DE4412800A1 - Use of fatty alkylaminopoly (alkyleneamino) carboxylic acid anions in aqueous lubricant solutions and their concentrates - Google Patents

Abstract

The invention concerns the use of fatty alkyl amino poly(alkylene amino)carboxylic acid anions of the general formula (I) in aqueous lubricant solutions for chain conveyors in food and/or beverage filling/bottling plants as well as in concentrates used to prepare these solutions.

Description

The present invention relates to the use of fatty alkylaminopoly (Alkylenamino) carboxylic acid anions, if desired in conjunction with customary solubilizers and other auxiliaries or additives in aq Lubricant solutions for transport chains in filling plants for life medium and / or drinks, especially in bottling plants. The Er The invention further relates to the use of fatty alkylaminopoly (alkylene amino) carboxylic anions in concentrates to prepare the aqueous Lubricant solutions by dilution with water. The invention relates in particular the use for lubricating and cleaning of automatic Chain and belt lubrication systems, which are used when filling food preferably drinks, in glass and plastic bottles (eg PET, PC), cans, jars, barrels, beverage containers (KEG), paper and paper cups container and the like can be used.

In bottle cellars and barrel cellars of beverage factories and at the Ab filling of food will be necessary for the transport of the corresponding Ge usually container conveyor belts or other conveyor systems be uses, which with suitable aqueous lubricant preparations via immersion lubrication systems or lubricated by automatic belt lubrication systems and be kept clean.

During dip lubrication systems hardly problems in terms of application nical properties in the choice of lubricant, it is Precipitates of sparingly soluble salts and microbiological deposits, the in the nozzles and filters of the central lubrication systems the continuous Operation of filling food, in particular beverages, considerable Lich so that the equipment after a certain period of operation  always switched off and cleaned.

The chain lubricants previously used as lubricants are based ei on the other hand, to fatty acids in the form of their water-soluble alkali or alka nolamin salts or fatty amines in the form of their organic or inorganic salts.

While both substance classes in the splash lubrication easily applicable are, they show in today's standard centralized chain lubrication systems a number of disadvantages. Thus, DE-A-23 13 330 describes lubricants soap-based, the aqueous mixtures of C₁₆-C₁₈ fatty acid salts and contain surface-active substances. Such lubricants on Sei Fenbasis have the following disadvantages:

• 1. There is a reaction with the water hardness, ie the alkaline earth Ions, and other water constituents to form sparingly soluble Metal soaps, called alkaline earth alkaline soaps.
• 2. There is a reaction between these lubricants on soaps base and dissolved in water or the product to be bottled carbon dioxide.
• 3. The application solution thus produced is always germ-promoting.
• 4. When using hard water ion exchangers are to Wasserent curing, which means an additional source of germination, or but the use of highly complexing products, what like which is ecologically questionable.
• 5. It comes to increased foaming, which in particular problems on Bottle inspector (automatic bottle control) causes and to a possible penetration of these lubricants in the Transportbe leads.
• 6. Most of these products contain solvents.
• 7. The cleaning effect of these products is poor, so that a sepa Discontinuous cleaning is always necessary.
• 8. Such soap-based lubricant formulations exhibit a pH-off pending performance.
• 9. Soap based lubricant formulations continue to exhibit a what water temperature dependence.
• 10. Soap-based lubricants show only a short storage stability, especially at low temperatures.  
• 11. The EDTA (ethylenediaminetetraacetate) contained in many products is known to be poorly biodegradable.
• 12. Such soap-based lubricant preparations are not for all transport goods made of plastic, since it is the application This means in many cases to Spannungsrißkorrosionsen on cargo comes.

Apart from these soap-based lubricants, the main ones are otherwise those based on fatty amines used. Thus, DE-A-36 31 describes 953 a method for lubricating chain-shaped bottle conveyor belts in beverage bottling plants, especially in breweries, as well as for Cleaning the bands by means of a liquid detergent, which thereby characterized in that the chain-shaped bottle conveyor belts with Belt lubricants based on neutralized primary fatty amines, which are preferably have 12 to 18 carbon atoms and an unsaturated portion of contain more than 10% smears.

EP-A-0 372 628 discloses fatty amine derivatives of the formulas

known as lubricant, wherein
R¹ is a saturated or unsaturated, branched or linear alkyl group having 8 to 22 carbon atoms;
R² is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms or -A-NH₂;
A is a linear or branched alkylene group having 1 to 8 C atoms; and
A¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms.

AU-A-510 524 describes aqueous chain lubricants which are N-fatty alkyl Contain β-aminopropionic acids. The concentrates contain around 10% by weight of the Active ingredient and are used with water by a factor of 100 to 300 diluted.  

In addition, from DE-A-39 05 548 lubricants based on N-alkylated fatty amine derivatives which are at least one secondary and / or tertiary amine.

The main disadvantages of these lubricants are the reaction with anions of the Water, in particular with sulphates, bicarbonates, phosphates and carbon from alkaline waters, as well as other water constituents. Farther can react with beverage residues (formation of black deposits).

In addition, these fatty amine-based lubricants are unsafe foaming foam behavior. Thus, the lubricants of EP-A-0 327 628 tend too much foaming, resulting in a subsequent cleaning of the on the belt transported goods required. Lubricant according to DE-A-39 05 548 have a rather low foaming on what to leads to a fast drainage of the applied lubricant film.

The main disadvantages of the above-mentioned lubricants are thus on the one hand the strong water dependence of soap based lubricants and others on the other hand, the regularly necessary system cleaning when using Lubricants based on fatty amines, also by the water ingredients is conditional. The precipitates used in both processes of State of the art occur, must be removed. For removal One uses a simple acid-base reaction. In the case of soaps For this purpose, fatty acid-based products are mixed with alkaline, complexing teletext cleaners are used, and as technical equivalents to be for products based on fatty amines organic or inorganic acids used as a cleaner.

Finally, in the prior art further chain lubricants are known, which do not have some of the disadvantages described above. So be EP-A-0 044 458 writes lubricant formulations that are virtually free of fatty acid soaps and which continue to be a carboxylated nonionic containing a beautiful surfactant and an acyl sarcosinate. The pH of these products is 7 to 11 and is thus preferably in the neutral to alkaline Area.  

Finally, DE-A-38 31 448 relates to aqueous, water-soluble, be feneless lubricant preparations, a process for their preparation and the use of these lubricant preparations, in particular as Lubricants for plate conveyor belts, which are used to transport glass bottles or polyethylene terephthalate bottles serve. The essentially neutral aqueous lubricant preparations (pH in the range of 6 to 8) include alkylbenzenesulfonates, alkoxylated alkanol phosphates and alkane carboxylic acids, optionally in addition to conventional solubilizers, solutions agents, defoamers and disinfectants.

However, these two amine-free products also show the following Disadvantage:

• 1. They are unfavorable from a microbiological point of view as they stand out create excellent growth conditions for microorganisms.
• 2. Furthermore, they show only a small cleaning power.
• 3. Finally, they also have a difficult to control Foaming behavior on.

International Patent Application WO 90/10053 describes lubricants based on linear poly (alkyleneamine) derivatives of fatty amines containing the largely avoid the aforementioned disadvantages. The Einsatzkonzentra tions of these fatty amine derivatives in chain lubricant concentrates is in Range of 10% by weight. The use of such agents leads to the neces from 0.1 to 0.5% to a considerable COD load of the waste water (COD = chemical oxygen demand).

The present invention is therefore based on the object, a new Lubricant preparation, in particular a chain lubricant, bereitu which does not have the disadvantages of the prior art and the to reduce wastewater pollution in significantly reduced application concentrations can be used. This means: Such lubrication medium should be at low use concentration a good coefficient of friction, ie an excellent lubricating effect, a metered foam behavior, a have good clear water solubility and a good cleaning effect.  

For the purposes of the present invention, the term "Klarwasserlöslickeit" coupled with the insensitivity of the lubricant components against over ingredients contained in natural waters such as Calcium and magnesium. For example, if the clear water solubility of a Lubricant formulation is not pronounced, so may be prolonged Plant shutdown, for example during a weekend, such Formulations react with the water ingredients. The here resul precipitates and turbidities in the application solutions of Lubricants lead to clogging of the filters in the short to medium term Nozzles of the belt lubrication system.

Surprisingly, it has been found that lubricants that are suitable grease Alkylaminopoly (alkyleneamino) carboxylic acid anions, a clear better clear water solubility and a technically more favorable Have foaming behavior as a lubricant based on unsubstituted and substituted fatty amines and in particular the required lubrication effect at significantly reduced levels of use and thus decrease unfolded wastewater loads.

The present invention thus relates to the use of fatty alkylamines nopoly (alkyleneamino) carboxylic acid anions of the general formula

in the form of the free acids or their water-soluble salts, wherein
R '' is a radical R or RO,
R is a substituted or unsubstituted, linear or branched, saturated or mono-, di- or triunsaturated alkyl radical having 8 to 20 C atoms, where the substituents are selected from amino, imino, hydroxyl and carboxy groups,
R 'is hydrogen, an alkyl group of 3 to 12 carbon atoms, a - (CH₂-CH₂-O) _1-3 -G group, a group - [(CH₂) _n -NH] _m - (CH₂) _p -COO ⁻ Or a group - [(CH₂) _n -NH] _m -H,
n independently of each other 2 or 3,
m independently of each other 2, 3 or 4,
p are independently 1, 2 or 3
mean, individually or in admixture with each other in aqueous Schmiermittellö solutions for transport chains in filling plants for food and / or Ge drinks and concentrates for preparing these aqueous Schmiermittellö solutions.

In the aforementioned general formula (I) come as substituents thus, the following radicals are suitable: n-octyl, n-nonyl, n-decyl, n-Un decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and the branched chain term isomers of said alkyl radicals. Instead of the saturated alkylre R can also be the corresponding - monounsaturated or polyunsaturated Alkyl radicals, which may also be linear or branched. The radicals mentioned above may also be substituted, wherein as Substituents one or more amine, imine, hydroxyl or carboxyl groups come into question.

Preferred are such fatty alkylaminopoly (alkyleneamino) carboxylic acid anions of the general formula (I) in which R '' = R and R is a linear, un substituted, saturated or unsaturated, preferably a saturated ter, alkyl radical having 8 to 20 carbon atoms, preferably having 12 to 18 carbon atoms means.

Preference is given to using compounds of the general formula (I) where R 'is hydrogen.

Furthermore, such Fettalkylaminopoly are (alkyleneamino) carboxylic acid anions  preferably, in which n is the number 3, that is, propylene diamine groups contain. As the carboxylic acid group, an acetic acid group is preferred used, d. H. the index p of the general formula (I) is preferably the value 1. In particular, the use of such Fettalkylaminopoly (al kylenamino) carboxylic acid anions, the poly (propylenediamino) vinegar acid derivatives of linear fatty amines having 8-20 carbon atoms and in particular with Represent 12 to 18 C atoms. It can, as in extraction from bold common chemical raw materials, mixtures with different alkyl radicals available.

In this case, the acid anions of the general formula (I) in the form of their water-soluble ammonium, alkylammonium or alkali metal salts, preferably example of their alkali metal salts and in particular their sodium salts be set.

The term "water-soluble" is understood to mean that the salts under the preferred use levels in the aqueous lubricant solution from 10 to 200 ppm acid anions form clear solutions.

If in this context of the concentration of carboxylic anions we are talking about the concentration of each of them Meant anions. Due to hydrolysis reactions it is expected that at the pH values of the ready-to-use aqueous lubricant solutions, ranging from 5 to 9, only part of the carboxylic acid introduced Re anions are present as free anions, while another part of the un dissociated acid forms. This applies accordingly for the below be wrote concentrates whose pH preferably in the range 4-7 lie The ratio between acid anions and undissociated acid depends at a given concentration and pH of the aqueous Lö tions are known to depend on the acidity of the acid used. to Adjustment of the pH is preferably carried out using lower carboxylic acids such as acetic acid or citric acid.

It is technically common to prepare the aqueous lubricant solutions Distribute on-site concentrates that are required by the user Concentration can be adjusted by dilution with water. Accordingly,  it is within the scope of the present invention that the Fettalkylaminopo ly (alkyleneamino) carboxylic acid anions of the general formula (I) in conc concentrations between 2 and 8 wt .-% in concentrates are used, the for preparing aqueous lubricant solutions by a factor of between 200 and 1000 are diluted with water. For those in these concentrates Preferably used carboxylic acids or their salts that applies standing executed.

As auxiliaries and / or additives in the concentrates according to the present In particular, solubilizers come into consideration in the invention For example, alcohols, polyols, ethers or polyethers, in particular Isopropanol, butyl glycol, butyl diglycol or ethylene glycol ethers and al alkoxylated carboxylic acids or their esters. The amount of to be used Solubilizer depends in each case on the fat used alkylaminopoly (alkyleneamino) carboxylic acid anions; the specialist becomes one zelfall the required amount of solubilizer by trial and error determine. In general, additions to solubilizers are in the range of 3 to 20 wt .-%, based on the total formulation, sufficient.

As auxiliaries and / or additives according to the present invention come furthermore, in particular nonionic and / or amphoteric surfactants, for example, alkoxylated fatty amines and alkoxylated fatty alcohols. These Surfactants can improve the wetting of the chains and plate conveyors if necessary in individual cases. In general are surfactant additives in the range of 1 to 5 wt .-%, based on the total formulation, sufficient for this.

Furthermore, the concept rates preferably include those for pH regulation required acids, in particular lower mono- or polybasic carbon acids (2-5 C-atoms) such as acetic acid, propionic acid, oxalic acid citric acid or tartaric acid. Acid concentrations from 1 to 10% by weight are usually sufficient.

With regard to an optimal Dosiermöglichkeit it is advantageous that the lubricant concentrates have a dynamic viscosity of less than 300 mPa · s, in particular less than 150 mPa · s, and particularly preferably  ranging from 20 to 100 mPa · s - each at 20 ° C - to have their To ensure pumpability. A separate adjustment of the viscosity on the above values is generally not required or done optionally by adding suitable amounts of the diluent What or a solubilizer.

The products according to the invention cause in contrast to standard Sei Fences no stress corrosion cracking in plastic containers and Kings Therefore, especially for PET containers (PET = polyethylene terephthalate), PC containers (PC = polycarbonate), Geracote or PVC containers (PVC = polyvinyl chloride) find use. Accordingly, the Lubricant solutions of the invention as chain lubricant to the fjord tion or transport of glass containers or bottles, plastic laminated glass, plastics, in particular polyethylene terephthalate or Polyvinyl chloride, tinplate or aluminum or painted or art find substance coated containers made of these metals.

The products according to the invention are compared to the known lubricants Fettaminbasis significantly better clear water-soluble, darü In addition, a metered foam behavior and an excellent lubrication effect at low use concentration. It can be through Choice of amine or anion the desired application egg properties of the lubricant concentrate or of the aqueous lubricant Set solution specifically.

In addition, the inventive lubricant concentrates and But also with advantage as a so-called cooling lubricants in the Metalworking use find.

Fettalkylaminopoly (alkyleneamino) carboxylic acid anions, the above according to general formula (I), literaturbe after Known methods were produced and are otherwise partly offered as commercial products, for example from Rhône-Poulenc as sodium salts under the name Amphionic SFB and Amphionic 25 B for use as biocidal ampholytes for cleaners.

The present invention will become more apparent from the following examples explained.

Examples

Examples 1 to 4 according to the invention show Formulations of lubrication medium concentrates and various performance data with determined the corresponding dilute aqueous application solutions wur which, these application solutions the respective concentrates in one Amount of 0.2 to 0.3 wt .-% contained. Further explanations of each because certain application-related data - frictional resistance, foam Behavior, clear water solubility and emergency running time - can be found next basis. For comparison, the comparative examples 1 to 5 are used.

All percentages refer to the following formulation examples on weight percent.

The experiments for measuring the frictional resistance, in the following short Called "coefficient of friction" are on a pilot scale bottle conveyor under the following conditions:

Measurement of the frictional resistance of 20 0.5 l Euro beer bottles filled with water as tension with a dynamometer.
Bottle transport speed: approx. 1 m / s
Spraying the bottle conveyor belt with 0.2 wt .-% iger Bandschmiermit tellösung, as mentioned in the examples.
Spray output of nozzles: 4 l / h, 1 nozzle per band.

The coefficient of friction "μ" given below results as the quotient the measured tension for a bottle to the weight of the bottle in Grams.

Furthermore, the products with hard water (16 ° d) according to the provisions DIN 53 902 tested.

Foaming behavior is assessed according to the following classes:
0 = foam-free
1 = isolated foam bubbles
2 = low foaming, not disturbing
3 = foaming, disturbing
4 = strong foaming, unacceptable, foam under the tape.

The coefficient of friction should be below 0.15 for adequate lubrication. at Exceeding 0.15 leaves the lubricating effect and thus the perfect Transport significantly after.

The clear water solubility of the application solutions should also have a be ensured longer period of testing to deposits in Kugelven tilfiltern, nozzles, spraying and distribution system, tape and cargo to ver avoid. For this purpose, a 0.3 wt .-% solution in 16 ° d water for 72 h stored and then assessed visually.

The foaming should be low, because excessive foam not only the workflow (automatic bottle inspector) and the work safety (slipping) bothers, but also the label aufwei and penetrate into the still unopened vessel. additionally is worsened by excessive foaming tendency of the coefficient of friction. A low foam development, however, is an advantage as it is a better Distribution of the lubricant on the conveyor belts conditionally.

Under experimental conditions, which are also used to determine the coefficient of friction and foaming behavior was used after a running time of 30 min the dosage of the chain conveyor belt lubricant turned off. From At this time, the bottles are only by adhering Kettentrans Lubricated portband lubricant. The time was measured in which the Lubrication without significant deterioration of the friction coefficient upright was holding. The end of the experiment (emergency period) was determined by if the coefficient of friction increased by 50% compared to the original value.

example 1 6.00% Fatty alkylaminopoly (propyleneamino) acetates (Na salts, Amphionic® SFB, Rhône Poulenc); R 'of general formula (I) = H 4.00% acetic acid   90.00% water

Friction coefficient: μ = 0.09; Foaming behavior: 1;
Clear water solubility: almost clear;
Emergency running time: 14 min.

example 2

6.00% fatty alkylaminopoly (propyleneamino) acetate as in Ex. 1
4.00% acetic acid
3.00% dicarboxylic acid ethoxylate
87.00% water

Friction coefficient: μ = 0.09;
Foaming behavior: 2;
Clear water solubility: absolutely clear;
Emergency running time: 14 min.

example 3

6.00% fatty alkylaminopoly (propyleneamino) acetate as in Ex. 1
3.00% citric acid
91.00% water

Friction coefficient: μ = 0.10;
Foaming behavior: 1;
Clear water solubility: almost clear;
Emergency running time: 14 min.

example 4

6.00% fatty alkylaminopoly (propyleneamino) acetate as in Ex. 1
3.00% carboxylic acid polyglycol ester
4.00% acetic acid
87.00% water

Friction coefficient: μ = 0.10;
Foaming behavior: 1;
Clear water solubility: absolutely clear;
Emergency running time: 14 min

Comparative Example 1 (soap-containing chain lubricant)

59.00% water
10.00% butyldiglycol
15.00% fatty acid (oil / linole)
9.00% ethylenediaminetetraacetate-Na4
4.00% monoethanolamine
3.00% potassium hydroxide

Coefficient of friction: μ = 0.12;
Foaming behavior: 3-4;
Clear water solubility: at 1% use up to 12.5 ° d clear water-soluble
Emergency running time: 5 min

Comparative Example 2 (alkylamine-based chain lubricant)

4.00% N, N-dimethyl-N-laurylammonium acetate
8.00% laurylpropylenediammonium acetate
88.00% water

Friction coefficient: μ = 0.10;
Foaming behavior: 1;
Clear solubility: opaline;
Emergency running time: 7 min

Comparative Example 3

15.00% N-cocoalkylaminopropionic acid
85.00% water

Coefficient of friction: μ = 0.14;
Foaming behavior: 2;
Clear solubility: opaline;
Emergency running time: 10 min

Comparative Example 4

15.00% sodium N-laurylaminodipropionate
14.00% acetic acid
3.00% C12-14 fatty alcohol with 5EO / 4PO
68.00% water

Friction coefficient: μ = 0.10;
Foaming behavior: 2;
Clear solubility: absolutely clear;
Emergency running time: 15 min

Comparative Example 5

15.00% N-cocoalkylaminopropionic acid
3.00% lauryl ether phosphoric acid ester
83.00% water

Friction coefficient: μ = 0.13;
Foaming behavior: 4;
Clear solubility: opaline;
Emergency running time: 7 min

Claims (12)

1. Use of fatty alkylaminopoly (alkyleneamino) carboxylic acid anions of the general formula in the form of the free acids or their water-soluble salts, wherein
R '' is a radical R or RO,
R is a substituted or unsubstituted, linear or branched, saturated or mono-, di- or triunsaturated alkyl radical having 8 to 20 C atoms, where the substituents are selected from amino, imino, hydroxyl and carboxy groups,
R 'is hydrogen, an alkyl group of 3 to 12 carbon atoms, a - (CH₂-CH₂-O) _1-3 -H group, a group - [(CH₂) _n -NH] _m - (CH₂) _p -COO ⁻ Or a group - [(CH₂) _n -NH] _m -H,
n independently of each other 2 or 3,
m independently of each other 2, 3 or 4,
p are independently 1, 2 or 3
mean, individually or in admixture with each other in aqueous Schmiermit tell solutions for transport chains in filling plants for food and / or drinks and in concentrates for preparing these aqueous lubricant solutions. 2. Use according to claim 1, characterized in that in the general mean of my formula (I)
R '' = R and
R is a linear, unsubstituted, saturated or unsaturated, preferably saturated, alkyl radical having 8 to 20 C atoms, preferably having 12 to 18 C atoms
mean. 3. Use according to one or both of claims 1 and 2, characterized ge indicates that in the general formula (I) n = 3 or p = 1, before preferably n = 3 and p = 1. 4. Use according to one or more of claims 1 to 3, characterized characterized in that in the general formula (I) R '= H. 5. Use according to one or more of claims 1 to 4, characterized characterized in that the acid anions of the general formula (I) in Form their water-soluble ammonium, alkylammonium or alkali metal tallsalts, preferably their alkali metal salts and in particular their Sodium salts are used. 6. Use according to one or more of claims 1 to 5, characterized characterized in that the aqueous lubricant solutions, the acid Anio of the general formula (I) in concentrations between 10 and 200 ppm included. 7. Use according to claim 6, characterized in that the aqueous Lubricant solutions have a pH in the range of 5 to 9. 8. Use according to one or more of claims 1 to 7 for smelting transport chains or conveyor belts in filling plants for Beverage bottles, in particular for bottles of glass, polyethylene tere phthalate, polycarbonate, geracote and / or polyvinylchloride. 9. Use according to one or more of claims 1 to 5, characterized  characterized in that the acid anions of the general formula (I) in Concentrations between 2 and 8 wt .-% in aqueous concentrates which are used to prepare aqueous lubricant solutions dilute a factor between 200 and 1000 with water. 10. Use according to claim 9, characterized in that the Konzentra te solubilizers, preferably selected from alcohols, polyalcohol ethers and polyethers, especially from isopropanol, butylglycol, Butyl diglycol, ethylene glycol ethers, and alkoxylated carboxylic acids and their esters, preferably in amounts between 3 and 20 wt .-% enthal th. 11. Use according to one or both of claims 9 and 10, characterized ge indicates that the concentrates are nonionic and / or amphoteric Surfactants, in particular alkoxylated fatty amines and / or alkoxylated Fatty alcohols, preferably in amounts between 1 and 5 wt .-% enthal th. 12. Use according to one or more of claims 9 to 11, characterized characterized in that the concentrates are lower mono- or polybasic Carboxylic acids having 2 to 5 carbon atoms, in particular acetic acid, propion acid, oxalic acid, tartaric acid and / or citric acid, preferably in Contains amounts of 1 to 10 wt .-% and preferably a pH in Range 4 to 7 have.