EP0541614A1 - Aspartic acid derivatives as complexing agents - Google Patents

Aspartic acid derivatives as complexing agents

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Publication number
EP0541614A1
EP0541614A1 EP91913596A EP91913596A EP0541614A1 EP 0541614 A1 EP0541614 A1 EP 0541614A1 EP 91913596 A EP91913596 A EP 91913596A EP 91913596 A EP91913596 A EP 91913596A EP 0541614 A1 EP0541614 A1 EP 0541614A1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
ammonium
aspartic acid
alkyl radicals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP91913596A
Other languages
German (de)
French (fr)
Inventor
Henry Rossmaier
Helmut Blum
Josef Steber
Hans-Jürgen Riebe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0541614A1 publication Critical patent/EP0541614A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to 3-hydroxy-2,2'-iminodisuccinic acid and its soluble salts, a process for their preparation and their use as complexing agents in washing and cleaning agents.
  • German Offenlegungsschrift DT 2241134 discloses N-substituted aminohydroxysuccinic acid derivatives which, depending on the type and number of substituents on the N atom bearing carboxyl groups, have a more or less good complexing ability, especially for alkaline earth metal ions.
  • Compounds of this type which have a high level of complexation are relatively difficult to decompose, while products which are more readily degradable have a comparatively low level of complexation.
  • 3-hydroxy-2,2'-iminodisuccinic acid and its soluble salts show both a high level of complexation not only for the alkaline earth metal ions which make up the water hardness but also for heavy metal ions, and also easy biodegradability and as a combination of the values for the complexing ability and unexpectedly superior properties for the biological degradability.
  • soluble substances are to be understood as meaning compounds which dissolve in water at 20 ° C. to more than 0.1 gram per liter.
  • the soluble salts of 3-hydroxy-2,2'-iminodisuccinic acid are preferably those which contain as cations those from the group comprising the ammonium and the alkali ions, the ammonium ions preferably being those of the general structural formula R 1 R 2 R3R 4 N +, in which R l, R 2, R 3 and R 4 are independently hydrogen, alkyl of 1 to 12 carbon atoms or hydroxy-substituted alkyl radicals having 2 to 3 carbon atoms, are.
  • R 1 R 2 R3R 4 N + in which R l, R 2, R 3 and R 4 are independently hydrogen, alkyl of 1 to 12 carbon atoms or hydroxy-substituted alkyl radicals having 2 to 3 carbon atoms, are.
  • A, B, Y and Z independently of one another represent a cation preferably from the group comprising hydrogen, ammonium and the alkali metal ions, the ammonium ions belonging to those of the general structural formula R1R2R3 4N +, in which R 1 , R2, R 3 and R 4 independently of one another are hydrogen, alkyl radicals having 1 to 12 carbon atoms or hydroxy-substituted alkyl radicals having 2 to 3 carbon atoms.
  • the 3-hydroxy-2,2'-iminodisuccinic acid according to the invention has better biodegradability and is more complex, particularly at higher temperatures, for example 70 to 98 ° C. ⁇ ability to perform (Table 1, Table 2).
  • the 3-hydroxy-2,2'-iminodisuccinic acid according to the invention or its salts according to formula (I) are prepared by reacting aspartic acid with epoxysuccinic acid, preferably in molar ratios of 1.05: 1 to 1: 1.05.
  • the reaction is preferably carried out in an aqueous or at least predominantly aqueous medium, the remaining solvent consisting of organic compounds which are inert under the reaction conditions, in particular methanol, ethanol and / or dioxane.
  • the reaction is preferably carried out under largely neutral to weakly basic conditions, that is to say with the addition of alkalis, preferably aqueous solutions of Alkaline or ammonium hydroxides, so that the acid groups of the reactants are present at least partially, preferably completely, in the form of carboxylate anions, preferably as alkali or ammonium carboxylates.
  • the ammonium hydroxide is preferably obtained from the compounds of the general formula R! R 2 R 3 R 4 N + OH-, in which R 1 , R 2 , R 3 and R 4 independently of one another are hydrogen, alkyl radicals with 1 to 12 C - Atoms or hydroxy-substituted alkyl radicals with 2 to 3 carbon atoms are selected.
  • hydroxides include, for example, ammonium hydroxide, methylammonium hydroxide, ethylammonium hydroxide, triethylammonium hydroxide, tributylammonium hydroxide, didecylmethylammonium hydroxide, didecyldimethylammonium hydroxide, diethanolammonium hydroxide and triethanolammonium hydroxide.
  • a particularly preferred embodiment of the production process consists in placing aspartic acid in water in such a way that a 20% by weight to 30% by weight solution or suspension is formed, about 2 mol equivalents of an alkali metal hydroxide, preferably sodium hydroxide, are added and then about 1 mol equivalent Add epoxysuccinic acid dialkali salt, preferably disodium salt. Subsequently, the mixture is preferably stirred until the reaction partners have completely reacted, which generally takes about 1 to 8 hours. To accelerate the reaction, it can be carried out at elevated temperature, for example at 80 to 100 ° C.
  • the tetraalkali salt of 3-hydroxy-2,2'-iminodisuccinic acid is obtained in almost quantitative yield as a more or less colorless solid.
  • 3-Hydroxy-2,2'-iminodisuccinic acid can be released from this or from the solvent-containing crude product in a manner known in principle by adding customary acids, for example hydrochloric acid or sulfuric acid.
  • the acidification step can be omitted if the salt is to be used as such.
  • the step of removing the solvent can be omitted if the product is to be incorporated into liquid formulations or intermediate products, for example pastes or slurries.
  • Epoxysuccinic acid is used in the context of the present application as a synonym for both ice- and trans-epoxysuccinic acid as well as for their mixtures, the trans-form as one of the enantiomers or as any mixture of both, for example as a racemate, may be present.
  • the term “aspartic acid” stands for di L- as well as for D-aspartic acid as well as for their mixtures, for example the racemate.
  • the term "3-hydroxy-2,2'-iminodibernstein acid” accordingly stands for all optical isomers of the constitution represented by this name and the mixtures of such isomers.
  • amino acid is preferably understood to mean the naturally occurring L-aspartic acid.
  • the ic- or trans-epoxysuccinic acid or its salts used as starting material can, for example, according to the method described by G.B. Payne and P.H. Williams in J. Org. Chem. 24 (1959), 54 described processes can be prepared from maleic acid or fumaric acid.
  • a preferred area of use of the 3-hydroxy-2,2'-imino-disuccinic acid according to the invention and their soluble salts is their use as complexing agents in washing or cleaning agents.
  • Such agents contain 0.01 to 20% by weight, preferably 0.1 to 5% by weight, of the complexing agent according to the invention. They can be present as solids, for example in powder or tablet form, or as more or less viscous liquids, for example in the form of solutions, suspensions or pastes.
  • Detergents and cleaning agents in which the compounds according to the invention are present can moreover contain all the constituents customary in such agents, in particular cleaning-active surfactants, builder substances, bleaching agents, inorganic neutral salts, solvents, graying inhibitors, enzymes, bleach activators, foam inhibitors, antimicrobial active substances and abrasives as well as dyes and fragrances.
  • Such agents if they are in solid form, can be prepared in a known manner, for example by spray drying or granulation, it being possible for ingredients which are not stable under such manufacturing conditions to be added subsequently.
  • Liquid formulations are preferably produced by simply mixing the constituents, which may be present as such or in the form of solutions.
  • Suitable builder substances include polycarboxylic acids, in particular polyacrylic acids, polymethacrylic acids, polymaleic acids and their copolymers, sheet silicates, in particular bentonites, and aluminum silicates, in particular zeolites.
  • the aforementioned acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts.
  • the zeolites preferably incorporated into the detergents are in particular those of the NaA or NaX type or mixtures thereof.
  • the agents according to the invention preferably contain zeolite builders in amounts of 5 to 50% by weight, in particular 15 to 40% by weight, optionally in combination with polymer polycarboxylic acids, preferably in amounts of up to 30% by weight. , in particular from 1 to 20% by weight, are contained in the agents according to the invention.
  • the use of the complexing agents according to the invention in the agents according to the invention has the advantage that the constituents which are optionally present at the same time and are sensitive to heavy metal ions, which include, in particular, optical brighteners, enzymes and bleaching agents which release active oxygen the heavy metal ion-catalyzed decomposition can be protected very effectively.
  • disodium di-potassium salt was prepared by reacting aspartic acid neutralized with potassium hydroxide with cis-epoxysuccinic acid di-sodium salt.
  • the concentrated solutions obtained in the preparation described above, which have an active substance content of over 40%, can also be used directly without spinning in and isolating the reaction product.
  • the Cu complex bond constant of the compound Bl was determined to be 6.4 by comparing the measurement data of ligand and ligand + metal titrations. Their Ca complex formation constant was also measured. The Ca complex binding constants of conventional complexing agents determined by the same method are given for comparison. Table 3: Complexation constants
  • a commercially available cooking detergent powder (Hl) was used, the 0.25% by weight of the complexing agent B1 (H2) according to the invention or 0.25% by weight of diethylenetriamine-penta- (methylenephosphonic acid) pentasodium salt (DETMP) (H3) was added.
  • the amount of detergent H1, H2 or H3 added was 140 g each per load; 4 washes each were carried out.
  • the average value of the reflectance of the washed test pieces over the 7 test applications mentioned was 69.2 when using the detergent W2 according to the invention.
  • the corresponding value was significantly worse (67.0) when using the complexing agent-free detergent Hl, the use of the phosphonate-containing agent H3 did not give a significantly better result than the use of H2.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Detergent Compositions (AREA)

Abstract

Du 3-hydroxy-2,2'-iminodiacide aspartique et ses sels solubles sont fabriqués par réaction d'acide aspartique ou de ses sels avec de l'acide succinique époxy ou ses sels. De tels dérivés d'acide aspartique sont utilisés comme agents complexants dans des produits pour le nettoyage et/ou la désinfection de surfaces solides ou de textiles.3-Hydroxy-2,2'-iminodiacid aspartic acid and its soluble salts are made by reacting aspartic acid or its salts with epoxy succinic acid or its salts. Such aspartic acid derivatives are used as complexing agents in products for cleaning and/or disinfecting solid surfaces or textiles.

Description

"Derivat der Aminobernsteinsäure als Komplexieruπgs ittel" "Derivative of aminosuccinic acid as complexing agent"
Die vorliegende Erfindung betrifft 3-Hydroxy-2,2'-iminodibernsteinsäure und ihre löslichen Salze, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Komplexierungsmittel in Wasch- und Reinigungsmitteln.The present invention relates to 3-hydroxy-2,2'-iminodisuccinic acid and its soluble salts, a process for their preparation and their use as complexing agents in washing and cleaning agents.
An Komplexierungsmittel, die in modernen Wasch- und Reinigungsmitteln verwendet werden sollen, wird in zunehmendem Maße zusätzlich zu der selbstverständlichen Forderung nach starkem Komplexierungsver ögen die Anforderung nach möglichst umweltschonendem Verhalten gestellt.Complexing agents that are to be used in modern detergents and cleaning agents are increasingly being required to behave as environmentally friendly as possible, in addition to the self-evident demand for high levels of complexing.
Aus der deutschen Offenlegungsschrift DT 2241134 sind N-substituierte A ino-hydroxybernsteinsäure - Derivate bekannt, die je nach Art und Anzahl der Carboxylgruppen tragenden Substituenten am N-Atom ein mehr oder weni¬ ger gutes Komplexierungsvermögen, besonders für Erdalkaliionen, besitzen. Derartige Verbindungen, die ein hohes Komplexierungsvermögen aufweisen, sind nur relativ schwer abbaubar, während leichter abbaubare Produkte ein vergleichsweise geringes Komplexierungsvermögen besitzen.German Offenlegungsschrift DT 2241134 discloses N-substituted aminohydroxysuccinic acid derivatives which, depending on the type and number of substituents on the N atom bearing carboxyl groups, have a more or less good complexing ability, especially for alkaline earth metal ions. Compounds of this type which have a high level of complexation are relatively difficult to decompose, while products which are more readily degradable have a comparatively low level of complexation.
Es bestand daher nach wie vor die Aufgabe, ein biologisch möglichst leicht abbaubares, möglichst stark ko plexierendes Mittel zu entwickeln.It was therefore still the task to develop an easily biodegradable and highly complex agent.
Überraschenderweise wurde nun gefunden, daß 3-Hydroxy-2,2'-iminodibern- steinsäure und ihre löslichen Salze sowohl ein hohes Komplexierungsver¬ mögen für die die Wasserhärte ausmachenden Erdalkaliionen wie auch für Schwermetallionen als auch leichte biologische Abbaubarkeit zeigen und als Kombination der Werte für das Komplexierungsvermögen und für die biolo¬ gische Abbaubarkeit unerwartet überlegene Eigenschaften aufweisen.Surprisingly, it has now been found that 3-hydroxy-2,2'-iminodisuccinic acid and its soluble salts show both a high level of complexation not only for the alkaline earth metal ions which make up the water hardness but also for heavy metal ions, and also easy biodegradability and as a combination of the values for the complexing ability and unexpectedly superior properties for the biological degradability.
Unter löslichen Substanzen sollen im Rahmen der vorliegenden Anmeldung Verbindungen verstanden werden, die sich in Wasser bei 20 °C zu mehr als 0,1 Gramm pro Liter lösen. Die löslichen Salze der 3-Hydroxy-2,2'-iminodibernsteinsäure sind vor zugsweise diejenigen, die als Kationen solche aus der die Ammonium- un die Alkaliionen umfassenden Gruppe enthalten, wobei die Ammoniumionen be vorzugt solche der allgemeinen Strukturformel R1R2R3R4N+, in der Rl , R2, R3 und R4 unabhängig voneinander Wasserstoff, Alkylreste mit 1 bis 12 C Atomen oder hydroxysubstituierte Alkylreste mit 2 bis 3 C-Atomen bedeuten, sind. Dabei können eine, zwei, drei oder alle vier Carbonsäuregruppen de 3-Hydroxy-2,2'-iminodibernsteinsäure in der Salzform vorliegen. Es handel sich folglich um Verbindungen der allgemeinen Formel (I),In the context of the present application, soluble substances are to be understood as meaning compounds which dissolve in water at 20 ° C. to more than 0.1 gram per liter. The soluble salts of 3-hydroxy-2,2'-iminodisuccinic acid are preferably those which contain as cations those from the group comprising the ammonium and the alkali ions, the ammonium ions preferably being those of the general structural formula R 1 R 2 R3R 4 N +, in which R l, R 2, R 3 and R 4 are independently hydrogen, alkyl of 1 to 12 carbon atoms or hydroxy-substituted alkyl radicals having 2 to 3 carbon atoms, are. One, two, three or all four carboxylic acid groups de 3-hydroxy-2,2'-iminodisuccinic acid can be present in the salt form. Consequently, they are compounds of the general formula (I)
in der A, B, Y und Z unabhängig voneinander ein Kation vorzugsweise aus der Gruppe umfassend Wasserstoff-, Ammonium- und die Alkalimetallionen bedeuten, wobei die Ammoniu ionen zu denen der allgemeinen Strukturformel R1R2R3 4N+ gehören, in der R1, R2, R3 und R4 unabhängig voneinander Was¬ serstoff, Alkylreste mit 1 bis 12 C-Atomen oder hydroxysubstituierte Al¬ kylreste mit 2 bis 3 C-Atomen bedeuten. in which A, B, Y and Z independently of one another represent a cation preferably from the group comprising hydrogen, ammonium and the alkali metal ions, the ammonium ions belonging to those of the general structural formula R1R2R3 4N +, in which R 1 , R2, R 3 and R 4 independently of one another are hydrogen, alkyl radicals having 1 to 12 carbon atoms or hydroxy-substituted alkyl radicals having 2 to 3 carbon atoms.
Im Vergleich mit den Verbindungen der deutschen Offenlegungsschrift DT 2241 134 zeigt sich, daß die erfindungsgemäße 3-Hydroxy-2,2'-iminodi- bernsteinsäure eine bessere biologische Abbaubarkeit und ein insbesondere bei höheren Temperaturen, zum Beispiel 70 bis 98°C, stärkeres Komplexie¬ rungsvermögen aufweist (Tabelle 1, Tabelle 2).In comparison with the compounds of German Offenlegungsschrift DT 2241 134, it can be seen that the 3-hydroxy-2,2'-iminodisuccinic acid according to the invention has better biodegradability and is more complex, particularly at higher temperatures, for example 70 to 98 ° C. ¬ ability to perform (Table 1, Table 2).
Die Herstellung der erfindungsgemäßen 3-Hydroxy-2,2'-iminodibernsteinsäure oder ihrer Salze gemäß Formel (I) erfolgt durch Reaktion von Asparagin¬ säure mit Epoxybemsteinsäure, vorzugsweise in Molverhältnissen von 1,05:1 bis 1:1,05. Die Reaktion wird vorzugsweise in wäßrigem oder zumindest überwiegend wäßrigem Medium ausgeführt, wobei das restliche Lösungsmittel aus unter den Reaktionsbedingungen inerten organischen Verbindungen, ins¬ besondere Methanol, Ethanol und/oder Dioxan, besteht. Vorzugsweise wird die Umsetzung unter weitgehend neutralen bis schwach basischen Bedingung¬ en, das heißt unter Zugabe von Laugen, vorzugsweise wäßrigen Lösungen von Alkal - oder Ammoniumhydroxiden, durchgeführt, so daß die Säuregruppen der Reaktanden zumindest teilweise, bevorzugt vollständig, in Form von Carboxylat-Anionen, bevorzugt als Alkali- oder Ammoniumcarboxylate, vor¬ l egen. Das Ammoniumhydroxid wird dabei vorzugsweise aus den Verbindungen der allgemeinen Formel R!R2R3R4N+ OH-, in der R1, R2, R3 und R4 unabhän¬ gig voneinander Wasserstoff, Alkylreste mit 1 bis 12 C-Atomen oder hydroxysubstituierte Alkylreste mit 2 bis 3 C-Atomen bedeuten, ausgewählt. Zu diesen Hydroxiden gehören zum Beispiel Ammoniumhydroxid, Methylammo- niu hydroxid, Ethylam oniumhydroxid, Triethylammoniumhydroxid, Tributyl- ammoniumhydroxid, Didecyl-methylamrnoniumhydroxid, Didecyl-dimethylammo- niumhydroxid, Diethanolammoniumhydroxid und Triethanolamoniumhydroxid.The 3-hydroxy-2,2'-iminodisuccinic acid according to the invention or its salts according to formula (I) are prepared by reacting aspartic acid with epoxysuccinic acid, preferably in molar ratios of 1.05: 1 to 1: 1.05. The reaction is preferably carried out in an aqueous or at least predominantly aqueous medium, the remaining solvent consisting of organic compounds which are inert under the reaction conditions, in particular methanol, ethanol and / or dioxane. The reaction is preferably carried out under largely neutral to weakly basic conditions, that is to say with the addition of alkalis, preferably aqueous solutions of Alkaline or ammonium hydroxides, so that the acid groups of the reactants are present at least partially, preferably completely, in the form of carboxylate anions, preferably as alkali or ammonium carboxylates. The ammonium hydroxide is preferably obtained from the compounds of the general formula R! R 2 R 3 R 4 N + OH-, in which R 1 , R 2 , R 3 and R 4 independently of one another are hydrogen, alkyl radicals with 1 to 12 C - Atoms or hydroxy-substituted alkyl radicals with 2 to 3 carbon atoms are selected. These hydroxides include, for example, ammonium hydroxide, methylammonium hydroxide, ethylammonium hydroxide, triethylammonium hydroxide, tributylammonium hydroxide, didecylmethylammonium hydroxide, didecyldimethylammonium hydroxide, diethanolammonium hydroxide and triethanolammonium hydroxide.
Eine besonders bevorzugte Ausführungsform des Herstellungsverfahrens be¬ steht darin, Asparaginsäure so in Wasser vorzulegen, daß eine 20 ge¬ wichtsprozentige bis 30 gewichtsprozentige Lösung oder Suspension ent¬ steht, etwa 2 Molequivalente eines Alkalihydroxids, vorzugsweise Natrium¬ hydroxid, zuzugeben und anschließend etwa 1 Molequivalent Epoxybernstein- säure-Dialkalisalz, vorzugsweise Dinatriumsalz, zuzusetzen. Anschließend rührt man bevorzugt bis zur vollständigen Umsetzung der Reaktionspartner, die in der Regel etwa 1 bis 8 Stunden benötigt. Zur Beschleunigung der Reaktion kann sie bei erhöhter Temperatur, zum Beispiel bei 80 bis 100 °C, durchgeführt werden. Nach Abziehen des Lösungsmittels, zum Beispiel mit Hilfe eines Rotationsverdampfers, erhält man in nahezu quantitativer Aus¬ beute das Tetraalkalisalz der 3-Hydroxy-2,2'-iminodibernsteinsäure als mehr oder weniger farblosen Feststoff. Aus diesem oder aus dem lösungs- mittelhaltigen Rohprodukt kann in im Prinzip bekannter Weise durch Zugabe üblicher Säuren, zum Beispiel Salzsäure oder Schwefelsäure, die 3- Hydroxy-2,2'-iminodibernsteinsäure freigesetzt werden. Der Ansäuerungs- schritt kann unterbleiben, wenn das Salz als solches weiter eingesetzt werden soll. Der Schritt des Entfernens des Lösungsmittels kann entfallen, wenn das Produkt in flüssige Formulierungen oder Zwischenprodukte, zum Beispiel in Pasten oder Slurries, eingearbeitet werden soll.A particularly preferred embodiment of the production process consists in placing aspartic acid in water in such a way that a 20% by weight to 30% by weight solution or suspension is formed, about 2 mol equivalents of an alkali metal hydroxide, preferably sodium hydroxide, are added and then about 1 mol equivalent Add epoxysuccinic acid dialkali salt, preferably disodium salt. Subsequently, the mixture is preferably stirred until the reaction partners have completely reacted, which generally takes about 1 to 8 hours. To accelerate the reaction, it can be carried out at elevated temperature, for example at 80 to 100 ° C. After the solvent has been stripped off, for example using a rotary evaporator, the tetraalkali salt of 3-hydroxy-2,2'-iminodisuccinic acid is obtained in almost quantitative yield as a more or less colorless solid. 3-Hydroxy-2,2'-iminodisuccinic acid can be released from this or from the solvent-containing crude product in a manner known in principle by adding customary acids, for example hydrochloric acid or sulfuric acid. The acidification step can be omitted if the salt is to be used as such. The step of removing the solvent can be omitted if the product is to be incorporated into liquid formulations or intermediate products, for example pastes or slurries.
"Epoxybemsteinsäure" wird im Rahmen der vorliegenden Anmeldung als Syno¬ nym sowohl für eis- als auch für trans-Epoxybernsteinsäure als auch für deren Gemische verwendet, wobei die trans-For als eines der Enantio eren oder als beliebiges Gemisch aus beiden, beispielsweise als Racemat, vor liegen kann. Der Begriff "Asparaginsäure" steht analog dazu sowohl für di L- als auch für die D-Asparaginsäure als auch für deren Gemische, zu Beispiel das Racemat. Die Bezeichnung "3-Hydroxy-2,2'-iminodibernstein säure" steht demgemäß für alle optischen Isomere der durch diesen Name wiedergegebenen Konstitution und die Gemische derartiger Isomere."Epoxysuccinic acid" is used in the context of the present application as a synonym for both ice- and trans-epoxysuccinic acid as well as for their mixtures, the trans-form as one of the enantiomers or as any mixture of both, for example as a racemate, may be present. Analogously, the term "aspartic acid" stands for di L- as well as for D-aspartic acid as well as for their mixtures, for example the racemate. The term "3-hydroxy-2,2'-iminodibernstein acid" accordingly stands for all optical isomers of the constitution represented by this name and the mixtures of such isomers.
Unbeschadet der oben gegebenen Definition wird unter "Asparaginsäure" vorzugsweise die natürlich vorkommende L-Asparaginsäure verstanden.Without prejudice to the definition given above, "aspartic acid" is preferably understood to mean the naturally occurring L-aspartic acid.
Die als Edukt eingesetzte eis- beziehungsweise trans-Epoxybernsteinsäure oder deren Salze können zum Beispiel nach dem von G.B. Payne und P.H. Williams in J. Org. Chem. 24 (1959), 54 beschriebenen Verfahren aus Maleinsäure beziehungsweise Fumarsäure hergestellt werden.The ic- or trans-epoxysuccinic acid or its salts used as starting material can, for example, according to the method described by G.B. Payne and P.H. Williams in J. Org. Chem. 24 (1959), 54 described processes can be prepared from maleic acid or fumaric acid.
Ein bevorzugtes Einsatzgebiet der erfindungsgemäßen 3-Hydroxy-2,2'-imino- dibernsteinsäure und ihrer löslichen Salze ist ihre Verwendung als Kom¬ plexierungsmittel in Wasch- oder Reinigungsmitteln. Derartige Mittel ent¬ halten 0,01 bis 20 Gew.-%, vorzugsweise 0,1 bis 5 Gew.-%, des erfindungs¬ gemäßen Ko plexierungs ittels. Sie können als Feststoffe, zum Beispiel pulver- oder tablettenförmig, oder als mehr oder weniger viskose Flüssig¬ keiten, zum Beispiel in Form von Lösungen, Suspensionen oder Pasten, vor¬ liegen.A preferred area of use of the 3-hydroxy-2,2'-imino-disuccinic acid according to the invention and their soluble salts is their use as complexing agents in washing or cleaning agents. Such agents contain 0.01 to 20% by weight, preferably 0.1 to 5% by weight, of the complexing agent according to the invention. They can be present as solids, for example in powder or tablet form, or as more or less viscous liquids, for example in the form of solutions, suspensions or pastes.
Wasch- und Reinigungsmittel, in denen die erfindungsgemäßen Verbindungen enthalten sind, können darüber hinaus alle in derartigen Mitteln üblichen Bestandteile, insbesondere reinigungsaktive Tenside, Buildersubstanzen, Bleichmittel, anorganische Neutralsalze, Lösungsmittel, Vergrauungsinhi- bitoren, Enzyme, Bleichaktivatoren, Schauminhibitoren, antimikrobielle Wirkstoffe und Abrasivmittel sowie Färb- und Duftstoffe, enthalten.Detergents and cleaning agents in which the compounds according to the invention are present can moreover contain all the constituents customary in such agents, in particular cleaning-active surfactants, builder substances, bleaching agents, inorganic neutral salts, solvents, graying inhibitors, enzymes, bleach activators, foam inhibitors, antimicrobial active substances and abrasives as well as dyes and fragrances.
Derartige Mittel können, wenn sie in fester Form vorliegen, in bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, hergestellt werden, wobei Inhaltstoffe, die unter derartigen Herstellbedingungen nicht stabil sind, nachträglich zugesetzt werden können. Flüssige Formulierungen werden bevorzugt durch einfaches Vermischen der Bestandteile, die als solche oder in Form von Lösungen vorliegen können, hergestellt.Such agents, if they are in solid form, can be prepared in a known manner, for example by spray drying or granulation, it being possible for ingredients which are not stable under such manufacturing conditions to be added subsequently. Liquid formulations are preferably produced by simply mixing the constituents, which may be present as such or in the form of solutions.
Zu den geeigneten Buildersubstanzen gehören Polycarbonsäuren, insbesondere Polyacrylsäuren, Polymethacrylsäuren, Polymaleinsäuren und deren Copo- ly ere, Schichtsilikate, insbesondere Bentonite, und Alu osilikate, ins¬ besondere Zeolithe. Die vorgenannten Säuren werden üblicherweise in Form ihrer Alkalisalze, insbesondere ihrer Natrium- oder Kaliumsalze, einge¬ setzt. Die vorzugsweise in die Waschmittel eingearbeiteten Zeolithe sind insbesondere solche des NaA- oder NaX-Typs oder deren Gemische. Vorzugs¬ weise enthalten die erfindungsgemäßen Mittel Zeolith-Builder in Mengen von 5 bis 50 Gew.-%, insbesondere von 15 bis 40 Gew.-%, gegebenenfalls in Kombination mit Polymer-Polycarbonsäuren, die vorzugsweise in Mengen bis zu 30 Gew.-%, insbesondere von 1 bis 20 Gew.-%, in den erfindungsgemäßen Mitteln enthalten sind.Suitable builder substances include polycarboxylic acids, in particular polyacrylic acids, polymethacrylic acids, polymaleic acids and their copolymers, sheet silicates, in particular bentonites, and aluminum silicates, in particular zeolites. The aforementioned acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts. The zeolites preferably incorporated into the detergents are in particular those of the NaA or NaX type or mixtures thereof. The agents according to the invention preferably contain zeolite builders in amounts of 5 to 50% by weight, in particular 15 to 40% by weight, optionally in combination with polymer polycarboxylic acids, preferably in amounts of up to 30% by weight. , in particular from 1 to 20% by weight, are contained in the agents according to the invention.
Die Verwendung der erfindungsgemäßen Komplexierungsmittel in den erfin¬ dungsgemäßen Mitteln hat zusätzlich zu der wasserenthärtenden Wirkung der Komplexierungsmittel den Vorteil, daß die gegebenenfalls gleichzeitig vorhandenen gegenüber Schwer etallionen empfindlichen Bestandteile, zu denen insbesondere optische Aufheller, Enzyme und Aktivsauerstoff-abge¬ bende Bleichmittel gehören, gegen die Schwermeta lionen-katalysierte Zer¬ setzung sehr effektiv geschützt werden.In addition to the water-softening effect of the complexing agents, the use of the complexing agents according to the invention in the agents according to the invention has the advantage that the constituents which are optionally present at the same time and are sensitive to heavy metal ions, which include, in particular, optical brighteners, enzymes and bleaching agents which release active oxygen the heavy metal ion-catalyzed decomposition can be protected very effectively.
BeispieleExamples
Beispiel 1example 1
Zu 13,3 g (0,1 Mol) L-Asparaginsäure in 50 ml Wasser wurden bei Raumtem¬ peratur unter Rühren 8,0 g (0,2 Mol) Natriumhydroxid und anschließend 17,6 g (0,1 Mol) cis-Epoxybernsteinsäure-di-Natriumsalz gegeben. Die klare, schwach gelbe Lösung wurde 8 Stunden unter Rückfluß erhitzt. An¬ schließend wurde das Lösungsmittel am Rotationsverdampfer (Vakuum) ent¬ fernt. Man erhielt 36,8 g 3-Hydroxy-2,2'-iminodibernsteinsäure-tetra- Natriumsalz (Bl) als C(3)-Epimerengemisch. Der farblose Feststoff enthielt laut !H-NMR ca. 5 Gew.-% Di-Natriumtartrat (Signal bei = 4,40). IR (KBr): [cm"1] = 3400 (0-H); 1590 (C=0 Carbonsäure); 1390.8.0 g (0.2 mol) of sodium hydroxide and then 17.6 g (0.1 mol) of cis were added to 13.3 g (0.1 mol) of L-aspartic acid in 50 ml of water at room temperature with stirring. Epoxy succinic acid disodium salt given. The clear, pale yellow solution was refluxed for 8 hours. The solvent was then removed on a rotary evaporator (vacuum). 36.8 g of 3-hydroxy-2,2'-iminodisuccinic acid tetra sodium salt (B1) were obtained as a C (3) epimer mixture. According to the H-NMR, the colorless solid contained about 5% by weight disodium tartrate (signal at = 4.40). IR (KBr): [cm " 1 ] = 3400 (0-H); 1590 (C = 0 carboxylic acid); 1390.
1H-NMR (250 MHz, D20) : [ppm] = 2,45 (m,2H-C(3')); 3,35 ( , H-C(2'))1H-NMR (250 MHz, D 2 0): [ppm] = 2.45 (m, 2H-C (3 ')); 3.35 (, HC (2 '))
3,45 und 3,50 (d und d, H-C(2)); 4,15 und 4,20 (d und d, H-C(3)).3.45 and 3.50 (d and d, H-C (2)); 4.15 and 4.20 (d and d, H-C (3)).
In analoger Weise wurde durch Umsetzung von mit Kaliumhydroxid neutrali sierter Asparaginsäure mit cis-Epoxybernsteinsäure-di-Natriumsalz da entsprechende Di-Natrium-di-Kaliumsalz hergestellt.In an analogous manner, the corresponding disodium di-potassium salt was prepared by reacting aspartic acid neutralized with potassium hydroxide with cis-epoxysuccinic acid di-sodium salt.
Die bei der oben beschriebenen Herstellung anfallenden konzentrierten Lö sungen, die einen Aktivsubstanzanteil von über 40 % aufweisen, können auch ohne Einrotieren und Isolierung des Reaktionsproduktes direkt weiterver¬ wendet werden.The concentrated solutions obtained in the preparation described above, which have an active substance content of over 40%, can also be used directly without spinning in and isolating the reaction product.
Beispiel 2: AbbaubarkeitstestExample 2: Degradability test
Nach dem modifizierten OECD-Screening-Test (EEC Directive 79/831, Annex V, Part C, 5.2.) wurde die aquatische Bioabbaubarkeit der in Tabelle 1 ange¬ gebenen Produkte geprüft. Aufgeführt ist die prozentuale Abbnahme des DOC-Wertes (dissolved organic carbon, in Lösung vorliegender Kohlenstoff) nach 28 Tagen unter aeroben Abbaubedingungen nach Voradaption der Bakte¬ rien gemäß der Zahn-Wellens-Methode (R. Zahn, H. Wellens, Chem. Ztg. 98 (1974), 228).According to the modified OECD screening test (EEC Directive 79/831, Annex V, Part C, 5.2.), The aquatic biodegradability of the products given in Table 1 was tested. The percentage decrease in the DOC value (dissolved organic carbon, carbon present in solution) is shown after 28 days under aerobic degradation conditions after pre-adaptation of the bacteria according to the Zahn-Wellens method (R. Zahn, H. Wellens, Chem. Ztg 98: 228 (1974).
Tabelle 1 : Biologische AbbaubarkeitTable 1: Biodegradability
Umsetzungsprodukt von Epoxy- bernsteinsäure-di-Natrium- Abbaubarkeit [%] salz mit dem Natriumsalz vonReaction product of epoxy succinic acid disodium degradability [%] salt with the sodium salt of
a) L-Asparaginsäure (Bl) 80-89 b) Glutaminsäure 51-57 c) Ethylendiamin 7-10 d) Alanin 12-14 Das erfindungsgemäße Produkt (Zeile a) ist im Vergleich mit den ähnlichen Verbindungen der Zeilen b bis d relativ leicht abbaubar.a) L-aspartic acid (Bl) 80-89 b) glutamic acid 51-57 c) ethylenediamine 7-10 d) alanine 12-14 The product according to the invention (line a) is relatively easily degradable in comparison with the similar compounds in lines b to d.
Beispiel 3: Tests zur KomplexierkapazitätExample 3: Complexing capacity tests
Lösungen von jeweils circa 1 g der in Tabelle 2 aufgeführten Substanzen in circa 250 ml destilliertem Wasser wurden durch Zugabe von 2 N NaOH auf einen pH-Wert von 11 eingestellt, jeweils 10 ml 2 gewichtsprozentige Na- triumcarbonat-Lösung wurden zugegeben und die bei den in Tabelle 2 ange¬ gebenen Temperaturen gehaltenen klaren Lösungen wurden mit 0,25 N Calcium- chlorid-Lösung bis zum Auftreten einer ersten Trübung titriert (Photo¬ metrische Bestimmung, Meßwellenlänge 400 nm). In analoger Weise wurde durch Titration mit wäßriger FeCl3-Lösung das Komplexierungsvermögen von Bl für Eisen zu 1139 mg Fe3+ pro g Komplexbildner bei 20°C und zu 289 mg Fe + pro g Komplexbildner bei 98°C bestimmt.Solutions of about 1 g each of the substances listed in Table 2 in about 250 ml of distilled water were adjusted to a pH of 11 by adding 2 N NaOH, 10 ml each of 2% by weight sodium carbonate solution were added and the two Clear solutions maintained in Table 2 were titrated with 0.25 N calcium chloride solution until a first turbidity occurred (photometric determination, measuring wavelength 400 nm). In an analogous manner, the complexing ability of Bl for iron was determined by titration with aqueous FeCl3 solution to be 1139 mg Fe 3+ per g complexing agent at 20 ° C. and 289 mg Fe + per g complexing agent at 98 ° C.
Tabelle 2 : KomplexierkapazitätTable 2: Complexing capacity
Umsetzungsprodukt von Epoxy- bernsteinsäure-di-Natrium- salz mit dem Natriumsalz vonReaction product of epoxy succinic acid di-sodium salt with the sodium salt of
a) L-Asparaginsäure (Bl) b) Glutaminsäure c) Ethylendiamin d) Alanin a) L-aspartic acid (Bl) b) glutamic acid c) ethylenediamine d) alanine
Durch Vergleich der Meßdaten von Ligand- und Ligand + Metall-Titrationen wurde die Cu-Komplexbindungskonstante der Verbindung Bl zu 6,4 bestimmt. Ebenso wurde ihre Ca-Komplexb ldungskonstante gemessen. Als Vergleich sind die nach dem gleichen Verfahren ermittelten Ca-Komplexbindungskonstanten üblicher Komplexierungsmittel angegeben. Tabelle 3 : KomplexbildungskonstantenThe Cu complex bond constant of the compound Bl was determined to be 6.4 by comparing the measurement data of ligand and ligand + metal titrations. Their Ca complex formation constant was also measured. The Ca complex binding constants of conventional complexing agents determined by the same method are given for comparison. Table 3: Complexation constants
Verbindung pKςa Connection pKς a
3-Hydroxy-2,2'-iminodibernsteinsäure (Bl) 5,8 Hydroxyethyl2,2'-iminodiessigsäure 4,6 Isoserin-N,N-diessigsäure 5,63-Hydroxy-2,2'-iminodisuccinic acid (B1) 5.8 Hydroxyethyl2,2'-iminodiacetic acid 4.6 isoserine-N, N-diacetic acid 5.6
Beispiel 4:Example 4:
Unter Verwendung eines handelsüblichen Kochwaschmittelpulvers wurde in einer Trommelwaschmaschine (Miele W 760) jeweils 3,5 kg saubere Füllwäsche mit jeweils 2,1 g mit einer bleichbaren Anschmutzung verunreinigten Tex- tilproben (Rotwein auf Baumwolle; Johannisbeere auf Baumwolle; Tee auf Baumwolle; Rotwein auf veredelter Baumwolle; Tee auf veredelter Baumwolle; Rotwein auf veredelter Baumwolle/Polyester; Tee auf veredelter Baumwolle/ Polyester) bei 90 °C mit Wasser des Härtegrades 16 °dH (160 mg CaO/Liter), dem 5 ppm Cu(II) zugesetzt worden waren, im Ein-Laugen-Verfahren gewaschen (Waschprogramm 241/22). Zum Einsatz kam ein handelsübliches Kochwaschmit¬ telpulver (Hl), dem 0,25 Gew.-% des erfindungsgemäßen Komplexierungsmit- tels Bl (H2) beziehungsweise 0,25 Gew.-% Diethylentriamin-penta-(methy- lenphosphonsäure)-penta-Natriumsalz (DETMP) (H3) zugegeben wurde. Die Zu¬ gabemenge der Waschmittel Hl, H2 oder H3 betrug jeweils 140 g pro Wasch¬ ladung; jeweils 4 Wäschen wurden durchgeführt. Der Durchschnittswert der Remission der gewaschenen Teststücke über die 7 genannten Testan- sch utzungen betrug bei Verwendung des erfindungsgemäßen Waschmittels W2 69,2. Der entsprechende Wert war bei Verwendung des komplexierungsmittel- freien Waschmittels Hl signifikant schlechter (67,0), die Verwendung des phosphonathaltigen Mittels H3 ergab kein signifikant besseres Ergebnis als die Verwendung von H2.Using a commercially available cooking detergent powder, 3.5 kg of clean laundry with 2.1 g each of textile samples contaminated with bleachable soiling (red wine on cotton; currant on cotton; tea on cotton; red wine on) was washed in a drum washing machine (Miele W 760) refined cotton; tea on refined cotton; red wine on refined cotton / polyester; tea on refined cotton / polyester) at 90 ° C with water of hardness 16 ° dH (160 mg CaO / liter) to which 5 ppm Cu (II) has been added were washed in the one-lye process (wash program 241/22). A commercially available cooking detergent powder (Hl) was used, the 0.25% by weight of the complexing agent B1 (H2) according to the invention or 0.25% by weight of diethylenetriamine-penta- (methylenephosphonic acid) pentasodium salt (DETMP) (H3) was added. The amount of detergent H1, H2 or H3 added was 140 g each per load; 4 washes each were carried out. The average value of the reflectance of the washed test pieces over the 7 test applications mentioned was 69.2 when using the detergent W2 according to the invention. The corresponding value was significantly worse (67.0) when using the complexing agent-free detergent Hl, the use of the phosphonate-containing agent H3 did not give a significantly better result than the use of H2.
Diese Waschergebnisse zeigen, daß die erfindungsgemäße Verbindung Bl die Perboratzersetzung durch Schwermetalle mindestens ebensogut unterdrückt wie ein bekanntermaßen gut wirksames Komplexierungsmittel aus der Klasse der Phosphonate. These washing results show that the compound B1 according to the invention suppresses the perborate decomposition by heavy metals at least as well as a known complexing agent from the class of the phosphonates.

Claims

Patentansprüche Claims
1. 3-Hydroxy-2,2'-iminodibernsteinsäure und ihre löslichen Salze.1. 3-hydroxy-2,2'-iminodisuccinic acid and its soluble salts.
2. Verbindungen nach Anspruch 1, dadurch gekennzeichnet, daß sie aus den Verbindungen nach Formel (I) ausgewählt werden,2. Compounds according to claim 1, characterized in that they are selected from the compounds of formula (I),
in der A, B, Y und Z unabhängig voneinander ein Kation aus der Gruppe umfassend Wasserstoff-, Ammonium- und die Alkalimetallionen bedeuten, wobei die Ammoniumionen aus denen der allgemeinen Formel R*-*R R3R4N+ ausgewählt werden, in der R-*-, R2, R3 und R4 unabhängig voneinander Wasserstoff, Alkylreste mit 1 bis 12 C-Atomen oder hydroxysubsti¬ tuierte Alkylreste mit 2 bis 3 C-Atomen bedeuten. in which A, B, Y and Z independently of one another are a cation from the group comprising hydrogen, ammonium and the alkali metal ions, the ammonium ions being selected from those of the general formula R * - * RR 3 R 4 N + in which R - * -, R 2 , R 3 and R 4 independently of one another denote hydrogen, alkyl radicals with 1 to 12 C atoms or hydroxy-substituted alkyl radicals with 2 to 3 C atoms.
3. Verbindungen gemäß Formel (I) nach Anspruch 2, dadurch gekennzeichnet, daß Kation A ein Alkaliion ist und daß A, B, Y und Z gleich sind.3. Compounds according to formula (I) according to claim 2, characterized in that cation A is an alkali ion and that A, B, Y and Z are the same.
4. Verfahren zur Herstellung von Verbindungen gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß Epoxybemsteinsäure oder ein Epoxybernsteinsäuremono- oder -disalz mit Asparaginsäure oder einem Asparaginsäure ono- oder -disalz umgesetzt wird.4. A process for the preparation of compounds according to any one of claims 1 to 3, characterized in that epoxy succinic acid or an epoxysuccinic acid mono- or -disalz is reacted with aspartic acid or an aspartic acid ono- or -disalz.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das Molver¬ hältnis von Epoxybemsteinsäure beziehungsweise des Epoxybernstein- säuresalzes zu Asparaginsäure beziehungsweise des Asparaginsäuresalzes im Bereich von 1,05 : 1 bis 1 : 1,05 liegt.5. The method according to claim 4, characterized in that the Molver¬ ratio of epoxy succinic acid or the epoxy succinic acid salt to aspartic acid or the aspartic acid salt is in the range from 1.05: 1 to 1: 1.05.
6. Verfahren nach einem der Ansprüche 4 oder 5, dadurch gekennzeichnet, daß ein Mono- oder Di- Ammonium- oder Alkalisalz der Asparaginsäure mit einem Mono- oder Di- Ammonium- oder Alkalisalz der Epoxybemsteinsäure umgesetzt wird, wobei die Ammoniumionen aus denen der allgemeinen Formel R!R2R3R4N+ ausgewählt werden, in der R1, R2, R3 und R4 unabhängig voneinander Wasserstoff, Alkylreste mit 1 bis 12 C Atomen oder hydroxysubstituierte Alkylreste mit 2 bis 3 C-Atomen be deuten.6. The method according to any one of claims 4 or 5, characterized in that a mono- or di-ammonium or alkali salt of aspartic acid is reacted with a mono- or di-ammonium or alkali salt of epoxy succinic acid, the ammonium ions from those of the general Formula R! R 2 R 3 R 4 N + can be selected in which R 1 , R 2 , R 3 and R 4 independently of one another denote hydrogen, alkyl radicals with 1 to 12 C atoms or hydroxy-substituted alkyl radicals with 2 to 3 C atoms.
7. Verfahren nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, daß Epoxybemsteinsäure als 20 gewichtsprozentige bis 30 gewichtspro zentige Lösung oder Suspension in Wasser vorgelegt wird, diese gege benenfalls vollständig oder teilweise durch Zugabe einer Lösung vo Ammonium- oder Alkalihydroxid neutralisiert wird, man die gegebenen falls vollständig oder teilweise durch eine Lösung von Ammonium- ode Alkalihydroxid neutralisierte Asparaginsäure zugibt, wobei das Ammo¬ niumhydroxid aus den Verbindungen der allgemeinen Formel R!R2R3R4N+ OH" ausgewählt wird, in der R1, R2, R3 und R4 unabhängig voneinander Wasserstoff, Alkylreste mit 1 bis 12 C-Atomen oder hy¬ droxysubstituierte Alkylreste mit 2 bis 3 C-Atomen bedeuten, und das Reaktionsgemisch 0,5 Stunden bis 8 Stunden bei Temperaturen von Raum¬ temperatur bis 100°C hält.7. The method according to any one of claims 4 to 6, characterized in that epoxy succinic acid is presented as a 20 percent by weight to 30 percent by weight solution or suspension in water, this is optionally completely or partially neutralized by adding a solution of ammonium or alkali hydroxide, one the aspartic acid, if appropriate completely or partially neutralized by a solution of ammonium or alkali hydroxide, is added, the ammonium hydroxide being selected from the compounds of the general formula R! R 2 R 3 R 4 N + OH "in which R 1 , R 2 , R 3 and R 4 independently of one another are hydrogen, alkyl radicals with 1 to 12 carbon atoms or hydroxy-substituted alkyl radicals with 2 to 3 carbon atoms, and the reaction mixture is from 0.5 hours to 8 hours at temperatures from room temperature to 100 ° C holds.
8. Mittel zum Reinigen und/oder.Desinfizieren von festen Oberflächen oder Textilien, dadurch gekennzeichnet, daß es 0,01 bis 20 Gew.-%, insbe¬ sondere 0,1 bis 5 Gew.-% eines Komplexierungsmittels gemäß einem der Ansprüche 1 bis 3 und 5 bis 50 Gew.-%, insbesondere 15 bis 40 Gew.- , Zeolith, gegebenenfalls in Kombination mit bis zu 30 Gew.-%, insbe¬ sondere von 1 bis 20 Gew.-%, Polymer-Polycarbonsäure, enthält. 8. Means for cleaning and / or disinfecting solid surfaces or textiles, characterized in that it contains 0.01 to 20% by weight, in particular 0.1 to 5% by weight, of a complexing agent according to one of claims 1 up to 3 and 5 to 50% by weight, in particular 15 to 40% by weight, zeolite, optionally in combination with up to 30% by weight, in particular from 1 to 20% by weight, of polymer-polycarboxylic acid .
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US5318726A (en) 1994-06-07
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