EP0859825B1 - Use of polymer aminodicarboxylic acids in detergents - Google Patents

Abstract

The use of polymer aminodicarboxylic acids in bleaching detergents, bleaching auxiliary agents and bleaching lyes facilitates effective stabilisation of the peroxo bleaches present. The conventional stabilizers can thus be largely or completely replaced and greater levels of stability of the peroxo compounds achieved than was hitherto possible.

Description

The subject of the present invention relates to the use polymeric aminodicarboxylic acids and their sodium salts and precursors in bleaching detergents, bleaching aids and detergents Bleaching liquors for textiles, such as those used in the household and in commerce become.

The bleaching detergents commonly used today contain essential ones Components builder substances, surfactants and bleach. While the surfactants generally have the task of wetting the textiles to be washed and to remove and disperse greasy soiling the main tasks of the builder in it, the negative effects of Water hardness, which can be seen as incrustations on the tissue, as deposits on the heating elements of the washing machine and in the impairment of the general Express washing performance, prevent. While earlier than builder substances soluble silicates, borates and especially polymeric phosphates have recently been used primarily water-insoluble Zeolites and polymeric polycarboxylic acids or their salts as builder substances used in detergents. The common one is particularly common Use of zeolites with co-builders, for example polymeric polycarboxylic acids, which improve the effectiveness of the zeolites. Younger Time has been suggested as builder substances or co-builder substances polymeric aminodicarboxylic acids and their salts or also precursors of these polymers, which only in water to the polymeric aminodicarboxylic acids hydrolyze, use in textile detergents. Be here for example only to the patent applications WO 93/06202, WO 94/10282, EP 612 842 and EP 592 265 and on the literature cited in these publications pointed out. The main focus of these substances is at the dispersing effect on pigments (primary washing action) and in the prevention of deposits (secondary washing effect).

Oxygen bleaches are predominantly used as bleaches in laundry detergents used, primarily inorganic peroxo compounds, like sodium perborate or sodium percarbonate, but are for this purpose also organic peroxo compounds, for example peroxocarboxylic acids been proposed. The inorganic peroxo compounds in water Release hydrogen peroxide are often used with activators the effectiveness of hydrogen peroxide at low temperatures increase. To prematurely break down the peroxo compounds to prevent the storage of the detergent and in the wash liquor bleaching detergents and bleaching aids additionally stabilizers for the peroxo compounds. It is primarily about Heavy metal complexing agents such as ethylenediaminetetraacetic acid, ethylenediaminetetramethylenephosphonic acid and other polyphosphonic acids or the salts of these acids. However, the use of these complexing agents often requires Compromise on other properties of the detergent, so that for these complexing agents for exchange substances that do not have these disadvantages have, is searched.

According to EP-A-0 454 126, polyamino acids or their derivatives are used as builders or co-builder used in detergent formulations. Are preferred here polyaspartic acid and polyglutamic acid. Such polyamino acids show excellent properties as calcium complexing agent. In contrast are amino acids, such as L-aspartic acid and L-glutamic acid, as complexing agents usable for transition metals such as iron, cobalt and nickel.

WO 96/34908 describes a process for the preparation of polymers with recurring Succinyl units, especially polysuccinimide and polyaspartic acid, described. An optionally substituted 1,4-butanedicarboxylic acid, Butenedicarboxylic acid or a derivative thereof with a triammonium salt combined with a polyvalent acid and with heating polymerized. Because of their complex-forming properties Heavy metals can also be used as stabilizers for bleaches in these polymers how hydrogen peroxide serve in bleaching processes. This patent application represents a document within the meaning of Article 54 (3) and (4) EPC.

One of the objects of the present invention was to improve to find the stabilization of the bleach in the textile washing process.

This object is achieved in that polymeric aminodicarboxylic acids, their salts or their hydrolysable to polymeric aminodicarboxylic acid Precursors for the stabilization of peroxo compounds in bleaching Textile detergents, bleaches or bleach or wash liquors for textile treatment be used. This use is the bleaching Detergents, bleaching aids or alkalis are the polymeric aminodicarboxylic acids or their salts or precursors in amounts of 1% by weight to 10 % By weight, in each case based on the total weight of the composition or the total weight of the active ingredients contained, on polymeric aminodicarboxylic acid or their salts or precursors.

The advantage of the new use is that the use of the previous one usual peroxide stabilizers are largely to completely dispensed with can, so that the disadvantages associated with these connections are avoided become. Surprisingly, by using the polymer Aminodicarboxylic acids can even achieve higher stabilization than with known stabilizers.

The polymeric aminodicarboxylic acids used according to the invention are it is formally polycondensation products of aminodicarboxylic acids, such as for example aspartic acid and glutamic acid, either alone or together with other polycondensable monomer units, such as aminocarboxylic acids, Hydroxycarboxylic acids, diamines and diols. Furthermore can the polymeric aminodicarboxylic acids on the functional groups be substituted, for example by alkyl, hydroxyalkyl or Alkoxyalkyl groups. According to the invention, those are preferably usable polymeric aminodicarboxylic acids containing at least 50 mol%, in particular at least 80 mol% of optionally substituted Aminodicarboxylic acid units contained in the molecule. Particularly preferred are in turn those polymeric aminodicarboxylic acids which as Aminodicarboxylic acid units, aspartic acid groups, if appropriate also may be substituted. In the same way, the soluble Salts of these polymers or precursors of these polymers, the only with water to the polymeric aminodicarboxylic acids or their salts hydrolyze, be used.

The preparation of the polymeric aminodicarboxylic acids used according to the invention has been described in numerous references, so that it is sufficient here, for example to those in the above-mentioned patent applications and in European patent application EP 256 366 and in the work of J. Kovacs et al (Journal Organische Chemie 26, 1084-1091 (1961)) to point out the manufacturing process.

Production by thermal polycondensation is of particular importance of aminodicarboxylic acids, if desired with the addition of Acids, polyols and / or polyamines with subsequent cyclic hydrolysis Substructures and, if necessary, neutralization, as well as the production by polycondensation of maleic acid monoammonium salt optionally with the addition of acid and with subsequent hydrolysis and Neutralization.

Polyaspartic acids are particularly preferred for the use according to the invention, accordingly by polycondensation of D-, L- or D, L-aspartic acid with the addition of acid or by polycondensation of maleic acid monoammonium salt optionally with the addition of acid and in each case subsequent hydrolysis and optionally neutralization of the intermediate formed polysuccinimides are produced.

M = H, AlkalimetallDepending on the type of linkage, the monomer units can be present in the polyaspartic acid or its salts in the form of an α or a β, with the following basic structure, possibly with a different α / β ratio:

M = H, alkali metal

The molecular weights of the polymeric aminodicarboxylic acids used according to the invention can fluctuate within wide limits. Polymers are preferred with molecular weights between about 1000 and about 30,000 g / mol, especially those with molecular weights between about 2000 g / mol and about 20,000 g / mol, each based on the acidic forms used. The Molecular weights can be controlled by appropriate control of the polycondensation reaction to adjust.

The stabilizing effect of the polymeric aminodicarboxylic acids is largely regardless of the composition of the detergent or wash liquor, in which they are used. So the ingredients in the detergents are used, which is also common in these detergents are. On the other hand, the choice of certain ingredients can be beneficial be when there is a synergistic interaction with certain ingredients the detergent results. This synergistic interaction need not be limited to the effect according to the invention.

For the use according to the invention of the polymeric aminodicarboxylic acids the detergents or bleaches or the bases 1% by weight up to 10 wt .-% of these polymers based on the total weight of the finished agent or on the total contained in the finished lye Active ingredients added. In particular, the amount added to them is Polymers 2% by weight to 7% by weight.

With the bleaching agents on which the stabilizing effect of polymeric aminodicarboxylic acids used according to the invention are bleaches that contain active oxygen. Special meaning comes to the inorganic bleaching agents, the active Contain oxygen bound in such a way that when these active ingredients dissolve hydrogen peroxide is released in water. Most important representative of this Perborates, in particular sodium perborate tetrahydrate, are substance classes and sodium perborate monohydrate, and what is referred to as sodium percarbonate Peroxohydrate of sodium carbonate. Other such bleaches are the peroxohydrates of the various phosphates and the peroxohydrate of Urea. Other suitable oxygen bleaches are Peroxohydrates of organic salts, for example sodium citrate peroxohydrate, and to name the peroxycarboxylic acids, especially those solid, largely water-insoluble peroxycarboxylic acids of the type Diperoxy-alpha, omega-alkanedicarboxylic acids and N-substituted omega-aminoalkane peroxycarboxylic acids. The polymers are preferred Aminodicarboxylic acids to stabilize sodium perborates or sodium percarbonate used.

The bleach content in bleaching detergents is preferred between about 5 and about 30% by weight, in particular between about 10 and about 25% by weight. In pure bleaching agents, which are also used as additives in washing liquors the content is usually higher, preferably between about 40 and about 90% by weight.

In addition to peroxo compounds, the hydrogen peroxide when dissolved in water can release the bleaching detergents, bleaching aids and bleaching wash liquors in which the polymeric aminodicarboxylic acids are used according to the invention, contain so-called bleach activators. These are mainly N-acyl and O-acyl compounds, which in are able to be stronger in the bleach with hydrogen peroxide to react bleaching peroxycarboxylic acids. The stabilizing effect the polymers used according to the invention also extend to these peracids so formed, without depending on the use of certain Activators would arrive. Suitable activators are in large numbers in the literature and include short chain activators Acyl residues such as tetraacetylethylenediamine, tetraacetylglycoluril and Pentaacetylglucose as well as activators with long chain acyl residues such as Isononanoyloxybenzenesulfonate. The activator content is generally like this chosen so that it is sufficient, about 10 to about 50 wt .-% of the released To activate hydrogen peroxide in the wash liquor.

Usually contain bleaching detergents and wash liquors in which the use according to the invention takes place as further active ingredients builder substances, Surfactants and, where appropriate, other active ingredients and auxiliaries. However, pure bleaching aids can also contain other substances Bleach and stabilizer included. As further ingredients are in particular graying inhibitors, foam regulators, optical Brighteners, fabric softening substances, neutral salts, enzymes, fragrances and to mention dyes. Other tools, for example for liquid ones Detergents are hydrotropes and organic solvents.

Under builder substances, also referred to as framework substances today, in the narrower sense, weakly acidic, neutral or alkaline reacting soluble and / or insoluble compounds which have the property Calcium and possibly magnesium ions to precipitate or be complex to tie. As with the surfactants, the ecological ones are preferred safe connections.

Today, as a builder, the fine crystalline is primarily found in detergents synthetic water-containing zeolites, especially the zeolites of types A, X and P, which are capable of calcium and magnesium ions bind by ion exchange and the washing effect of the surfactants support. Amorphous aluminosilicates and others are also suitable amorphous or crystalline silicates with exchange capacity.

As additional builder components, in particular together with the zeolites can be used, come in (co) polymeric polycarboxylates Consider, such as polyacrylates, polymethacrylates and especially copolymers from acrylic acid and maleic acid, preferably those with 50% to 10% maleic acid. The molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight from 50,000 to 100,000. Are also particularly preferred Terpolymers made from acrylic acid, maleic acid and vinyl acetate followed by Saponification are available. 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 the acid is at least 50%. Polyacetal carboxylic acids such as for example, they are described in U.S. Patents 4,144,226 and 4,146,495 are, as well as polymeric acids, which by polymerization of Obtain acrolein and subsequent disproportionation using alkalis and from acrylic acid units and vinyl alcohol units or acrol units are built up.

Examples of useful low molecular weight organic builders are the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetic acid (NTA), if such Use for ecological reasons is not objectionable.

In cases where a phosphate content is tolerated, phosphates also become used as builder substances, in particular pentasodium triphosphate, optionally also pyrophosphates and ortophosphates, the first Line act as a precipitant for water hardness.

Suitable inorganic, non-complexing builder salts are the bicarbonates, carbonates, borates or silicates of the alkalis, which are also referred to as "washing alkalis". Of the alkali silicates, the sodium silicates with a ratio of Na ₂ O: SiO ₂ such as 1: 1 to 1: 3.5 and the crystalline sodium disilicates with a layer structure are particularly worth mentioning. Combinations of sodium carbonate and sodium silicate are often used as builder materials, particularly in detergents which contain little or no phosphate or zeolite, in which case both substances can also be granulated together if necessary.

As far as the polymeric aminodicarboxylic acids effective in addition to their peroxide stabilizing effect also builder or cobuilder effect can also have a part of the otherwise necessary in the detergents Builder substances are eliminated. The builder content is included bleaching laundry detergents usually between about 10 and about 50 % By weight, in particular between about 15 and about 40% by weight, can, however, in Special cases are also above or below these values and, if necessary, for liquid detergents or bleaching aids, for example absence.

All surfactants customary in washing or cleaning agents also come as surfactants Surfactants, i.e. anionic, nonionic, zwitterionic and cationic surfactants. However, anionic and nonionic surfactants and mixtures of surfactants from these two classes are used. The type of surfactant and the surfactant content depend primarily depends on the area in which the funds are used. Whole bleaching aids in many cases without surfactant, the surfactant content in laundry detergents is higher and generally includes nonionic and anionic surfactants. In The proportion of surfactants is usually based on the total detergent between about 4% by weight and about 30% by weight, in particular between about 6% by weight and about 25% by weight, but also values above and below of these limits are possible.

Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are alkylbenzenesulfonates (C ₉ -C ₁₅ -alkyl) and olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates which are obtainable from C ₁₂ -C ₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, as well as the sulfosuccinic acid esters and the sulfonated glycerol esters of saturated fatty acids.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, for example coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols, and those secondary Alcohols of this chain length. The sulfuric acid monoesters of the long-chain primary and secondary alcohols (ether sulfates) ethoxylated with 1 to 6 moles of ethylene oxide are also suitable. Sulfated fatty acid monoglycerides are also suitable.

Soaps made from natural or synthetic, preferably saturated, fatty acids can also be used. Soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, are particularly suitable. Preferred are those which are composed of 50 to 100% of saturated C ₁₂ -C ₁₈ fatty acid soaps and 0 to 50% of oleic acid soap.

The anionic surfactants can be in the form of their sodium, potassium and ammonium salts as well as soluble salts of organic bases, such as mono-, di- or Triethanolamine are present. The sodium salts are preferably used.

The addition products from 1 to are especially suitable as nonionic surfactants 40, preferably 2 to 20 moles of ethylene oxide to 1 mole of a long chain aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides or alkanesulfonamides for the detergents according to the invention. The addition products of 8 to 20 moles of ethylene oxide are particularly important to primary alcohols, e.g. to coconut or tallow fatty alcohols Oleyl alcohol, on oxo alcohols, or on secondary alcohols with 8 to 18, preferably 12 to 18 carbon atoms. The corresponding ones can also be used Alkoxylation products that also contain propylene oxide in addition to ethylene oxide contain.

In addition to the water-soluble nonionic surfactants, not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues of interest in the molecule, especially when they are together used with water-soluble, non-ionic or anionic surfactants become.

Alkyl glycosides of the general formula RO- (G) _x can also be used as nonionic surfactants, in which R is a primary straight-chain or aliphatic radical which is methyl-branched in the 2-position and has 8 to 22, preferably 12 to 18, carbon atoms, and G is a symbol , which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10. The so-called alkyl glucosides in which G represents a glucose unit are particularly preferred, in particular those in which x has values between 1 and 3.

Long-chain amine oxides and are also suitable as nonionic surfactants Polyhydroxy fatty acid amides, such as those obtained by reductive amination of monosaccharides with ammonia or lower alkylamines and subsequent acylation are available with fatty acid esters.

Graying inhibitors are preferably suitable for bleaching detergents Carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and mixtures of these compounds. For example, are usable also polymers of vinyl pyrrolidone and hydrophilic polyamides and polyester.

Soap with a high content of C ₁₈ -C ₂₄ fatty acids, organopolysiloxanes, paraffins and long-chain amidic compounds are preferably used as foam regulators in bleaching detergents, it being advantageous to use mixtures of different regulators.

The optical brighteners are mostly derivatives of diaminostilbenedisulfonic acid or their alkali metal salts, and substituted 4,4'-distyryl diphenyls.

Enzymes come from the classes of proteases, lipases, amylases, Cutinases and cellulases and mixtures thereof. The enzymes can adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. Even the invention Polymers used aminodicarboxylic acids seem to inactivate the Counteract enzymes.

Since the stabilizing effect of the polymers used according to the invention Aminodicarboxylic acids in both solid and liquid, bleaching Detergents or bleaches as well as in the application the lye provided the textile unfolds, the polymers are usually already the ready-made bleaching detergents or Bleach added. The wash liquors then arise through dissolution the bleaching detergent in the necessary concentration in water or by adding bleaching aids to solutions of bleach-free Detergents in water. But it is also particularly in the commercial area usual, the washing and bleaching lye by separate dosing of individual Manufacture or refresh components. In these cases, too the addition of the polymers used according to the invention separately, either in solid form or in the form of stock solutions. In any case the effect of the polymers used according to the invention in the alkali is not to special conditions, such as special temperatures or pH values bound.

Examples

1. The peroxide stabilizing effect of the polymeric aminodicarboxylic acids used according to the invention was tested in the solution of a bleaching aid in water of 17 ° German hardness, to which copper ions were added in the form of a copper sulfate solution in order to trigger the peroxide decomposition. For comparison, polymeric polycarboxylic acids or polyphosphonic acids were used instead of polyaspartic acid. The contents in the examined solutions are shown in Table 1 below. example ingredients Content in grams per liter 1 NaBO ₃ x 4H ₂ O 1.00 2nd NaBO ₃ x 4H ₂ O
Maleic acid - acrylic acid - copolymer - Na salt 1.00
0.2225 3rd NaBO ₃ x 4H ₂ O
Maleic acid - acrylic acid - copolymer - Na salt
Diethylene triamine pentamethylene phosphonate 1.00
0.2225
0.025 4th NaBO ₃ x 4H ₂ O
Polyaspartic acid (mol. Weight 2500) produced according to EP 256 366 1.00
0.2225 5 NaBO ₃ x 4H ₂ O
Polyaspartic acid (mol. Wt. 17000) produced according to J. Org. Chem. 26 , 1084 (1961) 1.00
0.2225 After addition of the copper solution, 500 ml of the bleaching solution were heated to 60 ° C. in a 21-glass flask with stirring and held at this temperature for 30 minutes. During the heating and at 60 ° C., samples were taken repeatedly and checked iodometrically for their content of active oxygen. The following table 2 contains the active oxygen contents found as relative values, based on the values at 20 ° C. as 100%. The stabilizing effect of the polymeric aminodicarboxylic acids used according to the invention is immediately clear from the test results. Active oxygen levels (relative in%) temperature 1 2nd 3rd 4th 5 20 ° C 100 100 100 100 100 30 ° C 99.4 99.8 100 100 98.8 40 ° C 98.7 98.8 99.4 98.2 98.8 50 ° C 89.4 94.5 98.7 98.2 98.2 60 ° C 19.9 61.3 98.7 97.5 92.6 10 minutes at 60 ° C 2.5 23.9 98.1 97.5 86.5 20 minutes at 60 ° C 1.8 8.0 96.9 97.5 83.4 30 minutes at 60 ° C - 4.3 94.4 97.5 77.3

2. Practical test The effect of the polymeric aminodicarboxylic acids in the washing process was investigated in textile washing tests in household washing machines using standard soiling in the presence of 5 ppm copper in the wash liquor. In comparative experiments, polymeric polycarboxylic acids were used alone or together with aminophosphonic acids as heavy metal complexing agents instead of the polymeric aminodicarboxylic acids. In all tests, the cleaning ability was determined on the basis of the light emission of the washed fabrics and the peroxide-stabilizing effect on the basis of the analytically determined peroxide contents of the wash liquor. The detergents used had the following composition (in percent by weight): Sodium dodecylbenzenesulfonate 9% Sodium tallow fatty alcohol sulfate 4% Coconut alcohol + 5 EO 4% Tallow fatty alcohol with 5 EO 2% Coconut fatty acid sodium soap 1 % Zeolite A (calculated anhydrous) 24% Na ₂ CO ₃ 12% Sodium silicate (Na ₂ O: SiO ₂ = 3.3) 3% Sodium perborate monohydrate 16% Tetraacetylethylenediamine 5% Protease polymeric polycarboxylate or polymer 1 % Aminodicarboxylic acid (sodium salts) diethylenetriaminepentamethylenephosphonic acid 5.5% Sodium salt graying inhibitor, defoamer, optical brightener, salts from raw materials 0 or 0.4% and water Rest 100%

The 4 detergents A to D differ as follows: laundry detergent component A B C. D Maleic acid-acrylic acid copolymer (Sokalan CP5) x x Diethylene triamine pentamethylene phosphonate x Polyaspartic acid (MW 17000) according to J. Org. Chem. 26 , 1084 (1961) x Polyaspartic acid (MW 2500) according to EP 256 366 x

The washing tests themselves were carried out in a Miele washing machine type W 701 in the normal washing program without prewash under the following conditions: Washing temperature 60 ° C Amount of water in the wash cycle 20 liters Water hardness 16 ° d Detergent dosage 105 g / wash loading with white filling laundry 3 kg

The cleaning ability was on artificially produced soiling tested in the form of appropriate test fabrics with a size about 10 x 10 cm in addition to the white fill fabric in the washing machine were introduced. After the wash was finished, the Test fabric dried, ironed and using a reflectance photometer measured. The results are given in percent light reflectance on barium sulfate as white standard (100%). Show higher values purer tissue. In each case, three parallel experiments were carried out and averaged their results. Tables 3 and 4 show the Average values of the measured remissions for different test tissues. In addition it is stated which smallest difference is still significant the individual test tissues can be viewed (LSD).

a) Staub/Wollfett auf Baumwolle

b) Staub/Hautfett auf veredelter Baumwolle

c) Staub/Hautfett auf Polyester-Baumwolle-Mischgewebe

d) Milch/Kakao auf Baumwolle

e) Wimperntusche auf Polyester-Baumwolle-Mischgewebe

f) Rotwein auf Baumwolle

g) Waldbeere auf Polyester-Baumwolle-Mischgewebe

h) Johannisbeere auf Polyester-Baumwolle-Mischgewebe

i) Tee auf veredelter Baumwolle

k) Kaffee auf veredelter Baumwolle Waschmittel Cu-Zusatz Remissionswerte bei den Testanschmutzungen a - e a b c d e A 0 68,9 74,8 63,6 76,7 62,7 A 5 ppm 68,2 74,1 63,3 67,8 63,8 B 5 ppm 69,3 74,6 62,5 74,7 64,8 C 5 ppm 68,7 72,5 63,1 70,5 62,9 D 5 ppm 69,7 72,9 64,7 73,9 65,0 LSD 0,8 1,1 1,5 2,3 1,0

Waschmittel Cu-Zusatz Remissionswerte bei den Testanschmutzungen f - k f g h i k A 0 72,1 72,5 71,3 59,9 84,1 A 5 ppm 59,7 60,7 60,2 37,4 80,5 B 5 ppm 72,7 70,6 70,5 54,3 84,2 C 5 ppm 69,0 68,6 68,9 50,8 83,0 D 5 ppm 70,4 70,7 71,1 56,8 83,9 LSD 1,4 1,2 1,0 2,0 0,4 The following were used as test fabrics:

a) Dust / wool grease on cotton

b) Dust / skin fat on refined cotton

c) Dust / skin fat on polyester-cotton blend

d) Milk / cocoa on cotton

e) Mascara on polyester-cotton blend

f) red wine on cotton

g) wild berries on a polyester-cotton blend

h) Currant on polyester-cotton blend

i) Tea on processed cotton

k) Coffee on processed cotton laundry detergent Cu additive Remission values for the test soiling a - e a b c d e A 0 68.9 74.8 63.6 76.7 62.7 A 5 ppm 68.2 74.1 63.3 67.8 63.8 B 5 ppm 69.3 74.6 62.5 74.7 64.8 C. 5 ppm 68.7 72.5 63.1 70.5 62.9 D 5 ppm 69.7 72.9 64.7 73.9 65.0 LSD 0.8 1.1 1.5 2.3 1.0

laundry detergent Cu additive Remission values for the test soiling f - k f G H i k A 0 72.1 72.5 71.3 59.9 84.1 A 5 ppm 59.7 60.7 60.2 37.4 80.5 B 5 ppm 72.7 70.6 70.5 54.3 84.2 C. 5 ppm 69.0 68.6 68.9 50.8 83.0 D 5 ppm 70.4 70.7 71.1 56.8 83.9 LSD 1.4 1.2 1.0 2.0 0.4

From the results with the pigment-containing test soils a to c and e shows that the use of the polymeric aminodicarboxylic acids Washing performance compared to conventional detergents not affected. The result with the enzyme-specific soiling d clearly shows that the impairment of the enzyme effect by traces of copper when using the polymeric aminodicarboxylic acids is largely canceled. The Results with the bleachable test stains f to k make the bleach-stabilizing effect of the polymeric aminodicarboxylic acids clearly, which goes so far that in practice the addition of aminophosphonic acids can be dispensed with in all cases.

The bleach-stabilizing effect was also investigated by determining the active oxygen content in the wash liquor in the course of the washing process. Table 5 shows the mean values of the iodometric titration results after 4, 10 and 30 minutes of washing time in percent, based on the calculated starting content of active oxygen of 100% from the dosage. These values also clearly show the bleach-stabilizing effect of the polymeric aminodicarboxylic acids. laundry detergent CU addition Active oxygen levels during the washing process 4 min 10 min 30 min A 5 ppm 84.6 60.5 40.4 B 5 ppm 94.9 86.3 82.2 C. 5 ppm 89.6 80.2 70.4 D 5 ppm 98.8 92.2 89.7

Claims (7)

1. The use of polymeric aminodicarboxylic acid or salts or precursors thereof hydrolyzable to polymeric aminodicarboxylic acids in bleaching detergents, bleaching agents or bleaching or washing liquors for treating fabrics to stabilize peroxo bleaching agents present therein, characterized in that polymeric aminodicarboxylic acid or salts or precursors thereof are added to the bleaching laundry detergent, to the bleaching agent or to the liquor in a quantity of 1% by weight to 10% by weight, based on the total weight of the the detergent or bleaching agent or liquor or on the total weight of the active substances present.
2. The use claimed in claim 1, characterized in that the polymeric aminodicarboxylic acid or salt or precursor thereof is a polymer which consists to a large extent of aspartic acid or glutamic acid units or precursor units thereof.
3. The use claimed in claim 1 or 2, characterized in that more than 50 mole-% and preferably more than 80 mole-% of the polymer used consists of aspartic acid units.
4. The use claimed in claim 3, characterized in that the polymer used is obtained by polycondensation of aspartic acid, subsequent hydrolysis of the polysuccinimide formed and optionally neutralization.
5. The use claimed in claim 3, characterized in that the polymer used is obtained by polycondensation of maleic acid monoammonium salt, subsequent hydrolysis of the polysuccinimide formed and optionally neutralization.
6. The use claimed in any of claims 1 to 5, characterized in that polymeric aminodicarboxylic acid or salts or precursors thereof are added to the bleaching laundry detergent, to the bleaching agent or to the liquor in a quantity of 2% by weight to 7% by weight, based on the total weight of the detergent or bleaching agent or liquor or on the total weight of the active substances present.
7. The use claimed in any of claims 1 to 6, characterized in that the stabilized per compound is sodium perborate tetrahydrate, sodium perborate monohydrate, sodium percarbonate, hydrogen peroxide or a mixture of these per compounds.