EP0170791B1 - 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

Info

Publication number
EP0170791B1
EP0170791B1 EP85105496A EP85105496A EP0170791B1 EP 0170791 B1 EP0170791 B1 EP 0170791B1 EP 85105496 A EP85105496 A EP 85105496A EP 85105496 A EP85105496 A EP 85105496A EP 0170791 B1 EP0170791 B1 EP 0170791B1
Authority
EP
European Patent Office
Prior art keywords
granulate
weight
acid
tablets
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.)
Expired
Application number
EP85105496A
Other languages
German (de)
French (fr)
Other versions
EP0170791A1 (en
Inventor
Hans Kruse
Klaus Dr. Köster
Franz-Josef Dr. Carduck
Heinz-Manfred Wilsberg
Rolf Dr. Puchta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
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

Links

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 per-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 on the per-compounds prematurely and the per-compounds may thus 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 should contain the active substances in coordinated proportions and in the quantity matched to the capacity of a washing machine and should not have to be sorted out 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 features of the method according to the invention ensure that the tablet has a stability that prevents the tablet from disintegrating in the washing machine before use.
  • 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 are also perfect in the moist air of a laundry room Ensure storage for a long time.
  • 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 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 preferably contains a mixture of at least one activator for per compounds, at least one C 12 to C t8 alcohol ethoxylate , at least one nitrogen-containing compound from the quaternary ammonium compounds with a single C tO to C 20 alkyl or alkenyl radical and otherwise 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, sodium ⁇ -aminoalkyl or alkenylpropionic acid of the formula R-NH -CH 2 -CH Z -COONa, in which R is an alkyl or alkenyl radical having 10 to 20 carbon atoms, in particular 12 to 14 carbon atoms, comprehensive group, which is optionally granulated with an aqueous solution of a water-soluble salt of an alkane polyphosphonic acid.
  • 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 improved removal of bleachable textile soiling.
  • Addition products of ethylene oxide with fatty or especially 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 in many cases it is advisable to add foam regulators; in most cases, the development of foam must be dampened. Suitable foam damping agents are, for example, the known silicone oils.
  • the content of nonionic surfactants in the washing additives according to the invention especially promoted the removal of greasy or oily stains during washing.
  • Suitable quaternary ammonium compounds contain long-chain alkyl or alkenyl radicals 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, 1-hydroxyethane-1,1-diphosphonic acid, have been particularly suitable for this.
  • the granules are produced from the active substances mentioned by focusing on the solids, ie. h, on 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, d. h, the nonionic surfactant and, if appropriate, the heavy metal complexing agents dissolved in water are sprayed on.
  • 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, and the dusted granules are sprayed, for. B. with an aqueous sugar solution, in particular cane sugar or sorbitol solution and dries the granules.
  • the granules preferably contain about 50 to 90% by weight of active ingredients; the rest are auxiliary substances.
  • the bulk density of the granules sieved through a 2 mm sieve is preferably 600 to 700 g per liter.
  • the granules coated and dried with a protective layer are preferably 10 to 20 wt mixed.
  • 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.
  • a weight ratio of polyvinylpyrrolidone to the second tablet disintegrant in the range from 8: 1 to 2: 1 is particularly preferred.
  • the tablets are produced by using the dried granules at a pressure of 5x107 to 10 8 Pa tablets with a diameter of more than 30 mm and a height that is 0.75 to 1.1 times the tablet diameter, but at least 25 mm, pressed with a density of 0.8 to 1.2 g per cm 3 and a breaking strength of 60 to 120 N.
  • 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 Perverbindungen 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 per-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 on the per-compounds prematurely and the per-compounds may thus 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 should contain the active substances in coordinated proportions and in the quantity matched to the capacity of a washing machine and should not have to be sorted out 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 quartäre Ammoniumverbindungen, Fettaminderivate und Aminopropionsäurederivate umfassenden Gruppe, mit den Tablettierungshilfsmitteln und gegebenenfalls mit dem wasserlöslichen Salz einer Alkanpolyphosphonsäure unter Vermischen granuliert, das Granulat mit einem Feinteiligen inerten Material und/oder einem feinteiligen Adsorptionsmittel bepudert, und dann mit einem flüssigen Bindemittel besprüht, anschließend das Granulat auf einen Wassergehalt von höchstens 6 Gew.-% trocknet und hieraus nach Zugabe eines Tablettensprengmittels bei einem Druck von 5 x 107 bis 108 Pa Tabletten einesDurchmessers von mehr als 30 mm, einer Höhe, die das 0,75- bis 1,1- fache des Tablettendurchmessers, wenigstens aber 25 mm, beträgt, einer Dichte von 0,8 bis 1,2 g pro cm3 und einer Bruchfestigkeit von 60 bis 120 N, deren Form, Gewicht und Dichte so gewählt werden, daß die 15 bis 50 g schweren Tabletten einen für einen Waschgang ausreichenden Gehalt an waschkraftsteigenden Wirkstoffen, d.h. 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
  • Aminopropionsäurederivat
  • 2 bis 30 Gew.-Teile Aktivator für
  • Perverbindungen
  • 0 bis 5 Gew.-Teile
  • Schwermetallkomplexbildner
The object was achieved in that the powdered activator together with nonionic surfactants, with nitrogen-containing compounds from the group comprising quaternary ammonium compounds, fatty amine derivatives and aminopropionic acid derivatives, with the tabletting aids and optionally with the water-soluble salt of an alkane polyphosphonic acid while mixing, the granules with a Powdered inert material and / or a finely divided adsorbent, and then sprayed with a liquid binder, then the granules are dried to a water content of at most 6 wt .-% and from this after adding a tablet disintegrant at a pressure of 5 x 10 7 to 10 8 Pa tablets of a diameter of more than 30 mm, a height which is 0.75 to 1.1 times the tablet diameter, but at least 25 mm, a density of 0.8 to 1.2 g per cm 3 and one Breaking strength from 60 to 120 N, their shape, weight and D should be chosen so that the 15 to 50 g tablets have a sufficient amount of detergent-increasing active ingredients for one wash cycle, ie 10 to 30 g 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
  • Aminopropionic acid derivative
  • 2 to 30 parts by weight of activator for
  • Per connections
  • 0 to 5 parts by weight
  • Heavy metal complexing agent

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.have and the tablets of the laundry items are circulated during the washing process, so that the tablets dissolve quickly and completely, presses. The features of the method according to the invention ensure that the tablet has a stability that prevents the tablet from disintegrating in the washing machine before use. 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 are also perfect in the moist air of a laundry room Ensure storage for a long time. 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 Granulatsprengmittel 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 beschichtet 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. This envelops the active ingredient granules with a protective layer of binder and sugar that is largely or completely closed after drying. Drying the granules treated in this way to a water content of at most 6% by weight is necessary in order to make the granules free-flowing, i.e. that is, to make it possible to feed the pressing tools properly. 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 vorzugsweise, ein Gemisch aus wenigstens einem Aktivator für Perverbindungen, wenigstens einem C12- bis Ct8-Alkoholethoxylat, wenigstens einer stickstoffhaltigen Verbindung aus der quartäre Ammoniumverbindungen mit einem einzigen CtO - bis C20-Alkyl- oder Alkenylrest und im übrigen Cl- 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, β-Aminoalkyl- oder alkenylpropionsäure-Natriumsalz der Formel R-NH-CH2-CHZ-COONa, in der R einen Alkyl- oder Alkenylrest mit 10 bis 20 Kohlenstoffatomen, insbesondere 12 bis 14 Kohlenstoffatomen bedeutet, umfassenden Gruppe, 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 preferably contains a mixture of at least one activator for per compounds, at least one C 12 to C t8 alcohol ethoxylate , at least one nitrogen-containing compound from the quaternary ammonium compounds with a single C tO to C 20 alkyl or alkenyl radical and otherwise 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, sodium β-aminoalkyl or alkenylpropionic acid of the formula R-NH -CH 2 -CH Z -COONa, in which R is an alkyl or alkenyl radical having 10 to 20 carbon atoms, in particular 12 to 14 carbon atoms, comprehensive group, which is optionally granulated with an aqueous solution of a water-soluble salt of an alkane polyphosphonic acid. 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 conjunction with per compounds of the common heavy-duty detergents, in particular with the perborate that is usually used, the bleach activators mentioned lead to 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 or especially 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; in most cases, the development of foam must be dampened. Suitable foam damping agents are, for example, the known silicone oils. The content of nonionic surfactants in the washing additives according to the invention especially promoted the removal of greasy or oily stains 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-C2-COONa; geeignete quartäre Ammoniumverbindungen enthalten langkettige 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 -C 2 -COONa, is used to improve the removal of pigment contaminants from textiles. Suitable quaternary ammonium compounds contain long-chain alkyl or alkenyl radicals 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-(methylenphosphonsäure), Dimethylenaminomethandiphosphonsäuren, 1 - Hydroxyethan-1,1-diphosphonsäure, 1-Phosphonoethan-1,2-dicarbonsäure, 2-Phosphonobutan-1,2,3-tricarbonsäure und insbesondere das Hexanatriumsalz der Ethylendiaminotetramethylenphosphonsäure.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, 1-hydroxyethane-1,1-diphosphonic acid, have been particularly suitable for this. 1,2-dicarboxylic 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, on 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, d. h, the nonionic surfactant and, if appropriate, the heavy metal complexing agents dissolved in water are sprayed on. 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 z. B. mit einer wäßrigen Zuckerlösung, insbesondere Rohrzucker- oder Sorbitlösung und trocknet das Granulat. Das Granulat enthält vorzugsweise etwa 50 bis 90 Gew.-% Wirkstoffe; der Rest sind Hilfsstoffe. Das Schüttgewicht des über ein 2 mm-Sieb gesiebten Granulats liegt vorzugsweise 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, and the dusted granules are sprayed, for. B. with an aqueous sugar solution, in particular cane sugar or sorbitol solution and dries the granules. The granules preferably contain about 50 to 90% by weight of active ingredients; the rest are auxiliary substances. The bulk density of the granules sieved through a 2 mm sieve is preferably 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, eines Tablettensprengmittels, 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 10 to 20 wt mixed. 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 5x107 bis 108 Pa 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 60 bis 120 N verpreßt.The tablets are produced by using the dried granules at a pressure of 5x107 to 10 8 Pa tablets with a diameter of more than 30 mm and a height that is 0.75 to 1.1 times the tablet diameter, but at least 25 mm, pressed with a density of 0.8 to 1.2 g per cm 3 and a breaking strength of 60 to 120 N.

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
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 with 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

Ammoniumverbindung und/oder Fettaminderivat und/oder Aminopropionsäurederivat,

  • 2 bis 30 Gew.-Teile Aktivator für
  • Perverbindungen,
  • 0 bis 5 gew.-Teile
  • Schwermetallkomplexbildner.
Ammonium compound and / or fatty amine derivative and / or aminopropionic acid derivative,
  • 2 to 30 parts by weight of activator for
  • Per connections,
  • 0 to 5 parts by weight
  • Heavy metal complexing agent.

BeispieleExamples Beispiel 1example 1

In einem 130 I 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 C14/15-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.- %. In a 130 I Lödige mixer 5.16 kg of tetraacetylethylenediamine, tetradecyltrimethylammonium bromide 1.9 kg, 2.2 kg highly disperse precipitated silica and 0.4 kg of magnesium aluminum silicate, with continuous mixing, with a liquid of 5.16 kg C 14/15 -oxo alcohol with 7 moles of ethylene oxide, 1.3 kg of a 33 percent 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 waren 28,5 g schwer und wiesen eine Bruchfestigkeit von 100 N 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 N. 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 100 N, 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 N. 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. 80 N. 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. 80 N. 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 100 N 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, compressed with coated tools, gave 27.5 g tablets with a breaking strength of 100 N which dissolved in the washing machine in 5 minutes without residue.

Claims (11)

1. A process for the production of a washing additive in tablet form, in which an activator for per compounds and standard tabletting aids are mixed together and the resulting mixture is tabletted, characterized in that the powder-form activator is granulated and at the same time mixed together with nonionic surfactants, nitrogen-containing compounds from the group comprising quaternary ammonium compounds, fatty amine derivatives and aminopropionic acid derivatives, with the tabletting aids and, optionally, with the water-soluble salt of an alkane polyphosphonic acid, powdering the granulate with a finely divided inert material and/or a finely divided adsorbent, spraying it with a liquid binder, subsequently drying the granulate to a water content of at most 6 % by weight and, after the addition of a tablet distintegrating agent, forming the granulate by compression under a pressure of 5 x 107 to 108 Pa into tablets having a diameter of greater than 30 mm, a depth corresponding to 0.75 to 1.1 times their diameter, but at least 25 mm, a density of from 0.8 to 1.2 g/cm3 and a breaking strength of from 60 to 120 N, of which the shape, weight and density are selected in such a way that the tablets which weigh from 15 to 50 g contain sufficient detergency-boosting ingredients for one load of washing, i.e. contain 10 to 30 g active ingredients in the following quantities:
2 to 30 parts by weight non-ionic surfactant,
0.5 to 20 parts by weight quaternary ammonium compound and/or fatty amine derivative and/or aminopropionic acid derivative,
2 to 30 parts by weight activator for per compounds,
0 to 5 parts by weight heavy-metal complexing agent,
and the tablets are circulated by the pieces of laundry during the washing process so that they dissolve quickly and completely.
2. A process as claimed in Claim 1, characterized in that, before the granulate is formed, from 1 to 5 % by weight, based on the granulate without its protective layer, of a granulate disintegrating agent is added.
3. A process as claimed in claim 1 or 2, characterized in that from 10 to 20 % by weight, based on the granulate, of a tablet disintegrating agent, preferably a mixture of two different tablet disintegrating agents, more especially a mixture of crosslinked polyvinyl pyrrolidone and/or cellulose ethers and/or swellable magnesium aluminium silicate, are added to the dried granulate before tabletting.
4. A process as claimed in claim 3, characterized in that, where two diffferent disintegrating agents are mixed, crosslinked polyvinyl pyrrolidone is added in admixture with cellulose ethers and/or swellable magnesium aluminium silicate in a ratio by weight of from 8 : 1 to 2 : 1.
5. A process as claimed in any of claims 1 to 4, characterized in that at least one activator for per compounds is granulated and at the same time mixed with at least one C12-Cl8 alcohol ethoxylate, at least one nitrogen-containing compound from the group comprising quaternary ammonium compounds containing one C10-C20 alkyl or alkenyl radical and, for the rest, C1-C4 alkyl radicals, adducts of 1 to 6 moles ethylene oxide with 1 mole of a primary fatty amine containing a C10-C16 alkyl or alkenyl radical, the sodium salt of 0-aminoalkyl or alkenyl propionic acid corresponding to the formula R-NH-CH2-CH2-COONa, in which R is a C10-C16 alkyl or alkenyl radical, and optionally with an aqueous solution of a salt of an alkane polyphosphonic acid.
6. A process as claimed in any of claims 1 to 5, characterized in that the formation of the granulate is carried out in the presence of one or more water-insoluble or watersoluble powder-form carriers for the liquid or pasty active ingredients.
7. A process as claimed in any of claims 1 to 6, characterized in that the granulate is powdered with a finely disperse inert material and/or a finely divided adsorbent and sprayed with a sugar solution, preferably with a cane sugar or sorbitol solution, in such a way that, after drying to a water content of at most 6 % by weight in air at at most 90° C, the granulate flows freely and is covered with a coating of substantially inert material and/or adsorbent and sugar.
8. A process as claimed in any of claims 1 to 8, characterized in that the non-ionic surfactant used is a fatty alcohol or, more particularly, an oxoalcohol ethoxylate containing from 12 to 18 and preferably from 14 to 15 carbon atoms and from 3 to 10, preferably from 6 to 8 and, more especially, approximately 7 moles of ethylene oxide per mole of alcohol.
9. A process as claimed in any of claims 1 to 8, characterized in that a quaternary ammonium compound derived from ammonia containing a C10-C20 alkyl or alkenyl radical, preferably a Clo-Ci6 and, more especially, a C14 alkyl or alkenyl radical and, for the rest, 3 methyl groups, preferably tetradecyl trimethylammonium bromide, is used.
10. A process as claimed in any of claims 1 to 9, characterized in that a water-soluble salt of alkane polyphosphonic acids from the group comprising phosphonoalkane polyphosphonic acids and amino- and hydroxy-substituted alkane polyphosphonic acids, more especially alkali salts of aminotris-(methylenephosphonic acid), dimethylaminomethane diphosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and, preferably, the hexasodium salt of ethylenediaminetetramethylenephosphonic 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85105496T ATE36347T1 (en) 1984-05-14 1985-05-06 PROCESS FOR MAKING A LAUNDRY ADDITIVE IN TABLET FORM.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843417820 DE3417820A1 (en) 1984-05-14 1984-05-14 METHOD FOR PRODUCING A WASHING ADDITIVE IN TABLET FORM
DE3417820 1984-05-14

Publications (2)

Publication Number Publication Date
EP0170791A1 EP0170791A1 (en) 1986-02-12
EP0170791B1 true EP0170791B1 (en) 1988-08-10

Family

ID=6235780

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85105496A Expired EP0170791B1 (en) 1984-05-14 1985-05-06 Process for the production of a washing additive in the form of tablets

Country Status (6)

Country Link
US (1) US4642197A (en)
EP (1) EP0170791B1 (en)
JP (1) JPS60252699A (en)
AT (1) ATE36347T1 (en)
DE (2) DE3417820A1 (en)
ES (1) ES8607382A1 (en)

Families Citing this family (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61276896A (en) * 1985-06-03 1986-12-06 花王株式会社 Softener tablet for washing bath
GB8606804D0 (en) * 1986-03-19 1986-04-23 Warwick International Ltd Particulate bleach activator composition
US5002691A (en) * 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5112514A (en) * 1986-11-06 1992-05-12 The Clorox Company Oxidant detergent containing stable bleach activator granules
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
GB8711153D0 (en) * 1987-05-12 1987-06-17 Warwick International Ltd Bleach activator compositions
US5234616A (en) * 1987-10-30 1993-08-10 The Clorox Company Method of laundering clothes using a delayed onset active oxygen bleach composition
US5130044A (en) * 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
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
GB9022724D0 (en) * 1990-10-19 1990-12-05 Unilever Plc Detergent compositions
GB9114184D0 (en) * 1991-07-01 1991-08-21 Unilever Plc Detergent composition
GB9123058D0 (en) * 1991-10-30 1991-12-18 Unilever Plc Detergent composition
AU694422B2 (en) * 1993-04-01 1998-07-23 Johnsondiversey, Inc. Solid detergent briquettes
US5478501A (en) * 1994-04-07 1995-12-26 The Andrew Jergens Company Bathing composition containing coated cationic polymer
GB9422925D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
GB9422895D0 (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
ES2284164T3 (en) * 1996-12-06 2007-11-01 THE PROCTER & GAMBLE COMPANY PAD OF DETERGENT COVERED AND PROCEDURE TO PRODUCE THE SAME.
DE19758811B4 (en) 1997-03-11 2008-12-18 Henkel Ag & Co. Kgaa Detergent pellet
DE19710254A1 (en) * 1997-03-13 1998-09-17 Henkel Kgaa Shaped or active cleaning moldings for household use
CN1257536A (en) * 1997-03-24 2000-06-21 尤尼利弗公司 Detergent compositions
GB9711831D0 (en) * 1997-06-06 1997-08-06 Unilever Plc Cleaning compositions
GB2332442A (en) * 1997-12-17 1999-06-23 Procter & Gamble Detergent tablet
EP1047759A1 (en) 1998-01-13 2000-11-02 The Procter & Gamble Company A detergent granule containing disintegrant with improved dissolution
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
US6495509B1 (en) * 1998-04-27 2002-12-17 The Procter & Gamble Company Process for making non-particulate detergent product readily dispersible in water
DE19852136A1 (en) * 1998-11-12 2000-05-18 Henkel Kgaa Perfume-free detergent tablets
US6057280A (en) 1998-11-19 2000-05-02 Huish Detergents, Inc. Compositions containing α-sulfofatty acid esters and methods of making and using the same
GB2345701A (en) * 1999-01-12 2000-07-19 Procter & Gamble Particulate bleaching components
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
DE19912031A1 (en) * 1999-03-17 2000-09-21 Basf Ag Use of crosslinked polyvinylpyrrolidone to increase the rate of disintegration of compact particulate detergents and cleaners
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
DE10015661A1 (en) * 2000-03-29 2001-10-31 Henkel Kgaa Detergent tablets, include surfactant granules containing sugars, sugar acids and/or sugar acid salts for improved stability and solubility
US6342240B1 (en) 2000-04-07 2002-01-29 John S. Holman Disinfectant and odorizing system for an evaporation cooler
EP1373456A1 (en) * 2000-11-24 2004-01-02 Unilever N.V. Cleaning tablets
WO2002051975A1 (en) * 2000-12-22 2002-07-04 Unilever N.V. Detergent compositions
EP1219700A1 (en) * 2000-12-28 2002-07-03 Unilever Plc Cleaning compositions
US6586386B2 (en) * 2001-10-26 2003-07-01 Isp Investments Inc. Tablet of compacted particulate cleaning composition
US20050148488A1 (en) * 2002-05-15 2005-07-07 Maren Jekel Detergent tablets with active phase
US6669929B1 (en) * 2002-12-30 2003-12-30 Colgate Palmolive Company Dentifrice containing functional film flakes
DE602004008206T2 (en) * 2004-01-12 2008-05-08 The Procter & Gamble Company, Cincinnati Tablets with improved resistance to breakage
ATE371716T1 (en) * 2004-01-12 2007-09-15 Procter & Gamble TABLETS WITH IMPROVED BREAK RESISTANCE
GB2410496A (en) * 2004-01-31 2005-08-03 Reckitt Benckiser Nv Water softening tablets
US20070148213A1 (en) * 2005-12-22 2007-06-28 Sayed Ibrahim Film containing compositions
US8975221B2 (en) 2010-08-27 2015-03-10 Ecolab Usa Inc. Use of sugars in a stabilization matrix and solid compositions
WO2013171492A1 (en) 2012-05-18 2013-11-21 Warwick International Group Limited Activation of peroxygen bleach
US8877240B1 (en) 2014-01-09 2014-11-04 Chemlink Laboratories, Llc Tablet binding compositions
GB201918973D0 (en) * 2019-12-20 2020-02-05 Nicoventures Trading Ltd Particle

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2048331A1 (en) * 1970-10-01 1972-04-06 Henkel & Cie GmbH, 4000 Dusseldorf Solid, powdery to granular agents for the production of cold-acting bleaching liquors, in particular cold-acting bleaching liquors, and processes for the manufacture of these agents
DE2263939C2 (en) * 1972-07-03 1983-01-13 Henkel KGaA, 4000 Düsseldorf Bleach activator tablets suitable for use in laundry detergents containing perhydrates
FR2281160A1 (en) * 1974-08-06 1976-03-05 Nobel Hoechst Chimie Encapsulating and granulating glycoluril and ethylene diamine derivs. - with carboxylated long chain hydrocarbons, making them stable as activators in detergent and cleaning compsns.
BE9T1 (en) * 1977-06-29 1980-01-11 Procter & Gamble LAUNDRY ADDITIVE
EP0006655B1 (en) * 1978-06-26 1982-10-13 THE PROCTER & GAMBLE COMPANY Particulate detergent additive product
ES8400768A1 (en) * 1980-11-06 1983-11-01 Procter & Gamble Bleach activator compositions, preparation thereof and use in granular detergent compositions.

Also Published As

Publication number Publication date
US4642197A (en) 1987-02-10
DE3417820A1 (en) 1985-11-14
EP0170791A1 (en) 1986-02-12
ATE36347T1 (en) 1988-08-15
JPS60252699A (en) 1985-12-13
ES8607382A1 (en) 1986-06-01
ES543071A0 (en) 1986-06-01
DE3564286D1 (en) 1988-09-15

Similar Documents

Publication Publication Date Title
EP0170791B1 (en) Process for the production of a washing additive in the form of tablets
EP0692020B1 (en) Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same
EP0264701B1 (en) Cleaning agent tablets for the automatic dishwashing
EP0200163B1 (en) Bleaching agent, its preparation and its use
DE3827895A1 (en) PROCESS FOR PREPARING PHOSPHATE-REDUCED DETERGENT TABLETS
DE3545947A1 (en) PHOSPHATE-FREE, GRANULAR DETERGENT
DE69731189T3 (en) Tablets and process for their preparation
EP0200953A2 (en) Granular detergent
EP0965565A1 (en) Water-softening tablet
DE1087738B (en) Cleaning agent with bleaching, oxidizing and disinfecting effects
DE3842007A1 (en) FLUID TO PASTOESES, BLEACHING DETERGENT
EP0344629A1 (en) Granular adsorption material with improved flushing property
DE3024912A1 (en) PARTICULATE BLENDER
EP0541523B1 (en) Paste-like, phosphate-free detergent with reduced frothing tendency
EP0164703B1 (en) Additive for washing
WO1991015568A1 (en) Stable, bifunctional, phosphate-free detergent tablets for use in dishwashing machines
EP0871698B1 (en) Method of producing breakage-resistant detergent tablets
WO2004058931A1 (en) Bleach-containing washing or cleaning agents
EP0888449B1 (en) Solid surfactant and builder-containing washing and cleaning agent with a high bulk density or compound for such an agent
DE3639115A1 (en) STORAGE BLENDER MIXTURE WITH IMPROVED SOLUTION
EP0623593A2 (en) Process for neutralising the acid form of anionic surfactant, agglomerates and detergent thereby obtained
EP0354331A1 (en) Detergent additive with improved flushing property
EP0658190B1 (en) Process for producing detergent tablets
EP0450587B1 (en) Stable granules of peroxycarboxylic acid
EP0273377A2 (en) Phosphate-free detergent with a reduced foaming tendency

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19860712

17Q First examination report despatched

Effective date: 19870507

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE FR GB IT LI NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI NL

REF Corresponds to:

Ref document number: 36347

Country of ref document: AT

Date of ref document: 19880815

Kind code of ref document: T

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 3564286

Country of ref document: DE

Date of ref document: 19880915

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19920421

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19920424

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19920604

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19930503

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19930506

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19930510

Year of fee payment: 9

Ref country code: AT

Payment date: 19930510

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19930531

Ref country code: CH

Effective date: 19930531

Ref country code: BE

Effective date: 19930531

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19930531

Year of fee payment: 9

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19930531

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930506

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19940506

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19941201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19950201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST