EP0356974B1 - Cleaning and washing composition - Google Patents

Cleaning and washing composition Download PDF

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Publication number
EP0356974B1
EP0356974B1 EP89115874A EP89115874A EP0356974B1 EP 0356974 B1 EP0356974 B1 EP 0356974B1 EP 89115874 A EP89115874 A EP 89115874A EP 89115874 A EP89115874 A EP 89115874A EP 0356974 B1 EP0356974 B1 EP 0356974B1
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EP
European Patent Office
Prior art keywords
acid
weight
alanine
washing
salts
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EP89115874A
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German (de)
French (fr)
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EP0356974A3 (en
EP0356974A2 (en
Inventor
Richard Dr. Baur
Charalampos Dr. Gousetis
Wolfgang Dr. Trieselt
Werner Dr. Bochnitschek
Alfred Dr. Oftring
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BASF SE
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BASF SE
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    • 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
    • C11D3/30—Amines; Substituted amines ; Quaternized 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to detergents and cleaning agents for aqueous applications containing 2 to 25% by weight as softener, based on the total weight of the detergent, ⁇ -alanine-N, N-diacetic acid or its alkali metal or ammonium salts.
  • Detergents and cleaning agents for aqueous applications are generally composed of a combination of various surface-active substances and other auxiliaries.
  • softeners should be mentioned primarily, i.e. Substances that are able to bind the hardness constituents of water, especially Ca++ and Mg++ cations.
  • Nitrilotriacetic acid and its salts have recently been used as a replacement for the phosphates, but these compounds are also not fully satisfactory since they deposit deposits of hardness, e.g. on textile fabrics, not preventing them effectively enough.
  • the present invention was therefore based on detergents and cleaning agents for aqueous applications, which contain softeners which are even more effective than nitrilotriacetic acid.
  • detergents and cleaning agents for aqueous applications which contain 2 to 25% by weight, based on the total weight of the detergent, of ⁇ -alanine-N, N-diacetic acid or its alkali metal or ammonium salts as softener.
  • Beta-alanine-N, N-diacetic acid is biodegradable and can be produced particularly advantageously by reacting acrylic acid with iminodiacetic acid in an aqueous medium in large quantities (see our recent application P 38 29 859.7 - OZ 0050/40154).
  • ⁇ -alanine-N, N-diacetic acid is its lower binding capacity for heavy metal ions such as Cu2+ or Cd2+ compared to nitrilotriacetic acid, such as a comparison of the corresponding equilibrium constants on pages 564 and 565 in Organic Sequestering Agents, A.E. Martell, J. Wiley & Sons, Hew York (1959). This reduces the likelihood that traces of undegraded ⁇ -alanine-N, N-diacetic acid will release heavy metal ions deposited in river sediments.
  • the ⁇ -alanine-N, N-diacetic acid or its alkali metal or ammonium salts are used in amounts of 2 to 25, preferably in amounts of 5 to 15,% by weight.
  • Their alkali metal salts are used with particular advantage, the trisodium salt being particularly preferred.
  • the salts of ⁇ -alanine-N, N-diacetic acid with basic compounds such as potassium hydroxide, ammonia or primary, secondary or tertiary aliphatic organic amines having 1 to 4 carbon atoms in the aliphatic radicals such as methylamine, dimethylamine or trimethylamine can also be used .
  • Detergents generally also contain 5 to 50% by weight of other softeners 6 to 25% by weight of surface-active compounds as washing-active substances 5 to 35 wt% bleach 0 to 60% by weight of substances essential for the consistency of the preparation and in minor amounts other auxiliary substances such as bleach stabilizers, bleach activators, enzymes, graying inhibitors, foam regulators, corrosion inhibitors, optical brighteners, solubilizers, fragrances or dyes.
  • Cleaning agents generally contain other essential ingredients 30 to 80 wt .-% dirt-disrupting components 3 to 20% by weight of other agents which are able to bind hardening agents 2 to 10% by weight of surface-active substances 1 to 5% by weight of anti-corrosion agent 0 to 60% by weight of substances essential for the consistency of the preparation and in minor quantities other auxiliary substances such as enzymes, foam regulators, fragrances, solubilizers or disinfectants.
  • the washing and cleaning agents according to the invention can contain alkaline substances such as sodium carbonate, sodium silicate and sodium phosphate or complexing agents of an inorganic nature such as e.g.
  • Suitable phosphorus-containing organic complexing agents are methane diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl -1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, methylamino- or ethylaminodimethylene diphosphonic acid, ethylene diaminotetramethylene tetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphonoacetic acid, phosphonopropionic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonopropane-2,3- dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphonobutane-2,3,4-tricarboxylic acid and copolymers of vinylphosphonic acid and
  • Suitable hydroxymono- or polycarboxylic acids are glycolic acid, lactic acid, malic acid, tartronic acid, methyltartronic acid, gluconic acid, glyceric acid, citric acid, tartaric acid and salicylic acid.
  • Aminocarboxylic acids to be preferably used are glycine, glycylglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, iminodi- or triacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethyl-ethylenediaminetriacetic acid, diethylenetriamine-pentaacetic acid and polymerisation of a carboxylic acid, e.g. of acetic acid, succinic acid or tricarballylic acid, and subsequent saponification, or by condensation of polyamines with a molecular weight of 500 to 10,000 with chloroacetic or bromoacetic salts.
  • a carboxylic acid e.g. of acetic acid, succinic acid or tricarballylic acid, and subsequent saponification, or by condensation of polyamines with a molecular weight of 500 to 10,000 with chloroacetic or bromoacetic salts
  • Zeolite 4A whose production is described in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 24 on p. 120, is particularly suitable as an ion exchanger.
  • Suitable surfactants are those which contain at least one hydrophobic organic radical and one water-solubilizing ionic or nonionic group in the molecule.
  • the hydrophobic radical preferably consists of an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and particularly preferably 12 to 18 C atoms or an alkyl aromatic radical with 6 to 18, preferably 8 to 16 C atoms in the alkyl group.
  • anionic surfactants are the sodium, potassium and ammonium salts of carboxylic acids, sulfonic acids and sulfuric acid monoesters with the specified number of carbon atoms.
  • the surfactants of the sulfonate type include, in particular, alkylbenzenesulfonates with 9 to 15 carbon atoms in the alkyl radical, alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products receives.
  • alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
  • More useful sulfonate type surfactants are the methyl or ethyl esters of ⁇ -sulfo fatty acids.
  • Suitable sulfate-type surfactants are the salts mentioned of the sulfuric acid monoesters of primary and secondary alcohols. Sulfated fatty acid monoglycerides and sulfated reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols are also suitable.
  • carboxylates come in particular the sodium salts of natural fatty acids, i.e. the usual soaps.
  • Preferred cationic surfactants are dialkyldimethylammonium chlorides such as distearyldimethylammonium chloride and imidazolinium salts of the 1-alkylamidoethyl-1-methyl-2-alkylimidazolinium methoxysulfate type.
  • Suitable amphoteric surfactants which contain both anion and cation-active groups in the same molecule in aqueous solution are compounds of the alkyl betaines or alkyl sulfobetaines type.
  • Addition products of 4 to 40, preferably 4 to 20 moles of ethylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide are advantageously used as nonionic surfactants.
  • the addition products of 5 to 16 moles of ethylene oxide with primary or secondary alcohols with 8 to 18, preferably 12 to 18 C atoms, and with mono- or dialkylphenols with 6 to 14 C atoms in the alkyl radicals are particularly preferred.
  • non-or not completely water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • water-soluble addition products of ethylene oxide containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups can be used as nonionic surface-active substances of propylene glycol, alkylenediamine-polypropylene glycol and alkylpolypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, the polypropylene glycol chain probably functioning as the hydrophobic radical here.
  • Peroxy compounds such as sodium perborate tetrahydrate (NaBO2 ⁇ H2O2 ⁇ 3H2O), sodium perborate monohydrate (NaBO2 ⁇ H2O2), perborax (Na2B4O7 ⁇ 4H2O2) or peroxycarbonates such as Na2CO3 ⁇ 1.5H2O2 but also inorganic or organic active chlorine compounds such as e.g. Alkali hypochlorites or dichloro- and trichlorocyanuric acid into consideration.
  • water-soluble stabilizers are the organic complexing agents suitable as auxiliaries for binding the hardeners Ca2+ and Mg2+.
  • N-Diacylated and N, N'-tetraacylated amines such as N, N, N ', N'-tetraacetylmethylene diamine or ethylenediamine, N, N-diacetylaniline and N, N-diacetyl are preferred as activators for the bleaches which supply H2O2 in water p-toluidine, alkyl-N-sulfonyl-carbonamides such as N-methyl-N-mesyl-acetamide, N-methyl-N-mesylbenzamide, N-methyl-N-mesyl-p-nitrobenzamide and N-methyl-N-mesyl -p-methoxybenzamide, N-acylated cyclic hydrazides, acylated triazoles or urazoles such as, for example, monoacetylmaleic hydrazide, O, N, N-trisubstituted hydroxylamines such as O-benzoyl-N,
  • Graying inhibitors are auxiliaries which keep the loosened dirt suspended in the aqueous solution.
  • Water-soluble colloids of an organic nature are suitable for this.
  • the water-soluble salts of polymeric carboxylic acids, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch are preferred.
  • Water-soluble polyamides containing acidic groups and polyvinylpyrrolidone are also suitable.
  • Proteases carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureas, isomerases, lyases, transferases, desmolases or nucleases can be incorporated as enzymes.
  • enzymes obtained from bacterial strains or fungi such as Bacillus subtilis or Streptomyces griseus, in particular proteases or amylases, which are relatively resistant to alkali, per compounds and anionic surfactants and are still effective at temperatures up to 70 ° C.
  • Combinations of enzymes of different effects are preferably used, in particular combinations of proteases and amylases.
  • the textile detergents often advantageously contain optical brighteners.
  • diaminostilbenedisulfonic acid or its alkali metal salts such as e.g. the alkali metal salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid, for polyamide fibers 1,3-diaryl- 2-pyrazolines such as 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, for polyester fibers 2,5-di- (2-benzoxazolyl) -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) ) -ethylene used.
  • Alkaline detergents are generally added as a corrosion inhibitor with sodium and potassium silicates with a silicon dioxide / alkali oxide ratio ⁇ 1.
  • Dirt-disrupting components for cleaning agents are, in particular, alkaline substances such as sodium or potassium hydroxide, sodium or potassium carbonate, alkaline salts of orthophosphoric acid as well as sodium and potassium silicates with a silicon dioxide / alkali metal oxide ratio of 0.7 to 1.5 and organic and inorganic Acids such as hydrochloric acid, phosphoric acid, phosphoric acid esters, sulfuric acid, oxalic acid, citric acid, formic acid, amidosulfonic acid, adipic acid, glutaric acid or succinic acid are suitable.
  • alkaline substances such as sodium or potassium hydroxide, sodium or potassium carbonate, alkaline salts of orthophosphoric acid as well as sodium and potassium silicates with a silicon dioxide / alkali metal oxide ratio of 0.7 to 1.5
  • organic and inorganic Acids such as hydrochloric acid, phosphoric acid, phosphoric acid esters, sulfuric acid, oxalic acid, citric acid, formic acid, amidosulf
  • the detergents and cleaning agents according to the invention can be in powder or liquid form.
  • inorganic salts in particular sodium sulfate, are generally added, while water is the basis of most liquid preparations.
  • detergents which, based on the preparation as a whole, contain 10 to 30% by weight of zeolite and 5 to 15% by weight of the trisodium salt of ⁇ -alanine-N, N-diacetic acid.
  • the washing and cleaning agents according to the invention can be produced in a generally customary manner; e.g. the various constituents can be stirred into an aqueous slurry using water, which is then expediently dried in atomizing towers at 100.degree.
  • the detergents used in Examples B1 to B5 contained the trisodium salt of ⁇ -alanine-N, N-diacetic acid (ADA) to be used according to the invention, while in comparative examples V1 to V5 the trisodium salt of nitrilotriacetic acid (NTA ) has been used.
  • the detergents were out an aqueous slurry of its individual components by drying in atomizing towers at 100 ° C.
  • a measure of the deposits of hardening agents formed during the washing process is the proportion by weight of ash that remained when the washed test fabric was ashed.
  • Table 1 The composition of the detergents used and the proportions by weight of ash obtained are shown in Table 1. Table 1 also contains the exact ionic composition of the total hardness of the water used, which was also varied.

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Abstract

Cleaning and washing compositions for aqueous uses which contain as hardness remover 2 to 25% by weight, based on the total weight of the compositions, of beta -alanine-N,N-diacetic acid or the alkali metal or ammonium salts thereof.

Description

Die vorliegende Erfindung betrifft Waschmittel sowie Reinigungsmittel für wäßrige Anwendungen enthaltend als Enthärter 2 bis 25 Gew.-%, bezogen auf das Gesamtgewicht der Mittel, β-Alanin-N,N-diessigsäure oder deren Alkalimetall- oder Ammoniumsalze.The present invention relates to detergents and cleaning agents for aqueous applications containing 2 to 25% by weight as softener, based on the total weight of the detergent, β-alanine-N, N-diacetic acid or its alkali metal or ammonium salts.

Waschmitel sowie Reinigungsmittel für wäßrige Anwendungen sind im allgemeinen aus einer Kombination verschiedener grenzflächenaktiver Substanzen und weiteren Hilfsstoffen zusammengesetzt.Detergents and cleaning agents for aqueous applications are generally composed of a combination of various surface-active substances and other auxiliaries.

Unter den weiteren Hilfsmitteln sind in erster Linie Enthärter zu nennen, d.h. Substanzen, welche die Härtebildner des Wassers, vor allem Ca⁺⁺- und Mg⁺⁺-Kationen, zu binden vermögen.Among the other aids, softeners should be mentioned primarily, i.e. Substances that are able to bind the hardness constituents of water, especially Ca⁺⁺ and Mg⁺⁺ cations.

Als Enthärter verwendete man bisher hauptsächlich Phosphate, die jedoch aus Gründen der Umweltbelastung zunehmend unerwünscht sind.So far, mainly phosphates have been used as softeners, but they are increasingly undesirable due to environmental pollution.

Als Ersatz für die Phosphate dienen in neuerer Zeit die Nitrilotriessigsäure und ihre Salze, jedoch vermögen auch diese Verbindungen nicht voll zu befriedigen, da sie Ablagerungen der Härtebildner, z.B. auf textilen Geweben, nicht wirksam genug verhindern.Nitrilotriacetic acid and its salts have recently been used as a replacement for the phosphates, but these compounds are also not fully satisfactory since they deposit deposits of hardness, e.g. on textile fabrics, not preventing them effectively enough.

Der vorliegenden Erfindung lagen daher Waschmittel sowie Reinigungsmittel für wäßrige Anwendungen als Aufgabe zugrunde, welche Enthärter enthalten, die noch besser wirksam sind als Nitrilotriessigsäure.The present invention was therefore based on detergents and cleaning agents for aqueous applications, which contain softeners which are even more effective than nitrilotriacetic acid.

Demgemäß wurden Waschmittel sowie Reinigungsmittel für wäßrige Anwendungen gefunden, die als Enthärter 2 bis 25 Gew.-%, bezogen auf das Gesamtgewicht der Mittel, β-Alanin-N,N-diessigsäure oder deren Alkalimetall- oder Ammoniumsalze enthalten.Accordingly, detergents and cleaning agents for aqueous applications have been found which contain 2 to 25% by weight, based on the total weight of the detergent, of β-alanine-N, N-diacetic acid or its alkali metal or ammonium salts as softener.

β-Alanin-N,N-diessigsäure ist wie Nitrilotriessigsäure biologisch abbaubar und kann besonders vorteilhaft durch Umsetzung von Acrylsäure mit Iminodiessigsäure in wäßrigem Medium in großtechnischen Mengen hergestellt werden (siehe unsere jüngere Anmeldung P 38 29 859.7 - O.Z. 0050/40154).Beta-alanine-N, N-diacetic acid, like nitrilotriacetic acid, is biodegradable and can be produced particularly advantageously by reacting acrylic acid with iminodiacetic acid in an aqueous medium in large quantities (see our recent application P 38 29 859.7 - OZ 0050/40154).

Ein zusätzlicher Vorteil der β-Alanin-N,N-diessigsäure ist ihr im Vergleich zur Nitrilotriessigsäure geringeres Bindevermögen für Schwermetallionen wie Cu²⁺ oder Cd²⁺, wie ein Vergleich der entsprechenden Gleichgewichtskonstanten auf den Seiten 564 und 565 in Organic Sequestering Agents, A.E. Martell, J. Wiley & Sons, Hew York (1959), ausweist. Dies verringert die Wahrscheinlichkeit, daß Spuren nicht abgebauter β-Alanin-N,N-diessigsäure in Flußsedimenten abgelagerte Schwermetallionen wieder freisetzen.An additional advantage of β-alanine-N, N-diacetic acid is its lower binding capacity for heavy metal ions such as Cu²⁺ or Cd²⁺ compared to nitrilotriacetic acid, such as a comparison of the corresponding equilibrium constants on pages 564 and 565 in Organic Sequestering Agents, A.E. Martell, J. Wiley & Sons, Hew York (1959). This reduces the likelihood that traces of undegraded β-alanine-N, N-diacetic acid will release heavy metal ions deposited in river sediments.

Bezogen auf das Gesamtgewicht der erfindungsgemäßen Wasch- und Reinigungsmittel werden die β-Alanin-N,N-diessigsäure oder ihre Alkalimetall- oder Ammoniumsalze in Mengen von 2 bis 25, bevorzugt in Mengen von 5 bis 15 Gew.-% eingesetzt. Mit besonderem Vorteil werden ihre Alkalimetallsalze verwendet, wobei das Trinatriumsalz besonders bevorzugt wird. Jedoch können auch die Salze der β-Alanin-N,N-diessigsäure mit basischen Verbindungen wie Kaliumhydroxid, Ammoniak oder primären, sekundären oder tertiären aliphatischen organischen Aminen mit 1 bis 4 C-Atomen in den aliphatischen Resten wie Methylamin, Dimethylamin oder Trimethylamin eingesetzt werden.Based on the total weight of the washing and cleaning agents according to the invention, the β-alanine-N, N-diacetic acid or its alkali metal or ammonium salts are used in amounts of 2 to 25, preferably in amounts of 5 to 15,% by weight. Their alkali metal salts are used with particular advantage, the trisodium salt being particularly preferred. However, the salts of β-alanine-N, N-diacetic acid with basic compounds such as potassium hydroxide, ammonia or primary, secondary or tertiary aliphatic organic amines having 1 to 4 carbon atoms in the aliphatic radicals such as methylamine, dimethylamine or trimethylamine can also be used .

Die weiteren Bestandteile der erfindungsgemäßen Wasch- und Reinigungsmittel richten sich nach dem speziellen Verwendungszweck.The other constituents of the washing and cleaning agents according to the invention depend on the specific use.

Waschmittel enthalten im allgemeinen zusätzlich
5 bis 50 Gew.-% andere Enthärter
6 bis 25 Gew.-% grenzflächenaktive Verbindungen als waschaktive Substanzen
5 bis 35 Gew.-% Bleichmittel
0 bis 60 Gew.-% für die Konsistenz der Zubereitung wesentliche Stoffe
und in untergeordneten Mengen weitere Hilfsstoffe wie Bleichmittelstabilisatoren, Bleichmittelaktivatoren, Enzyme, Vergrauungsinhibitoren, Schaumregulatoren, Korrosionsschutzmittel, optische Aufheller, Lösungsvermittler, Duftstoffe oder Farbstoffe.Detergents generally also contain
5 to 50% by weight of other softeners
6 to 25% by weight of surface-active compounds as washing-active substances
5 to 35 wt% bleach
0 to 60% by weight of substances essential for the consistency of the preparation
and in minor amounts other auxiliary substances such as bleach stabilizers, bleach activators, enzymes, graying inhibitors, foam regulators, corrosion inhibitors, optical brighteners, solubilizers, fragrances or dyes.

Reinigungsmittel enthalten als weitere wesentliche Inhaltsstoffe im allgemeinen
30 bis 80 Gew.-% Schmutz aufschließende Komponenten
3 bis 20 Gew.-% andere Mittel die Härtebildner zu binden vermögen
2 bis 10 Gew.-% grenzflächenaktive Substanzen
1 bis 5 Gew.-% Korrosionsschutzmittel
0 bis 60 Gew.-% für die Konsistenz der Zubereitung wesentliche Stoffe
und in untergeordneten Mengen weitere Hilfsstoffe wie Enzyme, Schaumregulatoren, Duftstoffe, Lösungsvermittler oder Desinfektionsmittel.Cleaning agents generally contain other essential ingredients
30 to 80 wt .-% dirt-disrupting components
3 to 20% by weight of other agents which are able to bind hardening agents
2 to 10% by weight of surface-active substances
1 to 5% by weight of anti-corrosion agent
0 to 60% by weight of substances essential for the consistency of the preparation
and in minor quantities other auxiliary substances such as enzymes, foam regulators, fragrances, solubilizers or disinfectants.

Als zusätzliche, die Härtestoffe Ca²⁺ und Mg²⁺ bindende Hilfsmittel, können den erfindungsgemäßen Wasch- und Reinigungsmittel alkalische Stoffe wie Natriumcarbonat, Natriumsilicat und Natriumphosphat oder Komplexierungsmittel anorganischer Natur wie z.B. Pyrophosphat, Triphosphat, höhere Polyphosphate und Metaphosphate oder als Komplexbildner geeignete organische Verbindungen aus der Reihe der Alkanpolyphosphonsäuren, Amino- und Hydroxyalkanpolyphosphonsäuren, Phosphonocarbonsäuren, Polycarbonsäuren, Hydroxymono- oder -polycarbonsäuren und Aminocarbonsäuren sowie, bevorzugt für Waschmittel, Ionenaustauscher wie Natrium-aluminium-silicate (Zeolithe) zugesetzt werden, wobei man die komplexbildenden Säuren bevorzugt in Form ihrer wasserlöslichen Salze zugibt.As additional auxiliaries that bind the hardeners Ca²⁺ and Mg²⁺, the washing and cleaning agents according to the invention can contain alkaline substances such as sodium carbonate, sodium silicate and sodium phosphate or complexing agents of an inorganic nature such as e.g. Pyrophosphate, triphosphate, higher polyphosphates and metaphosphates or organic compounds suitable as complexing agents from the series of alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids, phosphonocarboxylic acids, polycarboxylic acids, hydroxymono- or polycarboxylic acids and aminocarboxylic acids and, preferably for detergents, aluminum exchangers such as sodium exchangers, Zeolites) are added, the complex-forming acids preferably being added in the form of their water-soluble salts.

Beispiele für geeignete phosphorhaltige organische Komplexbildner sind Methandiphosphonsäure, Propan-1,2,3-triphosphonsäure, Butan-1,2,3,4-tetraphosphonsäure, Polyvinylphosphonsäure, 1-Aminoethan-1,1-diphosphonsäure, 1-Amino-1-phenyl-1,1-diphosphonsäure, Aminotrimethylentriphosphonsäure, Methylamino- oder Ethylaminodimethylendiphosphonsäure, Ethylen-diaminotetramethylentetraphosphonsäure, 1-Hydroxyethan-1,1-diphosphonsäure, Phosphonoessigsäure, Phosphonopropionsäure, 1-Phosphonoethan-1,2-dicarbonsäure, 2-Phosphonopropan-2,3-dicarbonsäure, 2-Phosphonobutan-1,2,4-tricarbonsäure, 2-Phosphonobutan-2,3,4-tricarbonsäure sowie Mischpolymerisate aus Vinylphosphonsäure und Acrylsäure.Examples of suitable phosphorus-containing organic complexing agents are methane diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl -1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, methylamino- or ethylaminodimethylene diphosphonic acid, ethylene diaminotetramethylene tetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphonoacetic acid, phosphonopropionic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonopropane-2,3- dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphonobutane-2,3,4-tricarboxylic acid and copolymers of vinylphosphonic acid and acrylic acid.

Beispiele für Polycarbonsäuren sind Dicarbonsäuren der allgemeinen Formel HOOC-(CH₂)n-COOH mit n = 0 bis 8, außerdem Maleinsäure, Methylenmalonsäure, Citraconsäure, Mesaconsäure, Itaconsäure, nicht cyclische Polycarbonsäuren mit wenigstens 3 Carboxygruppen im Molekül, wie z.B. Tricarballylsäure, Aconitsäure, Ethylentetracarbonsäure, 1,1,3,3-Propan-tetracarbonsäure, 1,1,3,3,5,5-Pentan-hexacarbonsäure, Hexanhexacarbonsäure, cyclische Di- oder Polycarbonsäuren wie z.B. Cyclopentan-tetracarbonsäure, Cyclohexan-hexacarbonsäure, Tetrahydrofurantetracarbonsäure, Phthalsäure, Terephthalsäure, Benzoltri-, -tetra- oder -pentacarbonsäure, Mellithsäure und polymere Polycarbonsäuren wie z.B. die Homopolymerisate der Acrylsäure, Hydroxyacrylsäure, Maleinsäure, Itaconsäure, Mesaconsäure, Aconitsäure, Methylenmalonsäure und Citraconsäure, die Copolymerisate der obengenannten Carbonsäuren untereinander oder mit ethylenisch ungesättigten Verbindungen wie Ethylen, Propylen, Isobutylen, Vinylalkohol, Vinylmethylether, Furan, Acrolein, Vinylacetat, Acrylamid, Acrylnitril, Methacrylsäure und Crotonsäure, wobei Mischpolymerisate aus Acrylsäure (AS) und Maleinsäure (MAS) im Gewichtsverhältnis 60 : 40 und mit einem zahlenmittleren Molekulargewicht (M n) von 70 000 besonders bevorzugt sind, sowie die Carboxymethylether der Zucker, der Stärke und der Cellulose.Examples of polycarboxylic acids are dicarboxylic acids of the general formula HOOC- (CH₂) n -COOH with n = 0 to 8, also maleic acid, methylene malonic acid, citraconic acid, mesaconic acid, itaconic acid, non-cyclic polycarboxylic acids with at least 3 carboxy groups in the molecule, such as tricarballylic acid, aconitic acid, Ethylene tetracarboxylic acid, 1,1,3,3-propane-tetracarboxylic acid, 1,1,3,3,5,5-pentane-hexacarboxylic acid, hexane hexacarboxylic acid, cyclic di- or polycarboxylic acids such as, for example, cyclopentane-tetracarboxylic acid, cyclohexane-hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, phthalic acid, terephthalic acid, benzenetri-, tetra- or pentacarboxylic acid, mellitic acid and polymeric polycarboxylic acids such as, for example, the homopolymers of acrylic acid, mesa acid, hydroxyacrylic acid, hydroxyacrylic acid Aconitic acid, methylene malonic acid and citraconic acid, the copolymers of the abovementioned carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene, vinyl alcohol, vinyl methyl ether, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid and crotonic acid, with copolymers of acrylic acid (AS) and Maleic acid (MAS) in a weight ratio of 60:40 and with a number average molecular weight ( M n ) of 70,000 are particularly preferred, as are the carboxymethyl ethers of sugar, starch and cellulose.

Geeignete Hydroxymono- oder -polycarbonsäuren sind Glycolsäure, Milchsäure, Apfelsäure, Tartronsäure, Methyltartronsäure, Gluconsäure, Glycerinsäure, Citronensäure, Weinsäure und Salicylsäure.Suitable hydroxymono- or polycarboxylic acids are glycolic acid, lactic acid, malic acid, tartronic acid, methyltartronic acid, gluconic acid, glyceric acid, citric acid, tartaric acid and salicylic acid.

Bevorzugt zu verwendende Aminocarbonsäuren sind Glycin, Glycylglycin, Alanin, Asparagin, Glutaminsäure, Aminobenzoesäure, Iminodi- oder Triessigsäure, Hydroxyethyliminodiessigsäure, Ethylendiamintetraessigsäure, Hydroxyethyl-ethylendiamintriessigsäure, Diethylentriamin-pentaessigsäure sowie höhere Homologe, die durch Polymerisation eines N-Aziridylcarbonsäurederivates, z.B. der Essigsäure, Bernsteinsäure oder Tricarballylsäure, und anschließende Verseifung, oder durch Kondensation von Polyaminen mit einem Molekulargewicht von 500 bis 10 000 mit chloressigsauren oder bromessigsauren Salzen hergestellt werden können.Aminocarboxylic acids to be preferably used are glycine, glycylglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, iminodi- or triacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethyl-ethylenediaminetriacetic acid, diethylenetriamine-pentaacetic acid and polymerisation of a carboxylic acid, e.g. of acetic acid, succinic acid or tricarballylic acid, and subsequent saponification, or by condensation of polyamines with a molecular weight of 500 to 10,000 with chloroacetic or bromoacetic salts.

Als Ionenaustauscher kommt insbesondere der Zeolith 4A in Betracht, dessen Herstellung in Ullmanns Encyclopädie der technischen Chemie, 4. Auflage, Band 24 auf S. 120 beschrieben ist.Zeolite 4A, whose production is described in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 24 on p. 120, is particularly suitable as an ion exchanger.

Als grenzflächenaktive Substanzen sind solche geeignet, die im Molekül wenigstens einen hydrophoben organischen Rest und eine wasserlöslich machende ionische oder nichtionische Gruppe enthalten. Der hydrophobe Rest besteht bevorzugt aus einem aliphatischen Kohlenwasserstoffrest mit 8 bis 26, vorzugsweise 10 bis 22 und besonders bevorzugt 12 bis 18 C-Atomen oder aus einem alkylaromatischen Rest mit 6 bis 18, vorzugsweise 8 bis 16 C-Atomen in der Alkylgruppe.Suitable surfactants are those which contain at least one hydrophobic organic radical and one water-solubilizing ionic or nonionic group in the molecule. The hydrophobic radical preferably consists of an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and particularly preferably 12 to 18 C atoms or an alkyl aromatic radical with 6 to 18, preferably 8 to 16 C atoms in the alkyl group.

Besonders geeignete anionische Tenside sind die Natrium-, Kalium- und Ammoniumsalze von Carbonsäuren, Sulfonsäuren und Schwefelsäuremonoestern mit der angegebenen Anzahl an C-Atomen.Particularly suitable anionic surfactants are the sodium, potassium and ammonium salts of carboxylic acids, sulfonic acids and sulfuric acid monoesters with the specified number of carbon atoms.

Dabei kommen als Tenside vom Sulfonattyp insbesondere Alkylbenzolsulfonate mit 9 bis 15 C-Atomen im Alkylrest, Alken- und Hydroxyalkansulfonate sowie Disulfonate, wie man sie beispielsweise aus Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Weiter eignen sich Alkansulfonate, die aus Alkanen durch Sulfochlorierung oder Sulfoxydation und anschließende Hydrolyse bzw. Neutralisation oder durch Bisulfitaddition an Olefine erhältlich sind. Weiktere brauchbare Tenside vom Sulfonattyp sind die Methyl- oder Ethylester von α-Sulfofettsäuren.The surfactants of the sulfonate type include, in particular, alkylbenzenesulfonates with 9 to 15 carbon atoms in the alkyl radical, alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products receives. Also suitable are alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. More useful sulfonate type surfactants are the methyl or ethyl esters of α-sulfo fatty acids.

Geeignete Tenside vom Sulfattyp sind die genannten Salze der Schwefelsäuremonoester primärer und sekundärer Alkohole. Weiterhin eignen sich sulfatierte Fettsäuremonoglyceride sowie sulfatierte Umsetzungsprodukte von 1 bis 4 Mol Ethylenoxid mit primären oder sekundären Fettalkoholen oder Alkylphenolen.Suitable sulfate-type surfactants are the salts mentioned of the sulfuric acid monoesters of primary and secondary alcohols. Sulfated fatty acid monoglycerides and sulfated reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols are also suitable.

Von den Carboxylaten kommen insbesondere die Natriumsalze der natürlichen Fettsäuren, d.h. die üblichen Seifen, in Betracht.Of the carboxylates come in particular the sodium salts of natural fatty acids, i.e. the usual soaps.

Bevorzugte kationische Tenside sind Dialkyl-dimethyl-ammoniumchloride wie Distearyl-dimethyl-ammoniumchlorid und Imidazoliniumsalze vom Typ 1-Alkyl-amidoethyl-1-methyl-2-alkyl-imidazolinium-methoxysulfat.Preferred cationic surfactants are dialkyldimethylammonium chlorides such as distearyldimethylammonium chloride and imidazolinium salts of the 1-alkylamidoethyl-1-methyl-2-alkylimidazolinium methoxysulfate type.

Als amphotere Tenside, die in wäßriger Lösung im gleichen Molekül sowohl anion- als auch kationaktive Gruppen enthalten, kommen Verbindungen vom Typ der Alkylbetaine bzw. Alkylsulfobetaine in Betracht.Suitable amphoteric surfactants which contain both anion and cation-active groups in the same molecule in aqueous solution are compounds of the alkyl betaines or alkyl sulfobetaines type.

Als nichtionische Tenside werden vorteilhaft Anlagerungsprodukte von 4 bis 40, vorzugsweise 4 bis 20 Mol Ethylenoxid an 1 Mol Fettalkohol, Alkylphenol, Fettsäure, Fettamin, Fettsäureamid oder Alkansulfonamid verwendet. Besonders bevorzugt sind die Anlagerungsprodukte von 5 bis 16 Mol Ethylenoxid an primäre oder sekundäre Alkohole mit 8 bis 18, vorzugsweise 12 bis 18 C-Atomen, sowie an Mono- oder Dialkylphenole mit 6 bis 14 C-Atomen in den Alkylresten. Neben diesen wasserlöslichen nichtionischen Tensiden sind aber auch nicht bzw. nicht vollständig wasserlösliche Polyglycolether mit 1 bis 4 Ethylenglycoletherresten im Molekül von Interesse, insbesonder wenn sie zusammen mit wasserlöslichen nichtionischen oder anionischen Tensiden eingesetzt werden.Addition products of 4 to 40, preferably 4 to 20 moles of ethylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide are advantageously used as nonionic surfactants. The addition products of 5 to 16 moles of ethylene oxide with primary or secondary alcohols with 8 to 18, preferably 12 to 18 C atoms, and with mono- or dialkylphenols with 6 to 14 C atoms in the alkyl radicals are particularly preferred. In addition to these water-soluble nonionic surfactants, non-or not completely water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.

Weiterhin können als nichtionische grenzflächenaktive Substanzen die wasserlöslichen, 20 bis 250 Ethylenglycolethergruppen und 10 bis 100 Propylenglycolethergruppen enthaltenden Anlagerungsprodukte von Ethylenoxid an Propylenglycol, Alkylendiamin-polypropylenglycol und Alkylpolypropylenglycole mit 1 bis 10 C-Atomen in der Alkylkette verwendet werden, wobei hier vermutlich die Polypropylenglycolkette als hydrophober Rest fungiert.Furthermore, the water-soluble addition products of ethylene oxide containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups can be used as nonionic surface-active substances of propylene glycol, alkylenediamine-polypropylene glycol and alkylpolypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, the polypropylene glycol chain probably functioning as the hydrophobic radical here.

Als Bleichmittel kommen insbesondere Peroxyverbindungen wie Natriumperborattetrahydrat (NaBO₂ · H₂O₂ · 3H₂O), Natriumperboratmonohydrat (NaBO₂ · H₂O₂), Perborax (Na₂B₄O₇ · 4H₂O₂) oder Peroxycarbonate wie Na₂CO₃ · 1,5H₂O₂ aber auch anorganische oder organische Aktivchlorverbindungen wie z.B. Alkalihypochlorite oder Dichlor- und Trichlorcyanursäure in Betracht.Peroxy compounds such as sodium perborate tetrahydrate (NaBO₂ · H₂O₂ · 3H₂O), sodium perborate monohydrate (NaBO₂ · H₂O₂), perborax (Na₂B₄O₇ · 4H₂O₂) or peroxycarbonates such as Na₂CO₃ · 1.5H₂O₂ but also inorganic or organic active chlorine compounds such as e.g. Alkali hypochlorites or dichloro- and trichlorocyanuric acid into consideration.

Im allgemeinen ist es von Vorteil, gemeinsam mit den als Bleichmittel dienenden Peroxyverbindungen Stoffe einzuarbeiten, die die Peroxyverbindungen stabilisieren. Als wasserlösliche Stabilisatoren kommen z.B. die als Hilfsmittel zum Binden der Härtestoffe Ca²⁺ und Mg²⁺ geeigneten organischen Komplexbildner in Betracht. Besonders bevorzugt werden als wasserunlösliche Stabilisatoren, in Mengen von 0,5 bis 4 Gew.-% der gesamten Zubereitung, Magnesiumsilicate MgO : SiO₂ der Zusammensetzung 4 : 1 bis 1 : 4, vorzugsweise 2 : 1 bis 1 : 2 und insbesondere 1 : 1 eingesetzt.In general, it is advantageous to incorporate substances which stabilize the peroxy compounds together with the peroxy compounds serving as bleaching agents. Examples of water-soluble stabilizers are the organic complexing agents suitable as auxiliaries for binding the hardeners Ca²⁺ and Mg²⁺. Particularly preferred as water-insoluble stabilizers, in amounts of 0.5 to 4% by weight of the total preparation, are magnesium silicates MgO: SiO 2 of the composition 4: 1 to 1: 4, preferably 2: 1 to 1: 2 and in particular 1: 1 used.

Als Aktivatoren für die in Wasser H₂O₂ liefernden Bleichmittel werden bevorzugt N-diacylierte und N,N'-tetraacylierte Amine wie z.B. N,N,N',N'-Tetraacetylmethylendiamin oder -ethylendiamin, N,N-Diacetylanilin und N,N-Diacetyl-p-toluidin, Alkyl-N-sulfonyl-carbonamide wie N-Methyl-N-mesyl-acetamid, N-Methyl-N-mesylbenzamid, N-Methyl-N-mesyl-p-nitrobenzamid und N-Methyl-N-mesyl-p-methoxybenzamid, N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole wie z.B. Monoacetylmaleinsäurehydrazid, O,N,N-trisubstituierte Hydroxylamine wie O-Benzoyl-N,N-succinyl-hydroxylamin, O-Acetyl-N,N-succinyl-hydroxylamin, O-p-Methoxybenzoyl-N,N-succinylhydroxylamin, O-p-Nitrobenzoyl-N,N-succinylhydroxylamin und O,N,N-Triacetylhydroxylamin, N,N'-Diacyl-sulfurylamide wie z.B. N,N'-Dimethyl-N,N'-diacetyl-sulfurylamid und N,N'-Diethyl-N,N'-dipropionylsulfurylamid, Triacylcyanurate wie Triacetyl- oder Tribenzoylcyanurat, Carbonsäureanhydride wie Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid, Phthalsäureanhydrid und 4-Chlorphthalsäureanhydrid, Zuckerester wie z.B. Glucosepentaacetat, 1,3-Diacyl-4,5-diacyloxy-imidazolidine wie 1,3-Diformyl-4,5-diacetoxyimidazolidin, 1,3-Diacetyl-4,5-diacetoxy-imidazolidin und 1,3-Diacetyl-4,5-dipropionyloxy-imidazolidin, diacylierte 2,5-Diketopiperazine, wie z.B. 1,4-Diacetyl-2,5-diketopiperazin, 1,4-Dipropionyl-2,5-diketopiperazin und 1,4-Dipropionyl-3,6-dimethyl-2,5-diketopiperazin, das Natriumsalz der p-(Ethoxycarbonyloxy)-benzoesäure und der p-(Propoxycarbonyloxy)-benzolsulfonsäure sowie die Natriumsalze von alkylierten oder acylierten Phenolsulfonsäureestern wie p-Acetoxy-benzolsulfonsaure, 2-Acetoxy-5-nonyl-benzolsulfonsäure, 2-Acetoxy-5-propylbenzolsulfonsäure oder der Isononanoyloxiphenylsulfonsäure eingesetzt.N-Diacylated and N, N'-tetraacylated amines such as N, N, N ', N'-tetraacetylmethylene diamine or ethylenediamine, N, N-diacetylaniline and N, N-diacetyl are preferred as activators for the bleaches which supply H₂O₂ in water p-toluidine, alkyl-N-sulfonyl-carbonamides such as N-methyl-N-mesyl-acetamide, N-methyl-N-mesylbenzamide, N-methyl-N-mesyl-p-nitrobenzamide and N-methyl-N-mesyl -p-methoxybenzamide, N-acylated cyclic hydrazides, acylated triazoles or urazoles such as, for example, monoacetylmaleic hydrazide, O, N, N-trisubstituted hydroxylamines such as O-benzoyl-N, N-succinyl-hydroxylamine, O-acetyl-N, N-succinyl- hydroxylamine, Op-methoxybenzoyl-N, N-succinylhydroxylamine, Op-nitrobenzoyl-N, N-succinylhydroxylamine and O, N, N-triacetylhydroxylamine, N, N'-diacylsulfurylamides such as N, N'-dimethyl-N, N '-diacetyl-sulfurylamide and N, N'-diethyl-N, N'-dipropionylsulfurylamide, triacyl cyanurates such as triacetyl or tribenzoyl cyanurate, carboxylic anhydrides such as benzoic anhydride, m-chlorobenzoic anhydride, phthalic acid uric anhydride and 4-chlorophthalic anhydride, sugar esters such as glucose pentaacetate, 1,3-diacyl-4,5-diacyloxy-imidazolidine such as 1,3-diformyl-4,5-diacetoxyimidazolidine, 1,3-diacetyl-4,5-diacetoxy-imidazolidine and 1,3-diacetyl-4,5-dipropionyloxy-imidazolidine, diacylated 2,5-diketopiperazines, such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine and 1, 4-Dipropionyl-3,6-dimethyl-2,5-diketopiperazine, the sodium salt of p- (Ethoxycarbonyloxy) -benzoic acid and p- (propoxycarbonyloxy) -benzenesulfonic acid and the sodium salts of alkylated or acylated phenolsulfonic acid esters such as p-acetoxy-benzenesulfonic acid, 2-acetoxy-5-nonyl-benzenesulfonic acid, 2-acetoxy-5-propylbenzenesulfonic acid or Isononanoyloxiphenylsulfonic acid used.

Vergrauungsinhibitoren sind Hilfsmittel, die den abgelösten Schmutz in der wäßrigen Lösung suspendiert halten. Hierzu sind wasserlösliche Kolloide organischer Natur geeignet. Bevorzugt sind die wasserlöslichen Salze polymerer Carbonsäuren, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Weiterhin sind wasserlösliche, saure Gruppen enthaltende Polyamide sowie Polyvinylpyrrolidon geeignet.Graying inhibitors are auxiliaries which keep the loosened dirt suspended in the aqueous solution. Water-soluble colloids of an organic nature are suitable for this. The water-soluble salts of polymeric carboxylic acids, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch are preferred. Water-soluble polyamides containing acidic groups and polyvinylpyrrolidone are also suitable.

Als Enzyme können Proteasen, Carbohydrasen, Esterasen, Lipasen, Oxidoreduktasen, Katalasen, Peroxidasen, Ureasen, Isomerasen, Lyasen, Transferasen, Desmolasen oder Nukleasen eingearbeitet werden. Von besonderem Interesse sind die aus Bakterienstämmen oder Pilzen wie Bacillus subtilis oder Streptomyces griseus gewonnenen Enzyme, insbesondere Proteasen oder Amylasen, die gegenüber Alkali, Perverbindungen und anionischen Tensiden relativ beständig und bei Temperaturen bis zu 70°C noch wirksam sind.Proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureas, isomerases, lyases, transferases, desmolases or nucleases can be incorporated as enzymes. Of particular interest are the enzymes obtained from bacterial strains or fungi such as Bacillus subtilis or Streptomyces griseus, in particular proteases or amylases, which are relatively resistant to alkali, per compounds and anionic surfactants and are still effective at temperatures up to 70 ° C.

Bevorzugt verwendet man Kombinationen aus Enzymen verschiedener Wirkung, insbesondere Kombinationen aus Proteasen und Amylasen.Combinations of enzymes of different effects are preferably used, in particular combinations of proteases and amylases.

Die Textilwaschmittel enthalten in vorteilhafter Weise häufig optische Aufheller. Für Baumwolle werden bevorzugt Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze wie z.B. die Alkalimetallsalze der 4,4′-Bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilben-2,2′-disulfonsäure, für Polyamidfasern 1,3-Diaryl-2-pyrazoline wie z.B. 1-(p-Sulfamoylphenyl)-3-(p-chlorphenyl)-2-pyrazolin, für Polyesterfasern 2,5-Di-(2-benzoxazolyl)-thiophen und 1,2-Di-(5-methyl-2-benzoxazolyl)-ethylen eingesetzt.The textile detergents often advantageously contain optical brighteners. Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts such as e.g. the alkali metal salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid, for polyamide fibers 1,3-diaryl- 2-pyrazolines such as 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, for polyester fibers 2,5-di- (2-benzoxazolyl) -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) ) -ethylene used.

Alkalischen Waschmittel werden im allgemeinen als Korrosionsschutzmittel noch Natrium- und Kaliumsilicate mit einem Siliciumdioxid/Alkalioxid-Verhältnis ≧1 zugegeben.Alkaline detergents are generally added as a corrosion inhibitor with sodium and potassium silicates with a silicon dioxide / alkali oxide ratio ≧ 1.

Als Schmutz aufschließende Komponenten für Reinigungsmittel sind insbesondere alkalisch reagierende Substanzen wie z.B. Natrium- oder Kaliumhydroxid, Natrium- oder Kaliumcarbonat, alkalische Salze der Orthophosphorsäure sowie Natrium- und Kaliumsilicate mit einem Siliciumdioxid/Alkalimetalloxid-Verhältnis von 0,7 bis 1,5 sowie organische und anorganische Säuren wie Salzsäure, Phosphorsäure, Phosphorsäureester, Schwefelsäure, Oxalsäure, Citronensäure, Ameisensäure, Amidosulfonsäure, Adipinsäure, Glutarsäure oder Bernsteinsäure geeignet.Dirt-disrupting components for cleaning agents are, in particular, alkaline substances such as sodium or potassium hydroxide, sodium or potassium carbonate, alkaline salts of orthophosphoric acid as well as sodium and potassium silicates with a silicon dioxide / alkali metal oxide ratio of 0.7 to 1.5 and organic and inorganic Acids such as hydrochloric acid, phosphoric acid, phosphoric acid esters, sulfuric acid, oxalic acid, citric acid, formic acid, amidosulfonic acid, adipic acid, glutaric acid or succinic acid are suitable.

Die erfindungsgemäßen Wasch- und Reinigungsmittel können pulverförmig oder flüssig sein. Um den pulverförmigen Zubereitungen Eigenschaften wie "gute Rieselfähigkeit", "kein Zusammenbacken bei wechselnder Luftfeuchtigkeit" usw. zu verleihen, werden im allgemeinen anorganische Salze, insbesondere Natriumsulfat zugegeben, während Wasser die Basis der meisten flüssigen Zubereitungen ist.The detergents and cleaning agents according to the invention can be in powder or liquid form. In order to impart properties such as "good flowability", "no caking with changing atmospheric humidity" etc. to the powdered preparations, inorganic salts, in particular sodium sulfate, are generally added, while water is the basis of most liquid preparations.

Besonders bevorzugt sind Waschmittel, die, bezogen auf die gesamte Zubereitung, 10 bis 30 Gew.-% Zeolith und 5 bis 15 Gew.-% des Trinatriumsalzes der β-Alanin-N,N-diessigsäure enthalten.Particularly preferred are detergents which, based on the preparation as a whole, contain 10 to 30% by weight of zeolite and 5 to 15% by weight of the trisodium salt of β-alanine-N, N-diacetic acid.

Die Herstellung der erfindungsgemäßen Wasch- und Reinigungsmittel kann in allgemein üblicher Weise erfolgen; z.B. können die verschiedenen Bestandteile unter Verwendung von Wasser zu einem wäßrigen Brei verrührt werden, der dann zweckmäßigerweise in Zerstäubungstürmen bei 100°C getrocknet wird.The washing and cleaning agents according to the invention can be produced in a generally customary manner; e.g. the various constituents can be stirred into an aqueous slurry using water, which is then expediently dried in atomizing towers at 100.degree.

Beispiele B1 bis B5 und Vergleichsbeispiele V1 bis V5Examples B1 to B5 and comparative examples V1 to V5 Bestimmung der bei Verwendung verschiedener Waschmittel gebildeten Ablagerungen der HärtebildnerDetermination of the deposits of hardening agents formed when using different detergents

Hierzu wurden als Testgewebe 20 g Baumwollfrottee unter folgenden Versuchsbedingungen mehrfach gewaschen und gespült: Waschmaschine Launder-O-meter der Fa. Atlas, Chicago Zahl der Waschzyklen 20 Wassermenge pro Zyklus 125 ml zum Waschen 125 ml zum Spülen Gesamthärte des Wassers 4 mMol (Ca²⁺, Mg²⁺) Waschdauer pro Zyklus 30 min Waschtemperatur 60°C Waschmitteldosierung 8 g/l For this purpose, 20 g of cotton terry cloth were washed and rinsed several times under the following test conditions: Washing machine Launder-O-meter from Atlas, Chicago Number of wash cycles 20th Amount of water per cycle 125 ml for washing 125 ml for rinsing Total hardness of the water 4 mmol (Ca²⁺, Mg²⁺) Washing time per cycle 30 min Washing temperature 60 ° C Detergent dosage 8 g / l

Die in den Beispielen B1 bis B5 verwendeten Waschmittel enthielten das erfindungsgemäß zu verwendende Trinatriumsalz der β-Alanin-N,N-diessigsäure (ADA), während in den Vergleichsbeispielen V1 bis V5 an Stelle von ADA als Stand der Technik das Trinatriumsalz der Nitrilotriessigsäure (NTA) verwendet wurde. In allen Fällen wurden die Waschmittel aus einem wäßrigen Brei ihrer Einzelbestandteile durch Trocknung in Zerstäubungstürmen bei 100°C hergestellt. Ein Maß für die beim Waschprozeß entstandenen Ablagerungen der Härtebildner ist der Gewichtsanteil an Asche, der beim Veraschen des gewaschenen Testgewebes zurückblieb.The detergents used in Examples B1 to B5 contained the trisodium salt of β-alanine-N, N-diacetic acid (ADA) to be used according to the invention, while in comparative examples V1 to V5 the trisodium salt of nitrilotriacetic acid (NTA ) has been used. In all cases, the detergents were out an aqueous slurry of its individual components by drying in atomizing towers at 100 ° C. A measure of the deposits of hardening agents formed during the washing process is the proportion by weight of ash that remained when the washed test fabric was ashed.

Die Zusammensetzung der eingesetzten Waschmittel und die erhaltenen Gewichtsanteile Asche enthält Tabelle 1. Tabelle 1 enthält zusätzlich die genaue ionische Zusammensetzung der Gesamthärte des verwendeten Wassers, die zusätzlich variiert wurde.

Figure imgb0001
The composition of the detergents used and the proportions by weight of ash obtained are shown in Table 1. Table 1 also contains the exact ionic composition of the total hardness of the water used, which was also varied.
Figure imgb0001

Claims (4)

  1. A washing or cleaning agent for aqueous use containing from 2 to 25 % by weight, based on the total weight of the agent, of β-alanine-N,N-diacetic acid or an alkali metal or ammonium salt thereof as water softener.
  2. A washing or cleaning agent for aqueous use as claimed in claim 1, containing the trisodium salt of β-alanine-N,N-diacetic acid as water softener.
  3. A washing agent as claimed in claim 1 or 2, containing from 10 to 30 % by weight of zeolite and from 5 to 15 % by weight of the trisodium salt of β-alanine-N,N-diacetic acid.
  4. The use of β-alanine-N,N-diacetic acid or an alkali metal or ammonium salt thereof in amounts of from 2 to 25 % by weight of the total formulation as an auxiliary agent in washing or cleaning agents for aqueous use.
EP89115874A 1988-09-02 1989-08-29 Cleaning and washing composition Expired - Lifetime EP0356974B1 (en)

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AT89115874T ATE92952T1 (en) 1988-09-02 1989-08-29 DETERGENTS AND CLEANING AGENTS.

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DE3829847A DE3829847A1 (en) 1988-09-02 1988-09-02 WASHING AND CLEANING AGENT
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Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5362412A (en) * 1991-04-17 1994-11-08 Hampshire Chemical Corp. Biodegradable bleach stabilizers for detergents
ES2119796T3 (en) * 1991-05-15 1998-10-16 Hampshire Chemical Corp CLEANING COMPOSITIONS FOR HARD SURFACES CONTAINING BIODEGRADABLE CHELANTS.
US5186856A (en) * 1992-06-02 1993-02-16 Basf Corp. Aqueous prewash stain remover compositions with efficacy on tenacious oily stains
US5221496A (en) * 1992-06-02 1993-06-22 Basf Corp. Aqueous prewash stain remover compositions with efficacy on tenacious oily stains
DE4319798A1 (en) * 1993-06-15 1994-12-22 Henkel Kgaa Dishwashing detergent with reduced tendency to scale up
DE4319935A1 (en) * 1993-06-16 1994-12-22 Basf Ag Use of glycine-N, N-diacetic acid derivatives as complexing agents for alkaline earth and heavy metal ions
AU3690095A (en) * 1994-10-07 1996-05-02 Eka Chemicals Ab Bleaching agent
CZ285638B6 (en) * 1994-10-07 1999-10-13 Eka Chemicals Ab Particles containing peroxo-compound and agent containing thereof
DE4445820A1 (en) * 1994-12-21 1996-06-27 Hoechst Ag Process for developing irradiated, radiation-sensitive recording materials
DE19543162A1 (en) * 1995-11-18 1997-05-22 Basf Ag Solid textile detergent formulation made of inorganic builders, glycine-N, N-diacetic acid derivatives as organic cobuilders as well as anionic and non-ionic surfactants
JP3810847B2 (en) * 1996-01-22 2006-08-16 花王株式会社 High density powder detergent composition
JP3810854B2 (en) * 1996-01-22 2006-08-16 花王株式会社 High density powder detergent composition
GB2311537A (en) * 1996-03-29 1997-10-01 Procter & Gamble Rinse composition for dishwashers
GB2311536A (en) * 1996-03-29 1997-10-01 Procter & Gamble Dishwashing and laundry detergents
GB2311535A (en) * 1996-03-29 1997-10-01 Procter & Gamble Detergent compositions
GB2311538A (en) * 1996-03-29 1997-10-01 Procter & Gamble Detergent compositions
EP0834549A1 (en) * 1996-10-07 1998-04-08 The Procter & Gamble Company Cleaning compositions
JP3290382B2 (en) * 1997-07-18 2002-06-10 花王株式会社 Powder detergent composition
GB0522658D0 (en) 2005-11-07 2005-12-14 Reckitt Benckiser Nv Composition
GB0611206D0 (en) 2006-06-07 2006-07-19 Reckitt Benckiser Nv Detergent composition

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2371623A (en) * 1943-02-06 1945-03-20 Lever Brothers Ltd Method of preserving soap and resulting product
DE2125249A1 (en) * 1971-05-21 1972-11-30 Chemische Werke Hüls AG, 4370 Mari Builder substances for detergents and cleaning agents
CH621999A5 (en) * 1976-06-24 1981-03-13 Ciba Geigy Ag
US4265777A (en) * 1980-04-17 1981-05-05 The Procter & Gamble Company Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap
US4404128A (en) * 1981-05-29 1983-09-13 The Procter & Gamble Company Enzyme detergent composition
US4440663A (en) * 1981-09-14 1984-04-03 The Procter & Gamble Company Alkaline aqueous liquid detergent compositions containing normally unstable ester perfumes
EP0089136A3 (en) * 1982-03-10 1984-05-30 The Procter & Gamble Company Oral hygiene products
US4690771A (en) * 1985-08-05 1987-09-01 Colgate-Palmolive Company Phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
DE3829859A1 (en) * 1988-09-02 1990-03-22 Basf Ag METHOD FOR PRODUCING SS-ALANINE DIACETIC ACID OR ITS ALKALI METAL OR AMMONIUM SALTS

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KR960015370B1 (en) 1996-11-11
EP0356974A3 (en) 1990-04-11
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US4997587A (en) 1991-03-05
AU4095689A (en) 1990-03-08
ES2042913T3 (en) 1993-12-16
CA1326427C (en) 1994-01-25
AU620640B2 (en) 1992-02-20
JPH02163200A (en) 1990-06-22
DE58905235D1 (en) 1993-09-16
ATE92952T1 (en) 1993-08-15
DE3829847A1 (en) 1990-03-15

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