EP0126963B1 - Process for the production of cleaning agent tablets - Google Patents

Process for the production of cleaning agent tablets Download PDF

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Publication number
EP0126963B1
EP0126963B1 EP84104535A EP84104535A EP0126963B1 EP 0126963 B1 EP0126963 B1 EP 0126963B1 EP 84104535 A EP84104535 A EP 84104535A EP 84104535 A EP84104535 A EP 84104535A EP 0126963 B1 EP0126963 B1 EP 0126963B1
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Prior art keywords
weight
parts
tabletting
added
constituents
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EP84104535A
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German (de)
French (fr)
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EP0126963A1 (en
Inventor
Hans Kruse
Martin Dr. Witthaus
Theodor Dr. Altenschöpfer
Klaus Dr. Schumann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT84104535T priority Critical patent/ATE24547T1/en
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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
    • C11D7/16—Phosphates including polyphosphates
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—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
    • 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

Definitions

  • the present invention relates to a method for producing detergent tablets, in particular for use in automatic dishwashing.
  • Powder, granule or tablet detergents for dishes in dishwashers essentially consist of sodium tripolyphosphate, alkali silicate, mostly alkali metasilicate, and optionally a low-foaming, preferably chlorine-stable, nonionic surfactant and bleaching agents, preferably those that release chlorine in aqueous solution. They are mainly used to facilitate the removal of stains from tea, coffee or fruit juices.
  • the agents are strongly alkaline due to their high content of alkali silicates and sodium tripolyphosphate. Their working solutions have a pH value of around 11 to 12. An addition of sodium hydroxide is not intended, because the contact time that is usual in household dishwashers would then attack the too high alkalinity of porcelain, frosting decorations and glasses. This attack is called corrosion.
  • Silicate on the other hand, synergistically supports the cleaning power of the tripolyphosphate and inhibits corrosion in certain concentrations in the total tripolyphosphate / silicate mixture.
  • the known agents are generally produced by customary production processes, such as mixing or granulating.
  • the application is in powder or granule form in likewise usual concentrations, i.e. h, in amounts of about 30 to 50 g per machine filling.
  • detergent tablets which, after being compressed, have a high initial strength and dissolve quickly when used. They contain a high proportion of 4 to 13 percent by weight of nonionic surfactants. They are made by uniformly mixing together all of the ingredients in a routing drum to form granules which are preferably screened to a uniform size and then to tablets using pressures of about 1,472 to 34,335 MPa (15 to 350 kg / cm 2 ) be pressed. The detergent tablets obtained in this way dissolve so quickly in water that they are not suitable for use in dishwashers.
  • the present invention therefore relates to a process for the production of detergent tablets for automatic dishwashing by granulating the alkaline constituents, if appropriate in the presence of nonionic surfactants, adding tabletting aids and, if appropriate, further constituents and then compressing using compression pressures of more than 6,867 MPa (70 kg / cm 2 ), which is characterized in that a completely crystallized granulate with a bulk density of 800 to 1 200, preferably 850 to 1 100 g / l. won by (a) partially hydrating 10 to 60, preferably 25 to 40 parts by weight.
  • an anhydrous sodium tripolyphosphate which consists of 60 to 100% of one from phase 11 and has an average grain size of 0.05 to 0.5 mm
  • a continuously operating mixer (1st mixing stage) within an average residence time of 0.2 up to 5 seconds with such an amount of water as is necessary for the formation of 30 to less than 80 mol% tripolyphosphate hexahydrate and at the same time mechanical processing of the mixture such that at least 85% by weight thereof has a grain size of more than 0.2 mm and less than 2 wt .-% have a grain size of less than 0.1 mm.
  • further granulation aids such as anhydrous sodium carbonate, bicarbonate, sodium hydroxide or water glass can be used. 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 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 radical being substituted by ether or acetal groups or by polypropylene glycol ether radicals to reduce the tendency to foam.
  • the block polymers of ethylene oxide with polypropylene oxide are also suitable.
  • bleaching agents come the active oxygen-releasing compounds such as perborates, preferably in conjunction with bleach activators such as. B. tetraacetylethylenediamine (TAED) or tetraacetylglycoluril (TAGU) or peracids or their salts, e.g. B. the magnesium salt of monoperphthalic acid.
  • bleach activators such as. B. tetraacetylethylenediamine (TAED) or tetraacetylglycoluril (TAGU) or peracids or their salts, e.g. B. the magnesium salt of monoperphthalic acid.
  • TAED tetraacetylethylenediamine
  • TAGU tetraacetylglycoluril
  • peracids or their salts e.g. B. the magnesium salt of monoperphthalic acid.
  • compounds which release active chlorine are preferred, such as the salts of chlorine-substituted isocyanuric acids, in
  • 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 dyes or pigments such as. As phthalocyanine, stain and then mix approximately together with the bleaching agents. Fragrances, known bactericidal and dirt-suspending agents and corrosion inhibitors can also be added.
  • the mixing of the prefabricated granules with the other detergent components takes place in known mixing devices such as a Lödige mixer.
  • the finished granulate-containing mixture is preferably tableted as sodium acetate in amounts of 1 to 5, preferably 2 to 3% by weight and / or dicalcium phosphate dihydrate in amounts of 0.5 to 3, preferably 0.8 to 1.2 % By weight, based in each case on 100% of the total tablet granulate mixture, was added.
  • other known agents which improve the compressibility of the agents and the disintegration of the tablets during use can also be added. These include non-surface active alkali salts of mono- to tri-base organic carboxylic acids, e.g. As citrates, formates, benzoates, tartrates, oxalates and the like.
  • the granulate mixture prepared in this way can be pressed into any desired shape without any problems. Prismatic compacts with a hexagonal cross section are preferred. Its volume is determined by the desired tablet weight of approximately 20 g.
  • All known eccentric and rotary presses which can be used for the production of tablets with diameters of approximately 1.0 cm and more, are suitable for pressing the granulate mixture.
  • the compression pressure must be optimized for a given composition 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 78, 48 to 147. 15 MPa (800 to 1 500 kg / cm 2 ), preferably 93. 195 to 103.005 MPa (950 to 1 050 kg / cm 2 ) have been found to be optimal.
  • the tablets obtained by this process have an average density of 1.6 g / ml. In addition to high mechanical stability, they have a uniform porous structure with a large inner surface. They therefore disintegrate particularly quickly when used in the dishwasher and can be washed into the machine faster than the granular detergent used for tableting.
  • 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, 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. In addition to the mechanical stability, the tablets according to the invention also have excellent chlorine stability, although the water content of the tablets is approximately 10% by weight.

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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 for the production of tablet form detergent compositions is afforded, comprising: (a) the partial hydration of from 10 to 60 parts by weight of an anhydrous sodium polyphosphate to form from 30 mole percent to less than 80 mole percent of tripolyphosphate hexahydrate; (b) mixing the partial hydrate with from 20 to 70 parts by weight of a powder-form, substantially anhydrous sodium silicate (Na2O: SiO2=1:1 to 1:4); (c) spraying the mixture with water or an aqueous silicate solution; and (d) granulation by agitation, followed by crystallization, other detergent ingredients optionally being added along with bleaches or enzymes, and adding from 1 to 5% by weight of sodium acetate or from 0.5 to 3% by weight of dicalcium phosphate dihydrate or a mixture thereof as a tableting aid, followed by tableting under a pressure of more than 70 kp/cm2, leading to mechanically strong, but rapidly dissolving tablet form detergent compositions.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Reinigungsmitteltabletten, insbesondere zur Verwendung zum maschinellen Geschirrspülen.The present invention relates to a method for producing detergent tablets, in particular for use in automatic dishwashing.

Pulver-, granulat- oder tablettenförmige Reinigungsmittel für Geschirr in Geschirrspülmaschinen bestehen im wesentlichen aus Natriumtripolyphosphat, Alkalisilikat, meist Alkalimetasilikat, und gegebenenfalls aus einem schwach schäumenden, vorzugsweise chlorstabilen, nichtionischen Tensid sowie Bleichmitteln, vorzugsweise solchen, die in wäßriger Lösung Chlor abgeben. Sie dienen vor allem der Erleichterung der Entfernung von Flecken von Tee, Kaffee oder Obstsäften.Powder, granule or tablet detergents for dishes in dishwashers essentially consist of sodium tripolyphosphate, alkali silicate, mostly alkali metasilicate, and optionally a low-foaming, preferably chlorine-stable, nonionic surfactant and bleaching agents, preferably those that release chlorine in aqueous solution. They are mainly used to facilitate the removal of stains from tea, coffee or fruit juices.

Die Mittel sind wegen ihres hohen Gehaltes an Alkalisilikaten und Natriumtripolyphosphat stark alkalisch. Ihre Gebrauchslösungen haben einen pH-Wert von etwa 11 bis 12. Dabei ist ein Zusatz von Natriumhydroxid nicht vorgesehen, weil bei den in Haushaltsgeschirrspülmaschinen üblichen Kontaktzeiten die dann zu hohe Alkalinität Porzellan, Aufglasurdekors und Gläser angreifen würde. Man bezeichnet diesen Angriff als Korrosion. Silikat dagegen unterstützt die Reinigungskraft des Tripolyphosphats synergistisch und hemmt in bestimmten Konzentrationen im Gesamtgemisch Tripolyphosphat/Silikat die Korrosion.The agents are strongly alkaline due to their high content of alkali silicates and sodium tripolyphosphate. Their working solutions have a pH value of around 11 to 12. An addition of sodium hydroxide is not intended, because the contact time that is usual in household dishwashers would then attack the too high alkalinity of porcelain, frosting decorations and glasses. This attack is called corrosion. Silicate, on the other hand, synergistically supports the cleaning power of the tripolyphosphate and inhibits corrosion in certain concentrations in the total tripolyphosphate / silicate mixture.

Die Herstellung der bekannten Mittel erfolgt im allgemeinen nach üblichen Herstellungsverfahren, wie Mischen oder Granulieren. Die Anwendung erfolgt in Pulver- oder Granulatform in ebenfalls üblichen Konzentrationen, d. h, in Mengen von etwa 30 bis 50 g pro Maschinenfüllung.The known agents are generally produced by customary production processes, such as mixing or granulating. The application is in powder or granule form in likewise usual concentrations, i.e. h, in amounts of about 30 to 50 g per machine filling.

Derartige pulver- oder granulatförmige Mittel sind beispielsweise in den deutschen Offenlegungsschriften 23 50 295, 23 58 249 und 29 13 145 sowie in den deutschen Auslegeschriften 24 34 309 und 26 02 357 beschrieben.Such powdered or granular agents are described, for example, in German Offenlegungsschriften 23 50 295, 23 58 249 and 29 13 145 and in German patent specifications 24 34 309 and 26 02 357.

Nach der französischen Patentschrift 1 472 680 hat man aus einfachen Mischungen der bekannten Reinigungsmittelbestandteile unter Zusatz eines Tablettierungshilfsmittels und unter Anwendung eines Preßdruckes von etwa 6. 867 bis 98. 1 MPa (70 bis 1 000 kg/cm2) scheibenähnliche Tabletten, beispielsweise mit einem Durchmesser von 3 cm, einer Dicke von 1,2 cm und einem Gewicht von etwa 12 g, woraus sich eine Dichte von mehr als 1,4 g/ml errechnen läßt, hergestellt. Mit etwa 4 dieser Tabletten erreicht man praktisch den gleichen Erfolg wie mit einer pulverförmigen Reinigungsmittelfüllung von 50 g pro Maschinenlauf.According to French patent specification 1,472,680, from simple mixtures of the known cleaning agent components with the addition of a tabletting aid and using a compression pressure of approximately 6,867 to 98.1 MPa (70 to 1,000 kg / cm 2 ), disk-like tablets, for example with a Diameter of 3 cm, a thickness of 1.2 cm and a weight of about 12 g, from which a density of more than 1.4 g / ml can be calculated. With about 4 of these tablets you can achieve practically the same success as with a powdered detergent filling of 50 g per machine run.

Tabletten der vorstehend genannten Art sind auch in der deutschen Offenlegungsschrift 28 57 001 beschrieben. Sie werden ebenfalls durch Verpressen der bloßen Mischungen der Bestandteile unter Anwendung entsprechender Drucke hergestellt. Anstelle des pH-Wertes wird dort die Alkalinität dadurch bestimmt, daß man feststellt, wieviel n-Salzsäure erforderlich ist, um den pH-Wert einer Lösung von 100 g des Reinigungsmittels in Wasser auf pH 9 zu senken und vergleicht, für welche Menge Natriumhydroxid, in der gleichen Menge Wasser gelöst, die gleiche Menge n-Salzsäure benötigt wird. Das Ergebnis wird als « Alkalinitätsäquivalent bezeichnet. Die Werte liegen wie bei den bekannten Geschirreinigungsmitteln im allgemeinen über 15 g NaOH, bezogen auf 100 g Reinigungsmittel.Tablets of the type mentioned above are also described in German Offenlegungsschrift 28 57 001. They are also produced by pressing the mere mixtures of the components using appropriate pressures. Instead of the pH value, the alkalinity is determined there by determining how much n-hydrochloric acid is required to lower the pH value of a solution of 100 g of the cleaning agent in water to pH 9 and comparing the amount of sodium hydroxide, dissolved in the same amount of water, the same amount of n-hydrochloric acid is required. The result is called the “alkalinity equivalent”. As with the known dishwashing detergents, the values are generally above 15 g of NaOH, based on 100 g of detergent.

Die jeweilige Druckhöhe und die daraus resultierende Dichte der Tabletten wird stets durch den erforderlichen Kompromiß zwischen Festigkeit und Auflösungsgeschwindigkeit der Tabletten bestimmt. Weitere auf diese Eigenschaften Einfluß nehmende Faktoren sind die Natur der Bestandteile selbst und geeignete Tablettierungshilfsmittel.The respective pressure level and the resulting density of the tablets is always determined by the necessary compromise between strength and speed of dissolution of the tablets. Other factors influencing these properties are the nature of the constituents themselves and suitable tabletting aids.

Aus der US-A-3 417 024 sind Reinigungsmitteltabletten bekannt, die nach dem Zusammenpressen eine hohe anfängliche Festigkeit besitzen und sich bei der Anwendung schnell auflösen. Sie enthalten einen hohen Anteil von 4 bis 13 Gewichtsprozent nichtionischer Tenside. Ihre Herstellung erfolgt durch gleichförmiges Zusammenmischen aller Bestandteile in einer routierenden Trommel, wobei sich Granulate bilden, die vorzugsweise zu einheitlicher Größe abgesiebt werden und dann unter Anwendung von Drucken von etwa 1.472 bis 34. 335 MPa (15 bis 350 kg/cm2) zu Tabletten verpreßt werden. Die hierbei erhaltenen Waschmitteltabletten lösen sich so schnell in Wasser auf, daß sie nicht für eine Anwendung in Geschirrspülmaschinen geeignet sind.From US-A-3 417 024 detergent tablets are known which, after being compressed, have a high initial strength and dissolve quickly when used. They contain a high proportion of 4 to 13 percent by weight of nonionic surfactants. They are made by uniformly mixing together all of the ingredients in a routing drum to form granules which are preferably screened to a uniform size and then to tablets using pressures of about 1,472 to 34,335 MPa (15 to 350 kg / cm 2 ) be pressed. The detergent tablets obtained in this way dissolve so quickly in water that they are not suitable for use in dishwashers.

Es wurde nun überraschend gefunden, daß man zu Reinigungsmitteltabletten für das maschinelle Geschirrspülen kommt, die nicht nur eine gute mechanische Festigkeit, sondern vor allem eine hohe Auflösungsgeschwindigkeit besitzen, wenn man bei ihrer Herstellung die alkalisch reagierenden Bestandteile zunächst granuliert und erst dann unter Zusatz von Tablettierungshilfsmitteln, gegebenenfalls in Mischung mit weiteren Bestandteilen verpreßt. Dabei werden Preßdrücke von mehr als 6. 867 MPa (70 kg/cm2) angewendet.It has now surprisingly been found that detergent tablets for automatic dishwashing are obtained which not only have good mechanical strength, but above all have a high dissolution rate, if the alkaline-reacting constituents are first granulated in their preparation and only then with the addition of tabletting aids , optionally pressed in a mixture with other constituents. Compression pressures of more than 6,867 MPa (70 kg / cm 2 ) are used.

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 suitable method for granulating and mixing, which initiates the method according to the invention for the production of the tablets, is described in all details in German Offenlegungsschrift 29 13 145.

Die vorliegende Erfindung betrifft daher ein Verfahren zur Herstellung von Reinigungsmitteltabletten für das maschinelle Geschirrspülen durch Granulieren der alkalisch reagierenden Bestandteile, gegebenenfalls in Gegenwart von nichtionischen Tensiden, Zusatz von Tablettierungshilfsmitteln und gegebenenfalls weiteren Bestandteilen und anschließendem Verpressen unter Anwendung von Preßdrucken von mehr als 6. 867 MPa (70 kg/cm2), das dadurch gekennzeichnet ist, daß man einem vollständig auskristallisierten Granulat mit einem Schüttgewicht von 800 bis 1 200, vorzugsweise 850 bis 1 100 g/l. gewonnen durch (a) partielles Hydratisieren von 10 bis 60, vorzugsweise 25 bis 40 Gewichtsteilen. eines wasserfreien Natriumtripolyphosphats, das zu 60 bis 100 % aus einem solchen der Phase 11 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 Mischgutes, daß 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 Na20 : Si02 = 1 : 1 bis 1 : 4 und anschließendes Besprühen mit Wasser oder einer wäßrigen Lösung von 0.5 bis 5 Gewichtsteilen Natriumsilikat-Lösung in 2 bis 12, vorzugsweise 5 bis 12 Gewichtsteilen Wasser und (c) Granulieren durch Bewegen des Behandlungsgutes mit anschließender Durchkristallisation : gegebenenfalls weitere Reinigungsmittelbestandteile, Bleichmittel oder Enzyme zummischt, danach Tablettierhilfsmittel zusetzt, und das so vorbereitete Granulatgemisch in Tablettiermaschinenmatrizenbohrungen füllt und verpreßt.The present invention therefore relates to a process for the production of detergent tablets for automatic dishwashing by granulating the alkaline constituents, if appropriate in the presence of nonionic surfactants, adding tabletting aids and, if appropriate, further constituents and then compressing using compression pressures of more than 6,867 MPa (70 kg / cm 2 ), which is characterized in that a completely crystallized granulate with a bulk density of 800 to 1 200, preferably 850 to 1 100 g / l. won by (a) partially hydrating 10 to 60, preferably 25 to 40 parts by weight. of an anhydrous sodium tripolyphosphate, which consists of 60 to 100% of one from phase 11 and has an average grain size of 0.05 to 0.5 mm, in a continuously operating mixer (1st mixing stage) within an average residence time of 0.2 up to 5 seconds with such an amount of water as is necessary for the formation of 30 to less than 80 mol% tripolyphosphate hexahydrate and at the same time mechanical processing of the mixture such that at least 85% by weight thereof has a grain size of more than 0.2 mm and less than 2 wt .-% have a grain 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, in essential anhydrous sodium silicate of the composition Na 2 0: Si0 2 = 1: 1 to 1: 4 and subsequent spraying with water or an aqueous solution of 0.5 to 5 parts by weight of sodium silicate solution in 2 to 12, preferably 5 to 12 parts by weight of water and (c ) Granulate by moving the material to be treated with subsequent crystallization: if necessary, add further detergent components, bleach or enzymes, then add tabletting aids, and fill and compress the granulate mixture prepared in this way in tabletting machine matrix bores.

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 afterwards, further granulation aids such as anhydrous sodium carbonate, bicarbonate, sodium hydroxide or water glass can be used. but also water, paraffin oil, which can simultaneously serve as a foam suppressant, and / or low-foaming nonionic surfactants can be added. However, the amount of the surfactant additive should 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. Geeignet sind ferner die Blockpolymere des Ethylenoxids mit Polypropylenoxid.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 radical being substituted by ether or acetal groups or by polypropylene glycol ether radicals to reduce the tendency to foam. The block polymers of ethylene oxide with polypropylene oxide are also suitable.

Als Bleichmittel kommen die Aktivsauerstoff abspaltenden Verbindungen wie Perborate, 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. Bevorzugt werden jedoch Aktivchlor abspaltende Verbindungen wie die Salze von chlorsubstituierten Isocyanursäuren, insbesondere die reine Trichlorisocyanursäure selbst. Sie werden gegebenenfalls in Mengen von 0,5 bis 5, vorzugsweise 1 bis 3,5 Gew.-%. bezogen auf das zu verpressende Gemisch, zugemischt.As bleaching agents come the active oxygen-releasing compounds such as perborates, preferably in conjunction with bleach activators such as. B. tetraacetylethylenediamine (TAED) or tetraacetylglycoluril (TAGU) or peracids or their salts, e.g. B. the magnesium salt of monoperphthalic acid. However, compounds which release active chlorine are preferred, such as the salts of chlorine-substituted isocyanuric acids, in particular pure trichloroisocyanuric acid itself. They are optionally present in amounts of 0.5 to 5, preferably 1 to 3.5,% by weight. based on the mixture to be pressed, admixed.

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 und Korrosionsinhibitoren können zugesetzt werden.To further improve the external appearance of the detergents, part of the bleach-free granules can be bleached with stable dyes or pigments such as. As phthalocyanine, stain and then mix approximately together with the bleaching agents. Fragrances, known bactericidal and dirt-suspending agents and corrosion inhibitors can also be added.

Das Mischen des vorgefertigten Granulats mit den übrigen Reinigungsmittelbestandteilen erfolgt in bekannten Mischvorrichtungen wie beispielsweise einem Lödigemischer.The mixing of the prefabricated granules with the other detergent components takes place in known mixing devices such as a Lödige mixer.

Dem fertigen, granulathaltigen Gemisch werden als Tablettierungshilfsmittel bevorzugt Natriumacetat in Mengen von 1 bis 5, vorzugsweise 2 bis 3 Gew.-% und/oder Dicalcium-phosphat-dihydrat in Mengen von 0,5 bis 3, vorzugsweise 0,8 bis 1,2 Gew.-%, jeweils bezogen auf 100 % des gesamten Tablettengranulatgemisches, zugesetzt. Aber auch andere bekannte Mittel, die die Verpreßbarkeit der Mittel und den Zerfall der Tabletten bei der Anwendung verbessern, können zugesetzt werden. Dazu gehören nichtoberflächenaktive Alkalisalze ein- bis dreibasiger organischer Carbonsäuren, z. B. Citrate, Formiate, Benzoate, Tartrate, Oxalate und dergleichen.The finished granulate-containing mixture is preferably tableted as sodium acetate in amounts of 1 to 5, preferably 2 to 3% by weight and / or dicalcium phosphate dihydrate in amounts of 0.5 to 3, preferably 0.8 to 1.2 % By weight, based in each case on 100% of the total tablet granulate mixture, was added. However, other known agents which improve the compressibility of the agents and the disintegration of the tablets during use can also be added. These include non-surface active alkali salts of mono- to tri-base organic carboxylic acids, e.g. As citrates, formates, benzoates, tartrates, oxalates and the like.

Das so vorbereitete Granulatgemisch läßt sich störungsfrei zu jeder gewünschten Form verpressen. Bevorzugt werden prismatische Preßlinge mit hexagonalem Querschnitt. Ihr Volumen wird durch das gewünschte Tablettengewicht von etwa 20 g bestimmt.The granulate mixture prepared in this way can be pressed into any desired shape without any problems. Prismatic compacts with a hexagonal cross section are preferred. Its volume is determined by the desired tablet weight of approximately 20 g.

Anbackungen an den Preßwerkzeugen treten nicht auf. Die erhaltenen Tabletten zerfallen auch nach längerer Lagerung einwandfrei.Caking on the pressing tools does not occur. The tablets obtained disintegrate perfectly even after prolonged storage.

Zum Verpressen des Granulatgemisches sind alle bekannten Excenter- und Rundläuferpressen 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 78, 48 bis 147. 15 MPa (800 bis 1 500 kg/cm2), vorzugsweise 93. 195 bis 103. 005 MPa (950 bis 1 050 kg/cm2) als optimal erwiesen.All known eccentric and rotary presses, which can be used for the production of tablets with diameters of approximately 1.0 cm and more, are suitable for pressing the granulate mixture. The compression pressure must be optimized for a given composition 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 78, 48 to 147. 15 MPa (800 to 1 500 kg / cm 2 ), preferably 93. 195 to 103.005 MPa (950 to 1 050 kg / cm 2 ) have been found to be optimal.

Die nach diesem Verfahren erhaltenen Tabletten weisen eine Dichte von durchschnittlich 1,6 g/ml auf. besitzen neben einer hohen mechanischen Stabilität eine gleichmäßige poröse Struktur mit großer innerer Oberfläche. Sie zerfallen daher bei der Anwendung in der Geschirrspülmaschine besonders schnell und lassen sich schneller in die Maschinen einspülen als das zur Tablettierung verwendete granulatförmige Reinigungsmittel.The tablets obtained by this process have an average density of 1.6 g / ml. In addition to high mechanical stability, they have a uniform porous structure with a large inner surface. They therefore disintegrate particularly quickly when used in the dishwasher and can be washed into the machine faster than the granular detergent used for tableting.

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 neben der mechanischen Stabilität auch eine ausgezeichnete Chlorstabilität, obgleich der Wassergehalt der Tabletten ca. 10 Gew.-% beträgt.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, 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. In addition to the mechanical stability, the tablets according to the invention also have excellent chlorine stability, although the water content of the tablets is approximately 10% by weight.

BeispieleExamples Beispiel 1example 1

41.7 Gew.-% wasserfreies Natriummetasilikat und 38,6 Gew.-% Natriumtripolyphosphat wurden in Gegenwart von 6,7 Gew.-% wasserfreiem Natriumcarbonat mit 4,0Gew.-% Wasserglas 37/40 und 0,2 Gew-% weißem Paraffinöl mit einem Flammpunkt von 210 °C nach dem in der deutschen Auslegeschrift 2913 145 ausführlich beschriebenen Verfahren granuliert, in einem Lödigemischer mit 3,0 Gew.-% eines durch Phthalocyaninzusatz blau gefärbten gleichen Granulats (« Blausprenkel »), 1,0 Gew.-% Trichlorisocyanursäure und 2,0 Gew.-% Natriumacetat sowie 1,0 Gew.-% Dicalcium-phosphat-dihydrat vermischt. Jeweils 20 g dieser Mischung wurden über einen Vorratstrichter kontinuierlich nacheinander in eine regelmäßige Sechseckmatrizenbohrung einer Excenter-Tabiettiermaschine vom Typ Exakta 31 der Firma Fette eingefüllt und mit einem Preßdruck von 98. 1 MPa (1 000 kg/cm2) zu Preßlingen ( = Tabletten) mit einer Dichte von rund 1,4 g/ml verpreßt.41.7% by weight of anhydrous sodium metasilicate and 38.6% by weight of sodium tripolyphosphate were mixed with 4.0% by weight of 37/40 water glass and 0.2% by weight of white paraffin oil in the presence of 6.7% by weight of anhydrous sodium carbonate a flash point of 210 ° C., granulated according to the process described in detail in German Auslegeschrift 2913 145, in a Lödige mixer with 3.0% by weight of the same granulate ("blue speckles") colored blue by the addition of phthalocyanine, 1.0% by weight Trichloroisocyanuric acid and 2.0 wt .-% sodium acetate and 1.0 wt .-% dicalcium phosphate dihydrate mixed. In each case 20 g of this mixture were poured continuously in succession into a regular hexagon matrix bore in an excenter tabulating machine of the type Exakta 31 from Fette and with a pressing pressure of 98.1 MPa (1,000 kg / cm 2 ) into pressed pieces (= tablets) pressed with a density of around 1.4 g / ml.

Sie waren von feiner und 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 25 Minuten und damit zwei Minuten weniger als die Einspülzeit der gleichen Gewichtsmenge des unverpreßten Reinigungsmittels gleicher Zusammensetzung, jedoch ohne Tablettierungshilfsmittel.They were of fine and uniformly grained structure and of great stability. Their washing-in time using a grid-fitted metering box in a Miele G 5035 household dishwashing machine was 25 minutes, two minutes less than the washing-in time of the same amount by weight of the unpressed cleaning agent of the same composition, however without tableting aids.

Beispiele 2-6Examples 2-6

In entsprechender Weise wie in Beispiel 1 angegeben, wurden weitere Tabletten hergestellt, deren Zusammensetzung, Kenndaten und Eigenschaften in der nachfolgenden Tabelle wiedergegeben sind.
(Siehe Tabelle Seite 5 f.)

Figure imgb0001
In a manner corresponding to that given in Example 1, further tablets were produced, the composition, characteristics and properties of which are shown in the table below.
(See table on page 5 f.)
Figure imgb0001

Claims (6)

1. A process for the production of detergent tablets for dishwashing machines by granulation of the alkaline-reacting constituents, optionally in the presence of nonionic surfactants, addition of tabletting aids and, optionally, other constituents and subsequent tabletting under pressures of more than 6.887 MPa (70 kg/cm2), characterized in that to a completely crystallized granulate having a powder density of from 800 to 1200 and preferably from 850 to 1100 g/l, obtained by (a) partial hydration of from 10 to 60 parts by weight and preferably from 25 to 40 parts by weight of an anhydrous sodium tripolyphosphate, of which from 60 to 100 % consists of a phase II type and has an averagegrain size of from 0.05 to 0.5 mm. for 0.2 to 5 seconds (average residence time) in a continuous mixer (first mixing stage) with the quantity of water necessary to form from 30 to less than 80 mole % tripolyphosphate hexahydrate. the material being mixed simultaneously being mechanically treated in such a way that at least 85 % by weight thereof has a grain size of more than 0.2 mm and less than 2 % by weight a grain size of less than 0.1 mm, (b) mixing the partial hydrate after a residence time outside the mixer of from 5 to 60 seconds in a granulation mixer (second mixing stage), optionally together with up to 25 parts by weight of a granulation aid, with from 20 to 70 parts by weight and preferably with from 30 to 50 parts by weight of a powder-form, substantially anhydrous sodium silicate having the composition Na2O : SiO2 = 1 : 1 to 1 : 4 and subsequent spraying with water or with an aqueous solution of from 0.5 to 5 parts by weight sodium silicate solution in from 2 to 12 and preferably from 5 to 12 parts by weight water and (c) granulation by movement of the material being treated, followed by thorough crystallization, are optionally added other detergent constituents, bleaches or enzymes, after which tabletting aids are added and the granulate mixture thus prepared is introduced into the bores of tabletting machines and tabletted.
2. A process as claimed in Claim 1, characterized in that tabletting pressures of from 78.48 to 147.15 MPa (800 to 1500 kg/cm2) and preferably of from 93.195 to 103.005 MPa (950 to 1050 kg/cm2) are applied.
3. A process as claimed in Claims 1 and 2. characterized in that sodium acetate is added as the tabletting aid in a quantity of from 1 to 5 % by weight and preferably in a quantity of from 2 to 3 % by weight. based on 100 % of the granulate mixture as a whole.
4. A process as claimed in Claims 1 to 3, characterized in that dicalcium phosphate dihydrate is added as tabletting aid in a quantity of from 0.5 to 3 % by weight and preferably in a quantity of from 0.8 to 1.2 % by weight, based on 100 % of the granulate mixture as a whole.
5. A process as claimed in Claims 1 to 4, characterized in that a mixture of sodium acetate and dicalcium phosphate dihydrate is added.
6. A process as claimed in Claims 1 to 5, characterized in that coloring constituents are added as further detergent constituents.
EP84104535A 1983-05-02 1984-04-21 Process for the production of cleaning agent tablets Expired EP0126963B1 (en)

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