WO1996019557A2

WO1996019557A2 - Use of hydroxyalkylaminocarboxylic acids as complexing agents

Info

Publication number: WO1996019557A2
Application number: PCT/EP1995/004893
Authority: WO
Inventors: Birgit Potthoff-Karl; Beate Ehle; Richard Baur; Günter OETTER; Alfred Oftring
Original assignee: Basf Aktiengesellschaft
Priority date: 1994-12-22
Filing date: 1995-12-12
Publication date: 1996-06-27
Also published as: WO1996019557A3; DE4445931A1; EP0799296A2

Abstract

Hydroxyalkylaminocarboxylic acids have the general formula (I), in which R1 is hydrogen, a C¿1?-C4 alkyl residue or a group having the formulas -CHR?3¿-CH(OH)-R2 or -CH¿2?)n-COOM, in which n equals 1 to 4; R?2 and R3¿ represent independently from each other hydrogen, a phenyl residue or an alkyl or alkenyl residue that may in addition bear phenoxy groups, carboxylic acid C¿1?-C4-alkyl ester groups or ester groups derived from triglycerides based on unsaturated C10-C22 fatty acids and may be interrupted by non-adjacent oxygen atoms, the sum of all C atoms from both residues R?2 and R3¿ being at least 4; A is a linear or branched C¿1?-C6 alkylene group that may in addition bear a hydroxyl group and/or a group having the formula COOM, and R?1¿ and A may form together with the N atom a 5- or 6-membered ring; and M is hydrogen, alkaline metal, ammonium or substituted ammonium. These hydroxyalkylaminocarboxylic acids are useful as complexing agents for alkaline earth and heavy metal ions.

Description

Use of hydroxyalkylaminocarboxylic acids as complexing agents

description

The present invention relates to the use of hydroxyalkylaminocarboxylic acids of the general formula I.

in the

R ^{1 is} hydrogen, a Ci to C alkyl radical or a grouping of the formula

- HR ³ - CH (OH) - R ² or - (CH ₂ ) _n - COOM

where n stands for a number from 1 to 4, preferably 1 or 2,

R ² and R ³ independently of one another are hydrogen, a phenyl radical or an alkyl or alkenyl radical which additionally contains phenoxy groups, carboxylic acid C 1 -C 4 -alkyl ester groups or of triglycerides based on unsaturated C ₁ -C 2 -Fatty acid-derived ester groups and can be interrupted by non-adjacent oxygen atoms mean, the sum of the C atoms from both radicals R ² and R ³ must be at least 4,

A stands for a linear or branched Ci to C _δ alkylene group, which can additionally carry a hydroxyl group and / or a group of the formula COOM, where R ¹ and A together with the N atom form a five- or six-membered ring can form, and

M denotes hydrogen, alkali metal, ammonium or substituted ammonium,

as a complexing agent for alkaline earth and heavy metal ions.

Furthermore, the invention relates above all to the use of these hydroxyalkylaminocarboxylic acids in aqueous lubricant formulations for automatic conveyor systems, in particular as aqueous ones Chain lubricant formulations for belt cleaning in bottle filling and cleaning systems. The present application also relates to an aqueous lubricant or lubricant formulation which contains the hydroxyalkylaminocarboxylic acids mentioned.

In the beverage industry, e.g. in the breweries, bottle cleaning, filling and labeling are mostly carried out automatically. For example, semi-automatic systems transport around 2000 bottles per hour. Fully automatic systems can handle up to approximately 80,000 bottles per hour.

The bottles are usually transported to the bottling plants on belts, the so-called "plate belts *, which are usually made of stainless steel. These chain-like belts are lubricated with a chain lubricant, also called 'belt lubricant *'. Also have to be lubricated these conveyor belts, usually at more or less regular intervals, are cleaned.

The chain lubricant used in breweries is preferably soaps, especially potash lubricating soaps, which e.g. synthetic nonionic or ionic surfactants can be added.

A disadvantage of such chain lubricants is that the potash soaps are particularly sensitive to water hardness. For this reason, sequestering agents (complexing agents) such as ethylenediaminetetraacetic acid or nitrilotriacetic acid or their alkali metal salts are also usually added, which partially mask the hardness.

If water is hard, there are the known problems that hard water brings with it, ie the efficiency of the chain lubricant is reduced, and, for example, the calcium salts which have precipitated can lead to problems with lubrication because they do not, as the alkali soaps do, reduce the frictional resistance between the bottle and chain. There is also the risk that the carbonic acid in the water and the C0 ₂ from the air cause the fatty acids to fail, which can also lead to problems with lubrication.

EP-B 044 458 (1) discloses lubricants for bottle conveyor belts which contain polyether carboxylates and N-acyl sarcosinates as active substances. WO-A 93/18120 (2) describes clear water-soluble chain conveyor belt lubricants which contain iminodicarboxylates with a long-chain N-alkyl radical. But also the means from (1) and (2) have considerable disadvantages, with (1) the clear water solubility and the foaming behavior and with (2) the foaming behavior are in need of improvement.

It was therefore an object of the present invention to provide agents, in particular for lubricant and lubricant formulations, which have a sufficient complexing action, in particular to bind the water hardness, are largely ecologically harmless and also provide the necessary profile of properties the application, especially with regard to clear water solubility and foam behavior.

We have found that this object is achieved by the use of the hydroxyalkylaminocarboxylic acids I defined at the outset.

In a preferred embodiment, hydroxyalkylamino carboxylic acids of the general formula Ia are used

in which R ^{4 is} a C ₅ - to Ciβ-alkyl radical, in particular a Cζ- to Ci ₄ -alkyl radical, or a phenyl radical and M has the meaning given above.

In a further preferred embodiment, hydroxyalkylaminocarboxylic acids of the general formula Ib are used

R ^£ a Ce to C ₂ o alkyl or alkenyl group, especially a C _Θ - to Cie-alkyl, or represents a phenyl radical and M has the meaning given above, a.

The compounds I are known in principle. In Fette, Seifen, Anstrichmittel 68, No. 11, pp. 964-967 (1966) (3) by E. Ulsperger, some of the compounds Ia and Ib are explicitly described, reference being made to their surface-active properties. The compounds I, Ia and Ib are expediently prepared by reacting the underlying amino acids with the corresponding epoxides, as described in (3). The residual meanings in these starting components described in more detail below apply equally to the definition of the variables in the end products I, Ia and Ib.

As the underlying amino acids of the general formula

R ^l HNA COOM

come amino acids with primary amino groups (R - = H) such as glycine, alanine, ß-alanine, leucine, isoleucine, norleucine, valine or norvaline, amino acids with secondary amino groups such as sarcosine (R ¹ = CH ₃ ), amino acids Ring structure such as proline or amine acids with a hydroxyl group in the bridge member A such as serine, isoserine or homoserine into consideration. In the case of noncyclic compounds, the variable R ¹ thus preferably denotes hydrogen or methyl. The bridge member A primarily represents a linear or branched Ci to Cs alkylene group. Dibasic amino acids with primary amino groups such as aspartic or glutamic acid and those with secondary amino groups such as iminodiacetic acid (R ¹ = CH ₂ COOM) are also suitable.

The carboxyl group COOM can be present as a free acid group or as a salt, in particular as a sodium, potassium, ammonium or substituted ammonium salt (organic amine salt). The bases on which the organic amine salts are based are, in particular, tertiary amines such as trialkylamines having 1 to 4 carbon atoms in the alkyl radical, e.g. Trimethylamine, triethylamine or tri-n-butylamine, and trialkanolamines with 2 or 3 carbon atoms in the alkanol radical, e.g. Triethanolamine, tri-n-propanolamine or triisopropanolamine.

As corresponding epoxides of the general formula

^• CH CH R ³

are particularly suitable: (a) terminal epoxides, ie those in which R ^{2 is} a C - to usually C3o-alkyl or alkenyl radical or a phenyl radical and R ^{3 is} hydrogen;

(b) central epoxides, ie those in which R ² and R ³ each represent a C - to usually C ₃ o-alkyl or alkenyl radical or a phenyl radical, where the two radicals can be the same or different;

(c) Central epoxyalkane carboxylic acid C * _. - to C ₄ alkyl esters and corresponding triglyceride derivatives, in particular the corresponding epoxides of fatty acid alkyl esters such as epoxidized methyl oleic acid esters, ie those compounds in which one of the radicals R ² or R ^{3 is} a C ₄ - to usually C ₃ o- alkyl or alkenyl and the other is a C ₄ - ₃ o ~, which is preferably terminally a carboxylic acid Ci- to C ₄ -alkyl carries moiety be¬ indicated by usually C alkyl or alkenyl group;

(d) Glycidyl ether, ie those compounds in which R ^{2 is} a C ₃ to usually C ₂₉ alkyl or alkenyloxymethyl radical or a phenyloxymethyl radical and R ^{3 is} hydrogen.

A long-chain radical R ² or R ³ stands for branched or linear alkyl or alkenyl with 4 to usually 30 C atoms, in particular 6 to 18 C atoms, especially 8 to 14 C atoms.

The following alkyl or alkenyl groups are listed as examples of branched or linear long-chain radicals R ² and R ³ :

n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, iso- Tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hepta-decyl, n-octadecyl, eicosyl, hexadecenyl, hexadecadienyl, hexadecatrienyl, octadecenyl, octadecadienyl and octadecatrienyl.

Mixtures of different radicals R ² or R ³ can also occur, for example mixtures of n-decyl and n-dodecyl or n-dodecyl and n-tetradecyl.

Suitable Ci to C ₄ alkyl ester radicals in (c) are n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and in particular methyl and ethyl. As C ₃ to C ₂₉ alkyl or alkenyl groups in the alkyl or alkenyloxymethyl radicals in (d), all of the above-mentioned examples for long-chain radicals R ² or R ³ and n-propyl and isopropyl come into consideration .

If corresponding triglyceride derivatives are used in (c), they are triglycerides with, for example, 3 unsaturated fatty acids, the olefinic double bonds of which are partially or preferably completely epoxidized and which, with the amino acids mentioned, give the compounds I via these epoxide groups react. Depending on the degree of unsaturation of the fatty acids, up to 9, in particular up to 6, amino acid units can normally be bound to a triglyceride molecule. If double bonds have not been epoxidized or if the triglyceride carries 1 or 2 saturated fatty acid groups, 1 to 6, in particular 1 to 4, amino acid units are normally bound to a triglyceride molecule.

The unsaturated fatty acids in the triglycerides are the usual C ₁₀ to C ₂₂ fatty acids such as oleic acid, linoleic acid or linolenic acid. Triglycerides of vegetable or animal origin are found above all in soybean oil, rapeseed oil, olive oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, rapeseed oil, beef tallow or fish oil, these products, after epoxidation, also being used directly as starting materials for the preparation of the hydroxyalkylamino carboxylic acids I can serve.

The sum of the C atoms from the two radicals R ² and R ³ in the compounds I is usually from 4 to 60 in the absence of triglyceride structures.

The compounds I described and in particular Ia and Ib are outstandingly suitable as complexing agents for binding the calcium and magnesium water hardness in general in aqueous detergent formulations. In many applications, water hardness is a disruptive factor that must be excluded.

With particularly good results, the compounds I, Ia and Ib can be used in aqueous lubricant formulations for automatic conveyor systems. This includes in particular conveyor system lubrication systems for glass and plastic bottles, cans, glasses, barrels and cardboard packaging, especially in the beverage and food industry.

The compounds I, Ia and Ib are particularly suitable for aqueous chain lubricant formulations for the belt cleaning of bottle filling and cleaning systems. Here 7 it is for example beer, milk, soft drinks, fruit juice, sweet must, wine or mineral water bottles.

Chain lubricant formulations contain as surface active, i.e. cleaning component usually soaps, especially potash soaps, non-ionic or ionic surfactants, e.g. Fatty alcohol ethoxylates, fatty alcohol sulfates or fatty alcohol ether sulfates, or special surface-active agents such as a mixture of polyether carboxylates and N-acyl sarcosinates according to (1) or N-alkylimidodicarboxylates according to (2) or mixtures of the surfactants or surfactant-like compounds mentioned.

The surface-active compounds mentioned are more or less sensitive to water hardness, but especially soaps, and are therefore usually used together with water-hardness-binding agents. The hydroxyalkylaminocarboxylic acids I, Ia and Ib have proven to be particularly advantageous here; they can be advantageously combined with all of the surface-active agents mentioned, their advantage not only in binding water hardness or preventing precipitation of calcium or magnesium salts from formulation components, but also in part in a synergistic interaction with the surfactants with respect to. the cleaning effect is to be sought.

The present invention also relates to an aqueous one

Lubricant or lubricant formulation for automatic conveyor systems, containing, in addition to the lubricant or lubricant component and other customary auxiliaries, surfactants and hydroxyalkylaminocarboxylic acids I. The long-chain fatty acid such as oleic acid or its water-soluble one is used as the lubricant component

Salts, in particular alkali metal or amine salts, or a long-chain fatty amine such as oleylamine or stearylamine in the form of its inorganic or organic salts. The surfactants mentioned above can be considered. Typical auxiliaries are, for example, defoamers, corrosion inhibitors, solubilizers, viscosity improvers and preservatives or disinfectants.

A typical aqueous lubricant or lubricant formulation of this type, for example for chain lubricants, is composed as follows:

10 to 50% by weight of lubricants or lubricants 1 to 10% by weight of surfactants 1 to 20% by weight of hydroxyalkylaminocarboxylic acids I, Ia or Ib θ

0 to 20% by weight of conventional auxiliaries, the rest being water.

The compounds I, Ia and Ib described are generally suitable as complexing agents for alkaline earth and heavy metal ions.

Another use is therefore generally in technical cleaning agent formulations for hard surfaces made of metal, plastic, lacquer or glass.

For the cleaning of hard surfaces, technical cleaning agent formulations, in particular with improved properties in the removal of dirt, were sought. In order to reduce the wastewater load, it is also desirable to dispense entirely with organic solvents which are usually used in this case.

In addition to the lubricant or lubricant formulations for automatic conveying systems already mentioned, the areas of application for the described technical detergent formulations containing hydroxyalkylaminocarboxylic acids are in particular:

Alkaline rust remover

- Alkaline diving degreaser

All-purpose cleaner

Car detergent for brush and high pressure washing

Steam jet cleaner

Electrolytic degreasers, especially for steel

- Electrolytic rust remover

Electrolytic descaler

Highly alkaline cleaners

high pressure cleaner

Passivation agent for steel

- spray degreaser Aqueous cold cleaners

These cleaning agent formulations generally contain 0.1 to 30% by weight of hydroxyalkylaminocarboxylic acids I.

Formulations customary for the individual fields of use are known in principle to the person skilled in the art. As a rule, such formulations contain, in addition to the complexing agents, 1 to 35% by weight of surfactants of anionic or preferably nonionic nature, which are foaming or low-foaming depending on the intended use, and, if desired, further complexing agents, builders, foam steamers, emulsifiers, as further auxiliaries. Corrosion inhibitors, reducing agents, solubilizers, dispersants and preservatives in the concentrations customary for this. Depending on the application, other components with special effects can also be added. Organic solvents can largely be dispensed with in the formulations described.

Recipe suggestions for such technical cleaning formulations can be found, for example, in the Technical Information "Technical Cleaning Agents" TI / ES 1167d from January 1991 of BASF Aktiengesellschaft; the complexing agents of the prior art specified there are to be replaced by hydroxyalkylaminocarboxylic acids I.

Another use for hydroxyalkylaminocarboxylic acids I is in alkaline detergent formulations for the beverage and food industry, in particular for bottle cleaning in the beverage industry and for cleaning equipment in dairies, breweries, in canned goods, baked goods, the sugar, fat processing and meat processing industries.

Formulations in particular with improved properties in the removal of dirt were sought for the cleaning of containers and apparatus in the beverage and food industry. In order to reduce the wastewater pollution, it is also desirable to dispense entirely with organic solvents in such formulations.

The present alkaline detergent formulations generally have pH values from 8 to 14, preferably from 9 to 13, in particular from 10 to 12.

Another area of application for the cleaning agent formulations described is bottle cleaning in the beverage industry, in particular using automatic bottle washers. The soiled bottles contained, for example, beer, milk, soft drinks, fruit juices, sweet must, wine or mineral water.

Another area of application for the cleaning agent formulations described is apparatus cleaning in dairies. When cleaning butter makers, where the main focus is on degreasing, they can be used with an advantageous effect. In particular, however, where residues or deposits from calcium phosphate, other calcium salts, mostly organic acids and casein ("milk stone") have to be removed. B. with milk plate heaters, plate inserts from milk centrifuges or storage and transport tanks for milk, detergents containing hydroxyalkylaminocarboxylic acids I are outstandingly suitable.

Another area of application for the cleaning agent formulations described is apparatus cleaning in breweries. Above all, residues or deposits from calcium oxalate, hop resins and protein compounds ("beer stone") are to be removed, for example from cooking tanks, storage tanks or beer lines.

Another area of application for the cleaning agent formulations described is apparatus cleaning in the canning industry. When heating the tin cans filled and closed with food, usually in an autoclave, or when cleaning cans, e.g. B. in a continuous spraying machine, cleaning agents must be used that wash off the residues of the filling material without attacking the tinplate or its coating. In addition, the cleaning agent is intended to prevent scale deposits on the cans or in the apparatus.

Another area of application for the cleaning agent formulations described is apparatus cleaning in the baked goods industry, in particular the cleaning of baking and dough forms which are contaminated with burnt-on shortening and dough residues. The cleaning is usually done by boiling with the alkaline cleaning solutions or by washing in continuous spraying systems.

Another area of application for the cleaning agent formulations described is apparatus cleaning in the sugar industry. When sucrose is obtained from sugar beet or sugar cane, calcium salts containing impurities or residues are obtained, for the removal of which the hydroxyalkamino Formulations containing carboxylic acids I are also suitable.

Another area of application for the cleaning agent formulations described is apparatus cleaning in the fat-processing industry, which primarily produces lard, tallow, edible oils or fats or fatty oils hardened by catalytic hydrogenation from fats of animal or vegetable origin. B. margarine. In addition to their importance in the food sector, products of this type also represent important raw materials for the production of products for textile finishing, paints, leather care products, cosmetic preparations, candles, soaps, surfactants, lubricants, plasticizers, cement and asphalt additives and plastics.

Another area of application for the cleaning agent formulations described is apparatus cleaning in the meat processing industry. Here, in particular, water-stone-preventing cleaning agents must be used, e.g. B. in the so-called. Steam jet cleaning devices, in which a hot steam-liquid mixture is blasted onto the apparatus and equipment to be cleaned.

The alkaline detergent formulations containing the described hydroxyalkylaminocarboxylic acids I can be used largely free of organic solvents. A possible environmental impact is thus largely excluded.

Contains an aqueous cleaning agent formulation which is customary for the areas of application mentioned in the beverage and food industry

(i) 0.05 to 30% by weight, preferably 0.1 to 25% by weight, in particular 0.5 to 15% by weight, of hydroxyalkylaminocarboxylic acid I,

(ii) 2 to 50% by weight, preferably 5 to 40% by weight, in particular 8 to 25% by weight, of alkali metal hydroxide, carbonate, silicate or a mixture thereof and

(iii) 1 to 30% by weight, preferably 2 to 25% by weight, in particular 3 to 20% by weight of surfactants. Sodium and potassium hydroxide are particularly suitable as component (ii), but also sodium and potassium carbonate, * Mixtures of the alkalis mentioned can also be used.

All conventional anionic or non-ionic surfactants or mixtures thereof can be used as surfactants (iii), but alkyl sulfates, alkyl sulfonates, fatty alcohol alkoxylates, oxo alcohol alkoxylates, alkyl polyglucosides and fatty amine alkoxylates are particularly suitable.

This composition constitutes a basic formulation for all of the above-mentioned fields of application. The individual compositions within this basic formulation differ from one another due to the different types of food and beverage soiling, the different amounts of alkaline earth metal ions in these residues and deposits, and the differences to explain the sensitive materials of the containers and apparatus to be cleaned in the various fields of application. In this context it is also worth mentioning that the alkaline cleaning agent formulations described which contain the compounds I generally do not cause any corrosion, even with sensitive apparatus materials.

The basic formulation from components (i) to (iii) described above can also contain conventional auxiliaries in the concentrations customary here, for example disinfectants to achieve the desired degree of bacteriological purity, wetting agents, loose agents, corrosion inhibitors or preservatives.

A further use for hydroxyalkylaminocarboxylic acids I is in dishwashing detergent formulations, in particular in phosphate-free detergents for machine dishwashing in dishwashers in the household or in commercial establishments, for example. B. commercial kitchens or restaurants.

Another use for hydroxyalkylaminocarboxylic acids I is in bleaching baths in the paper industry. Here complexing agents are used in reductive bleaching, e.g. B. with sodium dithionite, or in the oxidative bleaching, for. B. with hydrogen peroxide, needed to increase the effectiveness of the bleaching process, ie to increase the whiteness of the wooden ship. The complexing agents thus serve to eliminate heavy metal cations, mainly iron, copper and especially manganese, which also have a disruptive effect on resin sizing with alum and sodium resinate due to the formation of insoluble salts. The deposition of iron on paper leads to "hot "spots where the oxidative catalytic destruction of cellulose begins.

A typical formulation of such an aqueous reductive bleaching bath in the paper industry for wood pulp (for example 4% consistency) contains 0.05 to 0.1% by weight of complexing agent I and about 1% by weight of sodium dithionite, in each case based on the wood grinding. The bath temperature is approx. 60, the bleaching time is usually 1 hour and the pH is approx. 5.8.

A typical formulation of such an aqueous oxidative bleaching bath in the paper industry for ground wood (for example 20% consistency) contains 0.05 to 0.15% by weight of complexing agent I, approx. 2% by weight of water glass, approx. 0 , 75% by weight NaOH and approx. 1% by weight H ₂ O ₂ , each based on the wood pulp. The bath temperature is approximately 50 ° C. and the bleaching time is normally 2 hours.

Another use for hydroxyalkylaminocarboxylic acids I is in photographic bleaching and bleach-fixing baths. In the photographic industry, these compounds can be used in baths which are prepared with hard water in order to prevent the precipitation of poorly soluble calcium and magnesium salts. The precipitations lead to gray veils on films and images as well as deposits in the tanks, which can thus advantageously be avoided. As iron IIII complexing agent solutions, they can advantageously be used in bleach-fixing baths, where they can replace the hexacyanoferrate solutions, which are harmful from an ecological point of view.

A typical aqueous photographic bleach or bleach-fix bath formulation of this type looks as follows:

Iron (III) complex with complexing agent I 0.04 to 0.4 mol / 1 free complexing agent I to 1.3 mol / 1

Sodium thiosulfate 0.2 to 2.0 mol / 1

Sodium sulfite 0.2 to 0.3 mol / 1

The pH of such a bath is usually 4 to 8.

Another use for hydroxyalkylaminocarboxylic acids I is in pretreatment and bleaching baths in the textile industry. Pretreatment baths are to be understood in particular as desizing baths and alkaline pretreatment or mercerization baths. In the textile industry, these compounds can thus be used to remove traces of heavy metals during the production process of natural and synthetic fibers such as cotton, Serve wool or polyester. This prevents many disturbances, such as dirt stains and stripes on the textile, loss of gloss, poor wettability, uneven dyeing and color defects.

A typical aqueous pretreatment bath of this type in textile production contains:

0.1 to 10% by weight of complexing agent I, 0.5 to 20% by weight of customary wetting or emulsifying agents,

0 to 10% by weight of a reducing agent such as sodium dithionite, 0 to 5% by weight of a buffer mixture for setting a pH between 5 and 10

as well as other conventional auxiliaries such as preservatives or desizing agents, e.g. B. enzymes such as lase.

Another use for hydroxyalkylaminocarboxylic acids I is in galvanic baths for masking contaminating heavy metal cations. They serve here as a replacement for the highly toxic cyanides.

The following copper bath may be mentioned as a typical composition of such an aqueous galvanic bath for the deposition of, for example, copper, nickel, zinc or gold:

approx. 10 g / 1 copper (II) sulfate pentahyrate 10 to 12 g / 1 formaldehyde 12 to 15 g / 1 complexing agent I 1 to 2 g / 1 of a C-. ₃ / Ci ₅ -oxo alcohol, which with 12 mol

Ethylene oxide and 6 mol of propylene oxide was reacted as a wetting agent

This bath is usually adjusted to pH 13 with sodium hydroxide solution; it can also contain conventional stabilizers such as amines or sodium cyanide.

As a further preferred use, copper, iron, manganese and zinc complexes of the compounds I are used in plant nutrition to correct heavy metal deficits. The heavy metals are added as chelates in order to prevent the precipitation as biologically inactive, insoluble salts.

In general, hydroxyalkylaminocarboxylic acids I can advantageously be used wherever precipitation of calcium, magnesium and heavy metal salts is to be disrupted and prevented in industrial processes, for example to prevent Formation of deposits and incrustations in boilers, pipelines, on spray nozzles or generally on smooth surfaces.

They can serve to stabilize phosphates in alkaline degreasing baths and prevent the precipitation of lime soaps and thereby prevent the "tarnishing" of non-ferrous surfaces and prolong the service life of alkaline cleaning baths.

The cooling water treatment with the compounds I prevented

Deposits or dissolve existing ones again. One advantage is the general applicability in alkaline medium and thus the elimination of corrosion problems.

When rubber is polymerized, they can be used to produce the redox catalysts used. In addition, they prevent the precipitation of iron hydroxide in the alkaline polymerization medium.

In powder detergent formulations for textile washing, the compounds I can be used as a complexing agent or as a builder. In addition to the conventional formulations (debris density approx. 450 g / 1), more and more compact and ultra-compact detergents (debris density ≥ 700 g / 1) are becoming increasingly important. Compact detergent formulations are known to have a higher content of detergent (tensides), builders (e.g. zeolites), bleaches and polymers than conventional powder detergents. In such compact detergent formulations, the compounds I are usually active in amounts of 0.1 to 25% by weight, in particular 1 to 15% by weight.

In liquid detergent formulations for textile washing, the compounds I can be used as complexing agents in an amount of 0.05 to 20% by weight, based on the total weight of the detergent formulation.

In liquid detergent formulations, the compounds I can also be used as preservatives, advantageously in an amount of 0.05 to 1% by weight, based on the total weight of the detergent formulation.

They prevent metal-catalyzed oxidative decomposition in soaps.

Further applications include, for example, applications in pharmaceuticals, cosmetics and foodstuffs, in order, for. B. the metal-catalyzed oxidation of olefinic double bindings and thus prevent the products from becoming rancid.

Further areas of application for the compounds I are flue gas scrubbing, namely the removal of NOχ from flue gases, H ₂ S oxidation, metal extraction and use as catalysts for organic syntheses, eg. B. the air oxidation of paraffins or the hydroformylation of olefins to alcohols.

An advantageous effect of the compounds I is bleach stabilization, for example in the bleaching of textiles, cellulose or paper stock. Traces of heavy metals such as iron, copper and manganese occur in the components of the bleaching bath itself, in the water and in the material to be bleached and catalyze the decomposition of the bleaching agent. The complexing agents I bind these metal ions and prevent the undesired decomposition of the bleaching system during storage and during use. This increases the efficiency of the bleaching system and damages to the goods to be bleached are suppressed.

A further advantageous effect of the hydroxyalkylaminocarboxylic acids I is the strong bleach-activating effect of complexes of the compounds I with manganese, in particular manganese of oxidation levels II and IV. Such complexes can be used as bleaching catalysts in amounts as a replacement for conventional bleach activators in textile detergent formulations use in the ppm range.

Hydroxyalkylaminocarboxylic acids I are particularly suitable for the purposes described because they are extremely effective complexing agents for alkaline earth metal ions and for heavy metal ions, in particular for calcium and manganese. Their calcium and manganese binding capacity are exceptionally high.

In contrast to, for example, ethylenediaminetetraacetic acid, the hydroxyalkylaminocarboxylic acids I, Ia and Ib used according to the invention are largely ecologically harmless since they are to a large extent biodegradable or eliminable. They are also toxicologically safe, which is also important for use in the food sector.

The hydroxyalkylaminocarboxylic acids I, Ia and Ib used according to the invention have the property profile necessary for the intended use, in particular in lubricant or lubricant formulations for automatic conveyor systems, in particular in particular, they are usually clearly water-soluble and very low-foaming.

The following examples are intended to illustrate the invention without being understood as a limitation.

example 1

Turbidity measurement on chain lubricant formulations compared to ethylenediaminetetraacetic acid

Compounds A and B to be used according to the invention were:

H ₃ C (CH ₂ ) s

CH2 COONa

f ² " ⁵ " j * ³

H ₃ C (CH ₂ ) CH CH ₂ 0 CH ₂ - H CH ₂ N CH2 COONa (B)

A was prepared from sarcosine and 1,2-epoxyoctane and B from sarcosine and 2-ethylhexylglycidyl ether in each case according to (3).

Ethylene diamine tetraacetic acid tetrasodium salt (EDTA-Na ₄ ) served as a comparison.

The chain lubricant formulation used was composed as follows:

Complexing agent (A, B or EDTA-Na ₄ ) 12% by weight of commercially available fatty acid ethoxylate 5% by weight of commercially available carboxylic acid mixture as solubilizer 5% by weight

Oleic acid 15% by weight

Triethanolamine 10% by weight

Monoethanolamine 5% by weight water 48% by weight

The corresponding oleic acid amine salt acts as a lubricating or sliding component. The complexing agent serves to bind water hard and to stabilize the oleic acid, since it prevents the precipitation of poorly soluble calcium oleate. The three formulations were each reacted with water having a hardness of 30 ° and diluted in a ratio of 1: 100, 1: 200 and 1: 300. After standing at room temperature for 3 hours, the turbidity was determined by nephelometric turbidity measurement. In this measuring method, the scattering of light is determined photometrically after irradiating the measurement solution, this scattering being determined by the interaction between the light rays and the particles or droplets in the solution, the number and size of which make up the degree of turbidity. The nephelometric turbidity unit (NTU), which is measured at 25 ° C. in aqueous solution and is determined by calibration on the basis of formazin as an artificial opacifier, serves as the measured variable. The higher the NTU value, the cloudy the solution.

Table 1 shows the results of the determinations.

Table 1

Complexing agent NTU values when diluted

1: 100 1: 200 1: 300

A 474 333 215

B 192 138 98

EDTA-Na 1040 365 252

These results are all the more surprising since comparatively small values are determined when determining the calcium binding capacity for A and B:

Ca-Bmdevermogen for A: 35 mg CaC0 ₃ / g complexing agent Ca-Bmdevermogen for B: 25 mg CaC0 ₃ / g complexing agent Ca-binding capacity for EDTA-Na ₄ (for comparison): 350 mg CaC0 ₃ / g complexing agent (determined according to the CCDK method).

Example 2

Foaming behavior of hydroxyalkylaminocarboxylic acids

In addition to A and B (see Example 1), the compounds C and D were used as compounds to be used according to the invention: H CH ₃ V y CH CH ₂ N CH2 COONa (C!

CH ₃

VO CH2 - CH CH ₂ NI CH2 COONa

C was prepared from sarcosine and styrene oxide and D from sarcosine and 2,3-epoxypropylphenyl ether in each case analogously to A and B.

The four complexing agents A to D were investigated according to the air introduction method. Table 2 shows the results of the determinations from which it can be seen that the compounds practically do not foam.

With the air introduction method, 200 ml of a 10% by weight solution of the product to be tested in distilled water are added to the foam cylinder. A precisely metered amount of air is then passed into the solution through a glass frit. The time is stopped until the foam has reached 1000 ml. If the amount of foam is smaller, the foam height in ml is noted after 5 minutes.

Table 2

Complexing agent foam height [ml]

A 0

B 60

C 5

D 10 Example 3

Turbidity measurement on aqueous polyether carboxylate solutions compared to N-oleoylsarcosinate.

A mixture according to (1)

Polyether carboxylate of the formula C12H25- (OC2H ₄ ) ₂ -COOH 9.0% by weight

N-oleoyl sarcosinate 6.0% by weight

Potassium hydroxide 1.6% by weight water 83.4% by weight

was prepared with water hardness 30 ° and diluted in a ratio of 1: 200 and 1: 300. After standing for 3 hours at room temperature, the NTU value (see Example 1) was determined.

The amino acid component N-oleoylsarcosinate of the comparative example was replaced in the mixture by the same amount of the complexing agents A or B to be used according to the invention, and the measurement was repeated.

Table 3 shows the results of the determinations.

Table 3

Aminoβ & urekomponent NTU value when diluted 1: 200 1: 300

N-oleoyl sarcosinate 1044 586

A 0.3 0.2

B 40 9

Example 4

Foaming behavior of the mixtures from Example 3

The three mixtures from Example 3 were investigated using the air introduction method (see above). For this purpose, 2 g of the mixture were dissolved in 1 liter of water, 100 ml of this solution were removed and placed in a foam tube. Air was blown in for 10 minutes and then the foam height was read. Table 4 shows the results of the determinations. Table 4

Amino acid component foam height [ml] immediately after 1 min after 5 min after 10 min

N-oleoyl sarcosinate 730 660 550 500

A 580 380 280 240

B 570 370 140 90

It can be seen from the data of Examples 3 and 4 that the hydroxyalkylaminocarboxylic acids to be used according to the invention represent a significant improvement in clarity and foaming behavior compared to the N-acyl sarcosinates according to (1).

Example 5

Turbidity measurement on aqueous N-alkyliminodicarboxylate solutions

A mixture according to (2) (example 1 there)

Sodium N-lauryl iminodipropionate 15% by weight

Acetic acid 14% by weight

Water 71% by weight

Instead of the sodium N-laurylimino dipropionate, 15% by weight of the complexing agents A or B to be used according to the invention were incorporated into the above mixture (with a corresponding reduction in the water content) and the determination was repeated.

Table 5 shows the results of the measurements. An analogous mixture according to (2) with 13% by weight of citric acid (example 3 there) instead of 14% by weight of acetic acid gave the same result.

Table 5

Complexing agent NTU value when diluted 1: 200 1: 300 without 1 1

A 2 1

B 8 3 The mixtures are practically identical in their clarity, no differences are perceptible to the naked eye.

Example 6 5 Foam behavior of the mixtures from Example 5

The three mixtures from Example 5 were examined analogously to Example 4 using the air introduction method (see above). Table 6 shows the results of the determinations. The analog mixtures with 10 13 wt .-% citric acid gave the same result.

Table 6

15 complexing agents foam height [ml] immediately after 1 min after 5 min after 10 min

without 650 480 370 320

20 A 0 0 0 0

B 10 0 0 0

It can be seen from the data of Examples 5 and 6 that mixtures according to (2) with the hydroxyalkyl 25-amino carboxylic acids to be used according to the invention bring no improvement in terms of clarity compared to mixtures without these complexing agents, but their presence reduces the tendency to foam practically to zero.

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Claims

claims

1. Use of hydroxyalkylaminocarboxylic acids of the general formula I

in the

R ^{1 is} hydrogen, a C ¹ -C ₄ -alkyl radical or a grouping of the formula

—CHR ³ —CH (OH) —R ² or - (CH ₂ ) _n —COOM

where n is a number from 1 to 4,

R ² and R ³ independently of one another are hydrogen, a phenyl radical or an alkyl or alkenyl radical which additionally contains phenoxy groups, carboxylic acid Ci to C ₄ alkyl ester groups or of triglycerides based on unsaturated Cio to C ₂₂ -Fatty acid-derived ester groups and can be interrupted by non-adjacent oxygen atoms mean, the sum of the carbon atoms from both radicals R ² and R ³ must be at least 4,

A stands for a linear or branched Ci to C ₆ alkylene group, which can additionally carry a hydroxyl group and / or a group of the formula COOM, where R ¹ and A together with the N atom form a five- or six-membered ring can form, and

M denotes hydrogen, alkali metal, ammonium or substituted ammonium,

as a complexing agent for alkaline earth and heavy metal ions.

2. Use according to claim 1 of hydroxyalkylaminocarboxylic acids of the general formula Ia

in which R ^{4 represents} a C ₅ - to C ₈ -alkyl radical or a phenyl radical and M has the meaning given above.

3. Use according to claim 1 of hydroxyalkylaminocarboxylic acids of the general formula Ib

R-- 0 CH ₂

in which R ^{5 represents} a C ₁ -C ₂ -alk-1 or -alkenyl radical or a phenyl radical and M has the meaning given above.

4. Use of hydroxyalkylaminocarboxylic acids according to claims 1 to 3 in technical cleaning agent formulations for hard surfaces made of metal, plastic, lacquer or glass.

5. Use of hydroxyalkylaminocarboxylic acids according to claims 1 to 3 in alkaline detergent formulations for the beverage and food industry.

6. Use of hydroxyalkylaminocarboxylic acids according to claims 1 to 3 in dishwashing detergent formulations.

7. Use of hydroxyalkylaminocarboxylic acids according to claims 1 to 3 in bleaching baths in the paper industry.

8. Use of hydroxyalkylaminocarboxylic acids according to claims 1 to 3 in photographic bleaching and bleach-fixing baths.

9. Use of hydroxyalkylaminocarboxylic acids according to claims 1 to 3 in pretreatment and bleaching baths in the textile industry.

10. Use of hydroxyalkylaminocarboxylic acids according to claims 1 to 3 in galvanic baths.

11. Use of hydroxyalkylaminocarboxylic acids according to claims 5 to 3 in plant nutrition.

12. Use of hydroxyalkylaminocarboxylic acids according to claims 1 to 3 as complexing agents for calcium and magnesium ions in aqueous detergent formulations. 10

13. Use of hydroxyalkylaminocarboxylic acids according to claim 12 in aqueous lubricant formulations for automatic conveyors.

15 14. Use of hydroxyalkylaminocarboxylic acids according to claim 12 in aqueous chain lubricant formulations for the belt cleaning of bottle filling and cleaning systems.

15. Aqueous lubricant or lubricant formulation for automatic conveyor systems, containing in addition to the lubricant or

Sliding component and other conventional auxiliaries surfactants and hydroxyalkylaminocarboxylic acids according to claim 12.

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