EP0228011B1 - Granular detergent with reduced phosphate content - Google Patents

Abstract

A phosphate-reduced, granular free-flowing detergent containing (a) from 5 to 40% nonionic surfactant, (b) from 3 to 20% anionic surfactant, (c) from 15 to 50% zeolite, (d) from 0.5 to 15% homopolymeric or copolymeric carboxylic acid or alkali metal salts thereof and (e) from 10 to 72.5% detergent constituents which are stable under spray-drying conditions, with the proviso that the detergent comprises a mixture of two powder components (A) and (B) in a weight ratio of from 1:5 to 3:1, component (A) containing from 50 to 100% of constituent (a), from 80 to 100% of constituent (c) and from 50 to 100% of constituent (d). Component (A) has an average particle size of from 0.4 to 0.8 mm and a powder density of from 500 to 800 g/l. Component (B) contains from 80 to 100% of constituent (b) and 100% of constituent (e), has a powder density of from 300 to 500 g/l and differs in its particle size distribution by at most 50% from the particle size distribution of component (A).

Description

The present invention relates to a reduced-phosphate detergent composed of a plurality of granular powder components, the essential constituents of which are fine-crystalline zeolites, nonionic surfactants from the class of polyglycol ether derivatives, anionic surfactants and homopolymeric or copolymeric carboxylic acids and, if appropriate, sodium tripolyphosphate and sodium silicate in a specific powder distribution. A phosphate-reduced is understood to mean a detergent which contains less than 5% by weight of P in the form of phosphates.

Fine-particle zeolites of the NaA and NaX type have repeatedly been proposed as phosphate substitutes. The synthetic zeolites are usually used in a form that is particularly suitable for further processing as a filter-moist, stabilized suspension containing approx. 50% water. For energy reasons and in the interest of a high degree of utilization of the hot spray towers, however, one is interested in keeping the water content of the batch to be sprayed as low as possible. Such spray batches usually contain 30 to at most 45 percent by weight of water, of which between 8 and 15 percent by weight remain in the product after the spray drying. The addition of the water-containing zeolite dispersions and further sprayable, often water-containing detergent components can lead to an undesirable increase in the water content in the slurry and thus to an increased energy requirement or a loss of capacity in the spraying systems. If the zeolite is added to the slurry as a pre-dried powder and thus the water content in the spray mixture is reduced, zeolite agglomerates can form which are deposited on the textiles during the washing treatment. These problems can occur in particular when the compositions contain water-soluble silicates such as sodium water glass.

Additional problems arise with the spray drying of phosphate-reduced detergents. It is known that a certain percentage of the triphosphate incorporated into the Siurry is hydrolyzed to ortho- or pyrophosphate in the course of spray drying. These hydrolyzed phosphates favor the incrustation of the washed textiles. It has now been shown that as the phosphate content decreases, the proportion of undesirable orthophosphates and pyrophosphates shifts to the disadvantage of the desired triphosphate, so that the proportion of low phosphates that promote incrustation is particularly high, especially in low-phosphate agents. However, removing the phosphate from the spraying process and subsequently adding it to the finished powder creates new problems, especially if the zeolite does not use spray drying. Then there are too small proportions of inorganic carrier substance in the slurry, based on the proportion of organic detergent constituents. The danger of dust explosions in the hot spray tower increases, and the formation of non-adhesive or abrasion-resistant spray particles is made more difficult.

Another problem arises from the use of nonionic surfactants. These compounds, which are distinguished by a very high cleaning ability, undesirably increase its viscosity when incorporated into the slurry in the presence of anionic surfactants. They also cause aerosol formation in the tower exhaust air (technically referred to as "pluming"). In DE-22 04 842-A 1 it was proposed to apply the nonionic surfactants to a carrier powder which contains, inter alia, bentonite and, as a particularly effective binder, microfine silicon dioxide. This premix can then be mixed into a spray-dried detergent powder. However, silicon dioxide is an active ingredient in washing, which means that it only causes additional costs and does not contribute to washing performance. The premix is prepared by granulating the powdered carriers with the aid of the liquid or melted nonionic surfactant. The production of uniform granules with a defined grain spectrum and bulk density encounters considerable difficulties with this process. Mixtures of these granules with specifically light spray drying powders therefore also have a more or less inconsistent particle size spectrum and tend to separate.

DE-25 07 926-B 2 teaches the use of finely crystalline aluminosilicates as carrier material for the nonionic surfactants, the composition of which comprises the zeolites of the NaA or NaX type. In this case too, a powdery zeolite is assumed. A teaching of the content that for the preparation of this pre-mix one has to start from a pre-made granulate of certain grain specification and - as indicated below - certain additives and proportions in order to avoid later segregation and to achieve optimal washing properties was not to be found in this reference either.

DE 27 53 680 A2 discloses a detergent composed of three powdered or granular powder components. The first powder component consists of a spray-dried powder and contains anionic and / or nonionic surfactants, skeletal salts including phosphates, zeolites, alkali metal silicates and carbonates. The second component consists of skeletal salts, which serve as carrier material, and silicone defoamers adsorbed on them. The third component consists of granules which are produced from perborate or another per compound or one or more builder substances, preferably phosphates, using nonionic surfactants as binders. However, the absorption capacity of perborate for nonionic surfactants is very limited, but this is not critical in the present case, since the third powder component essentially only takes on the task, the wetting properties and - associated with this - the flushing behavior to improve the powder mixture in washing machines. However, relatively small proportions of nonionic surfactant or of the third powder component are sufficient for this. The idea of using a prefabricated, phosphate-free carrier granulate which, due to its special composition and method of manufacture, can absorb high proportions of nonionic surfactants is foreign to this publication. In addition, the cited application does not contain any teaching of the content of how the aluminosilicates, polycarboxylates and surfactants to be used, if any, are to be distributed over the individual powder components in order to achieve optimum washing power with phosphate-reduced agents.

• 1. Schaffung eines phosphatreduzierten Waschmittels, das hinsichtlich seiner Schmutzentfemung (Primärwaschvermögen) und seiner Inkrustationsverhü_tung (Sekundärwaschvermögen) mit einem konventionellen phosphatreichen Waschmittel vergleichbar ist.
• 2. Vermeidung einer verstärkten Hydrolyse des Triphosphats, sofern dieses vorhanden ist, bei der Sprühtrocknung sowie eines zu hohen Anteils an organischer Substanz im Sprühansatz.
• 3. Entlastung der Sprühtürme bzw. Vermeidung eines überhöhten Energiebedarfs.
• 4. Vermeidung der Entstehung von Zeolith-Agglomeraten.
• 5. Verwendung eines abriebfesten, aber leicht in Wasser dispergierbaren Trägermaterials, das zur Aufnahme hoher Anteile an nichtionischen Tensiden beziehungsweise zur Erhöhung des Zeolith-Anteils im fertigen Waschmittel geeignet ist, und Überführung in ein Vorgemisch, das sich aufgrund seines Komspektrums zum Vermischen mit einem sprühgetrockneten Pulver eignet.
• 6. Beeinflussung des Litergewichtes des fertigen Mittels durch entsprechende Einstellung des Vorgemisches mit dem Ziel, durch Erhöhung des Litergewichts den Verpackungsbedarf zu vermindern.
• 7. Verbesserung der Pulvereigenschaften hinsichtlich Kornfestigkeit und Staubbildung, Vermeidung eines Entmischens, Erzielung einer hohen Rieselfähigkeit sowohl unmittelbar nach Herstellung als auch nach mehrmonatiger Lagerung und Erzielung günstiger Zerfalls- und Lösungseigenschaften bei Einbringen in die Waschlauge beziehungsweise beim Einspülen mit kaltem Leitungswasser in die Waschmaschine.
• 8. Eignung der Mehr-Komponenten-Gemische für die Aufnahme weiterer Pulverkomponenten, beispielsweise solche, die Bleichmittel, Persäurevorläufer, Enzyme und Schaumdepressoren enthalten.

The present invention is intended to solve the following problems or bring them closer to a solution.

• 1. Creating a phosphate-reduced detergent, which in terms of its soil removal (primary detergency), and its Inkrustationsverhü _t ung (secondary detergency) with a conventional phosphate-rich detergent is comparable.
• 2. Avoidance of increased hydrolysis of the triphosphate, if it is present, during spray drying and an excessive proportion of organic substance in the spray mixture.
• 3. Relief of the spray towers or avoidance of excessive energy requirements.
• 4. Avoiding the formation of zeolite agglomerates.
• 5. Use of an abrasion-resistant but easily water-dispersible carrier material, which is suitable for absorbing high proportions of nonionic surfactants or for increasing the proportion of zeolite in the finished detergent, and transferring it into a premix, which due to its spectrum of comprints can be mixed with a spray-dried one Powder is suitable.
• 6. Influencing the liter weight of the finished agent by adjusting the premix accordingly with the aim of reducing the packaging requirement by increasing the liter weight.
• 7.Improving the powder properties with regard to grain strength and dust formation, avoiding segregation, achieving a high flowability both immediately after manufacture and after several months of storage and achieving favorable disintegration and solution properties when introduced into the washing liquor or when rinsed with cold tap water in the washing machine.
• 8. Suitability of the multi-component mixtures for the inclusion of further powder components, for example those which contain bleaching agents, peracid precursors, enzymes and foam depressors.

• (a) 4 bis 40 Gewichtsprozent an nichtionischen Tensiden,
• (b) 3 bis 20 Gewichtsprozent an anionischen Tensiden, wobei das Gewichtsverhältnis von (a) und (b) 3 1 bis 1 : 2 beträgt,
• (c) 15 bis 50 Gewichtsprozent an feinkristallinem Zeolith,
• (d) 0,5 bis 5 Gewichtsprozent (berechnet als freie Säure) an homopolymeren oder copolymeren Carbonsäuren mit einem Molekulargewicht von 1000 bis 120 000 beziehungsweise deren Na- oder K-Salze,
• (e) 0 bis weniger als 20 Gew.-% Natriumtripolyphosphat,
• (f) 10 bis 72,5 Gewichtsprozent an sonstigen, unter den Bedingungen der Sprühtrocknung beständigen Waschmittelbestandteilen,
  mit der Maßgabe, daß das Gewichtsverhältnis der Komponenten (A) : (B) = 1 : 5 bis 3 1 beträgt und in der Pulverkomponente (A) 50 bis 100% des Bestandteils (a), 80 bis 100% des Bestandteils (c) und 50 bis 100% des Bestandteils (d) und in der Pulverkomponente (B) 80 bis 100% des Bestandteils (b) und 100% des Bestandteils (e) jeweils berechnet in Gewichtsprozent enthalten sind.

The invention relates to a detergent containing less than 5% P in the form of phosphates, consisting of a mixture of at least two granular powder components (A) and (B), in which component (A) contains finely crystalline synthetic zeolites of the NaA type or mixtures thereof Zeolite NaX, in which there is an excess of zeolite NaA, as well as nonionic surfactants from the class of the polyglycol ether derivatives and component (B) consists of a spray-drying product which may contain phosphates, characterized in that the mixture of the two components contains the following components:

• (a) 4 to 40 percent by weight of nonionic surfactants,
• (b) 3 to 20 percent by weight of anionic surfactants, the weight ratio of (a) and (b) 3 being 1 to 1: 2,
• (c) 15 to 50 percent by weight of finely crystalline zeolite,
• (d) 0.5 to 5 percent by weight (calculated as free acid) of homopolymeric or copolymeric carboxylic acids with a molecular weight of 1000 to 120,000 or their Na or K salts,
• (e) 0 to less than 20% by weight sodium tripolyphosphate,
• (f) 10 to 72.5 percent by weight of other detergent constituents which are stable under the conditions of spray drying,
  with the proviso that the weight ratio of components (A): (B) = 1: 5 to 3 1 and in powder component (A) 50 to 100% of component (a), 80 to 100% of component (c) and 50 to 100% of the component (d) and in the powder component (B) 80 to 100% of the component (b) and 100% of the component (e) are each calculated in percent by weight.

• A 1) 20 bis 30 Gewichtsteile feinkristalliner, synthetischer, gebundenes Wasser enthaltender Zeolith NaA und gegebenenfalls NaX,
• A 2) 0,5 bis 7,5 Gewichtsteile (berechnet auf Säureform) homo- oder copolymere Carbonsäure vom Molekulargewicht 1000 bis 120 000 in Form des Na- oder K-Salzes,
• A 3) 3 bis 6 Gewichtsteile bei einer Trocknungstemperatur von 145 _°C, entfembares Wasser,
• A 4) 0 bis 10 Gewichtsteile Natriumsulfat, Natriumcarbonat oder deren Gemische,
• A 5) 0 bis 2 Gewichtsteile eines nichtionischen Tensids aus der Klasse der Polyglykoletherderivate,
• A 6) 0 bis 10 Gewichtsteile Natriumnitrilotriacetat.

A granular adsorbent of the following composition serves as the starting material for the powder component (A):

• A 1) 20 to 30 parts by weight of finely crystalline, synthetic, bound water-containing zeolite NaA and optionally NaX,
• A 2) 0.5 to 7.5 parts by weight (calculated on the acid form) of homo- or copolymeric carboxylic acid with a molecular weight of 1000 to 120,000 in the form of the Na or K salt,
• A 3) 3 to 6 parts by weight at a drying temperature of 145 _° C., removable water,
• A 4) 0 to 10 parts by weight of sodium sulfate, sodium carbonate or mixtures thereof,
• A 5) 0 to 2 parts by weight of a nonionic surfactant from the class of the polyglycol ether derivatives,
• A 6) 0 to 10 parts by weight of sodium nitrilotriacetate.

The granular adsorbent has an average grain size of 0.4 to 0.8 mm, the proportion with a grain size of less than 0.1 mm and with a grain size of more than 1.6 mm in each case not more than 1 percent by weight. The bulk density is between 400 and 700 g / l, preferably 450 to 650 g / l.

The component (A 1) consists of synthetic, bound water-containing sodium aluminosilicate, preferably of the zeolite A type. Mixtures of zeolite NaX and an excess of zeolite NaA can also be used. The suitable zeolites have a calcium binding capacity which is determined according to DE 24 12 837 and which is in the range from 100 to 200 mg CaO / g. They are used as undried, stabilized suspensions that are still moist from their manufacture.

The component (A 2) consists of a homopolymeric and / or copolymeric carboxylic acid or its sodium or potassium salt, the sodium salts being preferred. Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid. Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene. In those copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 70 mole percent, preferably less than 60 mole percent. Copolymers of acrylic acid or methacrylic acid with maleic acid, as are characterized, for example, in EP 25 551-B 1, have proven to be particularly suitable. These are copolymers which contain 40 to 90 percent by weight of acrylic acid or methacrylic acid and 60 to 10 percent by weight of maleic acid. Those copolymers in which 50 to 85 percent by weight acrylic acid and 50 to 15 percent by weight maleic acid are present are particularly preferred.

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.

The molecular weight of the homopolymers or copolymers is generally 1,000 to 120,000, preferably 1,500 to 100,000. Their proportion of the adsorbent is 0.5 to 7.5 parts by weight and preferably 1 to 5 parts by weight. The resistance of the grains to abrasion increases with an increasing proportion of polyacid and its salts. Mixtures with 2 to 3 parts by weight of polyacid or its salts have optimal abrasion properties (in each case based on the granulate described above).

The moisture content which can be removed at a drying temperature of 145 _° C. is 3 to 6 parts by weight, preferably 3.5 to 5 parts by weight. Other amounts of water bound by the zeolite that are released at higher temperatures are not included in this amount.

The optional component (A 4), which preferably consists of sodium sulfate, acts as a stabilizer in water-containing zeolite dispersions and can to a certain extent improve the dissolving power of the granules in cold water. Proportions of 0.2 to 5 parts by weight have proven to be expedient for this.

As a further optional component (A 5), the adsorbent can contain nonionic surfactants in proportions of up to 2 parts by weight, preferably 0.2 to 1.5 parts by weight. Suitable nonionic surfactants are, in particular, ethoxylation products of linear or methyl-branched (oxo radical) alcohols with 12 to 18 carbon atoms and 3 to 15, preferably 4 to 6, ethylene glycol ether groups. Also useful are ethoxylation products of vicinal diols, amines, thioalcohols and fatty acid amides, which correspond to the fatty alcohol ethoxylates described with regard to the number of carbon atoms in the hydrophobic radical and the glycol ether groups. Alkylphenol polyglycol ethers having 5 to 12 carbon atoms in the alkyl radical and 3 to 15, preferably 4 to 10, ethylene glycol ether groups can also be used. Finally, block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics @, are also suitable. The nonionic surfactants are usually present when aqueous zeolite dispersions in which the surfactants function as dispersion stabilizers are used as the starting point for the production of the granular adsorbents. In individual cases, the nonionic surfactants can also be completely or partially replaced by other dispersion stabilizers, as described in DE 25 27 388. In addition, component (A) can contain optical brighteners to improve the whiteness. The proportion of brighteners in component (B) can then be reduced accordingly.

Another optional component of component (A) is sodium nitrilotriacetate (NTA), which can be present in proportions of up to 10 parts by weight, preferably 0.5 to 6 parts by weight. It is known that NTA often increases the hygroscopicity of washing powder. It was surprisingly found that this disadvantage can be avoided if all or most of the NTA is incorporated into component (A).

Otherwise, component (A) should be free from alkali metal silicates, in particular sodium silicate, since these interact with the zeolite to impair its dispersibility in the wash liquor.

The production of the granular adsorbent, by spray drying an aqueous, generally 50 to 65 wt .-% water containing batch of ingredients by means of nozzles into a drop zone, drying gases are introduced into the counter-current or direct current, which has an input temperature of 150 to 280 _° C and have an outlet temperature of 50 to 120 ° C. The dried grains should have a moisture content of 8 to 18 parts by weight that can be removed at 145 _° C.

The water content of the aqueous batch is preferably 55 to 62% by weight. Its temperature is advantageously 50 to 100 _° C and its viscosity 5,000 to 20,000 mPa.s. The atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar. The drying gas, which is generally obtained by burning heating gas or heating oil, is preferably conducted in countercurrent. When using so-called drying towers, into which the aqueous batch is sprayed in the upper part via several high-pressure nozzles, the inlet temperature, measured in the ring channel (ie immediately before entering the lower part of the tower), is 150 to 280 _° C, preferably 180 to 250 ° C and in particular 190 to 230 _° C. The exhaust gas laden with moisture leaving the tower usually has a temperature of 50 to 120 _° C., preferably 55 to 105 ° C.

The granular adsorbent essentially consists of rounded grains which have a very good flow behavior. This very good flow behavior is also given when the grains are impregnated with large proportions of nonionic surfactants, which can be up to 40% by weight, based on the adsorbate. With regard to these properties, it is superior to the carrier materials which have been disclosed hitherto and have been proposed as useful for detergents and cleaning agents.

The granular adsorbent is then impregnated with nonionic surfactants. These can be sprayed onto the spray product which is still warm or onto the spray product which has already cooled down or which has been warmed up again after cooling. The abrasion resistance and constancy of shape of the grains are so high if the specified proportions or manufacturing conditions are observed that even the freshly prepared, but especially the cooled and, if necessary, reheated, matured grains can be treated, mixed and conveyed with the liquid additives under the usual spray mixing conditions without the formation of fine fractions or coarser agglomerates.

The nonionic surfactants applied to the granular adsorbent can be of the same type as those used to stabilize the zeolite dispersion. Preferred nonionic surfactants are derived from primary fatty alcohols of natural or synthetic origin, which can be saturated, monounsaturated, linear or methyl-branched in the 2-position (oxo radical) and have 10 to 18 carbon atoms. Suitable fatty alcohols are lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and their mixtures, such as those present in coconut oil alcohol or tallow oil alcohol. The average number of glycol ether groups is 3 to 16. Mixtures which contain fractions with a lower and higher degree of ethoxylation, for example those with a degree of ethoxylation of 4 to 6 and a degree of ethoxylation of 9 to 14, are particularly useful, the mixing ratio generally being 4: 1 to Is 1: 4

Further suitable nonionic surfactants are ethoxylated alkylphenols which have 7 to 12 carbon atoms, preferably 8 to 10 carbon atoms in the alkyl group and 3 to 15, preferably 4 to 12, ethylene glycol ether groups. They can also be present in a mixture with the ethoxylated fatty alcohols mentioned above.

The granular adsorbent is also suitable for taking up surface active compounds containing amino groups or amide groups, which may optionally be ethoxylated and are insoluble or only slightly soluble in water, but are dispersible. They often have an effect that strengthens the primary washing power or are characterized by a high fat washing capacity. Examples of such compounds, which are also assigned to the nonionic surfactants, are fatty acid amides which are derived from ethanolamine, diethanolamine, propanolamine and isopropanolamine and from alkylated diamines. Examples of such diamines are N, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N-methyl-N-ethylethylenediamine, N, N'-dimethylethylenediamine, N, N'-dimethylpropylenediamine, N-methyl-N'- ethyl-propylenediamine and mixtures of such alkylated alkylenediamines. The fatty acid residues contained in the amides are derived from saturated or monounsaturated fatty acids having 10 to 18, preferably 12 to 18, carbon atoms, with particular preference being given to those fatty acids whose acyl residues are more than 50% by weight, in particular more than 65 wt .-% consist of those with 12 to 14 carbon atoms. Mixtures obtained from coconut fatty acids are particularly suitable, from which the fraction with 10 and fewer carbon atoms has been largely separated.

Further nonionic agents which are assigned to this class are ethoxylated N-alkylamines which contain on average 1 to 3 ethylene glycol ether groups and alkyl groups with 10 to 18, in particular 12 to 14, carbon atoms, as are contained, for example, in coconut alkyl or oxo radicals .

The grain size distribution is not significantly influenced by the impregnation of the granular adsorbent. Any small fine particles (grain size less than 0.1 mm) will be used but generally bound and cemented with the remaining grains, so that their share tends towards zero. However, the bulk density increases with the amount of nonionic surfactant applied. A further increase in the bulk density can be achieved by finally powdering the adsorbate. Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be used in proportions of 0.03 to 5% by weight, preferably 0.05 to 2% by weight, based on the loaded adsorbent. For example, B. finely powdered zeolites, silica airgel (aerosils), colorless or colored pigments, such as titanium dioxide and other powder materials already proposed for powdering granules or detergent particles, such as finely powdered sodium tripolyphosphate, sodium sulfate, magnesium silicate and carboxymethyl cellulose. The powdering improves the flowability even further and enables the granulate particles to be packed even more densely. Depending on the choice of granular adsorbent, the proportion of nonionic surfactants and the aftertreatment, the powder component (A) can have a bulk density between 450 and 800 g / l. By varying the quantitative ratio between the powder component (A) and the spray-dried powder component (B), the bulk density of the mixture according to the invention can be set within wide limits.

• 40 bis 75 Gew.-%, vorzugsweise 45 bis 70 Gew.-% Zeolith,
• 2 bis 15 Gew.-%, vorzugsweise 3 bis 12 Gew.-% (berechnet als freie Säure) (co-)polymere Carbonsäure als Na- oder K-Salz,
• 8 bis 20 Gew.-%, vorzugsweise 10 bis 18 Gew.-% bei 145 _°C entfembares Wasser,
• 0 bis 20 Gew.-%, vorzugsweise 0 bis 10 Gew.-% Natriumsulfat bzw. Natriumcarbonat,
• 10 bis 50 Gew.-%, vorzugsweise 15 bis 35 Gew.-% an nichtionischem Tensid,
• 0 bis 10 Gew.-% an Natriumnitrilotriacetat,
• 0 bis 5 Gew.-% an feinteiligem Puderungsmittel,
• 0 bis 1 Gew.-% optischer Aufheller.

Based on the above composition of the granular adsorbent and the proportion of adsorbed nonionic surfactant, the powder component (A) has the following composition:

• 40 to 75% by weight, preferably 45 to 70% by weight of zeolite,
• 2 to 15% by weight, preferably 3 to 12% by weight (calculated as free acid) (co) polymeric carboxylic acid as Na or K salt,
• 8 to 20% by weight, preferably 10 to 18% by weight of water which can be removed at 145 _° C.,
• 0 to 20% by weight, preferably 0 to 10% by weight sodium sulfate or sodium carbonate,
• 10 to 50% by weight, preferably 15 to 35% by weight, of nonionic surfactant,
• 0 to 10% by weight of sodium nitrilotriacetate,
• 0 to 5% by weight of finely divided powdering agent,
• 0 to 1% by weight of optical brighteners.

The granular powder component (B) contains anionic surfactants (component b). These contain at least one hydrophobic hydrocarbon residue and a water-solubilizing sulfonate or sulfate group in the molecule. The hydrophobic radical is a linear or 2-position methyl branched aliphatic hydrocarbon radical with 10 to 20, preferably 12 to 18 C atoms or an alkyl aromatic radical with 8 to 14, preferably 10 to 12 aliphatic C atoms.

Preferred surfactants of the sulfonate type are linear alkylbenzenesulfonates (C _9-13 -alkyl), furthermore alpha-olefin sulfonates, which are known to consist of mixtures of alkene and hydroxyalkanesulfonates and disulfonates and of monoolefins with a terminal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline ones or acidic hydrolysis of the sulfonation products are available. Also suitable are alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Other useful surfactants of the sulfonate type are the esters of alpha sulfo fatty acids, e.g. B. the alpha-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols (for example from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Sulfated reaction products of 1 to 3 moles of ethylene oxide with primary or secondary fatty alcohols are also suitable.

Soaps can also be used as anionic surfactants. The sodium salts of saturated fatty acids with 12 to 18 carbon atoms, such as lauric, myristic, palmitic and stearic acid, and oleic acid and mixtures thereof, are particularly suitable as such. Suitable mixtures are e.g. B. soaps obtained from tallow, coconut oil or palm kernel fatty acids. If soap is also used, it must be taken into account that it increases the swelling of the sprayed particles in the spray strand. The result of this is that soap-rich spray-drying batches lead to particularly loose and therefore specifically light powders.

Nonionic surfactants whose constitution corresponds to the ethoxylates present in component (A) can also be used. However, only those nonionic surfactants are preferably processed in component (B) which have a degree of ethoxylation of at least 5 or whose hydrophobic residue has at least 16 C atoms or which are characterized by both features. Such nonionic surfactants have no tendency to "piuming" or only to a very small extent. The liter weight of the spray powder (B) can be increased by adding nonionic surfactants to the spray mixture, ie these surfactants have the opposite effect as soap. The addition of paraffins or silicone oils works in the same sense. In this way it is possible to vary the liter weight of this component (B) within certain limits, for example in a range between 300 and 550 g / l, in particular 320 to 500 g / l. On the other hand, the proportion of nonionic surfactants in batch (B) should not be chosen too high, since - as already mentioned - this leads to an increase in viscosity in the slurry and a deteriorated flowability of the spray powder leads. A powder component (B) which contains only little or no proportions of nonionic surfactant, for example less than 5% by weight, in particular less than 2% by weight, based on component (B), is therefore preferred.

The powder component (B) can also contain polymeric carboxylic acids (components d) of the type described above (cf. component A3 of the granular adsorbent). This additive can improve the grain strength of the spray product. However, it is advantageous if this component is completely or largely contained in the powder component (A), since in this component the grain-strengthening property is particularly pronounced and is relevant for processability.

The powder component (B) may contain sodium tripolyphosphate as an optional component (e). Its proportion in component B is to be dimensioned such that the composite detergent contains less than 20% by weight (= less than 4.5% P). The content of the total agent is preferably 0 to 18.5% by weight, in particular 0 to 10% by weight. Depending on the mixing ratio, its proportion in component (B) can be 0 to 50% by weight, preferably 0 to 40% by weight and particularly preferably 10 to 30% by weight. These numbers refer to anhydrous phosphate. If tripolyphosphate is also used, it has been shown that the relatively high concentration of the tripolyphosphate in component (B) means that the losses due to hydrolysis to undesired orthophosphate and pyrophosphate are comparatively low.

The detergent auxiliaries summarized under component (f), which are stable under the conditions of spray drying or do not lose their activity, comprise washing alkalis, sequestering agents, perborate stabilizers, neutral salts, graying inhibitors, optical brighteners and agents which reduce the slurry viscosity or influence the bulk density of the spray product.

The preferred washing alkali is sodium silicate with the composition Na ₂ 0: Si0 ₂ = 1: 1 to 1: 3.5, preferably 1: 2 to 1: 3.3 and in particular 1: 2.2 to 1: 3. The above quantities refer to arithmetically on a sodium silicate with the composition 1: 2.5. Another suitable washing alkali is sodium carbonate. Optionally, sodium bicarbonate and sodium borate can also be present. Sodium silicate increases the washing ability, has an anti-corrosive effect and in particular improves the grain strength of the spray product, but without impairing its dissolving power, especially since component (B) is essentially free of zeolite. If the presence of larger, ie 2 to 3%, portions of sodium silicate in the agent according to the invention is desired, component (B) should be free of zeolite. Sodium carbonate present in component (B) improves the storage stability of the granular detergent mixture, especially in the case of increased atmospheric humidity. On the other hand, since high levels of sodium carbonate agents, e.g. B. those above 15 to 20 wt .-%, especially when larger proportions of component (A) are added to promote the incrustation of the washed textiles, it is advisable to complete this optional component as completely as possible, ie to 75 to 100% to incorporate into the powder component (B).

Group (f) also includes the sequestering agents from the class of aminopolycarboxylic acids and polyphosphonic acids, which are usually present in comparatively small quantities and act as so-called co-builders, stabilizers, precipitation inhibitors (threshold substances). The aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues. Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and their higher homologs, such as. B. Diethylenetriamine tetra (methylenephosphonic acid). The aforementioned polycarboxylic acids or polyphosphonic acids are usually used in the form of the sodium or potassium salts.

Suitable anti-graying agents are cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Mixtures of various cellulose ethers are also suitable, in particular mixtures of carboxymethyl cellulose and methyl cellulose.

Suitable optical brighteners are alkali metal salts of 4,4-bis- (2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 '"- amino) -stiiben-2,2'-disuifonic acid or compounds of the same structure which, instead of the morpholino group, carry other substituents containing amino groups, for example a diethanolamino group, or brighteners of the substituted diphenylstyryl type, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) diphenyl , 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl-4 '- (2-sulfostyryl) diphenyl.

A further constituent of the powder component (B) are neutral salts, in particular sodium sulfate in proportions of 0 to 25% by weight, preferably 1 to 10% by weight, and textile-softening sheet silicates or smectite clays in proportions of 0 to 22% by weight. , preferably 0 to 15% by weight. Other washing aids are additives that improve the powder structure, e.g. B. alkali salts or toluene, cumene or xylene sulfonic acid.

• 0 bis 5 Gew.-%, nichtionisches Tensid,
• 10 bis 25 Gew.-%, vorzugsweise 12 bis 20 Gew.-% Sulfonat- oder Sulfat-Tensid,
• 0 bis 6 Gew.-%, vorzugsweise 1 bis 5 Gew.-% Seife,
• 0 bis 50 Gew.-%, vorzugsweise 0 bis -40 Gew.-% Natriumtripolyphosphat,
• 0 bis 5 Gew.-%, vorzugsweise 0 bis 3 Gew.-% (berechnet als freie Säure) (co-)polymere Carbonsäure sowie deren Natrium- oder Kaliumsalze,
• 0 bis 12 Gew.-%, vorzugsweise 2 bis 10 Gew.-% Natriumsilikat,
• 0 bis 10 Gew.-%, vorzugsweise 0 bis 5 Gew.-% Natriumcarbonat,
• 0,1 bis 2 Gew.-%, vorzugsweise 0,2 bis 1 Gew.-% (berechnet als Säure) Sequestrierungsmittel aus der Klasse der Aminopolycarbonsäuren und Aminopolyphosphonsäuren sowie deren Natrium- oder Kaliumsalze,
• 0,5 bis 3 Gew.-% Vergrauungsinhibitoren,
• 0 bis 1 Gew.-% optische Aufheller
• 0 bis 20 Gew.-% Neutralsalze wie Natriumsulfat, Pulververbesserer und Schichtsilikate,
• 8 bis 20 Gew.-% adsorptiv gebundenes Wasser.

The powder component (B) therefore preferably has the following composition:

• 0 to 5% by weight, nonionic surfactant,
• 10 to 25% by weight, preferably 12 to 20% by weight, sulfonate or sulfate surfactant,
• 0 to 6% by weight, preferably 1 to 5% by weight of soap,
• 0 to 50% by weight, preferably 0 to -40% by weight sodium tripolyphosphate,
• 0 to 5% by weight, preferably 0 to 3% by weight (calculated as free acid) (co-) polymeric carboxylic acid and its sodium or potassium salts,
• 0 to 12% by weight, preferably 2 to 10% by weight, sodium silicate,
• 0 to 10% by weight, preferably 0 to 5% by weight, sodium carbonate,
• 0.1 to 2% by weight, preferably 0.2 to 1% by weight (calculated as acid), sequestering agents from the class of the aminopolycarboxylic acids and aminopolyphosphonic acids and their sodium or potassium salts,
• 0.5 to 3% by weight of graying inhibitors,
• 0 to 1% by weight of optical brighteners
• 0 to 20% by weight of neutral salts such as sodium sulfate, powder improvers and layered silicates,
• 8 to 20 wt .-% adsorptively bound water.

The spray drying of component (B) can be carried out under conditions as described above in the production of the granular adsorbent.

In addition to the granular powder components (A) and (B), the compositions can contain further powder components as a mixture component. These further powder components contain substances which are unstable under the conditions of spray drying or which lose their specific effect in whole or in part. These active ingredients are e.g. B. enzymes, bleaches, bleach activators, foam inhibitors and fragrances.

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 be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. They are preferably also in the form of granules with a comparable particle spectrum in order to prevent segregation.

The perhydrates and per-compounds usually used in washing and bleaching agents are suitable as bleaching components. The perhydrates preferably include sodium perborate, which can be present as a tetrahydrate or also as a monohydrate, furthermore the perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and urea. Sodium perborate tetrahydrate or monohydrate is preferably also used.

The bleach activators represent another optional powder component. The bleach activators include, in particular, N-acyl compounds and 0-acetylene compounds. Examples of suitable N-acyl compounds are polyacylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylenediamine and their higher homologues, and acylated glycolurils, such as tetraacetylglycoluril. Further examples are Na-cyanamide, N-alkyl-N-sulfonyl-carbonamides, N-acylhydantoins, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines. In addition to carboxylic acid anhydrides, such as phthalic anhydride and esters, such as Na (iso) nonanoyl phenol sulfonate, in particular acylated sugars, such as glucose pentaacetate, are suitable as O-acyl compounds. Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate. The bleach activators can also be granulated and coated with coating substances in order to avoid interactions with the per compounds. Since foam inhibitors (with the exception of high molecular weight fatty acid soaps) often lose all or part of their effectiveness when incorporated into the detergent slurry, they are also advantageously mixed into the detergent as a separate powder component. Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of various foam inhibitors, e.g. B. from silicones and paraffins are useful. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance and, in this form, have a particle size spectrum which corresponds to that of components (A) and (B).

If fragrances are used, they can be applied to one of the powder components. Likewise, one or more of the powder components can be colored or coated with pigments, for example in order to cover up the intrinsic colors of active ingredients or to give the powder mixture a colored, mottled appearance.

The average grain size or the proportion of the individual sieve fractions of the granular powder components (A) and (B) should not differ from one another by more than 50%. The content of dust-like components (sieve size less than 0.1 mm) as well as Grobkom (sieve size more than 1.6 mm) and in each case not more than 1% by weight. It has been shown that if these conditions are observed, there is no need to fear segregation of the two powder components, for example during transport, even if the liter weight of the two components differs considerably. It is also expedient to use the further powder constituent in a granular form which is not essential in terms of its spectrum of com, ie. H. does not deviate more than 50% from that of components (A) or (B).

The mixing ratio of the two components (A) and (B) is in the range from 1: 5 to 3: 1, preferably from 1: 4 to 2: 1 and should be chosen so that the distribution ratio of the components (a), ( c) and (d) moved within the scope of the definition of the invention. The proportion of optional powder components can fluctuate within larger limits. The percentage of per compound (preferably perborate) 5 to 30, preferably 7 to 25 wt .-%. Bleach activators can be present in amounts of 0.2 to 5% by weight. As already explained, both additives are preferably used in granular form. Since they generally only require relatively small amounts of granulating aid (usually less than 10%, based on the active ingredient) to be converted into stable granules, their proportion largely corresponds to the actual active ingredient content. Enzymes and foam inhibitors are usually used in proportions of 0.01 to at most 2% by weight, preferably 0.05 to 1% by weight, based on the active ingredient. In the active ingredient granules containing enzymes or foam inhibitors, however, the proportion of carrier substance, extender and coating material predominates by far and is in many cases more than 90%. Accordingly, the proportion of these granular powder constituents in the total mixture is generally 0.3 to 5% by weight.

The dosing and subsequent mixing of components (A) and (B) and the additional powder component can be carried out in individual stages or simultaneously. It is expedient to work continuously, with automatic belt scales in combination with free-fall mixers having proven particularly useful. Additional mechanically operated mixing devices are generally not required. If they are used, careful treatment of the powder mixture is recommended in order to avoid destruction of the hollow spherical structure of the spray powder and an undesirable increase in the proportion of fine particles and dust.

The agents according to the invention are distinguished by a high washing capacity, in particular by an excellent cleaning power against stubborn greasy soiling. Despite their comparatively high content of liquid non-ionic surfactants, they are extremely pourable and free-flowing and do not tend to grease cardboard packaging.

Examples

According to EP-A 0 184 794, spray-dried granules of the following composition were produced (GT = parts by weight):

The zeolite used had a particle size of 1 to 8 microns, the proportion over 8 microns being 6% by weight. There were no portions above 20 microns. A copolymer of acrylic acid and maleic acid (molar ratio 7: 3) with an average molecular weight of 70,000 in the form of the sodium salt was used as the polycarboxylic acid. A tallow alcohol reacted with 5 moles of ethylene oxide (EO) (30% cetyl alcohol, 70% stearyl alcohol) was used as the ethoxylated fatty alcohol.

• 70,3 Gewichtsteile des Granulates wurden in einem Sprühmischapparat, bestehend aus einer gegen die Horizontale geneigten, mit Mischorganen und Sprühdüsen ausgerüsteten zylindrischen Trommel (LÖDIGE-Mischer) mit 29,7 Gewichtsteilen eines geschmolzenen nichtionischen Tensidgemisches besprüht. Die Temperatur des Granulats betrug 20°C, die der Tensidschmelze 50_°C. Das Tensidgemisch bestand aus 16,7 GT C₁₆-C₁₈-Alkohol mit 5 EO und 13 GT gesättigtem C12--C14-Alkohol mit 3 EO. Nach dem Abkühlen wurde ein nichtklebendes, körniges Produkt mit ausgezeichneter Rieselfähigkeit erhalten. Das Schüttgewicht betrug 650 g/l, das Komspektrum war praktisch unverändert, lediglich der Anteil mit unter 0,1 mm betrug 0%.

The grain spectrum determined by sieve analysis gave the following weight distribution:

• 70.3 parts by weight of the granules were sprayed with 29.7 parts by weight of a melted nonionic surfactant mixture in a spray mixing apparatus consisting of a cylindrical drum (LÖDIGE mixer) equipped with mixing elements and spray nozzles inclined to the horizontal. The temperature of the granules was 20 ° C., that of the surfactant melt 50 _° C. The surfactant mixture consisted of 16.7 GT C ₁₆ -C ₁₈ alcohol with 5 EO and 13 GT saturated C12-C14 alcohol with 3 EO. To upon cooling, a non-sticky, granular product with excellent flowability was obtained. The bulk density was 650 g / l, the particle size spectrum was practically unchanged, only the proportion with less than 0.1 mm was 0%.

27% by weight of the granules impregnated with the nonionic surfactant (powder component A) were mixed with 44.2% by weight of a spray-dried powder (powder component B). The spray powder (B) contained nonionic surfactant, sodium dodecylbenzenesulfonate (Na-DBS), sodium tallow soap, sodium ethylenediaminetetra-methylenephosphonate (EDTMP), cellulose ether (CMC), sodium silicate (Na ₂ 0: Si0 ₂ = 1: 3.3) and the others Ingredients listed in Table 1. Granulated enzymes and sodium perborate, onto which a silicone defoamer and perfume oil had previously been sprayed, were added to other powder components. These powdery or granular constituents are summarized under the term "powder component C", the proportion of which is a total of 27% by weight.

The composition of the agent and other agents produced in the same way are listed in Table 1 (in% by weight).

In Examples 2, 3 and 4, the powder component (A) was additionally powdered with 3% by weight (based on this component) with zeolite NaA powder after the application of the nonionic surfactant.

Claims (9)

1. A phosphate-reduced detergent containing less than 5%_'P in the form of phosphates and consisting of a mixture of at least two granular powder components (A) and (B), in which component (A) contains finely crystalline synthetic zeolites of the NaA type or mixtures thereof with zeolite NaX, in which zeolite NaA is present in excess, and also nonionic surfactants from the group of polyglycol ether derivatives while component (B) consists of a spray-dried product optionally containing phosphates, characterized in that the mixture of the two components contains in all the following constituents:

(a) from 4 to 40% by weight of nonionic surfactants,

(b) from 3 to 20% by weight of anionic surfactants, the ratio by weight of (a) to (b) being from 3:1 to 1:2,

(c) from 15 to 50% by weight of finely crystalline zeolite,

(d) from 0.5 to 5% by weight (expressed as free acid) of homopolymeric or copolymeric carboxylic acids having a molecular weight of from 1000 to 120,000 or Na- or K-salts thereof,

(e) from 0 to less than 20% by weight sodium tripolyphosphate,

(f) from 10 to 72.5% by weight of other detergent constituents which are stable under the spray-drying conditions,
with the proviso that the ratio by weight of component (A) to component (B) is from 1:5 to 3:1 and powder component (A) contains from 50 to 100% of constituent (a), from 80 to 100% of constituent (c) and from 50 to 100% of constituent (d) while powder component (B) contains from 80 to 100% of constituent (b) and 100% of constituent (e), expressed in each case in percent by weight.

2. A detergent as claimed in Claim 1, characterized in that component (A) has the following composition:

from 40 to 75 % by weight and preferably from 45 to 70% by weight zeolite,

from 2 to 15 % by weight and preferably from 3 to 12% by weight (expressed as free acid) (co)polymeric carboxylic acid as Na or K salt,

from 8 to 20 % by weight and preferably from 10 to 18% by weight water removable at 145_°C,

from 0 to 20 % by weight and preferably from 0 to 10% by weight sodium sulfate or sodium carbonate,

from 10 to 50 % by weight and preferably from 15 to 35% by weight nonionic surfactant,

from 0 to 10 % by weight sodium nitrilotriacetate,

from 0 to 5 % by weight finely divided powdering agent,

from 0 to 1 % by weight optical brightener.

3. A detergent as claimed in claims 1 and 2, characterized in that component (A) has a powder density of 550 to 750 g/l.

4. A detergent as claimed in claim 1, characterized in that component (B) has the following composition:

from 0 to 5% by weight nonionic surfactant,

from 10 to 25% by weight and preferably from 12 to 20% by weight sulfonate or sulfate surfactant,

from 0 to 6% by weight and preferably from 1 to 5% by weight soap,

from 0 to 50% by weight and preferably 0 to 40% by weight sodium tripolyphosphate,

from 0 to 5% by weight and preferably 0 to 3% by weight (expressed as free acid) (co)polymeric carboxylic acid and sodium or potassium salts thereof,

from 0 to 12% by weight and preferably from 2 to 10% by weight sodium silicate,

from 0 to 10% by weight and preferably from 0 to 5% by weight sodium carbonate,

from 0.1 to 2% by weight and preferably from 0.2 to 1% by weight sequestering agent of the aminopolycarboxylic acid and aminopolyphosphonic acid type,

from 0.5 to 3% by weight redeposition inhibitors,

from 0 to 1% by weight optical brighteners,

from 0 to 20% by weight neutral salts, such as sodium sulfate, powder-improving additives and stabilizers, such as Mg-silicate,

from 8 to 20% by weight adsorbed water.

5. A detergent as claimed in claims 1 to 4, characterized in that the nonionic surfactant consists of ethoxylated alcohols containing 12 to 18 C atoms and 3 to 15 and preferably 4 to 6 ethylene glycol ether groups.

6. A detergent as claimed in claims 1 to 5, characterized in that the powder component A is free from alkali metal silicates.

7. A detergent as claimed in claims 1 to 6, characterized in that it contains other powder components containing enzymes, bleaches, bleach activators and foam inhibitors.

8. A process for the production of the detergent claimed in claims 1 to 7, characterized in that, to prepare component (A), an aqueous slurry containing constituents (c), (d) and optionally (e), or a part thereof, is spray-dried, the spray-dried granulate is impregnated with nonionic surfactants (constituent a) and the powder component (A) obtained is mixed with the spray-dried powder component (B) containing the other constituents.

9. A process as claimed in claim 8, characterized in that, after impregnation, powder component (A) is powdered with 0.1 to 5% by weight zeolite.