EP0010247B1 - Phosphate-free washing agent and process for its production - Google Patents

Description

The invention relates to a powdered laundry detergent which contains large amounts of water-insoluble, finely divided alkali metal alumosilicate cation exchangers and small amounts of certain water-soluble organic complexing agents, and an alkali silicate. The invention also relates to a method for producing this powdery agent.

• 0,7-1,5 Me₂O·Al₂O₃· 1,3-4 SiO₂,

und insbesondere der Zusammensetzung

• 0,7-1,1 Me₂0 - Al₂O₃· 1,3-3.3 Si0₂,

jeweils bezogen auf ihre wasserfreie Form, wobei Me Natrium oder Kalium bedeutet. Den Natriumalumosilikaten wird in der Praxis im allgemeinen der Vorzug gegeben. Nach der Lehre der DE-OS 2412837 werden die kationenaustauschenden Alumosilikate zur Verbesserung und Beschleunigung des Waschprozesses mit Vorteil zusammen mit wasserlöslichen Komplexbildnern eingesetzt.Detergents which contain a finely divided, water-insoluble, cation-exchanging alkali alumosilicate as a substitute for phosphate are described in German Offenlegungsschrift 2,412,837. The cation-exchanging properties of these aluminosilicates are evident in their calcium binding capacity, which is at least 50 mg CaO / g of the anhydrous substance and is in particular in the range from 100 to 200 mg CaO / g. The synthetically produced, bound water-containing, crystalline alkali alumosilicates of the composition are preferably used

• 0.7-1.5 Me ₂ O · Al ₂ O ₃ · 1.3-4 SiO _2,

and especially the composition

• 0.7-1.1 Me ₂ 0 - Al ₂ O ₃ .1.3-3.3 Si0 ₂ ,

each based on their anhydrous form, where Me means sodium or potassium. In practice, sodium aluminosilicates are generally preferred. According to the teaching of DE-OS 2412837, the cation-exchanging aluminosilicates are advantageously used together with water-soluble complexing agents to improve and accelerate the washing process.

German Offenlegungsschrift 2540510 describes a detergent for cold and 60 ° C washing, which essentially contains 5-20% by weight of a cation-exchanging aluminosilicate, 4-12% by weight of a surfactant component made from paraffin sulfonate and olefin sulfonate and 12-30% by weight .-% of a sodium silicate of the composition Na ₂ O · 1.6-2.8 Si0 ₂ , and preferably no soluble complexing agents, especially no detergent phosphates. However, this detergent has an unsatisfactory primary and secondary washing ability at all washing temperatures. The properties of this detergent cannot be significantly improved either by adding an active oxygen compound and when used under the conditions of the hot wash.

The revision of the teaching of German Offenlegungsschrift 2656009, which contains a phosphate-free detergent containing 12-25% by weight of a water-insoluble aluminosilicate zeolite, in particular of type 4A, 12-25% by weight sodium perborate or - leads to a similar result. percarbonate, 5-20% by weight of a sodium silicate of the composition Na ₂ O. 1 -3.2 Si0 ₂ , and 5-25% by weight of a conventional alkylbenzenesulfonate surfactant. According to the information in this reference, undesired deposits of the water-insoluble zeolite particles on the laundry are to be prevented by a detergent with this combination. In these agents, which are preferably produced by spray drying, the presence of an additional water-soluble builder is not provided; however, phosphorus-free organic and inorganic builders, such as. As alkali carbonate, borax, sodium nitrilotriacetate, sodium citrate, etc. may be present.

A further phosphate-free textile detergent based on the finely divided water-insoluble aluminum silicate cation exchangers, as well as the so-called washing alkalis, in particular the alkali carbonates and the alkali silicates, the latter in amounts of at least 3% by weight as a conventional water glass, is more organic from German Offenlegungsschrift 2 547 389 Complexing salts from the group of alkali metal salts of phosphorus-free polymeric polycarboxylic acids and phcphonic acids, and a surfactant component consisting of nonionic surfactants and optionally anionic surfactants are known. This detergent contains 0.1-2 parts by weight of the organic complexing agent per 1 part by weight of the water-insoluble aluminosilicate, based on the anhydrous compound.

The fact that residues of these water-insoluble particles would be observed on the washed textiles can be problematic when incorporating conventional alkali silicates into detergents which contain large amounts of water-insoluble aluminosilicate cation exchangers, because residues of these water-insoluble particles would then be observed on the washed textiles known. According to the teaching of this publication, this disadvantage is related to the use of a conventional alkali silicate, in particular oinesodium silicate of the composition Na ₂ O.2.0-3.4 Si0 ₂ , in small amounts of approximately 0.5-3% by weight on the entire detergent formulation - avoided. The effect found is described in this reference using detergent examples which, in addition to 18% by weight of the water-insoluble aluminosilicate, contain 24% by weight sodium triphosphate and 1-3% by weight Na ₂ O. 3.2 SiO ₂ and conventional surfactants, and which have been produced by spray drying,

Comparable washing results should also be obtained if, instead of the sodium triphosphate, other builder substances, such as. As sodium pyrophosphate or sodium nitrifotriacetate, specific polyphosphonates, such as. B. the alkali salts of ethane-1-hydroxy-1,1-diphosphonic acid or ethane-1,1,2-triphosphonic acid, or polyacetates, such as. B. sodium ethylenediaminetetraacetate and sodium nitrilotriacetate, carboxylates such as. 8. the alkali citrates, polycarboxylates, such as. B. polymeric compounds based on maleic acid, and inorganic salts such as alkali carbonates and bicarbonates, in amounts of 5-50, preferably 10-55 wt .-%, based on the total detergent, are used.

From the German Offenlegungsschrift 2542704, detergents containing water-insoluble aluminosilicate cation exchangers and alkali pyrophosphate are known as soluble framework substances. These agents contain an alkali silicate of the composition M ₂ O.1.6-4 SiO ₂ (M stands for sodium or potassium), which has been converted into a polymer with certain poorly soluble properties by dehydration. This measure ensures that when the wash liquor is prepared, the pyrophosphate first reacts with the hardness constituents of the water and this precipitates before the silicate polymer is split into a more soluble product by rehydration. The polymeric, sparingly soluble alkali silicate can be contained in the known detergents in amounts of 1-30% by weight, the water-insoluble aluminosilicate in amounts of 1-40% by weight.

Finally, German Offenlegungsschrift 2711 375 describes a powder detergent which contains no tripolyphosphate and pyrophosphate builders. As a builder, this agent can contain 5-50% by weight of a water-insoluble aluminosilicate cation exchanger in combination with 4-40% by weight of a magnesium ion-insensitive surfactant and larger amounts (approximately 13-40% by weight) of a readily soluble alkali silicate Composition M ₂ O · 1.4-2.7 SiO ₂ (where M means sodium or potassium). The magnesium ions in the wash solution are to be bound with this alkali silicate, which is used in larger quantities. To produce the solid powder detergents and cleaners in this reference, the constituents are mixed in an aqueous batch and preferably spray-dried. The detergent of Example 1 of DE-OS 2 711 375 is produced in two parts.

The subject of the applicant's older, unpublished German patent application P 2 814 083.2 is already a further developed phosphate-free, bleaching detergent based on cation-exchanging alkali alumosilicate, which, in addition to a selected surfactant component, certain water-soluble organic complexing agents of the type of the substituted phosphonic acids and their alkali salts selected from the group of the substituted alkane and triphosphonic acids in amounts of less than 1 wt .-% total. The compositions of this earlier patent application can additionally contain customary water-soluble sodium silicates of the composition Na ₂ O.1-3.5 SiO ₂ , in particular of the composition Na _2, in amounts of up to 7% by weight, preferably in amounts of 2-5% by weight O: SiO ₂ as 1: 2 to 1: 3.35, as a corrosion inhibitor.

As is known, the alkali silicates and, in particular, the sodium silicates thereof perform a number of functions as detergent constituents. The most important properties of alkali silicates include their effect as alkali carriers and buffer substances, the promotion of dirt detachment by means of the same electrostatic charge on the surfaces of the fibers and the dirt particles, the ability to emulsify and disperse the dirt, and the ability to trace heavy metals, especially iron and manganese to be removed from the wash water and thus to stabilize the perborate present, but also to bind the hardness formers of the water to a certain extent. Another chemical property of great importance when using modern detergents is the effect of the alkali silicates as corrosion inhibitors on the metal parts of the washing machines. Finally, another important property of the alkali silicates in the production of detergent powders by the process of hot spray drying is the positive influence on the strength of the resulting hollow spherical particles.

It has been shown that the finely divided cation-exchanging alkali alumosilicates, if they are used in large amounts in detergents to substitute the phosphates, assume the majority of the functions of the alkali silicate mentioned. E: However, it has also been shown that in order to avoid corrosion in the washing machines, detergents based on the water-insoluble aluminosilicates cannot do without alkali silicate.

The aim of the present invention is to further develop the use of the _'cation exchanging alkali metal alumosilicates in detergent compositions and to completely dispense with the usual detergent phosphates. A particular object of the present invention is to have the small amounts of alkali silicate required for corrosion inhibition present in the powder detergent in such a form that even when these agents are used under very critical washing conditions, residues such as those described below are found on the washed textiles of the prior art literature discussed above are not to be feared. - In particular to achieve this aim of the invention, the teachings of the prior art, which deal with the incorporation and functioning of alkali metal silicate in detergents containing aluminosilicate, could not provide any useful suggestions. It is also an object of the invention to increase the proportion of to keep water-soluble complexing agents, the presence of which in the detergents containing aluminosilicate important for achieving rapid water softening and a good washing result, so low that they do not pollute the waste water.

Finally, it is also an object of the invention, the phosphate-free detergent, which is the subject of the older German patent application P 2 814 083.2. To develop so that it not only has a good primary and secondary washing power, a good bleaching action and excellent fabric-protecting properties, but also in terms of residue formation is not inferior to the usual phosphate-containing detergents, which consist practically exclusively of water-soluble components.

It has been found that these and other objectives can be achieved with a phosphate-free detergent based on larger amounts of water-insoluble, cation-exchanging alkali aluminum silicate, water-soluble complexing agent salts, surfactants and small amounts of an alkali silicate, if a water-soluble, solid alkali silicate with a certain composition and with certain properties is available.

• (i) 20-65 Gew.-% eines wasserunlöslichen, feinverteilten, synthetisch hergestellten, kristallinen, gebundenes Wasser enthaltenden Alkalialumosilikats der Formel
  • 0.7-1,5 Me₂O . Al₂O₃ · 1,3-4,0 SiO₂,
  
  bezogen auf die wasserfreie Aktivsubstanz, das ein nach der in der Beschreibung angegebenen Bestimmungsmethode bei 22° C ermitteltes Calciumbindevermögen von 50 bis 200, vorzugsweise 100 bis 200 mg CaO/g wasserfreier Aktivsubstanz besitzt, und wobei in der Formel Me Natrium oder Kalium bedeutet:
• (ii) 5-30 Gew.-% einer Tensidkomponente, bestehend aus- wenigstens einem synthetischen anionischen, nichtionischen, amphoteren oder zwitterionischen Tensid, und gegebenenfalls schauminhibierenden Zusätzen; und
• (iii) 1-7, vorzugsweise 2-5 und insbesondere 2-3 Gew.-% eines festen, pulverförmigen Natriumsilikats der molaren Zusammensetzung Na₂O · 2,0-2,2 SiO₂, das einen Wassergehalt von 15-23, vorzugsweise von 18-21 Gew.-% aufweist, und dessen Löslichkeit in Wasser beim Bereiten einer 5%igen wäßrigen Lösung - indem man zu 95 g vorgelegtem Wasser von 20°C unter gleichförmigem Rühren mit etwa 180-200 Upm 5 g des Natriumsilikats auf einmal hinzugibt - nach 1 Minute mindestens 75 Gew.-%, vorzugsweise mindestens 85 Gew.-%, nach 3 Minuten mindestens 95 Gew.-%, und nach spätestens 25 Minuten 100 Gew.-% beträgt; und
• (iv) 0,05-0,75, vorzugsweise 0,2 bis 0,6 Gew.-% eines wasserlöslichen, organischen Komplexbildners aus der Gruppe der substituierten Alkandi- und -triphosphonsäuren in Form der Alkali- oder Erdalkalisalze;

wobei das Waschmittel ein Gemisch aus wenigstens 2 Pulverbestandteilen A) und B) darstellt, von denen

• A) ein durch Heißtrocknung einer wäßrigen Aufschlämmung der Bestandteile hergestellter Pulverbestandteil ist, der das wasserunlösliche Alkalialumosilikat gemäß (i), die Tensidkomponente gemäß (ii), gegebenenfalls ohne die oder einen Teil der nichtionischen Tenside, sowie gegebenenfalls die wasserlöslichen organischen komplexbildenden Gerüstsubstanzen gemäß (iv), enthält; und worin
• B) ein Pulverbestandteil ist, der das Natriumsilikatpulver gemäß (iii), gegebenenfalls zusammen mit den wasserlöslichen organischen komplexbildenden Gerüstsubstanzen gemäß (iv) und gegebenenfalls zusammen mit heißtrocknungsempfindlichen nichtionischen Tensiden sowie gegebenenfalls weiteren hydrolyse- und temperaturempfindlichen Waschmittelzusätzen, enthält.

The invention accordingly relates to a phosphate-free, water-insoluble aluminosilicate cation exchanger, surfactants, water-soluble complex-forming framework substances, small amounts of an alkali silicate and optionally a detergent containing a peroxy bleaching component, characterized in that it contains the following constituents:

• (i) 20-65% by weight of a water-insoluble, finely divided, synthetically produced, crystalline, bound water-containing alkali alumosilicate of the formula
  • 0.7-1.5 Me ₂ O. Al ₂ O ₃ .1.3-4.0 SiO ₂ ,
  
  based on the anhydrous active substance, which has a calcium binding capacity of 50 to 200, preferably 100 to 200 mg CaO / g of anhydrous active substance, determined at 22 ° C. using the determination method specified in the description, and in the formula Me means sodium or potassium:
• (ii) 5-30% by weight of a surfactant component consisting of at least one synthetic anionic, nonionic, amphoteric or zwitterionic surfactant and optionally foam-inhibiting additives; and
• (iii) 1-7, preferably 2-5 and in particular 2-3% by weight of a solid, powdered sodium silicate of the molar composition Na ₂ O.2.0-2.2 SiO ₂ , which has a water content of 15-23, preferably of 18-21% by weight, and its solubility in water when preparing a 5% aqueous solution - by adding 5 g of the sodium silicate to 95 g of water at 20 ° C. with uniform stirring at about 180-200 rpm once added - is at least 75% by weight after 1 minute, preferably at least 85% by weight, at least 95% by weight after 3 minutes, and 100% by weight after 25 minutes at the latest; and
• (iv) 0.05-0.75, preferably 0.2 to 0.6% by weight of a water-soluble, organic complexing agent from the group of substituted alkanedi- and triphosphonic acids in the form of the alkali or alkaline earth metal salts;

wherein the detergent is a mixture of at least 2 powder components A) and B), of which

• A) is a powder component produced by hot drying an aqueous slurry of the components, which contains the water-insoluble alkali alumosilicate according to (i), the surfactant component according to (ii), optionally without or some of the nonionic surfactants, and optionally the water-soluble organic complex-forming framework substances according to (iv ), contains; and in what
• B) is a powder constituent which contains the sodium silicate powder according to (iii), optionally together with the water-soluble organic complex-forming scaffolding substances according to (iv) and optionally together with non-ionic surfactants sensitive to drying and optionally further hydrolysis- and temperature-sensitive detergent additives.

The sodium silicate powder according to (iii) generally has a bulk density of 350-800 g / l, preferably 350 to 450 g / l and in particular approximately 400 g / l, its particle size distribution is in the range from 1 mm to 0.05 mm, wherein at least 80% of the particles are smaller than 0.5 mm.

Such readily water-soluble sodium silicate powder can be produced by spray drying or roller drying an aqueous 35-50% solution at a temperature of 100 to 120 ° C. in spray drying and 100 to 140 ° C. in roller drying. Particularly preferred detergents contain a roller-dried sodium silicate, which has been prepared by drying a 40 to 50% strength aqueous solution on a heated roller at 100 to 140 ° C. to a residual water content of 15-23, in particular 18 to 21,% by weight . Such a product is adjusted to a bulk density of 350-450 g / l, in particular about 400 g / l. It owns excellent solubility properties, so that after the solubility test given above it is already at least 99% dissolved in cold water at 20 ° C after 3 minutes. A product with these properties is commercially available under the name Portil AW.

It has been found that the use of the agents according to the invention for washing textiles not only achieves a good primary and secondary action, but also does not give rise to the problem of residue formation on the washed textiles discussed by experts. Surprisingly, it was rather observed that, with various types of residue determination methods, measured values were obtained which were more favorable with the agents according to the invention than with a comparative detergent which was composed only of water-soluble compounds.

An optimal washing effect, tissue protection during the washing in the presence of bleaching active oxygen compounds and perborate stability is achieved despite the absence of conventional stabilizers such as magnesium silicate and aminopolycarboxylates - as with the agents of the older German patent application P 2 814 083.2 -, which indicates the contribution of a minor addition of 0.05-0.75, preferably 0.2-0.6% by weight of the water-soluble, organic complexing agent from the group of substituted alkanedi- and triphosphonic acids, which are present in the form of the alkali or alkaline earth metal salts.

These organic complexing agents from the group of substituted alkanedi- and triphosphonic acids - which also include heterocyclically substituted compounds - include in particular those alkanedi- and triphosphonic acids or their alkali and Erdafkalisalze, whose alkane group by the hydroxyl, amino, phenyl or is substituted by a phenyl group carrying hydroxyl, amino or halogen groups. The alkane and triphosphonates from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 3-amino-1-hydroxypropane-1,1-diphosphonic acid, 1-amino are particularly preferred -1-p-chlorophenylmethane-1,1-diphosphonic acid, 1-hydroxy-1-p-chlorophenylmethane-1,1-diphosphonic acid, 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid, 1-hydroxybutane-1 , 1-diphosphonic acid and aminotrimethylene triphosphonic acid in the form of their alkali metal salts, in particular the sodium salts. Of these compounds, the sodium and calcium salts of 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxybutane 1,1-diphosphonic acid and aminotrimethylene triphosphonic acid are particularly preferred.

• a) 20-40 Gew.-% eines wasserunlöslichen, feinverteilten. synthetisch hergestellten, kristallinen, gebundenes Wasser enthaltenden Alkalialumosilikats der Formel
  • 0,7-1,5 Me₂O - Al₂O₃ · 1,3-4,0 SiO₂,
  
  bezogen auf die wasserfreie Aktivsubstanz=AS, das ein Calciumbindevermögen von 50-200, vorzugsweise 100-200 mg CaO/g AS besitzt, und wobei Me Natrium oder Kalium bedeutet;
• b) 5-20 Gew.-% einer Tensidkomponente, bestehend aus wenigstens einem anionischen, nichtionischen, amphoteren oder zwitterionischen Tensid, und gegebenenfalls schauminhibierenden Zusätzen;
• c) 0,05-0,75, vorzugsweise 0,2-0,6 Gew.-% eines organischen Komplexbildners aus der Gruppe der substituierten Alkandi- und -triphosphonsäuren und deren Alkalisalze;
• d) 10-35 Gew.-% einer anorganischen Perverbindung; und .
• e) bis zu 7 Gew.-% eines wasserlöslichen Natriumsilikats der Zusammensetzung Na₂O · 1-3,5 SiO₂,

und sind dadurch gekennzeichnet, daß sie als Komponente e) 2-5, insbesondere 2-3 Gew.-% eines festen, pulverförmigen Natriumsilikats der molaren Zusammensetzung Na₂O · 2,0-2,2 SiO₂, das einen Wassergehalt von 15-23, vorzugsweise 18-21 Gew.-% aufweist, und dessen Löslichkeit in Wasser beim Zubereiten einer 5%igen wäßrigen Lösung, indem man zu 95 g vorgelegtem Wasser von 20° C unter gleichförmigem Rühren bei etwa 180-200 Upm 5 g des Natriumsilikats auf einmal hinzugibt. nach 3 Minuten mindestens 99 Gew.-% beträgt, gemäß der oben definierten Komponente (iii) enthalten,
wobei das Waschmittel als Gemisch aus den drei Pulverbestandteilen A, B und C gemäß obiger Definition vorliegt und wobei die Komponente c) als Alkali- oder Erdalkalisalz vorhanden ist. In diesem Kochwaschmittel liegt demnach die anorganische Perverbindung als weiterer dritter Pulverbestandteil C vor, während der organische Phosphonatkomplexbildner sowohl im sprühgetrockneten Pulverbestandteil A enthalten als auch zusammen mit dem pulverförmigen Natriumsilikat bzw. dem Natriumperborat zugemischt sein kann. Die optimalen Eigenschaften des erfindungsgemäßen Waschmittels werden vor allem dann erreicht, wenn der organische Phosphonatkomplexbildner zusammen mit dem pulverförmigen Natriumsilikat bzw. dem Natriumborat vermischt, d. h. als Komponente der oben definierten Pulverbostandteile B oder C vorhanden ist. Bei einer Herstellung des Waschmittels in großtechnischem Maßstab wird im allgemeinen aus wirtschaftlichen Erwägungen derjenigen Variante, bei der die geringen Mengen an den oben definierten Phosphonatkomplexbildnern im durch Heißzerstäuben getrockneten Pulverbestandteil A enthalten sind, der Vorzug gegeben.The detergents according to the invention are used with particular advantage for the laundry and therefore preferably contain a peroxy bleach component. especially perborate. This bleaching component is present as a further powder component C) of the agent. Preferred cooking detergents contain - in a further development of the agents of the older German patent application P 2 814 083.2 - the following components:

• a) 20-40 wt .-% of a water-insoluble, finely divided. synthetically produced, crystalline, bound water-containing alkali alumosilicate of the formula
  • 0.7-1.5 Me ₂ O - Al ₂ O ₃ .1.3-4.0 SiO ₂ ,
  
  based on the anhydrous active substance = AS, which has a calcium binding capacity of 50-200, preferably 100-200 mg CaO / g AS, and where Me is sodium or potassium;
• b) 5-20% by weight of a surfactant component consisting of at least one anionic, nonionic, amphoteric or zwitterionic surfactant and optionally foam-inhibiting additives;
• c) 0.05-0.75, preferably 0.2-0.6% by weight of an organic complexing agent from the group of substituted alkanedi- and triphosphonic acids and their alkali salts;
• d) 10-35% by weight of an inorganic per compound; and .
• e) up to 7% by weight of a water-soluble sodium silicate of the composition Na ₂ O.1-3.5 SiO ₂ ,

and are characterized in that they contain as component e) 2-5, in particular 2-3% by weight of a solid, powdered sodium silicate of the molar composition Na ₂ O.2.0-2.2 SiO ₂ , which has a water content of 15 -23, preferably 18-21 wt .-%, and its solubility in water when preparing a 5% aqueous solution by adding to 95 g of water at 20 ° C with uniform stirring at about 180-200 rpm 5 g of Add sodium silicate all at once. after 3 minutes is at least 99% by weight, according to component (iii) defined above,
wherein the detergent is present as a mixture of the three powder components A, B and C as defined above and wherein component c) is present as an alkali or alkaline earth metal salt. Accordingly, the inorganic per-compound is present in this cooking detergent as a further third powder constituent C, while the organic phosphonate complexing agent is both contained in the spray-dried powder constituent A and can also be admixed together with the powdered sodium silicate or the sodium perborate. The optimal properties of the detergent according to the invention are achieved especially when the organic phosphonate complexing agent is mixed together with the powdered sodium silicate or sodium borate, ie as Component of the powder component B or C defined above is present. When the detergent is produced on an industrial scale, preference is generally given, for economic reasons, to the variant in which the small amounts of the phosphonate complexing agents defined above are contained in the powder component A dried by hot atomization.

• a) 30-40 Gew.-% eines wasserunlöslichen, feinverteilten, synthetisch hergestellten, kristallinen, gebundenes Wasser enthaltenden Natriumalumosilikats vom Typ des Zeoliths NaA mit einem Calciumbindevermögen von 100-200 mg CaO/g, bezogen auf die wasserfreie Substanz, und einerTeilchengröße von < 30µm und zu wenigstens 80% von 8-0,01 µm;
• b) 10 - 20 Gew.-% einer Tensidkomponente. bestehend aus wenigstens einem anionischen und/oder nichtionischen Tensid, und gegebenenfalls schauminhibierenden Zusätzen;
• c) 1,00-2,55 Gew.-% einer Stabilisatorkombination, bestehend aus:
  • c1) 0,05-0,75 Gew.-% eines organischen Komplexbildners aus der Gruppe der substituierten Alkandi- und -triphosphonsäuren, die in Form ihrer Alkali- und/oder Erdalkalisalze vorliegen,
  • c2) 0,8-1,5 Gew.-% Magnesiumsilikat, und
  • c3) 0,15-0,3 Gew.-% Ethylendiamintetraessigsäure-Natriumsalz,
  • jeweils bezogen auf das gesamte Waschmittel,
• d) 18-22 Gew.-% Natriumperborat-Tetrahydrat, und
• e) 2-3 Gew.-% eines festen, pulverförmigen Natriumsilikats der molaren Zusammensetzung Na₂O · 2,0-2,2 SiO₂, das einen Wassergehalt von 15-23, vorzugsweise 18-21 Gew.-% aufweist, und dessen Löslichkeit in Wasser beim Zubereiten einer 5%igen wäßrigen Lösung, indem man zu 95 g vorgelegtem Wasser von 20°C unter gleichförmigem Rühren bei etwa 180-200 Upm 5 g des Natriumsilikats auf einmal hinzugibt, nach 3 Minuten mindestens 99 Gew.-% beträgt,

wobei das Waschmittel als Gemisch aus den drei Pulverbestandteilen A), B) und C) vorliegt, von denen

• . A) ein durch Heißzerstäubungstrocknen einer wäßrigen Aufschlämmung der Bestandteile hergestellter Pulverbestandteil ist, der das wasserunlösliche Natriumalumosilikat a), die Tensidkomponente gemäß b), gegebenenfalls ohne einen Teil der nichtionischen Tenside, sowie die Stabilisatorkombination gemäß c) enthält;
• B) ein Pulverbestandteil ist, der das Natriumsilikatpulver gemäß e), gegebenenfalls zusammen mit heißtrocknungsempfindlichen nichtionischen Tensiden sowie gegebenenfalls weiteren hydrolyse- und temperaturempfindlichen Waschmittelzusätzen, enthält; und worin
• C) der aus der Peroxybleichkomponente Natriumperborat bestehende dritte weitere Pulverbestandteil ist.

So that a detergent produced in this way, which also contains optical brighteners of the diaminostilbenesulfonic acid type, has the properties of a conventional high-phosphate cooking detergent with regard to washing action, tissue protection and perborate stability, it was found that the phosphonate complexing agents defined above are part of a stabilizer combination in the powder component dried by hot atomization (tower powder) and must be present together with a more limited amount of sodium perborate in the detergent. This detergent therefore contains

• a) 30-40% by weight of a water-insoluble, finely divided, synthetically produced, crystalline, bound water-containing sodium aluminosilicate of the zeolite NaA type with a calcium binding capacity of 100-200 mg CaO / g, based on the anhydrous substance, and a particle size of < 30 µm and at least 80% of 8-0.01 µm;
• b) 10-20% by weight of a surfactant component. consisting of at least one anionic and / or nonionic surfactant, and optionally foam-inhibiting additives;
• c) 1.00-2.55% by weight of a stabilizer combination consisting of:
  • c1) 0.05-0.75% by weight of an organic complexing agent from the group of substituted alkanedi- and triphosphonic acids, which are present in the form of their alkali and / or alkaline earth metal salts,
  • c2) 0.8-1.5% by weight magnesium silicate, and
  • c3) 0.15-0.3% by weight of sodium ethylenediaminetetraacetic acid,
  • each based on the total detergent,
• d) 18-22% by weight sodium perborate tetrahydrate, and
• e) 2-3% by weight of a solid, powdered sodium silicate of the molar composition Na ₂ O.2.0-2.2 SiO ₂ , which has a water content of 15-23, preferably 18-21% by weight, and whose solubility in water when preparing a 5% aqueous solution by adding 5 g of the sodium silicate at once to 95 g of water at 20 ° C. with uniform stirring at about 180-200 rpm, after at least 99% by weight after 3 minutes amounts to

wherein the detergent is present as a mixture of the three powder components A), B) and C), of which

• . A) is a powder constituent which is produced by hot atomization drying of an aqueous slurry of the constituents and which contains the water-insoluble sodium aluminosilicate a), the surfactant component according to b), optionally without part of the nonionic surfactants, and the stabilizer combination according to c);
• B) is a powder component which contains the sodium silicate powder according to e), optionally together with nonionic surfactants sensitive to drying and optionally further hydrolysis and temperature-sensitive detergent additives; and in what
• C) the third additional powder constituent consisting of the peroxy bleach component sodium perborate.

As already stated, the detergent in powder component A) preferably contains conventional optical brighteners in the usual amounts.

• 0,7-1,1 Na₂O · 1,0Al₂O₃ · 1,3-2.4 SiO₂,

deren Wassergehalt je nach den Verarbeitungsbedingungen schwanken kann und im fertigen Waschpulver im allgemeinen bei 18-22 Gew.-% liegt. Derartige Alumosilikate werden u. a. auch als »Zeolith NaA« bezeichnet. Insbesondere werden solche Produkte dieser Zusammensetzung und Kristallstruktur eingesetzt, bei deren Herstellung durch geeignete Auswahl der Ansatzbedingungen dafür gesorgt wurde, daß die resultierenden Kristallite abgerundete Ecken und Kanten aufweisen und ihre Teilchengröße unterhalb 30 µm und zu wenigstens 80% im Bereich von 8-0,01 µm liegt, und der mittlere Teilchendurchmesser 3-6 µm beträgt. Derartige Alumosilikate mit abgerundeten Ecken und Kanten werden in der DE-OS 2 531 342 beschrieben.Suitable cation-exchanging alkali alumosilicates (i) or a) are in principle the crystalline products described in DE-OS 2412837 mentioned above, which generally have particle sizes below 50 μ, essentially below 40 μ and mostly in the range from 20-0.1 µ have. It is advantageous to use crystalline sodium aluminosilicates of the composition containing bound water in the agents according to the invention

• 0.7-1.1 Na ₂ O · 1,0Al ₂ O ₃ · SiO ₂ 1,3-2.4,

whose water content can fluctuate depending on the processing conditions and is generally 18-22% by weight in the finished washing powder. Such aluminosilicates are also referred to as “zeolite NaA”. In particular, products of this composition and crystal structure are used, in the production of which, by suitable selection of the starting conditions, it was ensured that the resulting crystallites have rounded corners and edges and their particle size below 30 μm and at least 80% in the range of 8-0.01 µm, and the average particle diameter is 3-6 µm. Such aluminosilicates with rounded corners and edges are described in DE-OS 2 531 342.

According to the observations of the assignee, when using the detergent according to the invention under the conditions of hot washing in the washing machine, both the calcium and the mugneslumions of the washing water - which are generally present in the Ca: Mg ratio in the ratio Ca: Mg such as about 5: 1 - by the way Alumosilicate bound. Trouble-free removal of calcium hardness and magnesium hardness is also achieved in artificially prepared hot wash liquors of 16 ° d and a ratio of calcium to magnesium ions of 1: 1.

• 0,7-1,35Na₂O · 1,0Al₂O₃ · 1,3-2.4SiO₂

einsetzt, das ein binäres Gemisch von 40 - 90% Partikeln des Zeoliths NaA und 10 bis 600% Partikeln des Zeoliths HS (Hydrosodalith) darstellt. Ein derartiges Alumosilikat weist in der erwärmten Waschflotte bereits ab einer Temperatur von 50°C ein Calciumbindevermögen von 100-165 mg CaO/g und ein Magnesiumbindevermögen von 50-110 mg MgO/g - jeweils bezogen auf die wasserfreie Substanz - auf. Diese Alumosilikat-Gemische, ihre Herstellung und ihre Verwendung in Wasch- und Reinigungsmitteln sind in der DE-OS 2 543 941 beschrieben, auf die als Offenbarung im Rahmen dieser Erfindung ebenfalls ausdrücklich Bezug genommen wird.An accelerated removal of the magnesium hardness, which already begins considerably below the boiling temperature, can be achieved if a sodium aluminosilicate of the composition is used

• 0,7-1,35Na ₂ O · 1,0Al ₂ O ₃ · ₂ 1,3-2.4SiO

used, which is a binary mixture of 40 - 90% particles of the zeolite NaA and 10 to 600% particles of the zeolite HS (hydrosodalite). Such an aluminosilicate already has a calcium binding capacity of 100-165 mg CaO / g and a magnesium binding capacity of 50-110 mg MgO / g - in each case based on the anhydrous substance - in the heated wash liquor from a temperature of 50 ° C. These aluminosilicate mixtures, their preparation and their use in detergents and cleaning agents are described in DE-OS 2 543 941, which is also expressly referred to as a disclosure within the scope of this invention.

• (ba1) 1 Gewichtsteil wenigstens eines nichtionischen Tensids aus der Gruppe der ethoxylierten aliphatischen C₁₀-C₂₀-Alkohole mit einem Ethoxylierungsgrad von 2-20;
• (ba2) 0,3-1,75, vorzugsweise 0,3-1,0 Gewichtsteile einer schauminhibierenden Alkaliseife aus C₁₂-C₂₂-Fettsäuren, enthaltend zu mehr als 50 Gew.-% Alkalisalze. von gesättigten. C₁₈-C₂₂-Fettsäuren, und die durch einen nichttensidischen Schauminhibitor im Verhältnis Seife zu nichttensidischem Schauminhibitor wie 25 : 1 bis 2 : 1 teilweise ersetzt sein kann; und
• (ba3) 0,5-6, vorzugsweise 0,8-4 Gewichtsteile eines anionischen Tensids vom Sulfonat- und/oder Sulfat-Typ.

The surfactant component (ii) or b) contained in the detergents according to the invention preferably consists of a combination (ba) of the composition:

• (ba1) 1 part by weight of at least one nonionic surfactant from the group of the ethoxylated aliphatic C ₁₀ -C ₂₀ alcohols with a degree of ethoxylation of 2-20;
• (ba2) 0.3-1.75, preferably 0.3-1.0 parts by weight of a foam-inhibiting alkali soap from C ₁₂ -C ₂₂ fatty acids, containing more than 50% by weight of alkali salts. of saturated. C ₁₈ -C ₂₂ fatty acids, and which can be partially replaced by a non-surfactant foam inhibitor in the ratio of soap to non-surfactant foam inhibitor such as 25: 1 to 2: 1; and
• (ba3) 0.5-6, preferably 0.8-4 parts by weight of an anionic surfactant of the sulfonate and / or sulfate type.

The detergents according to the invention, which contain a surfactant component according to (ba), show an excellent foam regulation during the entire boil washing program and when rinsing out the washing liquor, particularly when used in drum washing machines.

• (bbl) 1 Gewichtsteil wenigstens eines nichtionischen Tensids aus der Gruppe der ethoxylierten aliphatischen C₁₀-C₂₀-Alkohole mit einem Äthoxylierungsgrad von 2-20;
• (bb2) 0,05-0,75 Gewichtsteilen einer schauminhibierenden Alkaliseife aus C₁₂-C₂₂-Fettsäuren, enthaltend zu mehr als 50 Gew.-% Alkalisalze von gesättigten C₁₈-C₂₂-Fettsäuren ; und
• (bb3) 0,05-0,3, vorzugsweise 0,1-0,25 Gewichtsteilen einer Verbindung der Formel
  
  in der X-A- einen C₁₀-C₁₈-Fettsäurerest, oder X einen end- oder innenständigen β-Hydroxy-(C₈-C₂₂)-Alkylrest und in diesem Falle A eine einfache C-N-Vaienz oder einen gegebenenfalls mit Polyethylenglycolethergrup^pen substituierten Aminoalkylen- oder Polyaminopolyalkylenrest, Y Wasserstoff oder den Rest -(CH₂CH₂0)_m-H und n und m jeweils Zahlen zwischen 1 und 3 bedeuten,

Foam-regulated preparations which have the following combination (bb) as surfactant component (ii) or b) are preferred for removing, in particular, hydrophobic soiling

• (bbl) 1 part by weight of at least one nonionic surfactant from the group of the ethoxylated aliphatic C ₁₀ -C ₂₀ alcohols with a degree of ethoxylation of 2-20;
• (bb2) 0.05-0.75 parts by weight of a foam-inhibiting alkali soap from C ₁₂ -C ₂₂ fatty acids, containing more than 50% by weight of alkali salts of saturated C ₁₈ -C ₂₂ fatty acids; and
• (bb3) 0.05-0.3, preferably 0.1-0.25 parts by weight of a compound of the formula
  
  in the XA a C ₁₀ -C ₁₈ fatty acid residue, or X is a terminal or internal β-hydroxy- (C ₈ -C ₂₂₎ alkyl and in this case a simple A-Vaienz CN or an optionally with ^p Polyethylenglycolethergrup s substituted aminoalkylene or polyaminopolyalkylene radical, Y is hydrogen or the radical - (CH ₂ CH ₂ 0) _m -H and n and m each represent numbers between 1 and 3,

consists.

Detergents containing mixtures of the surfactant components (ba) and (bb) are also preferred. Preference is also given to detergents whose surfactant content consists of a mixture of the surfactant component (ba) and a surfactant type (bb3), ie. H. Compounds of the formula I exist, the surfactant type (bb3) being able to make up 5-25% by weight of the surfactant mixture and preferably consisting of coconut fatty acid monoethanolamide.

The anionic surfactants of the sulfonate and / or sulfate type of the surfactant component (ba) preferably consist of alkylbenzenesulfonates and / or of alkanesulfonates. The use of wash-active alkanesulfonates in the context of this surfactant component is particularly preferred in view of their rapid and complete biodegradation in the waste water and because of their low toxicity. It has surprisingly been found that in the detergents according to the invention, which contain a surfactant component (ba) with alkanesulfonate and optical brighteners, the problem known from DE-OS 2504276 of the incompatibility of the alkanesulfonates with the optical brighteners of the 4,4'-bis (triazinylamino) stilbene-2 type which are common in detergents , 2'-disulfonic acids, which lead to a yellow-greenish to yellow-gray discoloration of the detergent powder when it is stored, do not occur, so that the use of alkanesulfonates as anionic surfactants in the context of the invention does not affect the choice of specific alkanesulfonates compatible optical brighteners is bound.

When using the detergents according to the invention with a surfactant component (ba) in the hot wash in drum washing machines, the foam security during washing and rinsing is also ensured if the stated amounts of alkylbenzenesulfonate and / or _' alkanesulfonate up to a third of their amount due to the more foaming anionic Surfactants of the α-sulfofatty acid ester, olefin sulfonate, fatty alcohol sulfate and fatty alcohol polyglycol ether sulfate type, which also have good biodegradability and low toxicity, are replaced.

The nonionic surfactants contained in the combinations (ba) and (bb) from the group of ethoxylated aliphatic C ₁₀ -C ₂₀ alcohols with a degree of ethoxylation of 2-20 preferably consist of binary mixtures of separately produced ethylene oxide addition products with average degrees of ethoxylation on the one hand of 2-7 and on the other hand from 8-20 mol EO and a ratio of the low ethoxylated to the higher ethoxylated compound from 3: 1 to 1: 3.

Preferred nonionic surfactants are those whose aliphatic group is derived from primary alkanols and alkenols and which come from natural and synthetic sources. The ethoxylation products of natural ones are particularly preferred because of their good biodegradability in connection with the easy accessibility. Fatty alcohols with in particular C ₁₂ -C ₁₈ alkyl and alkenyl groups.

Also preferred are the ethoxylation products of the so-called oxo alcohols, which are obtained from olefins by hydroformylation and hydrogenation, and which are primary aliphatic alcohols with an α-methyl branch which does not impair biodegradability. If an ethoxylated fatty alcohol is replaced by an ethoxylated oxo alcohol with the same ratio of the hydrophobic and hydrophilic part of the molecule in the two surfactant components (ba) and (bb) defined above, the washability of hydrophobic dirt is improved with equivalent replacement.

The compounds (bb3) of the formula 1 contained in the surfactant component (bb) are the optionally still ethoxylated addition products of 1 mol of a low-molecular amine, in particular mono- or diethanolamine, ethylenediamine, diethylenetriamine or triethylenetetramine, on 1 mol of one end - Or internal C ₈ -C ₂₂ epoxyalkane, in particular C ₁₀ -C ₁₈ epoxyalkane. These compounds of the formula I have already been described as detergent additives for detergents in German Offenlegungsschrift 2 703 020. Compounds (bb3) of the formula 1 also include the ethanolamides of C ₈ -C ₁₈ fatty acids, preferably C ₁₂ -C ₁₄ fatty acids, and in particular the monoethanolamides, which are also particularly preferred. These compounds of the formula are therefore also to be regarded in the broadest sense as nonionic surfactants.

Ready-formulated compositions of the agents according to the invention generally contain in amounts of 1-50% by weight of further customary additives which improve the utility value, in particular a graying inhibitor, such as, for. B. carboxymethyl cellulose, enzymes, antimicrobials, optical brighteners, fabric softeners, dyes and fragrances, sodium sulfate as filler and water, which is bound in the crystals of the water-soluble salts and in particular in the aluminosilicates, and a proportion of about 2-18% by weight. % of the free-flowing detergent powder.

An essential characteristic of the detergents according to the invention is their presence as a mixture of the powder components A and B defined above, wherein in the case of the detergents with bleaching action there is a further powder component C containing the peroxy bleach component in the mixture.

The invention therefore also relates to a method for producing the detergents defined above. This method comprises in its most general form comprises preparing a powder component by Heißzerstäubungstrocknen an aqueous suspension, producing a further powder component by a variety of this method of drying method and mixing the powder components, optionally with the addition _n a Peroxybieichkompone - te, especially the sodium perborate as a further Powder component, characterized in that the above-defined water-insoluble alkali alumosilicates according to (i) or a), the above-defined surfactant component according to (ii) or b), optionally without the or part of the nonionic surfactants, and optionally the water-soluble complexing builders slurried according to (iv) with water and converted into powder component A by hot atomization, that further the sodium silicate powder defined above according to (iii) or e) optionally with the powdery, water-soluble, complex-forming framework substances according to (iv) mixed and optionally adding drying-sensitive nonionic surfactants and optionally further hydrolysis and temperature-sensitive detergent components to this powder, and the like the resulting powder component B is mixed with the powder component A in a conventional manner, the proportions of A and B being chosen so that the constituents (i), (ii) and (iii) are present in the quantitative ranges given above for the detergent in the resulting mixture .

The process for the preparation of the cooking detergent defined above, which contains a stabilizer combination c) in the tower powder component A, is further characterized in that the aluminosilicate a), the surfactant component b) and the stabilizer combination c), optionally without part of the nonionic surfactants from b ) and preferably optical brighteners and other additives such as graying inhibitors and sodium sulfate, slurried with water and converted into powder component A by hot atomization drying, that the sodium silicate powder defined above according to e) is optionally mixed with non-ionic surfactants sensitive to drying and optionally further hydrolysis and temperature-sensitive detergent components, and the resulting powder component B and the sodium perborate are mixed with the powder component A in a conventional manner, the proportions of A, B and C being chosen so that the constituents a) in the resulting mixture to e) are present in the quantitative ranges specified above for this detergent.

Among the compounds which serve as peroxy bleaching components and which supply H ₂ O ₂ in water, sodium perborate tetrahydrate (NaBO ₂ .H ₂ O ₂ .3H ₂ O) is of particular practical importance; the monohydrate compound (NaBO ₂ .H ₂ O ₂ ) can also be used. However, other H ₂ O ₂ supplying borates are also useful, e.g. B. the perborax Na ₂ B ₄ O ₇ .4 H ₂ O ₂ . These compounds can be partially or completely replaced by other active oxygen carriers, in particular by peroxy hydrates, such as peroxycarbonates (Na ₂ CO ₃ .1.5 H ₂ O ₂ ). Peroxypyrophosphates, citrate perhydrates, urea-H ₂ O ₂ or melamine-H ₂ 0 ₂ compounds as well as peracid salts providing H ₂ 0 ₂ , such as e.g. B. Caroate (KHSOs), Perbenzoate or Peroxyphthala'te to be replaced. Magnesium silicates MgO: Si0 ₂ = 4: 1 to 1: 4, preferably obtained by precipitation from aqueous solutions, are suitable as water-insoluble peroxystabilizers which, as a constituent of the stabilizer combination, preferably make up 0.8 to 1.5% of the weight of the entire preparation 2: 1 to 1: 2 and in particular 1: 1. The water-soluble stabilizers, which are preferably present together with the water-insoluble ones, are the organic heavy metal complexing agents of the amino or iminopolycarboxylic acid type, such as, for. B. the ethylenediaminotetraacetic acid, the diethylenetriaminopentaacetic acid or the iminotriacetic acid and their alkali and / or alkaline earth metal salts into consideration.

To prepare the powder component A, the aluminosilicates are expediently used in their still moist state, for example as an aqueous suspension or as a moist filter cake, and preferably by first adding these moist aluminosilicates, optionally with the addition of further water and a dispersant stable pumpable suspensions with an aluminosilicate content of approx. 40% by weight and above - based on the anhydrous substance - and a content of 0.3-4% by weight of the dispersant.

In principle, preferred dispersants are those compounds which are themselves active detergent constituents, and in particular those which are already intended as components of the agent according to the invention. Particularly preferred within the scope of the present invention as a stabilizing agent for aqueous Suspensione n _'of the aluminosilicates in the surfactant (ba) and (bb) contained ethoxylated aliphatic C ₁₀ -C ₂₀ alcohols with an average degree of ethoxylation of 2-7 mol of EO, or the compound of formula I present in combination (bb) as component (bb3). Pumpable stable aluminosilicate suspensions'u. a. with ethoxylated alcohols such as B. tallow alcohol +5 mot ethylene oxide or fatty acid ethanolamides such. B. lauric acid monoethanolamide as a dispersant are described in DE-OS 2 527 388 in more detail. The optionally ethoxylated adducts of epoxyalkanes and low molecular weight amines of the formula I defined above are described in detail in DE-OS 2 702 979 as dispersants for aluminosilicate suspensions.

The suspensions produced by mixing aluminosilicate, water and dispersant are notable for their high stability; they can be stored at room temperature or at higher temperatures, transported through pipelines, in tankers or in some other way before they are used in the process according to the invention for the preparation of powder component A). In general, the remaining constituents of powder component A) are introduced into the initially prepared suspensions of the aluminosilicate and the resulting aqueous, flowable mixture is subjected to spray drying. If the low ethoxylated aliphatic alcohols of the surfactant components and the compounds of the formula I of the surfactant component (bb) have not been used completely as suspension aids, their incorporation into the powder component B) is recommended, for example by spraying, because of their mostly liquid-viscous nature the silicate powder (iii).

As already stated, the aluminosilicates to be used are synthetic crystalline products; Mixtures of crystalline and amorphous products or semi-crystalline products can of course also be used for the purposes of the invention.

The preparation of the aluminosilicates can e.g. B. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed together or a solution in the solid state Component are reacted with the other component present as an aqueous solution. The desired aluminosilicates are also obtained by mixing the two components present in the solid state in the presence of water. Alurnosilicates can also be produced from Al (OH) ₃ , Al ₂ O ₃ or SiO ₂ by reaction with alkali silicate or aluminate solutions. The production can also be carried out by other known processes.

• 0,7-1,1 Na₂O · Al₂O₃ · 1,3-3,3 SiO₂.

Preferred aluminosilicates have a calcium binding capacity in the range of about 100-200 mg CaO / g ai, mostly about 100-180 mg CaO / g ai; this is found above all in compounds of the composition

• 0.7-1.1 Na ₂ O.Al ₂ O ₃ .1.3-3.3 SiO ₂ .

• 0,7-1,1 Na₂O · Al₂O₃ · 1,3-2,4SiO₂
• 0,7-1,1 Na₂O · Al₂O₃ · >2,4-3,3 SiO₂.

This empirical formula comprises two types of different crystal structures, which also differ in their empirical formulas. They are:

• 0.7-1.1 Na ₂ O. Al ₂ O ₃ · ₂ 1,3-2,4SiO
• 0.7-1.1 Na ₂ O.Al ₂ O _3. > 2.4-3.3 SiO ₂ .

The different crystal structures are shown in the X-ray diffraction diagram. For the manufacture, characterization and use for washing and cleaning these types of aluminosilicate, also referred to as zeolites NaA and NaX, reference is made to DE-OS 2 412 837.

The aluminosilicates, which are initially still moist from their manufacture and which can be present as aqueous suspensions or moist filter cakes, can be converted into dry powders in the customary manner by first mechanically removing part of the water and then drying them, e.g. B. at temperatures of 50-400 ° C. Depending on the drying conditions, the powder product, which looks dry on the outside, contains more or less, usually 5-35% by weight of bound water. Expediently, drying does not exceed 200 ° C. if the aluminosilicate is intended for use in detergents and cleaning agents; such aluminosilicate powders have a water content of about 18-22% by weight. However, the aluminosilicates do not need to be dried at all after their production if, according to the teaching of DE-OS 2 527 388, they are converted into a stable suspension with a certain dispersant and water and used for further processing into detergents. In addition to saving energy by eliminating the drying stage, this processing mode practically completely avoids agglomeration of the primary particles into undesirable larger particles (secondary particles), as is observed in conventional drying and therefore requires grinding and sieving measures.

With all information on the water or solids content or the content of active substance (= AS) of the aluminosilicates, however, reference is made to their condition, which is reached after drying for one hour at 800 ° C. During this drying, the adhering and bound water is practically completely removed. This reference value of the aluminosilicate dried at 800 ° C for 1 hour is particularly important for strengthening the calcium binding capacity.

The calcium binding capacity of the aluminosilicates is determined by adding 1 g of an aqueous solution containing 0.594 g CaCl ₂ (= 300 mg CaO / I = 30 ° dH) and diluted NaOH to a pH of 10 with 1 g aluminosilicate ( based on AS) and then the suspension is stirred vigorously for 15 min at a temperature of 22 or 50 or 90 ° C. After filtering off the aluminosilicate, the residual hardness x of the filtrate is determined. From this, the calcium binding capacity for the aluminosilicate is calculated to be (30-x) · 10 mg CaO / g AS.

For the determination of the magnesium-binding capacity in a manner analogous to an aqueous, 1.0877 g of MgCl ₂ · 6H ₂ O solution containing per liter (= 215 mg MgO / I = 30 ° d MgO) is used. The magnesium binding capacity is calculated as (30-x) 7.19 mg MgO / g AS.

The particle sizes of the aluminosilicates can e.g. B. determine by means of sedimentation analysis.

The surfactants contained in the agents according to the invention have at least one hydrophobic organic residue and one anionic, amphoteric or zwitterionic or nonionic group which makes water soluble. The hydrophobic radical is usually an aliphatic hydrocarbon radical with 8-26, preferably 10-22 and in particular 12-18 C atoms or an alkyl aromatic radical with 6-18, preferably 8-16 aliphatic C atoms.

Suitable synthetic anionic surfactants are in particular those of the sulfonate and sulfate type.

Cocos-, Palmkern- oder Talgfettsäuren, sowie die Olefinsulfonate, d. h. Gemiche aus Alien und Hydroxyalkansulfonaten sowie Disuifonaten, wie man sie beispielsweise aus Monoolefin mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließender alkalischer oder saurer Hydrolyse der Sulfonierungsprodukte erhält.Suitable surfactants of the sulfonate type are the alkylbenzenesulfonates with C _9-15 -alkyl groups and the alkanesulfonates which are obtainable from C ₁₂ -C ₁₃ -alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralisates or by bisulfite addition to olefins Consider. Other usable tonsides from the sulfant type are the esters of α-sulfo fatty acids, e.g. B. the α-sulfated methyl or ethyl ester of

Coconut, palm kernel or tallow fatty acids, as well as the olefin sulfonates, ie mixtures of alien and hydroxyalkanesulfonates and disulfonates, such as those obtained from monoolefin with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is obtained.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols such as. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol. Lauryl, myristyl, palmityl or stearyl alcohol, or the C ₁₀ - C ₂₀ oxo alcohols, and those secondary alcohols of this chain length.

The sulfuric acid monoesters of the aliphatic primary alcohols ethoxylated with 1-6 mol ethylene oxide or ethoxylated secondary alcohols or alkylphenols are also suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.

The anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.

The nonionic surfactants suitable according to the invention are the adducts of 1-40, preferably 2-20, moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10-20 carbon atoms from the group of alcohols, alkylphenols and carboxylic acids. The addition products of 8-20 moles of ethylene oxide with primary alcohols, such as, for. B. coconut oil or tallow fatty alcohols, on oleyl alcohol, on oxo alcohols of the corresponding chain lengths, or on corresponding secondary alcohols, and on mono- or dialkylphenols with 6-14 C atoms in the alkyl radicals. In addition to these water-soluble nonionics, non-fully or not fully water-soluble polyglycol ethers with 2-7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants. Because of their good biodegradability, the ethoxylation products of primary aliphatic alkanols and alkenols are of particular practical interest.

Typical representatives of the nonionic surfactants which can be used according to the invention and have an average degree of ethoxylation of 2-7 are, for example, the compounds coconut fatty alcohol 3-EO (EO = ethylene oxide), tallow fatty alcohol 5-EO, oleyl / cetyl alcohol 5-EO (iodine number 30-50 ), Tallow fatty alcohol 7-EO, synthetic C ₁₂ -C ₁₆ fatty alcohol 6-EO, C ₁₁ -C ₁₅ oxo alcohol 3-EO, C ₁₄ / C ₁₅ oxo alcohol 7-EO, iC ₁₅ - C ₁₇ alkanediol-5-EO (i = internal); sec-C ₁₁ -C ₁₅ alcohol-4-EO.

Exemplary representatives for the nonionic surfactants with an average degree of ethoxylation of 8-20, in particular 9-15, are the compounds coconut fatty alcohol-12-EO, synthetic C ₁₂ / C ₁₄ fatty alcohol-9-EO, oleyl / cetytalcohol-10 -EO, tallow fatty alcohol-14-EO, C ₁₁ -C ₁₅ -oxoalcohol-13-EO, C ₁₅ -C ₁₈ -oxoalcohol-15-EO, iC ₁₅ -C ₁₇ -alkanediol-9-EO, C ₁₄ / C ₁₅ -Oxoalcohol-11-EO, sec.-C ₁₁ -C ₁₅ -Alcohol-9-EO.

Furthermore, the non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups with polypropylene glycol, alkylenediamine polypropylene glycol and with alkylpolypropylene glycols having 1-10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical. Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide, N-tallow alkyl-N , N-dihydroxyethylamine oxide.

• 3.(N-Hexadecyl-N,N-dimethylammonio)-propansulfona_t;
• 3-(N-Talgalkyl-N,N-dimethylammonio)-2-hydroxypropansulfonat;
• 3-(N-Hexadecyl-N,N-bis(2-hydroxyethyl)-ammonio)-2-hydroxypropylsulfat;
• 3-(N-Cocosalkyl-N,N-bis(2,3-dihydroxypropyl)-ammonio)-propansulfonat;
• N-Tetradecyl-N,N-dimethylammonioacetat;
• N-Hexadecyl-N,N-bis(2,3-dihydroxypropyl)-ammonioacetat.

The amphoteric surfactants are compounds which contain both an anionic and a cationic group in the same molecule. Suitable compounds are the derivatives of aliphatic C ₈ -C ₁₈ amines with a water-solubilizing group, such as. B. the carboxy, sulfo or sulfato group. Typical representatives of the amphoteric surfactants are the sodium salts of 2-dodecylaminopropionic acid and 3-dodecylaminopropanesulfonic acid and similar compounds, such as. B. sulfated imidazoline derivatives. Derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C ₈ -C ₁₈ radical and another contains an anionic water-solubilizing carboxy, sulfo or sulfato group are preferred as zwitterionic surfactants. Typical examples of such surface-active betaines are the compounds

• 3. (N-hexadecyl-N, N-dimethylammonio) -propansulfona _t;
• 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate;
• 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonium) -2-hydroxypropyl sulfate;
• 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate;
• N-tetradecyl-N, N-dimethylammonioacetate;
• N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonium acetate.

Foam-suppressing soaps and non-surfactant foam inhibitors come into consideration as foam-inhibiting additives. The foam-suppressing action of the soaps generally increases with the degree of saturation and the C number of the fatty acid residue, so that soaps of natural and synthetic origin are particularly suitable as foam-inhibiting soaps, which have a high proportion of C ₁₈ -C ₂₂ fatty acids, for example the derivatives of hydrogenated fish oil and rapeseed oils. In practice, fatty acid mixtures with a chain length distribution of C, ₂ to C ₂₂ are mostly used, which consist of at least 50% by weight of C ₁₈ -C ₂₂ fatty acid salts (iodine number <5). Also suitable for combination with non-surfactant-like foam inhibitors are foam-suppressing soaps of saturated C ₁₂ -C ₁₈ fatty acids, in particular predominantly C ₁₆ -C ₁₈ fatty acids, for example the soap of hydrogenated tallow fatty acid. In these combinations, the ratio of soap to non-surfactant-like foam inhibitor from 20: 1 to 5: 1, the soap mainly dampens foaming when rinsing out the wash liquor.

The non-surfactant foam inhibitors optionally used in combination with the foam-inhibiting soaps are generally water-insoluble, mostly containing aliphatic C _a -C ₂₂ carbon radicals. Suitable non-surfactant foam inhibitors are e.g. B. the N-alkylaminotriazines, ie reaction products of 1 mole of cyanuric chloride with 2-3 moles of a mono- or dialkylamine with essentially 8-18 carbon atoms in the alkyl radical. Also suitable are propoxylated and / or butoxylated aminotriazines, e.g. B. the reaction products of 1 mol of melamine with 5-10 mol of propylene oxide and additionally 10-50 mol of butylene oxide and the aliphatic C ₁₈ -C ₄₀ ketones, such as. B. Stearon, the fatty ketones from hydrogenated tranfatty acid or tallow fatty acid etc. and also the paraffins and halogen paraffins with melting points below 100 ° C and polymeric organosilicon compounds of the type of silicone oils, in particular a polydimethylsiloxane activated by finely divided Si0 ₂ .

The compounds of the formula I contained in the agents according to the invention with the surfactant combination (bb) are primarily compounds in the case of the hydroxyalkylamines (in formula 1, X is a β-hydroxyalkyl radical and A is a simple C - N bond) which were prepared in a 1-stage or 2-stage reaction from terminal or internal epoxyalkanes by first reacting with mono- or diethanolamine or mono- or diisopropanolamine, with ammonia, an alkylenediamine, polyalkylene polyamine or hydroxyalkyl polyamine and optionally ethoxylating these addition products in a second stage .

The epoxyalkanes used as starting materials are obtained in a manner known per se from the corresponding olefins or olefin mixtures.

The terminal epoxyalkanes used were preferably those with chain lengths in the range of C ₁₂ -C ₁₈ for the preparation of the hydroxyalkylamines of the formula I.

• - C₁₁-C₁₄-Fraktion: C₁₁-Olefine ca. 22 Gew.-%, C₁₂-Olefine ca. 30 Gew.-%, C₁₃-Olefine ca. 26 Gew.-%, C₁₄-Olefine ca. 22 Gew.-%;
• C₁₅-C₁₈-Fraktion: C₁₅-Olefine ca. 26 Gew.-%, C₁₈-Olefine ca. 35 Gew.-%, C₁₇-Olefine ca. 32 Gew.-%, C₁₈-Olefine ca. 7 Gew.-%.

Internal monoolefins of a C ₁₁ -C ₁₄ fraction and a C ₁₅ -C ₁₈ fraction which were preferably used had the following chain length distribution:

• - C ₁₁ -C ₁₄ fraction: C ₁₁ olefins approx. 22% by weight, C ₁₂ olefins approx. 30% by weight, C ₁₃ olefins approx. 26% by weight, C ₁₄ olefins approx 22% by weight;
• C ₁₅ -C ₁₈ fraction: C ₁₅ olefins approx. 26% by weight, C ₁₈ olefins approx. 35% by weight, C ₁₇ olefins approx. 32% by weight, C ₁₈ olefins approx. 7% by weight.

• 1. Das Umsetzungsprodukt aus einem innenständigen C₁₁-C₁₄-Epoxyalkan und Diethanolamin; Trübungspunkt <0°C.
• 2. Das Umsetzungsprodukt aus einem innenständigen C₁₁-C₁₄-Epoxyalkan und Monoethanolamin; Trübungspunkt 34° C.
• 3. Das Umsetzungsprodukt aus einem innenständigen C₁₁-C₁₄-Epoxyalkan und Bis-Hydroxyethoxyethylamin; Trübungspunkt 44° C.
• 4. Das Umsetzungsprodukt aus einem innenständigen C₁₁-C₁₄-Epoxyalkan und Diethanolamin, zusätzlich ethoxyliert mit einem Mol Ethylenoxid; Trübungspunkt 32° C.
• 5. Das Umsetzungsprodukt aus einem innenständigen C₁₁-C₁₄-Epoxyalkan und Diethanolamin, zusätzlich ethoxyliert mit 2 Mol Ethylenoxid; Trübungspunkt 45° C.
• ₆. Das Umsetzungsprodukt aus einem innenständigen C₁₁-C₁₄-Epoxyalkan und Ethylendiamin, zusätzlich umgesetzt mit 4 Mol Ethylenoxid; Trübungspunkt 72,5° C.
• 7. Das Umsetzungsprodukt von α-Epoxyoctan und Ethylendiamin; Trübungspunkt 15° C.

Typical representatives of hydroxyalkylamines of the formula I are, for example, the following compounds (cloud points measured in aqueous butyl diglycol in accordance with DIN 53 917):

• 1. The reaction product of an internal C ₁₁ -C ₁₄ epoxyalkane and diethanolamine; Cloud point <0 ° C.
• 2. The reaction product of an internal C ₁₁ -C ₁₄ epoxyalkane and monoethanolamine; Cloud point 34 ° C.
• 3. The reaction product of an internal C ₁₁ -C ₁₄ epoxyalkane and bis-hydroxyethoxyethylamine; Cloud point 44 ° C.
• 4. The reaction product of an internal C ₁₁ -C ₁₄ epoxyalkane and diethanolamine, additionally ethoxylated with one mole of ethylene oxide; Cloud point 32 ° C.
• 5. The reaction product of an internal C ₁₁ -C ₁₄ epoxyalkane and diethanolamine, additionally ethoxylated with 2 moles of ethylene oxide; Cloud point 45 ° C.
• ₆ . The reaction product of an internal C ₁₁ -C ₁₄ epoxyalkane and ethylenediamine, additionally reacted with 4 moles of ethylene oxide; Cloud point 72.5 ° C.
• 7. The reaction product of α-epoxyoctane and ethylenediamine; Cloud point 15 ° C.

The compounds of the formula I in the surfactant combination (bb) in the case of the fatty acid ethanolamides (in the formula I XA- is a fatty acid residue) are preferably fatty acid monoethanolamides composed of individual fatty acids or fatty acid mixtures, in particular of the chain length range C ₁₀ -C ₁₈ , the natural ones or can be of synthetic origin. The fatty acids can be saturated and unsaturated; Monoethanolamides of mixed fatty acids from natural sources, such as, for example, are particularly suitable. B. the derivatives of the fatty acids available from coconut fat, palm kernel oil or tallow. Examples of such fatty acid monoethanolamides are the compounds: lauric acid monoethanolamide, coconut fatty acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, oleic acid monoethanolamide, tallow fatty acid monoethanolamide.

The detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure, which instead of Morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-Sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline as well as compounds of the same structure, which instead of the sulfamoyl group z. B. carry the methoxycarbonyl, 2-methoxyethoxycarbonyl, the acetylamino or the vinylsulfonyl group. Polyamide brighteners which can also be used are the substituted aminocoumarins, for example 4-methyl-7-dimethylamino- or 4-methyl-7-diethylamino-coumarin. The compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethy) -2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyryl are also useful as polyamide brighteners. As brighteners for polyester and polyamide fibers, the compounds are 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzox-azolyl) -naphtho [2,3-b] -thiophene and 1,2-di - (5-methyl-2-benzoxazolyl) ethylene suitable. Brighteners of the substituted 4,4'-distyryldiphenyis type may also be present; e.g. B. the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

The preparations may also contain graying inhibitors, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying. For this purpose, water-soluble colloids, usually of an organic nature, are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Carboxymethylated cellulose or starch in the form of its sodium salts and / or methyl celluloses are preferred. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc. Recoloring inhibitors of the polyvinylpyrrolidone type can also be used.

Examples

First, a manufacturing specification for the aluminosilicates is given; other known methods for producing the aluminosilicates can also be used.

The sodium aluminate solution was placed in a vessel with 151 contents and the sodium silicate solution was added with vigorous stirring. Was stirred with a stirrer with a dispersing disc at 3000 revolutions / min. Both solutions were at room temperature. An X-ray amorphous sodium aluminosilicate formed as the primary precipitation product under an exothermic reaction. After stirring for 10 minutes, the suspension of the precipitate was transferred to a crystallization container and heated to 80-130 ° C. for about 6 hours with stirring (250-500 revolutions / min) for the purpose of crystallization. After sucking off the lye from the crystal slurry and washing with deionized water up to a pH of approx. 10-11 of the washing water running off, the filter cake was either dried - e.g. B. 24 hours at 100 ° C - and then crushed into a fine powder, or an aqueous slurry, preferably an aqueous suspension of the aluminosilicate, was used to produce the detergents or cleaning agents. More precise information on the temperature, the duration of heating and the type of workup are given in the manufacturing instructions for the following individual representative aluminosilicate types.

Alumosilicate Im

• Precipitation approach:
  • 2.985 kg aluminate solution of the composition: 17.7% Na20, 15.8% Al ₂ O ₃ , 66.5% H ₂ O;
  • 0.150 kg of caustic soda, 9.420 kg of water and 2.445 kg of a 25.8% strength solution of a sodium silicate of the composition 1 Na ₂ O · 6 SiO ₂ , freshly prepared from commercially available water glass and slightly alkali-soluble silica;
• Precipitation:
  • Suspension of the amorphous precipitate was stirred for 10 min with an intensive stirrer (10,000 rpm);
• Crystallization:
  • 6 hours at 90 ° C;
• Drying:
  • 24 hours at 100 ° C;
• Composition:
  • 0.9 Na ₂ O.1 Al ₂ O ₃ - 2.04 SiO ₂ 4.3 H ₂ O (= 21.6% H ₂ O); Degree of crystallization:
  • fully crystalline;
• Calcium binding capacity:
  • 170 mg CaO / g AS;
• Particle size (by sedimentation analysis):
  • 100% less than 40 µ; 85-95% less than 10 µ; Maximum particle size distribution: 3 - 6 µ.

Alumosilicate R I

• Precipitation:
  • 7.63 kg of an aluminate solution of the composition: 13.2% Na ₂ O, 8.0% Al ₂ O ₃ , 78.8% H ₂ O;
  • 2.37 kg of a sodium silicate solution of the composition: 8.0% Na ₂ O, 26.9% SiO ₂ , 65.1% H ₂ O;
• Mixing ratio:
  • 3.24 Na ₂ O, 1.0 Al ₂ O ₃ , 1.78 SiO ₂ , 70.3 H ₂ O;
• Crystallization:
  • 6 hours at 90 ° C;
• Drying:
  • 24 hours at 100 ° C;
• Composition of the dried product:
  • 0.99 Na ₂ O. 1.00 Al ₂ O _3. 1.83 SiO ₂ . 4.0 H ₂ O (= 20.9% H ₂ O);
• Crystal shape:
  • cubic with very rounded corners and edges;
• average particle diameter (for the range 0-30 µm):
  • 5.4 µm; Maximum particle size distribution: is below 3 µm;
• Calcium binding capacity:
  • 172 mg CaO / g AS.

Alumosilicate F

• Precipitation:
  • 7.31 kg aluminate (14.8% Na ₂ O, 9.2% Al ₂ O ₃ , 76.0% H ₂ O);
  • 2.69 kg of silicate (8.0% Pa ₂ O, 26.9% SiO ₂ , 65.1% H ₂ O);
• Mixing ratio:
  • 3.17 Na ₂ O, 1.0 Al ₂ O ₃ , 1.82 SiO ₂ , 62.5 H ₂ O:
• Crystallization:
  • 6 hours at 90 ° C;
• Composition of the dried product:
  • 1.11 Na ₂ O · 1 Al ₂ O ₃ · 1.89 SiO _2. 3.1 H ₂ O (= 16.4% H ₂ O);
• Crystal structure:
  • Mixture of zeolite NaA and zeolite HS in a ratio of approx. 1: 1;
• Crystal shape:
  • rounded crystallites;
• average particle diameter (for the range 0 -30 µm):
  • 5.6 µm; Maximum particle size distribution: is below 3 µm;
• Calcium binding capacity:
  • 105 mg CaO / g AS at 50 ° C,
  • 120 mg CaO / g AS at 90 ° C;
• Magnesium binding capacity:
  • 15 mg MgO / g AS at 22 ° C,
  • 96 mg MgO / g AS at 90 ° C.

• »NatriurnsiIikat A«:
  • leicht lösliches Wasserglas in Pulverform der Zusammensetzung Na₂O · 2,0-2,2 SiO₂;
  • Wassergehalt ca. 18 Gew.-%; Teilchengröße ca. 1,0-0,05 mm; hergestellt durch Sprühtrocknung (Portil A®);
• »Natriunisilikat AW«:
  • leicht lösliches Wasserglas in Pulverform der Zusammensetzung Na₂O. 2,0-2,2 SiO₂;
  • Wassergehalt ca. 20 Gew.-%; Teilchengröße ca. 1,0-0,05 mm: hergestellt durch Walzentrocknung (Portil AW®);
• »ABS«
  • das Salz einer durch Kondensieren von geradkettigen Olefinen mit Benzol und Sulfonieren des so entstandenen Alkylbenzols erhaltenen Alkylbenzolsulfonsäure mit 10- 15, im wesentlichen 11 -13 Kohlenstoffatomen in der Alkylkette;
• »Alkansulfonat «:
  • ein über die Sulfoxidation von C_12-18-Paraffinen erhaltenes Sulfonat;
• »Fs-estersulfonat «:
  • ein aus hydriertem Palmkernfettsäuremethylester über die Sulfonierung mit SO₃ erhaltenes Sulfonat;
• »Olefinsulfonata«:
  • ein durch Sulfonieren von x-Olefinen mit 12-18 C-Atomen mit S0₃ und Hydrolysieren des Sulfonierungsprodukts mit Natronlauge erhaltenes Gemisch von Hydroxyalkan-, Alkan- und Disulfonaten;
• »Cocosalkoholsulfat«:
  • ein durch Sulfatieren des C_12/C₁₄-Schnitts des Cocosalkohols erhaltenes Sulfat;
• »Talgalkohol-3-EO-sulfat«
  • ein durch Sulfatieren eines ethoxylierten Talgalkohols, mittlerer Ethoxylierungsgrad=3, erhaltenes Sulfat;
• »TA-x EO«, »Ca-x EO«, »OCA-x EO«, »OXO-x EO«:
  • die Anlagerungsprodukte von x Mol Ethylenoxid (EO) an jeweils ein Mol technischen Talgalkohol (TA) bzw. Cocosalkohol (CA) bzw. Oleyl-/Cetylalkohol (Jodzahl 50) (OCA) bzw. an einen C_14/C₁₅-Oxoaikohol mit ca. 20% α-Methylverzweigung (OXO);
• »Seife A«:
  • eine aus einem gehärteten Gemisch gleicher Gewichtsteile von Talg- und Rübölfettsäure hergestellte Seife (Jodzahl=1);
• »Seife B«:
  • eine aus hydrierter Talgfettsäure hergestellte Seife (Jodzahl=11);
• »Schauminhibitor«:
  • Silikonöl »SAG 100«® der Firma Union Carbide and Carbon;
• »i-11 -14-DAA-x EO«:
  • das Umsetzungsprodukt aus innenständigem C₁₁-C₁₄-Epoxyalkan und Diethanolamin, gegebenenfalls mit x Mol Ethylenoxid umgesetzt;
• »i-11 -14-MAA«:
  • das Umsetzungsprodukt aus innenständigem C₁₁―C₁₄-Epoxyalkan und Monoethanolamin;
• »HEDP«:
  • das Salz der 1-Hydroxyethan-1,1-diphosphonsäure;*)
• »HBDP«: -
  • das Salz der 1-Hydroxybutan-1,1-diphosphonsäure;*)
• »ATMP«:
  • das Salz der Aminotrimethylentriphosphonsäure;*)
• »Perborat«:
  • ein technisches Produkt der ungefähren Zusammensetzung NaBO₂. H₂O₂ · 3 H₂O;
• »CMC«:
  • das Salz der Carboxymethylcellulose;
• »Enzyme«:
  • ein proteolytisches Enzym in Prillform (Maxatase P®) der Firma Gist-Brocades N. V.;
• »Aufheller«:
  • das Salz der4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilben-2,2'-disulfonsäure.

The following is a description of the detergents according to the invention. The salt-like constituents of the detergents mentioned in the examples - acidic surfactants, other organic salts and inorganic salts - are present as sodium salts, unless expressly stated otherwise. All percentages are percentages by weight. In the detergent examples, the amount of aluminosilicate given there is based on "active substance", ie on the anhydrous product. The proportion of the water bound in the aluminosilicate is listed together with the remaining water content of the agent. The names or abbreviations in the examples have the following meanings:

• "Sodium SiIate A":
  • easily soluble water glass in powder form with the composition Na ₂ O · 2.0-2.2 SiO ₂ ;
  • Water content approx. 18% by weight; Particle size approx. 1.0-0.05 mm; produced by spray drying (Portil A®);
• »Sodium silicate AW«:
  • easily soluble water glass in powder form with the composition Na ₂ O. 2.0-2.2 SiO ₂ ;
  • Water content approx. 20% by weight; Particle size approx. 1.0-0.05 mm: manufactured by roller drying (Portil AW®);
• "SECTION"
  • the salt of an alkylbenzenesulfonic acid obtained by condensing straight-chain olefins with benzene and sulfonating the resulting alkylbenzene with 10-15, essentially 11 -13 carbon atoms in the alkyl chain;
• "Alkanesulfonate":
  • a sulfonate obtained by sulfoxidation of C _12-18 paraffins;
• "Fs-estersulfonate":
  • a sulfonate obtained from hydrogenated palm kernel fatty acid methyl ester via sulfonation with SO ₃ ;
• "Olefinsulfonata":
  • a mixture of hydroxyalkane, alkane and disulfonates obtained by sulfonating x-olefins having 12-18 C atoms with SO ₃ and hydrolyzing the sulfonation product with sodium hydroxide solution;
• "Coconut alcohol sulfate":
  • a sulfate obtained by sulfating the C _{12 /} C _{14 section of} the coconut alcohol;
• "Tallow alcohol 3-EO sulfate"
  • a sulfate obtained by sulfating an ethoxylated tallow alcohol, average degree of ethoxylation = 3;
• »TA-x EO«, »Ca-x EO«, »OCA-x EO«, »OXO-x EO«:
  • the addition products of x moles of ethylene oxide (EO) to one mole of technical tallow alcohol (TA) or coconut alcohol (CA) or oleyl / cetyl alcohol (iodine number 50) (OCA) or to a C _{14 /} C ₁₅ oxo alcohol with approx 20% α-methyl branching (OXO);
• "Soap A":
  • a soap made from a hardened mixture of equal parts by weight of tallow and rapeseed oil fatty acid (iodine number = 1);
• "Soap B":
  • a soap made from hydrogenated tallow fatty acid (iodine number = 11);
• "Foam inhibitor":
  • "SAG 100" ® silicone oil from Union Carbide and Carbon;
• "I-11 -14-DAA-x EO":
  • the reaction product of internal C ₁₁ -C ₁₄ epoxyalkane and diethanolamine, optionally reacted with x mol of ethylene oxide;
• "I-11 -14-MAA":
  • the reaction product of internal C ₁₁ ―C ₁₄ epoxyalkane and monoethanolamine;
• "HEDP":
  • the salt of 1-hydroxyethane-1,1-diphosphonic acid; *)
• »HBDP«: -
  • the salt of 1-hydroxybutane-1,1-diphosphonic acid; *)
• "ATMP":
  • the salt of aminotrimethylene triphosphonic acid; *)
• "Perborate":
  • a technical product with the approximate composition NaBO ₂ . H ₂ O ₂ .3 H ₂ O;
• "CMC":
  • the salt of carboxymethyl cellulose;
• "Enzymes":
  • a proteolytic enzyme in prill form (Maxatase P®) from Gist-Brocades NV;
• "Brightener":
  • the salt of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid.

*) The phosphonates HEDP, HBDP and ATMP were used as sodium and calcium salts.

Tensidkomponente, Alumosilikat, CMC, Aufheller und Natriumsulfat über einen Slurryansatz

eine sprühgetrocknete Pulyerkomponente A herstellte und diese mit der aus dem Natriumsilikat und dem Phosphonatsalz bestehenden Pulverkomponente B und der aus dem Perborat bestehenden Pulverkomponente C vermischte. Bei der Herstellung der Waschmittel der Tabelle II wurde ein Gemisch aus dem Alumosilikat, den Tensiden, den Bestandteilen der Stabilisatorkombination sowie CMC, Aufheller und Natriumsulfat als Slurry-Ansatz sprühgetrocknet und dieses Turmpulver mit dem Natriumsilikat und dem Perborat vermischt. Enzyme und Duftstoffe wurden diesen Gemischen in üblicher Weise zugesetzt. Zur Vermeidung von Verlusten durch die Wasserdampfflüchtigkeit der niedrig ethoxylierten Fettalkohole wurden diese auch ganz oder teilweise aus dem Sprühtrocknungsansatz weggelassen und durch Aufsprühen auf die Pulverkomponenten B oder C in das Waschmittel eingebracht. Vergleichende Waschversuche mit einem handelsüblichen phosphathaitigen Kochwaschmittel ergaben hinsichtlich Primär- und Sekundärwaschvermögen, Perboratstabilität und Gewebeschonung eine Überlegenheit der erfindungsgemäßen Zusammensetzung in der Summe ihrer Eigenschaften. Überraschenderweise wurde bei einer vergleichenden Prüfung unter dem Gesichtspunkt der Rückstandsbildung ebenfalls festgestellt, daß die erfindungsgemäßen Waschmittel im Vergleich mit dem ausschließlich aus wasserlöslichen Verbindungen zusammengesetzten Handelsprodukt auf Phosphatbasis unter den gewählten extremen Testbedingungen überlegene Eigenschaften besitzen. Beispielsweise wurde durch Auflösen der Waschmittel in Wasser nach einer bestimmten Lösezeit der unlösliche Rückstand auf einem Sieb bestimmt, bzw. es wurde nach einer Feinwäsche von Hand der sichtbare Rückstand auf schwarzem Wollstoff beurteilt. Vergleichbar gute Wasch- und Testergebnisse wurden auch erhalten, wenn man in den Waschmittelrezepturen der Tabellen I und II das dort eingesetzte Alumosilikat durch die anderen genannten Alumosilikat-Typen, bzw. durch gleichartig zusammengesetzte, jedoch auf andere Weise hergestellte Alumosilikat-Typen ersetzte.The detergents in Table I were generally prepared in such a way that

Surfactant component, aluminosilicate, CMC, brightener and sodium sulfate using a slurry batch

produced a spray-dried powder component A and mixed it with the powder component B consisting of the sodium silicate and the phosphonate salt and the powder component C consisting of the perborate. In the preparation of the detergents in Table II, a mixture of the aluminosilicate, the surfactants, the constituents of the stabilizer combination and CMC, brightener and sodium sulfate was spray-dried as a slurry batch and this tower powder was mixed with the Sodium silicate and the perborate mixed. Enzymes and fragrances were added to these mixtures in the usual way. In order to avoid losses due to the volatility of steam of the low ethoxylated fatty alcohols, these were also completely or partially omitted from the spray drying batch and introduced into the detergent by spraying onto the powder components B or C. Comparative washing tests with a commercially available phosphate-containing cooking detergent showed that the composition according to the invention was superior in terms of primary and secondary washability, perborate stability and fabric protection in the sum of its properties. Surprisingly, it was also found in a comparative test from the point of view of residue formation that the detergents according to the invention have superior properties under the chosen extreme test conditions in comparison with the commercial product based exclusively on phosphate based on phosphate. For example, the insoluble residue on a sieve was determined by dissolving the detergents in water after a certain dissolution time, or the visible residue on black wool was assessed after a delicate wash by hand. Comparably good washing and test results were also obtained if, in the detergent formulations in Tables I and II, the aluminosilicate used there was replaced by the other aluminosilicate types mentioned, or by alumosilicate types of the same composition but produced in a different way.

Claims (12)

1. A phosphate-free detergent containing water-insoluble alumosilicate cation exchangers. sufactants, water-soluble complexing builders, an alkali silicate and, optionally, a peroxy bleach component and consisting of at least two powder constituents of which one contains the alumosilicate and a surfactant and the other the alkali silicate, characterised in that it contains the following constituents:

(i) from 20 to 65% by weight of a water-insoluble, finely particulate, synthetically produced crystalline alkali alumosilicate containing bound water and corresponding to the following formula

0.7-1.5 Me₂O - Al₂O₃ · 1.3 -4.0 SiO₂

(Me = sodium or potassium)

based on the anhydrous active substance, which has a calcium binding capacity determined at 22° C of trom 50 to 200 and preferably from 100 to 200 mg of CaO/g of anhydrous active substance;

(ii) from 5 to 30% by weight of a surfactant component consisting of at least one synthetic anionic, non-ionic, arnphoteric or zwitter-ionic surfactant and, optionally, foam-inhibiting additives;

(iii) from 1 to 7, preferably from 2 to 5 and more preferably from 2 to 3% by weight of a solid, powder-form sodium silicate which has the following molar composition Na₂⊙ · 2.0 - 2.2 SiO₂ and a water content of from 15 to 23 and preferably from 18 to 21% by weight and of which the solubility in water in the preparation of a 5% aqueous solution (by adding 5 g of the sodium silicate all at once with uniform stirring at about 180-200 r.p.m. to 95 g of water having a temperature of 20° C) amounts after 1 minute to at least 75% by weight, preferably to at least 85% by weight, after 3 minutes to at least 95% by weight and after at most 25 minutes to 100% by weight; and

(iv) from 0.05 to 0.75 and preferably from 0.2 to 0.6% by weight of a water-soluble organic complexing agent from the group of substituted alkane di- and tri-phosphonic acids in the form of the alkali metal of alkaline earth metal salts;

the detergent being a mixture of at least 2 powder constituents A) and B), of which

A) is a powder constituent obtained by drying an aqueous suspension of the constituents at elevated temperature and containing the water-insoluble alkali alumosilicate according to (i), the surfactant component according to (ii), otpionally without or with only part of the non-ionic surfactants, and optionally the water-soluble organic complexing buldiers according to (iv); whilst

B) is a powder constituent containing the sodium silicate powder according to (iii), optionally together with the water-soluble organic complexing builders according to (iv) and optionally together with non-ionic surfactants sensitive to high-temperature drying and optionally other hydrolysis- and temperature-sensitive detergent additives.

2. A detergent as claimed in claim 1, characterised in that the sodium silicate according to (iii) has an apparent density of from 350 to 800 g/I and preferably from 350 to 450 g/I and, more preferably, of the order of.400 g/I and a particle size distribution in the range from 1 to 0.05 mm, at least 80% of the particles being smaller than 0.5 mm.

3. A detergent as claimed in claims 1 and 2, characterised in that the sodium silicate of component (iii) in claim 1 is obtained by the spray-drying or roll-drying of an aqueous 35 to 50% solution at a temperature in the range from 100 to 120°C in the case of spray-drying and in the range from 100 to 140° C in the case of roll-drying.

4. A detergent as claimed in claims 1 to 3, characterised in that the sodium silicate of component (iii) in claim 1 is obtained by drying a 40 to 50% aqueous solution on a heated roll at 100 to 140" C to a residual water content of from 15 to 23 and, more particularly, from 18 to 21% by weight, has an apparent density of from 350 to 450 g/I and, more particularly, of the order of 400 g/I and has a solubility in water after 3 minutes of at least 99% as determined by the test defined in claim 1.

5. A detergent as claimed in claims 1 to 4, characterised in that it consists of the powder constituents A and B according to claim 1 and additionally of another powder constituent C containing the peroxy bleach component consisting in particular of sodium perborate.

6. A detergent as claimed in claims 1 to 5 containing

a) from 20 to 40% by weight of a water-insoluble, finely particulate, synthetically produced, crystalline alkali alumosilicate containing bound water and corresponding to the following formula

0.7 -1.5 Me₂O · Al₂O₃ · 1.3 -4.0 SiO₂

(Me =sodium or potassium)

based on the anhydrous active substance = AS, which has a calcium binding capacity of from 50 to 200 and preferably from 100 to 200 mg of CaO/g AS;

b) from 5 to 20% by weight of a surfactant component consisting of at least one anionic, non-ionic, amphoteric or zwitter-ionic surfactant and, optionally, foam-inhibiting additives;

c) from 0.05 to 0.75 and preferably from 0.2 to 0.6% by weight of an organic complexing agent from. the group of substituted alkane di- and tri-phosphonic acids and their alkali metal salts;

d) from 10 to 35% by weight of an inorganic per compound; and

e) up to 7% by weight of a water-soluble sodium silicate having the composition Na₂O · 1 - 3.5 Si0₂,

characterised in that it contains as component e) from 2 to 5 and more particularlv from 2 to 3% by weight of a solid, powaer-form sodium silicate which has the molar composition Na₂O · 2.0 -2.2 SiO₂ and a water content of from 15 to 23 and preferably from 13 to 21% by weight and of which the solubility in water in the preparation of a 5% aqueous solution (by the addition of 5 g of the sodium silicate all at once with uniform stirring at about 180 to 200 r.p.m. to 95 g of water having a temperature of 20° C) amounts after 3 minutes to at least 99% by weight according to component (iii) in claim 1, the detergent being a mixture of the three powder components A, B and C according to claims 1 and 5 and component (c) being present in the form of an alkali metal or alkaline earth metal salt.

7. A detergent as claimed in claims 1 to 6, characterised in that it contains the phosphonate defined in claim 1 together with the sodium silicate (iii) or e) as part ot the powder constituent B) according to claim 1.

8. A detergent as claimed in claims 1 to 5, characterised in that it has the following composition:

a) from 30 to 40% by weight of a water-insoluble, finely particulate, synthetically produced, crystalline sodium alumosilicate containing bound water of the zeolite NaA type with a calcium binding capacity of from 100 to 200 mg of CaO/g, based on the anhydrous substance, and a particle size of smaller than 30 µ, at least 80% of the particles being between 8 and 0.01 µ in size;

b) from 10 to 20% by weight of a surfactant component consisting of at least one anionic and/or non-ionic surfactant and, optionally, foam-inhibiting additives;

c) from 1 to 2.55% by weight of a stabiliser combination of

cl) from 0.05 to 0.75% by weight of an organic complexing agent from the group of substituted alkane di- and tri-phosphonic acids present in the form of their alkali metal and/or alkaline earth metal salts,

c2) from 0.8 to 1.5% by weight of magnesium silicate and

c3) from 0.15 to 0.3% by weight of ethylene diamine tetracetic acid in the form of the sodium salt, based in each case on the detergent as a whole,

d) from 18 to 22% by weight of sodium perborate tetrahydrate and

e) from 2 to 3% by weight of a solid, powder-form sodium silicate which has the molar composition Na₂O · 2.0-2.2 Si0₂ and which has a water content of from 15 to 23 and preferably from 18 to 21% by weight and of which the solubility in water in the preparation of a 5% aqueous solution (by the addition of 5 g of the sodium silicate all at once with uniform stirring at about 180-200 r.p.m. to 95 g of water having a temperature of 20° C) amounts after 3 minutes to at least 99% by weight,

the detergent being a mixture of the three powder constituents A), B) and C), of which

A) is a powder constituent obtained by the spray-drying of an aqueous suspension of the constituents at elevated temperature and containing the water-insoluble sodium alumosilicate a), the surfactant component according to b), optionally without some of the nan-ionic surfactants, and the stabiliser combination according to c)

B) is a powder constituent containing the sodium silicate powder according to e), optionally together with non-ionic surfactants sensitive to high-temperature drying and optionally other hydrolysis-and temperature-sensitive detergent additives; and

C) is the additional, third powder constituent consisting of the peroxy bleach component sodium perborate:

9. A detergent as claimed in claim 8, characterised in that it contains optical lighteners in the powder constituent A).

10. A process for producing the detergent claimed in claims 1 to 7, comprising the steps of preparing a powder component by drying an aqueous suspension at elevated temperature, preparing another powder component by a method different from the elevated-temperature drying method and mixing the two powder components, optionally in the presence of a peroxy bleach component as a further powder component, characterised in that the water-insoluble alkali alumosilicates (i) according to claim 1, the surfactant component (ii) according to claim 1, optionally without or with only part of the non-ionic surfactants, and optionally the water-soluble complexing builders (iv) according to claim 1 are suspended in water and the resulting suspension is converted by spray-drying at elevated temperature into the powder component A, in that the sodium silicate powder (iii) according.to.cfaim 1 is optionally mixed with powder-form water-soluble complexing builders (iv) according to claim 1 and non-ionic surfactants sensitive-to high-temperature drying and optionally other hydrolysis-sensitive and temperature-sensitive detergent components are optionally added to the resulting powder and the resulting powder component B is mixed with powder component A in the usual way, the proportions in which B and A are mixed being selected in such a way that constituents (i), (ii), (iii) and (iv) are present in the resulting mixture in the quantitative ranges indicated in claim 1.

11. A process as claimed in claim 10, characterised in that powder component B is prepared by mixing from 20 to 50 parts by weight of the sodium silicate powder (iii) with from 2 to 6 parts by weight of a powder form alkali metal or alkaline earth metal salt of the organic complexing agent from the group of substituted alkane di- and tri-phosphonic acids (iv), non-ionic surfactants are optionally added and the resulting powder is mixed with powder component A and optionally the other powder component C, the quantitative proportions being adjusted in accordance with the detergents claimed in claims 1 to 6.

12. A process for producing the detergent claimed in claims. 8 and 9, comprising the steps of preparing a powder component by spray-drying an aqueous suspension at elevated temperature, preparing another powder component by a method different from the elevated-temperature drying method and mixing the powder components in the presence ot the sodium perborate as a further powder component, characterised in that constituents a), b) and c), optionally without some of the non-ionic surfactants, and preferably optical lighteners and further additives, such as redeposition inhibitors and sodium sulfate, are suspended in water and converted into powder component A) by spray-drying at elevated temperature, in that the sodium silicate powder according to e) is optionaily mixed with non-ionic surfactants sensitive to high-temperature drying and optionally other hydrolysis-and temperature-sensitive detergent constituents and the resulting powder component B) and the sodium perborate as component C) are mixed with powder component A), the proportions in which A), B) and C) are mixed being selected in such a way that constituents a) to e) are present in the resulting mixture in the quantitative ranges indicated in claim 3 for the detergent.