EP0170791A1 - Process for the production of a washing additive in the form of tablets - Google Patents

Process for the production of a washing additive in the form of tablets Download PDF

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Publication number
EP0170791A1
EP0170791A1 EP85105496A EP85105496A EP0170791A1 EP 0170791 A1 EP0170791 A1 EP 0170791A1 EP 85105496 A EP85105496 A EP 85105496A EP 85105496 A EP85105496 A EP 85105496A EP 0170791 A1 EP0170791 A1 EP 0170791A1
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EP
European Patent Office
Prior art keywords
granules
tablets
tablet
acid
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85105496A
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German (de)
French (fr)
Other versions
EP0170791B1 (en
Inventor
Hans Kruse
Klaus Dr. Köster
Franz-Josef Dr. Carduck
Heinz-Manfred Wilsberg
Rolf Dr. Puchta
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT85105496T priority Critical patent/ATE36347T1/en
Publication of EP0170791A1 publication Critical patent/EP0170791A1/en
Application granted granted Critical
Publication of EP0170791B1 publication Critical patent/EP0170791B1/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected

Definitions

  • the present invention relates to a process for the preparation of a washing additive with active ingredients for improving the washability of bleachable stains, of greasy or oily stains and of pigment stains, the washing additive being obtained in the form of a tablet in the production by the process according to the invention.
  • the detergent tablets often contain, as active ingredients, alone or in combination with other active ingredients and conventional tabletting aids, a bleach activator for per compounds.
  • a bleach activator for per compounds.
  • Such a product is described for example in DE-OS 22 63 939.
  • Bleach activators in combination with the compounds normally found in modern universal detergents, improve the removal of bleachable stains.
  • the detergents In addition to per-compounds, the detergents generally also contain bleach activators; When storing the detergents which contain per-compounds and activators at the same time, difficulties often arise because the bleach activator acts prematurely on the per-compounds and thus becomes one Per compounds may lose their effectiveness.
  • washing additives which, in addition to a bleach activator, additionally contain nonionic surfactants, certain quaternary ammonium compounds for strengthening the washing power and, if appropriate, organic phosphonic acid derivatives (see DE-OS 28 57 153).
  • the last-mentioned patent application relates to washing additives in which the active ingredient combination mentioned is applied to a flexible carrier.
  • the carrier loaded with active substances is added to the washing machine when washing the laundry, where it develops its effect in the course of the washing process. After the washing process has ended, the flexible carrier for the active ingredients remains in the laundry and must be sorted out from it.
  • Tablet-like washing additives are often sensitive to mechanical stress or they do not dissolve quickly enough or only incompletely if the tablet composition and preparation are chosen so that the tablets are mechanically sufficiently stable.
  • the object of the present invention is therefore to provide a process for the preparation of a washing additive in tablet form, in which an activator for per compounds and customary tableting aids are mixed with one another and molded.
  • the washing additive according to the invention is intended to contain the active ingredients in coordinated proportions and in terms of their capacity contain a coordinated amount in a washing machine and do not have to be removed from the laundry after washing.
  • the washing additive should also be so stable that it can be handled comfortably; it must also dissolve quickly and completely in the wash liquor.
  • the powdered activator is granulated together with nonionic surfactants, with nitrogen-containing compounds from the group comprising quaternary ammonium compounds, fatty amine derivatives or aminopropionic acid derivatives, with the tabletting aids and, if appropriate, with the water-soluble salt of an alkane polyphosphonic acid, with the granules being mixed powdered a powdered adsorbent and sprayed with a liquid binder, then drying the granules to a water content of at most 6 wt .-% and from this after adding a tablet disintegrant tablets, their shape, weight and density is selected so that the tablets one for a wash have sufficient content of active ingredients to increase washing power and the tablets are circulated from the laundry items during the washing process, so that the tablets dissolve quickly and completely, presses.
  • the features of the method according to the invention ensure that on the one hand the tablet has a stability which prevents the tablet from disintegrating before use in the washing machine.
  • washing additives produced according to the invention in the washing machine have sufficient security against dissolution.
  • the procedural measures also result in tablets being obtained which ensure perfect storage over a long period even in the moist air of a laundry room.
  • the powdering and spraying of the granules with a liquid binder also has the effect that the surface of the granules containing the active ingredients is largely or completely covered.
  • a granulate containing the active ingredients is first prepared, which optionally additionally contains a water-soluble or water-insoluble powdery carrier material for the liquid or pasty active ingredient components and optionally a granule disintegrant.
  • This granulate therefore already contains all active ingredients and, in addition, aids that serve the safe manufacture and handling.
  • the granulate can be produced by known granulation processes, for example in a mixer or in a fluidized bed.
  • a mixer from Lödige, Paderborn, Federal Republic of Germany has proven itself.
  • the liquid or dissolved active ingredients or auxiliaries liquefied or liquefied by heating are preferably sprayed onto the powdered active ingredients or auxiliaries. It forms a granulate that contains all the active ingredients, which will be discussed in more detail later, and some auxiliary substances, such as.
  • a granule disintegrant causes the granule grain to disintegrate more quickly in the wash liquor and is therefore preferred. In many cases, it is advisable to mix up to 30 seconds after the granulate has formed; post-mixing for longer than a maximum of 30 seconds often leads to pulpy products.
  • The. Finished granules, which should contain no or only small amounts of dust-fine fractions, are then dusted with a finely divided inert material and / or a finely divided adsorbent, for example highly disperse silica and / or starch, e.g. B. potato starch and then sprayed a liquid binder, such as a sugar solution.
  • a finely divided inert material and / or a finely divided adsorbent for example highly disperse silica and / or starch, e.g. B. potato starch and then sprayed a liquid binder, such as a sugar solution.
  • the active ingredient granules are coated with a protective layer of binder and sugar that is largely or completely closed after drying.
  • a tablet disintegrant is added to the dried granules, combinations of two different tablet disintegrants having proven particularly useful. The addition of a tablet disintegrant causes the tablet to disintegrate quickly into the granules when the tablet comes into contact with the wash liquor. After mixing with tablet disintegrant, the tablets are compressed.
  • the pressing tools are expediently polished in order to prevent sticking. However, it is advantageous to use pressing tools that are coated with a non-stick layer.
  • the pressing conditions and the composition of the tablets ensure the mechanical stability on the one hand and the rapid disintegration of the tablets when used on the other.
  • the process product contains a mixture of at least one activator for per-compounds, at least one C 12 to C 18 alcohol ethoxylate, at least one nitrogen-containing compound from the quaternary ammonium compounds with a C 10 to C 20 alkyl or alkenyl radical, and the rest C 1 - to C 4 -alkyl radicals, adducts of 1 to 6 mol of ethylene oxide with 1 mol of a primary fatty amine with a long-chain alkyl or alkenyl radical with 10 to 16 carbon atoms, ⁇ -aminoalkyl or alkenylpropionic acid sodium salt
  • R-NH-CH 2 -CH 2 -COONa in which R is an alkyl or alkenyl group having 10 to 20 carbon atoms, in particular 12 to 14 carbon atoms, pe comprehensive Gru p-, which, if appropriate, with an aqueous solution of a water-soluble salt an alkane polyphosphonic acid granulated.
  • N-acyl and 0-acyl compounds are suitable as activators for per compounds.
  • Acetyl compounds have proven particularly useful. Examples include tetraacetylglycoluril or pentaacetylglucose or in particular tetraacetylethylenediamine.
  • the bleach activators mentioned lead to an improved removal of bleachable textile soiling.
  • Addition products of ethylene oxide with fatty alcohols or, in particular, oxo alcohols, which have 12 to 18, preferably 14 to 15, carbon atoms are particularly suitable as nonionic surfactants.
  • the best effects are achieved with oxo alcohol ethoxylates which contain 3 to 10, preferably 6 to 8 and in particular about 7 moles of ethylene oxide per mole of alcohol.
  • foam regulators most of the time, the development of foam must be dampened.
  • Suitable foam suppressants are, for example, the known silicone oils.
  • the content of nonionic surfactants in the washing additives according to the invention primarily promotes the removal of greasy or oily soiling during washing.
  • Suitable quaternary ammonium compounds contain as long-chain alkyl or alkenyl radical with 10 to 20, preferably alkyl groups with 10 to 16 and in particular about 14 carbon atoms.
  • the suitable quaternary ammonium compounds contain 3 identical or different alkyl groups with 1 to 4 carbon atoms. In particular, these short alkyl groups are methyl groups.
  • a particularly suitable and therefore preferred quaternary ammonium compound is tetradecyltrimethylammonium bromide.
  • All or part of the quaternary ammonium compound can be replaced by the above-mentioned fatty amine ethoxylate.
  • An example of a particularly suitable fatty amine ethoxylate is the adduct of 2 moles of ethylene oxide with primary coconut alkyl amine; this product is therefore also preferred.
  • a compound of the formula R-NH-CH 2 -CH 2 -COONa can also be used.
  • a compound in which R is a cocoalkyl radical is preferred.
  • the washing additive advantageously contains small amounts of chelating agents.
  • Water-soluble salts of alkane polyphosphonic acid from the group of the phosphonoalkane polycarboxylic acids and the amino- and hydroxy-substituted alkane polyphosphonic acids, in particular the alkali salts of amino-tris (methylenephosphonic acid), dimethyleneaminomethane diphosphonic acids, have been particularly suitable for this purpose ; 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonoethane-1,2-dicarbon acid, 2-phosphonobutane-1,2,3-tricarboxylic acid and in particular the hexasodium salt of ethylenediaminotetramethylenephosphonic acid.
  • the granules are produced from the active substances mentioned by focusing on the solids, ie. H. to the bleach activator and the quaternary ammonium compound, to which, for example, highly disperse silica and granule disintegrant, for example, as a powdery carrier material for the liquid or pasty active ingredients, the liquid or liquefied or dissolved active ingredients, i. H. sprayed on the nonionic surfactant and optionally the heavy metal complexing agents dissolved in water.
  • a disintegrant suitable as a granule component is, for example, swellable magnesium aluminum silicate.
  • the amount of disintegrant in the granules is preferably in the range from 1 to 5% by weight and in the base material in the range from 5 to 20% by weight, based in each case on the granules without a protective layer.
  • the granules are covered with a protective layer.
  • the granules are dusted with the finely divided inert material and / or the finely divided adsorbent, the dusted granules are sprayed with an aqueous sugar solution, in particular cane sugar or sorbitol solution, and the granules are dried.
  • the granules contain about 50 to 90% by weight of active ingredient; the rest are auxiliary substances.
  • the bulk density of the granules sieved through a 2 mm sieve is 600 to 700 g per liter.
  • the granules coated and dried with a protective layer are preferably mixed with 10 to 20% by weight, based on the granules, of a tablet disintegrant, preferably a mixture of two different tablet disintegrants, in particular a mixture of crosslinked polyvinylpyrrolidone and / or cellulose ethers and / or swellable magnesium aluminum silicate .
  • a tablet disintegrant preferably a mixture of two different tablet disintegrants, in particular a mixture of crosslinked polyvinylpyrrolidone and / or cellulose ethers and / or swellable magnesium aluminum silicate .
  • the effect of a single tablet disintegrant can be increased by adding up to 7% by weight (based on the tablet weight) of an alkali salt of short-chain organic mono- or polycarboxylic acids, e.g. B. Na acetate or Na citrate can be increased.
  • the tablet preparation is carried out by adding from the dried granulate at a pressure of 500 to 1000 kp / cm 2 tablets with a diameter of more than 30 mm and a height, the fold 1,1-0.75 to the tablet diameter, at least but is 25 mm, with a density of 0.8 to 1.2 g per cm3 and a breaking strength of 6 to 12 kg.
  • the dried granules were then mixed gently with so much crosslinked polyvinylpyrrolidone (PVP) and sodium carboxymethyl cellulose (CMC) as tablet disintegrants that 80 parts by weight of granules account for 15 parts by weight of PVP and 5 parts by weight of CMC. This mixing took place in a Patterson-Kelley-Cron-Flow blender. A coated granulate with a bulk density of 535 g per liter was obtained.
  • PVP polyvinylpyrrolidone
  • CMC sodium carboxymethyl cellulose
  • the tablets obtained dissolved within 6 minutes in a wash cycle with a 30 ° C wash program (Miele washing machine, type 430) without residue.
  • the soiled laundry washed with it was significantly cleaner than without the addition of a detergent booster tablet despite the 2/3 nominal dosage of a cheap detergent.

Abstract

A powdery activator for per compounds is granulated by, at the same time, mixing it together with nonionic surface-active compounds certain nitrogen-containing compounds and, optionally, the water-soluble salt of an alkane polyphosphonic acid. The granulate thus obtained is powdered with a powdery absorbent and the powdered granulate is sprayed with a liquid binder and dried to a water content of at most 6% by weight. After the addition of a tablet disintegrating agent, the dried granulate is formed by compression under special conditions into tablets having special properties. When added to a wash liquor containing a standard detergent containing a per compound, the tablets improve the removal of fatty/oily stains, pigment-containing soil and bleachable stains.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines Waschzusatzes mit Wirkstoffen zur Verbesserung der Auswaschbarkeit von bleichbaren Anschmutzungen, von fett- oder ölartigen Anschmutzungen und von Pigmentverschmutzungen, wobei der Waschzusatz bei der Herstellung nach dem erfindungsgemäßen Verfahren in Form einer Tablette erhalten wird.The present invention relates to a process for the preparation of a washing additive with active ingredients for improving the washability of bleachable stains, of greasy or oily stains and of pigment stains, the washing additive being obtained in the form of a tablet in the production by the process according to the invention.

Tablettenförmige Waschzusätze sind seit langem bekannt. Als Wirkstoffe enthalten die Waschzusatz-Tabletten häufig allein oder in Kombination mit anderen Wirkstoffen und üblichen Tablettierungshilfsmitteln einen Bleichaktivator für Perverbindungen. Ein solches Produkt ist beispielsweise in der DE-OS 22 63 939 beschrieben. Bleichaktivatoren bewirken im Zusammenspiel mit den in den modernen Universalwaschmitteln normalerweise vorhandenen Per- verbindungen eine verbesserte Entfernung von bleichbaren Flecken. Die Waschmittel enthalten zwar in der Regel neben Perverbindungen auch Bleichaktivatoren; bei der Lagerung der Waschmittel, die gleichzeitig Perverbindungen und Aktivatoren enthalten, treten aber häufig dadurch Schwierigkeiten auf, daß der Bleichaktivator vorzeitig auf die Perverbindungen einwirkt und es so zu einem Wirkungsverlust der Perverbindungen kommen kann. Bei der Wäsche von stark verschmutzter Kleidung, wie beispielsweise Berufskleidung, wird außer auf eine einwandfreie Entfernung von bleichbaren Anschmutzungen auch auf die Entfernung von fett- oder ölartigen Verschmutzungen und von Pigmentverschmutzungen Wert gelegt. Zur Verbesserung der Entfernung der genannten Schmutzarten sind daher auch Waschzusätze beschrieben worden, die außer einem Bleichaktivator zusätzlich nichtionische Tenside, bestimmte quartäre Ammoniumverbindungen zur Waschkraftverstärkung und gegebenenfalls organische Phosphonsäurederivate enthalten (siehe DE-OS 28 57 153). Die zuletzt genannte Patentanmeldung betrifft Waschzusätze, bei denen die genannte Wirkstoffkombination auf einem flexiblen Träger aufgetragen ist. Der mit Wirkstoffen beladene Träger wird beim Waschen der Wäsche mit in die Waschmaschine gegeben, wo er im Laufe des Waschvorganges seine Wirkung entfaltet. Nach Beendigung des Waschvorganges verbleibt der flexible Träger für die Wirkstoffe in der Wäsche und muß aus dieser aussortiert werden.Tablet-like washing additives have been known for a long time. The detergent tablets often contain, as active ingredients, alone or in combination with other active ingredients and conventional tabletting aids, a bleach activator for per compounds. Such a product is described for example in DE-OS 22 63 939. Bleach activators, in combination with the compounds normally found in modern universal detergents, improve the removal of bleachable stains. In addition to per-compounds, the detergents generally also contain bleach activators; When storing the detergents which contain per-compounds and activators at the same time, difficulties often arise because the bleach activator acts prematurely on the per-compounds and thus becomes one Per compounds may lose their effectiveness. When washing heavily soiled clothing, such as work clothes, in addition to the flawless removal of bleachable soiling, great importance is also attached to the removal of greasy or oily soiling and pigment soiling. To improve the removal of the types of dirt mentioned, washing additives have therefore also been described which, in addition to a bleach activator, additionally contain nonionic surfactants, certain quaternary ammonium compounds for strengthening the washing power and, if appropriate, organic phosphonic acid derivatives (see DE-OS 28 57 153). The last-mentioned patent application relates to washing additives in which the active ingredient combination mentioned is applied to a flexible carrier. The carrier loaded with active substances is added to the washing machine when washing the laundry, where it develops its effect in the course of the washing process. After the washing process has ended, the flexible carrier for the active ingredients remains in the laundry and must be sorted out from it.

Tablettenförmige Waschzusätze sind häufig empfindlich gegenüber mechanischer Beanspruchung oder sie lösen sich nicht schnell genug oder nur unvollständig auf, wenn man die Tablettenzusammensetzung und -herstellung so wählt, daß die Tabletten mechanisch ausreichend stabil sind. Aufgabe der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung eines Waschzusatzes in Tablettenform, bei dem man einen Aktivator für Perverbindungen und übliche Tablettierungshilfsmittel miteinander vermischt und formt, bereitzustellen. Der erfindungsgemäße Waschzusatz soll die Wirkstoffe in aufeinander abgestimmten Mengenverhältnissen und in der auf das Fassungsvermögen einer Waschmaschine abgestimmten Menge enthalten und nach dem Waschen nicht aus der Wäsche aussortiert werden müssen. Der Waschzusatz soll zudem so stabil sein, daß man ihn bequem handhaben kann; er muß sich außerdem in der Waschflotte rasch und vollständig auflösen.Tablet-like washing additives are often sensitive to mechanical stress or they do not dissolve quickly enough or only incompletely if the tablet composition and preparation are chosen so that the tablets are mechanically sufficiently stable. The object of the present invention is therefore to provide a process for the preparation of a washing additive in tablet form, in which an activator for per compounds and customary tableting aids are mixed with one another and molded. The washing additive according to the invention is intended to contain the active ingredients in coordinated proportions and in terms of their capacity contain a coordinated amount in a washing machine and do not have to be removed from the laundry after washing. The washing additive should also be so stable that it can be handled comfortably; it must also dissolve quickly and completely in the wash liquor.

Die Aufgabe wurde erfindungsgemäß dadurch gelöst, daß man den pulverförmigen Aktivator zusammen mit nichtionischen Tensiden, mit stickstoffhaltigen Verbindungen aus der quartären Ammoniumverbindungen, Fettaminderivate bzw. Aminopropionsäurederivate umfassenden Gruppe, mit den Tablettierungshilfsmitteln und gegebenenfalls mit dem wasserlöslichen Salz einer Alkanpolyphosphonsäure unter Vermischen granuliert, das Granulat mit einem pulverförmigen Adsorptionsmittel bepudert und mit einem flüssigen Bindemittel besprüht, anschließend das Granulat auf einen Wassergehalt von höchstens 6 Gew.-% trocknet und hieraus nach Zugabe eines Tablettensprengmittels Tabletten, deren Form, Gewicht und Dichte so gewählt wird, daß die Tabletten einen für einen Waschgang ausreichenden Gehalt an waschkraftsteigernden Wirkstoffen aufweisen und die Tabletten von den Wäschestücken während des Waschvorganges mit umgewälzt werden, so daß die Tabletten sich schnell und vollständig auflösen, preßt. Durch die erfindungsgemäßen Verfahrensmerkmale wird gewährleistet, daß die Tablette einerseits eine Stabilität aufweist, die verhindert, daß die Tablette vor dem Gebrauch in der Waschmaschine zerfällt. Andererseits weisen erfindungsgemäß hergestellte Waschzusätze in der Waschmaschine eine ausreichende Auflösesicherheit auf. Die Verfahrensmaßnahmen bewirken außerdem, daß man Tabletten erhält, die auch in der feuchten Luft einer Waschküche eine einwandfreie Lagerung über längere Zeit gewährleisten. Durch das Bepudern und das Besprühen des Granulats mit einem flüssigen Bindemittel wird außerdem bewirkt, daß die Oberfläche des die Wirkstoffe enthaltenden Granulats weitgehend oder vollständig abgedeckt ist.The object was achieved in that the powdered activator is granulated together with nonionic surfactants, with nitrogen-containing compounds from the group comprising quaternary ammonium compounds, fatty amine derivatives or aminopropionic acid derivatives, with the tabletting aids and, if appropriate, with the water-soluble salt of an alkane polyphosphonic acid, with the granules being mixed powdered a powdered adsorbent and sprayed with a liquid binder, then drying the granules to a water content of at most 6 wt .-% and from this after adding a tablet disintegrant tablets, their shape, weight and density is selected so that the tablets one for a wash have sufficient content of active ingredients to increase washing power and the tablets are circulated from the laundry items during the washing process, so that the tablets dissolve quickly and completely, presses. The features of the method according to the invention ensure that on the one hand the tablet has a stability which prevents the tablet from disintegrating before use in the washing machine. On the other hand, washing additives produced according to the invention in the washing machine have sufficient security against dissolution. The procedural measures also result in tablets being obtained which ensure perfect storage over a long period even in the moist air of a laundry room. The powdering and spraying of the granules with a liquid binder also has the effect that the surface of the granules containing the active ingredients is largely or completely covered.

Bei der erfindungsgemäßen Herstellung des Waschzusatzes stellt man zunächst ein die Wirkstoffe enthaltendes Granulat her, das gegebenenfalls zusätzlich ein wasserlösliches oder wasserunlösliches pulveriges Trägermaterial für die flüssigen oder pastösen Wirkstoffbestandteile und gegebenenfalls ein Granulat-Sprengmittel enthält. Dieses Granulat enthält also bereits alle Wirkstoffe und darüber hinaus noch Hilfsmittel, die der sicheren Herstellung und Handhabung dienen.In the production of the washing additive according to the invention, a granulate containing the active ingredients is first prepared, which optionally additionally contains a water-soluble or water-insoluble powdery carrier material for the liquid or pasty active ingredient components and optionally a granule disintegrant. This granulate therefore already contains all active ingredients and, in addition, aids that serve the safe manufacture and handling.

Die Herstellung des Granulats kann nach bekannten Granulierverfahren erfolgen, beispielsweise in einem Mischer oder in der Wirbelschicht. Bewährt hat sich ein Mischer der Fa. Lödige, Paderborn, Bundesrepublik Deutschland. In einem solchen Mischer sprüht man vorzugsweise die flüssigen bzw. gelösten bzw. durch Erwärmen verflüssigten Wirkstoffe bzw. Hilfsstoffe auf die pulverförmigen Wirkstoffe bzw. Hilfsstoffe auf. Es bildet sich dabei ein Granulat aus, das alle Wirkstoffe, auf die später näher eingegangen wird, und einige Hilfsstoffe, wie z. B. Trägerstoffe für flüssige Bestandteile und/oder 1 bis 5 Gew.-% eines Granulat-Sprengmittels, bezogen auf das Granulat ohne Schutzschicht, enthält. Die Zugabe eines Granulat-Sprengmittels bewirkt einen schnelleren Zerfall des Granulat-Korns in der Waschflotte und ist daher bevorzugt. In vielen Fällen ist ein Nachmischen von bis zu 30 Sekunden Dauer nach der Granulatbildung zweckmäßig; längeres Nachmischen als maximal 30 Sekunden führt häufig zu breiigen Produkten. Das. fertige Granulat, das keine oder nur geringe Mengen an staubfeinen Anteilen enthalten sollte, bestäubt man dann mit einem feinteiligen inerten Material und/oder einem feinteiligen Adsorptionsmittel, beispielsweise hochdisperse Kieselsäure und/oder Stärke, z. B. Kartoffelstärke und sprüht dann ein flüssiges Bindemittel, beispielsweise eine Zuckerlösung, auf. Dadurch umhüllt man das Wirkstoffgranulat mit einer nach dem Trocknen weitgehend oder vollständig geschlossenen Schutzschicht aus Bindemittel und Zucker. Das Trocknen des so behandelten Granulats auf einen Wassergehalt von höchstens 6 Gew.-% ist erforderlich, um das Granulat gut rieselfähig, d. h., einwandfrei den Preßwerkzeugen zuführbar zu machen. Das Trocknen ist ferner erforderlich um ein Verkleben an den Tabletten-Preßwerkzeugen zu verhindern, ferner um auch nach der Lagerung gutlösliche Tabletten zu erhalten. Zweckmäßigerweise trocknet man beispielsweise in der Wirbelschicht bei maximal 90 °C Lufttemperatur. Nun erfolgt die Zugabe eines Tablettensprengmittels zu dem getrockneten Granulat, wobei sich Kombinationen von zwei verschiedenen Tablettensprengmitteln besonders bewährt haben. Die Zugabe eines Tablettensprengmittels bewirkt einen schnellen Zerfall der Tablette in das Granulat, wenn die Tablette in Kontakt mit der Waschflotte kommt. Nach dem Abmischen mit Tablettensprengmittel erfolgt das Verpressen zu Tabletten. Die Preßwerkzeuge sind zweckmäßigerweise poliert, um ein Verkleben zu verhindern. Vorteilhaft ist aber die Verwendung von Preßwerkzeugen, die mit einer Antihaftschicht be- schichtet sind. Die Preßbedingungen und die Zusammensetzung der Tabletten gewährleisten die mechanische Stabilität einerseits und den raschen Zerfall der Tabletten bei der Anwendung andererseits.The granulate can be produced by known granulation processes, for example in a mixer or in a fluidized bed. A mixer from Lödige, Paderborn, Federal Republic of Germany has proven itself. In such a mixer, the liquid or dissolved active ingredients or auxiliaries liquefied or liquefied by heating are preferably sprayed onto the powdered active ingredients or auxiliaries. It forms a granulate that contains all the active ingredients, which will be discussed in more detail later, and some auxiliary substances, such as. B. Carriers for liquid components and / or 1 to 5 wt .-% of a granule disintegrant, based on the granules without a protective layer. The addition of a granule disintegrant causes the granule grain to disintegrate more quickly in the wash liquor and is therefore preferred. In many cases, it is advisable to mix up to 30 seconds after the granulate has formed; post-mixing for longer than a maximum of 30 seconds often leads to pulpy products. The. Finished granules, which should contain no or only small amounts of dust-fine fractions, are then dusted with a finely divided inert material and / or a finely divided adsorbent, for example highly disperse silica and / or starch, e.g. B. potato starch and then sprayed a liquid binder, such as a sugar solution. Thereby the active ingredient granules are coated with a protective layer of binder and sugar that is largely or completely closed after drying. The drying of the granules treated in this way to a water content of at most 6 wt. Drying is also necessary in order to prevent sticking to the tablet pressing tools and also to obtain tablets which are readily soluble even after storage. It is expedient to dry, for example, in the fluidized bed at an air temperature of max. Now a tablet disintegrant is added to the dried granules, combinations of two different tablet disintegrants having proven particularly useful. The addition of a tablet disintegrant causes the tablet to disintegrate quickly into the granules when the tablet comes into contact with the wash liquor. After mixing with tablet disintegrant, the tablets are compressed. The pressing tools are expediently polished in order to prevent sticking. However, it is advantageous to use pressing tools that are coated with a non-stick layer. The pressing conditions and the composition of the tablets ensure the mechanical stability on the one hand and the rapid disintegration of the tablets when used on the other.

An Wirkstoffen enthält das Verfahrensprodukt ein Gemisch aus wenigstens einem Aktivator für Perverbindungen, wenigstens einem C12-- bis C18-Alkoholethoxylat, wenigstens einer stickstoffhaltigen Verbindung aus der quartäre Ammoniumverbindungen mit einem C10- bis C20-Alkyl- oder Alkenylrest und im übrigen C1- bis C4-Alkylresten, Anlagerungsprodukte von 1 bis 6 Mol Ethylenoxid an 1 Mol eines primären Fettamins mit einem langkettigen Alkyl-oder Alkenylrest mit 10 bis 16 Kohlenstoffatomen, ß-Aminoalkyl- oder -alkenylpropionsäure-Natriumsalz der Formel R-NH-CH2-CH2-COONa, in der R einen Alkyl- oder Alkenylrest mit 10 bis 20 Kohlenstoffatomen, insbesondere 12 bis 14 Kohlenstoffatomen bedeutet, umfassenden Grup- pe, das man gegebenfalls mit einer wäßrigen Lösung eines wasserlöslichen Salzes einer Alkanpolyphosphonsäure granuliert. Die Herstellung eines Granulats mit den genannten Wirkstoffen ist ein weiterer Gegenstand der Erfindung.The process product contains a mixture of at least one activator for per-compounds, at least one C 12 to C 18 alcohol ethoxylate, at least one nitrogen-containing compound from the quaternary ammonium compounds with a C 10 to C 20 alkyl or alkenyl radical, and the rest C 1 - to C 4 -alkyl radicals, adducts of 1 to 6 mol of ethylene oxide with 1 mol of a primary fatty amine with a long-chain alkyl or alkenyl radical with 10 to 16 carbon atoms, β-aminoalkyl or alkenylpropionic acid sodium salt Formula R-NH-CH 2 -CH 2 -COONa, in which R is an alkyl or alkenyl group having 10 to 20 carbon atoms, in particular 12 to 14 carbon atoms, pe comprehensive Gru p-, which, if appropriate, with an aqueous solution of a water-soluble salt an alkane polyphosphonic acid granulated. Another object of the invention is the production of granules with the active ingredients mentioned.

Als Aktivator für Perverbindungen sind N-Acyl- und 0-Acylverbindungen geeignet. Besonders bewährt haben sich Acetylverbindungen. Beispiele hierfür sind Tetraacetylglykoluril oder Pentaacetylglucose oder insbesondere Tetraacetylethylendiamin. In Verbindung mit Perverbindungen der gebräuchlichen Vollwaschmittel; insbesondere mit dem üblicherweise verwendeten Perborat, führen die genannten Bleichaktivatoren zu einer verbesserten Entfernung bleichbarer Textilverschmutzungen.N-acyl and 0-acyl compounds are suitable as activators for per compounds. Acetyl compounds have proven particularly useful. Examples include tetraacetylglycoluril or pentaacetylglucose or in particular tetraacetylethylenediamine. In connection with per connections of the common heavy duty detergents; especially with the commonly used perborate, the bleach activators mentioned lead to an improved removal of bleachable textile soiling.

Als nichtionische Tenside kommen vor allem Anlagerungsprodukte von Ethylenoxid an Fett- oder insbesondere Oxoalkohole infrage, die 12 bis 18, vorzugsweise 14 bis 15 Kohlenstoffatome aufweisen. Die besten Wirkungen erzielt man mit Oxoalkohol-Ethoxylaten, die 3 bis 10, vorzugsweise 6 bis 8 und insbesondere etwa 7 Mol Ethylenoxid pro Mol Alkohol enthalten. In vielen Fällen ist es zweckmäßig, Schaumregulatoren zuzusetzen; meistens muß die Schaumentwicklung gedämpft werden. Geeignete Schaumdämpfungsmittel sind beispielsweise die bekannten Silikonöle. Durch den Gehalt der erfindungsgemäßen Waschzusätze an nichtionischen Tensiden wird vor allem die Entfernung von fett- oder ölartigen Verschmutzungen beim Waschen gefördert.Addition products of ethylene oxide with fatty alcohols or, in particular, oxo alcohols, which have 12 to 18, preferably 14 to 15, carbon atoms are particularly suitable as nonionic surfactants. The best effects are achieved with oxo alcohol ethoxylates which contain 3 to 10, preferably 6 to 8 and in particular about 7 moles of ethylene oxide per mole of alcohol. In many cases it is advisable to add foam regulators; most of the time, the development of foam must be dampened. Suitable foam suppressants are, for example, the known silicone oils. The content of nonionic surfactants in the washing additives according to the invention primarily promotes the removal of greasy or oily soiling during washing.

Der Verbesserung der Entfernung von Pigmentverschmutzungen aus Textilien dient der Gehalt der erfindungsgemäßen Mittel an bestimmten stickstoffhaltigen Verbindungen, beispielsweise an quartären Ammoniumverbindungen und/ oder primären Fettaminen und/oder den Verbindungen der Formel R-NH-CH2-CH2 -COONa; Geeignete quartäre Ammoniumverbindungen enthalten als langkettigen Alkyl- oder Alkenylrest mit 10 bis 20, vorzugsweise Alkylgruppen mit 10 bis 16 und insbesondere etwa 14 Kohlenstoffatomen. Im übrigen enthalten die geeigneten quartären Ammoniumverbindungen 3 gleiche oder verschiedene Alkylgruppen mit 1 bis 4 Kohlenstoffatomen. Insbesondere handelt es sich bei diesen kurzen Alkylgruppen um Methylgruppen. Eine besonders gut geeignete und daher bevorzugte quartäre Ammoniumverbindung ist Tetradecyltrimethylammoniumbromid. Die quartäre Ammoniumverbindung kann ganz oder teilweise durch das oben genannte Fettamin-Ethoxylat ersetzt werden. Ein Beispiel für ein besonders gut geeignetes Fettamin-Ethoxylat ist das Anlagerungsprodukt von 2 Mol Ethylenoxid an primäres Kokosalkylamin; dieses Produkt ist daher ebenfalls bevorzugt. Anstelle oder gemeinsam mit der quartären Ammoniumverbindung und dem Fettaminderivat kann auch eine Verbindung der Formel R-NH-CH2-CH2-COONa eingesetzt werden. Bevorzugt ist eine Verbindung, in der R ein Kokosalkylrest ist.The content of certain nitrogen-containing compounds, for example quaternary ammonium compounds and / or primary fatty amines and / or the compounds of the formula R-NH-CH 2 -CH 2 -COONa, is used to improve the removal of pigment contaminants from textiles. Suitable quaternary ammonium compounds contain as long-chain alkyl or alkenyl radical with 10 to 20, preferably alkyl groups with 10 to 16 and in particular about 14 carbon atoms. In addition, the suitable quaternary ammonium compounds contain 3 identical or different alkyl groups with 1 to 4 carbon atoms. In particular, these short alkyl groups are methyl groups. A particularly suitable and therefore preferred quaternary ammonium compound is tetradecyltrimethylammonium bromide. All or part of the quaternary ammonium compound can be replaced by the above-mentioned fatty amine ethoxylate. An example of a particularly suitable fatty amine ethoxylate is the adduct of 2 moles of ethylene oxide with primary coconut alkyl amine; this product is therefore also preferred. Instead of or together with the quaternary ammonium compound and the fatty amine derivative, a compound of the formula R-NH-CH 2 -CH 2 -COONa can also be used. A compound in which R is a cocoalkyl radical is preferred.

Zur Komplexierung von störenden Schwermetallionen enthält der Waschzusatz zweckmäßigerweise geringe Mengen von Chelatbildnern. Besonders geeignet haben sich hierfür wasserlösliche Salze von Alkanpolyphosphonsäure aus der Gruppe der Phosphonoalkanpolycarbonsäuren und der amino-und hydroxysubstituierten Alkanpolyphosphonsäuren, insbesondere die Alkalisalze der Amino-tris-(methylenphosphon- säure), Dimethylenaminomethandiphosphonsäuren; 1-Hydroxyethan-1,1-diphosphonsäure, 1-Phosphonoethan-1,2-dicarbonsäure, 2-Phosphonobutan-1,2,3-tricarbonsäure und insbesondere das Hexanatriumsalz der Ethyllendiaminotetramethylenphosphonsäure.In order to complex disruptive heavy metal ions, the washing additive advantageously contains small amounts of chelating agents. Water-soluble salts of alkane polyphosphonic acid from the group of the phosphonoalkane polycarboxylic acids and the amino- and hydroxy-substituted alkane polyphosphonic acids, in particular the alkali salts of amino-tris (methylenephosphonic acid), dimethyleneaminomethane diphosphonic acids, have been particularly suitable for this purpose ; 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonoethane-1,2-dicarbon acid, 2-phosphonobutane-1,2,3-tricarboxylic acid and in particular the hexasodium salt of ethylenediaminotetramethylenephosphonic acid.

Aus den genannten Wirkstoffen stellt man das Granulat her, indem man auf die Feststoffe, d. h. auf den Bleichaktivator und die quartäre Ammoniumverbindung, denen man gegebenenfalls als pulveriges Trägermaterial für die flüssigen oder pastösen Wirkstoffe beispielsweise hochdisperse Kieselsäure und Granulatsprengmittel zugemischt hat, die flüssigen bzw. verflüssigten oder gelösten Wirkstoffe, d. h. das nichtionische Tensid und gegebenenfalls den in Wasser gelösten Schwermetallkomplexbildnern aufsprüht. Ein als Granulatbestandteil geeignetes Sprengmittel ist beispielsweise quellfähiges Magnesiumaluminiumsilikat.The granules are produced from the active substances mentioned by focusing on the solids, ie. H. to the bleach activator and the quaternary ammonium compound, to which, for example, highly disperse silica and granule disintegrant, for example, as a powdery carrier material for the liquid or pasty active ingredients, the liquid or liquefied or dissolved active ingredients, i. H. sprayed on the nonionic surfactant and optionally the heavy metal complexing agents dissolved in water. A disintegrant suitable as a granule component is, for example, swellable magnesium aluminum silicate.

Der Gehalt des Granulats an Sprengmittel liegt vorzugsweise im Bereich von 1 bis 5 Gew.-% und an Trägermaterial im Bereich von 5 bis 20 Gew.-%, jeweils bezogen auf das Granulat ohne Schutzschicht.The amount of disintegrant in the granules is preferably in the range from 1 to 5% by weight and in the base material in the range from 5 to 20% by weight, based in each case on the granules without a protective layer.

Um beim Verpressen Tabletten mit der erforderlichen Bruchfestigkeit zu erhalten und um einen Austritt des nichtionischen Tensids und gegebenenfalls der übrigen Wirkstoffe aus dem Granulatkorn beim Verpressen zu verhindern, überzieht man die Granulatkörner mit einer Schutzschicht. Man bestäubt hierzu das Granulat mit dem genannten feinteiligen inerten Material und/oder dem feinteiligen Adsorptionsmittel, besprüht das bestäubte Granulat mit einer wäßrigen Zuckerlösung, insbesondere Rohrzucker- oder Sorbitlösung und trocknet das Granulat. Das Granulat enthält etwa 50 bis 90 Gew.-% Wirkstoffs; der Rest sind Hilfsstoffe. Das Schüttgewicht des über ein 2 mm-Sieb gesiebten Granulats liegt bei 600 bis 700 g pro Liter.In order to obtain tablets with the required breaking strength during compression and to prevent the nonionic surfactant and possibly the other active substances from escaping from the granulate during compression, the granules are covered with a protective layer. For this purpose, the granules are dusted with the finely divided inert material and / or the finely divided adsorbent, the dusted granules are sprayed with an aqueous sugar solution, in particular cane sugar or sorbitol solution, and the granules are dried. The granules contain about 50 to 90% by weight of active ingredient; the rest are auxiliary substances. The bulk density of the granules sieved through a 2 mm sieve is 600 to 700 g per liter.

Das mit einer Schutzschicht überzogene und getrocknete Granulat wird vorzugsweise mit 10 bis 20 Gew.-%, bezogen auf das Granulat,einesTablettensprengmittels, vorzugsweise eines Gemisches aus zwei verschiedenen Tablettensprengmitteln, insbesondere eines Gemisches aus vernetztem Polyvinylpyrrolidon und/oder Celluloseethern und/oder quellfähigem Magnesiumaluminiumsilikat vermischt. Die Wirkung eines einzelnen Tablettensprengmittels kann durch Zusatz von bis zu 7 Gew.-% (bezogen auf das Tablettengewicht) eines Alkalisalzes kurzkettiger organischer Mono-oder Polycarbonsäuren, z. B. Na-Acetat oder Na-Citrat gesteigert werden. Im Fall der bevorzugten Zugabe eines Polyvinylpyrrolidon enthaltenden Tablettensprengmittelgemischs ist ein Gewichtsverhältnis von Polyvinylpyrrolidon zu dem zweiten Tablettensprengmittel im Bereich von 8 : 1 bis 2 : 1 besonders bevorzugt.The granules coated and dried with a protective layer are preferably mixed with 10 to 20% by weight, based on the granules, of a tablet disintegrant, preferably a mixture of two different tablet disintegrants, in particular a mixture of crosslinked polyvinylpyrrolidone and / or cellulose ethers and / or swellable magnesium aluminum silicate . The effect of a single tablet disintegrant can be increased by adding up to 7% by weight (based on the tablet weight) of an alkali salt of short-chain organic mono- or polycarboxylic acids, e.g. B. Na acetate or Na citrate can be increased. In the case of the preferred addition of a tablet disintegrant mixture containing polyvinylpyrrolidone, a weight ratio of polyvinylpyrrolidone to the second tablet disintegrant in the range from 8: 1 to 2: 1 is particularly preferred.

Die Tablettenherstellung erfolgt, indem man aus dem getrockneten Granulat bei einem Druck von 500 bis 1000 kp/cm2 Tabletten mit einem Durchmesser von mehr als 30 mm und einer Höhe, die das 0,75- bis 1,1-fache des Tablettendurchmessers, wenigstens aber 25 mm beträgt, mit einer Dichte von 0,8 bis 1,2 g pro cm3 und einer Bruchfestigkeit von 6 bis 12 kg verpreßt.The tablet preparation is carried out by adding from the dried granulate at a pressure of 500 to 1000 kp / cm 2 tablets with a diameter of more than 30 mm and a height, the fold 1,1-0.75 to the tablet diameter, at least but is 25 mm, with a density of 0.8 to 1.2 g per cm3 and a breaking strength of 6 to 12 kg.

Zum Verpressen des Granulats sind die bekannten Exzenter-und Rundläuferpressen geeignet, sofern sie bei den oben angegebenen Tablettenabmessungen ein Verdichtungsverhältnis von ca. 2,2 : 1 bis 1,8 : 1 erreichen. Die 15 bis 50 g schweren-Tabletten enthalten ca. 10 bis 30 g Wirkstoffe in folgenden Mengenverhältnissen:

  • 2 bis 30 Gew.-Teile nichtionisches Tensid,
  • 0,5 bis 20 Gew.-Teile quartäre Ammoniumverbindung und/oder Fettaminderivat und/oder Verbindungen der Formel R-NH-CH2-CH2-GOONA,
  • 2 bis 30 Gew.-Teile Aktivator für Perverbindungen, 0 bis Gew -Teile Schwenmetallkomplexbildner.
The known eccentric and rotary presses are suitable for pressing the granules, provided that they achieve a compression ratio of approximately 2.2: 1 to 1.8: 1 in the tablet dimensions specified above. The 15 to 50 g tablets contain approx. 10 to 30 g of active ingredients in the following proportions:
  • 2 to 30 parts by weight of nonionic surfactant,
  • 0.5 to 20 parts by weight of quaternary ammonium compound and / or fatty amine derivative and / or compounds of the formula R-NH-CH 2 -CH 2 -GOONA,
  • 2 to 30 parts by weight of activator for per compounds, 0 to parts by weight of heavy metal complexing agent.

BEISPIELEEXAMPLES Beispiel 1example 1

In einem 130 1 Lödige-Mischer wurden 5,16 kg Tetraacetylethylendiamin, 1,9 kg Tetradecyltrimethylammoniumbromid, 2,2 kg hochdisperse Fällungskieselsäure und 0,4 kg Magnesiumaluminiumsilikat unter ständigem Mischen mit einer Flüssigkeit aus 5,16 kg C14 /C15-Oxoalkohol mit 7 Mol Ethylenoxid, 1,3 kg einer 33 gewichtsprozentigen wäßrigen Lösung des Hexanatriumsalzes der Ethylendiaminotetramethylenphosphonsäure und 0,26 kg eines schäumdämpfenden Silikonöls besprüht. Nach einem 30 Sekunden dauernden Nachmischen erhielt man ein gleichmäßiges Granulat, das sich "fettig" anfühlte. Unter weiterem Mischen gab man 0,9 kg hochdisperse Kieselsäure und 1,08 kg feinteilige Kartoffelstärke hinzu; damit überzog man die Granulatoberfläche. Auf das Granulat sprühte man anschließend 1,62 kg einer wäßrigen 70 gewichtsprozentigen Sorbitlösung zu und trocknete 3 Minuten lang mit Luft von 50 bis 60 °C; der Wassergehalt des Granulats betrug 5 Gew.-%.5.16 kg of tetraacetylethylenediamine, 1.9 kg of tetradecyltrimethylammonium bromide, 2.2 kg of highly dispersed precipitated silica and 0.4 kg of magnesium aluminum silicate were mixed with a liquid of 5.16 kg of C 14 / C 15 oxo alcohol in a 130 1 Lödige mixer sprayed with 7 moles of ethylene oxide, 1.3 kg of a 33% by weight aqueous solution of the hexasodium salt of ethylenediaminotetramethylenephosphonic acid and 0.26 kg of a foam-suppressing silicone oil. After re-mixing for 30 seconds, uniform granules were obtained which felt "greasy". With further mixing, 0.9 kg of highly disperse silica and 1.08 kg of finely divided potato starch were added; this covered the granulate surface. Then 1.62 kg of an aqueous 70 percent by weight sorbitol solution were sprayed onto the granules and dried for 3 minutes with air at 50 to 60 ° C .; the water content of the granules was 5 % by weight.

Das getrocknete Granulat vermischte man anschließend schonend mit soviel vernetztem Polyvinylpyrrolidon (PVP) und Na-Carboxymethylcellulose (CMC) als Tablettensprengmittel, daß auf 80 Gew.-Teile Granulat 15 Gew.-Teile PVP und 5 Gew.-Teile CMC entfallen. Diese Vermischung erfolgte in einem Patterson-Kelley-Cron-Flow- Blender. Man erhielt ein beschichtetes Granulat mit einem Schüttgewicht von 535 g pro Liter.The dried granules were then mixed gently with so much crosslinked polyvinylpyrrolidone (PVP) and sodium carboxymethyl cellulose (CMC) as tablet disintegrants that 80 parts by weight of granules account for 15 parts by weight of PVP and 5 parts by weight of CMC. This mixing took place in a Patterson-Kelley-Cron-Flow blender. A coated granulate with a bulk density of 535 g per liter was obtained.

In einer Excenterpresse erfolgte mit unbeschichtetem poliertem Preßwerkzeug die Pressung von 35 mm-Tabletten. Die Tabletten mit einer Höhe von 29,5 mm wären 28,5 g schwer und wiesen eine Bruchfestigkeit von 10 kg auf, die wie folgt bestimmt wurde:

  • In einem Tension und Compression Tester der Fa. Chatillon wurde die Tablette auf eine Matrize mit einer Fräsung, die etwas kleiner als der Tablettendurchmesser ist, gelegt. Die Matrize wurde auf einem Amboß mit motorischer Kraft gegen ein Dynamometer mit keilförmiger Schneide bewegt. Die Bewegung wurde bis zum Bruch der Tablette fortgesetzt. Die beim Bruch der Tablette abgelesene Kraft ist die Bruchfestigkeit in kg. Diese Methode der Bestimmung der Bruchfestigkeit ist in W.A. Ritschel, "Die Tablette", Edition Cantor KG, Aulendorf in Württemberg, 1960, Seite 312 und 313 näher beschrieben.
35 mm tablets were pressed in an eccentric press using an uncoated, polished pressing tool. The tablets with a height of 29.5 mm were 28.5 g heavy and had a breaking strength of 10 kg, which was determined as follows:
  • In a tension and compression tester from Chatillon, the tablet was placed on a die with a milling that is slightly smaller than the tablet diameter. The die was moved on a motor anvil against a wedge shaped dynamometer. The movement continued until the tablet broke. The force read when the tablet breaks is the breaking strength in kg. This method of determining the breaking strength is described in more detail in WA Ritschel, "Die Tablette", Edition Cantor KG, Aulendorf in Württemberg, 1960, pages 312 and 313.

Die erhaltenen Tabletten lösten sich innerhalb von 6 Minuten in einem Waschgang mit 30 °C-Waschprogramm (Miele-Waschautomat, Typ 430) rückstandslos auf. Die damit gewaschene angeschmutzte Wäsche war trotz 2/3-Soll-Dosierung eines Billigwaschmittels deutlich sauberer als ohne Zusatz einer Waschkraftverstärkertablette.The tablets obtained dissolved within 6 minutes in a wash cycle with a 30 ° C wash program (Miele washing machine, type 430) without residue. The soiled laundry washed with it was significantly cleaner than without the addition of a detergent booster tablet despite the 2/3 nominal dosage of a cheap detergent.

Beispiel 2Example 2

Verwendete man das Grundgranulat von Beispiel 1 und bestäubte 85 Gew.-Teile mit 10 Gew.-Teilen Polyvinylpyrrolidon und 5 Gew.-Teilen quellfähigem Magnesiumaluminiumsilikat, erhielt man aus dem Granulat (Schüttgewicht ca. 600 g pro Liter), 30 g schwere Tabletten mit einer Bruchfestigkeit von ca. 8 kg. Nach 10 Minuten sind diese Tabletten in der Waschmaschine rückstandslos aufgelöst.If the base granules from Example 1 were used and 85 parts by weight dusted with 10 parts by weight of polyvinylpyrrolidone and 5 parts by weight of swellable magnesium aluminum silicate, 30 g of tablets were obtained from the granules (bulk density approx. 600 g per liter) a breaking strength of approx. 8 kg. After 10 minutes, these tablets are completely dissolved in the washing machine.

Beispiel 3Example 3

Vermischte man wie in den vorangegangenen Beispielen 83 Gew.-Teile Grundgranulat mit 12 Gew.-Teilen Polyvinylpyrrolidon und 5 Gew.-Teilen wasserfreiem Natriumacetat, erhielt man ein Produkt mit einem Schüttgewicht von 580 g pro Liter; dieses Produkt ergab, mit beschichteten Werkzeugen verpreßt, 27,5 g schwere Tabletten mit einer Bruchfestigkeit von 10 kg, die sich in der Waschmaschine in 5 Minuten rückstandslos auflösten.If 83 parts by weight of base granules were mixed with 12 parts by weight of polyvinylpyrrolidone and 5 parts by weight of anhydrous sodium acetate, as in the preceding examples, a product with a bulk density of 580 g per liter was obtained; this product, pressed with coated tools, gave 27.5 g tablets with a breaking strength of 10 kg, which dissolved in the washing machine in 5 minutes without residue.

Claims (11)

1. Verfahren zur Herstellung eines Waschzusatzes in Tablettenform, bei dem man einen Aktivator für Perverbindungen und übliche Tablettierungshilfsmittel miteinander vermischt und formt, dadurch gekennzeichnet, daß man den pulverförmigen Aktivator zusammen mit nichtionischen Tensiden, mit stickstoffhaltigen Verbindungen aus der quartäre Ammoniumverbindungen, Fettaminderivate bzw. Aminopropionsäurederivate umfassenden Gruppe mit den Tablettierungshilfsmitteln und gegebenenfalls mit dem wasserlöslichen Salz einer Alkanpolyphosphonsäure unter Vermischen granuliert, das Granulat mit einem pulverförmigen Adsorptionsmittel bepudert und mit einem flüssigen Bindemittel besprüht, anschließend das Granulat auf einen Wassergehalt von höchstens 6 Gew.-% trocknet und hieraus nach Zugabe eines Tablettensprengmittels Tabletten, deren Form, Gewicht und Dichte so gewählt wird, daß die Tabletten einen für einen Waschgang ausreichenden Gehalt an waschkraftsteigernden Wirkstoffen aufweisen und die Tabletten von den Wäschestücken während des Waschvorganges mit umgewälzt werden, so daß die Tabletten sich schnell und vollständig auflösen, preßt.1. A process for the preparation of a washing additive in tablet form, in which an activator for per compounds and customary tableting aids are mixed with one another and shaped, characterized in that the powdered activator together with nonionic surfactants, with nitrogen-containing compounds from the quaternary ammonium compounds, fatty amine derivatives or aminopropionic acid derivatives Comprehensive group with the tableting aids and optionally with the water-soluble salt of an alkane polyphosphonic acid with mixing, the granules are powdered with a powdery adsorbent and sprayed with a liquid binder, then the granules are dried to a water content of at most 6 wt .-% and from this after adding one Tablet disintegrant tablets, the shape, weight and density of which are chosen so that the tablets have a sufficient amount of detergent-increasing active ingredients for one wash cycle and the tablet n of the laundry items are circulated during the washing process, so that the tablets dissolve quickly and completely, presses. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man vor der Bildung des Granulats 1 bis 5 Gew.-%, bezogen auf das Granulat ohne Schutzschicht, eines Granulat-Sprengmittels zusetzt.2. The method according to claim 1, characterized in that before the formation of the granules 1 to 5 wt .-%, based on the granules without a protective layer, a granule disintegrant is added. 3. Verfahren nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß man dem getrockneten Granulat vor dem Verpressen 10 bis 20 Gew.-%, bezogen auf das Granulat, eines Tablettensprengmittels, vorzugsweise eines Gemisches aus zwei verschiedenen Tablettensprengmitteln, insbesondere eines Gemisches aus vernetztem Polyvinylpyrrolidon und/oder Celluloseethern und/oder quellfähigem Magnesiumaluminiumsilikat, zusetzt.3. The method according to claims 1 or 2, characterized in that the dried granules before pressing 10 to 20 wt .-%, based on the granules, of a tablet disintegrant, preferably a mixture of two different tablet disintegrants, in particular a mixture of crosslinked Polyvinylpyrrolidone and / or cellulose ethers and / or swellable magnesium aluminum silicate is added. 4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man im Fall der Zumischung von zwei verschiedenen Tablettensprengmitteln vernetztes Polyvinylpyrrolidon im Gemisch mit Celluloseethern und/oder quellfähigem Magnesiumaluminumsilikat im Gewichtsverhältnis 8 : 1 bis 2 : 1 zusetzt.4. The method according to claim 3, characterized in that in the case of admixing two different tablet disintegrants, crosslinked polyvinylpyrrolidone in a mixture with cellulose ethers and / or swellable magnesium aluminum silicate is added in a weight ratio of 8: 1 to 2: 1. 5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man aus dem getrockneten Granulat bei einem Druck von 500 bis 1000 kp/cm2 Tabletten mit einem Durchmesser von mehr als 30 mm und einer Höhe, die das 0,75- bis 1,1-fache des Tablettendurchmesens, wenigstens aber 25 mm beträgt, mit einer Dichte von 0,8 bis 1,2 g pro cm3 und einer Bruchfestigkeit von 6 bis 12 kg verpreßt.5. The method according to any one of claims 1 to 4, characterized in that from the dried granules at a pressure of 500 to 1000 kp / cm 2 tablets with a diameter of more than 30 mm and a height that the 0.75- up to 1.1 times the tablet diameter, but at least 25 mm, with a density of 0.8 to 1.2 g per cm 3 and a breaking strength of 6 to 12 kg. 6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man wenigstens einen Aktivator für Perverbindungen mit wenigstens einem C12- bis C18-A1- koholethoxylat, mit wenigstens einer stickstoffhaltigen Verbindung aus der quartäre Ammoniumverbindungen mit einem C10 - bis C20 -Alkyl- oder Alkenylrest und im übrigen C1- bis C4-Alkylresten, Anlagerungsprodukte von 1 bis 6 Mol Ethylenoxid an 1 Mol eines primären Fettamins mit einem C10 - bis C16 -Alkyl- oder Alksnylrest, ß-Aminoalkyl- oder alkenylpropionsäure-Natrlum--COONa, salz der Formel R-NH-CH2-CH2-COONa, in der R einen C10 - bis C16-Alkyl- oder Alkenylrest bedeutet, umfassenden Gruppe und gegebenenfalls mit einer wäßrigen Lösung eines Salzes einer Alkanpolyphosphonsäure unter Vermischen granuliert.6. The method according to any one of claims 1 to 5, characterized in that at least one activator for per compounds with at least one C 12 - to C 18 -A1- alcohol ethoxylate, with at least one nitrogen-containing compound from the quaternary ammonium compounds with a C 10 - to C 20 alkyl or alkenyl and, in addition, C 1 to C 4 alkyl, addition products of 1 to 6 moles of ethylene oxide with 1 mole of a primary fatty amine with a C 10 to C 16 alkyl or alkenyl radical, β-aminoalkyl, or alkenylpropionic acid sodium -COONa, salt of the formula R-NH-CH 2 -CH 2 -COONa, in which R is a C 10 - to C 16 -alkyl or alkenyl radical, comprehensive group and optionally granulated with an aqueous solution of a salt of an alkane polyphosphonic acid with mixing . 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Granulatbildung unter Zugabe eines oder mehrerer wasserunlöslicher oder wasserlöslicher pulveriger Trägermaterialien für die flüssigen oder pastösen Wirkstoffbestandteile vornimmt.7. The method according to any one of claims 1 to 6, characterized in that the granulate formation is carried out with the addition of one or more water-insoluble or water-soluble powdery carrier materials for the liquid or pasty active ingredient components. 8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man das Granulat so mit einem feindispersen inerten Material und/oder einem feinteiligen Adsorptionsmittel bepudert und mit einer Zuckerlösung, vorzugsweise mit einer Rohrzucker- oder Sorbitlösung besprüht, daß das Granulat nach dem Trocknen auf einen Wassergehalt von höchstens 6 Gew.-% mit Luft mit einer Temperatur von höchstens 90 °C gut rieselfähig ist und eine äußere Schicht aus im wesentlichen inertem Material und/oder Adsorptionsmittel und Zucker aufweist.8. The method according to any one of claims 1 to 7, characterized in that the granules are powdered with a finely dispersed inert material and / or a finely divided adsorbent and sprayed with a sugar solution, preferably with a cane sugar or sorbitol solution, that the granules after Drying to a water content of at most 6% by weight with air at a temperature of at most 90 ° C. is free-flowing and has an outer layer of essentially inert material and / or adsorbent and sugar. 9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man ein nichtionisches Tensid vom Typ Fettalkohol- oder insbesondere Oxoalkoholethoxylat mit 12 bis 18, vorzugsweise 14 bis 15 Kohlenstoffatomen und 3 bis 10, vorzugsweise 6 bis 8 und insbesondere etwa 7 Mol Ethylenoxid pro Mol Alkohol verwendet.9. The method according to any one of claims 1 to 8, characterized in that a nonionic surfactant of the fatty alcohol or in particular oxo alcohol ethoxylate having 12 to 18, preferably 14 to 15 carbon atoms and 3 to 10, preferably 6 to 8 and in particular about 7 moles Ethylene oxide used per mole of alcohol. 10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß man eine quartäre von Ammoniak abgeleitete Ammoniumverbindung mit einem C10- bis C20-Alkyl- oder Alkenylrest, vorzugsweise einem C10- bis C16- und insbesondere einem C14-Alkyl- oder Alkenylrest und im übrigen drei Methylgruppen, vorzugsweise Tetradecyltrimethylammoniumbromid verwendet.10. The method according to any one of claims 1 to 9, characterized in that a quaternary ammonium-derived ammonium compound having a C 10 - to C 20 alkyl or alkenyl radical, preferably a C10 to C 16 - and in particular a C14-alkyl - Or alkenyl and three methyl groups, preferably tetradecyltrimethylammonium bromide. 11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß man ein wasserlösliches Salz von Alkanpolyphosphonsäuren aus der Gruppe der Phosphonoalkanpolyphosphonsäuren und der amino- und hydroxysubstituierten Alkanpolyphosphonsäuren, insbesondere Alkalisalze der Amino-tris-(methylenphosphonsäure), Dimethylaminomethandiphosphonsäuren, 1-Hydroxyethan-1,1- diphosphonsäure, 1-Phosphonoethan-1,2-dicarbonsäure, 2-Phosphonobutan-1,2,4-tricarbonsäure und vorzugsweise das Hexanatriumsalz der Ethylendiaminotetramethylenphosphonsäure verwendet.11. The method according to any one of claims 1 to 10, characterized in that a water-soluble salt of alkane polyphosphonic acids from the group of phosphonoalkane polyphosphonic acids and the amino and hydroxy-substituted alkane polyphosphonic acids, especially alkali salts of amino-tris (methylenephosphonic acid), dimethylaminomethane diphosphonic acids, 1-hydroxyl acids -1,1- diphosphonic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and preferably the hexasodium salt of ethylenediaminotetramethylenephosphonic acid is used.
EP85105496A 1984-05-14 1985-05-06 Process for the production of a washing additive in the form of tablets Expired EP0170791B1 (en)

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AT85105496T ATE36347T1 (en) 1984-05-14 1985-05-06 PROCESS FOR MAKING A LAUNDRY ADDITIVE IN TABLET FORM.

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DE3417820 1984-05-14
DE19843417820 DE3417820A1 (en) 1984-05-14 1984-05-14 METHOD FOR PRODUCING A WASHING ADDITIVE IN TABLET FORM

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EP (1) EP0170791B1 (en)
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EP0238341A2 (en) * 1986-03-19 1987-09-23 Warwick International Group Plc Granular bleach activator compositions
EP0522766A2 (en) * 1991-07-01 1993-01-13 Unilever Plc Detergent compositions in tablet form
GB2260989A (en) * 1991-10-30 1993-05-05 Unilever Plc Shaped detergent compositions
WO1994023010A1 (en) * 1993-04-01 1994-10-13 Unilever N.V. Solid detergent briquettes
GB2345701A (en) * 1999-01-12 2000-07-19 Procter & Gamble Particulate bleaching components
EP1036839A2 (en) * 1999-03-17 2000-09-20 Basf Aktiengesellschaft Tablets and particulate detergents comprising cross-linked polyvinylpyrrolidone and its use
WO2003038021A3 (en) * 2001-10-26 2003-06-12 Isp Investments Inc Tablet of compacted particulate cleaning composition

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JPH0637633B2 (en) * 1986-11-26 1994-05-18 サンスタ−株式会社 Tablet type cleaning composition and method for producing the same
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US5234616A (en) * 1987-10-30 1993-08-10 The Clorox Company Method of laundering clothes using a delayed onset active oxygen bleach composition
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US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
DE4010533A1 (en) * 1990-04-02 1991-10-10 Henkel Kgaa Prodn. of high-density detergent granules
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US5478501A (en) * 1994-04-07 1995-12-26 The Andrew Jergens Company Bathing composition containing coated cationic polymer
GB9422895D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
GB9422925D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
GB9422924D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
GB2318575A (en) * 1996-10-22 1998-04-29 Unilever Plc Detergent tablet
US6169062B1 (en) 1996-12-06 2001-01-02 The Procter & Gamble Company Coated detergent tablet
DE69637030T2 (en) * 1996-12-06 2007-12-27 The Procter & Gamble Company, Cincinnati Coated cleaning agent in tablet form and manufacturing method therefor
DE19709991C2 (en) 1997-03-11 1999-12-23 Rettenmaier & Soehne Gmbh & Co Detergent compact and process for its manufacture
DE19710254A1 (en) * 1997-03-13 1998-09-17 Henkel Kgaa Shaped or active cleaning moldings for household use
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GB9802390D0 (en) 1998-02-04 1998-04-01 Unilever Plc Detergent compositions
GB9807992D0 (en) 1998-04-15 1998-06-17 Unilever Plc Water softening and detergent compositions
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DE19901064A1 (en) * 1999-01-14 2000-07-20 Henkel Kgaa Aid granules for washing and cleaning active moldings
DE19901063A1 (en) * 1999-01-14 2000-07-20 Henkel Kgaa Aid granules for washing and cleaning active moldings
DE19919444B4 (en) * 1999-04-29 2016-06-30 Henkel Ag & Co. Kgaa Detergent tablets with binder compound, process for its preparation and use of binder compounds
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US6342240B1 (en) 2000-04-07 2002-01-29 John S. Holman Disinfectant and odorizing system for an evaporation cooler
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US6669929B1 (en) * 2002-12-30 2003-12-30 Colgate Palmolive Company Dentifrice containing functional film flakes
ES2293198T3 (en) * 2004-01-12 2008-03-16 THE PROCTER & GAMBLE COMPANY PADS WITH RESISTANCE TO THE IMPROVED ROTUA.
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Cited By (12)

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EP0238341A2 (en) * 1986-03-19 1987-09-23 Warwick International Group Plc Granular bleach activator compositions
EP0238341A3 (en) * 1986-03-19 1988-08-17 Warwick International Limited Granular bleach activator compositions
EP0522766A2 (en) * 1991-07-01 1993-01-13 Unilever Plc Detergent compositions in tablet form
EP0522766A3 (en) * 1991-07-01 1993-04-07 Unilever Plc Detergent compositions in tablet form
US5407594A (en) * 1991-07-01 1995-04-18 Lever Brothers Company, Division Of Conopco, Inc. Detergent tablets having specific particle size distribution
GB2260989A (en) * 1991-10-30 1993-05-05 Unilever Plc Shaped detergent compositions
WO1994023010A1 (en) * 1993-04-01 1994-10-13 Unilever N.V. Solid detergent briquettes
GB2345701A (en) * 1999-01-12 2000-07-19 Procter & Gamble Particulate bleaching components
EP1036839A2 (en) * 1999-03-17 2000-09-20 Basf Aktiengesellschaft Tablets and particulate detergents comprising cross-linked polyvinylpyrrolidone and its use
EP1036839A3 (en) * 1999-03-17 2001-04-18 Basf Aktiengesellschaft Tablets and particulate detergents comprising cross-linked polyvinylpyrrolidone and its use
WO2003038021A3 (en) * 2001-10-26 2003-06-12 Isp Investments Inc Tablet of compacted particulate cleaning composition
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DE3564286D1 (en) 1988-09-15
ES543071A0 (en) 1986-06-01
US4642197A (en) 1987-02-10
ES8607382A1 (en) 1986-06-01
JPS60252699A (en) 1985-12-13
ATE36347T1 (en) 1988-08-15
EP0170791B1 (en) 1988-08-10
DE3417820A1 (en) 1985-11-14

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