EP0114308B1 - Spray-dried multi-component washing agent - Google Patents

Abstract

1. A detergent consisting of a mixture of at least two powder components prepared by spray drying and containing from 30 to 50 % by weight of a finely crystalline, synthetic sodium alumosilicate which contains bound water, corresponds to the following formula 0.7.1.1 Na2 O.Al2 O3 .1.3 - 3.3 SiO2 and has a calcium binding power of at least 100 mg CaO/g active substance and from 50 to 70 % by weight of other standard detergent constituents, characterized in that the powder components have the following compositions : Ist powder component : from 60 to 80 % by weight alumosilicate of formula (I), from 2 to 10 % by weight sodium sulfate, expressed as anhydrous salt, from 1 to 5 % by weight of a nonionic surfactant of the polyethylene glycol ether derivative type having an HLB-value of from 7.5 to 11, from 0 to 8 % by weight of a polyphosphonic acid or an alkali metal or ammonium salt thereof and from 10 to 25 % by weight water 2nd powder component : from 20 to 45 % by weight alumosilicate of formula (I) from 20 to 40 % by weight of at least one anionic, non-ionic or zwitter-ionic surfactant, from 10 to 50 % by weight of phosphate-free washing alkalis and, optionally, co-builders and neutral salts, from 1 to 10 % by weight of other detergent constituents selected from the group comprising optical brighteners, re-deposition inhibitors and stabilizers and from 5 to 15 % by weight water, the mixing ratio of powder component 1 to powder component 2 being from 1:2 to 1:7.

Description

die ein Calciumbindevermögen von 50 bis 200 mg insbesondere von wenigstens 100 mg/g CaO Aktivsubstanz (AS) aufweisen. Diese können, wie es heißt, nach allen in der Technik bekannten Verfahren zu Waschmitteln von pulveriger bis körniger Beschaffenheit verarbeitet werden. Näher offenbart sind Verfahren, bei denen pulvrige, d. h. zuvor getrocknete Alumosilikate entweder mit den anderen Waschmittelbestandteilen, auch öligen bis pastenförmigen, vermischt bzw. in pulvriger Form in wäßrige Aufschlämmungen (Slurries) der übrigen Waschmittelbestandteile eingearbeitet und anschließend sprühgetrocknet werden. Die gleiche Arbeitsweise wird in der jüngeren DE-AS 2 422 655 vorgeschlagen. Der Nachteil dieser Arbeitsweise besteht darin, daß die als feuchte Filterkuchen anfallenden synthetischen Alumosilikate zwei Trocknungsprozessen unterworfen werden, was in ungünstigen Fällen zu Kornvergr- öberungen und teilweise Aktivitätseinbußen führen kann und überdies zu einem erhöhten Energieverbrauch führt.DE-AS 2 412 837 discloses low-phosphate or phosphate-free detergents containing alkali alumosilicates, which are able to replace all or part of the phosphate as a detergent builder. These are preferably finely crystalline, synthetically produced, water-insoluble, bound water-containing sodium aluminosilicates of the formula

which have a calcium binding capacity of 50 to 200 mg, in particular of at least 100 mg / g CaO active substance (AS). These can, as is said, be processed into detergents of powdery to granular nature by all processes known in the art. Methods are disclosed in which powdery, ie previously dried, aluminosilicates are either mixed with the other detergent constituents, also oily to pasty, or incorporated in powder form into aqueous slurries of the remaining detergent constituents and then spray-dried. The same procedure is proposed in the more recent DE-AS 2 422 655. The disadvantage of this method of operation is that the synthetic aluminosilicates obtained as moist filter cakes are subjected to two drying processes, which in unfavorable cases can lead to grain enlargement and partial loss of activity and moreover leads to increased energy consumption.

DE-AS 2 615 698 (D 5394) conveys the teaching that aqueous slurries or filter-moist pastes of synthetic aluminosilicate. by stabilizing 0.2 to 7% by weight of a dispersant, which includes certain nonionic surfactants, carboxyl group-containing polymers and phosphonic acids, and 0.2 to 7% of a non-phosphorus-containing inorganic salt, such as sodium sulfate. These stabilized suspensions can also be used to produce powdery products, e.g. B. softening agents or after incorporation into detergent slurries can be further processed into customary washing powders. The latter procedure has proven to be particularly advantageous when the content of the spray-dried washing powder for aluminosilicates does not significantly exceed 30% by weight and is in particular in the range between 15 and 25% by weight. In this area there are no problems when preparing and processing the slurry even under less favorable process conditions, and the washing powders obtained are notable for good wettability and distributability when dissolved in the wash liquor. However, if the proportion of water-insoluble aluminosilicate in phosphate-free or low-phosphate detergents is increased to significantly more than 30% by weight, based on the spray product, increased attention is required when preparing and processing the relatively water-rich, but relatively viscous slurries in order to achieve this Avoid occurrence of inhomogeneities. In addition, it can e.g. B. in older washing machines with unfavorably designed inductors due to the increased proportion of insoluble components to a delayed dissolution and dispersion of the detergent in the wash liquor.

These problems are solved by the present invention.

mit einem Calciumbindevermögen von wenigstens 100 mg CaO/g Aktivsubstanz und 50 bis 70 Gew.-% an weiteren üblichen Waschmittelbestandteilen, dadurch gekennzeichnet, daß die Pulverkomponenten wie folgt zusammengesetzt sind :

• 1. Pulverkomponente :
  • 60 bis 80 Gew.-% Alumosilikat der Formel (I),
  • 2 bis 10 Gew.-% Natriumsulfat, gerechnet als wasserfreies Salz,
  • 1 bis 5 Gew.-% eines nichtionischen Tensids aus der Klasse der Polyethylenglykoletherderivate mit einem HLB-Wert von 7 bis 11,
  • 0 bis 8 Gew.-% einer Polyphosphonsäure bzw. ihrer Alkalimetall- oder Ammoniumsalze,
  • 10 bis 25 Gew.-% Wasser,
• 2. Pulverkomponente :
  • 20 bis 45 Gew.-% Alumosilikat der Formel (I),
  • 25 bis 40 Gew.-% mindestens eines anionischen, nichtionischen oder zwitterionischen Tensids,
  • 10 bis 50 Gew.-% an phosphatfreien Waschalkalien sowie ggf. Co-Buildern und Neutralsalzen,
  • 1 bis 10 Gew.-% an sonstigen Waschmittelbestandteilen aus der Klasse der optischen Aufheller, Vergrauungsinhibitoren und Stabilisatoren,
  • 5 bis 15 Gew.-% Wasser,

wobei das Mischungsverhältnis von 1. zu 2. Pulverkomponente 1 : 2 bis 1 : 7 beträgt.The invention relates to a detergent consisting of a mixture of at least two powder components produced by spray drying and containing 30 to 50% by weight of a finely crystalline, synthetic, bound water-containing sodium aluminosilicate of the formula (I)

with a calcium binding capacity of at least 100 mg CaO / g active substance and 50 to 70% by weight of other common detergent ingredients, characterized in that the powder components are composed as follows:

• 1. Powder component:
  • 60 to 80% by weight of aluminosilicate of the formula (I),
  • 2 to 10% by weight sodium sulfate, calculated as an anhydrous salt,
  • 1 to 5% by weight of a nonionic surfactant from the class of the polyethylene glycol ether derivatives with an HLB value of 7 to 11,
  • 0 to 8% by weight of a polyphosphonic acid or its alkali metal or ammonium salts,
  • 10 to 25% by weight of water,
• 2. Powder component:
  • 20 to 45% by weight of aluminosilicate of the formula (I),
  • 25 to 40% by weight of at least one anionic, nonionic or zwitterionic surfactant,
  • 10 to 50% by weight of phosphate-free washing alkalis and, if necessary, co-builders and neutral salts,
  • 1 to 10% by weight of other detergent components from the class of optical brighteners, graying inhibitors and stabilizers,
  • 5 to 15% by weight of water,

wherein the mixing ratio of 1st to 2nd powder component is 1: 2 to 1: 7.

The invention furthermore relates to a process for the preparation of the compositions according to the above definition of the invention, which is characterized in that a slurry of the 1st powder component containing 35 to 50% by weight aluminosilicate and 40 to 60% by weight water and the other constituents spray dried in a manner known per se and mixed with the second powder component, which was obtained by spray drying a slurry containing 50 to 32% by weight of water, in the stated mixing ratio.

The aluminosilicates of formula I are used in the usual hydrated, finely crystalline form, i. H. they have practically no particles larger than 30 fJ.m and preferably consist at least 80% of particles smaller than 10 wm. Their calcium binding capacity, which is determined according to the information in DE 2 412 837, relates to the active substance content (AS), which corresponds to an aluminosilicate dehydrated by heating at 800 ° C. for one hour. Synthetic zeolites of the NaA and NaX type and mixtures thereof are particularly useful.

gehorchen soll. Besonders geeignet sind z. B. Talgfettalkohole mit 4 bis 6 Glykolethergruppen.The 1st powder component also contains sodium sulfate in proportions of 2 to 10, preferably 3 to 8% by weight, based on anhydrous salt. Another constituent are nonionic surfactants, which are present in proportions of 1 to 5, preferably 2 to 4, parts by weight and have an HLB value of 7.5 to 11, in particular 8 to 10. Examples of such nonionic surfactants are ethoxylation products of saturated and monounsaturated linear or, in the 1st position, methyl-branched, primary alcohols with 12 to 20 C atoms and 2 to 7, in particular 3 to 6, ethylene glycol ether groups, the content E of glycol ether groups (in weight % based on the surfactant molecule) of the relationship

obey. Z are particularly suitable. B. tallow fatty alcohols with 4 to 6 glycol ether groups.

Further suitable nonionic surfactants of this group are ethoxylated amines, fatty acids and fatty acid amides with 10 to 20, in particular 12 to 18, carbon atoms, for example. B. fatty acid mono- or diethanolamides. Examples of such compounds are listed, for example, in DE-A1-2615698.

Polyphosphonic acids or their. Come as an optional component of the first powder component. Sodium, potassium or ammonium salts in question, the ammonium salts also being understood to be the salts derived from organic ammonium bases, such as mono-, di- or triethanolamine. Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and their higher homologs, such as. B. Diethylenetriaminepenta- (methylenephosphonic acid).

Further usable phosphonic acids or phosphonocarboxylic acids are also listed in DE-A1-2615698.

The proportion of polyphosphonic acids or their salts in the 1st powder component is 0 to 8, preferably 1 to 7% by weight. The water content is between 10 and 25, preferably between 12 and 20% by weight, which means both the water of crystallization or adsorptively bound and the water escaping when the aluminosilicate is heated to a temperature of 800 ° C.

The mixing of the constituents contained in the first powder component is expediently carried out after the synthesis of the sodium aluminosilicate. For this purpose, the aluminosilicate which is still moist or is in aqueous suspension or is present as a filter cake is mixed with the additives, for example by introducing the filter cake into an aqueous solution of the additives or washing the filter cake on the filter with the aqueous solution , so that the adhering water is replaced by the applied solution. The suspensions of the aluminosilicates obtained in this way are notable for a particularly long shelf life, ie. H. they do not tend to segregate or settle solid, non-redispersible residues. They can be stored and transported in this form. They are further processed to the 1st powder component preferably by spray drying, it being possible to use the processes customary in the production of detergents, ie. H. Drying with hot temperatures of 150-360 °, preferably 200-300 ° C, drying gases in spray towers, nozzle or disk atomization of the suspension, product guidance in cocurrent or countercurrent and linear or cyclonic guidance of the drying gas.

The same process conditions can also be used for the spray drying of the 2nd powder component.

The second powder component also consists of a spray-dried mixture which, in addition to aluminosilicates of the formula I, contains customary detergent constituents which are stable under the conditions of hot spray drying. These include the usual anionic or nonionic surfactants, phosphate-free co-builders, as well as washing alkalis and neutral salts, as well as other auxiliaries usually contained in detergents.

Suitable anionic surfactants are those of the sulfonate or sulfate type, in particular alkylbenzenesulfonates, olefin sulfonates, alkyl sulfonates and α-sulfofatty acid esters, primary alkyl sulfates and the sulfates of ethoxylated, 2 to 3 glycol ether groups having higher molecular weight alcohols. Also suitable are alkali soaps of fatty acids of natural or synthetic origin, for example the sodium soaps of coconut, palm or tallow fatty acids and, if foam control is desired, also those of hydrogenated rapeseed or fish oil fatty acids. Alkyl betaines and especially alkyl sulfobetaines are suitable as zwitterionic surfactants. The anionic surfactants are preferably in the form of the sodium salts. If the anionic and zwitterionic compounds mentioned have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 12 to 18 carbon atoms. In the compounds having an araliphatic hydrocarbon radical, the preferably unbranched alkyl chains contain 6 to 16, in particular 10 to 14, carbon atoms. Suitable nonionic surfactants are ethoxylated alcohols with 12 to 18 carbon atoms and an average of 3 to 20, preferably 5 to 15, glycol ether groups. Mixtures of ethoxylated, primary C ₁₄ -C ₁₈ alcohols, such as tallow fatty alcohol or oleyl alcohol, of which a part thereof has 10 to 16 glycol ether groups and a second part has 3 to 7 glycol ether groups. The quantitative ratio of the two parts can be, for example, 4: 1 to 1: 4.

Further suitable nonionic surfactants are those which are derived from the abovementioned compounds and have both ethylene glycol and propylene glycol ether groups, for example alcohols with 10 to 30 ethylene glycol ether groups and 1 to 30 propylene glycol ether groups; also ethoxylation products of alkylphenols, fatty acid amides and fatty acids. The water-soluble polyethylene oxyadducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain can also be used. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Nonionic compounds of the amine oxide and sulfoxide type, which can optionally also be ethoxylated, can also be used.

The second powder component also contains phosphate-free washing alkalis, which include the alkali silicates, alkali carbonates or bicarbonates, and alkali borates, preferably in the form of the sodium salts. The sodium silicate can have a ratio of Si0 ₂ to Na ₂ 0 of 1: 1 to 1: 3.5.

The second powder component can additionally contain so-called co-builders, which are able to increase the effect of sodium almosilicates considerably even in small amounts. Particularly suitable as co-builders are polyphosphonic acids or their alkali metal salts, as described as optional components of the first powder component.

Other co-builders that may be present in the second powder component are aminopolycarboxylic acids with a complexing action. These include in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. The salts of diethylenetriamineopentaacetic acid and the higher homologues of the aminopolycarboxylic acid mentioned are also suitable.

The polymeric carboxylic acids with a molecular weight of at least 350 are also suitable in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, polymethacrylic acid, poly-a-hydroxyacrylic acid, polymaleic acid, polyitaconic acid, polymesaconic acid, polybutene tricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene, vinyl methyl ether or furan.

Neutral salts, in particular sodium sulfate, and magnesium silicate acting as a stabilizer for per compounds also come into consideration as further constituents. Further washing aids that may be present in the spray-trickled second powder component are graying inhibitors and optical brighteners and additives that improve the powder structure, for example alkali metal salts or toluene, cumoyl or xylene sulfonic acid.

Suitable graying inhibitors are, in particular, carboxymethyl cellulose, methyl cellulose, furthermore water-soluble polyesters and polyamides from polyvalent carboxylic acids and glycols or diamines, which have free carboxyl groups, betain groups or sulfobetaine groups capable of salt formation, and polymers or copolymers of vinyl alcohol, vinyl amide and acrylamide, colloidally soluble in water, acrylamides and acrylamides .

Suitable optical brighteners are the alkali salts of 4,4-bis (-2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group, a methylamino group or a p-methoxyethylamino group instead of the morpholino group. 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.

Other additives that are added to the two powder components or their mixtures separately after spray drying are enzymes from the class of proteases, lipases and amylases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be embedded in coating substances or subsequently granulated onto the spray-dried second powder component. Fragrances and anti-foaming agents, such as silicones or paraffin hydrocarbons to avoid loss of effectiveness, are also generally used subsequently added to the spray-dried 2nd powder component.

The perhydrates and per-compounds commonly 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 as a monohydrate, furthermore the perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and urea. These perhydrates are preferably used together with bleach activators.

Sodium perborate tetrahydrate in combination with bleach activators is preferred as the bleaching component. The bleach activators include in particular N-acyl compounds and 0-acyl compounds. Examples of suitable N-acyl compounds are multiply acylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylenediamine or their higher homologues, and acylated glycolurils, such as tetraacethylglycoluril. Further examples are N-alkyl-N-sulfonyl-carbonamides, N-acylhydantoins, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines. In addition to carboxylic acid anhydrides, acylated sugars such as glucose pentaacetate are particularly suitable as 0-acyl compounds.

Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate.

The bleach activators can be coated with coating substances in order to avoid interactions with the per-compounds, especially during the storage of powdery mixtures, as described for example in DE-PS 1 162 967, DE-PS 2138 584, DE-PS 2 220 296, DE- OS 2 338 412, DE-OS 2 650 429 and DE-OS 3 011 998. Particularly suitable coating substances are water-soluble polymers, such as polyethylene glycol, cellulose ethers, cellulose esters, water-soluble starch ethers and starch esters, and nonionic surfactants of the alkoxylated alcohol, alkylphenol, fatty acid and fatty acid amide type. The polyphosphonic acids to be used according to the invention can be mixed with the bleach activators before they are coated or coated, so that they are enclosed by the coating material together with them. This can have an additional stabilizing effect.

The mixing of the two powder components can be carried out using conventional mixing devices, the mechanical stressing of the spray products being as low as possible in order to avoid destruction of the structure and increased formation of dust or fine-grained fractions. One can also proceed in such a way that the aqueous batches of the two components are sprayed simultaneously via separate nozzles in a spray tower, the nozzles being able to be arranged in a common plane in the upper part of the spray tower or in different planes, as is the case, for example, in FIG British Patent 1 189 543 is apparent. By spraying together, the process step of subsequently mixing the two powder components can be saved.

• 1. Pulverkomponente
  • 6-75 % Natriumalumosilikate der Formel I
  • 3-8 % Natriumsulfat
  • 2-4 % nichtionisches Tensid mit einem HLB-Wert von 8-10
  • 1-7 % Polyphosphonsäure bzw. deren Natriumsalz
  • 12-22 % Wasser
• 2. Pulverkomponente
  • 25-40 % Natriumalumosilikat der Formel I
  • 25-35 % anionische und nichtionische Tenside
  • 4-20 % Waschalkalien aus der Klasse der Silikate sowie des Carbonats bzw. Bicarbonats des Natriums
  • 0,2 bis 5 % komplexierend wirkende polyanionische Co-Builder
  • 0 bis 20 % Neutralsalze sowie Mg-Silikat
  • 0,5 bis 3 % Vergrauungsinhibitoren
  • 0,1 bis 1 % optische Aufheller
  • 7 bis 14 % Wasser.

After mixing, the detergents according to the invention preferably have the following composition (details in percent by weight):

• 1. Powder component
  • 6-75% sodium aluminosilicates of formula I.
  • 3-8% sodium sulfate
  • 2-4% non-ionic surfactant with an HLB value of 8-10
  • 1-7% polyphosphonic acid or its sodium salt
  • 12-22% water
• 2. Powder component
  • 25-40% sodium aluminosilicate of formula I.
  • 25-35% anionic and nonionic surfactants
  • 4-20% washing alkalis from the class of silicates and carbonate or bicarbonate of sodium
  • 0.2 to 5% complexing polyanionic co-builders
  • 0 to 20% neutral salts and Mg silicate
  • 0.5 to 3% graying inhibitors
  • 0.1 to 1% optical brighteners
  • 7 to 14% water.

• 30-45 % Natriumalumosilikat der Formel I
• 10-20 % Tenside
• 10-25 % Perverbindungen
• 50-10 % an den sonstigen vorgenannten Bestandteilen, wobei sich deren Anteil im einzelnen aus den vorgegebenen Mischungsverhältnissen ergibt.

Per compounds, bleach activators and enzymes can be considered as the third powder component. The mixing ratio of the components to one another is preferably such that the detergent as a whole contains the following essential constituents:

• 30-45% sodium aluminosilicate of formula I.
• 10-20% surfactants
• 10-25% per connections
• 50-10% of the other components mentioned above, where their share results from the specified mixing ratios.

The agents according to the invention are distinguished by their favorable use and dispersibility in the wash liquor. Their production poses no problems when preparing and processing the slurries into spray products. The mixtures show no tendency to segregate during transport and storage.

Examples

The composition of the agents is shown in the following table. The 1st powder component comprises the components (a) - (e), the 2nd powder component the components (f) - (s). The components (t) - (x) were subsequently mixed into the spray-dried mixture of the two powder components, the perfume oil (x) having been sprayed onto the sodium perborate beforehand.

• c) = C_16-18-Talgalkohol 5-fach ethoxyliert
• g₁) = n-Dodecylbenzolsulfonat (Na-Salz)
• d₁) = 1-Hydroxethan-1,1-diphosphonat-Na
• d₂ = Aminotri-(methylenphosphonat)-Na
• g₂) = C_13-15 n-Alkansulfonat (Na-Salz)
• g₃) = C_14-17 Alphaolefinsulfonat (Na-Salz)
• g₄) = Alphasulfofettsäuremethylester aus hydrierter Palmkernfettsäure (Na-Salz)
• g_s) = Talgfettalkoholsulfat (Na-Salz)
• h) = Seife aus Talgfettsäuren (Na-Salz)
• i₁) = Talgalkohol 15-fach ethoxyliert
• i₂) = Talgfettalkohol 5-fach ethoxyliert
• i₃) = technischer Oleylalkohol 10-fach ethoxyliert
• k₁) = Na₂0 : SiO₂ = 1 : 3,3
• k₂) = Na₂O : Si0₂ = 1 : 2
• m₁) = 1-Hydroxyethan-1,1-diphosphonat-Na
• m₂) = Aminotri-(methylenphosphonat)-Na
• m₃) = Ethylendiamin-tetra-(methylenphosphonat)-Na
• o) = Carboxymethylcellulose (Na-Salz)
• p) ₌ Methylcellulose
• t) = Natriumperborat-tetrahydrat in den Beispielen 1-3 und 5-7, Monohydrat im Beispiel 4
• u) = Tetraacetylethylendiamin
• v) = Bakterienprotease
• w) = Silicon-Entschäumer.

As far as the chosen names are not understandable by themselves, they are characterized in more detail below:

• c) = C _16-18 tallow alcohol 5-fold ethoxylated
• g ₁ ) = n-dodecylbenzenesulfonate (Na salt)
• d ₁ ) = 1-hydroxethane-1,1-diphosphonate Na
• d ₂ = aminotri- (methylenephosphonate) Na
• g ₂ ) = C _13-15 n-alkanesulfonate (Na salt)
• g ₃ ) = C _14-17 alpha olefin sulfonate (Na salt)
• g ₄ ) = methyl alphasulfofatty acid from hydrogenated palm kernel fatty acid (Na salt)
• g _s ) = tallow fatty alcohol sulfate (Na salt)
• h) = soap from tallow fatty acids (Na salt)
• i ₁ ) = tallow alcohol ethoxylated 15 times
• i ₂ ) = tallow fatty alcohol 5-fold ethoxylated
• i ₃ ) = technical oleyl alcohol ethoxylated 10 times
• k ₁ ) = Na ₂ 0: SiO ₂ = 1: 3.3
• k ₂ ) = Na ₂ O: Si0 ₂ = 1: 2
• m ₁ ) = 1-hydroxyethane-1,1-diphosphonate Na
• m ₂ ) = aminotri- (methylenephosphonate) Na
• m ₃ ) = ethylenediamine tetra (methylene phosphonate) Na
• o) = carboxymethyl cellulose (Na salt)
• p) ₌ methyl cellulose
• t) = sodium perborate tetrahydrate in Examples 1-3 and 5-7, monohydrate in Example 4
• u) = tetraacetylethylenediamine
• v) = bacterial protease
• w) = silicone defoamer.

mit einem bei 22 °C bestimmten Ca-Bindevermögen von 170 mg CaO/g und einer mittleren Teilchengröße von 4,8 µm (100 % kleiner als 15 µm) verwendet.A synthetically produced crystalline zeolite of the NaA type of the formula was used as the aluminosilicate

with a Ca binding capacity of 170 mg CaO / g determined at 22 ° C and an average particle size of 4.8 µm (100% smaller than 15 µm).

The first powder component was prepared from a 50% by weight mixture, the second powder component from a 55% by weight aqueous mixture by spray drying via nozzles by means of countercurrent heating gases having an inlet temperature of 280 ° C. and an outlet temperature of 84 ° C. .

The bulk weights of the 1st powder component were between 550 and 630 g / I, those of the 2nd powder component between 360 and 400 g / I. The powder components were mixed using belt scales in free-fall mixers.

No problems or no segregation occurred when preparing, homogenizing and storing the aqueous spray mixtures. The powder mixtures proved to be free-flowing and could be washed in perfectly in automatic washing machines, ie there was no residue formation in the washing-in devices.

Claims (9)

1. A detergent consisting of a mixture of at least two powder components prepared by spray drying and containing from 30 to 50 % by weight of a finely crystalline, synthetic sodium alumosilicate which contains bound water, corresponds to the following formula

and has a calcium binding power of at least 100 mg CaO/g active substance and from 50 to 70 % by weight of other standard detergent constituents, characterized in that the powder components have the following compositions:

Ist powder component:

from 60 to 80 % by weight alumosilicate of formula (I),

from 2 to 10 % by weight sodium sulfate, expressed as anhydrous salt,

from 1 to 5% by weight of a nonionic surfactant of the polyethylene glycol ether derivative type having an HLB-value of from 7.5 to 11,

from 0 to 8 % by weight of a polyphosphonic acid or an alkali metal or ammonium salt thereof and

from 10 to 25 % by weight water

2nd powder component:

from 20 to 45 % by weight alumosilicate of formula (I),

from 20 to 40 % by weight of at least one anionic, non-ionic or zwitter-ionic surfactant,

from 10 to 50 % by weight of phosphate-free washing alkalis and, optionally, co-builders and neutral salts,

from 1 to 10 % by weight of other detergent constituents selected from the group comprising optical brighteners, re-deposition inhibitors and stabilizers and

from 5 to 15 % by weight water,

the mixing ratio of powder component 1 to powder component 2 being from 1 : 2 to 1 : 7.

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

from 65 to 75 % by weight sodium alumosilicate of formula (I),

from 3 to 8 % by weight sodium sulfate,

from 2 to 4 % by weight nonionic surfactant having an HLB-value of from 8 to 10,

from 1 to 7 % by weight polyphosphonic acid or a salt thereof,

from 12 to 22 % by weight water.

3. A detergent as claimed in Claims 1 and 2, characterized in that the nonionic surfactant in the 1st powder component consists of a saturated or monounsaturated primary alcohol reacted with from 2 to 7 moles ethylene oxide.

4. A detergent as claimed in Claims 1 and 2, characterized in that the polyphosphoric acid in the 1st powder component consists of 1-hydroxyethane-1,1-diphosphoric acid, aminotri-(methylenephosphoric acid), ethylenediamine tetra-(methylenephosphoric acid) or higher homologs thereof.

5. A detergent as claimed in Claim 1, characterized in that the 2nd powder component has the following composition :

from 25 to 40 % by weight sodium alumosilicate of formula (I),

from 25 to 35 % by weight anionic or nonionic surfactants,

from 4 to 20 % by weight washing alkalis selected from the group comprising silicates and sodium carbonate or bicarbonate,

from 0.2 to 5 % by weight complexing polyanionic cobuilders,

from 0 to 20 % by weight neutral salts and/or magnesium silicate,

from 0.5 to 3 % by weight re-deposition inhibitors,

from 0.05 to 1 % by weight optical brighteners,

from 7 to 14 % by weight water.

6. A detergent as claimed in Claims 1 to 5, characterized by an additional content of other powder components consisting of per compounds, bleach activators or enzymes and also mixtures thereof.

7. A detergent as claimed in Claims 1 to 6, characterized in that the mixture of all the powder components contains the following constituents :

from 30 to 45 % by weight alumosilicates of formula (I),

from 10 to 20 % by weight surfactants,

from 10 to 25 % by weight per compounds,

from 10 to 50 % by weight other detergent constituents.

8. A process for producing the detergent claimed in Claims 1 to 7, characterized in that a suspension containing from 35 to 50 % by weight alumosilicates of formula (I), from 40 to 60 % by weight water and the other constituents of the 1st powder component is spraydried in known manner and mixed in a ratio of from 1 : 2 to 1 : 7 with the 2nd powder component prepared by spray drying of a suspension of the constituents containing from 50 to 32 % by weight water.

9. A process as claimed in Claim 8, characterized in that the aqueous suspensions of the 1st and 2nd powder components are simultaneously sprayed into a drying tower through separate nozzles.