EP0340590A1 - Detergent additive - Google Patents

Abstract

An additive in granular to powder form, for use in detergents or in a laundering process, contains (A) fine crystalline, synthetic, hydrated NaA-type zeolite, (B) polycarboxylate polymers derived from acrylic acid as well as its copolymers with maleic acid in the form of the Na salts, and (C) sodium perborate monohydrate and/or tetrahydrate. The weight ratios of A:B lie between 30:1 and 4:1, of A:C between 12:1 and 2:1, and of B:C between 2:1 and 1:10, the weights of the constituents A and B being calculated on the dry basis and that of C as the monohydrate. The product consists of a dry mixture of at least two components in powder form, the first of which contains constituents A and B in the form of a spray-dried granular material and the second of which contains the sodium perborate.

Description

The invention relates to a detergent additive which is present in a mixture with granular detergents or spatially separated from them and is advantageously used in washing processes in which a poor washing result is to be expected as a result of increased water hardness.

When using hard tap water, for example with degrees of hardness above 18 ° dH (corresponding to 180 mg CaO / liter), but in particular above 25 ° dH (250 mg CaO / liter), the washing result with a usual detergent dosage of 5 to 8 g / l 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 in the washing machine increases significantly. 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 remedies, contrary to the recommendation, which increases the problems identified considerably. On the other hand, if higher dosing is required, the proportion of surfactants in wash water and later in the wastewater is increased. However, this increase in surfactant concentration usually does not lead to a comparable increase in white gray which is why one can consider the additional consumption of surfactants as a waste. One way out is the additional use of additional softening agents with a high content of polymeric phosphates.

The problems associated with underdosing of the detergent in the presence of very hard water have been exacerbated by the introduction of low-phosphate detergents, especially since the additional polyphosphate-based softeners are also to be critically evaluated and replaced by more environmentally friendly additives. From DE 25 27 388 it is known that water-insoluble aluminosilicates (zeolites) obtained by spray drying aqueous dispersions can be used in their place. DE 33 16 513-A1 discloses granules which contain alkali alumosilicates (zeolites) and polymeric polycarboxylates and can be used in detergents and cleaning agents and as softeners. The content of mono- or copolymeric polycarboxylic acid or its alkali salt should be 5 to 30% by weight and in the examples is 8 to 11.5%. However, these proportions are based on a water-containing zeolite, ie containing 21 to 22% by weight of structural water, which is evident from claim 8 and from the examples according to which the aluminosilicate slurry used contains 61% by weight of zeolite A. The technically possible maximum content of a zeolite slurry is 50% zeolite A, based on the anhydrous substance. The proportion of polymeric acid, based on anhydrous zeolite, is therefore 6 to 37% by weight and in the examples 9.8 to 14% by weight. It is therefore comparatively high and makes the funds correspondingly expensive. Nevertheless, the effect of these agents is comparatively low with regard to a simultaneous improvement in washing power.

A similarly composed softening agent with a reduced polymeric acid content is known from DE 36 14 779-A1. To increase the effectiveness or to compensate for the under-balance of polymeric acid, the agent also contains citric acid or its salts and soda. The effect of these agents also appears to be increasing, especially when used in very hard water. In addition, the relatively high proportion of organic matter (in the example 10.5% citrate) still seems to be in need of improvement with regard to minimal waste water pollution. The soda content can also interfere in some cases due to the formation of insoluble calcium carbonate.

• A) feinkristallinem, synthetischem, gebundenes Wasser enthalten­dem Zeolith vom Typ NaA,
• B) polymeren Polycarboxylaten, abgeleitet von Acrylsäure sowie dessen Copolymeren mit Maleinsäure in Form der Natriumsalze,
• C) Natriumperborat in Form des Monohydrats und/oder Tetrahy­drats,

wobei die Gewichtsverhältnisse von A : B = 30 : 1 bis 4 : 1, von A : C = 12 : 1 bis 2 : 1 und von B : C = 2 : 1 bis 1 : 10 be­tragen, mit der Maßgabe, daß die Anteile der Bestandteile A und B als wasserfreie Substanzen und der Bestandteile C als Monohy­drat berechnet werden.The invention, with which these problems are solved, is a granular to powdery additive to be used in detergents or 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 its copolymers with maleic acid in the form of the sodium salts,
• C) sodium perborate in the form of the monohydrate and / or tetrahydrate,

wherein the weight ratios are from A: B = 30: 1 to 4: 1, from A: C = 12: 1 to 2: 1 and from B: C = 2: 1 to 1:10, with the proviso that the proportions components A and B are calculated as anhydrous substances and component C as monohydrate.

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 CaO / g (according to the information in DE 22 24 837). Their particle size is usually in the range from 1 to 10 μm.

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. Copolymers of acrylic acid or methacrylic acid with maleic acid, such as are characterized, for example, in EP 25 551-B1 have proven to be particularly suitable. These are copolymers which contain 40 to 90 percent 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 a mixture thereof. Mathematically, the content of the agents and the mixing ratios are based on the monohydrate, even if component B should consist entirely or partially of the tetrahydrate. Agents in which the perborate is present as a monohydrate are particularly preferred.

The weight ratio of A: B is 30: 1 to 4: 1, preferably 14: 1 to 6: 1, that of A: C 10: 1 to 2: 1, preferably 7.5: 1 to 3: 1 and that of B: C 2: 1 to 1:10, preferably 1: 1 to 1: 4, components A and B being counted as anhydrous substances.

The agents preferably contain the constituents in granular form, the average particle size of the particles being between 0.1 and 1.2 mm and the proportion of dust-like components (below 0.05 mm). less than 1% by weight, in particular less than 0.5% by weight and the proportion of coarse fractions (over 1.6 mm) should be less than 2% by weight, preferably less than 1% by weight. The granular agents preferably consist of a dry, homogeneous mixture of at least 2 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 1st powder component may contain other additives, which, for. B. 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 (water-free calculated) component D, its weight ratio A: D is preferably 20: 1 to 4: 1.

Other constituents, which may be present in a small amount in the first component, are nonionic surfactants which have an HLB value of at most 12 and which consist of ethoxylation products of linear or methyl-branched (oxo radical) alcohols or also alkyphenols. As is known, these additives serve to stabilize aqueous zeolite suspensions and can therefore also be contained in agents of the type claimed, in the manufacture of which such suspensions are used. Examples include C₁₂₁₁₆ alcohols with 3 to 5 EO and C₁₆₋₁₈ alcohols (tallow alcohol) with 4 to 7 EO. The weight ratio of this constituent designated E in such means can be A: E = 100: 1 to 20: 1, usually 50: 1 to 30: 1 and around therefore only contains small amounts of surfactant, whose influence on the washing result is correspondingly small.

Other optional components of the 1st powder component are, for example, the water-soluble salts, e.g. B. the sodium salts of phosphonic acids (component G). Suitable phosphonic acids or phosphonic acid salts are 1-hydroxyethane-1,1-diphosphonate, ethylene diamine tetramethylene phosphonate (EDTMP) and diethylene triamine pentamethylene phosphonate. The weight ratio of A: F can be 600: 1 to 40: 1.

The agents can contain further powder components which are mixed in dry form with the two powder components mentioned above.

A preferred further powder component consists of a powdery to granular peracid precursor (bleach activator) from the class of the N-acyl compounds and O-acyl compounds. Examples of suitable N-acyl compounds are polyacylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylenediamine and their higher homologues, and acylated glycolurils, such as tetraacetylglycoluril. Further examples are N-alkyl-N-sulfonylcarbonamides, N-acylhydantoins, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and imidazolines. In addition to carboxylic acid anhydrides such as phthalic anhydride and esters such as Na (iso) nonanoylphenol sulfonate, acylated sugars such as glucosopentaacetate are also suitable as O-acyl compounds. Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate. In order to avoid interactions with the perborate, the bleach activators can be granulated and coated with water-soluble coating substances. Particularly suitable coating agents are water-soluble polymers, for example wise cellulose ethers, such as carboxymethyl cellulose (as sodium salt), or C chain polymers, such as the (co) polymers mentioned under B, polycarboxylic acids and their salts, and also polyvinyl alcohol and mixtures of water-soluble polymers.

• A) 40 bis 60 Gew.-% feinkristalliner, synthetischer Zeolith vom Typ NaA,
• B)2 bis 10 Gew.-% polymeres Polycarboxylat, abgeleitet von Acrylsäure und dessen Copolymeren mit Maleinsäure in Form der Natriumsalze,
• C) 5 bis 20 Gew.-% Natriumperborat in Form des Monohydrats oder Tetrahydrats,
• D) 0 bis 30 Gew.-% Natriumsulfat,
• E) 0 bis 3 Gew.-% mindestens eines Tensids aus der Klasse der Alkyl- oder Alkenylpolyglykolether mit einem HLB-Wert von höchstens 12,
• F) 0 bis 1 Gew.-% an Polyphosphonsäure in Form der Alkalimetall­salze,
• G) 0 bis 10 Gew.-% eines Persäurevorläufers,

mit der Maßgabe, daß die Mengen, mit Ausnahme des Bestandteils C, auf wasserfreie Substanz und die Menge des Bestandteils C auf Monohydrat bezogen sind und wobei 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) 5 to 20% by weight of sodium perborate in the form of the monohydrate or tetrahydrate,
• D) 0 to 30% by weight sodium sulfate,
• E) 0 to 3% by weight of at least one surfactant from the class of the alkyl or alkenyl polyglycol ethers with an HLB value of at most 12,
• F) 0 to 1% by weight of polyphosphonic acid in the form of the alkali metal salts,
• G) 0 to 10% by weight of a peracid precursor,

with the proviso that the amounts, with the exception of component C, are based on anhydrous substance and the amount of component C is based on monohydrate 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) 3 bis 7,5 Gew.-% des Natriumsalzes einer Acrylsäure-Maleinsäu­re-copolymeren im Gewichtsverhältnis 10 : 1 bis 1 : 1 und ei­nem Molekulargewicht von 20 000 bis 150 000,
• C) 7,5 bis 15 Gew.-% Natriumperborat, berechnet als Monohydrat,
• D) 2 bis 20 Gew.-% Natriumsulfat,
• E) 1 bis 2 Gew.-% eines mit 3 bis 7 Mol Ethylenoxid umgesetzten linearen C812-18-Alkohols,
• F) 2 bis 8 Gew.-% Tetraacetylethylendiamin.

The compositions preferably have the following composition:

• A) 45 to 55% by weight of finely crystalline, synthetic zeolite of the NaA type,
• B) 3 to 7.5% 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) 7.5 to 15% by weight sodium perborate, calculated as monohydrate,
• D) 2 to 20% by weight sodium sulfate,
• E) 1 to 2% by weight of a linear C812-18 alcohol reacted with 3 to 7 mol of ethylene oxide,
• F) 2 to 8% by weight of tetraacetylethylenediamine.

In the aforementioned formulations, components A, B and D to F are preferably combined in a spray-dried powder component (1st powder component). The components C and G form two separate powder components, which are mixed with the first powder component in dry form.

It was highly surprising that agents of the claimed composition show a better effect in binding calcium salts and enhancing the builder effect than conventional agents which have higher proportions of "classic" softening agents. Zeolites, soda, polymeric polycarboxylates and polyacids such as citric acid are considered "classic" softeners. It was not known that perborates, in combination with some of the "classic" softening agents mentioned, advantageously support their specific action and have a builder effect, provided the water used has a high calcium hardness. In addition to the unexpected softening and builder effect, however, the agents still have a pronounced bleaching action, which is particularly important when the consumer underdoses the bleach-containing detergent and does not use any other additives. With simultaneous use of the agents according to the invention and conventional detergents, the following advantages result:
- the washing power, in particular with regard to preventing tissue graying and ash, is considerably 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 compared to 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.

Examples

The following granular mixtures specified in the table were produced. The comparison formulations designated V relate to agents known from DE 33 16 513 and DE 36 14 779. 1 2nd 3rd V1 V2 Zeolite NaA 50.0 50.0 55.0 60.0 62.5 Polycarboxylate 5.0 5.0 7.5 10.0 4.5 EDTMP 0.2 0.2 - - - TA ethoxylate 1.3 1.3 1.4 1.9 - Sodium sulfate 12.0 3.0 4.0 11.5 - NaBO₃-H₂O 10.0 - 15.0 - - NaBO₃-4H₂O - 17.0 - - - TAED 4.7 6.6 - - - CMC 0.2 0.2 - - 0.3 water rest rest rest rest rest soda - - - - 5.1 Na citrate - - - - 10.5

The synthetic zeolite used (calculated anhydrous) had a particle size between 0.5 and 8 microns. In Examples 1 and 2, the polycarboxylate consisted of the Na salt of a copolymer of acrylic acid and maleic acid with a molecular weight of approximately 70,000 (Sokalan CP5 ^(R) ) and in Example 3 of a Na polyacrylate with a molecular weight of 20,000 EDTMP stands for the hexasodium salt of ethylenediaminetetramethylenephosphonic acid. TA ethoxylate is technical tallow alcohol, reacted with 5 ethylene oxide (HLB value = 9.2) and served as a suspension stabilizer for the zeolite master batch. All of these constituents, as well as the sodium sulfate and the water, are constituents of the first powder component, which were 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 served as a coating substance for the TAED according to the information in EP 37026. In comparative experiment V2, CMC served as a granulation aid for the overall product.

The application test was carried out in a practical manner in a household washing machine with a horizontally arranged washing drum (type Miele W 433) with the use of a commercially available detergent. The composition of this agent was (in% by weight) Na dodecylbenzenesulfonate 8.0 Fatty alcohol ethoxylate 5.8 Tallow soap 1.5 Cellulose ether 0.8 opt. Brightener 0.1 enzyme 0.5 Na hydroxyethane diphosphonate 0.3 Silicone defoamer 0.2 Zeolite NaA 25.0 Na silicate 1: 3.3 3.3 sodium 7.5 Polycarboxylate (Sokalan) 4.0 Sodium perborate tetrahydrate 26.0 TAED 2.5 Sodium sulfate, water, minor components rest

Washing conditions:

• I = Kaolin/Ruß/Hautfett auf Baumwolle
• II = Kaolin/Ruß/Hautfett auf veredelter Baumwolle
• III = Tee auf Baumwolle
• IV = Kaffee auf Baumwolle,

4maliges Nachspülen mit Leitungswasser, Schleudern, Trocknen. Optische Auswertung mit Zeiß-Reflektometer bei 460 µm (Ausblen­dung Aufheller-Effektes), 3 Versuche mit Mittelwertbildung.Washing temperature 90 ° C
Soapy program (without prewash)
Water hardness 28 ° d (280 mg CaO per liter)
3.5 kg of soiled household linen plus textile samples with test soiling I - VI

• I = kaolin / soot / skin fat on cotton
• II = kaolin / soot / skin fat on refined cotton
• III = tea on cotton
• IV = coffee on cotton,

Rinsing 4 times with tap water, spinning, drying. Optical evaluation with Zeiss reflectometer at 460 µm (suppression of brightener effect), 3 experiments with averaging.

The other test conditions are shown in the following table. The column "target" indicates the dosage of the detergent W compared to the correct target value 1. The addition of softening agents according to the invention according to Example 1 is marked B1. V1 and V2 denote additions according to comparative experiment V1 and V2.

dosage

% Remission W Should additive I. II III IV 0̸ 82 g 0.6 - 65.2 67.0 70.0 78.7 70.2 82 g 0.6 66 g B1 73.5 78.8 81.2 81.6 78.8 82 g 0.6 66 g V1 69.2 75.4 74.3 79.3 74.6 82 g 0.6 66 g V2 70.7 76.8 74.0 78.5 75.0 140 g 1 - 74.5 77.9 81.1 82.4 78.9

As the results show, the underperformance achieved by underdosing the detergent is largely compensated for by the addition of the agent B1 according to the invention. It must be taken into account here that remission differences of 2% and more can be understood by the consumer. The known comparison products do not achieve the advantageous effect of the agent according to the invention.

In addition, multiple washing treatments were carried out to determine the deposits on the tissues.

Washing conditions

Household washing machine (AEG Turnette AS ^R )
25 washing cycles with detergent, additives and conditions as described in the example above
Ashing of cotton fabric after 25 washes

dosage

W Should additive % Ashes 82g 0.6 - 2.8 82g 0.6 66g B1 0.7 82g 0.6 66g V1 0.9 82g 0.6 66g V2 0.8 140g 1.0 - 2.6

The results show that the additive B1 according to the invention, despite the lower content of "classic" softening agents, exceeds the incrustation-inhibiting performance of the comparison products.

Claims (10)

1. Granular to powdery additive to be used in detergents or 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 its copolymers with maleic acid in the form of the sodium salts,
C) sodium perborate in the form of the monohydrate and / or tetrahydrate,
wherein the weight ratios are from A: B = 30: 1 to 4: 1, from A: C = 12: 1 to 2: 1 and from B: C = 2: 1 to 1:10, with the proviso that the proportions components A and B are calculated as anhydrous substances and component C as monohydrate. 2. Composition according to claim 1, characterized by the weight ratios A: B = 14: 1 to 6: 1, A: C = 7.5: 1 to 3: 1 and B: C = 1: 1 and 1: 4. 3. Composition according to claim 1 and 2, characterized in that it consists of a dry mixture of at least two powder components, of which the first component is in the form of spray-dried granules and contains the constituents A and B and a second powder component consists of the sodium perborate. 4. Composition according to one or more of claims 1 to 3, characterized by a content of (D) sodium sulfate, which (calculated as anhydrous substance) is present in the ratio of A: D = 20: 1 to 4: 3. 5. Composition according to one or more of claims 1 to 3, characterized in that the 1st powder component as Be Component (E) contains at least one surfactant from the class of alkyl and alkenyl polyglycol ethers with an HLB value of at most 12 in the ratio A: E = 100: 1 to 20: 1. 6. Composition according to one or more of claims 1 to 6, characterized in that the 1st powder component contains (F) polyphosphonic acids in the form of the alkali metal salts with a weight ratio of A: F = 600: 1 to 40: 1. 7. Composition according to one or more of claims 1 to 6, characterized by a content of a further powder component consisting of a (G) peracid precursor, the weight ratio of C to G being 1: 1 to 10: 1. 8. Composition according to one or more of claims 1 to 6, characterized by a content of
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) 5 to 20% by weight of sodium perborate in the form of the monohydrate or tetrahydrate,
D) 0 to 30% by weight sodium sulfate,
E) 0 to 3% by weight of at least one surfactant from the class of the alkyl or alkenyl polyglycol ether with an HLB value of at most 12,
F) 0 to 1% by weight of polyphosphonic acid in the form of the alkali metal salts,
G) 0 to 10% by weight of a peracid precursor,
with the proviso that the amounts, with the exception of component C, are based on anhydrous substance and the amount of component C is based on monohydrate, and the total amount of bound water, which is contained in the components with the exception of C, is up to 20 wt .-%. 9. Composition according to claim 8, characterized by a content of A) 45 to 55% by weight of finely crystalline, synthetic zeolite of the NaA type, B) 3 to 7.5% by weight of the sodium salt of a copolymer of acrylic acid and maleic acid in a weight ratio of 10: 1 to 1: 1 with a molecular weight of 20,000 to 150,000, C) 7.5 to 15% by weight sodium perborate, calculated as monohydrate, D) 2 to 20% by weight sodium sulfate, E) 1 to 2 wt .-% of a reacted with 3 to 7 moles of ethylene oxide linear C₁₂₋₁₈ alcohol. 10. Use of an agent according to one or more of the preceding claims as an additive in detergents and washing processes.