EP0411436A2 - Use of derivatives of 2-hydroxy-3-aminopropionic acid as complexants, stabilizer for bleaching compositions and builder for washing and cleaning agents - Google Patents

Use of derivatives of 2-hydroxy-3-aminopropionic acid as complexants, stabilizer for bleaching compositions and builder for washing and cleaning agents Download PDF

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Publication number
EP0411436A2
EP0411436A2 EP90114141A EP90114141A EP0411436A2 EP 0411436 A2 EP0411436 A2 EP 0411436A2 EP 90114141 A EP90114141 A EP 90114141A EP 90114141 A EP90114141 A EP 90114141A EP 0411436 A2 EP0411436 A2 EP 0411436A2
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Prior art keywords
groups
coox
general formula
group
hydroxy
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German (de)
French (fr)
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EP0411436A3 (en
EP0411436B1 (en
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Richard Dr. Baur
Charalampos Dr. Gousetis
Stefan Dr. Birnbach
Michael Dr. Kneip
Alfred Dr. Oftring
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds

Definitions

  • the invention further relates to these new compounds, a process for their preparation, their use as complexing agents for heavy metal or alkaline earth metal ions and the complexing agents containing them.
  • DE-A 21 03 453 (1) relates to ⁇ -hydroxy- ⁇ -aminocarboxylic acids of the general formula IV in which R7 and R8 each represent an aliphatic, cycloaliphatic or araliphatic radical, but R7 and R8 denote no methyl group and also mean, inter alia, hydrogen, alkylol groups or the radical -CH2-CH (OH) -COOH. Furthermore, one of the radicals R7 or R8 can carry a second substituted amino group -NR7R8.
  • the compounds IV serve to mask metal ions, in particular heavy metal cations, by complexing in aqueous solution.
  • the object of the present invention was therefore to provide complexing agents which are more suitable as bleach stabilizers.
  • X stands for alkali metal ions such as lithium or in particular sodium or potassium or for the ammonium ion, which can be partially or completely substituted by C1-C4-alkyl groups or C1-C4-hydroxyalkyl groups.
  • the salts of tertiary amines should be mentioned here.
  • Preferred tertiary amines are trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine and trialkanolamines such as triethanolamine or triisopropanolamine.
  • the compounds Ia which are a subgroup of the compounds I, are new.
  • the compounds I and especially the compounds Ia are expediently reacted by reacting a glycidic acid derivative of the general formula II in which Z represents the groups -OX, -OR6 or -N (R2) 2, where R6 denotes a C1-C4-alkyl radical and the two radicals R2 are the same or different, with ammonia or one of the amines of the general formulas IIIa or IIIb and subsequent hydrolysis of carboxylic acid amide or carboxylic ester groups still present.
  • Glycidic acid derivatives II which can be used are, for example, glycidic acid, optionally in the form of its sodium, potassium or ammonium salt, glycidic acid amide, N-methylglycidic acid amide, N, N-dimethylglycidic acid amide, glycidic acid methyl ester or glycidic acid ethyl ester. The best results are achieved with glycidamide.
  • Examples of primary amines IIIa are glycine, aspartic acid, serine, 2-methylserine, 2- (hydroxymethyl) serine, 1-amino-2-hydroxysuccinic acid, ethanolamine, ethanolamine methyl ether, ethanolamine (2-hydroxyethyl) ether, sorbitylamine, glycopyranosylamine, glusofuranosylamine, polyvinylamine , 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and 2-hydroxypropane-1,3-diamine.
  • secondary amines IIIb examples include sarcosine, iminodisuccinic acid, iminodi (2-hydroxysuccinic acid), ethanolaminoacetic acid, diethanolamine, disorbitylamine and polyethyleneimine.
  • glycine aspartic acid, ethanolamine, ethanolaminoacetic acid, diethanolamine and sarcosine are preferred.
  • Polyamines with primary and secondary amino functions such as diethylenetriamine and triethylenetetramine can also be used.
  • the carboxyl groups present in part in the amines mentioned above can also occur in the form of the alkali metal or the optionally substituted ammonium salts.
  • the reaction of the glycidic acid derivative II with ammonia or an amine IIIa or IIIb is generally carried out in water, an organic solvent such as methanol, ethanol, n-propanol, isopropanol, tert-butanol, dioxane or tetrahydrofuran or in mixtures of these solvents at temperatures from 10 to 100 ° C, preferably 40 to 80 o C, and a pH value of 4 to 10, preferably 6 to 9, carried out.
  • an organic solvent such as methanol, ethanol, n-propanol, isopropanol, tert-butanol, dioxane or tetrahydrofuran or in mixtures of these solvents at temperatures from 10 to 100 ° C, preferably 40 to 80 o C, and a pH value of 4 to 10, preferably 6 to 9, carried out.
  • the molar ratio of II to ammonia or amine is usually 2.8: 1 to 3.7: 1, in particular 3.0. : 1 to 3.3: 1, for ammonia, 1.8: 1 to 2.7: 1, in particular 2.0: 1 to 2.3: 1, for primary amines IIIa and 0.8: 1 to 1, 5: 1, in particular 1.0: 1 to 1.2: 1, in the case of secondary amines IIIb; the ratios given each relate to an amino group in the compound IIIa or IIIb.
  • the reaction is followed by hydrolysis of carboxylic acid amide and carboxylic ester groups still present to give carboxyl groups which, in a manner known per se, in an aqueous reaction medium in the presence of bases such as sodium or potassium hydroxide solution or of acids such as sulfuric or hydrochloric acid, generally at temperatures of 20 up to 110 ° C, in particular 40 to 100 o C, is carried out.
  • bases such as sodium or potassium hydroxide solution or of acids such as sulfuric or hydrochloric acid
  • compounds I and Ia are obtained as free carboxylic acids or in the form of salts, usually as alkali metal salts.
  • the desired salts I or Ia can then be prepared from the free acids without difficulty by neutralization with the appropriate bases, for example amine bases.
  • the compounds I and Ia can be isolated from their solutions in pure form without any problems. Spray or freeze drying, crystallization and precipitation are particularly suitable for this. The solutions can often also be used directly for the purposes of the invention.
  • the compounds I are outstandingly suitable for complexing heavy metal or alkaline earth metal ions such as iron, copper, manganese, zinc, calcium or magnesium or mixtures of such ions. Because of this ability, they have a variety of technical applications. Since the compounds I are biodegradable substances, they can be used advantageously wherever wastewater is produced in large quantities during use and must first be treated before it reaches the surface waters.
  • Areas of use and uses include, for example, detergents and cleaning agents for the household, industrial cleaning agents, electroplating technology, water treatment and polymerizations, the photographic industry, the textile industry and the paper industry, and various applications in pharmaceuticals, cosmetics, foodstuffs and in Plant nutrition into consideration.
  • a bleach stabilization for example for sodium perborates such as NaBO2 ⁇ H2O2 ⁇ 3 H2O, peroxycarbonates, peroxyphosphonates, citrate perhydrates, urea and melamine-H2O2 adducts, caroates, perbenzoates, alkane dipercarboxylic acids, peroxyphthalates and detergents and alkali metal acetates and detergents in the hydrogen peroxide bleaching of textiles, cellulose or paper raw materials.
  • Traces of heavy metals such as iron, copper and manganese occur in the washing powder itself, in the water and in the textile goods and catalyze the decomposition of the per compound or the hydrogen peroxide resulting from it.
  • the complexing agents I bind these metal ions and prevent the undesired decomposition of the bleaching system during storage and in the wash liquor. This increases the efficiency of the bleaching system and fiber damage is suppressed.
  • the compounds I can be used as so-called preservatives, advantageously in an amount of 0.05 to 1% by weight, based on the total weight of the detergent formulation.
  • the compounds I prevent, for example, metal-catalyzed oxidative decomposition.
  • They can be used to stabilize phosphates in alkaline degreasing baths and prevent the precipitation of lime soaps and thereby prevent the "tarnishing" of non-ferrous surfaces and extend the service life of alkaline cleaning baths.
  • the cooling water treatment with the compounds I prevents deposits or dissolves existing ones.
  • a particular advantage is the possibility of application in an alkaline medium and thus the elimination of corrosion problems.
  • the complexing agents I can be used in developer or fixing 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 haze on films and images, as well as deposits in the tanks, which can thus advantageously be avoided.
  • They can be used as iron III chelate solutions can be used advantageously in bleaching and bleach-fixing baths and thus replace the hexacyanoferrate solutions, which are questionable for ecological reasons.
  • copper, iron, manganese and zinc complexes with I can be used to remedy heavy metal deficits. These heavy metals are added as chelates to prevent precipitation as biologically inactive insoluble salts.
  • flue gas scrubbing namely the simultaneous removal of NO x and SO2 from flue gases, desulfurization according to Wellman-Lord, H2S oxidation, metal extraction and applications as catalysts for organic syntheses, for example air oxidation of paraffins and Hydroformylation of olefins to alcohols.
  • the compounds I with their excellent complex-forming properties, can be recommended to a very special extent as bleach stabilizers and as builders in detergents and cleaning agents in the fields of application mentioned.
  • the present invention also relates to compositions for complexing heavy metal or alkaline earth metal ions or mixtures thereof which, depending on the intended use, contain the compounds Ia in an amount of 0.01 to 99% by weight, based on the total amount of the preparations.
  • the present invention furthermore relates to detergents and cleaning agents which are 0.01 to 20% by weight, preferably 0.05 to 10% by weight referred to the total amount of preparation, one or more of the compounds I included.
  • detergents and cleaning agents which are 0.01 to 20% by weight, preferably 0.05 to 10% by weight referred to the total amount of preparation, one or more of the compounds I included.
  • amounts from 1 to 10% by weight are preferred
  • amounts from 0.05 to 1% by weight are particularly preferred.
  • amounts of 0.1 to 2% by weight are preferred.
  • the compounds I in their capacity as complexing agents, builders and bleach stabilizers in detergent and cleaning agent formulations, can also be used together with other agents of the prior art, the general properties with respect to sequestration, incrustation inhibition, graying inhibition, primary washing action and bleaching action, under certain circumstances, significantly improved can be.
  • Detergent and cleaning agent formulations with the compounds I generally contain, as additional constituents, based on the total weight, 6 to 25% by weight of surfactants, 15 to 50% by weight of builders and optionally co-builders and 5 to 30% by weight. % Auxiliaries such as enzymes, foam regulators, corrosion inhibitors, optical brighteners, fragrances, dyes or formulation aids such as Sodium sulfate in the usual amounts for this.
  • the 2-hydroxy-3-aminopropionic acid derivatives I are excellent complexing agents. In their capacity as builders in sweeteners and cleaning agents to improve the whitening effect and to prevent deposits on the fabric, the compounds I are comparable to, for example, ethylenediaminetetraacetic acid or 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid. However, bleach stabilization shows a clearly superior effect compared to the prior art agents mentioned.
  • the pH of the reaction solution was kept between 8 and 8.5 by adding a further 88 g of 50% strength by weight sodium hydroxide solution. Then was 30 minutes at 50 ° C and then 3 hours at 80 ° C. stirred. After adding a further 100 g of 50% strength by weight sodium hydroxide solution, the solution was then stirred at 80 ° C. for 2 hours and then at 100 ° C. for 1.5 hours, during which the ammonia formed outgassed.
  • the resulting solution was spray-dried and the light brown powder thus obtained was recrystallized from a water-methanol mixture.
  • the title compound was obtained in the form of a colorless crystal powder with a melting point> 280 ° C. in a yield of 74%.
  • This compound was prepared analogously to Example 1 by reacting aspartic acid with glycidamide in a molar ratio of 1: 2.2 in a yield of 55%. After recrystallization, it had a melting point of 125 ° C. (with decomposition).
  • This compound was prepared analogously to Example 1 by reacting serine with glycidamide in a molar ratio of 1: 2.2 in a yield of 57%. After recrystallization, it had a melting point of 120 ° C. (with decomposition).
  • This compound was prepared analogously to Example 2 by reacting ethanolamine with glycidamide. It is known from the literature reference (1).
  • This compound was prepared analogously to Example 2 by reacting ammonia with glycidamide. It is known from the literature reference (1).
  • This compound was prepared analogously to Example 1 by reacting equimolar amounts of sarcosine with glycidamide in a yield of 94%. After recrystallization, it had a melting point of> 310 o C.
  • the hydrogen peroxide responsible for the bleaching effect in detergent formulations containing sodium peroxide is catalytically decomposed by heavy metal ions (Fe, Cu, Mn) primarily in the wash liquor, but also when stored dry. This decomposition process can be prevented or at least delayed by complexing the heavy metal ions.
  • the peroxide-stabilizing effect of the complexing agents is checked for a certain period of time via the residual peroxide content after leaving a wash liquor containing heavy metals at a higher temperature.
  • the hydrogen peroxide content was determined immediately after preparation and after leaving the wash liquor at 60 ° C. or 80 ° C. for 2 or 1 hour by titration with potassium permanganate in acid solution. As a result, the percentage of H2O2 still present after this period was given in the table below.
  • the test was carried out in such a way that a solution of 6.5 g / l of the formulation (1) in water of hardness 25 ° dH was heated to 80 ° C. and for test purposes with 2.5 ppm of a mixture of the ions Fe3+, Cu2+ and Mn2+ in the ratio 8: 1: 1, used in the form of their sulfates, was added.
  • a solution of 6.5 g / l of the formulation (1) in water of hardness 25 ° dH was heated to 80 ° C. and for test purposes with 2.5 ppm of a mixture of the ions Fe3+, Cu2+ and Mn2+ in the ratio 8: 1: 1, used in the form of their sulfates, was added.
  • the H2O2 content was measured before adding heavy metals and after leaving the wash liquor at 80 ° C for 2 hours.
  • the following table shows the results of the tests, the 2-hydroxy-3-aminopropionic acid derivatives I in their sodium salt form from Examples 1 to 6 having ethylenediaminetetraacetic acid tetrasodium salt (EDTA-Na4) and 2-hydroxy-3-aminopropionic acid N, N-diacetic acid trisodium salt (ISDA-Na3) according to reference (2) were compared.
  • the values illustrate the superior effect of compounds I.

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Abstract

The use of 2-hydroxy-3-aminopropionic acid derivatives of the general formula I …<IMAGE>… in which X is hydrogen, an alkali metal or ammonium which can be substituted by C1-C4-alkyl groups or C1-C4-hydroxyalkyl groups, and in which the groups Y<1> and Y<2> have the following meanings … …  A) omega -substituted alkyl groups of the general formula… -(CH2)m-R<1>… in which R<1> is hydrogen, a hydroxyl group or the groups -COOX, -NH-CH(COOX)-CH2-COOX or -NY<1>Y<2>, and m has values from 1 to 20, with the exception of the value m = 1 in the case where Y<1> and Y<2> are identical and R<1> is the group -COOX, …  B) polyether groups of the general formula… -(CH2CH2O)m-R<2>… in which R<2> is hydrogen or a C1-C4-alkyl group, …  C) beta -hydroxy-substituted groups of the general formula …<IMAGE>… in which R<3> is the groups -COOX, -CH2OH and -CH2-NY<1>Y<2> and n has values from 1 to 5, …  D) alpha -carboxy-substituted groups of the general formula …<IMAGE>… in which R<4> is hydrogen, a methyl group or a hydroxymethyl group, and R<5> is a hydroxymethyl group or the groups -CH(OH)-COOX or -(CH2)p-COOX where p is 1 or 2, …  E) pyranosyl or furanosyl groups of the general formula …<IMAGE>… in which q has the value 3 or 2, or …  F) polymer residues of polyvinylamine or polyethyleneimine as complexing agents, bleach stabilisers and builders in detergents and cleaners. …

Description

Die vorliegende Erfindung betrifft die Verwendung von 2-Hydroxy-3-amino­propionsäure-Derivaten der allgemeinen Formel I

Figure imgb0001
in der X für Wasserstoff, ein Alkalimetall oder Ammonium, das durch C₁-C₄-­Alkylgruppen oder C₁-C₄-Hydroxyalkylgruppen substituiert sein kann, steht und in der die Gruppen Y¹ und Y² folgende Bedeutungen haben

  • A) ω-substituierte Alkylgruppen der allgemeinen Formel
    -(CH₂)m-R¹
    in der R¹ Wasserstoff, eine Hydroxylgruppe oder die Gruppen -COOX, -NH-CH(COOX)-CH₂-COOX oder -NY¹Y² bezeichnet und m Werte von 1 bis 20 hat, mit Ausnahme des Wertes m = 1 für den Fall, daß Y¹ und Y² gleich sind und R¹ die Gruppe -COOX bedeutet,
  • B) Polyethergruppen der allgemeinen Formel
    -(CH₂CH₂O)m-R²
    in der R² Wasserstoff oder eine C₁-C₄-Alkylgruppe bedeutet,
  • C) β-hydroxysubstituierte Gruppen der allgemeinen Formel
    Figure imgb0002
     in der R³ für die Gruppen -COOX, -CH₂OH und -CH₂-NY¹Y² steht und n Werte von 1 bis 5 hat,
  • D) α-carboxysubstituierte Gruppen der allgemeinen Formel
    Figure imgb0003
     in der R⁴ Wasserstoff, eine Methylgruppe oder eine Hydroxymethylgruppe bezeichnet und R⁵ eine Hydroxymethylgruppe oder die Gruppen -CH(OH)-COOX oder -(CH₂)p-COOX bedeutet, wobei p 1 oder 2 ist,
  • E) Pyranosyl- oder Furanosylgruppen der allgemeinen Formel
    Figure imgb0004
     in der q den Wert 3 oder 2 hat, oder
  • F) Polymerreste von Polyvinylamin oder Polyethylenimin
als Komplexbildner, Bleichmittelstabilisatoren und Gerüststoffe in Wasch- und Reinigungsmitteln. Außerdem betrifft die Erfindung Wasch- und Reinigungsmittel, die die Verbindungen I enthalten.The present invention relates to the use of 2-hydroxy-3-aminopropionic acid derivatives of the general formula I.
Figure imgb0001
 in which X represents hydrogen, an alkali metal or ammonium, which can be substituted by C₁-C₄-alkyl groups or C₁-C₄-hydroxyalkyl groups, and in which the groups Y¹ and Y² have the following meanings
  • A) ω-substituted alkyl groups of the general formula
    - (CH₂) m -R¹
    in which R¹ denotes hydrogen, a hydroxyl group or the groups -COOX, -NH-CH (COOX) -CH₂-COOX or -NY¹Y² and m has values from 1 to 20, with the exception of the value m = 1 for the case that Y¹ and Y² are the same and R¹ represents the group -COOX,
  • B) polyether groups of the general formula
    - (CH₂CH₂O) m -R²
    in which R² is hydrogen or a C₁-C₄ alkyl group,
  • C) β-hydroxy-substituted groups of the general formula
    Figure imgb0002
     in which R³ represents the groups -COOX, -CH₂OH and -CH₂-NY¹Y² and n has values from 1 to 5,
  • D) α-carboxy-substituted groups of the general formula
    Figure imgb0003
     in which R⁴ denotes hydrogen, a methyl group or a hydroxymethyl group and R⁵ denotes a hydroxymethyl group or the groups -CH (OH) -COOX or - (CH₂) p -COOX, where p is 1 or 2,
  • E) Pyranosyl or furanosyl groups of the general formula
    Figure imgb0004
     in which q has the value 3 or 2, or
  • F) polymer residues of polyvinylamine or polyethyleneimine
as complexing agents, bleach stabilizers and builders in washing and cleaning agents. The invention also relates to detergents and cleaning agents which contain the compounds I.

Die Verbindungen I sind zum Teil neue Stoffe. Deshalb betrifft die Erfin­dung weiterhin diese neuen Verbindungen, ein Verfahren zu ihrer Herstel­lung, ihre Verwendung als Komplexbildner für Schwermetall- oder Erdalkali­metallionen sowie die sie enthaltenden Komplexierungsmittel.Some of the compounds I are new substances. Therefore, the invention further relates to these new compounds, a process for their preparation, their use as complexing agents for heavy metal or alkaline earth metal ions and the complexing agents containing them.

Die DE-A 21 03 453 (1) betrifft α-Hydroxy-β-aminocarbonsäuren der allgemeinen Formel IV

Figure imgb0005
in der R⁷ und R⁸ jeweils einen aliphatischen, cycloaliphatischen oder araliphatischen Rest bedeuten, wobei R⁷ und R⁸ aber keine Methylgruppe bezeichnen und darüber hinaus unter anderem auch Wasserstoff, Alkylol­gruppen oder den Rest -CH₂-CH(OH)-COOH bedeuten. Weiterhin kann einer der Reste R⁷ oder R⁸ eine zweite substituierte Aminogruppe -NR⁷R⁸ tragen. Die Verbindungen IV dienen zur Maskierung von Metallionen, insbesondere von Schwermetallkationen, durch Komplexierung in wäßriger Lösung.DE-A 21 03 453 (1) relates to α-hydroxy-β-aminocarboxylic acids of the general formula IV
Figure imgb0005
 in which R⁷ and R⁸ each represent an aliphatic, cycloaliphatic or araliphatic radical, but R⁷ and R⁸ denote no methyl group and also mean, inter alia, hydrogen, alkylol groups or the radical -CH₂-CH (OH) -COOH. Furthermore, one of the radicals R⁷ or R⁸ can carry a second substituted amino group -NR⁷R⁸. The compounds IV serve to mask metal ions, in particular heavy metal cations, by complexing in aqueous solution.

In der DE-A 37 12 330 (2) werden 2-Hydroxy-3-aminopropionsäure-N,N-di­essigsäure und ihre Derivate der allgemeinen Formel V beschrieben

(Y₅-CH₂)₂N-CH₂-

Figure imgb0006
-COZ      V
in der Y⁵ unter anderem für den Rest -COOX steht und z die Gruppe -OX, -OR⁶ oder -N(R²)₂ bedeutet, wobei R⁶ einen C₁-C₄-Alkylrest bezeichnet. Die Verbindungen V werden als Komplexbildner für Schwermetall- und Erdalkali­metallionen sowie als Bleichmittelstabilisatoren und Gerüststoffe in Wasch- und Reinigungsmitteln empfohlen. Allerdings läßt ihre bleichmittel­stabilisierende Wirkung zu wünschen übrig.DE-A 37 12 330 (2) describes 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid and its derivatives of the general formula V.

(Y₅-CH₂) ₂N-CH₂-
Figure imgb0006
-COZ V
in which Y⁵ is, inter alia, the radical -COOX and z is the group -OX, -OR⁶ or -N (R²) ₂, where R⁶ denotes a C₁-C₄-alkyl radical. The compounds V are recommended as complexing agents for heavy metal and alkaline earth metal ions and as bleach stabilizers and builders in detergents and cleaning agents. However, their bleach stabilizing effect leaves something to be desired.

Aufgabe der vorliegenden Erfindung war es deshalb, als Bleichmittel­stabilisatoren besser geeignete Komplexbildner bereitzustellen.The object of the present invention was therefore to provide complexing agents which are more suitable as bleach stabilizers.

Demgemäß wurde die Verwendung der eingangs definierten 2-Hydroxy-3-amino­propionsäure-Derivate I als Komplexbildner, Bleichmittelstabilisatoren und Gerüststoffe in Wasch- und Reinigungsmitteln gefunden.We have found that this object is achieved by using the 2-hydroxy-3-aminopropionic acid derivatives I defined at the outset as complexing agents, bleach stabilizers and builders in detergents and cleaning agents.

Die Verbindungen I können als freie Carbonsäuren (X = H) oder in einer partiellen (beim Vorliegen mehrerer Carboxylgruppen) oder vollständigen Salzform auftreten. Im letzteren Fall steht X dann für Alkalimetallionen wie Lithium oder insbesondere Natrium oder Kalium oder für das Ammonium­ion, das partiell oder vollständig durch C₁-C₄-Alkylgruppen oder C₁-C₄-­Hydroxyalkylgruppen substituiert sein kann. Insbesondere sind hier die Salze von tertiären Aminen zu nennen. Bevorzugte tertiäre Amine sind Trimethylamin, Triethylamin, Tri-n-propylamin, Triisopropylamin, Tri-n-butylamin, Triisobutylamin sowie Trialkanolamine wie Triethanolamin oder Triisopropanolamin.The compounds I can occur as free carboxylic acids (X = H) or in a partial (if several carboxyl groups are present) or complete salt form. In the latter case, X then stands for alkali metal ions such as lithium or in particular sodium or potassium or for the ammonium ion, which can be partially or completely substituted by C₁-C₄-alkyl groups or C₁-C₄-hydroxyalkyl groups. In particular, the salts of tertiary amines should be mentioned here. Preferred tertiary amines are trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine and trialkanolamines such as triethanolamine or triisopropanolamine.

Die Gruppen Y¹ und Y² haben folgende Bedeutungen:

  • A) ω-substituierte Alkylgruppen der allgemeinen Formel
    -(CH₂)m-R¹
    in der R¹ vor allem Wasserstoff, eine Hydroxylgruppe oder die Gruppe -COOX, daneben aber auch die Gruppen -NH-CH(COOX)-CH₂-COOX oder -NY¹Y² bezeichnet und m Werte von 1 bis 20, vorzugsweise 1 bis 6, hat, mit Ausnahme des Wertes m = 1 für den Fall, daß Y¹ und Y² gleich sind und R¹ die Gruppe -COOX bedeutet; als Beispiel für die Gruppe -NY¹Y² ist der Rest
    Figure imgb0007
     zu nennen;
  • B) Polyethergruppen der allgemeinen Formel
    -(CH₂CH₂O)m-R²
    in der R² Wasserstoff oder eine C₁-C₄-Alkylgruppe, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl oder n-Butyl, bedeutet;
  • C) β-hydroxysubstituierte Gruppen der allgemeinen Formel
    Figure imgb0008
     in der R³ für vor allem die Gruppen -COOX und -CH₂OH, daneben aber auch für die Gruppe -CH₂-NY¹Y² steht und n Werte von 1 bis 5 hat; bevorzugte Werte für n sind 1 und 4;
  • D) α-carboxysubstituierte Gruppen der allgemeinen Formel
    Figure imgb0009
     in der R⁴ Wasserstoff, eine Methylgruppe oder eine Hydroxymethylgruppe bezeichnet und R⁵ eine Hydroxymethylgruppe oder die Gruppen -CH(OH)-COOX oder -(CH₂)p-COOX bedeutet, wobei p 1 oder 2 ist;
  • E) Pyranosyl- oder Furanosylgruppen der allgemeinen Formel
    Figure imgb0010
     in der q den Wert 3 oder 2 hat; bevorzugte Gruppen sind der Gluco­pyranosyl-Rest (q = 3) und der Glucofuranosyl-Rest (q = 2); oder
  • F) Polymerreste von Polyvinylamin oder Polyethylenimin.
The groups Y¹ and Y² have the following meanings:
  • A) ω-substituted alkyl groups of the general formula
    - (CH₂) m -R¹
    in which R¹ is especially hydrogen, a hydroxyl group or the group -COOX, but also the groups -NH-CH (COOX) -CH₂-COOX or -NY¹Y² and m has values from 1 to 20, preferably 1 to 6, except for the value m = 1 when Y¹ and Y² are the same and R¹ is -COOX; the rest is an example of the group -NY¹Y²
    Figure imgb0007
     to call;
  • B) polyether groups of the general formula
    - (CH₂CH₂O) m -R²
    in which R² is hydrogen or a C₁-C₄ alkyl group, for example methyl, ethyl, n-propyl, iso-propyl or n-butyl;
  • C) β-hydroxy-substituted groups of the general formula
    Figure imgb0008
     in which R³ is mainly the groups -COOX and -CH₂OH, but also the group -CH₂-NY¹Y² and n has values from 1 to 5; preferred values for n are 1 and 4;
  • D) α-carboxy-substituted groups of the general formula
    Figure imgb0009
     in which R⁴ denotes hydrogen, a methyl group or a hydroxymethyl group and R⁵ denotes a hydroxymethyl group or the groups -CH (OH) -COOX or - (CH₂) p -COOX, where p is 1 or 2;
  • E) Pyranosyl or furanosyl groups of the general formula
    Figure imgb0010
     in which q has the value 3 or 2; preferred groups are the glucopyranosyl residue (q = 3) and the glucofuranosyl residue (q = 2); or
  • F) polymer residues of polyvinylamine or polyethyleneimine.

Besonders bevorzugt werden für die Gruppen Y¹ und Y² die Bedeutungen A, C und D.The meanings A, C and D are particularly preferred for the groups Y 1 and Y 2.

Gegenstand der vorliegenden Anmeldung sind weiterhin 2-Hydroxy-3-amino­propionsäure-Derivate der allgemeinen Formel Ia

Figure imgb0011
in der X für Wasserstoff, ein Alkalimetall oder Ammonium, das durch C₁-C₄-Alkylgruppen oder C₁-C₄-Hydroxyalkylgruppen substituiert sein kann, steht und in der die Gruppen Y³ und Y⁴ folgende Bedeutungen haben:

  • A) ω-substituierte Alkylgruppen der allgemeinen Formel
    -(CH₂)m-R⁹
    in der R⁹ die Gruppen -COOX, -NH-CH(COOX)-CH₂-COOX oder -NY³Y⁴ oder für den Fall, daß m den Wert 1 hat, Wasserstoff bezeichnet und m Werte von 1 bis 20 hat, mit Ausnahme des Wertes m = 1 für den Fall, daß Y³ und Y⁴ gleich sind und R⁹ die Gruppe -COOX bedeutet,
  • B) Polyethergruppen der allgemeinen Formel
    -(CH₂CH₂O)m-R²
    in der R² Wasserstoff oder eine C₁-C₄-Alkylgruppe bedeutet,
  • C) β-hydroxysubstituierte Gruppen der allgemeinen Formel
    Figure imgb0012
     in der R¹⁰ für die Gruppen -COOX, -CH₂OH und -CH₂-NY³Y⁴ steht und n Werte von 1 bis 5 hat, mit Ausnahme des Wertes n = 1 für den Fall, daß Y³ und Y⁴ gleich sind und R¹⁰ die Gruppe -COOX bedeutet,
  • D) α-carboxysubstituierte Gruppen der allgemeinen Formel
    Figure imgb0013
     in der R⁴ Wasserstoff, eine Methylgruppe oder eine Hydroxymethylgruppe bezeichnet und R⁵ eine Hydroxymethylgruppe oder die Gruppen -CH(OH)-COOX oder -(CH₂)p-COOX bedeutet, wobei p 1 oder 2 ist,
  • E) Pyranosyl- oder Furanosylgruppen der allgemeinen Formel
    Figure imgb0014
     in der q den Wert 3 oder 2 hat, oder
  • F) Polymerreste von Polyvinylamin oder Polyethylenimin.
The present application also relates to 2-hydroxy-3-aminopropionic acid derivatives of the general formula Ia
Figure imgb0011
 in which X represents hydrogen, an alkali metal or ammonium, which can be substituted by C₁-C₄-alkyl groups or C₁-C₄-hydroxyalkyl groups, and in which the groups Y³ and Y⁴ have the following meanings:
  • A) ω-substituted alkyl groups of the general formula
    - (CH₂) m -R⁹
    in the R⁹ the groups -COOX, -NH-CH (COOX) -CH₂-COOX or -NY³Y⁴ or in the case where m is 1, denotes hydrogen and m has values from 1 to 20, with the exception of the value m = 1 in the event that Y³ and Y⁴ are the same and R⁹ is the group -COOX,
  • B) polyether groups of the general formula
    - (CH₂CH₂O) m -R²
    in which R² is hydrogen or a C₁-C₄ alkyl group,
  • C) β-hydroxy-substituted groups of the general formula
    Figure imgb0012
     in which R¹⁰ represents the groups -COOX, -CH₂OH and -CH₂-NY³Y⁴ and n has values from 1 to 5, with the exception of the value n = 1 in the case where Y³ and Y⁴ are the same and R¹⁰ represents the group -COOX ,
  • D) α-carboxy-substituted groups of the general formula
    Figure imgb0013
     in which R⁴ denotes hydrogen, a methyl group or a hydroxymethyl group and R⁵ denotes a hydroxymethyl group or the groups -CH (OH) -COOX or - (CH₂) p -COOX, where p is 1 or 2,
  • E) pyranosyl or furanosyl groups of the general formula
    Figure imgb0014
     in which q has the value 3 or 2, or
  • F) polymer residues of polyvinylamine or polyethyleneimine.

Die Verbindungen Ia, welche eine Untergruppe der Verbindungen I darstellen, sind neu.The compounds Ia, which are a subgroup of the compounds I, are new.

Die Verbindungen I und insbesondere die Verbindungen Ia werden zweck­mäßigerweise durch Umsetzung eines Glycidsäurederivates der allgemeinen Formel II

Figure imgb0015
in der Z für die Gruppen -OX, -OR⁶ oder -N(R²)₂ steht, wobei R⁶ einen C₁-C₄-Alkylrest bezeichnet und die beiden Reste R² gleich oder verschieden sind, mit Ammoniak oder einem der Amine der allgemeinen Formeln IIIa oder IIIb
Figure imgb0016
 und anschließende Hydrolyse noch vorhandener Carbonsäureamid- oder Carbonsäureestergruppen hergestellt.The compounds I and especially the compounds Ia are expediently reacted by reacting a glycidic acid derivative of the general formula II
Figure imgb0015
 in which Z represents the groups -OX, -OR⁶ or -N (R²) ₂, where R⁶ denotes a C₁-C₄-alkyl radical and the two radicals R² are the same or different, with ammonia or one of the amines of the general formulas IIIa or IIIb
Figure imgb0016
 and subsequent hydrolysis of carboxylic acid amide or carboxylic ester groups still present.

Als Glycidsäurederivate II können beispielsweise Glycidsäure, gegebenen­falls in Form ihres Natrium-, Kalium- oder Ammoniumsalzes, Glycidsäure­amid, N-Methylglycidsäureamid, N,N-Dimethylglycidsäureamid, Glycidsäure­methylester oder Glycidsäureethylester verwendet werden. Die besten Ergebnisse erzielt man mit Glycidsäureamid.Glycidic acid derivatives II which can be used are, for example, glycidic acid, optionally in the form of its sodium, potassium or ammonium salt, glycidic acid amide, N-methylglycidic acid amide, N, N-dimethylglycidic acid amide, glycidic acid methyl ester or glycidic acid ethyl ester. The best results are achieved with glycidamide.

Beispiele für primäre Amine IIIa sind Glycin, Asparaginsäure, Serin, 2-­Methylserin, 2-(Hydroxymethyl)serin, 1-Amino-2-hydroxybernsteinsäure, Eth­anolamin, Ethanolaminmethylether, Ethanolamin(2-hydroxyethyl)ether, Sor­bitylamin, Glycopyranosylamin, Glusofuranosylamin, Polyvinylamin, 1,2-­Ethylendiamin, 1,3-Propylendiamin, 1,4-Butylendiamin und 2-Hydroxypropan-­1,3-diamin.Examples of primary amines IIIa are glycine, aspartic acid, serine, 2-methylserine, 2- (hydroxymethyl) serine, 1-amino-2-hydroxysuccinic acid, ethanolamine, ethanolamine methyl ether, ethanolamine (2-hydroxyethyl) ether, sorbitylamine, glycopyranosylamine, glusofuranosylamine, polyvinylamine , 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and 2-hydroxypropane-1,3-diamine.

Beispiele für sekundäre Amine IIIb sind Sarkosin, Iminodibernsteinsäure, Iminodi(2-hydroxybernsteinsäure), Ethanolaminoessigsäure, Diethanolamin, Disorbitylamin und Polyethylenimin.Examples of secondary amines IIIb are sarcosine, iminodisuccinic acid, iminodi (2-hydroxysuccinic acid), ethanolaminoacetic acid, diethanolamine, disorbitylamine and polyethyleneimine.

Von den genannten Aminen IIIa und IIIb werden Glycin, Asparaginsäure, Ethanolamin, Ethanolaminoessigsäure, Diethanolamin und Sarkosin bevorzugt.Of the amines IIIa and IIIb mentioned, glycine, aspartic acid, ethanolamine, ethanolaminoacetic acid, diethanolamine and sarcosine are preferred.

Es können auch Polyamine mit primären und sekundären Aminofunktionen wie Diethylentriamin und Triethylentetramin eingesetzt werden.Polyamines with primary and secondary amino functions such as diethylenetriamine and triethylenetetramine can also be used.

Die in den oben genannten Aminen zum Teil vorhandenen Carboxylgruppen können auch in Form der Alkalimetall- oder der gegebenenfalls substituier­ten Ammoniumsalze auftreten.The carboxyl groups present in part in the amines mentioned above can also occur in the form of the alkali metal or the optionally substituted ammonium salts.

Die Umsetzung des Glycidsäurederivates II mit Ammoniak oder einem Amin IIIa oder IIIb wird in der Regel in Wasser, einem organischen Lösungsmittel wie Methanol, Ethanol, n-Propanol, iso-Propanol, tert.­Butanol, Dioxan oder Tetrahydrofuran oder in Mischungen dieser Lösungs­mittel bei Temperaturen von 10 bis 100°C, vorzugsweise 40 bis 80oC, und einem pH-Wert von 4 bis 10, vorzugsweise 6 bis 9, vorgenommen.The reaction of the glycidic acid derivative II with ammonia or an amine IIIa or IIIb is generally carried out in water, an organic solvent such as methanol, ethanol, n-propanol, isopropanol, tert-butanol, dioxane or tetrahydrofuran or in mixtures of these solvents at temperatures from 10 to 100 ° C, preferably 40 to 80 o C, and a pH value of 4 to 10, preferably 6 to 9, carried out.

Das Molverhältnis von II zu Ammoniak bzw. Amin beträgt üblicherweise 2,8 : 1 bis 3,7 : 1, insbesondere 3,0. : 1 bis 3,3 : 1, bei Ammoniak, 1,8 : 1 bis 2,7 : 1, insbesondere 2,0 : 1 bis 2,3 : 1, bei primären Aminen IIIa und 0,8 : 1 bis 1,5 : 1, insbesondere 1,0 : 1 bis 1,2 : 1, bei sekundären Aminen IIIb; die angegebenen Verhältnisse beziehen sich jeweils auf eine Aminogruppe in der Verbindung IIIa oder IIIb.The molar ratio of II to ammonia or amine is usually 2.8: 1 to 3.7: 1, in particular 3.0. : 1 to 3.3: 1, for ammonia, 1.8: 1 to 2.7: 1, in particular 2.0: 1 to 2.3: 1, for primary amines IIIa and 0.8: 1 to 1, 5: 1, in particular 1.0: 1 to 1.2: 1, in the case of secondary amines IIIb; the ratios given each relate to an amino group in the compound IIIa or IIIb.

An die Umsetzung schließt sich eine Hydrolyse noch vorhandener Carbon­säureamid- und Carbonsäureestergruppen zu Carboxylgruppen an, welche in an sich bekannter Weise in wäßrigem Reaktionsmedium in Gegenwart von Basen wie Natron- oder Kalilauge oder von Säuren wie Schwefel- oder Salzsäure in der Regel bei Temperaturen von 20 bis 110°C, insbesondere 40 bis 100oC, durchgeführt wird.The reaction is followed by hydrolysis of carboxylic acid amide and carboxylic ester groups still present to give carboxyl groups which, in a manner known per se, in an aqueous reaction medium in the presence of bases such as sodium or potassium hydroxide solution or of acids such as sulfuric or hydrochloric acid, generally at temperatures of 20 up to 110 ° C, in particular 40 to 100 o C, is carried out.

Entsprechend den Reaktionsbedingungen erhält man die Verbindungen I bzw. Ia als freie Carbonsäuren oder in Form von Salzen, üblicherweise als Alkalimetallsalze. Aus den freien Säuren können dann durch Neutralisation mit den entsprechenden Basen, beispielsweise Aminbasen, die gewünschten Salze I bzw. Ia ohne Schwierigkeiten hergestellt werden.Depending on the reaction conditions, compounds I and Ia are obtained as free carboxylic acids or in the form of salts, usually as alkali metal salts. The desired salts I or Ia can then be prepared from the free acids without difficulty by neutralization with the appropriate bases, for example amine bases.

Die Verbindungen I bzw. Ia lassen sich aus ihren Lösungen problemlos in reiner Form isolieren. Hierfür bieten sich insbesondere Sprüh- oder Gefriertrocknung, Kristallisation und Fällung an. Häufig lassen sich die Lösungen auch unmittelbar für die erfindungsgemäßen Zwecke verwenden.The compounds I and Ia can be isolated from their solutions in pure form without any problems. Spray or freeze drying, crystallization and precipitation are particularly suitable for this. The solutions can often also be used directly for the purposes of the invention.

Die Verbindungen I sind in hervorragender Weise dazu geeignet, Schwer­metall- oder Erdalkalimetallionen wie beispielsweise Eisen, Kupfer, Mangan, Zink, Calcium oder Magnesium oder Gemische solcher Ionen zu komplexieren. Aufgrund dieser Fähigkeit weisen sie eine Vielzahl von technischen Anwendungsmöglichkeiten auf. Da es sich bei den Verbindungen I um biologisch abbaubare Substanzen handelt, können sie überall dort vor­teilhaft eingesetzt werden, wo bei der Anwendung Abwasser in größeren Mengen anfällt und erst behandelt werden muß, bevor es in die Oberflächen­gewässer gelangt.The compounds I are outstandingly suitable for complexing heavy metal or alkaline earth metal ions such as iron, copper, manganese, zinc, calcium or magnesium or mixtures of such ions. Because of this ability, they have a variety of technical applications. Since the compounds I are biodegradable substances, they can be used advantageously wherever wastewater is produced in large quantities during use and must first be treated before it reaches the surface waters.

Als Einsatzgebiete und Verwendungszwecke kommen beispielsweise Wasch- und Reinigungsmittel für den Haushalt, industrielle Reinigungsmittel, die Gal­vanotechnik, die Wasserbehandlung und die Polymerisationen, die photo­graphische Industrie, die Textilindustrie und die Papierindustrie sowie verschiedene Anwendungen in Pharmazeutika, in der Kosmetik, bei Nahrungs­mitteln und bei der Pflanzenernährung in Betracht.Areas of use and uses include, for example, detergents and cleaning agents for the household, industrial cleaning agents, electroplating technology, water treatment and polymerizations, the photographic industry, the textile industry and the paper industry, and various applications in pharmaceuticals, cosmetics, foodstuffs and in Plant nutrition into consideration.

Ihre vorteilhafte Wirkung liegt auch in einer Bleichmittelstabilisierung, beispielsweise für Natriumperborate wie NaBO₂·H₂O₂·3 H₂O, Peroxycarbonate, Peroxyphosphonate, Citratperhydrate, Harnstoff- und Melamin-H₂O₂-Addukte, Caroate, Perbenzoate, Alkandipercarbonsäuren, Peroxyphthalate und Alkali­metallhypochlorite in Wasch- und Reinigungsmitteln und bei der Wasser­stoffperoxidbleiche von Textilien, Zellstoff oder Papierrohstoff. Spuren von Schwermetallen wie Eisen, Kupfer und Mangan kommen im Waschpulver selbst, im Wasser und im Textilgut vor und katalysieren die Zersetzung der Perverbindung oder des daraus entstandenen Wasserstoffperoxids. Die Komplexbildner I binden diese Metallionen und verhindern die unerwünschte Zersetzung des Bleichsystems während der Lagerung und in der Waschflotte. Dadurch erhöht sich die Effizienz des Bleichsystems und Faserschädigungen werden zurückgedrängt.Their advantageous effect also lies in a bleach stabilization, for example for sodium perborates such as NaBO₂ · H₂O₂ · 3 H₂O, peroxycarbonates, peroxyphosphonates, citrate perhydrates, urea and melamine-H₂O₂ adducts, caroates, perbenzoates, alkane dipercarboxylic acids, peroxyphthalates and detergents and alkali metal acetates and detergents in the hydrogen peroxide bleaching of textiles, cellulose or paper raw materials. Traces of heavy metals such as iron, copper and manganese occur in the washing powder itself, in the water and in the textile goods and catalyze the decomposition of the per compound or the hydrogen peroxide resulting from it. The complexing agents I bind these metal ions and prevent the undesired decomposition of the bleaching system during storage and in the wash liquor. This increases the efficiency of the bleaching system and fiber damage is suppressed.

In flüssigen Waschmittelformulierungen können die Verbindunge I als soge­nannte Konservierungsmittel, zweckmäßigerweise in einer Menge von 0,05 bis 1 Gew.-% bezogen auf das Gesamtgewicht der Waschmittelformulierung, ein­gesetzt werden.In liquid detergent formulations, the compounds I can be used as so-called preservatives, advantageously in an amount of 0.05 to 1% by weight, based on the total weight of the detergent formulation.

In Seifen verhindern die Verbindungen I beispielsweise metallkatalysierte oxidative Zersetzungen.In soaps, the compounds I prevent, for example, metal-catalyzed oxidative decomposition.

Weiterhin dienen sie in hervorragender Weise in Wasch- und Reinigungs­mitteln als Gerüststoff (Builder), um Ausfällungen und Inkrustationen auf dem Gewebe zu verhindern.Furthermore, they serve as an excellent builder in detergents and cleaning agents to prevent precipitation and incrustation on the fabric.

Sie können in vorteilhafter Weise überall dort eingesetzt werden, wo bei technischen Verfahren Ausfällungen von Calcium-, Magnesium- und Schwer­metallsalzen stören und verhindert werden sollen, beispielsweise zur Verhinderung von Ablagerungen und Verkrustungen in Kesseln, Rohrleitungen, an Sprühdüsen oder allgemein an glatten Oberflächen.They can be used in an advantageous manner wherever precipitation of calcium, magnesium and heavy metal salts is to be disrupted and prevented in technical processes, for example to prevent deposits and incrustations in boilers, pipelines, on spray nozzles or generally on smooth surfaces.

Sie können zur Stabilisierung von Phosphaten in alkalischen Entfettungs­bädern und Verhinderung der Ausfällung von Kalkseifen dienen und ver­hindern dadurch das "Anlaufen" von Nichteisenoberflächen und verlängern die Standzeiten von alkalischen Reinigerbädern.They can be used to stabilize phosphates in alkaline degreasing baths and prevent the precipitation of lime soaps and thereby prevent the "tarnishing" of non-ferrous surfaces and extend the service life of alkaline cleaning baths.

Sie können als Komplexbildner in alkalischen Entrostungs- und Entzunde­rungsbädern verwendet werden sowie in galvanischen Bädern anstelle von Cyaniden.They can be used as complexing agents in alkaline rust removal and descaling baths as well as in galvanic baths instead of cyanides.

Die Kühlwasserbehandlung mit den Verbindungen I verhindert Ablagerungen bzw. löst bereits vorhandene wieder auf. Ein besonderer Vorteil ist die Anwendungsmöglichkeit in alkalischem Medium und damit die Beseitigung von Korrosionsproblemen.The cooling water treatment with the compounds I prevents deposits or dissolves existing ones. A particular advantage is the possibility of application in an alkaline medium and thus the elimination of corrosion problems.

Bei der Polymerisation von Kautschuk können sie zur Herstellung der dabei verwendeten Redoxkatalysatoren verwendet werden. Sie verhindern zusätzlich das Ausfallen von Eisenhydroxid im alkalischen Polymerisationsmilieu.When polymerizing rubber, they can be used to produce the redox catalysts used. They also prevent the precipitation of iron hydroxide in the alkaline polymerization environment.

In der photographischen Industrie können die Komplexbildner I in Ent­wickler- oder Fixierbädern, die mit hartem Wasser angesetzt werden, ver­wendet werden, um die Ausfällung schwerlöslicher Calcium- und Magnesium-­Salze zu verhindern. Die Ausfällungen führen zur Grauschleiern auf Filmen und Bildern sowie Ablagerungen in den Tanks, die somit vorteilhaft vermieden werden können. Sie können als Eisen-III-Chelatlösungen vorteilhaft in Bleich- und Bleichfixierbädern eingesetzt werden und so die aus ökologischen Gründen bedenklichen Hexacyanoferratlösungen ersetzen.In the photographic industry, the complexing agents I can be used in developer or fixing 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 haze on films and images, as well as deposits in the tanks, which can thus advantageously be avoided. They can be used as iron III chelate solutions can be used advantageously in bleaching and bleach-fixing baths and thus replace the hexacyanoferrate solutions, which are questionable for ecological reasons.

In der Textilindustrie können sie zur Entfernung von Schwermetallspuren während des Herstellungs- bzw. Färbeprozesses von natürlichen und synthe­tischen Fasern dienen. Dadurch werden viele Störungen verhindert, bei­spielsweise Schmutzflecken und Streifen auf dem Textilgut, Verlust des Glanzes, schlechte Benetzbarkeit, unegale Färbungen und Farbfehler.In the textile industry, they can be used to remove traces of heavy metals during the manufacturing or dyeing process of natural and synthetic fibers. This prevents many faults, for example dirt stains and stripes on the textile, loss of gloss, poor wettability, uneven dyeing and color errors.

In der Papierindustrie können sie zur Eliminierung von Schwermetallionen, insbesondere Eisenionen, verwendet werden. Die Ablagerung von Eisen auf Papier führt zu "heißen Flecken", an denen die oxidative katalytische Zerstörung der Zellulose beginnt. Ferner katalysieren Schwermetallionen die Zersetzung von H₂O₂, welches für die Papierbleichung eingesetzt wird.They can be used in the paper industry to eliminate heavy metal ions, especially iron ions. The deposition of iron on paper leads to "hot spots" where the oxidative catalytic destruction of cellulose begins. Heavy metal ions also catalyze the decomposition of H₂O₂, which is used for paper bleaching.

Weiterhin kommen beispielsweise Anwendungen in Pharmazeutika, Kosmetika und Nahrungsmitteln in Betracht, um die metallkatalysierte Oxidation von olefinischen Doppelbindungen und damit das Ranzigwerden der Erzeugnisse zu verhindern.Applications in pharmaceuticals, cosmetics and foodstuffs are also considered, for example, in order to prevent the metal-catalyzed oxidation of olefinic double bonds and thus the rancidity of the products.

In der Pflanzenernährung können zur Behebung von Schwermetalldefiziten Kupfer-, Eisen-, Mangan- und Zink-Komplexe mit I verwendet werden. Diese Schwermetalle werden als Chelate zugegeben, um die Ausfällung als biologisch inaktive unlösliche Salze zu verhindern.In plant nutrition, copper, iron, manganese and zinc complexes with I can be used to remedy heavy metal deficits. These heavy metals are added as chelates to prevent precipitation as biologically inactive insoluble salts.

Weitere Anwendungsgebiete für die Verbindungen I sind die Rauchgaswäsche, und zwar die gleichzeitige Entfernung von NOx und SO₂ aus Rauchgasen, die Entschwefelung nach Wellman-Lord, die H₂S-Oxidation, die Metallextraktion sowie Anwendungen als Katalysatoren für organische Synthesen, z.B. Luft­oxidation von Paraffinen und Hydroformylierung von Olefinen zu Alkoholen.Further areas of application for the compounds I are flue gas scrubbing, namely the simultaneous removal of NO x and SO₂ from flue gases, desulfurization according to Wellman-Lord, H₂S oxidation, metal extraction and applications as catalysts for organic syntheses, for example air oxidation of paraffins and Hydroformylation of olefins to alcohols.

Die Verbindungen I mit ihren hervorragenden komplexbildenden Eigenschaften können unter den genannten Anwendungsgebieten in ganz besonderem Maße als Bleichmittelstabilisatoren und als Gerüststoffe in Wasch- und Reinigungsmitteln empfohlen werden.The compounds I, with their excellent complex-forming properties, can be recommended to a very special extent as bleach stabilizers and as builders in detergents and cleaning agents in the fields of application mentioned.

Gegenstand der vorliegenden Erfindung sind auch Mittel zur Komplexierung von Schwermetall- oder Erdalkalimetallionen oder Gemischen hiervon, die je nach Anwendungszweck die Verbindungen Ia in einer Menge von 0,01 bis 99 Gew.-%, bezogen auf die Gesamtmenge der Zubereitungen, enthalten.The present invention also relates to compositions for complexing heavy metal or alkaline earth metal ions or mixtures thereof which, depending on the intended use, contain the compounds Ia in an amount of 0.01 to 99% by weight, based on the total amount of the preparations.

Weiterhin sind Gegenstand der vorliegenden Erfindung Wasch- und Reini­gungsmittel, die 0,01 bis 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-% be­ zogen auf die Gesamtmenge der Zübereitung, einer oder mehrerer der Ver­bindungen I enthalten. Bei einer Verwendung bevorzugt als Gerüststoff sind Mengen von 1 bis 10 Gew.-%, bei einer Verwendung bevorzugt als Bleich­mittelstabilisator, beispielsweise für Perborate, sind Mengen von 0,05 bis 1 Gew.-% besonders bevorzugt. Bei einer Verwendung insbesondere als Komplexbildner in Waschmitteln sind Mengen von 0,1 bis 2 Gew.-% bevorzugt.The present invention furthermore relates to detergents and cleaning agents which are 0.01 to 20% by weight, preferably 0.05 to 10% by weight referred to the total amount of preparation, one or more of the compounds I included. When used preferably as a builder, amounts from 1 to 10% by weight are preferred, when used as a bleach stabilizer, for example for perborates, amounts from 0.05 to 1% by weight are particularly preferred. When used in particular as a complexing agent in detergents, amounts of 0.1 to 2% by weight are preferred.

Die Verbindungen I können in ihrer Eigenschaft als Komplexbildner, Gerüst­stoff und Bleichmittelstabilisator in Wasch- und Reinigungsmittelformulie­rungen auch zusammen mit anderen Mitteln des Standes der Technik verwendet werden, wobei die allgemeinen Eigenschaften im Hinblick auf Sequestrie­rung, Inkrustationsinhibierung, Vergrauungsinhibierung, Primärwaschwirkung und Bleichwirkung unter Umständen deutlich verbessert werden können.The compounds I, in their capacity as complexing agents, builders and bleach stabilizers in detergent and cleaning agent formulations, can also be used together with other agents of the prior art, the general properties with respect to sequestration, incrustation inhibition, graying inhibition, primary washing action and bleaching action, under certain circumstances, significantly improved can be.

Wasch- und Reinigungsmittelformulierungen mit den Verbindungen I enthalten in der Regel als zusätzliche Bestandteile, bezogen auf das Gesamtgewicht, 6 bis 25 Gew.-% Tenside, 15 bis 50 Gew.-% Builder und gegebenenfalls Co-­Builder und 5 bis 30 Gew.-% Hilfsstoffe wie Enzyme, Schaumregulatoren, Korrosionsinhibitoren, optische Aufheller, Duftstoffe, Farbstoffe oder Formulierhilfsmittel wie z.B. Natriumsulfat in den hierfür üblichen Mengen.Detergent and cleaning agent formulations with the compounds I generally contain, as additional constituents, based on the total weight, 6 to 25% by weight of surfactants, 15 to 50% by weight of builders and optionally co-builders and 5 to 30% by weight. % Auxiliaries such as enzymes, foam regulators, corrosion inhibitors, optical brighteners, fragrances, dyes or formulation aids such as Sodium sulfate in the usual amounts for this.

Die 2-Hydroxy-3-aminopropionsäure-Derivate I sind hervorragende Komplex­bildner. In ihrer Eigenschaft als Gerüststoff in Nasch- und Reinigungs­mitteln zur Verbesserung der Weißwaschwirkung und zur Verhinderung von Ablagerungen auf dem Gewebe sind die Verbindungen I mit beispielsweise Ethylendiamintetraessigsäure oder 2-Hydroxy-3-aminopropionsäure-N,N-di­essigsäure vergleichbar. Eine deutlich überlegene Wirkung im Vergleich zu den genannten Mitteln des Standes der Technik zeigt sich jedoch bei der Bleichmittelstabilisierung.The 2-hydroxy-3-aminopropionic acid derivatives I are excellent complexing agents. In their capacity as builders in sweeteners and cleaning agents to improve the whitening effect and to prevent deposits on the fabric, the compounds I are comparable to, for example, ethylenediaminetetraacetic acid or 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid. However, bleach stabilization shows a clearly superior effect compared to the prior art agents mentioned.

HerstellungsbeispieleManufacturing examples Beispiel 1example 1 Nitrilo-di(2-hydroxy-3-aminopropionsäure)monoessigsäure-TrinatriumsalzNitrilodi (2-hydroxy-3-aminopropionic acid) monoacetic acid trisodium salt

Zu einer Lösung von 37,5 g (0,5 mol) Glycin in 150 g Wasser, die mit 0,6 g 50 gew.-%iger Natronlauge auf einen pH-Wert von 8 eingestellt worden war, wurden bei 50°C innerhalb von 1 Stunde 478,5 g einer 20 gew.-%igen wäßrigen Glycidsäureamid-Lösung (entsprechend 1,1 mol Glycidsäureamid) ge­tropft. Während des Zutropfens wurde der pH-Wert der Reaktionslösung durch Zugabe weiterer 88 g 50 gew.-%iger Natronlauge zwischen 8 und 8,5 gehal­ten. Anschließend wurde 30 Minuten bei 50°C und danach 3 Stunden bei 80°C nachgerührt. Nach Zugabe weiterer 100 g 50 gew.-%iger Natronlauge wurde die Lösung dann 2 Stunden bei 80°C und danach 1,5 Stunden bei 100°C gerührt, wobei das entstandene Ammoniak ausgaste.A solution of 37.5 g (0.5 mol) of glycine in 150 g of water, which had been adjusted to a pH of 8 with 0.6 g of 50% strength by weight sodium hydroxide solution, was at 50 ° C. inside 478.5 g of a 20% strength by weight aqueous glycidamide solution (corresponding to 1.1 mol of glycidamide) were added dropwise in the course of 1 hour. During the dropping, the pH of the reaction solution was kept between 8 and 8.5 by adding a further 88 g of 50% strength by weight sodium hydroxide solution. Then was 30 minutes at 50 ° C and then 3 hours at 80 ° C. stirred. After adding a further 100 g of 50% strength by weight sodium hydroxide solution, the solution was then stirred at 80 ° C. for 2 hours and then at 100 ° C. for 1.5 hours, during which the ammonia formed outgassed.

Die Lösung wurde nach dem Abkühlen mit dem dreifachen Volumen an Methanol versetzt. Der gebildete Niederschlag wurde abfiltriert und aus einer Wasser-Methanol-Mischung umkristallisiert. Man erhielt die Titelverbindung in Form eines farblosen Kristallpulvers, das oberhalb 300°C schmolz, in einer Ausbeute von 66 %.After cooling, three times the volume of methanol was added to the solution. The precipitate formed was filtered off and recrystallized from a water-methanol mixture. The title compound was obtained in the form of a colorless crystal powder which melted above 300 ° C. in a yield of 66%.

Beispiel 2Example 2 N-(2-Hydroxyethyl)-2-hydroxy-3-aminopropionsäure-N-monoessigsäure-­DinatriumsalzN- (2-hydroxyethyl) -2-hydroxy-3-aminopropionic acid-N-monoacetic acid disodium salt

282 g (1,0 mol) Ethanolaminoessigsäure-Natriumsalz wurden mit der äquimo­laren Menge Glycidsäureamid analog Beispiel 1 umgesetzt, mit dem Unter­schied, daß eine Natronlauge-Zugabe erst nach erfolgter Umsetzung zum Zwecke der Hydrolyse der Carbonsäureamidgruppe erfolgte.282 g (1.0 mol) of ethanolaminoacetic acid sodium salt were reacted with the equimolar amount of glycidamide analogously to Example 1, with the difference that sodium hydroxide solution was not added until after the reaction had been carried out for the purpose of hydrolysis of the carboxamide group.

Die resultierende Lösung wurde sprühgetrocknet und das hierbei erhaltene hellbraune Pulver aus einer Wasser-Methanol-Mischung umkristallisiert. Man erhielt die Titelverbindung in Form eines farblosen Kristallpulvers mit einem Schmelzpunkt >280°C in einer Ausbeute von 74 %.The resulting solution was spray-dried and the light brown powder thus obtained was recrystallized from a water-methanol mixture. The title compound was obtained in the form of a colorless crystal powder with a melting point> 280 ° C. in a yield of 74%.

Beispiel 3Example 3 Nitrilo-di(2-hydroxy-3-aminopropionsäure)monobernsteinsäure-Tetra­natriumsalzNitrilodi (2-hydroxy-3-aminopropionic acid) monosuccinic acid tetrasodium salt

Diese Verbindung wurde analog Beispiel 1 durch Umsetzung von Asparagin­säure mit Glycidsäureamid im molaren Verhältnis von 1 : 2,2 in einer Ausbeute von 55 % hergestellt. Sie hatte nach Umkristallisation einen Schmelzpunkt von 125°C (unter Zersetzung).This compound was prepared analogously to Example 1 by reacting aspartic acid with glycidamide in a molar ratio of 1: 2.2 in a yield of 55%. After recrystallization, it had a melting point of 125 ° C. (with decomposition).

Beispiel 4Example 4 Nitrilo-di(2-hydroxy-3-aminopropionsäure)mono(2-carboxy-2-aminoethanol)-­TrinatriumsalzNitrilodi (2-hydroxy-3-aminopropionic acid) mono (2-carboxy-2-aminoethanol) trisodium salt

Diese Verbindung wurde analog Beispiel 1 durch Umsetzung von Serin mit Glycidsäureamid im molaren Verhältnis von 1 : 2,2 in einer Ausbeute von 57 % hergestellt. Sie hatte nach Umkristallisation einen Schmelzpunkt von 120°C (unter Zersetzung).This compound was prepared analogously to Example 1 by reacting serine with glycidamide in a molar ratio of 1: 2.2 in a yield of 57%. After recrystallization, it had a melting point of 120 ° C. (with decomposition).

Beispiel 5Example 5 Nitrilo-di(2-hydroxy-3-aminopropionsäure)monoethanolamin-DinatriumsalzNitrilodi (2-hydroxy-3-aminopropionic acid) monoethanolamine disodium salt

Diese Verbindung wurde analog Beispiel 2 durch Umsetzung von Ethanolamin mit Glycidsäureamid hergestellt. Sie ist aus der Literaturstelle (1) bekannt.This compound was prepared analogously to Example 2 by reacting ethanolamine with glycidamide. It is known from the literature reference (1).

Beispiel 6Example 6 Nitrilo-tri(2-hydroxy-3-aminopropionsäure)-TrinatriumsalzNitrilo-tri (2-hydroxy-3-aminopropionic acid) trisodium salt

Diese Verbindung wurde analog Beispiel 2 durch Umsetzung von Ammoniak mit Glycidsäureamid hergestellt. Sie ist aus der Literaturstelle (1) bekannt.This compound was prepared analogously to Example 2 by reacting ammonia with glycidamide. It is known from the literature reference (1).

Beispiel 7Example 7 N-methyl-2-hydroxy-3-aminopropionsäure-N-monoessigsäure-DinatriumsalzN-methyl-2-hydroxy-3-aminopropionic acid-N-monoacetic acid disodium salt

Diese Verbindung wurde analog Beispiel 1 durch Umsetzung äquimolarer Mengen von Sarkosin mit Glycidsäureamid in einer Ausbeute von 94 % herge­stellt. Sie hatte nach Umkristallisation einen Schmelzpunkt von >310oC.This compound was prepared analogously to Example 1 by reacting equimolar amounts of sarcosine with glycidamide in a yield of 94%. After recrystallization, it had a melting point of> 310 o C.

Anwendungstechnische EigenschaftenApplication properties Bestimmung der Nariumperboratstabilisierung in WaschflottenDetermination of sodium perborate stabilization in wash liquors

Das für die Bleichwirkung in natriumperborathaltigen Waschmittelformu­lierungen verantwortliche Wasserstoffperoxid wird durch Schwermetallionen (Fe, Cu, Mn) vornehmlich in der Waschflotte, aber auch schon bei trockener Lagerung katalytisch zersetzt. Durch Komplexierung der Schwermetallionen läßt sich dieser Zersetzungsprozeß verhindern oder zumindest verzögern. Die peroxidstabilisierende Wirkung der Komplexbildner wird über den Rest­peroxidgehalt nach Belassen einer schwermetallhaltigen Waschflotte bei höherer Temperatur für eine bestimmte Zeitdauer geprüft.The hydrogen peroxide responsible for the bleaching effect in detergent formulations containing sodium peroxide is catalytically decomposed by heavy metal ions (Fe, Cu, Mn) primarily in the wash liquor, but also when stored dry. This decomposition process can be prevented or at least delayed by complexing the heavy metal ions. The peroxide-stabilizing effect of the complexing agents is checked for a certain period of time via the residual peroxide content after leaving a wash liquor containing heavy metals at a higher temperature.

Der Gehalt an Wasserstoffperoxid wurde unmittelbar nach Zubereitung und nach Belassen der Waschflotte bei 60°C oder 80°C für 2 oder 1 Stunde durch Titration mit Kaliumpermanganat in saurer Lösung bestimmt. Als Ergebnis wurde in der unten angeführten Tabelle jeweils der Prozentsatz an nach diesem Zeitraum noch vorhandenem H₂O₂ angegeben.The hydrogen peroxide content was determined immediately after preparation and after leaving the wash liquor at 60 ° C. or 80 ° C. for 2 or 1 hour by titration with potassium permanganate in acid solution. As a result, the percentage of H₂O₂ still present after this period was given in the table below.

Zur Prüfung auf Perboratstabilisierung dienten zwei Waschmittelformu­lierungen (1) und (2); die nachfolgenden Prozentangaben beziehen sich jeweils auf das Gewicht.

  • (1) Zusammensetzung der phosphatreichen Formulierung:
    19,3 % Natrium-C₁₂-Alkylbenzolsulfonat (50 %ige wäßrige Lösung)
    15,4 % Natriumperborat-Tetrahydrat
    30,8 % Natriumtriphosphat
    2,6 % Copolymer aus Maleinsäure und Acrylsäure (Gewichtsverhältnis 50:50, mittlere Molmasse 50.000)
    31,0 % wasserfreies Natriumsulfat
    0,9 % Komplexbildner 1 oder Vergleichssubstanz
  • (2) Zusammensetzung der phosphatarmen Formulierung:
    15 % Natrium-C₁₂-Alkylbenzolsulfonat (50 %ige wäßrige Lösung)
    5 % Anlagerungsprodukt von 11 Mol Ethylenoxid an 1 Mol Talgfettalkohol
    20 % Natriumperborat-Tetrahydrat
    6 % Natriummetasilicat·5 H₂O
    1,25 % Magnesiumsilicat
    20 % Natriumtriphosphat
    31,75 % wasserfreies Natriumsulfat
    1 % Komplexbildner I oder Vergleichssubstanz
Two detergent formulations (1) and (2) were used to test for perborate stabilization; the following percentages each relate to the weight.
  • (1) Composition of the high-phosphate formulation:
    19.3% sodium C12 alkylbenzenesulfonate (50% aqueous solution)
    15.4% sodium perborate tetrahydrate
    30.8% sodium triphosphate
    2.6% copolymer of maleic acid and acrylic acid (weight ratio 50:50, average molecular weight 50,000)
    31.0% anhydrous sodium sulfate
    0.9% complexing agent 1 or reference substance
  • (2) Composition of the low-phosphate formulation:
    15% sodium C12 alkylbenzenesulfonate (50% aqueous solution)
    5% adduct of 11 moles of ethylene oxide with 1 mole of tallow fatty alcohol
    20% sodium perborate tetrahydrate
    6% sodium metasilicate · 5 H₂O
    1.25% magnesium silicate
    20% sodium triphosphate
    31.75% anhydrous sodium sulfate
    1% complexing agent I or reference substance

Die Prüfung wurde so durchgeführt, daß eine Lösung von 6,5 g/l der Formu­lierung (1) in Wasser der Härte 25°dH auf 80°C erwärmt und zu Testzwecken mit 2,5 ppm einer Mischung der Ionen Fe³⁺, Cu²⁺ und Mn²⁺ im Verhältnis 8 : 1 : 1, eingesetzt in Form ihrer Sulfate, versetzt wurde. Durch Titra­tion mit KMnO₄ in saurer Lösung wurde der H₂O₂-Gehalt vor der Schwerme­tallzugabe und nach 2stündigem Belassen der Waschflotte bei 80°C gemessen.The test was carried out in such a way that a solution of 6.5 g / l of the formulation (1) in water of hardness 25 ° dH was heated to 80 ° C. and for test purposes with 2.5 ppm of a mixture of the ions Fe³⁺, Cu²⁺ and Mn²⁺ in the ratio 8: 1: 1, used in the form of their sulfates, was added. By titration with KMnO₄ in acidic solution, the H₂O₂ content was measured before adding heavy metals and after leaving the wash liquor at 80 ° C for 2 hours.

Ebenso wurde eine Lösung von 8 g/l der Formulierung (2) in Wasser der Härte 25°dH auf 60°C erwärmt und analog zum oben beschriebenen Verfahren behandelt. Der Restgehalt an H₂O₂ wurde nach 1stündigem Belassen der Waschflotte bei 60°C bestimmt.Similarly, a solution of 8 g / l of formulation (2) in water hardness 25 ° dH was heated to 60 ° C and treated analogously to the process described above. The residual H₂O₂ content was determined after leaving the wash liquor at 60 ° C for 1 hour.

Die folgende Tabelle zeigt die Ergebnisse der Prüfungen, wobei die 2-­Hydroxy-3-aminopropionsäure-Derivate I in ihrer Natriumsalz-Form aus den Beispielen 1 bis 6 mit Ethylendiamintetraessigsäure-Tetranatriumsalz (EDTA-Na₄) sowie 2-Hydroxy-3-aminopropionsäure-N,N-diessigsäure-Tri­natriumsalz (ISDA-Na₃) gemäß Literaturstelle (2) verglichen wurden. Die Werte verdeutlichen die überlegene Wirkung der Verbindungen I. Tabelle Bleichmittelstabilisator Natriumperboratstabilisierung [Rest-% H₂O₂] Formulierung (1) Formulierung (2) Beispiel 1 60,6 90,0 Beispiel 2 36,5 89,0 Beispiel 3 51,8 79,4 Beispiel 4 52,2 84,2 Beispiel 5 25,5 57,4 Beispiel 6 51,8 80,7 zum Vergleich: EDTA-Na₄ 20,0 34,0 ISDA-Na₃ 43,4 82,0 ohne 20,0 28,0 The following table shows the results of the tests, the 2-hydroxy-3-aminopropionic acid derivatives I in their sodium salt form from Examples 1 to 6 having ethylenediaminetetraacetic acid tetrasodium salt (EDTA-Na₄) and 2-hydroxy-3-aminopropionic acid N, N-diacetic acid trisodium salt (ISDA-Na₃) according to reference (2) were compared. The values illustrate the superior effect of compounds I. table Bleach stabilizer Sodium perborate stabilization [residual% H₂O₂] Wording (1) Wording (2) example 1 60.6 90.0 Example 2 36.5 89.0 Example 3 51.8 79.4 Example 4 52.2 84.2 Example 5 25.5 57.4 Example 6 51.8 80.7 for comparison: EDTA-Na₄ 20.0 34.0 ISDA-Na₃ 43.4 82.0 without 20.0 28.0

Claims (7)

1. Verwendung von 2-Hydroxy-3-aminopropionsäure-Derivaten der allgemeinen Formel I
Figure imgb0017
 in der X für Wasserstoff, ein Alkalimetall oder Ammonium, das durch C₁-C₄-Alkylgruppen oder C₁-C₄-Hydroxyalkylgruppen substituiert sein kann, steht und in der die Gruppen Y¹ und Y² folgende Bedeutungen haben
A) ω-substituierte Alkylgruppen der allgemeinen Formel
-(CH₂)m-R¹
in der R¹ Wasserstoff, eine Hydroxylgruppe oder die Gruppen -COOX, -NH-CH(COOX)-CH₂-COOX oder -NY¹Y² bezeichnet und m Werte von 1 bis 20 hat, mit Ausnahme des Wertes m = 1 für den Fall, daß Y¹ und Y² gleich sind und R¹ die Gruppe -COOX bedeutet,
B) Polyethergruppen der allgemeinen Formel
-(CH₂CH₂O)m-R²
in der R² Wasserstoff oder eine C₁-C₄-Alkylgruppe bedeutet,
C) β-hydroxysubstituierte Gruppen der allgemeinen Formel
Figure imgb0018
 in der R³ für die Gruppen -COOX, -CH₂OH und -CH₂-NY¹Y² steht und n Werte von 1 bis 5 hat,
D) α-carboxysubstituierte Gruppen der allgemeinen Formel
Figure imgb0019
 in der R⁴ Wasserstoff, eine Methylgruppe oder eine Hydroxymethyl­gruppe bezeichnet und R⁵ eine Hydroxymethylgruppe oder die Gruppen -CH(OH)-COOX oder -(CH₂)p-COOX bedeutet, wobei p 1 oder 2 ist,
E) Pyranosyl- oder Furanosylgruppen der allgemeinen Formel
Figure imgb0020
 in der q den Wert 3 oder 2 hat, oder
F) Polymerreste von Polyvinylamin oder Polyethylenimin
als Komplexbildner, Bleichmittelstabilisatoren und Gerüststoffe in Wasch- und Reinigungsmitteln.1. Use of 2-hydroxy-3-aminopropionic acid derivatives of the general formula I
Figure imgb0017
 in which X represents hydrogen, an alkali metal or ammonium, which can be substituted by C₁-C₄-alkyl groups or C₁-C₄-hydroxyalkyl groups, and in which the groups Y¹ and Y² have the following meanings
A) ω-substituted alkyl groups of the general formula
- (CH₂) m -R¹
in which R¹ denotes hydrogen, a hydroxyl group or the groups -COOX, -NH-CH (COOX) -CH₂-COOX or -NY¹Y² and m has values from 1 to 20, with the exception of the value m = 1 for the case that Y¹ and Y² are the same and R¹ represents the group -COOX,
B) polyether groups of the general formula
- (CH₂CH₂O) m -R²
in which R² is hydrogen or a C₁-C₄ alkyl group,
C) β-hydroxy-substituted groups of the general formula
Figure imgb0018
 in which R³ represents the groups -COOX, -CH₂OH and -CH₂-NY¹Y² and n has values from 1 to 5,
D) α-carboxy-substituted groups of the general formula
Figure imgb0019
 in which R⁴ denotes hydrogen, a methyl group or a hydroxymethyl group and R⁵ denotes a hydroxymethyl group or the groups -CH (OH) -COOX or - (CH₂) p -COOX, where p is 1 or 2,
E) Pyranosyl or furanosyl groups of the general formula
Figure imgb0020
 in which q has the value 3 or 2, or
F) polymer residues of polyvinylamine or polyethyleneimine
as complexing agents, bleach stabilizers and builders in washing and cleaning agents. 2. Verwendung von 2-Hydroxy-3-aminopropionsäure-Derivaten I nach Anspruch 1, bei denen die Gruppen Y¹ und Y² folgende Bedeutungen haben A) ω-substituierte Alkylgruppen der allgemeinen Formel
-(CH₂)m-R¹
in der R¹ Wasserstoff, eine Hydroxylgruppe oder die Gruppe -COOX bezeichnet und m Werte von 1 bis 6 hat, mit Ausnahme des Wertes m = 1 für den Fall, daß Y¹ und Y² gleich sind und R¹ die Gruppe -COOX bedeutet, C) β-hydroxysubstituierte Gruppen der allgemeinen Formel
Figure imgb0021
 in der R³ für die Gruppen -COOX und -CH₂OH steht und n Werte von bis 5 hat, oder D) α-carboxysubstituierte Gruppen der allgemeinen Formel
Figure imgb0022
 in der R⁴ Wasserstoff, eine Methylgruppe oder eine Hydroxymethyl­gruppe bezeichnet und R⁵ eine Hydroxymethylgruppe oder die Gruppen -CH(OH)-COOX oder -(CH₂)p-COOX bedeutet, wobei p 1 oder 2 ist. 2. Use of 2-hydroxy-3-aminopropionic acid derivatives I according to claim 1, in which the groups Y¹ and Y² have the following meanings A) ω-substituted alkyl groups of the general formula
- (CH₂) m -R¹
in which R¹ denotes hydrogen, a hydroxyl group or the group -COOX and m has values from 1 to 6, with the exception of the value m = 1 if Y¹ and Y² are the same and R¹ denotes the group -COOX, C) β-hydroxy-substituted groups of the general formula
Figure imgb0021
 in which R³ represents the groups -COOX and -CH₂OH and n has values from to 5, or D) α-carboxy-substituted groups of the general formula
Figure imgb0022
 in which R⁴ denotes hydrogen, a methyl group or a hydroxymethyl group and R⁵ denotes a hydroxymethyl group or the groups -CH (OH) -COOX or - (CH₂) p -COOX, where p is 1 or 2. 3. 2-Hydroxy-3-aminopropionsäure-Derivate der allgemeinen Formel Ia
Figure imgb0023
 in der X für Wasserstoff, ein Alkalimetall oder Ammonium, das durch C₁-C₄-Alkylgruppen oder C₁-C₄-Hydroxyalkylgruppen substituiert sein kann, steht und in der die Gruppen Y³ und Y⁴ folgende Bedeutungen haben A) ω-substituierte Alkylgruppen der allgemeinen Formel
-(CH₂)m-R⁹
in der R⁹ die Gruppen -COOX, -NH-CH(COOX)-CH₂-COOX oder -NY³Y⁴ oder für den Fall, daß m den Wert 1 hat, Wasserstoff bezeichnet und m Werte von 1 bis 20 hat, mit Ausnahme des Wertes m = 1 für den Fall, daß Y³ und Y⁴ gleich sind und R⁹ die Gruppe -COOX bedeutet, B) Polyethergruppen der allgemeinen Formel
-(CH₂CH₂O)m-R²
in der R² Wasserstoff oder eine C₁-C₄-Alkylgruppe bedeutet, C) β-hydroxysubstituierte Gruppen der allgemeinen Formel
Figure imgb0024
 in der R¹⁰ für die Gruppen -COOX, -CH₂OH und -CH₂-NY³Y⁴ steht und n Werte von 1 bis 5 hat, mit Ausnahme des Wertes n = 1 für den Fall, daß Y³ und Y⁴ gleich sind und R¹⁰ die Gruppe -COOX bedeutet, D) α-carboxysubstituierte Gruppen der allgemeinen Formel
Figure imgb0025
 in der R⁴ Wasserstoff, eine Methylgruppe oder eine Hydroxymethyl­gruppe bezeichnet und R⁵ eine Hydroxymethylgruppe oder die Gruppen -CH(OH)-COOX oder -(CH₂)p-COOX bedeutet, wobei p 1 oder 2 ist, E) Pyranosyl- oder Furanosylgruppen der allgemeinen Formel
Figure imgb0026
 in der q den Wert 3 oder 2 hat, oder F) Polymerreste von Polyvinylamin oder Polyethylenimin. 3. 2-hydroxy-3-aminopropionic acid derivatives of the general formula Ia
Figure imgb0023
 in which X represents hydrogen, an alkali metal or ammonium, which can be substituted by C₁-C₄-alkyl groups or C₁-C₄-hydroxyalkyl groups, and in which the groups Y³ and Y⁴ have the following meanings A) ω-substituted alkyl groups of the general formula
- (CH₂) m -R⁹
in the R⁹ the groups -COOX, -NH-CH (COOX) -CH₂-COOX or -NY³Y⁴ or in the case where m is 1, denotes hydrogen and m has values from 1 to 20, with the exception of the value m = 1 in the event that Y³ and Y⁴ are the same and R⁹ is the group -COOX, B) polyether groups of the general formula
- (CH₂CH₂O) m -R²
in which R² is hydrogen or a C₁-C₄ alkyl group, C) β-hydroxy-substituted groups of the general formula
Figure imgb0024
 in which R¹⁰ represents the groups -COOX, -CH₂OH and -CH₂-NY³Y⁴ and n has values from 1 to 5, with the exception of the value n = 1 in the case where Y³ and Y⁴ are the same and R¹⁰ represents the group -COOX , D) α-carboxy-substituted groups of the general formula
Figure imgb0025
 in which R⁴ denotes hydrogen, a methyl group or a hydroxymethyl group and R⁵ denotes a hydroxymethyl group or the groups -CH (OH) -COOX or - (CH₂) p -COOX, where p is 1 or 2, E) pyranosyl or furanosyl groups of the general formula
Figure imgb0026
 in which q has the value 3 or 2, or F) polymer residues of polyvinylamine or polyethyleneimine. 4. Verfahren zur Herstellung von 2-Hydroxy-3-aminopropionsäure-­Derivaten Ia gemäß Anspruch 3, dadurch gekennzeichnet, daß man ein Glycidsäurederivat der allgemeinen Formel II
Figure imgb0027
 in der Z für die Gruppe -OX, -OR⁶ oder -N(R²)₂ steht, wobei R⁶ einen C₁-C₄-Alkylrest bezeichnet und die beiden Reste R² gleich oder verschieden sind, mit Ammoniak oder einem der Amine der allgemeinen Formeln IIIa oder IIIb
Figure imgb0028
 umsetzt und anschließend noch vorhandene Carbonsäureamid- oder Carbonsäureestergruppen hydrolysiert.4. A process for the preparation of 2-hydroxy-3-aminopropionic acid derivatives Ia according to claim 3, characterized in that a glycidic acid derivative of the general formula II
Figure imgb0027
 in which Z represents the group -OX, -OR⁶ or -N (R²) ₂, where R⁶ denotes a C₁-C₄ alkyl radical and the two radicals R² are the same or are different, with ammonia or one of the amines of the general formulas IIIa or IIIb
Figure imgb0028
 implemented and then hydrolyzed carboxylic acid amide or carboxylic ester groups still present. 5. Verwendung von 2-Hydroxy-3-aminopropionsäure-Derivaten Ia gemäß An­spruch 3 als Komplexbildner für Schwermetall- oder Erdalkalimetall­ionen.5. Use of 2-hydroxy-3-aminopropionic acid derivatives Ia according to claim 3 as complexing agents for heavy metal or alkaline earth metal ions. 6. Mittel zur Komplexierung von Schwermetall- oder Erdalkalimetallionen, enthaltend 0,01 bis 99 Gew.-%, bezogen auf die Gesamtmenge der Zube­reitung, einer oder mehrerer Verbindungen der allgemeinen Formel Ia gemäß Anspruch 3.6. Agent for complexing heavy metal or alkaline earth metal ions containing 0.01 to 99 wt .-%, based on the total amount of the preparation, of one or more compounds of the general formula Ia according to claim 3. 7. Wasch- und Reinigungsmittel, enthaltend 0,01 bis 20 Gew.-%, bezogen auf die Gesamtmenge der Zubereitung, einer oder mehrerer Verbindungen der allgemeinen Formel I gemäß Anspruch 1 oder 2.7. washing and cleaning agents containing 0.01 to 20 wt .-%, based on the total amount of the preparation, of one or more compounds of the general formula I according to claim 1 or 2.
EP90114141A 1989-08-03 1990-07-24 Use of derivatives of 2-hydroxy-3-aminopropionic acid as complexants, stabilizer for bleaching compositions and builder for washing and cleaning agents Expired - Lifetime EP0411436B1 (en)

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DE3925727A DE3925727A1 (en) 1989-08-03 1989-08-03 USE OF 2-HYDROXY-3-AMINOPROPIONSAFE DERIVATIVES AS COMPLEX BUILDERS, BLEACHING STABILIZERS AND TABLETS IN WASHING AND CLEANING AGENTS
DE3925727 1989-08-03

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EP0411436A3 EP0411436A3 (en) 1991-05-29
EP0411436B1 EP0411436B1 (en) 1998-02-04

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Cited By (6)

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EP0509382A2 (en) * 1991-04-17 1992-10-21 Hampshire Chemical Corporation Biodegradable bleach stabilizers for detergents
EP0588289A2 (en) * 1992-09-17 1994-03-23 Fuji Photo Film Co., Ltd. Photographic processing composition and processing method
WO1994012606A1 (en) * 1992-12-03 1994-06-09 Basf Aktiengesellschaft Iminodiacetic acid derivates used in cleaning compositions for the beverage and food industry, and for hard metallic, plastic, lacquered or glass surfaces
WO1994026691A1 (en) * 1993-05-19 1994-11-24 Akzo Nobel N.V. (2-carboxy-3-hydroxy-propyl)-iminodiacetic acid and derivatives
WO1996019557A2 (en) * 1994-12-22 1996-06-27 Basf Aktiengesellschaft Use of hydroxyalkylaminocarboxylic acids as complexing agents
US6180590B1 (en) 1996-03-26 2001-01-30 Basf Aktiengesellschaft Washing power enhancer for detergents

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US6440476B2 (en) 1997-01-03 2002-08-27 Nalco Chemical Company Method to improve quality and appearance of leafy vegetables by using stabilized bromine
US5942126A (en) * 1997-01-03 1999-08-24 Nalco Chemical Company Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling
EP2476314A4 (en) * 2009-09-07 2015-04-29 Lion Corp Disinfectant composition and disinfecting method

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509382A2 (en) * 1991-04-17 1992-10-21 Hampshire Chemical Corporation Biodegradable bleach stabilizers for detergents
EP0509382A3 (en) * 1991-04-17 1993-01-13 W.R. Grace & Co.-Conn. Biodegradable bleach stabilizers for detergents
EP0588289A2 (en) * 1992-09-17 1994-03-23 Fuji Photo Film Co., Ltd. Photographic processing composition and processing method
EP0588289A3 (en) * 1992-09-17 1994-07-27 Fuji Photo Film Co Ltd Photographic processing composition and processing method
WO1994012606A1 (en) * 1992-12-03 1994-06-09 Basf Aktiengesellschaft Iminodiacetic acid derivates used in cleaning compositions for the beverage and food industry, and for hard metallic, plastic, lacquered or glass surfaces
WO1994026691A1 (en) * 1993-05-19 1994-11-24 Akzo Nobel N.V. (2-carboxy-3-hydroxy-propyl)-iminodiacetic acid and derivatives
WO1996019557A2 (en) * 1994-12-22 1996-06-27 Basf Aktiengesellschaft Use of hydroxyalkylaminocarboxylic acids as complexing agents
WO1996019557A3 (en) * 1994-12-22 1996-08-29 Basf Ag Use of hydroxyalkylaminocarboxylic acids as complexing agents
US6180590B1 (en) 1996-03-26 2001-01-30 Basf Aktiengesellschaft Washing power enhancer for detergents

Also Published As

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US5112530A (en) 1992-05-12
DE3925727A1 (en) 1991-02-07
JPH03148243A (en) 1991-06-25
EP0411436A3 (en) 1991-05-29
DE59010804D1 (en) 1998-03-12
EP0411436B1 (en) 1998-02-04

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