EP0291869A2 - Phosphate-free detergent with a reduced incrustation tendency - Google Patents

Phosphate-free detergent with a reduced incrustation tendency Download PDF

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Publication number
EP0291869A2
EP0291869A2 EP88107689A EP88107689A EP0291869A2 EP 0291869 A2 EP0291869 A2 EP 0291869A2 EP 88107689 A EP88107689 A EP 88107689A EP 88107689 A EP88107689 A EP 88107689A EP 0291869 A2 EP0291869 A2 EP 0291869A2
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EP
European Patent Office
Prior art keywords
weight
acid
composition according
alkali metal
component
Prior art date
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EP88107689A
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German (de)
French (fr)
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EP0291869A3 (en
Inventor
Günther Dr. Vogt
Hans Dr. Andree
Gertrud Nienhaus
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0291869A2 publication Critical patent/EP0291869A2/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • Phosphate-free detergents with a content of finely crystalline aluminosilicates as a phosphate substitute, sodium carbonate or sodium silicates as washing alkali and polyanionic compounds from the class of the aminoalkane polyphosphonic acids and the homo- or copolymeric polycarboxylic acids derived from acrylic acid, methacrylic acid, maleic acid and olefinically unsaturated, copolymerizable compounds are known.
  • the preferred phosphonic acids or phosphonic acid salts are ethylene diamine tetramethylene phosphonate (EDTMP) and diethylene triamine pentamethylene phosphonate, mostly in the form of their sodium salts.
  • Preferred polymeric polycarboxylic acids are copolymers of maleic acid with vinyl methyl ethers and in particular maleic acid with acrylic acid in a ratio of 1: 5 to 1: 1 with a molecular weight of 10,000 to 150,000. These polyacids are also usually present in the compositions as sodium salts.
  • the amounts of aminoalkanephosphonates used are usually 0.1 to 1% by weight, those of copolymers 3 to 6% by weight, based on the composition.
  • the complexing and retarding properties (so-called threshold effect) of these additives are often not sufficient to limit the formation of fiber incrustations to the desired extent. It has been shown that the incrustations increase with frequent washing of the textiles with hard water and can eventually reach an undesirable extent. This increase in incrustations manifests itself in an increasing hardening and graying of the tissue and can be followed quantitatively by determining the tissue ash.
  • the task was therefore to reduce the tendency to form such incrustations.
  • a detergent that contains less than 0.1% inorganically bound phosphorus is understood to be phosphate-free.
  • An essential feature of the invention is the joint use of the aminoalkane polyphosphonates and / or polymer carboxylic acids listed under (d) together with the hydroxyalkane diphosphonate mentioned under (f). It is true that the use of the hydroxyalkane phosphonate (component f) in washing and cleaning detergents have long been known, but after the aminoalkane phosphonates listed under (d1) or the polymers according to (d2) were found, this compound was not used in modern phosphate-free agents, since the hydroxyalkane phosphonate is known to have a much lower sequestering capacity than the aminoalkane phosphonates according to (d1) and also has practically no threshold properties comparable to the polymers according to (d2).
  • Suitable aminoalkanephosphonic acids according to component (d1) are preferably ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetrimainpentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. Their proportion in the compositions, calculated on free acid, is preferably 0.1 to 1% by weight, in particular 0.1 to 0.5% by weight.
  • ETMP ethylenediamine tetramethylenephosphonate
  • DTPMP diethylenetrimainpentamethylenephosphonate
  • Their proportion in the compositions, calculated on free acid is preferably 0.1 to 1% by weight, in particular 0.1 to 0.5% by weight.
  • Suitable as (co) polymeric polycarboxylates are polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those made from 50% to 90% acrylic acid and 50% to 10% maleic acid.
  • the molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a particularly be preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of acid is at least 50%.
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups and saponifying to give the sodium or potassium salts.
  • polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.
  • the content of (co) polymeric polycarboxylic acids in the composition, based on free acid (component d2), is preferably 0.5 to 5% by weight and in particular 1 to 4% by weight.
  • the agents can contain component (d1) and (d2) individually or both simultaneously, with simultaneous use being preferred.
  • the mixing ratio (d1): (d2) is, for example, 1: 1 to 1:30, preferably 1: 5 to 1:20.
  • the 1-hydroxyethane-1,1-diphosphonate (component f) is also preferably present as the sodium salt.
  • the disodium salt reacts neutrally, the tetrasodium salt alkaline (pH 9). Its proportion, based on acid, is 0.05 to 1, preferably 0.1 to 0.7% by weight and in particular 0.1 to 0.5% by weight.
  • the weight ratio of (d1) to (f) is 3: 1 to 1: 6, preferably 2: 1 to 1: 4 and of (d2) to (f) 40: 1 to 2: 1, preferably 20: 1 to 4: 1.
  • the agents according to the invention contain anionic or nonionic surfactants (component a) as further constituents. These include soaps, surfactants of the sulfonate and sulfate type as well as nonionic compounds, e.g. B. from the class of polyglycol ether derivatives.
  • the content of the agent in component (a) is 5 to 35, preferably 8 to 20% by weight.
  • Suitable soaps are derived from natural or synthetic, saturated or monounsaturated fatty acids with 12 to 22 carbon atoms. Are particularly suitable from natural fatty acids such. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C12 ⁇ 18 fatty acid soaps and 0 to 50% of oleic acid soap.
  • Useful sulfonate type surfactants are linear alkyl benzene sulfonates (C9 ⁇ 13 alkyl) and olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from C12 ⁇ 18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtainable from C12 ⁇ 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, and also alpha-sulfo fatty acids and their esters, e.g. B. the alpha-sulfonated hydrogenated coconut, palm kernel or tallow fatty acids and their methyl or ethyl esters and mixtures thereof.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or Ste aryl alcohol, or the C10 ⁇ 18 oxo alcohols and the sulfuric acid esters of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable.
  • Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
  • Surfactants containing sulfonate groups are preferred, and among these in turn the alkylbenzenesulfonates, alpha-sulfofatty acid ester salts and the alpha-sulfofatty acid ester disalts.
  • the anionic surfactants are usually in the form of their sodium salts. Their proportion, based on the composition, is generally 2 to 15% by weight, preferably 5 to 12% by weight.
  • Addition products of 2 to 20, preferably 3 to 15 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols and alkylphenols can be used as nonionic surfactants.
  • non-fully or not fully water-soluble polyglycol ethers with 2 to 6 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.
  • Further suitable nonionic surfactants are alkyl glycosides or alkyl polyglycosides, the alkyl group of which has 8 to 18, preferably 10 to 16, carbon atoms.
  • the content of the agents in nonionic surfactants or nonionic surfactant mixtures is preferably 3 to 10% by weight and in particular 3 to 7% by weight.
  • Component (b) consists of finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 22 24 837). Their particle size is usually in the range from 1 to 10 ⁇ m.
  • the content of (b) is 10 to 40, preferably 12 to 25% by weight.
  • Their proportion in the agents can be 1 to 8% by weight, in particular 2 to 5% by weight.
  • the sodium silicate improves the grain stability and the grain structure of the powdery or granular agents and has a favorable effect on the washing-in and dissolving behavior of the agents when they are put into washing machines. It also has an anti-corrosive effect and improves washability. It was known that larger proportions, i.e. H.
  • washing alkali is sodium carbonate, the proportion of which is up to 15% by weight, preferably 2 to 12% by weight and in particular 5 to 10% by weight.
  • the total amount of sodium silicate and sodium silicate is 4 to 20% by weight, preferably 5 to 15% by weight and in particular 7 to 12% by weight.
  • graying inhibitors Dirt carriers
  • bleaching agents bleach activators
  • optical brighteners foam inhibitors
  • enzymes enzymes
  • textile-softening substances as well as neutral salts and water.
  • the washing and cleaning agents can contain graying inhibitors, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
  • graying inhibitors water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • Carboxymethyl cellulose (Na salt), methyl cellulose and mixtures thereof are preferably used. The proportion of the compounds is generally 0.2 to 2, preferably 0.5 to 1.5,% by weight.
  • H2O2 sodium perborate tetrahydrate
  • NaBO2. H2O2. 3 H2O sodium perborate tetrahydrate
  • NaBO2. H2O2 monohydrate
  • H2O2 supplying borates, for example the perborax Na2B4O7. 4 H2O2.
  • These compounds can be partially or completely by other active acid carriers, especially by peroxy hydrates, such as peroxycarbonates (Na2CO3.
  • H2O2 peroxypyrophosphates, citrate perhydrates, urea-H2O2- or melamine-H2O2 compounds as well are replaced by H2O2-delivering peracidic salts or peracids such as perbenzoates, peroxyphthalates, diperazelaic acid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the preparations.
  • N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetyl-ethylenediamine, and also carboxylic anhydrides, such as benzoic anhydride and Phthalic anhydride and esters of polyols such as glucose pentaacetate.
  • the detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or similarly structured compounds which have a instead of the morpholino group Carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
  • Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; e.g. the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can adsor on carriers be beer and / or embedded in coating substances to protect them against premature decomposition.
  • Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
  • Bis-acylamides derived from C12 ⁇ 20 fatty acids and C2 ⁇ 6 diamines or from C12 ⁇ 20 alkylamines and C2 ⁇ 6 dicarboxylic acids are also useful.
  • Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicones and paraffins or waxes or from bis-acylamides and paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • Layered silicates from the bentonite and smectite class e.g. B. those according to DE 23 34 899 and EP 26 529.
  • synthetic layered silicates which, after suspension in water (16 ° dH, room temperature), have a swelling capacity - which is the quotient of the sediment volume (V s ) / total volume (V) after previous treatment with excess soda solution, careful washing and 20 hours after the slurry in 9 parts by weight of water / one part by weight of layered silicate - of V s / V less than 0.6, in particular less than 0.4, and synthetic layered silicates, which are mixed-crystalline and have structure-determining saponite and / or hectorite-like crystal phases, which are interspersed in an irregular arrangement with crystalline alkali polysilicate.
  • Layered silicates of this type are characterized in more detail in DE 35 26 405.
  • the layered silicate content can be, for example, 5 to 20% by weight.
  • the agents can be prepared in the customary manner, ie by spray drying the constituents which are stable under these conditions and then admixing the heat-sensitive components, such as bleaching agents, enzymes, fragrances and foam inhibitors.
  • Other suitable processes are the granulation of the constituents, water, salt solutions, polymer solutions and / or nonionic surfactants being able to be used as the granulation liquid.
  • the proportion of alkali silicate can be increased to proportions of more than 2.5 to 3% by weight without risk of increased ash formation, and thus the grain strength and pourability of the finished granular powder can be increased , because the addition of HEDP counteracts ash formation.
  • Granular detergents of the following composition were produced and tested.
  • the constituents mentioned in the 1st to 9th place and the main amount of sodium sulfate were mixed to form an aqueous spray batch and spray-dried in a test tower.
  • the perborate, the bleach activator and the granules were subsequently added to the spray product.
  • the amounts relate to% by weight.
  • the test was carried out under practical conditions in household washing machines.
  • the machines were loaded with 3.5 kg of normally soiled household linen (bed linen, table linen, underwear) and 0.5 kg of test fabric.
  • Strips of standardized cotton fabric (Krefeld laundry research institute), nettle, knitwear (cotton jersey) and terry toweling were used as the test fabric. Washing conditions: tap water of 16 ° C (equivalent to 160 g CaO / liter), prewash 5 g / l at 15 to 30 ° C, main wash 7.5 g / l at 25 to 92 ° C (heating time 15 min., 15 min. at 92 ° C), liquor ratio (kg of laundry to liter of wash liquor) in the main wash cycle 1: 4, rinse 5 times with tap water, spin off and tumble dry. After 50 washing cycles, the ash content of the textile samples was determined quantitatively.
  • EDTMP stands for the hexasodium salt of ethylenediaminetetramethylenephosphonic acid (1 g salt corresponds to 0.77 g free acid)
  • HEDP stands for the tetrasodium salt of 1-hydroxy-1,1-ethanediphosphonic acid (1 g salt corresponds to 0.7 g free acid )
  • AMC for the sodium salt of a copolymer of acrylic acid and maleic acid in a molar ratio of 4: 1, molecular weight 70,000, pH 9 (partially neutralized, 1 g of salt corresponds to approximately 0.82 g of free acid).
  • the amounts of the salts used (and the proportion calculated for free acid in parentheses) are given in percent by weight. The difference in quantity of up to 5% by weight is attributable to sodium sulfate.
  • the mean value of the ash content determined from all textile samples was 9.2% by weight after 50 washes in the absence of the 3 components.
  • the amounts in Table 2 relate to the salts.
  • the difference up to 5% consists of sodium sulfate.
  • the experiment S represents the standard.

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Abstract

Detergents containing (a) 5 to 35 % of customary surfactants, (b) 10 to 40 % of microcrystalline zeolite, (c) 4 to 20 % of alkali metal silicates or carbonates and 0.1 to 5 % of (d1) aminoalkanephosphonates and/or (d2) copolymers of (meth)acrylic acid and maleic acid and (e) 5 - 80 % of other detergent ingredients are considerably improved in terms of their incrustation-preventing properties when they additionally contain (f) 0.05 to 1 % (based on free acid) of 1-hydroxyethane-1,1-diphosphonic acid in the form of the alkali metal salts. The ratio of (d1) to (f) is 3 : 1 to 1 : 6 and of (d2) to (f) is 40 : 1 to 2 : 1.

Description

Phosphatfreie Waschmittel mit einem Gehalt an feinkristallinen Alu­mosilikaten als Phosphatsubstitut, Natriumcarbonat bzw. Natrium­silikaten als Waschalkali und polyanionischen Verbindungen aus der Klasse der Aminoalkanpolyphosphonsäuren sowie der homo- ­bzw. copolymeren Polycarbonsäuren, abgeleitet von Acrylsäure, Methacrylsäure, Maleinsäure und olefinischen ungesättigten, co­polymerisierbaren Verbindungen sind bekannt. Als bevorzugte Phosphonsäuren bzw. phosphonsaure Salze werden Ethylendiamin-­tetramethylenphosphonat (EDTMP) und Diethylentriamin-pentame­thylenphosphonat, meist in Form ihrer Natriumsalze, eingesetzt. Bevorzugte polymere Polycarbonsäuren sind Copolymere der Male­insäure mit Vinylmethylethern und insbesondere der Maleinsäure mit Acrylsäure im Verhältnis 1 : 5 bis 1 : 1 mit einem Moleku­largewicht von 10 000 bis 150 000. Auch diese Polysäuren liegen in den Mitteln üblicherweise als Natriumsalze vor. Die eingesetzten Mengen Aminoalkanphosphonaten betragen üblicherweise 0,1 bis 1 Gew.-%, die an Copolymeren 3 bis 6 Gew.-%, bezogen auf die Mit­tel. Die komplexierenden und fällungsverzögernden Eigenschaften (sogen. Threshold-Effekt) dieser Zusätze reichen jedoch vielfach nicht aus, um die Ausbildung von Faserinkrustationen im ge­wünschten Maße einzuschränken. Es hat sich nämlich gezeigt, daß die Inkrustationen bei häufigem Waschen der Textilien mit hartem Wasser stark zunehmen und schließlich ein unerwünschtes Ausmaß annehmen können. Diese Zunahme der Inkrustationen äußert sich in einer zunehmenden Verhärtung und Vergrauung des Gewebes und kann durch Bestimmung der Gewebeasche quanti­tativ verfolgt werden.Phosphate-free detergents with a content of finely crystalline aluminosilicates as a phosphate substitute, sodium carbonate or sodium silicates as washing alkali and polyanionic compounds from the class of the aminoalkane polyphosphonic acids and the homo- or copolymeric polycarboxylic acids derived from acrylic acid, methacrylic acid, maleic acid and olefinically unsaturated, copolymerizable compounds are known. The preferred phosphonic acids or phosphonic acid salts are ethylene diamine tetramethylene phosphonate (EDTMP) and diethylene triamine pentamethylene phosphonate, mostly in the form of their sodium salts. Preferred polymeric polycarboxylic acids are copolymers of maleic acid with vinyl methyl ethers and in particular maleic acid with acrylic acid in a ratio of 1: 5 to 1: 1 with a molecular weight of 10,000 to 150,000. These polyacids are also usually present in the compositions as sodium salts. The amounts of aminoalkanephosphonates used are usually 0.1 to 1% by weight, those of copolymers 3 to 6% by weight, based on the composition. However, the complexing and retarding properties (so-called threshold effect) of these additives are often not sufficient to limit the formation of fiber incrustations to the desired extent. It has been shown that the incrustations increase with frequent washing of the textiles with hard water and can eventually reach an undesirable extent. This increase in incrustations manifests itself in an increasing hardening and graying of the tissue and can be followed quantitatively by determining the tissue ash.

Es bestand daher die Aufgabe, die Tendenz zur Bildung derarti­ger Inkrustationen zu vermindern.The task was therefore to reduce the tendency to form such incrustations.

Gegenstand der Erfindung, mit der diese Aufgabe gelöst wird, sind Waschmittel mit einem Gehalt an

  • (a) 5 bis 35 Gew.-% mindestens eines wasserlöslichen Tensides aus der Klasse der anionischen und nichtionischen Verbin­dungen,
  • (b) 10 bis 40 Gew.-% an feinkristallinem synthetischen Zeolith NaA,
  • (c) 4 bis 20 Gew.-% an Waschalkalien aus der Klasse der Alkali­metallsilikate und -carbonate,
  • (d) 0,1 bis 5 Gew.-%, bezogen auf freie Säure, an mindestens einer der folgenden Verbindungen in Form der Alkalimetall­salze:
    • (d1) einer Aminoalkanpolyphosphonsäure,
    • (d2) einem linearen Polymeren oder Copolymeren der Acryl­säure, Methacrylsäure und der Maleinsäure,
  • (e) 5 bis 80 Gew.-% an sonstigen Waschmittelbestandteilen,
    dadurch gekennzeichnet, daß die Mittel
  • (f) 0,05 bis 1 Gew.-%, bezogen auf freie Säure, 1-Hydroxy­ethan-1,1-diphosphonat in Form der Alkalimetallsalze enthält mit der Maßgabe, daß das Gewichtsverhältnis der Komponen­ten (d1) : (f) = 3 : 1 bis 1 : 6 und der Komponenten (d2) : (f) = 40 : 1 bis 2 : 1 beträgt.
The invention with which this object is achieved are detergents containing
  • (a) 5 to 35% by weight of at least one water-soluble surfactant from the class of the anionic and nonionic compounds,
  • (b) 10 to 40% by weight of finely crystalline synthetic zeolite NaA,
  • (c) 4 to 20% by weight of washing alkalis from the class of the alkali metal silicates and carbonates,
  • (d) 0.1 to 5% by weight, based on free acid, of at least one of the following compounds in the form of the alkali metal salts:
    • (d1) an aminoalkane polyphosphonic acid,
    • (d2) a linear polymer or copolymer of acrylic acid, methacrylic acid and maleic acid,
  • (e) 5 to 80% by weight of other detergent components,
    characterized in that the means
  • (f) 0.05 to 1% by weight, based on free acid, contains 1-hydroxyethane-1,1-diphosphonate in the form of the alkali metal salts with the proviso that the weight ratio of components (d1): (f) = 3 : 1 to 1: 6 and the components (d2): (f) = 40: 1 to 2: 1.

Als phosphatfrei wird ein Waschmittel verstanden, das weniger als 0,1 % anorganisch gebundenen Phosphor enthält.A detergent that contains less than 0.1% inorganically bound phosphorus is understood to be phosphate-free.

Wesentliches Merkmal der Erfindung ist die gemeinsame Verwen­dung der unter (d) aufgeführten Aminoalkanpolyphosphonate und bzw. oder Polymercarbonsäuren zusammen mit dem unter (f) ge­nannten Hydroxyalkan-diphosphonat. Zwar ist die Verwendung des Hydroxyalkanphosphonats (Komponente f) in Wasch- und Rei­ nigungsmitteln bereits seit langem bekannt, jedoch wurde diese Verbindung nach Auffindung der unter (d1) aufgeführten Amino­alkanphosphonate bzw. der Polymeren gemäß (d2) nicht in neuzeitlichen phosphatfreien Mitteln eingesetzt, da das Hydroxyalkanphosphonat bekannterweise ein sehr viel geringeres Sequestrierungsvermögen als die Aminoalkanphosphonate gemäß (d1) besitzt und auch praktisch keine den Polymeren gemäß (d2) vergleichbaren Threshold-Eigenschaften aufweist. Es war daher im hohen Maße überraschend, daß die gleichzeitige Verwendung der Phosphonate (d1) und (f) eine wesentlich verbesserte Inkrustations-Inhibierung bewirkt als die alleinige Verwendung nur eines der beiden Phosphonattypen. Das gleiche gilt für die gemeinsame Verwendung der Polymeren gemäß (d2) und der Komponente (f). Die synergistische Wirkung der aus allen 3 Komponenten bestehenden Kombination ist besonders ausgeprägt.An essential feature of the invention is the joint use of the aminoalkane polyphosphonates and / or polymer carboxylic acids listed under (d) together with the hydroxyalkane diphosphonate mentioned under (f). It is true that the use of the hydroxyalkane phosphonate (component f) in washing and cleaning detergents have long been known, but after the aminoalkane phosphonates listed under (d1) or the polymers according to (d2) were found, this compound was not used in modern phosphate-free agents, since the hydroxyalkane phosphonate is known to have a much lower sequestering capacity than the aminoalkane phosphonates according to (d1) and also has practically no threshold properties comparable to the polymers according to (d2). It was therefore highly surprising that the simultaneous use of the phosphonates (d1) and (f) brings about a significantly improved inhibition of incrustation than the use of only one of the two types of phosphonate. The same applies to the joint use of the polymers according to (d2) and component (f). The synergistic effect of the combination consisting of all 3 components is particularly pronounced.

Als Aminoalkanphosphonsäuren gemäß Komponente (d1) kommen vorzugsweise Ethylendiamin-tetramethylenphosphonat (EDTMP), Diethylentrimain-pentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugweise in Form der neutral reagierenden Natriumsalze, z. B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa-Natriumsalz der DTPMP, einge­setzt. Ihr Anteil in den Mitteln, auf freie Säure berechnet, be­trägt vorzugsweise 0,1 bis 1 Gew.-%, insbesondere 0,1 bis 0,5 Gew.-%.Suitable aminoalkanephosphonic acids according to component (d1) are preferably ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetrimainpentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. Their proportion in the compositions, calculated on free acid, is preferably 0.1 to 1% by weight, in particular 0.1 to 0.5% by weight.

Als (co-)polymere Polycarboxylate (Komponente d2) eignen sich Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 90 % Acrylsäure und 50 % bis 10 % Maleinsäure. Das Molekulargewicht der Homopolymeren liegt im allgemeinen zwischen 1000 bis 100 000, das der Copolymeren zwischen 2000 und 200 000, vorzugsweise 50 000 bis 120 000, bezogen auf freie Säure. Ein besonders be­ vorzugtes Acrylsäure-Maleinsäure-Copolymer weist ein Molekular­gewicht von 50 000 bis 100 000 auf.Suitable as (co) polymeric polycarboxylates (component d2) are polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those made from 50% to 90% acrylic acid and 50% to 10% maleic acid. The molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid. A particularly be preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.

Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylether, in denen der Anteil der Säure mindestens 50 % beträgt. Brauchbar sind ferner Polyacetalcarbon­säuren, wie sie beispielsweise in den US-Patentschriften 4 144 226 und 4 146 495 beschrieben sind und durch Polymerisation von Estern der Glykolsäure, Einführung stabiler terminaler Endgrup­pen und Verseifung zu den Natrium- oder Kaliumsalzen erhalten werden. Geeignet sind ferner polymere Säuren, die durch Poly­merisation von Acrolein und Disproportionierung des Polymers nach Canizzaro mittels starker Alkalien erhalten werden. Sie sind im wesentlichen aus Acrylsäureeinheiten und Vinylalkoholeinheiten beziehungsweise Acroleineinheiten aufgebaut.Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of acid is at least 50%. Also useful are polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups and saponifying to give the sodium or potassium salts. Also suitable are polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.

Der Gehalt der Mittel an (co-)polymeren Polycarbonsäuren be­trägt, auf freie Säure bezogen (Komponente d2), vorzugsweise 0,5 bis 5 Gew.-% und insbesondere 1 bis 4 Gew.-%.The content of (co) polymeric polycarboxylic acids in the composition, based on free acid (component d2), is preferably 0.5 to 5% by weight and in particular 1 to 4% by weight.

Die Mittel können die Komponente (d1) und (d2) einzeln oder auch beide gleichzeitig enthalten, wobei die gleichzeitige Ver­wendung bevorzugt ist. Bei gleichzeitiger Anwesenheit beträgt das Mischungsverhältnis (d1) : (d2) beispielsweise 1 : 1 bis 1 : 30, vorzugsweise 1 : 5 bis 1 : 20.The agents can contain component (d1) and (d2) individually or both simultaneously, with simultaneous use being preferred. In the case of simultaneous presence, the mixing ratio (d1): (d2) is, for example, 1: 1 to 1:30, preferably 1: 5 to 1:20.

Das 1-Hydroxyethan-1,1-diphosphonat (Komponente f) liegt eben­falls vorzugsweise als Natriumsalz vor. Das Dinatriumsalz reagiert neutral, das Tetranatriumsalz alkalisch (pH 9). Sein Anteil, auf Säure bezogen, beträgt 0,05 bis 1, vorzugsweise 0,1 bis 0,7 Gew.-% und insbesondere 0,1 bis 0,5 Gew.-%. Das Gewichtsver­hältnis von (d1) zu (f) beträgt 3 : 1 bis 1 : 6, vorzugsweise 2 : 1 bis 1 : 4 und von (d2) zu (f) 40 : 1 bis 2 : 1, vorzugsweise 20 : 1 bis 4 : 1.The 1-hydroxyethane-1,1-diphosphonate (component f) is also preferably present as the sodium salt. The disodium salt reacts neutrally, the tetrasodium salt alkaline (pH 9). Its proportion, based on acid, is 0.05 to 1, preferably 0.1 to 0.7% by weight and in particular 0.1 to 0.5% by weight. The weight ratio of (d1) to (f) is 3: 1 to 1: 6, preferably 2: 1 to 1: 4 and of (d2) to (f) 40: 1 to 2: 1, preferably 20: 1 to 4: 1.

Als weitere Bestandteile enthalten die erfindungsgemäßen Mittel anionische bzw. nichtionische Tenside (Komponente a). Hierzu zählen Seifen, Tenside vom Sulfonat- und Sulfat-Typ sowie nicht­ionische Verbindungen, z. B. aus der Klasse der Polyglykolether­derivate. Der Gehalt der Mittel an der Komponente (a) beträgt 5 bis 35, vorzugsweise 8 bis 20 Gew.-%.The agents according to the invention contain anionic or nonionic surfactants (component a) as further constituents. These include soaps, surfactants of the sulfonate and sulfate type as well as nonionic compounds, e.g. B. from the class of polyglycol ether derivatives. The content of the agent in component (a) is 5 to 35, preferably 8 to 20% by weight.

Geeignete Seifen leiten sich von natürlichen oder synthetischen, gesättigten oder einfach ungesättigten Fettsäuren mit 12 bis 22 C-Atomen ab. Geeignet sind insbesondere aus natürlichen Fett­säuren, z. B. Kokos-, Palmkern- oder Talgfettsäuren abgeleitete Seifengemische. Bevorzugt sind solche, die zu 50 bis 100 % aus gesättigten C₁₂₋₁₈-Fettsäureseifen und zu 0 bis 50 % aus Ölsäure­seife zusammengesetzt sind.Suitable soaps are derived from natural or synthetic, saturated or monounsaturated fatty acids with 12 to 22 carbon atoms. Are particularly suitable from natural fatty acids such. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C₁₂₋₁₈ fatty acid soaps and 0 to 50% of oleic acid soap.

Brauchbare Tenside vom Sulfonattyp sind lineare Alkylbenzolsulfo­nate (C₉₋₁₃-Alkyl) und Olefinsulfonate, d.h. Gemische aus Alken- ­und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie bei­spielsweise aus C₁₂₋₁₈-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische Hydrolyse der Sulfonierungsprodukte erhält. Geeignet sind auch Alkansulfonate, die aus C₁₂₋₁₈-Alka­nen durch Sulfochlorierung oder Sulfoxydation und anschließende Hydrolyse bzw. Neutralisation erhältlich sind, sowie alpha-Sulfo­fettsäuren und deren Ester, z. B. die alpha-sulfonierte hydrier­te Kokos-, Palmkern- oder Talgfettsäuren und deren Methyl- oder Ethylester sowie deren Gemische.Useful sulfonate type surfactants are linear alkyl benzene sulfonates (C₉₋₁₃ alkyl) and olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from C₁₂₋₁₈ monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are obtainable from C₁₂₋₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, and also alpha-sulfo fatty acids and their esters, e.g. B. the alpha-sulfonated hydrogenated coconut, palm kernel or tallow fatty acids and their methyl or ethyl esters and mixtures thereof.

Geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester aus primären Alkoholen natürlichen und synthetischen Ursprungs, d.h. aus Fettalkoholen, wie z.B. Kokosfettalkoholen, Talgfettal­koholen, Oleylalkohol, Lauryl-, Myristyl-, Palmityl- oder Ste­ arylalkohol, oder den C₁₀₋₁₈-Oxoalkoholen sowie die Schwefelsäu­reester sekundärer Alkohole dieser Kettenlänge. Auch die Schwe­felsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten aliphatischen primären Alkohole bzw. ethoxylierten sekundären Alkohole bzw. Alkylphenole sind geeignet. Ferner eignen sich sul­fatierte Fettsäurealkanolamide und sulfatierte Fettsäuremonogly­ceride.Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or Ste aryl alcohol, or the C₁₀₋₁₈ oxo alcohols and the sulfuric acid esters of secondary alcohols of this chain length. The sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.

Sulfonatgruppen enthaltende Tenside sind bevorzugt und unter diesen wiederum die Alkylbenzolsulfonate, Alpha-Sulfofettsäure­estersalze und die Alpha-Sulfofettsäureester-disalze. Die an­ionischen Tenside liegen üblicherweise in Form ihrer Natriumsalze vor. Ihr Anteil, bezogen auf das Mittel, beträgt im allgemeinen 2 bis 15 Gew.-%, vorzugsweise 5 bis 12 Gew.-%.Surfactants containing sulfonate groups are preferred, and among these in turn the alkylbenzenesulfonates, alpha-sulfofatty acid ester salts and the alpha-sulfofatty acid ester disalts. The anionic surfactants are usually in the form of their sodium salts. Their proportion, based on the composition, is generally 2 to 15% by weight, preferably 5 to 12% by weight.

Als nichtionische Tenside sind Anlagerungsprodukte von 2 bis 20, vorzugsweise 3 bis 15 Mol Ethylenoxid an 1 Mol einer Verbindung mit im wesentlichen 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole und Alkylphenole verwendbar. Besonders wichtig sind die Anlagerungsprodukte von 7 bis 15 Mol Ethylenoxid an primäre Alkohole, wie z.B. an Kokos- oder Talgfettalkohole, an Oleylalkohol, an Oxoalkohole, oder an 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 Nonionics sind aber auch nicht bzw. nicht vollständig wasserlösliche Polyglykolether mit 2 bis 6 Ethylen­glykoletherresten im Molekül von Interesse, insbesondere, wenn sie zusammen mit wasserlöslichen nichtionischen oder anionischen Tensiden eingesetzt werden. Weitere geeignete nichtionische Ten­side sind Alkylglycoside bzw. Alkylpolyglycoside, deren Alkyl­gruppe 8 bis 18, vorzugsweise 10 bis 16 C-Atome aufweist. Der Gehalt der Mittel an nichtionischen Tensiden bzw. nichtionischen Tensidgemischen beträgt vorzugsweise 3 bis 10 Gew.-% und ins­besondere 3 bis 7 Gew.-%.Addition products of 2 to 20, preferably 3 to 15 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols and alkylphenols can be used as nonionic surfactants. The addition products of 7 to 15 mol of ethylene oxide with primary alcohols, such as, for example, with coconut oil or tallow fatty alcohols, with oleyl alcohol, with oxo alcohols, or with secondary alcohols having 8 to 18, preferably 12 to 18, carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in the alkyl radicals. In addition to these water-soluble nonionics, non-fully or not fully water-soluble polyglycol ethers with 2 to 6 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. Further suitable nonionic surfactants are alkyl glycosides or alkyl polyglycosides, the alkyl group of which has 8 to 18, preferably 10 to 16, carbon atoms. The content of the agents in nonionic surfactants or nonionic surfactant mixtures is preferably 3 to 10% by weight and in particular 3 to 7% by weight.

Die Komponente (b) besteht aus feinkristallinen, synthetischen wasserhaltigen Zeolithen vom Typ NaA, die ein Calciumbindever­mögen im Bereich von 100 bis 200 mg CaO/g (gemäß den Angaben in DE 22 24 837) aufweisen. Ihre Teilchengröße liegt üblicherweise im Bereich von 1 bis 10 µm. Der Gehalt an (b) beträgt 10 bis 40, vorzugsweise 12 bis 25 Gew.-%.Component (b) consists of finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 22 24 837). Their particle size is usually in the range from 1 to 10 μm. The content of (b) is 10 to 40, preferably 12 to 25% by weight.

Geeignete Waschalkalien (Komponente c) sind Alkalimetallsilicate, insbesondere Natriumsilicate der Zusammensetzung Na₂O : SiO₂ = 1 : 1 bis 1 : 3,5, vorzugsweise 1 : 2 bis 1 : 3,35. Ihr Anteil in den Mitteln kann 1 bis 8 Gew.-%, insbesondere 2 bis 5 Gew.-% betragen. Das Natriumsilikat verbessert die Kornstabilität und die Kornstruktur der pulverförmigen bzw. granularen Mittel und wirkt sich günstig auf das Einspül- und Lösungsverhalten der Mittel bei Eingabe in Waschautomaten aus. Außerdem wirkt es antikorrosiv und verbessert das Waschvermögen. Zwar war be­kannt, daß größere Anteile, d. h. solche von mehr als 2 bis 3 Gew.-% an Alkalisilikaten in zeolithhaltigen Waschmitteln zu einem irreversiblen Agglomerieren der Zeolithpartikel führen, die sich auf den Textilien absetzen und deren Aschewert erhöhen und das Aussehen beeinträchtigen können. Überraschend wurde jedoch ge­funden, daß durch die erfindungsgemäße Kombination der Kompo­nenten (d) und (f) dieser nachteilige Einfluß weitgehend auf­gehoben wird und der aus den genannten Gründen erwünschte Gehalt an Natriumsilikat angehoben werden kann, ohne die ge­nannten Nachteile in Kauf nehmen zu müssen.Suitable washing alkalis (component c) are alkali metal silicates, in particular sodium silicates of the composition Na₂O: SiO₂ = 1: 1 to 1: 3.5, preferably 1: 2 to 1: 3.35. Their proportion in the agents can be 1 to 8% by weight, in particular 2 to 5% by weight. The sodium silicate improves the grain stability and the grain structure of the powdery or granular agents and has a favorable effect on the washing-in and dissolving behavior of the agents when they are put into washing machines. It also has an anti-corrosive effect and improves washability. It was known that larger proportions, i.e. H. those of more than 2 to 3% by weight of alkali silicates in zeolite-containing detergents lead to irreversible agglomeration of the zeolite particles, which settle on the textiles and increase their ash value and can impair the appearance. Surprisingly, however, it has been found that the combination of components (d) and (f) according to the invention largely eliminates this disadvantageous influence and the sodium silicate content desired for the reasons mentioned can be increased without having to accept the disadvantages mentioned.

Als Waschalkali (Komponente c) kommt ferner Natriumcarbonat in Frage, dessen Anteil bis zu 15 Gew.-%, vorzugsweise 2 bis 12 Gew.-% und insbesondere 5 bis 10 Gew.-% beträgt. Die Gesamt­menge an Natriumsilikat und Natriumsilikat beträgt 4 bis 20 Gew.-%, vorzugsweise 5 bis 15 Gew.-% und insbesondere 7 bis 12 Gew.-%.Also suitable as washing alkali (component c) is sodium carbonate, the proportion of which is up to 15% by weight, preferably 2 to 12% by weight and in particular 5 to 10% by weight. The total amount of sodium silicate and sodium silicate is 4 to 20% by weight, preferably 5 to 15% by weight and in particular 7 to 12% by weight.

Zu den sonstigen Waschmittelbestandteilen (Komponente e), deren Anteil 5 bis 80 Gew.-%, vorzugsweise 10 bis 50 Gew.-% beträgt, zählen Vergrauungsinhibitoren (Schmutzträger), Bleichmittel, Bleichaktivatoren, optische Aufheller, Schauminhibitoren, Enzyme, textilweichmachende Stoffe, Farb- und Duftstoffe sowie Neutral­salze und Wasser.The other detergent components (component e), the proportion of which is 5 to 80% by weight, preferably 10 to 50% by weight, include graying inhibitors (dirt carriers), bleaching agents, bleach activators, optical brighteners, foam inhibitors, enzymes, textile-softening substances, color - and fragrances as well as neutral salts and water.

Als Bestandteil dieser Komponente (e) können die Wasch- und Reinigungsmittel Vergrauungsinhibitoren enthalten, die den von der Faser abgelösten Schmutz in der Flotte suspendiert halten und so das Vergrauen verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, wie beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelantine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die oben genannten Stärkeprodukte verwenden, wie z.B. abgebaute Stärke, Aldehydstärken usw. Auch Polyvinylpyrrolidon ist brauchbar. Carboxymethylcellulose (Na-Salz), Methylcellulose und deren Gemische werden bevorzugt eingesetzt. Der Anteil der Verbindun­gen beträgt im allgemeinen 0,2 bis 2, vorzugsweise 0,5 bis 1,5 Gew.-%.As a component of this component (e), the washing and cleaning agents can contain graying inhibitors, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying. For this purpose, water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Carboxymethyl cellulose (Na salt), methyl cellulose and mixtures thereof are preferably used. The proportion of the compounds is generally 0.2 to 2, preferably 0.5 to 1.5,% by weight.

Unter den als Bleichmittel dienenden, in Wasser H₂O₂ liefernden Verbindungen haben das Natriumperborat-tetrahydrat (NaBO₂ . H₂O₂ . 3 H₂O) und das -monohydrat (NaBO₂ . H₂O₂) besondere Bedeutung. Es sind aber auch andere H₂O₂ liefernde Borate brauchbar, z.B. der Perborax Na₂B₄O₇ . 4 H₂O₂. Diese Verbin­dungen können teilweise oder vollständig durch andere Aktiv­säurestoffträger, insbesondere durch Peroxyhydrate, wie Peroxy­carbonate (Na₂CO₃ . 1,5 H₂O₂), Peroxypyrophosphate, Citratper­hydrate, Harnstoff-H₂O₂- oder Melamin-H₂O₂-Verbindungen sowie durch H₂O₂ liefernde persaure Salze oder Persäuren, wie Per­benzoate, Peroxyphthalate, Diperazelainsäure oder Diperdode­kandisäure ersetzt werden.Of the compounds used as bleaching agents which supply H₂O₂ in water, sodium perborate tetrahydrate (NaBO₂. H₂O₂. 3 H₂O) and monohydrate (NaBO₂. H₂O₂) are of particular importance. But there are also other H₂O₂ supplying borates, for example the perborax Na₂B₄O₇. 4 H₂O₂. These compounds can be partially or completely by other active acid carriers, especially by peroxy hydrates, such as peroxycarbonates (Na₂CO₃. 1.5 H₂O₂), peroxypyrophosphates, citrate perhydrates, urea-H₂O₂- or melamine-H₂O₂ compounds as well are replaced by H₂O₂-delivering peracidic salts or peracids such as perbenzoates, peroxyphthalates, diperazelaic acid or diperdodecanedioic acid.

Um beim Waschen bei Temperaturen unterhalb 80°C, insbesondere im Bereich von 40 bis 60°C, eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Präparate eingearbeitet werden. Beispiele hierfür sind mit H₂O₂ organische Persäuren bildende N-Acyl- bzw. O-Acyl-Verbindungen, vorzugsweise N,N′-­tetraacylierte Diamine, wie N,N,N′,N′-Tetraacetyl-ethylendiamin, ferner Carbonsäureanhydride, wie Benzoesäureanhydrid und Phthalsäureanhydrid und Ester von Polyolen, wie Glucosepenta­acetat.In order to achieve an improved bleaching effect when washing at temperatures below 80 ° C., in particular in the range from 40 to 60 ° C., bleach activators can be incorporated into the preparations. Examples include N-acyl or O-acyl compounds which form organic peracids with H₂O₂, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetyl-ethylenediamine, and also carboxylic anhydrides, such as benzoic anhydride and Phthalic anhydride and esters of polyols such as glucose pentaacetate.

Die Waschmittel können als optische Aufheller für Baumwolle ins­besondere Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4′-­Bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilben-2,2′-­disulfonsäure oder gleichartig aufgebaute Verbindungen, die an­stelle der Morpholinogruppe eine Diethanolaminogruppe, eine Me­thylaminogruppe oder eine 2-Methoxyethylaminogruppe tragen. Als Aufheller für Polyamidfasern kommen solche vom Typ der 1,3-Di­aryl-2-pyrazoline in Frage, beispielsweise die Verbindung 1-(p-­Sulfamoylphenyl)-3-(p-chlorphenyl)-2-pyrazolin. Weiterhin können Aufheller vom Typ des substituierten 4,4′-Distyryl-diphenyls an­wesend sein; z.B. die Verbindung 4,4′-Bis-(4-chlor-3-sulfosty­ryl)-diphenyl. Auch Gemische der vorgenannten Aufheller können verwendet werden.The detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or similarly structured compounds which have a instead of the morpholino group Carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; e.g. the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen und Amylasen bzw. deren Gemische in Frage. Besonders geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzy­matische Wirkstoffe. Die Enzyme können an Trägerstoffen adsor­ biert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen.Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can adsor on carriers be beer and / or embedded in coating substances to protect them against premature decomposition.

Geeignete Schauminhibitoren sind Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure, Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure. Auch von C₁₂₋₂₀-Fettsäuren und C₂₋₆-­Diaminen bzw. von C₁₂₋₂₀-Alkylaminen und C₂₋₆-Dicarbonsäuren abgeleitete Bis-acylamide sind brauchbar. Mit Vorteil werden auch Gemische verschiedener Schauminhibitoren verwendet, z. B. sol­che aus Silikonen und Paraffinen oder Wachsen bzw. aus Bis-acyl­amiden und Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren an eine granulare, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden.Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Bis-acylamides derived from C₁₂₋₂₀ fatty acids and C₂₋₆ diamines or from C₁₂₋₂₀ alkylamines and C₂₋₆ dicarboxylic acids are also useful. Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicones and paraffins or waxes or from bis-acylamides and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

Als textilweichmachende Zusätze eignen sich Schichtsilikate aus der Klasse der Bentonite und Smectite, z. B. solche gemäß DE 23 34 899 und EP 26 529. Geeignet sind ferner synthetische feinteilige Schichtsilikate mit smectitähnlicher Kristallphase und verringertem Quellvermögen der Formel
MgO(M₂O)a(Al₂O₃)b(SiO₂)c(H₂O)n
mit M = Natrium, gegebenenfalls zusammen mit Lithium mit der Maß­gabe, daß das Molverhältnis Na/Li wenigstens 2 beträgt, a = 0,05 bis 0,4, b = 0 bis 0,3, c = 1,2 bis 2 und n = 0,3 bis 3, wobei (H₂O)nfür das in der Kristallphase gebundene Wasser steht. Ge­eignet sind ferner synthetische Schichtsilikate, die nach Sus­pension in Wasser (16 °dH, Raumtemperatur) ein Quellvermögen -­bstimmt als Quotient des Sedimentvolumens (Vs)/Gesamtvolumen (V) nach vorheriger Behandlung mit überschüssiger Sodalösung, sorgfältigem Waschen und 20 Stunden nach Aufschlämmung in 9 Gewichtsteilen Wasser/ein Gewichtsteil Schichtsilikat - von Vs/V kleiner als 0,6, insbesondere kleiner als 0,4 besitzen, sowie synthetische Schichtsilikate, die mischkristallin ausgebildet sind und dabei strukturbestimmende saponit- und/oder hectoritähnliche Kristallphasen aufweisen, welche in unregelmäßiger Anordnung mit kristallinem Alkalipolysilikat durchsetzt sind. Derartige Schicht­silikate sind in DE 35 26 405 näher gekennzeichnet. Der Gehalt an Schichtsilikaten kann beispielsweise 5 bis 20 Gew.-% betragen.Layered silicates from the bentonite and smectite class, e.g. B. those according to DE 23 34 899 and EP 26 529. Also suitable are synthetic fine-layered silicates with smectite-like crystal phase and reduced swelling capacity of the formula
MgO (M₂O) a (Al₂O₃) b (SiO₂) c (H₂O) n
with M = sodium, optionally together with lithium, provided that the Na / Li molar ratio is at least 2, a = 0.05 to 0.4, b = 0 to 0.3, c = 1.2 to 2 and n = 0.3 to 3, where (H₂O) n stands for the water bound in the crystal phase. Also suitable are synthetic layered silicates which, after suspension in water (16 ° dH, room temperature), have a swelling capacity - which is the quotient of the sediment volume (V s ) / total volume (V) after previous treatment with excess soda solution, careful washing and 20 hours after the slurry in 9 parts by weight of water / one part by weight of layered silicate - of V s / V less than 0.6, in particular less than 0.4, and synthetic layered silicates, which are mixed-crystalline and have structure-determining saponite and / or hectorite-like crystal phases, which are interspersed in an irregular arrangement with crystalline alkali polysilicate. Layered silicates of this type are characterized in more detail in DE 35 26 405. The layered silicate content can be, for example, 5 to 20% by weight.

Die Herstellung der Mittel kann in üblicher Weise, d. h. durch Sprühtrocknen der unter diesen Bedingungen beständigen Bestand­teile und anschließendes Zumischen der hitzeempfindlichen Kompo­nenten, wie Bleichmittel, Enzyme, Duftstoffe und Schauminhibito­ren erfolgen. Weitere geeignete Verfahren sind das Granulieren der Bestandteile, wobei Wasser, Salzlösungen, Polymerlösungen und/oder nichtionische Tenside als Granulierflüssigkeit verwendet werden können. Von besonderem Wert ist der Befund, daß trotz der Anwesenheit von Zeolithen der Anteil des Alkalisilikats ohne Gefahr einer erhöhten Aschebildung auf Anteile von mehr als 2,5 bis 3 Gew.-% gesteigert und damit die Kornfestigkeit und Schütt­fähigkeit des fertigen granularen Pulvers gesteigert werden kann, da der Zusatz an HEDP einer Aschebildung entgegenwirkt.The agents can be prepared in the customary manner, ie by spray drying the constituents which are stable under these conditions and then admixing the heat-sensitive components, such as bleaching agents, enzymes, fragrances and foam inhibitors. Other suitable processes are the granulation of the constituents, water, salt solutions, polymer solutions and / or nonionic surfactants being able to be used as the granulation liquid. Of particular value is the finding that despite the presence of zeolites, the proportion of alkali silicate can be increased to proportions of more than 2.5 to 3% by weight without risk of increased ash formation, and thus the grain strength and pourability of the finished granular powder can be increased , because the addition of HEDP counteracts ash formation.

BeispieleExamples

Es wurden granulare Waschmittel nachstehender Zusammensetzung hergestellt und getestet. Die an 1. bis 9. Stelle genannten Be­standteile sowie die Hauptmenge des Natriumsulfats wurden zu einem wäßrigen Sprühansatz gemischt und in einem Versuchsturm sprühgetrocknet. Das Perborat, der Bleichaktivator und die Gra­nulate wurden dem Sprühprodukt nachträglich zugemischt. Die Mengen beziehen sich auf Gew.-%.
7,0 Na-Dodecylbenzolsulfonat
1,5 Na-Talgseife
6,5 C₁₂₋₁₈-Fettalkohol + 3 - 5 EO
25,0 Zeolith NaA
10,0 Natriumcarbonat
2,5 Na-Silikat (Na₂O : SiO₂ = 1 : 3,3)
0,8 Celluloseether
0,2 optische Aufheller
5,0 Phosphonat/Copolymer/Na-Sulfat-Gemisch
25,0 Na-Perborat-tetrahydrat
2,0 Tetraacetylethylendiamin
0,5 Enzymgranulat
0,2 Siliconentschäumer-Granulat
Rest Natriumsulfat, WasserGranular detergents of the following composition were produced and tested. The constituents mentioned in the 1st to 9th place and the main amount of sodium sulfate were mixed to form an aqueous spray batch and spray-dried in a test tower. The perborate, the bleach activator and the granules were subsequently added to the spray product. The amounts relate to% by weight.
7.0 Na dodecylbenzenesulfonate
1.5 Na tallow soap
6.5 C₁₂₋₁₈ fatty alcohol + 3 - 5 EO
25.0 zeolite NaA
10.0 sodium carbonate
2.5 Na silicate (Na₂O: SiO₂ = 1: 3.3)
0.8 cellulose ether
0.2 optical brighteners
5.0 phosphonate / copolymer / Na sulfate mixture
25.0 Na perborate tetrahydrate
2.0 tetraacetylethylenediamine
0.5 enzyme granules
0.2 silicone defoamer granules
Balance sodium sulfate, water

Die Prüfung erfolgte unter praxisnahen Bedingungen in Haus­haltswaschmaschinen. Hierzu wurden die Maschinen mit 3,5 kg normal verschmutzter Haushaltswäsche (Bettwäsche, Tischwäsche, Leibwäsche) und 0,5 kg Testgewebe beschickt. Als Testgewebe wurden Streifen aus standardisiertem Baumwollgewebe (Wäsche­forschungsanstalt Krefeld), Nessel, Wirkware (Baumwolltrikot) und Frottiergewebe verwendet. Waschbedingungen: Leitungswasser von 16 °C (äquivalent 160 g CaO/Liter), Vorwaschgang 5 g/l bei 15 bis 30 °C, Hauptwaschgang 7,5 g/l bei 25 bis 92 °C (Aufheiz­ zeit 15 min., 15 min. bei 92 °C), Flottenverhältnis (kg Wäsche zu Liter Waschlauge) im Hauptwaschgang 1 : 4, 5maliges Nachspülen mit Leitungswasser, Abschleudern und Trocknen im Tumbler. Nach 50 Waschzyklen wurde der Aschegehalt der Textilproben quantitativ bestimmt.The test was carried out under practical conditions in household washing machines. For this purpose, the machines were loaded with 3.5 kg of normally soiled household linen (bed linen, table linen, underwear) and 0.5 kg of test fabric. Strips of standardized cotton fabric (Krefeld laundry research institute), nettle, knitwear (cotton jersey) and terry toweling were used as the test fabric. Washing conditions: tap water of 16 ° C (equivalent to 160 g CaO / liter), prewash 5 g / l at 15 to 30 ° C, main wash 7.5 g / l at 25 to 92 ° C (heating time 15 min., 15 min. at 92 ° C), liquor ratio (kg of laundry to liter of wash liquor) in the main wash cycle 1: 4, rinse 5 times with tap water, spin off and tumble dry. After 50 washing cycles, the ash content of the textile samples was determined quantitatively.

In der folgenden Tabelle 1 steht EDTMP für das Hexanatriumsalz der Ethylendiamintetramethylenphosphonsäure (1 g Salz entspre­chen 0,77 g freier Säure), HEDP für das Tetranatriumsalz der 1-Hydroxy-1,1-ethandiphosphonsäure (1 g Salz entsprechen 0,7 g freier Säure), AMC für das Natriumsalz eines Copolymeren aus Acrylsäure und Maleinsäure im Molverhältnis 4 : 1, Molekular­gewicht 70 000, pH-Wert 9 (teilneutralisiert, 1 g Salz entsprechen ca. 0,82 g freie Säure). Die Mengen der eingesetzten Salze (und darunter in Klammern gesetzt der auf freie Säure berechnete An­teil) sind jeweils in Gewichtsprozent angegeben. Die Mengendif­ferenz bis 5 Gew.-% entfällt auf Natriumsulfat.In Table 1 below, EDTMP stands for the hexasodium salt of ethylenediaminetetramethylenephosphonic acid (1 g salt corresponds to 0.77 g free acid), HEDP stands for the tetrasodium salt of 1-hydroxy-1,1-ethanediphosphonic acid (1 g salt corresponds to 0.7 g free acid ), AMC for the sodium salt of a copolymer of acrylic acid and maleic acid in a molar ratio of 4: 1, molecular weight 70,000, pH 9 (partially neutralized, 1 g of salt corresponds to approximately 0.82 g of free acid). The amounts of the salts used (and the proportion calculated for free acid in parentheses) are given in percent by weight. The difference in quantity of up to 5% by weight is attributable to sodium sulfate.

Der Mittelwert des von sämtlichen Textilproben bestimmten Asche­gehaltes betrug bei Abwesenheit der 3 Komponenten nach 50 Wäschen 9,2 Gew.-%. Angegeben ist die prozentuale Veränderung des Aschegehaltes (+ = Zunahme, - = Abnahme) gegenüber diesem Standard.The mean value of the ash content determined from all textile samples was 9.2% by weight after 50 washes in the absence of the 3 components. The percentage change in ash content (+ = increase, - = decrease) compared to this standard is given.

Die niedrigsten Aschenwerte (stärkste Reduktion gegenüber dem Standard) werden gemäß Beispiel 1 bis 3 durch die Kombination der Komponenten (d1), (d2) und (f) erzielt. Aber auch die 2-­Stoff-Kombinationen gemäß Beispiel 5 bis 9 führen noch zu einer deutlichen Aschereduzierung gegenüber den in den folgenden Vergleichsversuchen beschriebenen Kombinationen. In diesen Ver­ gleichsversuchen wurden zusätzlich folgende bekannte Komplex­bildner untersucht, und zwar
NTA = Trinatriumsalz der Nitrilotriessigsäure
EDTA = Tetranatriumsalz der Ethylendiamintetraessigsäure
DTPMP= Heptanatriumsalz der Diethylentriaminpentamethylen­phosphonsäureThe lowest ash values (strongest reduction compared to the standard) are achieved according to Examples 1 to 3 by the combination of components (d1), (d2) and (f). However, the 2-substance combinations according to Examples 5 to 9 also lead to a significant reduction in ash compared to the combinations described in the following comparative experiments. In these ver The following known complexing agents were additionally tested, namely
NTA = trisodium salt of nitrilotriacetic acid
EDTA = tetrasodium salt of ethylenediaminetetraacetic acid
DTPMP = heptasodium salt of diethylenetriaminepentamethylenephosphonic acid

Die Mengenangaben in Tabelle 2 beziehen sich auf die Salze. Die Differenz bis 5 % besteht aus Natriumsulfat. Der Versuch S re­präsentiert den Standard.The amounts in Table 2 relate to the salts. The difference up to 5% consists of sodium sulfate. The experiment S represents the standard.

Die Ergebnisse zeigen, daß bereits geringe Zusätze an HEDP zu einem erheblichen Rückgang der Textilinkrustation führen. Eine entsprechende Anhebung der Anteile an Aminopolyphosphonsäuren (EDTMP bzw. DTPMP) oder an Copolymeren führt nicht zu einem vergleichbaren Rückgang der Aschewerte. Ein Ersatz durch ande­re Komplexierungsmittel (EDTA, NTA) bewirkt nichts oder sogar eine Anhebung der Inkrustationen.The results show that even small additions of HEDP lead to a significant decrease in textile incrustation. A corresponding increase in the proportions of aminopolyphosphonic acids (EDTMP or DTPMP) or of copolymers does not lead to a comparable decrease in the ash values. Replacement with other complexing agents (EDTA, NTA) does nothing or even increases the incrustation.

Beispiel 10Example 10

In dem Mittel gemäß Versuch A (Tabelle 2) wurde der Anteil des Natriumsilikats auf Kosten des Anteils an Natriumsulfat schritt­weise auf 3,7, 5 und 6 Gew.-% angehoben, wobei die Aschewerte gegenüber dem Standard um 35 %, 37 % und 38 % anstiegen. So­fern 0,4 % HEDP (Na-Salz) zugesetzt wurden, war keine Zunahme der Aschewerte festzustellen. Eine Erhöhung des EDTMP-Anteils in gleicher Höhe führte nicht zu einer vergleichbaren Verbes­serung, d. h. die Aschewerte stiegen um 22 % an.

Figure imgb0001
Figure imgb0002
 In the agent according to test A (Table 2), the proportion of sodium silicate was gradually increased to 3.7, 5 and 6% by weight at the expense of the proportion of sodium sulfate, the ash values being 35%, 37% and 38 compared to the standard % increased. If 0.4% HEDP (Na salt) was added, there was no increase in the ash values. An increase in the EDTMP share by the same amount did not lead to a comparable improvement, ie the ash values rose by 22%.
Figure imgb0001
Figure imgb0002

Claims (7)

1. Waschmittel mit einem Gehalt an (a) 5 bis 35 Gew.-% mindestens eines wasserlöslichen Ten­sides aus der Klasse der anionischen und nichtionischen Verbindungen, (b) 10 bis 40 Gew.-% an feinkristallinem synthetischen Zeolith NaA, (c) 4 bis 20 Gew.-% an Waschalkalien aus der Klasse der Al­kalimetallsilikate und -carbonate, (d) 0,1 bis 5 Gew.-%, bezogen auf freie Säure, an minde­stens einer der folgenden Verbindungen in Form der Al­kalimetallsalze:
(d1) einer Aminoalkanpolyphosphonsäure,
(d2) einem linearen Polymeren oder Copolymeren der Acrylsäure, Methacrylsäure und der Maleinsäure, (e) 5 bis 80 Gew.-% an sonstigen Waschmittelbestandteilen,
dadurch gekennzeichnet, daß die Mittel (f) 0,05 bis 1 Gew.-%, bezogen auf freie Säure, 1-Hydroxy­ethan-1,1-diphosphonat in Form der Alkalimetallsalze enthält mit der Maßgabe, daß das Gewichtsverhältnis der Komponenten (d1) : (f) = 3 : 1 bis 1 : 6 und der Kom­ponenten (d2) : (f) = 40 : 1 bis 2 : 1 beträgt. 1. Detergent containing (a) 5 to 35% by weight of at least one water-soluble surfactant from the class of the anionic and nonionic compounds, (b) 10 to 40% by weight of finely crystalline synthetic zeolite NaA, (c) 4 to 20% by weight of washing alkalis from the class of the alkali metal silicates and carbonates, (d) 0.1 to 5% by weight, based on free acid, of at least one of the following compounds in the form of the alkali metal salts:
(d1) an aminoalkane polyphosphonic acid,
(d2) a linear polymer or copolymer of acrylic acid, methacrylic acid and maleic acid, (e) 5 to 80% by weight of other detergent components,
characterized in that the means (f) 0.05 to 1% by weight, based on free acid, contains 1-hydroxyethane-1,1-diphosphonate in the form of the alkali metal salts with the proviso that the weight ratio of components (d1): (f) = 3 : 1 to 1: 6 and the components (d2): (f) = 40: 1 to 2: 1. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die Komponente (d1) aus Ethylendiamintetra-(methylenphospho­nat) besteht.2. Composition according to claim 1, characterized in that component (d1) consists of ethylenediaminetetra (methylenephosphonate). 3. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die Komponente (d2) aus dem Copolymeren aus Acrylsäure und der Maleinsäure im Verhältnis 50 : 50 bis 90 : 10 mit einem Molekulargewicht von 50 000 bis 100 000 besteht.3. Composition according to claim 1, characterized in that component (d2) consists of the copolymer of acrylic acid and maleic acid in a ratio of 50:50 to 90:10 with a molecular weight of 50,000 to 100,000. 4. Mittel nach den Ansprüchen 1 bis 3, dadurch gekennzeich­net, daß das Mischungsverhältnis von (d1) : (d2) 1 : 1 bis 1 : 30, vorzugsweise 1 : 5 bis 1 : 20 beträgt.4. Composition according to claims 1 to 3, characterized in that the mixing ratio of (d1): (d2) is 1: 1 to 1: 30, preferably 1: 5 to 1:20. 5. Mittel nach den Ansprüchen 1 bis 4, dadurch gekennzeich­net, daß das Gewichtsverhältnis (d1) : (f) 2 : 1 bis 1 : 4 beträgt.5. Composition according to claims 1 to 4, characterized in that the weight ratio (d1): (f) is 2: 1 to 1: 4. 6. Mittel nach den Ansprüchen 1 bis 5, dadurch gekennzeich­net, daß das Gewichtsverhältnis von Komponente (d2) : (f) 20 : 1 bis 4 : 1 beträgt.6. Composition according to claims 1 to 5, characterized in that the weight ratio of component (d2): (f) is 20: 1 to 4: 1. 7. Mittel nach den Ansprüchen 1 bis 6, dadurch gekennzeich­net, daß die Komponenten (d1), (d2) und (f) in Form der Natriumsalze vorliegen.7. Composition according to claims 1 to 6, characterized in that the components (d1), (d2) and (f) are in the form of the sodium salts.
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DK279888D0 (en) 1988-05-20
DK279888A (en) 1988-11-22
DE3717227A1 (en) 1988-12-01
US4919845A (en) 1990-04-24

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