EP0988358A1 - Aqueous lubricant composition comprising a monoamine - Google Patents

Aqueous lubricant composition comprising a monoamine

Info

Publication number
EP0988358A1
EP0988358A1 EP97928192A EP97928192A EP0988358A1 EP 0988358 A1 EP0988358 A1 EP 0988358A1 EP 97928192 A EP97928192 A EP 97928192A EP 97928192 A EP97928192 A EP 97928192A EP 0988358 A1 EP0988358 A1 EP 0988358A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
concentrate according
concentrate
deposition
lubricating
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
EP97928192A
Other languages
German (de)
French (fr)
Other versions
EP0988358B1 (en
Inventor
Klaus Dr. Schober
Frank Hermann
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.)
Calvatis GmbH
Original Assignee
LHS UK Ltd
Laporte ESD Ltd
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 LHS UK Ltd, Laporte ESD Ltd filed Critical LHS UK Ltd
Priority to SI9730677T priority Critical patent/SI0988358T1/en
Publication of EP0988358A1 publication Critical patent/EP0988358A1/en
Application granted granted Critical
Publication of EP0988358B1 publication Critical patent/EP0988358B1/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
    • 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
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/28Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/30Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
    • C10M129/32Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 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
    • 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
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/28Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/30Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
    • C10M129/36Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms containing hydroxy groups
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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
    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06Amines, 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
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    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
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    • 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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    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
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    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24Polyethers
    • C10M145/26Polyoxyalkylenes
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02Water
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    • 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
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    • 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
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    • 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
    • C10M2207/124Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
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    • 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
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    • 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
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    • 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
    • C10M2209/108Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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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
    • C10M2215/08Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
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    • C10M2215/08Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • C10M2215/082Amides [having hydrocarbon substituents containing less than thirty carbon atoms] containing hydroxyl groups; Alkoxylated derivatives
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/26Amines
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    • C10M2215/24Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
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    • 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
    • C10N2040/44Super vacuum or supercritical use
    • 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
    • C10N2040/50Medical uses
    • 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
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01Emulsions, colloids, or micelles

Definitions

  • the invention relates to lubricant compositions which derive their lubricating properties from monoamines, especially coco-monoamines, and are suitable, in particular, for lubricating conveyor belts in the food and beverage industry. Specifically, the invention relates to such lubricant compositions free of soap.
  • bottle cleaning, filling and labelling is carried out mainly by automation.
  • high-performance lubricants need to be used on the bottle conveyor facilities to guarantee problem- free conveying of the bottles.
  • the filling performance of filling equipment has increased over the years as a result of technological progress. Requirements regarding the performance of the belt lubricants have increased correspondingly.
  • soap-based lubricants have many times been suggested, and are in general use today.
  • soap-containing lubricants A major disadvantage of soap-containing lubricants is their sensitivity to hard water. Soaps tend to react with water hardness forming salts (mainly Ca 2+ or Mg 2+ salts) , to form the so-called lime soaps which are difficult to dissolve or even insoluble and strongly reduce the lubrication performance of the lubricant. Frequently, this leads to the formation of deposits on the conveyor belts and finally to operating problems.
  • strong complexing agents such as EDTA
  • EDTA are added to soap-containing lubricants or the application needs to be restricted to very soft water (which, however, is not generally available) .
  • EDTA especially is practically not biodegradable.
  • Soap-based lubricant also have other disadvantages, since they can promote the proliferation of germs and other microorganisms .
  • a soap- free lubricant composition which contains no complexing agent.
  • the lubricant composition comprises alkyl polyether carboxylic acid salts combined with acyl sarcosinates .
  • a method for lubricating a conveyor belt which comprises the steps of lubricating the belt with a soap- free lubricant based on neutralized primary fatty amines, and cleaning the belt with cationic cleaning agents or organic acids .
  • the reason for this is that the amines used for lubrication form precipitates with anions, which strongly reduce the lubricating effect and can clogg spray nozzles etc.
  • EP-Bl 0 384 282 (which has been consolidated with EP 0 593 420) discloses the use of secondary and/or tertiary amines and/or salts thereof in lubricating formulations for PET or PC bottles. Generally, the amines are used as such, without the addition of surfactant, complexing agent or cosolvent.
  • WO 94/03562 discloses the use of polyamine derivatives of fatty amines and/or salts thereof. It is claimed that these amines are per se not very sensitive to process water anions such as sulfate, bicarbonate etc.
  • the examples show that the lubricants of WO 94/03562 were only tested at low alkalinity (pH below 8) , and were not tested with respect to their water hardness resistance. As such, the fatty amine salt-based lubricants of this art would not be expected to provide sufficient lubrication combined with the absence of precipitation problems in hard water application.
  • a soap-free lubricant on mainly two components, one of which is an alkyl diamine, optionally neutralized with an organic acid, and the other of which is a polyether carboxylic acid.
  • the lubricants can be used between pH 6.5 and 7.
  • the lubricant solution is made from a corresponding concentrate by adding soft water.
  • Lubricating solutions based on diamines or higher amines can be used without the extra cleaning efforts described in
  • a deposition- preventing component can be a single chemical species or may comprise a plurality of such species. Especially, said component can be a mixture of two, three or more chemical components.
  • deposition-preventing component terms like “deposit-preventing agent”, “anti-deposition compound” and “dispersant” may be used, in the context of this invention. Such somewhat varying terminology reflects the great variability of the inventive lubricant addivites, and all these terms should be regarded as synonyms.
  • this deposition-preventing component is part of the aqueous lubricant concentrate composition, and is present in the concentrate when this is mixed with the process water, in the central dosing unit of the lubricant spray system. It would of course be possible to, instead, add such a deposit-preventing agent separately, in the central dosing unit, or add it to the process water, and such embodiments, while presently considered uneconomical, should be considered as equivalent embodiments of the invention's preferred embodiment that comprises both monoamine compound and the anti-deposit compound in the same concentrate.
  • the definition of the deposit-preventing compound or dispersant as used in this specification is that it either completely prevents the formation of solid precipitate, e. g. by neutralizing the anions before they can react with the monoamine content of the concentrate, or at least prevents the formation of aggregates of solid precipited particles, which aggregates would be large enough to be retained by sieves, or incapable of passing through nozzles.
  • the agent is also capable of preventing the formation of deposits of such solids on sieves, in nozzles, etc. which would block or clogg said sieves, nozzles, etc.
  • the anti-deposit compounds of the invention actually prevent the formation of particles big enough to be visible to the naked eye, although what appears to be clear solutions may in fact be micro-dispersions or micro- suspensions .
  • tensides other than soap
  • Conventional soaps are not to be understood as comprised by the term "tenside” in the context of this specification.
  • the invention prefers anionic, non-ionic or amphoteric tensides, since these do not only suggest themselves for use with glass bottles, metal cans etc., but also for use with PET and PC bottles, which show high sensitiveness to cationic tensides. Of course, where this is no problem, such as in the handling of glass bottles, cationic tensides can also be used.
  • the invention is thus also based on the surprising finding that in the presence of tensides, the harmful deposits are not formed from the reaction of monoamines and anions, while still, a highly efficient and persistent lubricant solution film is formed on the belt or chain.
  • ether carboxylic acids fatty alcohol alkoxylates
  • amphoteric substances such as amphoteric alkyl monoamine or polyamine carboxylates, betaines, sulfobetaines and the like. Details will be discussed hereinafter, and are also the subject matter of various of the attached claims.
  • One important aspect of the invention is that tensides which per se show no anti-deposition effect, and which are uneffective when used alone, provide improved anti- deposition efficiency when combined with each other, to form a multi-compound anti-deposition component.
  • some amphoteric, anionic and nonionic tensides have been tested and found to have, per se, no pertinent dispersing or anti- deposition effect. However, when combined, they exhibit excellent such effects.
  • the best inventive products presently known use dispersing systems comprising at least one amphoteric tenside combined with at least one anionic tenside and at least one nonionic tenside.
  • the relativ content of anionic tenside (s) is often higher than that of nonionic tenside (s)
  • the content of amphoteric tenside is generally the lowest of the three.
  • the concentration of anti-deposition agent or compound in the concentrate is relatively high, generally higher than that of the lubricating amine agent. Often, it is about two times the concentration of the amine. It is preferred that it should not be higher than three times the amine concentration, to avoid negative effects on the lubricating film.
  • polymeric dispersants i.e. relatively low molecular weight polymers derived from vinylic monomers .
  • Such compounds are known as dispersants in e. g. the paper making industry, in sludge treatments etc.
  • dispersants comprise homopolymers and copolymers based on acrylic acid and its derivatives, with molecular weights ranging up to 100.000.
  • deposit-preventing compounds usable according to this invention is formed by organic or even inorganic substances which can react, with the anions in the process water, before the harmful precipitates formed by the reaction of these anions with the monoamines in the concentrate, are deposited.
  • Examples of such deposit- preventing compounds are alkaline or base- forming agents, such as alkanolamines, e.g. triethanolamine, or low molecular weight polyamines, e.g. hexamethylene diamine, capable of forming cations together with an acid component of the formulation.
  • the present most preferred embodiments of the invention use a combination of (at least) one amphoteric , (at least) one anionic and (at least) one nonionic tenside as the deposit- preventing component.
  • amphoteric tenside can be selected from a variety of compounds, especially those corresponding to one of the following general formulae (I) - (III) .
  • amphoteric tensides corresponds to the general formula (I)
  • R x is a linear, branched, saturated or unsaturated alkyl residue with 8 to 22 carbon atoms, or a corresponding alkoxy residue
  • R 2 is H, Na, K or N(R 3 ) 3 with R 3 » alkyl or hydroxyalkyl
  • R 4 is H, alkyl, hydroxyalkyl, R 5 -COO-R 2 or
  • a preferred dispersant comprises an alkyl monoamine carboxylate corresponding to the general formula (I) , wherein R x is cocoalkyl, R 4 is H, R 5 is ethylene, R 2 is H and n is 1.
  • alkyl monoamine carboxylates can be obtained under the tradename "Amphora CP1" from CECA Atochem S.A., France.
  • amphoteric tenside is an alkyl polyamine carboxylic acid corresponding to the general formula (I) , wherein R is cocoalkyl, R 2 and R 4 are H, R 5 is ethylene and n is 3.
  • This product can be obtained under the tradename "Triamphoram CP1", also from CECA Atochem S.A.
  • An alternatively preferred class of amphoteric tensides comprises betaines of the general formula (II) ,
  • R 6 is R x or R- t -CONH- (CH 2 ) n , R x and n having the same meaning as in formula (I) , and R 7 and R 8 are equal or different alkyl or hydroxyalkyl substituents .
  • R 6 is cocoalkyl and R 7 and R 8 are hydroxyethyl, or R 6 is cocoamidopropyl and R 7 and R 8 are methyl.
  • Such dispersants can be obtained under the tradenames "Tegotain N192” from Goldschmidt, Germany, “Amphotensid B4" from Zschimmer und S ⁇ hwarz, also Germany, and “Amphoteen 24" from Akzo Nobel. - 13 -
  • amphoteric tenside can advantageously comprise a sulfobetaine corresponding to the general formula (III)
  • R 6 , R 7 and R 8 have the same meaning as in formula (II), and R 9 is linear or branched alkyl or hydroxyalkyl.
  • R 6 is lauryl
  • R 7 and R 8 are methyl and R 9 is 2- hydroxypropyl
  • R 6 is cocoamidopropyl
  • R 7 and R 8 are methyl and R 9 is 2 -hydroxypropyl .
  • Such sulfobetaines can be obtained from Witco/Rewo Chemische Werke GmbH, Germany, under the tradename “Rewoteric AM HC” , and from Rhone Poulenc, France, under the “Mirataine CBS” tradename.
  • the anionic tenside of the presently most preferred embodiment of the invention can broadly be selected from the class of anionic polyether compounds.
  • Suitable such polyether compounds comprise alkyl polyether carbonic acids, alkyl polyether sulfates and sulfosuccinates, and alkyl polyether phosphates.
  • the polyether compound can have a comparable alkylamido group.
  • the most preferred anionic tensides are presently selected from alkyl polyether carbonic acids and alkyl polyether sulfates . It is specifically preferred that the dispersant comprises an alkyl polyether compound corresponding to the general formula (IV)
  • R x and R 2 have the same meaning as in formula (I) , R 10 and R 1X are alkyl residues, and p is an integer from 1 to 20.
  • R x is oleyl
  • R 10 is ethylene
  • R X1 is methylene
  • p is 5 to 9
  • R 2 is H.
  • the dispersant may comprise a compound of the general formula (V)
  • R x and R 2 have the same meaning as in formula (I) , and n and m are integers from 1 to 10. More specifically preferred, R x is a natural, a Ziegler synthetic, or an oxosynthetic alkyl, n is 2 , m is 1, 2 or 3 and R 2 is sodium.
  • Such compounds can be obtained from Manro Products Ltd.,
  • Suitable alkylpolyether phosphates comprise “Marlopor FC” from Huls, Germany.
  • a very advantageous product is "Tensuccin HM 935" from ICI, an alkylpolyethoxysulfosuccinate-disodium salt .
  • Suitable alkylamido polyether sul osuccinates comprise "Lankropol KS6" from Akcros .
  • the third element in the presently most preferred embodiments is a nonionic tenside.
  • This can for example be a nonionic fatty alcohol alkoxylate, an alkylpolyglucoside or an alkylpolyether carbonic acid monoalkylolamide .
  • Preferred alkyl polyalkoxylates comprise "Synperonic LF/RA 30" from ICI, England, and “Plurafac LF 431" from BASF, Germany.
  • Plurafac is a (-OCH 3 ) -terminated fatty alcohol alkoxylate.
  • Preferred alkyl polyglucosides can be obtained from Henkel, Germany, under the "Glucopon” tradename, especially as “Glucopon 600 CSUP” .
  • Preferred alkylpolyethercarboxy-monoalkylolamides comprise KAO's product "Aminol A 15".
  • the best inventive combination (as far as dispersing performance is concerned) comprises an amphoteric tenside like "Triamphoran CP1" , an alkyl polyether carboxylic acid anionic tenside like "Alypo RO 50", and either an alkyl polyalkoxylate such as “Plurafac LF 431” or an alkyl polyether carboxylic acid monoethanolamide, such as "Aminol A 15".
  • Nonionic aklyl polyalkoxylate such as "Plurafac LF 431” can exhibit an anti-deposition effect which lasts for more than one week, even without any loss of clarity.
  • Combinations of an amhoteric with an anionic, but without a nonionic tenside may be successful, and so may combinations of an amphoteric with a nonionic, but without an anionic tenside.
  • the relative amounts of monoamine lubricating agent (or agents) and deposit-preventing compound (or compounds) will be selected, so that the amount of dispersant is high enough to prevent deposit formation, but not so high that the lubricating film- forming properties of the diluted lubricating solution suffer.
  • different dipersants may have to be combined to experimentally determine the best selection.
  • the formulations may additionally contain solubilisers in the form of mono- or polyhydric alcohols (usually lower aliphatic alcohols or glycols) or polyalkyleneglycols .
  • the formulation will generally further contain a disinfectant, such as 4, 4-Dimethyl oxazolidine.
  • a disinfectant such as 4, 4-Dimethyl oxazolidine.
  • the pH of the concentrate is below neutrality.
  • a suitable excess amount of acid usually formic, acetic or lactic acid, is added.
  • the individual components can generally be used in acid or salt form.
  • demineralised water is introduced into a mixing vessel equipped with a stirrer. Subsequently, the components in the acid or the salt form are added. Generally, this takes the form of addition of a preformed concentrate comprising all components. However, it is of course possible to prepare an aqueous lubricant composition of this invention by adding the individual components to the water one by one .
  • Fig. 1 represents a diagramatic representation of a bottle conveyor facility on which the reported experiments were carried out
  • Fig. 2 shows a graphic representation of the sliding friction coefficients achieved with different lubricants and lubricant compositions .
  • Concentrates were made up from 3% coco-monoamine; 3,5% formic acid; various deposition-preventing compounds at varying overall amounts, and as defined in the TABLE, plus completely demineralized water (to 100%) . Percentages here and in the TABLE are based on total concentrate composition.
  • the TABLE shows, for each example, the anti-deposition (or deposition-preventing) effect in terms of the turbidity (and, in case, precipitation) observed, when a 0.3% solution of the concentrate in Ladenburg town water was left standing. Turbidity was determined by inspection (non- apparative) .
  • the symbols in the corresponding column in the TABLE have the following meanings :
  • compositions with at least four "+” would be regarded as commercially fully usable. Compositions with inferior test results may, however, also be suitable under corresponding conditions (e.g. where softer water is easily available) .
  • a lubricant composition according to the invention was made up (similar to Example 8 above) as follows:
  • A is "Armeen CD” from Akzo; B is “Triamphoram CPl” from CECA Atochem S.A.; C is “Akypo RO 50” from KAO Corp., Japan; D is “Plurafac LF 431” from BASF AG, Germany.)
  • Fig. 2 shows the sliding friction coefficients of various application solutions (at 90 ppm amine) of mono-, di- and triamines, and of the inventive solution (similar to Example 8) .
  • the sliding friction coefficient represents a measure of the performance of the lubricant and is calculated using the formula
  • coco-monoamine formulated without the inventive dispersant is unusable in practise, due to the above- discussed precipitation problems.
  • the inventive product similar to Example 8 is decidedly superior as compared to the di- and triamines, which presently form the industrial standard.
  • An improvement of the order of 0.2 units in the sliding friction coefficiency in practise means a very relevant improvement.
  • the inventive monoamine-based products produce practically no foam in application. This is a major benefit, since the known and presently used di- and triamine-based products generate huge volumes of foam. These foams are very stable, and have to be removed by rinsing. This causes increased effort and expenditure, and also puts increased strain on the plant and municipal waste water systems.

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Abstract

The invention is directed to an aqueous lubricant concentrate composition which is usable for the preparation of an aqueous lubricating solution for lubricating conveyor belts and conveyor chains in the food and beverage industry. The composition comprises at least one monoamine compound as the main lubricating agent; an effective amount of a deposition-preventing component capable of preventing the deposition of solids from the lubricating solution under lubricating application conditions at least to such an extent that said lubricating application is not impaired by such depositions, without impairing the lubricating film-forming properties of the aqueous lubricating solution, and optionally further comprises a disinfectant, and other customary additives.

Description

AQUEOUS LUBRICANT COMPOSITION COMPRISING A MONOAMINE
The invention relates to lubricant compositions which derive their lubricating properties from monoamines, especially coco-monoamines, and are suitable, in particular, for lubricating conveyor belts in the food and beverage industry. Specifically, the invention relates to such lubricant compositions free of soap.
In the food and beverage industry, e. g. in breweries or bottling operations at mineral water sources, bottle cleaning, filling and labelling is carried out mainly by automation. As a rule, high-performance lubricants need to be used on the bottle conveyor facilities to guarantee problem- free conveying of the bottles. The filling performance of filling equipment has increased over the years as a result of technological progress. Requirements regarding the performance of the belt lubricants have increased correspondingly. In parallel, greater environmental awareness of the users has resulted in a demand for more environmentally and userfriendly chemicals particularly when these are sprayed openly in premises, as is the case with belt lubricants, and where the lubricant liquid dripping off the belt may pass directly into the effluent (waste water) from the plant.
In the art, soap-based lubricants have many times been suggested, and are in general use today.
A major disadvantage of soap-containing lubricants is their sensitivity to hard water. Soaps tend to react with water hardness forming salts (mainly Ca2+ or Mg2+ salts) , to form the so-called lime soaps which are difficult to dissolve or even insoluble and strongly reduce the lubrication performance of the lubricant. Frequently, this leads to the formation of deposits on the conveyor belts and finally to operating problems. To avoid this precipitation of lime soap, strong complexing agents (such as EDTA) are added to soap-containing lubricants or the application needs to be restricted to very soft water (which, however, is not generally available) . For ecological reasons, the use of strong complexing agents in lubricants which pass into the waste water discharged from the plant is undesirable, since these complexing agents have poor biological degradability. EDTA especially is practically not biodegradable.
Soap-based lubricant also have other disadvantages, since they can promote the proliferation of germs and other microorganisms .
There have been attempts in the art at solving these problems, through alternative lubricants which comprise no soap. Generally, these alternative lubricants attempt to replace soap with specific amino compounds.
In EP-Bl 0 044 458, a soap- free lubricant composition is disclosed which contains no complexing agent. The lubricant composition comprises alkyl polyether carboxylic acid salts combined with acyl sarcosinates .
From EP-Bl 0 260 508, a method for lubricating a conveyor belt is known, which comprises the steps of lubricating the belt with a soap- free lubricant based on neutralized primary fatty amines, and cleaning the belt with cationic cleaning agents or organic acids . The reason for this is that the amines used for lubrication form precipitates with anions, which strongly reduce the lubricating effect and can clogg spray nozzles etc.
From EP-Bl 0 372 628 and EP-A1 0 538 916 another substitute for soap-based lubricants is known, which is based on di- or polyalkyl amines or corresponding di- or polyalkyl aminoalkyl carboxylic acids. The aqueous lubricating solutions made from these compounds are used at pH-values between 5 and 8.
EP-Bl 0 384 282 (which has been consolidated with EP 0 593 420) discloses the use of secondary and/or tertiary amines and/or salts thereof in lubricating formulations for PET or PC bottles. Generally, the amines are used as such, without the addition of surfactant, complexing agent or cosolvent.
WO 94/03562 discloses the use of polyamine derivatives of fatty amines and/or salts thereof. It is claimed that these amines are per se not very sensitive to process water anions such as sulfate, bicarbonate etc. The examples show that the lubricants of WO 94/03562 were only tested at low alkalinity (pH below 8) , and were not tested with respect to their water hardness resistance. As such, the fatty amine salt-based lubricants of this art would not be expected to provide sufficient lubrication combined with the absence of precipitation problems in hard water application.
In DE-C2 42 44 536, it is suggested to base a soap-free lubricant on mainly two components, one of which is an alkyl diamine, optionally neutralized with an organic acid, and the other of which is a polyether carboxylic acid. The lubricants can be used between pH 6.5 and 7. The lubricant solution is made from a corresponding concentrate by adding soft water.
In DE-A1 43 15 21 (and corresponding EP 0 623 666) of the present applicant, it has been suggested to prepare soap- free lubricants on the basis of polyamines, which can optionally be combined with organic acids, to adjust the pH of the concentrate to between 4 and 8. The fatty monoamines suggested in EP 0 260 508 provide a better lubricating effect, at comparable concentrations, than the di-, tri- and polyamines later suggested in the art, as above discussed. The di- and higher amines of the younger art are more expensive than the monoamines of EP 0 260 508, since they are made from these monoamines. The di- and higher amines of the younger art avoid some of the precipitation problems, in the presence of carbonate, sulfate and especially phosphate anions, which EP 0 260 508 suggests to deal with by an extra cleaning step.
Lubricating solutions based on diamines or higher amines can be used without the extra cleaning efforts described in
EP 0 260 508. However, diamines and especially higher amines create increased foaming problems, as compared with monoamines. One therefore generally has to use defoaming agents in such products, but even then, such products produce large amounts of foam in practical application.
An important parameter in determining the quality of any such lubricant is the sliding friction coefficient provided by the diluted lubricating solution as actually used. Generally, a sliding friction coefficient between 0.10 and 0.14, at customary amine concentrations of the order of 100 ppm in the actual use solution, is achievable with state of the art diamine and higher amine based lubricants. A value of 0.10 would be considered very good; a value higher than 0.14 would be considered unacceptable.
It would be much easier to reach sliding friction coefficients at around 0.10 or even smaller, with monoamines as suggested in EP 0 260 508, but at the necessary concentrations in the actual use solution, reaction between monoamines and anions such as carbonate, sulfate and phosphate is so massive and fast, already in the central dosing unit, that sieves and nozzles of the spray applicator system are clogged within very short.
Apparently, the steps suggested in EP 0 260 508, which require a lot of extra effort, especially in switching the spray system from lubricant to cleaning composition and back, have prevented the industry from adopting this approach. Rather, the trend over the last decade has been in developing new lubricants based on other amines, i. e. di-, tri- and higher amines, to deal with the precipitation problem.
Against this background, it is an important object of this invention to provide an aqueous lubricating solution (and a concentrate for making this solution) , which makes it possible to achieve sliding friction coefficients of 0.10 and less, as low as 0.08 and even down to about 0.06.
It is another important object of this invention to provide an aqueous lubricating solution (and a concentrate for preparing it) , which uses monoamines as the lubricating agent without being sensitive to problems caused by deposits in the presence of anions such as carbonate, sulfate and phosphate.
It is a further important object of this invention to provide an excellent aqueous lubricating composition (and a concentrate for preparing it) at reduced cost, and especially without any need for extra cleaning steps or the use of acidic or complexing cleaning solutions .
Further objects and advantages of the invention will be notable from the following discussion and description of preferred embodiments. The invention focusses, like EP 0 260 508, on the use of neutralized primary fatty amines, which have excellent lubricating properties. It thus turns away from the accepted wisdom in the art, that the use of monoamines is best avoided, and di- and higher amines should instead be used.
Instead of permitting a certain build-up of solid precipitate deposits in the apparatus, then remove the lubricant solution from the system, add a cleaning solution to the system, dissolve the deposits and then again replace the cleaning solution by the lubricating solution, as in EP 0 260 508, the invention teaches to already prevent the formation of such deposits, and thus removes the need for dealing with them after they have started to build up in the apparatus .
To achieve this, the invention teaches to add a deposition- preventing component to the monoamine-containing lubricant. In the context of this specification, a deposition- preventing component can be a single chemical species or may comprise a plurality of such species. Especially, said component can be a mixture of two, three or more chemical components. Instead of "deposition-preventing component", terms like "deposit-preventing agent", "anti-deposition compound" and "dispersant" may be used, in the context of this invention. Such somewhat varying terminology reflects the great variability of the inventive lubricant addivites, and all these terms should be regarded as synonyms. As suggested and claimed here, this deposition-preventing component is part of the aqueous lubricant concentrate composition, and is present in the concentrate when this is mixed with the process water, in the central dosing unit of the lubricant spray system. It would of course be possible to, instead, add such a deposit-preventing agent separately, in the central dosing unit, or add it to the process water, and such embodiments, while presently considered uneconomical, should be considered as equivalent embodiments of the invention's preferred embodiment that comprises both monoamine compound and the anti-deposit compound in the same concentrate.
In any case, the definition of the deposit-preventing compound or dispersant as used in this specification is that it either completely prevents the formation of solid precipitate, e. g. by neutralizing the anions before they can react with the monoamine content of the concentrate, or at least prevents the formation of aggregates of solid precipited particles, which aggregates would be large enough to be retained by sieves, or incapable of passing through nozzles. The agent is also capable of preventing the formation of deposits of such solids on sieves, in nozzles, etc. which would block or clogg said sieves, nozzles, etc.
The exact mechanism by which the invention achieves its objects is not yet completely clarified, and it is possible that several somewhat different mechanisms are involved, likely depending at least partly on the choice of deposit- preventing agent. It is thus possible that with some agents of the invention, no solid precipitate particles are ever formed, whereas in other cases, very small microparticles are formed which, however, are prevented from aggregating or agglomerating and/or from settling on sieves, in nozzles, etc., to form clogging deposits. In the most preferred embodiments it is however notable that the aqueous lubricating solutions, as made up ready for use, remain completely clear to the naked eye, i. e. do not at all get cloudy, at least over the usual residence times of the aqueous solution in the apparatus and actually much longer, often for weeks.
It is therefore presently surmised, although the applicant does not want to be bound to any specific scientific theory, that the anti-deposit compounds of the invention actually prevent the formation of particles big enough to be visible to the naked eye, although what appears to be clear solutions may in fact be micro-dispersions or micro- suspensions .
One important class of deposit-preventing compounds as according to the present invention comprises tensides (other than soap), also known as surface active agents. Conventional soaps are not to be understood as comprised by the term "tenside" in the context of this specification. Generally, the invention prefers anionic, non-ionic or amphoteric tensides, since these do not only suggest themselves for use with glass bottles, metal cans etc., but also for use with PET and PC bottles, which show high sensitiveness to cationic tensides. Of course, where this is no problem, such as in the handling of glass bottles, cationic tensides can also be used.
One reason why the use of such tensides, combined with monoamines, to prevent the deposit of solid precipitates in the presence of anions, has not before been suggested, is probably that tensides generally counteract the formation of the necessary lubricating film on the conveyor belt or conveyor chain. To achieve the necessary lubrication, a sufficiently thick and effective film of aqueous lubricating solution must be formed on the surface of the belt or chain. Tensides, especially in high concentration, can weaken or even destroy this film, and thus reduce the lubricating effect of the amine.
The invention is thus also based on the surprising finding that in the presence of tensides, the harmful deposits are not formed from the reaction of monoamines and anions, while still, a highly efficient and persistent lubricant solution film is formed on the belt or chain.
Among the tensides which have been found to provide the desired effect, are ether carboxylic acids, fatty alcohol alkoxylates, and a variety of amphoteric substances such as amphoteric alkyl monoamine or polyamine carboxylates, betaines, sulfobetaines and the like. Details will be discussed hereinafter, and are also the subject matter of various of the attached claims.
One important aspect of the invention is that tensides which per se show no anti-deposition effect, and which are uneffective when used alone, provide improved anti- deposition efficiency when combined with each other, to form a multi-compound anti-deposition component. Thus, some amphoteric, anionic and nonionic tensides have been tested and found to have, per se, no pertinent dispersing or anti- deposition effect. However, when combined, they exhibit excellent such effects.
The best inventive products presently known use dispersing systems comprising at least one amphoteric tenside combined with at least one anionic tenside and at least one nonionic tenside. In these, the relativ content of anionic tenside (s) is often higher than that of nonionic tenside (s) , and the content of amphoteric tenside is generally the lowest of the three. The concentration of anti-deposition agent or compound in the concentrate is relatively high, generally higher than that of the lubricating amine agent. Often, it is about two times the concentration of the amine. It is preferred that it should not be higher than three times the amine concentration, to avoid negative effects on the lubricating film. Another consideration is that the addition of tenside generally reduces the lubricating effect of the amine. Monoamines, especially coco-monoamine, provide even much lower friction coefficients (down to 0.03) in the absence of tensides. However, the concentration will be selected, in practise, to optimize the anti-deposition effect and this will be generally feasible without approaching harmful tenside concentrations.
Generally, it is also possible to achieve the invention's effect by the use of deposit-preventing compounds which are not tensides.
It is thus possible to use polymeric dispersants, i.e. relatively low molecular weight polymers derived from vinylic monomers . Such compounds are known as dispersants in e. g. the paper making industry, in sludge treatments etc. Generally, such dispersants comprise homopolymers and copolymers based on acrylic acid and its derivatives, with molecular weights ranging up to 100.000.
Another class of deposit-preventing compounds usable according to this invention is formed by organic or even inorganic substances which can react, with the anions in the process water, before the harmful precipitates formed by the reaction of these anions with the monoamines in the concentrate, are deposited. Examples of such deposit- preventing compounds are alkaline or base- forming agents, such as alkanolamines, e.g. triethanolamine, or low molecular weight polyamines, e.g. hexamethylene diamine, capable of forming cations together with an acid component of the formulation.
The presently preferred embodiments use tensides (except soap) as the deposit-preventing compound. Such preferred embodiments will now be described in more detail.
The present most preferred embodiments of the invention use a combination of (at least) one amphoteric , (at least) one anionic and (at least) one nonionic tenside as the deposit- preventing component.
Herein, the amphoteric tenside can be selected from a variety of compounds, especially those corresponding to one of the following general formulae (I) - (III) .
One preferred class of amphoteric tensides corresponds to the general formula (I)
wherein Rx is a linear, branched, saturated or unsaturated alkyl residue with 8 to 22 carbon atoms, or a corresponding alkoxy residue; R2 is H, Na, K or N(R3)3 with R3 » alkyl or hydroxyalkyl; R4 is H, alkyl, hydroxyalkyl, R5-COO-R2 or
[(CH2)mN]x-R5-COO-R2
R5-COO-R2,
wherein R5 is alkyl or hydroxyalkyl, n and m are integers from 1 to 10 and x is an integer from 1 to 50. More specifically, a preferred dispersant comprises an alkyl monoamine carboxylate corresponding to the general formula (I) , wherein Rx is cocoalkyl, R4 is H, R5 is ethylene, R2 is H and n is 1.
Such alkyl monoamine carboxylates can be obtained under the tradename "Amphora CP1" from CECA Atochem S.A., France.
The presently most preferred amphoteric tenside is an alkyl polyamine carboxylic acid corresponding to the general formula (I) , wherein R is cocoalkyl, R2 and R4 are H, R5 is ethylene and n is 3. This product can be obtained under the tradename "Triamphoram CP1", also from CECA Atochem S.A.
An alternatively preferred class of amphoteric tensides comprises betaines of the general formula (II) ,
wherein R6 is Rx or R-t-CONH- (CH2) n, Rx and n having the same meaning as in formula (I) , and R7 and R8 are equal or different alkyl or hydroxyalkyl substituents . Of these betaines, some compounds have been found to be specifically advantageous. In these, R6 is cocoalkyl and R7 and R8 are hydroxyethyl, or R6 is cocoamidopropyl and R7 and R8 are methyl.
Such dispersants can be obtained under the tradenames "Tegotain N192" from Goldschmidt, Germany, "Amphotensid B4" from Zschimmer und Sσhwarz, also Germany, and "Amphoteen 24" from Akzo Nobel. - 13 -
Also alternatively, the amphoteric tenside can advantageously comprise a sulfobetaine corresponding to the general formula (III)
R7
I
R6-N+-R9-S03- (III)
wherein R6, R7 and R8 have the same meaning as in formula (II), and R9 is linear or branched alkyl or hydroxyalkyl. Preferably, R6 is lauryl, R7 and R8 are methyl and R9 is 2- hydroxypropyl, or R6 is cocoamidopropyl, R7 and R8 are methyl and R9 is 2 -hydroxypropyl .
Such sulfobetaines (or sultaines) can be obtained from Witco/Rewo Chemische Werke GmbH, Germany, under the tradename "Rewoteric AM HC" , and from Rhone Poulenc, France, under the "Mirataine CBS" tradename.
The anionic tenside of the presently most preferred embodiment of the invention can broadly be selected from the class of anionic polyether compounds. Suitable such polyether compounds comprise alkyl polyether carbonic acids, alkyl polyether sulfates and sulfosuccinates, and alkyl polyether phosphates. Instead of an alkyl group, the polyether compound can have a comparable alkylamido group.
The most preferred anionic tensides are presently selected from alkyl polyether carbonic acids and alkyl polyether sulfates . It is specifically preferred that the dispersant comprises an alkyl polyether compound corresponding to the general formula (IV)
R ι" tO-R10] p-0- (Rxl) -COO-R- (IV)
wherein Rx and R2 have the same meaning as in formula (I) , R10 and R1X are alkyl residues, and p is an integer from 1 to 20.
Especially, Rx is oleyl, R10 is ethylene and RX1 is methylene, p is 5 to 9 and R2 is H.
Such dispersants can be obtained from KAO, Japan under the tradenames "Akypo RO 50" (m=5) , "Akypo RO 90" (m=9) , and "Akypo RLM 100".
As an alternative anionic tenside, the dispersant may comprise a compound of the general formula (V)
R1-tO-(CH2)n]m-OS03-R2 (V)
wherein Rx and R2 have the same meaning as in formula (I) , and n and m are integers from 1 to 10. More specifically preferred, Rx is a natural, a Ziegler synthetic, or an oxosynthetic alkyl, n is 2 , m is 1, 2 or 3 and R2 is sodium.
Such compounds can be obtained from Manro Products Ltd.,
England, under the "Manro BES" tradename. A preferred product is "Tensagex DLM 970", obtainable from Hickson, England. Suitable alkylpolyether phosphates comprise "Marlopor FC" from Huls, Germany.
In another preferred class of anionic tenside, i.e. the alkyl polyether sulfosuccinates, a very advantageous product is "Tensuccin HM 935" from ICI, an alkylpolyethoxysulfosuccinate-disodium salt .
Suitable alkylamido polyether sul osuccinates comprise "Lankropol KS6" from Akcros .
The third element in the presently most preferred embodiments is a nonionic tenside. This can for example be a nonionic fatty alcohol alkoxylate, an alkylpolyglucoside or an alkylpolyether carbonic acid monoalkylolamide .
Preferred alkyl polyalkoxylates comprise "Synperonic LF/RA 30" from ICI, England, and "Plurafac LF 431" from BASF, Germany. Plurafac is a (-OCH3) -terminated fatty alcohol alkoxylate.
Preferred alkyl polyglucosides can be obtained from Henkel, Germany, under the "Glucopon" tradename, especially as "Glucopon 600 CSUP" .
Preferred alkylpolyethercarboxy-monoalkylolamides comprise KAO's product "Aminol A 15".
"Synperonic LF/RA 30" and "Pluarfac LF 431" are presently most preferred.
Presently, the best inventive combination (as far as dispersing performance is concerned) comprises an amphoteric tenside like "Triamphoran CP1" , an alkyl polyether carboxylic acid anionic tenside like "Alypo RO 50", and either an alkyl polyalkoxylate such as "Plurafac LF 431" or an alkyl polyether carboxylic acid monoethanolamide, such as "Aminol A 15". In these, there is generally a smaller amount (based on overall concentrate, with about 3% coco-monoamine and about 3,5%. formic acid) of about 1% amphoteric tenside, combined with about 3% anionic and about 2% nonionic tenside.
It is not alway necessary to have all three (above- discussed) types of tenside combined in the anti-deposit or dispersant component.
Combinations of anionic and nonionic tensides can be very successful. Thus, a combination of an (anionic) alkyl polyether carboxylic, such as "Akypo RO 50" and a
(nonionic) aklyl polyalkoxylate, such as "Plurafac LF 431" can exhibit an anti-deposition effect which lasts for more than one week, even without any loss of clarity.
Combinations of an amhoteric with an anionic, but without a nonionic tenside, may be successful, and so may combinations of an amphoteric with a nonionic, but without an anionic tenside.
Some of these may even be more successful than a combination of all three types, as the experiments reported hereinafter show. There appear to be strong influences both of the specific combination selected and the respective rations of individual tensides in the combination. It is presently not yet possible to give a general rule for the influence of all structural and quantitative parameters, on the dispersing effectiveness.
Generally, the relative amounts of monoamine lubricating agent (or agents) and deposit-preventing compound (or compounds) will be selected, so that the amount of dispersant is high enough to prevent deposit formation, but not so high that the lubricating film- forming properties of the diluted lubricating solution suffer. To achieve this, different dipersants may have to be combined to experimentally determine the best selection.
To advantageously influence the storage stability and flow properties of the lubricant concentrates, the formulations may additionally contain solubilisers in the form of mono- or polyhydric alcohols (usually lower aliphatic alcohols or glycols) or polyalkyleneglycols .
The formulation will generally further contain a disinfectant, such as 4, 4-Dimethyl oxazolidine.
As a rule, the pH of the concentrate is below neutrality. To achieve this, a suitable excess amount of acid, usually formic, acetic or lactic acid, is added.
For the preparation of the lubricant concentrates according to the invention, the individual components can generally be used in acid or salt form.
The appropriate amount of demineralised water is introduced into a mixing vessel equipped with a stirrer. Subsequently, the components in the acid or the salt form are added. Generally, this takes the form of addition of a preformed concentrate comprising all components. However, it is of course possible to prepare an aqueous lubricant composition of this invention by adding the individual components to the water one by one .
The superior properties of the lubricant composition according to the invention will now be shown in further detail by way of the following examples, in association with the attached drawing. In the drawing
Fig. 1 represents a diagramatic representation of a bottle conveyor facility on which the reported experiments were carried out
Fig. 2 shows a graphic representation of the sliding friction coefficients achieved with different lubricants and lubricant compositions .
For the turbidity tests reported below, Ladenburg town water (25° total German water hardness, 15° carbonate hardness, 10° non-carbonate hardness) was used.
Examples 1 - 19
Concentrates were made up from 3% coco-monoamine; 3,5% formic acid; various deposition-preventing compounds at varying overall amounts, and as defined in the TABLE, plus completely demineralized water (to 100%) . Percentages here and in the TABLE are based on total concentrate composition.
TABLE
10
12 1% Triamphoram CP 1 7,7% Tensuccin HM 2% Plurafac LF 431 ++++ 935
13 1% Triamphoram CP 1 4,3% Tensagex DLM 2% Plurafac LF 431 +++ 970
14 1% Triamphoram CP 1 3% Akypo RLM 100 2% Plurafac LF 431 ++
15 1% Amphoram CP 1 3% Akypo RO 50 2% Plurafac LF 431 +
16 2% Amphoteen 24 3% Akypo RO 50 2% Plurafac LF 431 ++
17 2% Amphotensid B4 3% Akypo RO 50 2% Plurafac LF 431 +
18 1,3% Rewoteric AM 3% Akypo RO 50 2% Plurafac Lf 431 + HC
19 2,6% Triamphoram CP 3% Akypo RO 50 1% Plurafac LF 431 ++++
1
10
The TABLE shows, for each example, the anti-deposition (or deposition-preventing) effect in terms of the turbidity (and, in case, precipitation) observed, when a 0.3% solution of the concentrate in Ladenburg town water was left standing. Turbidity was determined by inspection (non- apparative) . The symbols in the corresponding column in the TABLE have the following meanings :
- turbidity visible immediately; precipitates forming after 1 hour + strong precipitation, after 24 hours ++ strong precipitation, after 48 hours +++ some precipication after 96 hours ++++ no turbidity visible for 7 days, later some turbidity and little precipitation +++++ no or very little turbidity after more than 14 days
Compositions with at least four "+" would be regarded as commercially fully usable. Compositions with inferior test results may, however, also be suitable under corresponding conditions (e.g. where softer water is easily available) .
To determine the lubricating performance of lubricants according to the invention and their individual components, an in-house bottle conveyor facility was used, as is illustrated diagramatically in Fig. 1. The belt speed and the spray volume per unit of time were kept constant during the measurements. The lubricant solutions were prepared from said local (Ladenburg) town water (25° German hardness). A 0.3% aqueous solution (by weight) of the lubricant concentrate was used for the comparative measurements . from said local (Ladenburg) town water (25° German hardness). A 0.3% aqueous solution (by weight) of the lubricant concentrate was used for the comparative measurements .
A lubricant composition according to the invention was made up (similar to Example 8 above) as follows:
Component
A 3% Coco-monoamine
B 1% Coco- (NH-CH2-CH2-CH2)3-COOH
C 3% Oleyl- (0-CH2-CH2)5-0-CH2-COOH
D 2% alkoxylated fatty alcohol, ether capped E 3% formic acid, 85% in water
F 88% water, demineralized.
(pH < 7)
(A is "Armeen CD" from Akzo; B is "Triamphoram CPl" from CECA Atochem S.A.; C is "Akypo RO 50" from KAO Corp., Japan; D is "Plurafac LF 431" from BASF AG, Germany.)
For comparison of lubricating efficiency, several mono-, di- and triamines were formulated without the inventive dispersant, as follows:
3% amine
3% acetic acid, 60% in water 84% water, demineralized
Fig. 2 shows the sliding friction coefficients of various application solutions (at 90 ppm amine) of mono-, di- and triamines, and of the inventive solution (similar to Example 8) . The sliding friction coefficient represents a measure of the performance of the lubricant and is calculated using the formula
K=F/G
K sliding friction coefficient
F force measured on the measuring facility of the bottle conveying plant (Fig. 1) G weight of the bottles used in the test.
The lower the sliding friction coefficient, the greater the lubricating effect. Fig. 2 clearly shows that coco- monoamine provides the lowest sliding friction coefficient (K = 0.03, glass) .
However, coco-monoamine formulated without the inventive dispersant is unusable in practise, due to the above- discussed precipitation problems. With sliding friction coefficiency at K = 0.075 (glass) and 0.102 (PET), the inventive product similar to Example 8 is decidedly superior as compared to the di- and triamines, which presently form the industrial standard. An improvement of the order of 0.2 units in the sliding friction coefficiency in practise means a very relevant improvement.
The inventive monoamine-based products produce practically no foam in application. This is a major benefit, since the known and presently used di- and triamine-based products generate huge volumes of foam. These foams are very stable, and have to be removed by rinsing. This causes increased effort and expenditure, and also puts increased strain on the plant and municipal waste water systems.

Claims

C L A I S
1. An aqueous lubricant concentrate composition, usable for the preparation of an aqueous lubricating solution for lubricating conveyor belts and conveyor chains in the food and beverage industry, comprising at least one monoamine compound as the main lubricating agent; further comprising an effective amount of a deposition- preventing component capable of preventing the deposition of solids from the lubricating solution under lubricating application conditions at least to such an extent that said lubricating application is not impaired by such depositions, without impairing the lubricating film- forming properties of the aqueous lubricating solution, and optionally comprising a disinfectant, and other customary additives.
2. The concentrate according to claim 1, wherein the monoamine compound comprises at least one, preferably primary, fatty amine, such as a C8-C22 fatty amine, and especially a C12-C18 fatty amine.
3. The concentrate according to claim 2, wherein the fatty amine comprises, and preferably substantially consists of, coco-monoamine compounds.
4. The concentrate according to any one of claims 1 to 3, further comprising an acid, especially a lower alkyl carboxylic acids such as formic acid, acetic acid and lactic acid, in an amount at least sufficient to neutralize the amine content of the concentrate.
5. The concentrate according to claim 4, having a pH-value between 3 and 8, preferably between 4 and 7. - -.5 -
6. The concentrate according to any one of claims 1 to 5, comprising at least one tenside or surface-active agent (except soap) as the deposition-preventing component.
7. The concentrate according to claim 6, said component comprising at least two tensides selected from anionic, amphoteric and non-ionic tensides, at least one of said tensides being anionic and at least one of said tensides being amphoteric or nonionic.
8. The concentrate according to claim 6 or 7, said component comprising one (or more) amphoteric tenside (s) , one (or more) anionic tenside (s) and one (or more) nonionic tenside (s).
9. The concentrate of claim 6, said component comprising a cationic tenside.
10. The concentrate according to claim 7 or 8, wherein the concentrate comprises at least one of an amphoteric alkyl monoamine or polyamine carboxylic acid or carboxylate, or a betaine, especially an alkyl or alkylamido betaine or sulfobetaine.
11. The concentrate according to claim 7 or 8, wherein the concentrate comprises at least one of a nonionic fatty alcohol alkoxylate, a fatty amine alkoxylate, an alkyl polyglucoside and an alkyl polyether carbonic acid monoalkylolamide .
12. The concentrate according to claim 7 or 8, wherein the concentrate comprises at least one anionic polyether compound, especially at least one of - an alkyl polyether carbonic acid, an alkyl polyether sulfate, an alkyl polyether sulfosuccinate, an alkyl polyether phosphate or a corresponding alkylamido polyether compound.
13. The concentrate according to claim 10, wherein the deposition-preventing component comprises at least one compound of the general formula (I)
wherein Rx is a linear, branched, saturated or unsaturated alkyl residue having 8 to 22 carbon atoms or a corresponding alkoxy residue, R2 is H, Na, K or N(R3)3, wherein R3 is alkyl or hydroxyalkyl, R4 is H, alkyl, hydroxyalkyl, R5-C00-R2 or
[(CH2).aN]x-R5-C00-R2
R5-COO-R2,
R5 is alkyl or hydroxyalkyl, n and m are integers from 1 to 10, and x is an integer from 1 to 50.
14. The concentrate according to claim 13, wherein the deposition-preventing component comprises an alkyl amine carboxylic acid corresponding to the general formula (I) wherein Rx is cocoalkyl, R4 is H, Rs is ethylene, R2 is H and n is 1.
15. The concentrate according to claim 13, wherein the deposition-preventing component comprises an alkyl polyamine carboxylic acid corresponding to the general formula (I) , wherein Rx is cocoalkyl, R4 is H, R5 is ethylene, R2 is H and n is 3.
16. The concentrate according to claim 10, wherein the deposition-preventing component comprises a betaine of the general formula (II)
R6-N+-CH2-COO" (II)
Rv=8
wherein R6 is Rx or R-CONH- (CH2) -n, with Rx and n having the same meaning as in formula (I) , and R7 and R8 are equal or different alkyl or hydroxyalkyl substituents .
17. The concentrate according to claim 16, wherein R6 is cocoalkyl and R7 and R8 are hydroxyethyl .
18. The concentrate according to claim 16, wherein R6 is cocoamidopropyl, and R7 and R8 are methyl.
19. The concentrate according to claim 10, wherein the deposit-preventing component comprises a sulfobetaine corresponding to the general formula (III)
R7
R6-N+-R9-S03. (Ill)
R8
wherein R6, R7 and R8 have the same meaning as in formula (II), and R9 is linear or branched alkyl or hydroxyalkyl.
20. The concentrate according to claim 19, wherein R6 is lauryl, R7 and R8 are methyl and R9 is 2-hydroxypropyl .
21. The concentrate according to claim 19, wherein R6 is cocoamidopropyl , R7 and R8 are methyl, and R9 is
2-hydroxypropyl .
22. The concentrate according to claim 11, wherein the deposition-preventing component comprises a C8- C22 alkylolalkoxylate, especially a
23. The concentrate according to claim 12, wherein the deposition-preventing component comprises an alkyl polyether compound corresponding to the general formula (IV)
Ri-.O-Rio-p-O-fR- -COO-R- (IV)
wherein Rx and R2 have the same meaning as in formula (I) , R10 and Rlx are alkylene and p is an integer from 1 to 20.
24. The concentrate according to claim 23, wherein Rx is C9-C1X alkyl , R10 is ethylene, RX1 is methylene or ethylene , p is 3 to 9 and R2 is H.
25. The concentrate according to claim 23, wherein Rx ist C16-C22 alkyl or alkenyl, especially oleyl, R10 is ethylene, R1X is methylene or ethylene, especially methylene, p is 5 to 9, and R2 is H.
26. The concentrate according to claim 12, wherein the deposition-preventing component comprises a compound of the general formula (V)
R.-tO-(CH2) m-OS03-R2 (V) wherein Rx and R2 have the same meaning as in formula (I) , and n and m are integers from 1 to 10.
27. The concentrate according to claim 26, wherein Rx is a natural, Ziegler synthetic or oxosynthetic alkyl, n is 2 , m is 1, 2 or 3 and R2 is sodium.
28. The concentrate according to any one of claims 1 to 5, wherein the deposition-preventing component comprises a polymeric dispersant, substantially without surface-active properties, e.g. a polyalkyleneglykole.
29. The concentrate according to any one of claims 1 to 5, wherein the deposition-preventing component comprises cations formed from an alkaline or base-forming agent, especially an alkanolamine or low molecular weight polyamine, and an acid, said cations being capable of reacting with deposition- forming anions such as carbonate, sulfate and phosphate to form soluble or dispersible solid microparticle reaction products.
30. The concentrate according to claim 29, wherein the concentrate comprises organic acid salts of triethanolamine or hexamethylene die-mine.
31. The concentrate according to any one of claims 1 to 30, comprising (in weight-%, based on total concentrate): - 0.1 to 99%, preferably 0.5 to 10% and most preferred 1 to 5% fatty monoamine compound,
0.01 to 50, preferably 0.1 to 15% and most preferred 1 to 10% of the deposition-preventing component, sufficient acid, especially lower alkyl carboxylic acid, to provide a pH lower than 8 to the _ ^ _
concentrate, in case, further customary additives, and water.
32. The concentrate according to claim 31, comprising: about 3% by weight coco-monoamine; about 1% amphoteric alkyl mono- or polyamino carboxylic acid; - about 3% alkoxylated ether carboxylic acid; about 2% alkoxylated fatty alcohol ether and about 3% lower alkyl carboxylic acid.
33. An aqueous lubricant composition, especially for belt or chain conveyors in the bottling industry, comprising the concentrate ingredients defined in any one of claims 1 to 32 plus a major amount of water, and especially containing between 10 and 500, preferably about 90 ppm of monoamine lubricating agent.
34. Use of the concentrate according to any one of claims 1 to 32, for preparing an aqueous lubricating solution, especially as defined in claim 33, wherein the concentrate contains from 1 to 30% by weight, based on total concentrate, of a fatty monoamine lubricating agent, especially coco-monoamine and the lubricating solution has a sliding friction coefficient, at about 90 ppm monoamine concentration, of less than 0.10, preferably less than 0.08.
EP97928192A 1997-06-12 1997-06-12 Aqueous lubricant composition comprising a monoamine Expired - Lifetime EP0988358B1 (en)

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DE29719408U DE29719408U1 (en) 1997-06-12 1997-06-12 Aqueous lubricant compositions based on monoamines
PCT/EP1997/003080 WO1998056881A1 (en) 1997-06-12 1997-06-12 Aqueous lubricant composition comprising a monoamine

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WO1998056881A1 (en) 1998-12-17
GB2329644A (en) 1999-03-31
EP0988358B1 (en) 2004-09-15
AU738450B2 (en) 2001-09-20
GB9815622D0 (en) 1998-09-16
DE29719408U1 (en) 1998-03-19
AU3258297A (en) 1998-12-30

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