EP0460035B1 - Water-softening agent in granular to powder form - Google Patents

Abstract

The invention concerns a water-softening agent in granular to powder form which can be used in conjunction with a detergent or for washing and which contains (A) fine-crystalline, synthetic, hydrated zeolite of the type NaA, (B) polymer polycarboxylates, derived from acrylic acids and their copolymers with maleic acid in the form of the sodium salt, (C) sodium perborate in the form of the monohydrate and/or tetrahydrate and (D) at least one linear 1,2-alkanediol with a C10 to C18 chain length and/or their ethoxylation products with not more than 3 ethoxy groups. The agent consists of a dry mixture of at least two powder components; the first component contains the constituents (A) and (B) in the form of a spray-dried granulate, and the second powder component contains sodium perborate (C). Constituent (D) can be mixed with each powder component or with a mixture thereof or granulated.

Description

The invention relates to a water softener, which is used in addition to a detergent to improve the washing result, especially if a poor washing result is to be expected with high water hardness.

When using hard tap water, for example with degrees of hardness above 18 ° d (corresponding to 180 mg Ca0 / liter), but especially above 25 ° d (250 mg Ca0 / liter), the washing result with a usual detergent dosage of 5 to 8 g / liter already significantly affected. At the same time, the formation of fiber incrustations, associated with graying of the fabric, and harmful limescale deposits on the heating elements of the washing machine increases considerably. Although this tendency can be countered by adding more detergent, the consumer is generally not prepared to do so. From customer observations it is known that the majority of customers regularly under-dose the funds contrary to the recommendation, which increases the problems shown considerably. On the other hand, if the dosage is too high, the proportion of surfactants in the wash liquor and later in the wastewater is increased. However, this increase in the surfactant concentration usually does not lead to a comparable increase in the degree of whiteness, which is why the additional consumption of surfactants can be regarded as a waste. So far, a way out has been the additional use of softening agents with a high content of polymeric phosphates.

The problems associated with the underdosing of the detergent in the presence of very hard water have been exacerbated by the introduction of low-phosphate and phosphate-free detergents, especially since the known polyphosphate-based softeners are to be assessed critically and should or have been replaced by more environmentally compatible products.

From German patent application 25 27 388 it is known that the agglomerates of zeolite and dispersant (for example a polymeric polycarboxylate) obtainable by spray drying stabilized aqueous zeolite suspensions can be used as water softeners.

From the German patent application 33 16 513 granules are known which contain zeolites and polymeric polycarboxylates and can be used as softening agents. The content of homo- or copolymeric polycarboxylic acid or its alkali salt should be 5 to 30% by weight, based on the hydrated zeolite.

German patent application 36 14 779 (EP-A-0.243.908) discloses a softening agent with a similar composition based on zeolite, polymeric polycarboxylate, sodium citrate, soda and preferably carboxymethyl cellulose.

The subject of German patent application 38 14 855 (EP-A-0.340.590, state of the art according to Art 54 (3) (4) EPC) is a detergent additive which can be used as a softening agent and is based on zeolite, polymeric polycarboxylates and sodium perborate.

It has now been found that the performance of the known water softening agents can be improved if zeolite, polymeric polycarboxylates and sodium perborate are used in certain combinations and relatively small amounts of a surfactant are added.

• (A) feinkristallinem, synthetischem, gebundenes Wasser enthaltendem Zeolith vom Typ NaA,
• (B) polymeren Polycarboxylaten, abgeleitet von Acrylsäure sowie deren Copolymeren mit Maleinsäure in Form der Natriumsalze,
• (C) Natriumperborat (in Form des Monohydrats und/oder Tetrahydrats)
• (D) einem oder mehreren linearen 1,2-Alkandiolen der Kettenlänge C₁₀ bis C₁₈ und/oder deren Ethoxylierungsprodukten mit vorzugsweise 1 bis 3 Ethoxygruppen,

wobei die Gewichtsverhältnisse von (A) zu (B) 30 : 1 bis 4 : 1, von (A) zu (C) 30 : 1 bis 1,6 : 1, von (A) zu (D) 55 : 1 bis 4 : 1, von (B) zu (C) 5 : 1 bis 1 : 12,5, von (B) zu (D) 10 : 1 bis 1 : 5 und von (C) zu (D) 25 : 1 bis 1 : 5 betragen, mit der Maßgabe, daß die Anteile der Bestandteile (A), (B) und (D) als wasserfreie Substanzen und der Bestandteil (C) als Monohydrat berechnet werden.The invention accordingly relates to a granular to pulverulent water softener which can be used as an additive with detergents or for washing processes, characterized by a content of

• (A) finely crystalline, synthetic, bound water-containing zeolite of the NaA type,
• (B) polymeric polycarboxylates derived from acrylic acid and their copolymers with maleic acid in the form of the sodium salts,
• (C) sodium perborate (in the form of the monohydrate and / or tetrahydrate)
• (D) one or more linear 1,2-alkanediols of chain length C₁₀ to C₁₈ and / or their ethoxylation products with preferably 1 to 3 ethoxy groups,

wherein the weight ratios of (A) to (B) 30: 1 to 4: 1, from (A) to (C) 30: 1 to 1.6: 1, from (A) to (D) 55: 1 to 4 : 1, from (B) to (C) 5: 1 to 1: 12.5, from (B) to (D) 10: 1 to 1: 5 and from (C) to (D) 25: 1 to 1 : 5, with the proviso that the proportions of components (A), (B) and (D) are calculated as anhydrous substances and component (C) as a monohydrate.

The component (A) 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 Ca0 / g (according to the information in German patent application 24 12 837). The average particle size is in the range from 1 to 10 µm (measurement method: Coulter counter).

Component (B) consists of homopolymers of acrylic acid and / or copolymers of acrylic acid with maleic acid, which are in the form of the sodium salts. The polyacrylic acid can have, for example, a molecular weight of 2,000 to 200,000, preferably 5,000 to 100,000. They have proven to be particularly suitable Copolymers of acrylic acid or methacrylic acid with maleic acid have been found to be characterized, for example, in EP-A-0.025.551. These are copolymers which contain 40 to 90% by weight of acrylic acid. Copolymers in which 50 to 85% by weight of acrylic acid and 50 to 15% by weight of maleic acid are present are particularly preferred.

Component (C) consists of sodium perborate, which can be present as a monohydrate, tetrahydrate or as a mixture of these. The content of the agents and the mixing ratios are based on the perborate monohydrate, even if the component (C) should consist entirely or partially of the tetrahydrate. Preferred agents are those in which the oxygen-containing bleaching agent is present as a perborate monohydrate.

Component (D) consists of linear 1,2-alkanediols with a chain length of 10 to 18 carbon atoms, which can be ethoxylated with 0 to 3 ethoxy units. Of these, diols with C₁₀ to C₁₄ chain numbers, ie 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 1,2-tridecanediol and 1,2- Tetradecanediol and their ethoxylates, the number of ethoxy groups being limited to a maximum of 3. The 1,2-alkanediols can also be used in a mixture with their ethoxylated derivatives, the degree of ethoxylation corresponding to a statistical distribution. In general, these are terminally ethoxylated derivatives. 1,2-Dodecanediol and the ethoxylated diols 1,2-dodecanediol.1EO and 1,2-dodecanediol.2EO are particularly preferred.

The production of 1,2-alkanediols is known. It is carried out in particular by reacting epoxidized 1,2-alkenes with water at temperatures from 180 to 250 ° C. and a pressure of 15 to 40 bar, as described in German application 38 14 850.

The ethoxylated derivatives of 1,2-alkanediols can be obtained in a manner known per se by reaction with ethylene oxide under the action of customary alkaline catalysts or using calcined hydrotalcites, as described in German application 38 13 910. The latter method has the advantage that the reaction products have a narrow bandwidth or homolog distribution, the distribution curve being very close to that calculated according to Poisson.

The weight ratio of (A) to (B) is 30: 1 to 4: 1, preferably 14: 1 to 5: 1, that of (A) to (C) 30: 1 to 1.6: 1, preferably 11: 1 to 3: 1, that from (A) to (D) 55: 1 to 4: 1, preferably 28: 1 to 7.5: 1, that from (B) to (C) 5: 1 to 1:12 , 5, preferably 1.6: 1 to 1: 4, that of (B) to (D) 10: 1 to 1: 5, preferably 4: 1 to 1: 4, and that of (C) to (D) 25: 1 to 1: 5, preferably 7.5: 1 to 1: 1, the components (A), (B) and (D) being counted as anhydrous substances.

The agents preferably used in granular form consist of a dry, homogeneous mixture of at least two powder components, of which the first component is in the form of spray-dried granules. It can be obtained by spray drying a slurry which contains the zeolite as an aqueous suspension in a mixture with the sodium salt of the (co) -polymeric acids in the stated mixing ratio.

This first powder component can contain further additives which, for example, can advantageously change the granulate structure, the bulk density or the flow behavior. These additives include, for example, sodium sulfate, which is essentially in anhydrous form. Referred to as (anhydrously calculated) component (E), its weight ratio (A): (E) is preferably 20: 1 to 4: 1.

Because zeolites are preferably used in stabilized aqueous suspensions, the agents according to the invention can also contain these stabilizers. Stabilizers frequently used in practice are ethoxylated linear or methyl-branched (oxo radical) alcohols, for example C₁₂-C₁₆ alcohols with 3 to 5 ethylene oxide groups (EO) and C₁₆-C₁₈ alcohols (tallow alcohol) with 4 to 7 EO. This applies to both detergents and softeners. The stabilizing agents can be contained in the claimed agents in amounts of approximately 1 to 2% by weight.

Because of its thermal sensitivity, perborate (C) is not spray-dried together with the constituents of the first powder component, but is only subsequently mixed into the spray product. It thus forms the base powder for the second powder component.

Component (D) can be mixed with each powder component of the water softening agent according to the invention, if appropriate after previous granulation or spray drying, and with the mixture of the powder components mentioned and then granulated. However, a certain powder component of the additive is preferably treated in this way and this surfactant-containing premix is then combined with the other powder components. A spray product made of (A + B) and sodium sulfate (E) are particularly suitable for this purpose. The weight ratio of (D) to (E) can be 5: 1 to 1: 30. The use of the granular or powdery perborate (C) as a starting material for the premix, in particular for the premix of (C) and the ethoxylated diol derivatives (D), has also proven to be expedient, with uniform mixing of the components by spraying on ( D) on (C) in the form of a fine spray.

The agents can also contain further powder components which are neither suitable for processing together with the perborate nor for hot spray drying and which are likewise mixed in a dry form with the aforementioned powder components. These include bleach activators, in particular powdery to granular peracid precursors from the class of N-acyl compounds and O-acyl compounds. Examples of suitable N-acyl compounds are multiply acylated alkylenediamines, such as tetraacetylethylenediamine (TAED), and acylated glycolurils, for example tetraacetylglycoluril. In addition to carboxylic anhydrides such as phthalic anhydride and esters such as Na (iso) nonanoylphenol sulfonate, acylated sugars such as glucose pentaacetate are also suitable as O-acyl compounds. Preferred bleach activators are tetraacetylethylenediamine and glucose pentaacetate. The bleach activators can be granulated and coated with water-soluble coating substances in order to avoid premature interaction with perborate. Particularly suitable coating agents are water-soluble polymers, for example cellulose ethers, such as carboxymethyl cellulose (as sodium salt), or carbon chain polymers, such as the (co) -polymeric polycarboxylic acids and their salts mentioned under (B).

• (A) 40 bis 60 Gew.-% feinkristalliner, synthetischer Zeolith vom Typ NaA,
• (B) 2 bis 10 Gew.-% polymeres Polycarboxylat, abgeleitet von Acrylsäure und deren Copolymeren mit Maleinsäure in Form der Natriumsalze,
• (C) 2 bis 25 Gew.-% Natriumperborat in Form des Monohydrats oder Tetrahydrats (berechnet als Monohydrat),
• (D) 1 bis 10 Gew.-% eines oder mehrerer linearer 1,2-Alkandiole der Kettenlänge C₁₀ bis C₁₈ mit 0 bis 3 Ethoxygruppen,
• (E) 0 bis 30 Gew.-% Natriumsulfat,
• (F) 0 bis 10 Gew.-% eines Persäurevorläufers,
• (G) 0 bis 2 Gew.-% eines mit 3 bis 7 Mol Ethylenoxid umgesetzten linearen oder methylverzweigten C₁₂-C₁₈-Alkohols,

wobei die Mengen, mit Ausnahme des Bestandteils (C), auf wasserfreie Substanz bezogen sind und die Gesamtmenge an gebundenem Wasser, das in den Bestandteilen mit Ausnahme von (C) enthalten ist, bis zu 20 Gew.-% beträgt.Agents of the specified composition can therefore have the following composition:

• (A) 40 to 60% by weight of finely crystalline, synthetic zeolite of the NaA type,
• (B) 2 to 10% by weight of polymeric polycarboxylate derived from acrylic acid and its copolymers with maleic acid in the form of the sodium salts,
• (C) 2 to 25% by weight sodium perborate in the form of the monohydrate or tetrahydrate (calculated as monohydrate),
• (D) 1 to 10% by weight of one or more linear 1,2-alkanediols of chain length C₁₀ to C₁₈ with 0 to 3 ethoxy groups,
• (E) 0 to 30% by weight sodium sulfate,
• (F) 0 to 10% by weight of a peracid precursor,
• (G) 0 to 2% by weight of a linear or methyl-branched C₁₂-C₁₈ alcohol reacted with 3 to 7 mol of ethylene oxide,

wherein the amounts, with the exception of component (C), are based on anhydrous substance and the total amount of bound water contained in the components with the exception of (C) is up to 20% by weight.

• (A) 45 bis 55 Gew.-% feinkristalliner, synthetischer Zeolith vom Typ NaA,
• (B) 4 bis 8 Gew.-% des Natriumsalzes eines Acrylsäure-Maleinsäure-copolymeren im Gewichtsverhältnis 10 : 1 bis 1 : 1 und einem Molekulargewicht von 20 000 bis 150 000,
• (C) 5 bis 15 Gew.-% Natriumperborat, berechnet als Monohydrat,
• (D) 2 bis 6 Gew.-% eines oder mehrerer linearer 1,2-Alkandiole der Kettenlänge C₁₀ bis C₁₄ mit 0 bis 3 Ethoxygruppen unter besonderer Bevorzugung von 1,2-Dodecandiol und 1,2-Dodecandiol·2EO,
• (E) 2 bis 20 Gew.-% Natriumsulfat,
• (F) 2 bis 8 Gew.-% Tetraacetylethylendiamin,
• (G) 1 bis 2 Gew.-% eines mit 3 bis 7 Mol Ethylenoxid umgesetzten linearen C₁₂-C₁₈-Alkohols.

The compositions preferably have the following composition:

• (A) 45 to 55% by weight of finely crystalline, synthetic zeolite of the NaA type,
• (B) 4 to 8% by weight of the sodium salt of an acrylic acid-maleic acid copolymer in a weight ratio of 10: 1 to 1: 1 and a molecular weight of 20,000 to 150,000,
• (C) 5 to 15% by weight sodium perborate, calculated as monohydrate,
• (D) 2 to 6% by weight of one or more linear 1,2-alkanediols of chain length C₁₀ to C₁₄ with 0 to 3 ethoxy groups, with particular preference for 1,2-dodecanediol and 1,2-dodecanediol · 2EO,
• (E) 2 to 20% by weight sodium sulfate,
• (F) 2 to 8% by weight of tetraacetylethylene diamine,
• (G) 1 to 2 wt .-% of a reacted with 3 to 7 moles of ethylene oxide linear C₁₂-C₁₈ alcohol.

The agents of the claimed composition show a better effect than conventional agents with higher proportions of "classic" softening agents in terms of binding calcium salts and enhancing the builder effect. Zeolites, soda, polymeric polycarboxylates and polyacids such as citric acid are considered "classic" softeners. It has not previously been known of perborates that, in combination with some of the "classic" softening agents mentioned, they advantageously support their specific action and have a builder effect, provided the water used has a high calcium hardness.

• die Primärwaschkraft sowie die Verhinderung von Gewebevergrauungen und Gewebeaschen werden erheblich verbessert, insbesondere wenn das konventionelle Waschmittel in Bezug auf die Wasserhärte unterdosiert wird,
• es wird ein zusätzlicher Bleicheffekt erzielt,
• das Abwasser wird gegenüber einem konventionellen Waschprozeß bei hoher Wasserhärte sehr viel weniger belastet, und zwar sowohl gegenüber einem Waschprozeß, bei dem das konventionelle Waschmittel entsprechend hoch dosiert wird, als auch bei einem Waschprozeß mit Unterdosierung des Waschmittels und Ausgleich mit einem konventionellen Wasserenthärtungsmittel.

In addition to the increased softening and builder effect, the agents according to the invention, in addition to a pronounced bleaching effect through the addition of a detergency booster (D), also have a significantly improved primary detergency, which is particularly useful when the consumer underdoses the bleach-containing heavy-duty detergent and does not use any other additives . With simultaneous use of the agent according to the invention and conventional detergents, the following advantages result:

• the primary washing power and the prevention of tissue graying and ash are significantly improved, especially if the conventional detergent is underdosed in relation to the water hardness,
• an additional bleaching effect is achieved,
• The wastewater is much less polluted than a conventional washing process with high water hardness, both against a washing process in which the conventional detergent is dosed accordingly high, as well as in a washing process with underdosing of the detergent and compensation with a conventional water softener.

B E I S P I E L E

The following granular to powdery mixtures 1 to 4 shown in Table 1 were prepared.

Agent No. 1 contained a conventional detergent booster of the QAV type, agent No. 2 and agent No. 3 contained 1,2-dodecanediol and 1,2-dodecanediol.2EO, respectively, which were mixed with the mixture of the other powder components and granulated . In agent no.4, 1,2-dodecanediol.2EO had been applied to perborate monohydrate.

The synthetic zeolite used (calculated anhydrous) had a particle size between 0.5 and 8 microns. The agents 1 to 4 of the polycarboxylate consisted of the sodium salt of a copolymer of acrylic acid and maleic acid with a molecular weight of approximately 70,000 (Sokalan CP5 ^(R) ).

TA ethoxylate is technical tallow alcohol, reacted with 5 mol ethylene oxide (HLB value = 9.2) and served as a suspension stabilizer for the zeolite master batch.

All of these ingredients, as well as sodium sulfate and water, are ingredients of the first powder component obtained by spray drying an aqueous slurry. The granules had a grain size of 0.1 to 0.8 mm (average grain size 0.4 mm).

TAED stands for tetraacetylethylenediamine. CMC is the sodium salt of carboxymethyl cellulose and was used as a coating substance for the TAED according to the information in European patent application 37 026.

The application test was carried out both in a launderometer and in a household washing machine with a horizontally arranged washing drum (type Miele W 760) using a commercially available phosphate-free detergent. When evaluating Tables 2 to 4, it must be taken into account that in tests, both in the launderometer and in the washing machine, remission differences of 2% and more can be reproduced by the consumer (optical evaluation with Zeiss reflectometer at 465 nm; suppression of the brightener Effect). In the visual assessment, however, differences of 0.5 grades are significant (maximum grade 6.0 means no brightening).

The composition of the detergent was (in% by weight):

1. Try the launderometer

Weitere Versuchsbedingungen sind in Tabelle 2 enthalten. Die Spalte "Soll" gibt die Dosierung des Waschmittels "W" gegenüber dem korrekten Sollwert 1 für den Härtebereich 4 (28 °d) an. Der Zusatz an Enthärtungsmittel ist mit der oben für die entsprechenden Mittel angegebenen Nummer gekennzeichnet. Wie die Ergebnisse in Tabelle 2 zeigen, ist die durch die Unterdosierung des Waschmittels erzielte Minderleistung weitgehend durch den Zusatz der erfindungsgemäßen Mittels Nr. 2 kompensiert. Mittel Nr. 1 mit einem üblichen QAV erreichte nicht die vorteilhafte Wirkung des erfindungsgemäßen Mittels.

Further test conditions are contained in Table 2. The column "target" indicates the dosage of the detergent "W" compared to the correct target value 1 for the hardness range 4 (28 ° d). The addition of softening agent is marked with the number given above for the corresponding agent. As the results in Table 2 show, the underperformance achieved by underdosing the detergent is largely compensated for by the addition of agent No. 2 according to the invention. Agent No. 1 with a conventional QAV did not achieve the beneficial effect of the agent according to the invention.

2. Try in the washing machine

The target dosage for water hardness range 4 (28 ° d) is 234 g per washing machine. An underdosing is typical, in which only 70% of the target value is used (164 g). An even stronger underdosing (40%) leads to extremely high underperformance, which, however, is largely compensated for by the use of agents 2 to 4 according to the invention (tables 3 and 4).

Claims (7)

1. A granular to powder-form water softener suitable for use as an additive with detergents or in washing processes, characterized by a content of

   (A) finely crystalline, synthetic zeolite containing bound water of the NaA type,

   (B) polymeric polycarboxylates derived from acrylic acid and copolymers thereof with maleic acid in the form of the sodium salts,

   (C) sodium perborate (in the form of the monohydrate and/or tetrahydrate),

   (D) one or more linear 1,2-alkanediols having a chain length of C₁₀ to C₁₈ and/or ethoxylation products thereof preferably containing 1 to 3 ethoxy groups,

   the ratio by weight of (A) to (B) being 30:1 to 4:1, the ratio by weight of (A) to (C) being 30:1 to 1.6:1, the ratio by weight of (A) to (D) being 55:1 to 4:1, the ratio by weight of (B) to (C) being 5:1 to 1:12.5, the ratio by weight of (B) to (D) being 10:1 to 1:5 and the ratio by weight of (C) to (D) being 25:1 to 1:5, with the proviso that components (A), (B) and (D) are expressed as anhydrous substances while component (C) is expressed as monohydrate.
2. A water softener as claimed in claim 1, characterized in that the ratio by weight of (A) to (B) is 14:1 to 5:1, the ratio by weight of (A) to (C) is 11:1 to 3:1, the ratio by weight of (A) to (D) is 28:1 to 7.5:1, the ratio by weight of (B) to (C) is 1.6:1 to 1:4, the ratio by weight of (B) to (D) is 4:1 to 1:4 and the ratio by weight of (C) to (D) is 7.5:1 to 1:1.
3. A water softener as claimed in claim 1 or 2, characterized in that it consists of a dry mixture of at least two powder components, of which the first component is present in the form of spray-dried granules and components (A) and (B) and the second powder component contains sodium perborate.
4. A water softener as claimed in any of claims 1 to 3, characterized by a content of (E) sodium sulfate which (expressed as anhydrous substance) is present in a ratio of (A) to (E) of 20:1 to 4:3.
5. A detergent as claimed in any of claims 1 to 4, characterized by a content of

   (A) 40 to 60% by weight finely crystalline, synthetic zeolite of the NaA type,

   (B) 2 to 10% by weight polymeric polycarboxylate derived from acrylic acid and copolymers thereof with maleic acid in the form of the sodium salts,

   (C) 2 to 25% by weight sodium perborate in the form of the monohydrate or tetrahydrate (expressed as monohydrate),

   (D) 1 to 10% by weight of one or more linear C₁₀₋₁₈ 1,2-alkanediols containing 0 to 3 ethoxy groups,

   (E) 0 to 30% by weight sodium sulfate,

   (F) 0 to 10% by weight of a peracid precursor,

   (G) 0 to 2% by weight of a linear or methyl-branched C₁₂₋₁₈ alcohol reacted with 3 to 7 mol ethylene oxide,

   the quantities - except for component (C) - being based on anhydrous substance and the total quantity of bound water present in the components except for (C) being up to 20% by weight.
6. A water softener as claimed in claim 5, characterized by a content of

   (A) 45 to 55% by weight finely crystalline synthetic zeolite of the NaA type,

   (B) 4 to 8% by weight of the sodium salt of a copolymer of acrylic acid and maleic acid in a ratio by weight of 10:1 to 1:1 having a molecular weight of 20,000 to 150,000,

   (C) 5 to 15% by weight sodium perborate expressed as monohydrate,

   (D) 2 to 6% by weight of one or more linear C₁₀₋₁₄ 1,2alkanediols containing 0 to 3 ethoxy groups, 1,2-dodecanediol, 1,2-dodecanediol·1EO and 1,2-dodecanediol·2EO being particularly preferred,

   (E) 2 to 20% by weight sodium sulfate,

   (F) 2 to 8% by weight tetraacetyl ethylenediamine,

   (G) 1 to 2% by weight of a linear C₁₂₋₁₈ alcohol reacted with 3 to 7 mol ethylene oxide.
7. The use a granular to powder-form water softener containing

   (A) finely crystalline, synthetic zeolite containing bound water of the NaA type,

   (B) polymeric polycarboxylates derived from acrylic acid and copolymers thereof with maleic acid in the form of the sodium salts,

   (C) sodium perborate (in the form of the monohydrate and/or tetrahydrate),

   (D) one or more linear 1,2-alkanediols having a chain length of C₁₀ to C₁₈ and/or ethoxylation products thereof preferably containing 1 to 3 ethoxy groups,

   the ratio by weight of (A) to (B) being 30:1 to 4:1, the ratio by weight of (A) to (C) being 30:1 to 1.6:1, the ratio by weight of (A) to (D) being 55:1 to 4:1, the ratio by weight of (B) to (C) being 5:1 to 1:12.5, the ratio by weight of (B) to (D) being 10:1 to 1:5 and the ratio by weight of (C) to (D) being 25:1 to 1:5, with the proviso that components (A), (B) and (D) are expressed as anhydrous substances while component (C) is expressed as monohydrate,
      as an additive with detergents or in washing processes.