EP0658190A1 - Process for producing detergent tablets. - Google Patents

Process for producing detergent tablets.

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Publication number
EP0658190A1
EP0658190A1 EP93919188A EP93919188A EP0658190A1 EP 0658190 A1 EP0658190 A1 EP 0658190A1 EP 93919188 A EP93919188 A EP 93919188A EP 93919188 A EP93919188 A EP 93919188A EP 0658190 A1 EP0658190 A1 EP 0658190A1
Authority
EP
European Patent Office
Prior art keywords
tablets
weight
mixture
tabletting
sodium metasilicate
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
EP93919188A
Other languages
German (de)
French (fr)
Other versions
EP0658190B1 (en
Inventor
Hans Kruse
Horst Pruehs
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0658190A1 publication Critical patent/EP0658190A1/en
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Publication of EP0658190B1 publication Critical patent/EP0658190B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/14—Silicates
    • 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
    • C11D17/0091—Dishwashing 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/16—Phosphates including polyphosphates

Definitions

  • the present invention relates to a method for producing detergent tablets, in particular for use in machine dishwashing, both in the commercial and in the household sector.
  • Powder, granular or tablet-shaped detergents for dishes in dishwashers essentially consist of sodium tripolyphosphate, alkali silicate, mostly alkali metasilicate, and optionally a weakly foaming, nonionic surfactant and bleaching agents, preferably those which give off active oxygen in aqueous solution. They are primarily used to facilitate the removal of stains from tea, coffee or fruit juices.
  • the known agents are generally produced by customary production processes, such as mixing or granulating and / or further pressing.
  • disk-like tablets have been produced from simple mixtures of the known detergent components with the addition of a tabletting aid, not specified, and using a compression pressure of about 70 to 1000 kg / cm 2 .
  • Tablets of the type mentioned above are aucl. described in German Offenlegungsschrift 28 57 001. They are also produced by pressing the mere mixtures of the components using appropriate pressures.
  • Lubricants, lubricants and disintegrants such as insoluble stearate are used as tableting aids ze, fatty acids, fatty alcohols, starch, polyethylene glycol, Aerosil (R) , colloidal silica, alginates, Veegum (R) , sugar, gelatin and zeolites.
  • the present invention relates in particular to a process for the production of alkaline detergent tablets for machine dishwashing in commercial and domestic use, wherein a completely crystallized granulate with a bulk density of 800 to 1200, preferably 850 to 1100 g / l, obtained by (a) partial Hydrating 10 to 60, preferably 25 to 40, parts by weight of an anhydrous sodium tripolyphosphate, which consists of 60 to 100% of one of phase II and has an average grain size of 0.05 to 0.5 mm, in a continuously operating mixer ( 1.
  • further granulating aids such as anhydrous sodium carbonate, bicarbonate, sodium hydroxide or water glass, but also water, paraffin oil, which can simultaneously serve as a foam suppressant, and / or low-foaming nonionic surfactants can be added.
  • the amount of the surfactant additive should, however, be limited to 0.1 to 2, preferably 0.2 to 0.5,% by weight, since otherwise undesired foaming can occur when the tablets are used in the dishwashers in connection with the soiling of the dishes.
  • Suitable low-foaming nonionic surfactants are the known ethoxylation products of long-chain alcohols and alkylphenols, the free hydroxyl group of the polyethylene glycol ether residue being substituted by ether or acetal groups or by polypropylene glycol ether residues to reduce the tendency to foam.
  • Fatty alcohol polyethylene glycol ethers whose free hydroxyl groups are etherified with an n-alkyl radical (for example methyl, ethyl, propyl, butyl, pentyl) and are therefore particularly alkali-stable are particularly suitable.
  • the block polymers of ethylene oxide with polypropylene oxide are also suitable.
  • Suitable bleaching agents are preferably compounds which release active oxygen, such as perborates and percarbonates, preferably in conjunction with bleach activators such as, for example, tetraacetylethylene diamine (TAED) or tetraacetylglycoluril (TAGU) or peracids or their salts, for example the magnesium salt of monoperphthalic acid.
  • bleach activators such as, for example, tetraacetylethylene diamine (TAED) or tetraacetylglycoluril (TAGU) or peracids or their salts, for example the magnesium salt of monoperphthalic acid.
  • compounds which release active chlorine such as the salts of chlorine-substituted isocyanuric acids, in particular pure trichloroisocyanuric acid itself, can also be used. If appropriate, they are mixed in amounts of 0.5 to 15, preferably 1 to 10,% by weight, based on the mixture to be pressed.
  • enzymes can be used to improve the cleaning performance, preferably commercial amylases in amounts of 0.2 to 2, preferably 0.5 to 1% by weight.
  • part of the bleach-free granules can be bleached with stable bleaching agents or coloring pigments such as e.g. Phthalocyanine, stain and then mix in together with the bleaching agents.
  • Fragrances, known bactericidal and dirt-suspending agents, foam inhibitors and corrosion inhibitors can also be added.
  • the mixing of the prefabricated granules with the other cleaning agent constituents takes place in known mixing devices such as, for example, a Lödige mixer.
  • the finished granulate-containing mixture is then used as tableting aid sodium metasilicate pentahydrate and / or sodium metasilicate nonahydrate in amounts of about 0.5 to 15, preferably about 8 up to 12% by weight, based on 100% of the total tablet granule mixture.
  • An improvement in the pressing properties is obtained by adding about 0.5 to 5% by weight, preferably about 1 to 3% by weight, of paraffin oil.
  • Pressing tools are used for pressing, the stamp surfaces of which are coated with a plastic (e.g. Delrin). Caking on the pressing tools does not occur. The tablets obtained disintegrate perfectly even after prolonged storage.
  • a plastic e.g. Delrin
  • All known eccentric and rotary presses are suitable for pressing the granulate mixture, which can be used for the production of tablets with diameters of approximately 1.0 cm and more.
  • the compression pressure must be optimized so that the tablets obtained are stable enough for a given weight on the one hand so that they are not damaged during packaging and transport, but on the other hand disintegrate quickly enough during use. This optimum is usually determined by the person skilled in the art by routine trial and error.
  • the density of the tablets is then - for a given mixture - a consequence of the pressure applied.
  • a compression pressure of 100 to 800, preferably 200 to 500 kp / cm 2 has proven to be optimal.
  • the tablets obtained by this process have an average density of 1.3-1.6 g / cm 3 , possess, in addition to high mechanical stability, a uniform porous structure with a large inner surface. They therefore disintegrate particularly quickly when used in the dishwasher.
  • the tablets according to the invention can also contain other inorganic phosphate substitutes.
  • the preferred inorganic phosphate substitutes include the synthetically produced zeolites of the NaA or NaX type, as described, for example, in US Pat. Nos. 2,882,243 and 2,882,244. They are used in amounts of 3 to 30% by weight, preferably 5 to 10% by weight, and are added in the second mixing stage.
  • the zeolites have an additional corrosion-inhibiting effect with regard to decorative glazes on porcelain or ceramic, which goes beyond that of the known tripolyphosphate / metasilicate mixtures.
  • the tablets according to the invention have excellent mechanical stability. By compressing the granules, pores remain in the tablets, which allow the water to penetrate more quickly into the interior of the tablets. Rapid dissolution of the readily soluble, admixed, hydrated sodium metasilicates leads to rapid disintegration into the individual granulate particles, which in turn can be dissolved more quickly as individual particles.
  • the detergent tablet could also be used in household dishwashers without using the pre-wash program.
  • the tablets can also be used in commercial dishwashers, where they can be added to the tank water by hand or by an automatic cleaning dosing device. Since the cleaning solution is used directly, a quick dissolution of the tablets was necessary for this.
  • the detergent solution was used for several rinsing cycles, with constant dilution using fresh water and, accordingly, from time to time, subsequent dosing with new, snow-soluble tablets had to be carried out in accordance with the following dosage scheme.
  • the dosing was carried out in a further experiment in a commercial dishwasher (box-type slide-through machine) using a rinsing-out meter in which 2 kg of these readily soluble tablets were deposited in the form of a sieve from the storage container.
  • a rinsing-out meter in which 2 kg of these readily soluble tablets were deposited in the form of a sieve from the storage container.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

A process is disclosed for producing detergent tablets for both industrial and household dish-washing machines. The alkaline reacting components, and if required other components, are granulated then sodium metasilicate pentahydrate and/or sodium metasilicate nanohydrate are pressed with additives facilitating the production of tablets.

Description

"Verfahren zur Herstellung von Reinigungstabletten"  "Process for the production of cleaning tablets"
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Reinigungsmitteltabletten, insbesondere zur Verwendung zum maschinellen Geschirrspülen, sowohl im gewerblichen als auch im Haushaltsbereich. The present invention relates to a method for producing detergent tablets, in particular for use in machine dishwashing, both in the commercial and in the household sector.
Pulver, granulat- oder tablettenförmige Reinigungsmittel für Geschirr in Geschirrspülmaschinen bestehen im wesentlichen aus Natriumtripolyphosphat, Alkalisilikat, meist Alkalimetasilikat, und gegebenenfalls aus einem schwach schäumenden, nichtionischen Tensid sowie Bleichmitteln, vorzugsweise solchen, die in wäßriger Lösung Aktivsauerstoff abgeben. Sie dienen vor allem der Erleichterung der Entfernung von Flecken von Tee, Kaffee oder Obstsäften. Powder, granular or tablet-shaped detergents for dishes in dishwashers essentially consist of sodium tripolyphosphate, alkali silicate, mostly alkali metasilicate, and optionally a weakly foaming, nonionic surfactant and bleaching agents, preferably those which give off active oxygen in aqueous solution. They are primarily used to facilitate the removal of stains from tea, coffee or fruit juices.
Die Herstellung der bekannten Mittel erfolgt im allgemeinen nach üblichen Herstellungsverfahren, wie Mischen oder Granulieren und/oder weiterem Verpressen. The known agents are generally produced by customary production processes, such as mixing or granulating and / or further pressing.
Nach der französischen Patentschrift 1 472680 hat man aus einfachen Mischungen der bekannten Reinigungsmittelbestandteile unter Zusatz eines nicht näher bezeichneten Tablettierungshilfsmittels und unter Anwendung eines Preßdruckes von etwa 70 bis 1000 kg/cm2 scheibenähnliche Tabletten hergestellt. According to French patent specification 1 472680, disk-like tablets have been produced from simple mixtures of the known detergent components with the addition of a tabletting aid, not specified, and using a compression pressure of about 70 to 1000 kg / cm 2 .
Tabletten der vorstehend genannten Art sind aucl. in der deutschen Offenlegungsschrift 28 57 001 beschrieben. Sie werden ebenfalls durch Verpressen der bloßen Mischungen der Bestandteile unter Anwendung entsprechender Drucke hergestellt. Als Tablettierhilfsmittel werden Gleit-, Schmier- und Sprengmittel wie unlösliche Stearatsal ze, Fettsäuren, Fettalkohole, Stärke, Polyethylenglykol, Aerosil(R), kolloidale Kieselsäure, Alginate, Veegum(R), Zucker, Gelatine und Zeolithe genannt. Tablets of the type mentioned above are aucl. described in German Offenlegungsschrift 28 57 001. They are also produced by pressing the mere mixtures of the components using appropriate pressures. Lubricants, lubricants and disintegrants such as insoluble stearate are used as tableting aids ze, fatty acids, fatty alcohols, starch, polyethylene glycol, Aerosil (R) , colloidal silica, alginates, Veegum (R) , sugar, gelatin and zeolites.
Ein besonders gut geeignetes Verfahren zum Granulieren und Mischen, das das erfindungsgemäße Verfahren zur Herstellung der Tabletten einleitet, ist in allen Einzelheiten in der deutschen Offenlegungsschrift 29 13 145 beschrieben. A particularly well-suited method for granulating and mixing, which initiates the method for producing the tablets according to the invention, is described in all details in German Offenlegungsschrift 29 13 145.
Aus der deutschen Offenlegungsschrift 33 15 950 ist ein Verfahren zur Herstellung von Reinigungsmitteltabletten durch partielles Hydratisieren von wasserfreiem Natriumtripolyphosphat zu Tripolyphosphat-Hexahydrat, Vermischen des Teilhydrats mit pulverförmigem und im wesentlichen wasserfreiem Natriumsilikat (Na2O : SiO2 = 1 : 1 bis 1 : 4), Besprühen des Gemisches mit Wasser oder wäßriger Silikatlösung, Granulierung durch Bewegen mit anschließender Durchkristallisation, wobei gegebenenfalls weitere Reinigungsmittelbestandteile, Bleichmittel oder Enzyme zugemischt werden können, Natriumacetat und/oder Dicalciumphosphat-dihydrat als Tablettierungshilfsmittel und Tablettieren des Gemisches unter einem Druck von mehr als 70 kp/cm2 bekannt. German Offenlegungsschrift 33 15 950 describes a process for producing detergent tablets by partially hydrating anhydrous sodium tripolyphosphate to tripolyphosphate hexahydrate, mixing the partial hydrate with powdered and essentially anhydrous sodium silicate (Na 2 O: SiO 2 = 1: 1 to 1: 4 ), Spraying the mixture with water or aqueous silicate solution, granulation by agitation with subsequent crystallization, where appropriate further detergent components, bleaching agents or enzymes can be admixed, sodium acetate and / or dicalcium phosphate dihydrate as tableting aids and tableting the mixture under a pressure of more than 70 kp / cm 2 known.
Die jeweilige Druckhöhe und die daraus resultierende Dichte der Tabletten wird stets durch den erforderlichen Kompromiß zwischen Festigkeit und Auflösungsgeschwindigkeit der Tabletten bestimmt. Wichtige auf diese Eigenschaften Einfluß nehmende Faktoren sind neben der Natur der Bestandteile selbst vor allem geeignete Tablettierungshilfsmittel, die die Aufgabe haben, die Tablettierung technisch zu ermöglichen und zur Erreichung der anwendungstechnischen Anforderungen an die Tablette wesentlich beitragen. Aus der deutschen Offenlegungsschrift 36 34813 sind Reinigungsmitteltabletten für das maschinelle Geschirrspülen bekannt, die als Tablettierhilfsmittel ein Gemisch aus Natriumacetat und sprühgetrocknetem Zeolith NaA enthalten. Sie können auch Natriummetasilikatpentahydrat in Mengen von 11,3 Gew.-% und mehr enthalten. Bei der dort beschriebenen Verpressung der Bestandteilsgemische entwickelte dieser Anteil jedoch keine Tablettierhilfsmittelwirkung, d.h. die Gemische ohne Natriumacetat und Zeolith NaA klebten beim Verpressen in der Matrize. The respective pressure level and the resulting density of the tablets is always determined by the necessary compromise between strength and dissolution rate of the tablets. In addition to the nature of the constituents themselves, important factors influencing these properties are, above all, suitable tabletting aids, which have the task of making tableting technically possible and making a significant contribution to meeting the application requirements for the tablet. German Offenlegungsschrift 36 34813 discloses detergent tablets for automatic dishwashing, which contain a mixture of sodium acetate and spray-dried zeolite NaA as tabletting aids. They can also contain sodium metasilicate pentahydrate in amounts of 11.3% by weight and more. In the compression of the constituent mixtures described there, however, this portion did not develop a tabletting aid effect, ie the mixtures without sodium acetate and zeolite NaA adhered to the die when pressed.
Es wurde nun überraschend gefunden, daß man zu Reinigungsmitteltabletten für das maschinelle Geschirrspülen mit guter mechanischer Festigkeit und hoher Auflösungsgeschwindigkeit kommt und bei deren Herstellung die alkalisch reagierenden Bestandteile zunächst granuliert und erst dann unter Zusatz von Tablettierungshilfsmitteln, gegebenenfalls in Mischung mit weiteren Bestandteilen bei Preßdrukken von mehr als 70 kp/cm2 verpreßt wurden, wenn man als Tablettierhilfsmittel Natriummetasilikatpentahydrat und/oder Natriummetasilikatnonahydrat einsetzt. Durch die Einarbeitung dieses Tablettierhilfsmittels wird eine besonders gute Löslichkeit bewirkt, wodurch der Einsatz sowohl in gewerblichen als auch in Haushaltsgeschirrspülmaschinen ermöglicht wird. It has now surprisingly been found that detergent tablets for automatic dishwashing with good mechanical strength and high dissolution rate are obtained and the alkaline-reacting constituents are first granulated during their production and only then with the addition of tabletting aids, if appropriate in a mixture with other constituents, in the case of compression pressures of more than 70 kp / cm 2 were pressed if sodium metasilicate pentahydrate and / or sodium metasilicate nonahydrate are used as tableting aids. The incorporation of this tabletting aid results in particularly good solubility, which enables use in both commercial and household dishwashers.
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Reinigungsmitteltabletten für das maschinelle Geschirrspülen im gewerblichen und im Haushaltsbereich durch partielles Hydratisieren von wasserfreiem Natriumtripolyphosphat zu Tripolyphosphat-Hexahydrat, Vermischen des Teilhydrats mit pulverförmigem und im wesentlichen wasserfreiem Natriumsilikat (Na2O : SiO2 = 1 : 1 bis 1 : 4), Besprühen des Gemisches mit Wasser oder wäßriger Silikatlösung, Granulierung durch Bewegen mit anschließender Durchkristallisation, wobei gegebenenfalls weitere Reinigungsmittelbestandteile, Bleichmittel oder Enzyme zugemischt werden können, Zugabe von Tablettierungshilfsmitteln und Tablettieren des Gemisches unter einem Druck von mehr als 70 kp/cm2, das dadurch gekennzeichnet ist, daß als Tablettierhilfsmittel etwa 0,5 bis 15 Gew.-%, bezogen auf 100 % des gesamten Tablettengranulatgemisches, Natriummetasilikat und/oder Natriummetasilikatmonohydrat eingesetzt wird. The present invention relates to a process for the production of detergent tablets for machine dishwashing in the commercial and household sectors by partially hydrating anhydrous sodium tripolyphosphate to tripolyphosphate hexahydrate, mixing the partial hydrate with powdered and essentially anhydrous sodium silicate (Na 2 O: SiO 2 = 1: 1 to 1: 4), spraying the mixture with water or aqueous silicate solution, granulation by agitation with subsequent crystallization, where further detergent constituents, bleaching agents or enzymes can be admixed, adding tabletting aids and tableting the mixture under a pressure of more than 70 kp / cm 2 , which is characterized in that about 0.5 to 15% by weight as tableting aids, based on 100% of the total tablet granulate mixture, sodium metasilicate and / or sodium metasilicate monohydrate is used.
Die vorliegende Erfindung betrifft insbesondere ein Verfahren zur Herstellung von alkalischen Reinigungsmitteltabletten für das maschinelle Geschirrspülen im gewerblichen und im Haushaltsbereich, wobei man ein vollständig auskristallisiertes Granulat mit einem Schüttgewicht von 800 bis 1200, vorzugsweise 850 bis 1100 g/l, gewonnen durch (a) partielles Hydratisieren von 10 bis 60, vorzugsweise 25 bis 40 Gewichtstellen, eines wasserfreien Natriumtripolyphosphats, das zu 60 bis 100 % aus einem solchen der Phase II besteht und eine mittlere Korngröße von 0,05 bis 0,5 mm aufweist, in einem kontinuierlich arbeitenden Mischer (1. Mischstufe) innerhalb einer mittleren Verweilzeit von 0,2 bis 5 Sekunden mit einer solchen Wassermenge, wie zur Ausbildung von 30 bis weniger als 80 Mol-% Tripolyphosphat-Hexahydrat erforderlich ist und gleichzeitig solchem mechanischen Bearbeiten des Mischguts, das mindestens 85 Gew.-% davon eine Korngröße von über 0,2 mm und weniger als 2 Gew.-% eine Korngröße von weniger als 0,1 mm aufweisen, (b) Vermischen des Teilhydrates nach einer Verweilzeit außerhalb des Mischers von 5 bis 60 Sekunden in einem Granulationsmischer (2. Mischstufe), gegebenenfalls zusammen mit bis zu 25 Gewichtsteilen eines Granulierhilfsmittels mit 20 bis 70, vorzugsweise 30 bis 50 Gewichtsteilen eines pulverförmigen, im wesentlichen wasserfreien Natriumsilikats der Zusammensetzung Na2O : SiO2 = 1 : 1 bis 1 : 4 und anschließendes Besprühen mit Wasser oder einer wäßrigen Lösung von 0,5 bis 5 Gewichtstei len Natriumsilikat-Lösung in 2 bis 12, vorzugsweise 5 bis 12 Gewichtsteilen Wasser und (c) Granulieren durch Bewegen des Behandlungsgutes mit anschließender Durchkristallisation, wobei man (d) gegebenenfalls weitere Reinigungsmittelbestandteile, Bleichmittel oder Enzyme zumischt, danach (e) Tablettierhilfsmittel zusetzt, (f) in Tablettiermaschinenmatrizenbohrungen füllt und bei Preßdrukken von mehr als 70 kp/cm2 verpreßt, das dadurch gekennzeichnet ist, daß man als Tablettierhilfsmittel Natriummetasilikatpentahydrat und/oder Natriummetasilikatnonahydrat einsetzt. The present invention relates in particular to a process for the production of alkaline detergent tablets for machine dishwashing in commercial and domestic use, wherein a completely crystallized granulate with a bulk density of 800 to 1200, preferably 850 to 1100 g / l, obtained by (a) partial Hydrating 10 to 60, preferably 25 to 40, parts by weight of an anhydrous sodium tripolyphosphate, which consists of 60 to 100% of one of phase II and has an average grain size of 0.05 to 0.5 mm, in a continuously operating mixer ( 1. Mixing stage) within an average residence time of 0.2 to 5 seconds with such an amount of water as is necessary for the formation of 30 to less than 80 mol% of tripolyphosphate hexahydrate and at the same time such mechanical processing of the mixture which is at least 85% by weight. -% thereof a grain size of more than 0.2 mm and less than 2 wt .-% a grain size have a size of less than 0.1 mm, (b) mixing the partial hydrate after a dwell time outside the mixer of 5 to 60 seconds in a granulation mixer (2nd Mixing stage), optionally together with up to 25 parts by weight of a granulating aid with 20 to 70, preferably 30 to 50 parts by weight of a powdery, essentially anhydrous sodium silicate of the composition Na 2 O: SiO 2 = 1: 1 to 1: 4 and subsequent spraying with water or an aqueous solution of 0.5 to 5 parts by weight len sodium silicate solution in 2 to 12, preferably 5 to 12 parts by weight of water and (c) granulating by moving the material to be treated with subsequent crystallization, (d) optionally adding further detergent constituents, bleaching agents or enzymes, then (e) adding tabletting aids, ( f) fills in tabletting machine matrix bores and is pressed at pressures of more than 70 kp / cm 2 , which is characterized in that sodium metasilicate pentahydrate and / or sodium metasilicate nonahydrate are used as tableting aids.
Gleichzeitig mit der Zugabe des festen Natriumsilikats oder im Anschluß daran können weitere Granulierhilfsmittel wie wasserfreies Natriumcarbonat, -bicarbonat, Natriumhydroxid oder Wasserglas, aber auch Wasser, Paraffinöl, das gleichzeitig als Schaumunterdrücker dienen kann, und/oder schwachschäumende nichtionische Tenside zugesetzt werden. Die Menge des Tensidzusatzes ist jedoch auf 0,1 bis 2, vorzugsweise 0,2 bis 0,5 Gew.-% zu beschränken, da sonst bei Einsatz der Tabletten in die Geschirrspülmaschinen in Verbindung mit den Geschirranschmutzungen unerwünschtes Schäumen auftreten kann. Simultaneously with the addition of the solid sodium silicate or subsequently, further granulating aids such as anhydrous sodium carbonate, bicarbonate, sodium hydroxide or water glass, but also water, paraffin oil, which can simultaneously serve as a foam suppressant, and / or low-foaming nonionic surfactants can be added. The amount of the surfactant additive should, however, be limited to 0.1 to 2, preferably 0.2 to 0.5,% by weight, since otherwise undesired foaming can occur when the tablets are used in the dishwashers in connection with the soiling of the dishes.
Als schwachschäumende nichtionische Tenside eignen sich die bekannten Ethoxylierungsprodukte von langkettigen Alkoholen und Alkylphenolen, wobei zur Verminderung der Schaumneigung die freie Hydroxylgruppe des Polyethylenglykoletherrestes durch Ether- oder Acetalgruppen bzw. durch Polypropylenglykoletherreste substituiert sind. Hierbei sind besonders Fettalkohol-polyethylenglykolether geeignet, deren freie Hydroxylgruppen mit einem n-Alkylrest (z.B. Methyl-, Ethyl-, Propyl-, Butyl-, Pentyl-) verethert sind und dadurch besonders alkalistabil werden. Geeignet sind ferner die Blockpolymere des Ethylenoxids mit Polypropylenoxid. Als Bleichmittel kommen vorzugsweise Aktivsauerstoff abspaltende Verbindungen wie Perborate und Percarbonate, vorzugsweise in Verbindung mit Bleichaktivatoren wie z.B. Tetraacetylethylendiamin (TAED) oder Tetraacetylglykoluril (TAGU) oder Persäuren bzw. ihre Salze, z.B. das Magnesiumsalz der Monoperphthalsäure in Betracht. Aber auch Aktivchlor abspaltende Verbindungen wie die Salze von chlorsubstituierten Isocyanursäuren, insbesondere die reine Trichlorisocyanursäure selbst, können eingesetzt werden. Sie werden gegebenenfalls in Mengen von 0,5 bis 15, vorzugsweise 1 bis 10 Gew.-%, bezogen auf das zu verpressende Gemisch, zugemischt. Suitable low-foaming nonionic surfactants are the known ethoxylation products of long-chain alcohols and alkylphenols, the free hydroxyl group of the polyethylene glycol ether residue being substituted by ether or acetal groups or by polypropylene glycol ether residues to reduce the tendency to foam. Fatty alcohol polyethylene glycol ethers whose free hydroxyl groups are etherified with an n-alkyl radical (for example methyl, ethyl, propyl, butyl, pentyl) and are therefore particularly alkali-stable are particularly suitable. The block polymers of ethylene oxide with polypropylene oxide are also suitable. Suitable bleaching agents are preferably compounds which release active oxygen, such as perborates and percarbonates, preferably in conjunction with bleach activators such as, for example, tetraacetylethylene diamine (TAED) or tetraacetylglycoluril (TAGU) or peracids or their salts, for example the magnesium salt of monoperphthalic acid. However, compounds which release active chlorine, such as the salts of chlorine-substituted isocyanuric acids, in particular pure trichloroisocyanuric acid itself, can also be used. If appropriate, they are mixed in amounts of 0.5 to 15, preferably 1 to 10,% by weight, based on the mixture to be pressed.
Sofern keine Bleichmittel zugemischt werden, können zur Verbesserung der Reinigungsleistung Enzyme eingesetzt werden, bevorzugt handelsübliche Amylasen in Mengen von 0,2 bis 2, vorzugsweise 0,5 bis 1 Gew.-%. If no bleaching agents are added, enzymes can be used to improve the cleaning performance, preferably commercial amylases in amounts of 0.2 to 2, preferably 0.5 to 1% by weight.
Zur weiteren Verbesserung des äußeren Erscheinungsbildes der Reinigungsmittel kann man einen Teil des bleichmittelfreien Granulates mit bleichmittelstabilen Farbstoffen oder Farbpigmenten wie z.B. Phthalocyanin, anfärben und dann etwa zusammen mit den Bleichmitteln, zumischen. Auch Duftstoffe, bekannte bakterizide und schmutzsuspendierende Mittel, Schauminhibitoren und Korrosionsinhibitoren können zugesetzt werden. To further improve the external appearance of the cleaning agents, part of the bleach-free granules can be bleached with stable bleaching agents or coloring pigments such as e.g. Phthalocyanine, stain and then mix in together with the bleaching agents. Fragrances, known bactericidal and dirt-suspending agents, foam inhibitors and corrosion inhibitors can also be added.
Das Mischen des vorgefertigten Granulats mit den übrigen Reinigungsmittelbestandtei len erfolgt in bekannten Mischvorrichtungen wie beispielsweise einem Lödigemischer. The mixing of the prefabricated granules with the other cleaning agent constituents takes place in known mixing devices such as, for example, a Lödige mixer.
Dem fertigen, granulathaltigen Gemisch werden dann als Tablettierungshilfsmittel Natriummetasilikatpentahydrat und/oder Natriurnmetasilikatnonahydrat in Mengen von etwa 0,5 bis 15, vorzugsweise etwa 8 bis 12 Gew.-%, bezogen auf 100 % des gesamten Tablettengranulatgemisches, zugesetzt. Eine Verbesserung der Preßeigenschaften wird durch Zusatz von etwa 0,5 bis 5 Gew.-%, vorzugsweise etwa 1 bis 3 Gew.-%, Paraffinöl erhalten. The finished granulate-containing mixture is then used as tableting aid sodium metasilicate pentahydrate and / or sodium metasilicate nonahydrate in amounts of about 0.5 to 15, preferably about 8 up to 12% by weight, based on 100% of the total tablet granule mixture. An improvement in the pressing properties is obtained by adding about 0.5 to 5% by weight, preferably about 1 to 3% by weight, of paraffin oil.
Zur Verpressung werden Preßwerkzeuge eingesetzt, deren Stempeloberflachen mit einem Kunststoff beschichtet sind (z.B. Delrin). Anbackungen an den Preßwerkzeugen treten nicht auf. Die erhaltenen Tabletten zerfallen bei Anwendung auch nach längerer Lagerung einwandfrei. Pressing tools are used for pressing, the stamp surfaces of which are coated with a plastic (e.g. Delrin). Caking on the pressing tools does not occur. The tablets obtained disintegrate perfectly even after prolonged storage.
Zum Verpressen des Granulatgemisches sind alle bekannten Excenterund Rundlauferpressen geeignet, die zur Herstellung von Tabletten mit Durchmessern von etwa 1,0 cm und mehr eingesetzt werden können. Der Preßdruck muß bei vorgegebener Zusammensetzung so optimiert werden, daß die erhaltenen Tabletten bei vorgegebenem Gewicht einerseits stabil genug sind, um beim Verpacken und Transport nicht beschädigt zu werden, andererseits bei der Anwendung aber schnell genug zerfallen. Dieses Optimum wird vom Fachmann üblicherweise durch routinemäßiges Ausprobieren ermittelt. Die Dichte der Tabletten ist dann - bei vorgegebener Mischung - eine Folge des angewendeten Preßdrucks. Beim Verpressen der erfindungsgemäßen Tablettenbestandteile hat sich ein Preßdruck von 100 bis 800, vorzugsweise 200 bis 500 kp/cm2 als optimal erwiesen. All known eccentric and rotary presses are suitable for pressing the granulate mixture, which can be used for the production of tablets with diameters of approximately 1.0 cm and more. For a given composition, the compression pressure must be optimized so that the tablets obtained are stable enough for a given weight on the one hand so that they are not damaged during packaging and transport, but on the other hand disintegrate quickly enough during use. This optimum is usually determined by the person skilled in the art by routine trial and error. The density of the tablets is then - for a given mixture - a consequence of the pressure applied. When compressing the tablet components according to the invention, a compression pressure of 100 to 800, preferably 200 to 500 kp / cm 2 has proven to be optimal.
Die nach diesem Verfahren erhaltenen Tabletten weisen eine Dichte von durchschnittlich 1,3 - 1,6 g/cm3 auf, besitzet, neben einer hohen mechanischen Stabilität eine gleichmäßige poröse Struktur mit großer innerer Oberfläche. Sie zerfallen daher bei der Anwendung in der Geschirrspülmaschine besonders schnell. Die erfindungsgemäßen Tabletten können in Kombination mit dem eingesetzten Phosphat noch andere anorganische Phosphataustauschstoffe enthalten. Zu den bevorzugten anorganischen Phosphataustauschstoffen gehören die synthetisch hergestellten Zeolithe vom Typ NaA oder NaX, wie sie beispielsweise in den US-amerikanischen Patentschriften 2,882,243 und 2,882,244 beschrieben sind. Sie werden in Mengen von 3 bis 30, vorzugsweise von 5 bis 10 Gew.-% eingesetzt und in der 2. Mischstufe zugegeben. Neben ihrer reinigungsverstärkenden Wirkung zeigen die Zeolithe eine zusätzliche korrosionsinhibierende Wirkung in bezug auf Dekorglasuren auf Porzellan oder Keramik, die über die der bekannten Tripolyphosphat/Metasilikat-Mischungen hinausgeht. Die erfindungsgemäßen Tabletten besitzen eine ausgezeichnete mechanische Stabilität. Durch Verpressen des Granulats verbleiben Poren in den Tabletten, die ein schnelleres Eindringen des Wassers in das Tabletteninnere ermöglichen. Ein schnelles Auflösen der gut löslichen zugemischten hydratisierten Natriummetasilikate führt zu einem schnellen Zerfall in die einzelnen Granulatpartikeln, die sich als Einzelpartikeln wiederum schneller lösen lassen. The tablets obtained by this process have an average density of 1.3-1.6 g / cm 3 , possess, in addition to high mechanical stability, a uniform porous structure with a large inner surface. They therefore disintegrate particularly quickly when used in the dishwasher. In combination with the phosphate used, the tablets according to the invention can also contain other inorganic phosphate substitutes. The preferred inorganic phosphate substitutes include the synthetically produced zeolites of the NaA or NaX type, as described, for example, in US Pat. Nos. 2,882,243 and 2,882,244. They are used in amounts of 3 to 30% by weight, preferably 5 to 10% by weight, and are added in the second mixing stage. In addition to their cleaning-enhancing effect, the zeolites have an additional corrosion-inhibiting effect with regard to decorative glazes on porcelain or ceramic, which goes beyond that of the known tripolyphosphate / metasilicate mixtures. The tablets according to the invention have excellent mechanical stability. By compressing the granules, pores remain in the tablets, which allow the water to penetrate more quickly into the interior of the tablets. Rapid dissolution of the readily soluble, admixed, hydrated sodium metasilicates leads to rapid disintegration into the individual granulate particles, which in turn can be dissolved more quickly as individual particles.
B e i s p i e l Example
47,7 Gew.-% wasserfreies Natriummetasilikat und 35,6 Gew.-% Natriumtripolyphosphat wurden in Gegenwart von 7,1 Gew.-% wasserfreiem Natriumcarbonat mit 1,4 Gew.-% Wasserglas 3.0, 1,0 Gew.-% einer schaumdrückenden Komposition A gemäß EP 150 387 und 7,2 Gew.-% Wasser nach dem in der deutschen Auslegeschrift 29 13 145 ausführlich beschriebenen Verfahren granuliert, 80,27 Gew.-% dieses Granulats wurden in einem Lödigemischer mit 6,9 Gew.-% Natriumperboratmonohydrat, 11,33 Gew.-% Natriummetasilikatpentahydrat und 1,5 Gew.- % weißem Paraffinöl mit einem Flammpunkt von 210°C vermischt. Das Litergewicht des Gemisches betrug 1000 g. Jeweils 40 g dieser Mischung wurden über einen Vorratstrichter kontinuierlich nacheinander in eine kreisförmige Matrizenbohrung einer Excenter-Tablettiermaschine vom Typ EK - IV der Firma Korsch eingefüllt und mit einem Preßdruck von 20 - 50 kN zu Preßlingen (= Tabletten) mit einer Dichte von rund 1,5 g/cm3 verpreßt. Der Tablettendurchmesser betrug 38 mm, die Tablettenhöhe 23,5 - 24 mm. Die Bruchfestigkeit nach der Herstellung war > 140 N, nach einem Tag > 500 N. 47.7% by weight of anhydrous sodium metasilicate and 35.6% by weight of sodium tripolyphosphate were in the presence of 7.1% by weight of anhydrous sodium carbonate with 1.4% by weight of water glass 3.0, 1.0% by weight of a foam-suppressing composition A according to EP 150 387 and 7.2% by weight of water are granulated by the process described in detail in German Ausleeschschrift 29 13 145, 80.27% by weight of this granulate were mixed in a Lödige mixer with 6.9% by weight. % Sodium perborate monohydrate, 11.33% by weight sodium metasilicate pentahydrate and 1.5% by weight white paraffin oil mixed with a flash point of 210 ° C. The liter weight of the mixture was 1000 g. In each case 40 g of this mixture were poured into a circular matrix bore of an EK-IV type eccentric tabletting machine from the Korsch company one after the other via a storage funnel and, with a compression pressure of 20-50 kN, into compacts (= tablets) with a density of around 1. 5 g / cm 3 pressed. The tablet diameter was 38 mm, the tablet height 23.5 - 24 mm. The breaking strength after production was> 140 N, after one day> 500 N.
Sie waren von gleichmäßig gekörnter Struktur und von großer Stabilität. Ihre Einspülzeit über einen mit einem Gitter versehenen Dosierkasten in einer Haushaltsgeschirrspülmaschine vom Typ Miele G 5035 betrug nur 25 Minuten. Aufgrund ihrer guten Löslichkeit konnte die Reinigertablette auch in der Haushaltsgeschirrspülmaschine ohne Verwendung des Vorspülprogramms zur Anwendung kommen. Die Tabletten können auch in gewerblichen Geschirrspülmaschinen zum Einsatz kommen, wobei sie dem Tankwasser von Hand oder durch ein automatisches Reinigungsdosiergerät zugegeben werden können. Da die Reinigungslösung direkt zur Anwendung gelangt, war insbesondere hierfür eine schnelle Auflösung der Tabletten erforderlich. Die Reinigerlösung wurde für mehrere Spülgänge verwendet, wobei eine ständige Verdünnung durch Frischwasser erfolgte und dementsprechend von Zeit zu Zeit eine Nachdosierung mit neuen, schneilöslichen Tabletten entsprechend folgendem Dosierungsschema erfolgen mußte. They were of uniformly grained structure and of great stability. It took just 25 minutes to wash it in using a grating metering box in a Miele G 5035 household dishwasher. Due to its good solubility, the detergent tablet could also be used in household dishwashers without using the pre-wash program. The tablets can also be used in commercial dishwashers, where they can be added to the tank water by hand or by an automatic cleaning dosing device. Since the cleaning solution is used directly, a quick dissolution of the tablets was necessary for this. The detergent solution was used for several rinsing cycles, with constant dilution using fresh water and, accordingly, from time to time, subsequent dosing with new, snow-soluble tablets had to be carried out in accordance with the following dosage scheme.
Neben der manuellen Zugabe der Tabletten erfolgte die Dosierung in einem weiteren Versuch in einer gewerblichen Geschirrspülmaschine (Kastendurchschubmaschine) über ein Ausspüldosiergerät, in dem 2 kg dieser leicht löslichen Tabletten aus dem Vorratsbehälter in Form eines Siebes deponiert wurden. Durch Aufsprühen von Wasser auf den lose geschüttelten Tablettenhaufen wurden diese in Lösung gebracht und der Wirkstoff in die Spülflotte gefördert bis die erforderliche Konzentration erreicht war. Die Dosiermenge wurde über die Leitfähigkeit geregelt. In addition to the manual addition of the tablets, the dosing was carried out in a further experiment in a commercial dishwasher (box-type slide-through machine) using a rinsing-out meter in which 2 kg of these readily soluble tablets were deposited in the form of a sieve from the storage container. By spraying water onto the loosely shaken tablets, the tablets were brought into solution and the active ingredient was conveyed into the rinse liquor until the required concentration was reached. The dosing quantity was regulated via the conductivity.

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung von Reinigungsmitteltabletten für das maschinelle Geschirrspülen im gewerblichen und im Haushaltsbereich durch partielles Hydratisieren von wasserfreiem Natriumtripolyphosphat zu Tripolyphosphat-Hexahydrat, Vermischen des Teilhydrats mit pulverförmigem und im wesentlichen wasserfreiem Natriumsilikat (Na2O : SiO2 = 1 : 1 bis 1 : 4), Besprühen des Gemisches mit Wasser oder wäßriger Silikatlösung, Granulierung durch Bewegen mit anschließender Durchkristallisation, wobei gegebenenfalls weitere Reinigungsmittelbestandteile, Bleichmittel oder Enzyme zugemischt werden können, Zugabe von Tablettierungshilfsmitteln und Tablettieren des Gemisches unter einem Druck von mehr als 70 kp/cm2, dadurch gekennzeichnet, daß als Tablettierhilfsmittel etwa 0,5 bis 15 Gew.-%, bezogen auf 100 % des gesamten Tablettengranulatgemisches, Natriummetasilikatpentahydrat und/oder Natriummetasilikatnanohydrat eingesetzt wird. 1.Procedure for the production of detergent tablets for automatic dishwashing in the commercial and household sectors by partially hydrating anhydrous sodium tripolyphosphate to tripolyphosphate hexahydrate, mixing the partial hydrate with powdered and essentially anhydrous sodium silicate (Na 2 O: SiO 2 = 1: 1 to 1 : 4), spraying the mixture with water or aqueous silicate solution, granulation by agitation with subsequent crystallization, where appropriate further detergent components, bleaching agents or enzymes can be admixed, addition of tabletting aids and tabletting of the mixture under a pressure of more than 70 kp / cm 2 , characterized in that about 0.5 to 15% by weight, based on 100% of the total tablet granulate mixture, of sodium metasilicate pentahydrate and / or sodium metasilicate nanohydrate is used as the tabletting aid.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das Tablettierungshilfsmittel in Mengen von etwa 8 bis 12 Gew.-%, bezogen auf 100 % des gesamten Tablettengranulatgemisches, zusetzt. 2. The method according to claim 1, characterized in that the tabletting aid in amounts of about 8 to 12 wt .-%, based on 100% of the total tablet granulate mixture, is added.
EP93919188A 1992-09-04 1993-08-26 Process for producing detergent tablets Expired - Lifetime EP0658190B1 (en)

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DE4229650A DE4229650C1 (en) 1992-09-04 1992-09-04 Process for the manufacture of cleaning tablets
DE4229650 1992-09-04
PCT/EP1993/002307 WO1994005768A1 (en) 1992-09-04 1993-08-26 Process for producing detergent tablets

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TR28788A (en) * 1993-05-25 1997-03-25 Henkel Ecolab Gmbh & Co Ohg Methods and equipment for machine-dishwashing cleaning.
DE19502774A1 (en) * 1995-01-27 1996-08-01 Henkel Kgaa Process for the manufacture of break-resistant cleaning tablets
ES2146027T3 (en) * 1995-11-13 2000-07-16 Unilever Nv SOLID DETERGENT BLOCK.
WO1997018291A1 (en) * 1995-11-13 1997-05-22 Unilever N.V. Solid detergent block
ES2289415T3 (en) † 2000-11-27 2008-02-01 THE PROCTER & GAMBLE COMPANY PROCEDURE FOR MANUFACTURING A WATER SOLUBLE BAG.
WO2008094878A1 (en) * 2007-02-01 2008-08-07 Johnsondiversey, Inc. Detergent dispenser assembly and method, flowable detergent powders, and methods for making and using the same

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US4409118A (en) * 1981-04-03 1983-10-11 Warner-Lambert Company Tablet forming cleanser composition and method of preparation
DE3315950A1 (en) * 1983-05-02 1984-11-15 Henkel KGaA, 4000 Düsseldorf METHOD FOR PRODUCING DETERGENT TABLETS
DE3541145A1 (en) * 1985-11-21 1987-05-27 Henkel Kgaa UNIFORMED DETERGENT TABLETS FOR MACHINE DISHWASHER
DE3634813A1 (en) * 1986-10-13 1988-04-14 Henkel Kgaa DETERGENT TABLETS FOR MACHINE DISHWASHER

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