EP1646706A1 - Chain lubricants - Google Patents

Chain lubricants

Info

Publication number
EP1646706A1
EP1646706A1 EP03817929A EP03817929A EP1646706A1 EP 1646706 A1 EP1646706 A1 EP 1646706A1 EP 03817929 A EP03817929 A EP 03817929A EP 03817929 A EP03817929 A EP 03817929A EP 1646706 A1 EP1646706 A1 EP 1646706A1
Authority
EP
European Patent Office
Prior art keywords
concentrate
chain
lubricant solution
group
mixtures
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP03817929A
Other languages
German (de)
French (fr)
Other versions
EP1646706B1 (en
Inventor
Annett Lossack
Stefan Kuepper
Michael Schneider
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 Inc
Original Assignee
Ecolab Inc
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 Ecolab Inc filed Critical Ecolab Inc
Publication of EP1646706A1 publication Critical patent/EP1646706A1/en
Application granted granted Critical
Publication of EP1646706B1 publication Critical patent/EP1646706B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C10M173/00Lubricating compositions containing more than 10% water
    • C10M173/02Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • 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
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/122Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • 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
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/14Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/141Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
    • 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
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/281Esters of (cyclo)aliphatic monocarboxylic acids
    • 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
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/282Esters of (cyclo)aliphatic oolycarboxylic acids
    • 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
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • C10M2207/402Castor oils
    • 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
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • 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
    • 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
    • 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
    • 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/62Food grade properties
    • 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
    • C10N2040/38Conveyors or chain belts

Definitions

  • the present invention is directed to a concentrate and lubricant solution for the use as a lubricant for the lubrication of conveyor belt systems in food and beverage plants.
  • conveyor chains are made of different materials, i.e. plastico or metal.
  • the conveyors link the various optional treatment stages of the filling process, such as e.g. unpacker, bottle washing machine, filler, sealer, labeler, packer, etc.
  • the containers can come in a wide variety of forms, in particular glass and plastic bottles, cans, jars, casks, drink containers (KEG), paper and cardboard containers.
  • the conveyor chainss must be lubricated by suitable means such that excessive friction on the containers is avoided.
  • Diluted aqueous solutions containing suitable antifriction agents are conventionally used for lubrication.
  • the conveyor chains are brought into contact with the aqueous solutions by immersion or spraying, for example, whereby reference is then made to splash lubrication plants or automatic belt lubrication sys-o terns.
  • a lubricant is applied to the surface of the chains, whereby the friction coefficient of the chain with the container should not exceed a specific value. Otherwise the chain will be damaged involving further costs. Moreover, the container can fall down on the chains during5 transportation which will result in ceasing of filling said container since such bottles and cans have to be removed manually. Thus, a reliable lubrication of the chains with the lubricant used is very important.
  • the chain lubricants that have been used so far and are still used today as lubricating agents for conveyor belt systems are mainly based on fatty acids in the form of their water-soluble alkali or alkanol amine salts or on fatty amines, preferably in the form of their organic or inorganic salts, i.e. their acetates, s
  • Such lubricants are for example described in DE-A-36 31 953, EP-A-0 372 628, DE-A-39 05 548, DE-A-42 06 506, and WO 94/03562.
  • amine-free lubricants are known and described for example in WO 03/027217 A1.
  • This document relates to the use of an oil-in-water emulsion for lubricating a conveyor belt system. It contains wax esters, like cetyl palmitate,o hydrogenated castor oil, glyceryl stearate, ethoxylated behenyl alcohol, formic acids and betaines as zwitterionic amphoteric surfactants.
  • Residues and abraded material can collect in this film and lead to hygiene problems and breakdowns in operation.
  • container are made of glass or a plastic material such as a polyester.
  • PET Poly(ethylene terephthalate)
  • lubricants known in the prior art show a similar behavior. They are either suitable as lubricant for transporting container made of a plastic material or container made of glass. None of the compositions known in the prior art are capable of serving as lubricant in a bottling plant for all types of container material such as glass bottles, plastic bottles as well as cans.
  • the technical problem underlying the present invention is the provision of a lubricant suitable for container such as bottles made of glass, bottles made of a plastic material such as polyester or cans in a bottling plant, whereby the chains used in the bottling plant may be made of a metal and/or a plastic material. Furthermore, the lubricant shall provide good adhesion to the chains, display good lubricating properties and shall form a film on the chains that can easily be removed, if necessary.
  • a concentrate for use as chain lubricant comprising: a) at least one ester selected from the group consisting of monoesters and diesters represented by the aa) general formula (1) R 1 -COOR 2 (1) ab) general formula (2) R 1 OOC-R 3 -COOR 2 (2) ac) general formula (3) R 1 -COOR 3 OOC-R 2 (3), and mixtures thereof, whereby R 1 is a C ⁇ -C 22 -alkyl group or a Cs-C 22 -alkenyl group, R 2 is a C ⁇ -C 22 -alkyl group or a C 8 -C 22 -alkenyl group, R 1 and R 2 being the same or a different, R 3 is a C 2 -Ci 6 -alkylene group, and the sum of carbon atoms present in R 1 , R 2 and R 3 of each monoester or diester being at least 10, and b) at least one anionic surfactant
  • R 1 is an alkyl group having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 ,
  • R 1 is an alkenyl group having 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 carbon atoms
  • R 2 is an alkyl group having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 carbon atoms
  • R 2 is an alkenyl group having 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , or 22 carbon atoms.
  • R 3 is an alkylene group having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 ,
  • the concentrate further comprises at least one amphoteric surfactant.
  • the sum of carbon atoms present in R 1 , R 2 and R 3 of each monoester or diester is at least 12, even more preferred at leasto 15, and most preferred at least 20.
  • the concentrate may be an emulsion or microemulsion being preferably an oil-in-water or a water-in-oil emulsion.
  • the concentrate comprises 0,001 to 20 wt.-% of the ester and/or 0,001 to 20 wt.-% of the anionic surfactant and/or 0,001 to 20 wt.-% of thes amphoteric surfactant, whereby optionally the balance is a liquid being preferably water.
  • 0,01 to 15 wt-% of the ester is present in the concentrate.
  • 0,1 to 12 wt.-%, even more preferred 0,15 to 10 wt.- %, preferably 0,2 to 8 wt.-% and even more preferred 0,25 to 6 wt.-% of the estero is present in the concentrate.
  • 0,01 to 15 wt.-%, even more preferred 0,1 to 12, wt.-%, preferably 0,15 to 10 wt.-%, even more preferred 0,2 to 8 wt. % and most preferred 0,25 to 6 wt-% of the anionic surfactant is present in the concentrate.
  • 0,01 to 15 wt.-%, even more preferred 0,1 to 12, wt.-%, preferably 0,15 to 10 wt.-%, even more preferred 0,2 to 8 wt. % and most preferred 0,25 to 6 wt-% of the amphoteric surfactant is present in the concentrate.
  • the ester is preferably selected from the group consisting of methyl ester or isopropyl ester of fatty acids having 12 to 22 carbon atoms, methyl laura- te, methyl stearate, methyl oleate, methyl erucate, isopropyl palmitate, isopropyl myristate, isopropyl stearate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl palmitate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oley oleate, oleyl erucate, erucyl erucate, cetyl palmitate, behen
  • the anionic surfactant is preferably selected from the group consist- ing of sulfonate salt, alkali sulfonate salt, alkyl benzene sulfonic acid, alkali alkyl benzene sulfonate, alkyl sulfonic acid, alkali alkyl sulfonate, alkali alkyl sulfate, alkali alkenyl sulfate, fatty acid ether sulfate, fatty alcohol sulfonate, secondary alkane sulfonate sodium salt and mixtures thereof.
  • the amphoteric surfactant is preferably selected from the group consisting of ampholyte, betaine, alkylbetaine, N-alkylbetaine, glycinate, am- phoacetate, amphodiacetate, hydroxysultaine, amine oxide, lecithine, carboxyclic acid, sphingomyceline, amino alkene acid, sodium alkyl iminopropionate and mixtures thereof.
  • the concentrate further comprises at least one glyceride selected from the group consisting of triglyceride, diglyceride, monoglyceride, fatty acid triglyceride of fatty acids having 8 to 22 carbon atoms, glyceryl stearate and mixtures thereof.
  • the glycerides can be naturally occurring vegetable oils such as olive oil, raps seed oil, sunflower oil, soy oil, peanut oil, almond oil, palm kernel oil or the fluid part of coconut oil or palm kernel oil.
  • the glycerides can be of animal occurrence.
  • the glycerides are castor oil, prefer- rably hydrogenated castor oil.
  • the mono and diesters and glycerides as oily components of the composition according to the present invention are liquid at a temperature of 20 °C. It is also possible that higher melting fats and esters of the general formulae (1), (2) or (3) as given above are used in an amount so that the mixture of the oily compounds is liquid at a temperature of 20 °C.
  • the concentrate according to the present invention comprises of from 0,015 to 15 wt.-% of the glyceride.
  • glyceride Preferably, 0,05 to 10 wt-%, even more preferred 0,1 to 5 wt.-%, even more preferred 0,2 to 3 wt.-% and most preferred 0,3 to 2 wt.-% of the glyceride is present in the concentrate.
  • the concentrate further comprises a hydrocarbon oil, whereby preferably 0,01 to 15 wt.-% of the hydrocarbon oil, more preferred 0,015 to 10 wt.-%, even more preferred 0,05 to 5 wt.-%, most preferred, 0,1 to 3 wt.-% of the hydrocarbon oil is present in the concentrate.
  • 0,2 to 2 wt-% and even more preferred 0,3 to 1 ,5 wt-% of the hydrocarbon oil is present in the concentrate.
  • the concentrate may comprise at least one further emulsifier being different from the compounds as defined above.
  • the emulsifier is selected from the group consisting of nonionic emulsifier, ethylene oxide adducts with fatty alcohols having 16 to 22 car- - o -
  • the further emulsifier is present in the concentrate according to the present invention, preferably 0,005 to 20 wt-% of the emulsifier is present in the concentrate. Preferably 0,01 to 15 wt-%, more preferred 0,025 to 10 wt-%, even more preferred 0,05 to 5 wt-% and most preferred 0,075 to 3 wt-% of the emulsifier is present in the concentrate.
  • the concentrate may comprise a further co-emulsifier, whereby the co-emulsifier is preferably of the type of a saturated fatty alcohol having 16 to 22 carbon atoms and/or a partial ester of polyols having 3 - 6 carbon atoms with a fatty acid having 14 to 22 carbon atoms.
  • the co-emulsifier is preferably of the type of a saturated fatty alcohol having 16 to 22 carbon atoms and/or a partial ester of polyols having 3 - 6 carbon atoms with a fatty acid having 14 to 22 carbon atoms.
  • the concentrate may further comprise at least one additive selected from the group consisting of disinfectant, preservative, thickener, solubilizer, antifoaming agent, corrosion inhibitor, alkaline substance, sequestering agent, complexing agent and mixtures thereof.
  • Preferred preservatives are formic acid, benzoic acid, and peracetic acid.
  • Another suitable additive is preferably glyceride stearate, glycerine diglycerine, a diglycerine monoester, a glycerine diester, glycerine and mixtures thereof.
  • a preferred disinfectant is selected from the group of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, biphenylenes, biphenyl alkanes, urea derivatives, oxygen acetales, nitrogen acetales, oxygen formales, nitrogen formales, benzamidines, isothi- azolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2- dibromo-2,4-dicyano butane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores, peroxides, peracids, peracetic acid, CI0 2 , quatenary ammonium compounds, glu- coprotamine and mixtures thereof.
  • the present invention is directed further to a lubricant solution com- prising the concentrate as defined above and a suitable diulent.
  • the diluent is preferably water and a degree of dilution of the concentrate with water is preferably of from 1 :20 to 1 :5.000. In another preferred embodiment the degree of dilution of the concentrate with water is of from 1 :30 to 1 :2000, more preferred 1 :40 to 1 :1000 and most preferred 1 :50 to 1 :500.
  • the concentrate or the lubricant solution according to the present invention can be used as a lubricant.
  • a chain being preferably a part of a bottling plant which is preferably a conveyer chain or a conveyer belt is lubricated with the concentrate or lubricant solution according to the present invention.
  • the chain has an outer surface comprising a metal and/or a plastic material. With said chain container such as bottles and/or cans are transported.
  • the container or bottles are preferably made of glass or a plastic material, being preferably a polyester such as poly(ethylene terephthalate) or polycarbonate, poly(ethylene naphthenate) or polyurethane.
  • the container such as cans are made of a metal.
  • the bottle is a refutable bottle being preferably a refillable plastic bottle such as a refillable poly(ethylene terephthalate) bottle (REFPET).
  • the container being preferably bottles and/or cans are empty or filled with preferably food or beverage
  • the concentrate or lubricant solution is used as antistatic agent.
  • a further object of the present invention is the provision of a process of conveying container being preferably bottles and/or cans on a chain being preferably a conveyer chain or a conveyer belt, whereby the concentrate or lubricant solution is applied to the chain, preferably on the area of the chain with which the container being preferably bottles and/or cans are transported.
  • the concentrate or lubricant solution can be applied to the chain by application means customary to a person skilled in the art.
  • the concentrate or lubricant solution is sprayed to the chain by means of a nozzle or applied by immersion of the chain.
  • the concentrate or lubricant solution can be applied to the bottom of the container to be conveyed. This can be done by spraying or immersing the bottom of the container in the concentrate or lubricant solution.
  • the concentrate or lubricant solution is not applied continuously but periodically to the chain.
  • the time in which the concentrate or lubricant solution is applied to the chain is shorter than the time in which no concentrate or lubricant solution is applied to the chain.
  • the time in which no concentrate or lubricant solution is applied to the chain is twice as long, preferably three times as long, more preferred four times as long and most preferred five times as long as the time in which the concentrate or lubricant solution is applied to the chain.
  • the sum of the time in which the concentrate or lubricant solution is applied to the chain with the time in which the concentrate or lubricant solution is not applied to the chain is less than 10 minutes, more preferred less than 8 minutes, even more preferred less than 6 minutes and most preferred less than 4 minutes.
  • the concentrate and lubricant solution according to the present invention is superior compared with the compositions known in the prior art. Due to an extremely high lubricant persistency on the chains such as conveyor chains or conveyor belts compared with conventional state of the art techniques the lubri- cant dosage can be adjusted very flexibly to approximately 1 minute dosage and 5 minutes pause. The frequency of dosing can be extended according to the customer's condition and demands to a wider time frame or to a combination of lubrication dosage, followed by pure water dosage until the lubrication film is used up.
  • the concentrate and lubricant solution according to the present invention has an excellent emergency lubrication behavior, which means that a dried lubrication film is capable of lubricating sufficiently. Moreover, a dried lubrication film can be reanimated only with a small amount of water.
  • the formulations according to the present invention are foam-free or very low on foam so that very high use-concentrations during the application are possible.
  • a cleaning and/or disinfecting substance can be integrated into the concentrate or lubricant solution.
  • a further advantage of the concentrate and lubricant solution according to the present invention is that the lubricant comprises compounds only which are compatible with milk, soft-drinks and beer.
  • the new concentrate and lubricant solution offers an environmentally favorable concept with significant lubricant and water savings up to 70 to 80 % which influences also, to a large extent, waste water treatment costs and provides energy saving opportunities.
  • the new concentrate and lubricant solution according to the invention displays a new range of amine free lubricants for all kind of containers and is suitable for plastic and metal conveyors. It can be applied as a one part solution with integrated disinfectants as well as a two component system in combination with a disinfecting product.
  • the lubrification is excellent compared to the known amine acetate lubricants.
  • the lubricant has high water hardness and ion compatibility.
  • the concentrate was manufactured by mixing the ingredients given in table 1 according to methods known to a person skilled in the art. First, Lamesoft ® PW 45 BENZ, the alkyl betaine and the secondary alkane sufonate sodium salt are mixed. Subsequently water is added and the obtained solution is stirred. At last formic acid is added under stirring. Optionally, the concentrate can be filtered at any step of production of the concentrate. Table 1
  • Lamesoft ® PW 45 BENZ was purchased from Cognis Deutschland GmbH & Co. KG and is produced according to the teaching of EP 0 345 586, (emulsion of nonionic wax-like constituents and emulsifier comprising >20-40 wt-% cetyl palmitate, >5-10 wt-% beheneth-10, >1-5 wt-% hydrogenated castor oil, >1-5 wt-% glyceryl stearate, > 40-70 wt-% water, 0,2 wt-% benzoic acid).
  • Lamesoft ® PW 45 can be used (same composition as Lamesoft ® PW 45 BENZ with the exception that formic acid is present instead of benzoic acid)
  • the concentrate according to table 1 was diluted with water in a ratio of concen- trate to water of 1 :333 (0,3 wt-% of the concentrate in water) to obtain a lubricant solution for use as lubricant in the test run.
  • the obtained lubricant solution was applied to a conveyor chain of a bottling plant by means of a nozzle.
  • the bottling plant had a conveyer chain made of metal.
  • An obstacle having a load cell was positioned at the end of the conveyor chain so as to measure the tensile stress of the bottles pushed against said obstacle.
  • Either bottles made of glass or refillable bottles made of poly(ethylene terephthalate) (REFPET; 1 L or 1 ,5L volume) were transported with the conveyer chain.
  • the lu- bricant solution was either dosed for 50 seconds to the chain and subsequently 50 seconds no lubricant solution was applied to the chain or the lubricant solution was applied for 1 minute to the chain followed by a 5 minute pause of dosage.
  • the friction coefficient is the quotient of the tensile stress measured with the weight of the bottles pushed against the obstacle (table 2, 4 th column).
  • the friction coefficient for the emergency run was measured as follows: The obtained lubricant solution was applied for 5 minutes to the running conveyor chain. Subsequently, for each test run several test bottles characterized in table 2 were positioned on the conveyor chain. The bottles were transported on the conveyor chain and pushed against the obstacle positioned at the end of the conveyor chain. For 35 minutes the lubricant solution was applied to the chain in a 10 second dosage / 10 second pause sequence.
  • the friction coefficient for the emergency run is the quotient of the measured tensile stress with the weight of the bottles pushed against the obstacle (table 2, 5 th column).
  • the lubricant solution according to the present invention offers a superior dosing concept.
  • the efficiency of the concentrate and lubricant solution according to the present invention was not depending on the hardness of the water used.
  • TNO Nutrition and Food Research Code of Practice, "Guidelines for an Industrial Code of Practice for Refillable Polyester Based Bottles", Edition 2, 2000).
  • Three new test bottles made of PET are filled with tap water.
  • the bottom of the bottles is dipped for a short moment (approx. 5 s) in the concentrate of table 1 so that the whole bottom of the bottle is in contact with the concentrate (approx. 5 cm deep). Excess concentrate is drained off the bottle (approx. 10s).
  • each test bottle is pressurized with carbon dioxide via a connecting tube and the pressure is increased to approx. 7,5 bar for 30 s.
  • the test bottles are stored under a constant pressure of 7,5 ⁇ 0,2 bar for 72 hours at room temperature and after- wards the pressure is decreased in approx. 30 s to zero.
  • the bottles are emptied and rinsed thoroughly, first with tap water and finally with demineralized water. After drying, the bottom of each bottle is examined visually whether deviations (e.g. haziness, whitening, cracks) occurred.
  • the concentrate of the present invention exhibited a superior test result compara- ble with the best lubricants known in the prior art.
  • the test bottles were not detrimentally affected by the concentrate of the present invention. No cracks in the test bottles occurred.
  • the test bottles remained clear which means that no haziness occurred during testing.
  • the concentrate of the present invention is superior compared with the compositions known in the prior art.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The present invention is directed to a concentrate for use as chain lubricant comprising: a) at least one ester selected from the group consisting of monoesters and diesters represented by the aa) general formula (1) R1-COOR2; ab) general formula (2) R1OOC-R3-COOR2 ; ac) general formula (3) R1-COOR3OOC-R2, and mixtures thereof, whereby R1 is a C1-C22-alkyl group or a C8-C22-alkenyl group, R2 is a C1-C22-alkyl group or a C8-C22-alkenyl group, R1 and R2 being the same or a different, R3 is a C2-C16-alkylene group, and the sum of carbon atoms present in R1, R2 and R3 of each monoester or diester being at least 10, and b) at least one anionic surfactant, and a lubricant solution comprising the concentrate and a suitable diluent.

Description

Chain lubricants
[0001] The present invention is directed to a concentrate and lubricant solution for the use as a lubricant for the lubrication of conveyor belt systems in food and beverage plants.
5 [0002] In the food industry, in particular in beverage plants, the containers that are to be filled in the filling plants are transported by means of conveyors in a wide variety of designs and materials, for example by means of apron conveyors or chain-type arrangements, which will be referred to in general terms below as conveyor chains. The conveyor chains are made of different materials, i.e. plastico or metal. The conveyors link the various optional treatment stages of the filling process, such as e.g. unpacker, bottle washing machine, filler, sealer, labeler, packer, etc. The containers can come in a wide variety of forms, in particular glass and plastic bottles, cans, jars, casks, drink containers (KEG), paper and cardboard containers. To ensure that the operation proceeds smoothly, the conveyor chainss must be lubricated by suitable means such that excessive friction on the containers is avoided. Diluted aqueous solutions containing suitable antifriction agents are conventionally used for lubrication. The conveyor chains are brought into contact with the aqueous solutions by immersion or spraying, for example, whereby reference is then made to splash lubrication plants or automatic belt lubrication sys-o terns.
[0003] In order to minimize the abrasion of the chains, a lubricant is applied to the surface of the chains, whereby the friction coefficient of the chain with the container should not exceed a specific value. Otherwise the chain will be damaged involving further costs. Moreover, the container can fall down on the chains during5 transportation which will result in ceasing of filling said container since such bottles and cans have to be removed manually. Thus, a reliable lubrication of the chains with the lubricant used is very important. [0004] The chain lubricants that have been used so far and are still used today as lubricating agents for conveyor belt systems are mainly based on fatty acids in the form of their water-soluble alkali or alkanol amine salts or on fatty amines, preferably in the form of their organic or inorganic salts, i.e. their acetates, s Such lubricants are for example described in DE-A-36 31 953, EP-A-0 372 628, DE-A-39 05 548, DE-A-42 06 506, and WO 94/03562.
[0005] Also, amine-free lubricants are known and described for example in WO 03/027217 A1. This document relates to the use of an oil-in-water emulsion for lubricating a conveyor belt system. It contains wax esters, like cetyl palmitate,o hydrogenated castor oil, glyceryl stearate, ethoxylated behenyl alcohol, formic acids and betaines as zwitterionic amphoteric surfactants.
[0006] From the point of view of the user, however, the chain lubricants used still present the problem that they either adhere too poorly to the chains or attach too strongly to the chains. s [0007] Where chain lubricants adhere too poorly to the chains they drip onto the ground soon after application, with the result that the lubricating effect on the chains, which are several meters in length, is extremely dependent on the proximity to the metering point. The same problem occurs at places where there is a risk of the lubrication film rapidly being removed from the surface by spilled beverage.0 The consequence is that very different qualities of lubrication can occur from one section to another. In critical sections this commonly leads to bottles falling over and even to interruption of the filling operation.
[0008] Where chain lubricants adhere very well to the chains, as is the case with fluoro groups containing surfactants, for example, which have very good wet-5 ting properties, a firmly adhering film is formed on the conveyor chains, which cannot easily be removed by rinsing with water. ~ __) ~
[0009] Residues and abraded material can collect in this film and lead to hygiene problems and breakdowns in operation.
[0010] Generally, container are made of glass or a plastic material such as a polyester. Poly(ethylene terephthalate) (PET) is very often used to manufacture plastic bottles.
[0011] In case that glass bottles are transported the lubrication of the com- position according to the state of the art is not sufficient. Glass bottles can fall off the conveyor chain and thus a secure transportation of glass bottles can not be assured. Furthermore, due to an insufficient lubrication the abrasion of the chains used is not acceptable.
[0012] Other lubricants known in the prior art show a similar behavior. They are either suitable as lubricant for transporting container made of a plastic material or container made of glass. None of the compositions known in the prior art are capable of serving as lubricant in a bottling plant for all types of container material such as glass bottles, plastic bottles as well as cans.
[0013] For convenience reasons a manufacturer of for instance beverage wants to fill all kinds of containers like glass bottles, plastic bottles as well as cans with the same bottling plant. At present he has to use a specific lubricant for each type of container to be filled. Thus, further costs and a significant downtime of the bottling plant are due to the specific selection or exchange of lubricants for each type of container to be filled.
[0014] The technical problem underlying the present invention is the provision of a lubricant suitable for container such as bottles made of glass, bottles made of a plastic material such as polyester or cans in a bottling plant, whereby the chains used in the bottling plant may be made of a metal and/or a plastic material. Furthermore, the lubricant shall provide good adhesion to the chains, display good lubricating properties and shall form a film on the chains that can easily be removed, if necessary.
[0015] The technical problem underlying the present invention is solved by a concentrate for use as chain lubricant comprising: a) at least one ester selected from the group consisting of monoesters and diesters represented by the aa) general formula (1) R1-COOR2 (1) ab) general formula (2) R1OOC-R3-COOR2 (2) ac) general formula (3) R1-COOR3OOC-R2 (3), and mixtures thereof, whereby R1 is a Cι-C22-alkyl group or a Cs-C22-alkenyl group, R2 is a Cι-C22-alkyl group or a C8-C22-alkenyl group, R1 and R2 being the same or a different, R3 is a C2-Ci6-alkylene group, and the sum of carbon atoms present in R1, R2 and R3 of each monoester or diester being at least 10, and b) at least one anionic surfactant.
[0016] Preferably, R1 is an alkyl group having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 ,
12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 carbon atoms or R1 is an alkenyl group having 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , or 22 carbon atoms. [0017] Preferably, R2 is an alkyl group having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 carbon atoms or R2 is an alkenyl group having 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , or 22 carbon atoms.
[0018] Preferably R3 is an alkylene group having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 ,
5 12, 13, 14, 15, or 16 carbon atoms.
[0019] Preferably, the concentrate further comprises at least one amphoteric surfactant.
[0020] In a preferred embodiment the sum of carbon atoms present in R1, R2 and R3 of each monoester or diester is at least 12, even more preferred at leasto 15, and most preferred at least 20.
[0021] The concentrate may be an emulsion or microemulsion being preferably an oil-in-water or a water-in-oil emulsion.
[0022] Preferably, the concentrate comprises 0,001 to 20 wt.-% of the ester and/or 0,001 to 20 wt.-% of the anionic surfactant and/or 0,001 to 20 wt.-% of thes amphoteric surfactant, whereby optionally the balance is a liquid being preferably water.
[0023] In a preferred embodiment 0,01 to 15 wt-% of the ester is present in the concentrate. Preferably, 0,1 to 12 wt.-%, even more preferred 0,15 to 10 wt.- %, preferably 0,2 to 8 wt.-% and even more preferred 0,25 to 6 wt.-% of the estero is present in the concentrate.
[0024] Preferably, 0,01 to 15 wt.-%, even more preferred 0,1 to 12, wt.-%, preferably 0,15 to 10 wt.-%, even more preferred 0,2 to 8 wt. % and most preferred 0,25 to 6 wt-% of the anionic surfactant is present in the concentrate. [0025] Preferably, 0,01 to 15 wt.-%, even more preferred 0,1 to 12, wt.-%, preferably 0,15 to 10 wt.-%, even more preferred 0,2 to 8 wt. % and most preferred 0,25 to 6 wt-% of the amphoteric surfactant is present in the concentrate.
[0026] The ester is preferably selected from the group consisting of methyl ester or isopropyl ester of fatty acids having 12 to 22 carbon atoms, methyl laura- te, methyl stearate, methyl oleate, methyl erucate, isopropyl palmitate, isopropyl myristate, isopropyl stearate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl palmitate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oley oleate, oleyl erucate, erucyl erucate, cetyl palmitate, beheneth-10, esters of technical aliphatic alcohol mixtures with technical aliphatic carboxylic acids, esters of saturated and/or unsaturated fatty alcohols having 12 to 22 carbon atoms with saturated and/or unsaturated fatty acids having 12 to 22 carbon atoms, naturally occurring monoester or waxy ester mixtures as occurring in jojoba oil or sperm oil, di-n-butyl adipate, di-n-butyl sebacate, di-(2-ethylhexyl) adipate, di-(2-hexyldecyl) succinate, di-isotridecyl acealate, ethylenglycol dioleate, ethylenglycol-di- isotridecanoate, propyleneglycol-di-(2-ethylhexanoate), butanediol-di-isostearate, neopentylglycol-di-caprylate and mixtures thereof.
[0027] The anionic surfactant is preferably selected from the group consist- ing of sulfonate salt, alkali sulfonate salt, alkyl benzene sulfonic acid, alkali alkyl benzene sulfonate, alkyl sulfonic acid, alkali alkyl sulfonate, alkali alkyl sulfate, alkali alkenyl sulfate, fatty acid ether sulfate, fatty alcohol sulfonate, secondary alkane sulfonate sodium salt and mixtures thereof.
[0028] The amphoteric surfactant is preferably selected from the group consisting of ampholyte, betaine, alkylbetaine, N-alkylbetaine, glycinate, am- phoacetate, amphodiacetate, hydroxysultaine, amine oxide, lecithine, carboxyclic acid, sphingomyceline, amino alkene acid, sodium alkyl iminopropionate and mixtures thereof. [0029] Optionally, the concentrate further comprises at least one glyceride selected from the group consisting of triglyceride, diglyceride, monoglyceride, fatty acid triglyceride of fatty acids having 8 to 22 carbon atoms, glyceryl stearate and mixtures thereof. The glycerides can be naturally occurring vegetable oils such as olive oil, raps seed oil, sunflower oil, soy oil, peanut oil, almond oil, palm kernel oil or the fluid part of coconut oil or palm kernel oil. Moreover the glycerides can be of animal occurrence. In a preferred embodiment the glycerides are castor oil, prefer- rably hydrogenated castor oil. Preferably, the mono and diesters and glycerides as oily components of the composition according to the present invention are liquid at a temperature of 20 °C. It is also possible that higher melting fats and esters of the general formulae (1), (2) or (3) as given above are used in an amount so that the mixture of the oily compounds is liquid at a temperature of 20 °C.
[0030] Preferably, the concentrate according to the present invention comprises of from 0,015 to 15 wt.-% of the glyceride.
[0031] Preferably, 0,05 to 10 wt-%, even more preferred 0,1 to 5 wt.-%, even more preferred 0,2 to 3 wt.-% and most preferred 0,3 to 2 wt.-% of the glyceride is present in the concentrate.
[0032] In a preferred embodiment the concentrate further comprises a hydrocarbon oil, whereby preferably 0,01 to 15 wt.-% of the hydrocarbon oil, more preferred 0,015 to 10 wt.-%, even more preferred 0,05 to 5 wt.-%, most preferred, 0,1 to 3 wt.-% of the hydrocarbon oil is present in the concentrate. In a further preferred embodiment 0,2 to 2 wt-% and even more preferred 0,3 to 1 ,5 wt-% of the hydrocarbon oil is present in the concentrate.
[0033] The concentrate may comprise at least one further emulsifier being different from the compounds as defined above.
[0034] Preferably, the emulsifier is selected from the group consisting of nonionic emulsifier, ethylene oxide adducts with fatty alcohols having 16 to 22 car- - o -
bon atoms, partial esters of polyols having 3 to 6 carbon atoms with fatty acids having 14 to 22 carbon atoms and mixtures thereof.
[0035] In case the further emulsifier is present in the concentrate according to the present invention, preferably 0,005 to 20 wt-% of the emulsifier is present in the concentrate. Preferably 0,01 to 15 wt-%, more preferred 0,025 to 10 wt-%, even more preferred 0,05 to 5 wt-% and most preferred 0,075 to 3 wt-% of the emulsifier is present in the concentrate.
[0036] The concentrate may comprise a further co-emulsifier, whereby the co-emulsifier is preferably of the type of a saturated fatty alcohol having 16 to 22 carbon atoms and/or a partial ester of polyols having 3 - 6 carbon atoms with a fatty acid having 14 to 22 carbon atoms.
[0037] The concentrate may further comprise at least one additive selected from the group consisting of disinfectant, preservative, thickener, solubilizer, antifoaming agent, corrosion inhibitor, alkaline substance, sequestering agent, complexing agent and mixtures thereof.
[0038] Preferred preservatives are formic acid, benzoic acid, and peracetic acid.
[0039] Another suitable additive is preferably glyceride stearate, glycerine diglycerine, a diglycerine monoester, a glycerine diester, glycerine and mixtures thereof.
[0040] A preferred disinfectant is selected from the group of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, biphenylenes, biphenyl alkanes, urea derivatives, oxygen acetales, nitrogen acetales, oxygen formales, nitrogen formales, benzamidines, isothi- azolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2- dibromo-2,4-dicyano butane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores, peroxides, peracids, peracetic acid, CI02, quatenary ammonium compounds, glu- coprotamine and mixtures thereof.
[0041] The present invention is directed further to a lubricant solution com- prising the concentrate as defined above and a suitable diulent.
[0042] The diluent is preferably water and a degree of dilution of the concentrate with water is preferably of from 1 :20 to 1 :5.000. In another preferred embodiment the degree of dilution of the concentrate with water is of from 1 :30 to 1 :2000, more preferred 1 :40 to 1 :1000 and most preferred 1 :50 to 1 :500.
[0043] The concentrate or the lubricant solution according to the present invention can be used as a lubricant.
[0044] Preferably, a chain being preferably a part of a bottling plant which is preferably a conveyer chain or a conveyer belt is lubricated with the concentrate or lubricant solution according to the present invention.
[0045] In a preferred embodiment the chain has an outer surface comprising a metal and/or a plastic material. With said chain container such as bottles and/or cans are transported.
[0046] In case that container such as bottles are transported with the chain, the container or bottles are preferably made of glass or a plastic material, being preferably a polyester such as poly(ethylene terephthalate) or polycarbonate, poly(ethylene naphthenate) or polyurethane. Preferably, the container such as cans are made of a metal. It is preferred that the bottle is a refutable bottle being preferably a refillable plastic bottle such as a refillable poly(ethylene terephthalate) bottle (REFPET). [0047] Preferably, when transported with the chain the container being preferably bottles and/or cans are empty or filled with preferably food or beverage
[0048] Preferably, the concentrate or lubricant solution is used as antistatic agent.
[0049] A further object of the present invention is the provision of a process of conveying container being preferably bottles and/or cans on a chain being preferably a conveyer chain or a conveyer belt, whereby the concentrate or lubricant solution is applied to the chain, preferably on the area of the chain with which the container being preferably bottles and/or cans are transported.
[0050] The concentrate or lubricant solution can be applied to the chain by application means customary to a person skilled in the art. Preferably, the concentrate or lubricant solution is sprayed to the chain by means of a nozzle or applied by immersion of the chain. Alternatively, the concentrate or lubricant solution can be applied to the bottom of the container to be conveyed. This can be done by spraying or immersing the bottom of the container in the concentrate or lubricant solution.
[0051] In a preferred process, the concentrate or lubricant solution is not applied continuously but periodically to the chain. Preferably, for each period the time in which the concentrate or lubricant solution is applied to the chain is shorter than the time in which no concentrate or lubricant solution is applied to the chain. Preferably, the time in which no concentrate or lubricant solution is applied to the chain is twice as long, preferably three times as long, more preferred four times as long and most preferred five times as long as the time in which the concentrate or lubricant solution is applied to the chain. Preferably, for each period the sum of the time in which the concentrate or lubricant solution is applied to the chain with the time in which the concentrate or lubricant solution is not applied to the chain is less than 10 minutes, more preferred less than 8 minutes, even more preferred less than 6 minutes and most preferred less than 4 minutes. [0052] The concentrate and lubricant solution according to the present invention is superior compared with the compositions known in the prior art. Due to an extremely high lubricant persistency on the chains such as conveyor chains or conveyor belts compared with conventional state of the art techniques the lubri- cant dosage can be adjusted very flexibly to approximately 1 minute dosage and 5 minutes pause. The frequency of dosing can be extended according to the customer's condition and demands to a wider time frame or to a combination of lubrication dosage, followed by pure water dosage until the lubrication film is used up.
[0053] Unexpectedly, the concentrate and lubricant solution according to the present invention has an excellent emergency lubrication behavior, which means that a dried lubrication film is capable of lubricating sufficiently. Moreover, a dried lubrication film can be reanimated only with a small amount of water.
[0054] Advantageously, the formulations according to the present invention are foam-free or very low on foam so that very high use-concentrations during the application are possible.
[0055] In a preferred embodiment a cleaning and/or disinfecting substance can be integrated into the concentrate or lubricant solution.
[0056] A further advantage of the concentrate and lubricant solution according to the present invention is that the lubricant comprises compounds only which are compatible with milk, soft-drinks and beer.
[0057] Due to the flexible dosage concept, the new concentrate and lubricant solution offers an environmentally favorable concept with significant lubricant and water savings up to 70 to 80 % which influences also, to a large extent, waste water treatment costs and provides energy saving opportunities.
[0058] Unexpectedly, there is no influence of the water hardness on the capability of the concentrate and lubricant solution according to the present invention over a wide range of water hardnesses, i.e. between 0° and 25° German hardness.
[0059] The new concentrate and lubricant solution according to the invention displays a new range of amine free lubricants for all kind of containers and is suitable for plastic and metal conveyors. It can be applied as a one part solution with integrated disinfectants as well as a two component system in combination with a disinfecting product. The lubrification is excellent compared to the known amine acetate lubricants. Furthermore, when using the product according to the invention in the case of PET bottles and plastic container reduced stress cracking is observed. The lubricant has high water hardness and ion compatibility.
[0060] The following examples describe the invention in more detail without limiting it to the specific scope mentioned in the examples.
Examples
1. Preparation of the concentrate and lubricant solution
The concentrate Was manufactured by mixing the ingredients given in table 1 according to methods known to a person skilled in the art. First, Lamesoft® PW 45 BENZ, the alkyl betaine and the secondary alkane sufonate sodium salt are mixed. Subsequently water is added and the obtained solution is stirred. At last formic acid is added under stirring. Optionally, the concentrate can be filtered at any step of production of the concentrate. Table 1
1) Lamesoft® PW 45 BENZ was purchased from Cognis Deutschland GmbH & Co. KG and is produced according to the teaching of EP 0 345 586, (emulsion of nonionic wax-like constituents and emulsifier comprising >20-40 wt-% cetyl palmitate, >5-10 wt-% beheneth-10, >1-5 wt-% hydrogenated castor oil, >1-5 wt-% glyceryl stearate, > 40-70 wt-% water, 0,2 wt-% benzoic acid). Alternatively, Lamesoft® PW 45 can be used (same composition as Lamesoft® PW 45 BENZ with the exception that formic acid is present instead of benzoic acid)
The concentrate according to table 1 was diluted with water in a ratio of concen- trate to water of 1 :333 (0,3 wt-% of the concentrate in water) to obtain a lubricant solution for use as lubricant in the test run.
2. Test run in a bottling plant
The obtained lubricant solution was applied to a conveyor chain of a bottling plant by means of a nozzle. The bottling plant had a conveyer chain made of metal. An obstacle having a load cell was positioned at the end of the conveyor chain so as to measure the tensile stress of the bottles pushed against said obstacle. Either bottles made of glass or refillable bottles made of poly(ethylene terephthalate) (REFPET; 1 L or 1 ,5L volume) were transported with the conveyer chain. The lu- bricant solution was either dosed for 50 seconds to the chain and subsequently 50 seconds no lubricant solution was applied to the chain or the lubricant solution was applied for 1 minute to the chain followed by a 5 minute pause of dosage. The friction coefficient is the quotient of the tensile stress measured with the weight of the bottles pushed against the obstacle (table 2, 4th column).
The friction coefficient for the emergency run was measured as follows: The obtained lubricant solution was applied for 5 minutes to the running conveyor chain. Subsequently, for each test run several test bottles characterized in table 2 were positioned on the conveyor chain. The bottles were transported on the conveyor chain and pushed against the obstacle positioned at the end of the conveyor chain. For 35 minutes the lubricant solution was applied to the chain in a 10 second dosage / 10 second pause sequence.
Subsequently, the dosage of the lubricant solution was ceased and after 15 minutes the tensile stress of the bottles with the obstacle was measured. The friction coefficient for the emergency run is the quotient of the measured tensile stress with the weight of the bottles pushed against the obstacle (table 2, 5th column).
Table 2
As can be seen from table 2 the friction coefficients measured do not significantly depend on the material of the bottle. The lubrication of the conveyer chain was sufficient in the entire test run. Furthermore the emergency run, which means that the application of lubricant to the chain was ceased, was successful over a suffi- cient period of time (15 minutes), since the friction coefficient was sufficiently low. A further test exhibited that the emergency run was successful for a longer period of time such as 1 ,5 to 2 hours. Furthermore, no bottle fell down onto the chain during the entire test runs.
Since the lubrication solution is applied to the chain in a 50 second lubrication dosage followed by a 50 second pause or, alternatively, in a 1 minute lubrication dosage followed by a 5 minute pause the lubricant solution according to the present invention offers a superior dosing concept.
Due to said novel dosage concept, the amount of lubricant necessary is decreased significantly which results in a waste water reduction and, thus, in a significant cost reduction. Furthermore, a persistent film build up after drying of the lubricant solution on the surface of the conveyer chain. Said film can easily be reactivated by spraying water onto said film.
The efficiency of the concentrate and lubricant solution according to the present invention was not depending on the hardness of the water used.
3. TNO test
The TNO method was performed to determine the material compatibility (TNO Nutrition and Food Research, Code of Practice, "Guidelines for an Industrial Code of Practice for Refillable Polyester Based Bottles", Edition 2, 2000).
Three new test bottles made of PET are filled with tap water. The bottom of the bottles is dipped for a short moment (approx. 5 s) in the concentrate of table 1 so that the whole bottom of the bottle is in contact with the concentrate (approx. 5 cm deep). Excess concentrate is drained off the bottle (approx. 10s). Subsequently, each test bottle is pressurized with carbon dioxide via a connecting tube and the pressure is increased to approx. 7,5 bar for 30 s. The test bottles are stored under a constant pressure of 7,5 ± 0,2 bar for 72 hours at room temperature and after- wards the pressure is decreased in approx. 30 s to zero. The bottles are emptied and rinsed thoroughly, first with tap water and finally with demineralized water. After drying, the bottom of each bottle is examined visually whether deviations (e.g. haziness, whitening, cracks) occurred.
The concentrate of the present invention exhibited a superior test result compara- ble with the best lubricants known in the prior art. The test bottles were not detrimentally affected by the concentrate of the present invention. No cracks in the test bottles occurred. The test bottles remained clear which means that no haziness occurred during testing. Thus, the concentrate of the present invention is superior compared with the compositions known in the prior art.

Claims

Claims
1. A concentrate for use as chain lubricant comprising: a) at least one ester selected from the group consisting of monoesters and diesters represented by the
5 aa) general formula (1) R1-COOR2 (1) ab) general formula (2) R1OOC-R3-COOR2 (2) ac) general formula (3)o R1-COOR3OOC-R2 (3), and mixtures thereof, whereby R1 is a Cι-C22-alkyl group or a Cs-C22-alkenyl group, R2 is a Cι-C22-alkyl group or a C_-C22-alkenyl group, R1 and R2 being the same or a different,s R3 is a C2-C-i6-alkylene group, and the sum of carbon atoms present in R1, R2 and R3 of each monoester or diester being at least 10, and b) at least one anionic surfactant.
2. The concentrate according to claim 1 , characterized in that the concentrateo further comprises at least one amphoteric surfactant.
3. The concentrate according to claim 1 or 2, characterized in that the concentrate is an emulsion or microemulsion being preferably an oil-in-water or a wa- ter-in-oil emulsion.
4. The concentrate according to any of the preceding claims, characterized in that 0,001 to 20 wt-% of the ester and/or 0,001 to 20 wt-% of the anionic surfactant and/or 0,001 to 20 wt-% of the amphoteric surfactant are present in the concentrate, whereby optionally the balance is a liquid being preferably water.
5. The concentrate according to any of the preceding claims, characterized in that 0,01 to 15 wt-% of the ester is present in the concentrate.
6. The concentrate according to any of the preceding claims, characterized in that 0,01 to 15 wt-% of the anionic surfactant is present in the concentrate.
7. The concentrate according to any of the preceding claims, characterized in that 0,01 to 15 wt-% of the amphoteric surfactant is present in the concentrate.
8. The concentrate according to any of the preceding claims, characterized in that the ester is selected from the group consisting of methyl ester or isopropyl ester of fatty acids having 12 to 22 carbon atoms, methyl laurate, methyl stearate, methyl oleate, methyl erucate, isopropyl palmitate, isopropyl myristate, isopropyl stearate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl palmitate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oley oleate, oleyl erucate, erucyl erucate, cetyl palmitate, beheneth-10, esters of technical aliphatic alcohol mixtures with technical aliphatic carboxylic acids, esters of saturated and/or unsaturated fatty alcohols having 12 to 22 carbon atoms with saturated and/or unsaturated fatty acids having 12 to 22 carbon atoms, naturally occur- ring monoester or waxy ester mixtures as occurring in jojoba oil or sperm oil, din-butyl adipate, di-n-butyl sebacate, di-(2-ethylhexyl) adipate, di-(2-hexyldecyl) succinate, di-isotridecyl acealate, ethylenglycol dioleate, ethylenglycol-di- isotridecanoate, propyleneglycol-di-(2-ethylhexanoate), butanediol-di- isostearate, neopentylglycol-di-caprylate and mixtures thereof.
9. The concentrate according to any of the preceding claims, characterized in that the anionic surfactant is selected from the group consisting of sulfonate salt, al- kali sulfonate salt, alkyl benzene sulfonic acid, alkali alkyl benzene sulfonate, alkyl sulfonic acid, alkali alkyl sulfonate, alkali alkyl sulfate, alkali alkenyl sulfate, fatty acid ether sulfate, fatty alcohol sulfonate, secondary alkane sulfonate sodium salt and mixtures thereof.
10. The concentrate according to any of the preceding claims, characterized in that the amphoteric surfactant is selected from the group consisting of ampholyte, betaine, alkylbetaine, N-alkylbetaine, glycinate, amphoacetate, amphodiace- tate, hydroxysultaine, amine oxide, lecithine, carboxyclic acid, sphingomyce- line, amino alkene acid, sodium alkyl iminopropionate and mixtures thereof.
11.The concentrate according to any of the preceding claims, characterized in that the concentrate further comprises at least one glyceride selected from the group consisting of triglyceride, diglyceride, monoglyceride, fatty acid triglyceride of fatty acids having 8 to 22 carbon atoms, glyceryl stearate and mixtures thereof.
12. The concentrate according to claim 11, characterized in that the concentrate comprises of from 0,01 to 15 wt-% of the glyceride.
13. The concentrate according to any of the preceding claims, characterized in that the concentrate further comprises a hydrocarbon oil.
14. The concentrate according to claim 13, characterized in that the concentrate comprises of from 0,01 to 15 wt-% of the hydrocarbon oil.
15. The concentrate according to any of the preceding claims, characterized in that the concentrate further comprises at least one emulsifier being different from the compounds defined in the preceding claims.
16. The concentrate according to claim 15, characterized in that the emulsifier is selected from the group consisting of nonionic emulsifier, ethylene oxide ad- ducts with fatty alcohols having 16 to 22 carbon atoms, partial esters of polyols having 3 to 6 carbon atoms with fatty acids having 14 to 22 carbon atoms and mixtures thereof.
17. The concentrate according to claim 15 or 16, characterized in that the concen- trate comprises of from 0,005 to 20 wt-% of the emulsifier.
18. The concentrate according to any of the preceding claims, characterized in that concentrate further comprises at least one additive selected from the group consisting of disinfectant, preservative, thickener, solubilizer, anti-foaming agent, corrosion inhibitor, alkaline substance, sequestering agent, complexing agent and mixtures thereof.
19. A lubricant solution comprising the concentrate according to any of the preceding claims and a suitable diluent.
20. The lubricant solution according to claim 19, characterized in that the diluent is water and the degree of dilution of the concentrate with water is preferably of from 1 :20 to 1 :5000.
21. Use of the concentrate or the lubricant solution according to any of the preceding claims as lubricant. terized in that a chain being preferably a conveyor chain or a conveyor belt is lubricated.
23. Use of the concentrate or the lubricant solution according to claim 21 or 22, characterized in that the chain has an outer surface comprising a metal and/or a plastic material.
24. Use of the concentrate or lubricant solution according to any of the claims 21 to 22, characterized in that container such as bottles and/or cans are transported with the chain.
25. Use of the concentrate or lubricant solution according to claims 24, characterized in that the container such as bottles are made of glass or a plastic material being preferably a polyester such as poly(ethylene terephthalate) or polycarbonate, poly(ethylene naphthenate), polyurethane.
26. Use of the concentrate or lubricant solution according to claims 24, character- ized in that the container such as cans are made of a metal.
27. Use of the concentrate or lubricant solution according to any of the claims 24 to 26, characterized in that the container being preferably bottles and/or cans are empty or filed with preferably food and/or beverage.
28. Use of the concentrate or the lubricant solution according to any of the claims 1 to 20 as antistatic agent.
29. Process of conveying container being preferably bottles and/or cans on a chain being preferably a conveyor chain or a conveyor belt, whereby the concentrate or lubricant solution according to any of the claims 1 to 20 is applied to the chain, preferably on the area of the chain with which the container being preferably bottles and/or cans are transported.
30. The process according to claim 29, characterized in that the concentrate or lubricant solution is not applied continuously to the chain.
31.The process according to claim 30, characterized in that the time in which the concentrate or lubricant solution is applied to the chain is shorter than the time in which no concentrate or lubricant solution is applied to the chain. .
EP03817929.7A 2003-07-24 2003-07-24 Chain lubricants Expired - Lifetime EP1646706B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2003/008125 WO2005014764A1 (en) 2003-07-24 2003-07-24 Chain lubricants

Publications (2)

Publication Number Publication Date
EP1646706A1 true EP1646706A1 (en) 2006-04-19
EP1646706B1 EP1646706B1 (en) 2016-02-03

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EP (1) EP1646706B1 (en)
AU (1) AU2003258535A1 (en)
ES (1) ES2570277T3 (en)
WO (1) WO2005014764A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7745381B2 (en) 2005-03-15 2010-06-29 Ecolab Inc. Lubricant for conveying containers
US7741257B2 (en) 2005-03-15 2010-06-22 Ecolab Inc. Dry lubricant for conveying containers
WO2008062428A2 (en) * 2006-08-06 2008-05-29 Belle Kumar Novel antimicrobial formulations incorporating alkyl esters of fatty acids and nanoemulsions thereof
DE102006038311A1 (en) * 2006-08-15 2008-02-21 Cognis Ip Management Gmbh Lecithin emulsions as conveyor lubricants
US8716200B2 (en) 2006-09-13 2014-05-06 Ecolab Usa Inc. Conveyor lubricants including emulsion of a lipophilic compound and an emulsifier and/or an anionic surfactant and methods employing them
JP5131258B2 (en) * 2009-09-18 2013-01-30 協同油脂株式会社 Metal processing oil, metal processing method and metal processed product
US9359579B2 (en) 2010-09-24 2016-06-07 Ecolab Usa Inc. Conveyor lubricants including emulsions and methods employing them
EP4410935B1 (en) 2013-03-11 2026-01-21 Ecolab USA Inc. Lubrication of transfer plates using oil in water emulsions
FR3004461B1 (en) * 2013-04-11 2015-04-24 Molydal Sa NEW LUBRICATING COMPOSITIONS
FR3027915B1 (en) * 2014-10-29 2018-02-16 Oleon Nv LUBRICATING COMPOSITIONS COMPRISING A DI-ISOTRIDECYL ADIPATE ALTERNATIVE
WO2016131543A1 (en) * 2015-02-19 2016-08-25 Klüber Lubrication München Se & Co. Kg Water-based lubricants for conveyor belts
DE102016001519A1 (en) * 2015-02-19 2016-09-08 Klüber Lubrication München Se & Co. Kg Water-based lubricants for conveyor belts
EP3298114B1 (en) 2015-05-22 2025-07-02 Diversey, Inc. Method and composition for an anion tolerant lubricant
CN115516067A (en) * 2020-06-05 2022-12-23 埃科莱布美国股份有限公司 Mineral oil based dry lubricant for plastic conveyors
WO2022043045A1 (en) 2020-08-28 2022-03-03 Unilever Ip Holdings B.V. Detergent composition

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3213024A (en) * 1962-07-17 1965-10-19 Socony Mobil Oil Co Inc High temperature lubricant
DE19934170A1 (en) * 1999-07-21 2001-01-25 Henkel Kgaa Cooling lubricant used for cutting, drilling, turning, sawing, grinding, honing or lapping contains elemental sulfur
ATE288387T1 (en) * 1999-08-16 2005-02-15 Ecolab Inc METHOD FOR LUBRICATION OF BOXES TRANSPORTED ON A CONVEYOR BELT
US20020115573A1 (en) * 2000-12-15 2002-08-22 Hei Kim Person Lubricants formulated and qualified for contact with food compositions and related business methods
US6576298B2 (en) * 2000-09-07 2003-06-10 Ecolab Inc. Lubricant qualified for contact with a composition suitable for human consumption including a food, a conveyor lubrication method and an apparatus using droplets or a spray of liquid lubricant
EP1197544A1 (en) * 2000-10-10 2002-04-17 Polygon Chemie AG Conveyor or chain lubricant based on esters

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005014764A1 *

Also Published As

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WO2005014764A1 (en) 2005-02-17
ES2570277T3 (en) 2016-05-17
EP1646706B1 (en) 2016-02-03
AU2003258535A1 (en) 2005-02-25

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