf Oberflächen, die mit den Formulierungen oder Lösungen in Kontakt stehen, keine weitere Vermehrung von Mikroorganismen erfolgt.29. Use according to one of claims 1 to 28, characterized in that no further proliferation of microorganisms occurs on surfaces that are in contact with the formulations or solutions.
30. Verwendung nach einem der Ansprüche 1 bis 29, dadurch gekennzeichnet, daß auf Oberflächen, die mit den Formulierungen oder Lösungen in Kontakt stehen, die Anzahl der Mikroorganismen reduziert wird.30. Use according to one of claims 1 to 29, characterized in that the number of microorganisms is reduced on surfaces that are in contact with the formulations or solutions.
3 I .Verwendung nach einem der Ansprüche 1 bis 30 für den Transport von Gebinden in der Lebensmittelindustrie. 3 I .Use according to one of claims 1 to 30 for the transport of containers in the food industry.
EP00967633A 1999-09-07 2000-08-29 Lubricants containing fluorine Withdrawn EP1210400A2 (en)

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DE19942534 1999-09-07
DE19942534A DE19942534A1 (en) 1999-09-07 1999-09-07 Lubricants containing fluorine
PCT/EP2000/008394 WO2001018157A2 (en) 1999-09-07 2000-08-29 Anti-friction lubricants containing fluorine

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BR (1) BR0013786A (en)
CA (1) CA2383287C (en)
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US6653263B1 (en) 2003-11-25
DE19942534A1 (en) 2001-03-08
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AR026157A1 (en) 2003-01-29
GT200000148A (en) 2002-02-23
AU7774100A (en) 2001-04-10
PL353086A1 (en) 2003-10-06
WO2001018157A2 (en) 2001-03-15
CA2383287A1 (en) 2001-03-15
US20030139305A1 (en) 2003-07-24
BR0013786A (en) 2002-05-14
US6962897B2 (en) 2005-11-08
WO2001018157A3 (en) 2001-08-02
JP2003509535A (en) 2003-03-11

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