EP0224129B1 - Uniformly composed detergent tablets for mechanical dish-washing - Google Patents

Uniformly composed detergent tablets for mechanical dish-washing Download PDF

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Publication number
EP0224129B1
EP0224129B1 EP86115739A EP86115739A EP0224129B1 EP 0224129 B1 EP0224129 B1 EP 0224129B1 EP 86115739 A EP86115739 A EP 86115739A EP 86115739 A EP86115739 A EP 86115739A EP 0224129 B1 EP0224129 B1 EP 0224129B1
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EP
European Patent Office
Prior art keywords
tablets
weight
anhydrous
sodium metasilicate
triphosphate
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 - Lifetime
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EP86115739A
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German (de)
French (fr)
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EP0224129A3 (en
EP0224129A2 (en
Inventor
Hans Kruse
Jochen Dr. Jacobs
Theodor Dr. Altenschöpfer
Peter. Dr. Jeschke
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT86115739T priority Critical patent/ATE59403T1/en
Publication of EP0224129A2 publication Critical patent/EP0224129A2/en
Publication of EP0224129A3 publication Critical patent/EP0224129A3/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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents

Definitions

  • Machine dishwashing generally consists of a pre-rinse cycle, a cleaning cycle, one or more intermediate rinse cycles, a rinse cycle and a drying cycle. This applies to machine washing in the home as well as in business.
  • HGSM HGSM
  • the pre-clearing zone corresponds in principle to the pre-rinse cycle of an HGSM.
  • the cleaning agent added to the cleaning zone is used in the so-called pre-clearing zone to support the cleaning of the adhering food residues.
  • GGSM in which the pre-clearing zone is only operated with fresh water, but a pre-clearing zone with cleaning agent solution is more effective than pre-clearing with fresh water alone.
  • One or more tablets can be dosed, for example, in a free part of the cutlery basket, but also elsewhere in the machine.
  • tablet-shaped cleaning agents are adequately described in the patent literature.
  • DE-OS 16 17 088 tablets for machine dishwashing which are obtained by pressing a powdery mixture of sodium silicate with a Na 2 0: Si0 2 ratio of 1: 3.25 to 2: 1 and a water content of 0 up to 20%, polymeric alkali phosphates, active chlorine compounds, low-foaming non-ionic surfactants compatible with the active chlorine compounds, fillers such as alkali metal carbonates, chlorides or sulfates, white paraffin oil and tablet binders, which are said to be stable in storage and transport.
  • Such tablets are also known from DE-OS 28 57 001 which contain essentially the same constituents but are said to have a particularly high level of alkalinity, which can be achieved, inter alia, by adding alkali metal hydroxide.
  • a high level of alkalinity is unsuitable for the use of the agents in the household, because improper handling of the agents can lead to skin irritation and also damage the decor.
  • the present invention was therefore based on the object of developing a tablet with a broad dissolution profile which is dissolved to at least 10% by weight of the incoming cold tap water in the pre-rinse cycle of an HGSM, with a pH value of at least 10.0 in the rinse liquor developed and with good hot water solubility still at least 65 wt .-%, preferably at least 70 wt .-%, is available for the cleaning cycle.
  • the dissolution profile here means the ratio of portions of the tablet dissolved from the usual HGSM under the conditions of the pre-rinse cycle to the entire tablet.
  • the object was achieved by uniformly composed detergent tablets with a broad dissolution profile for machine dishwashing, containing alkaline components from the group of alkali metal silicates and pentaalkali metal phosphates, active chlorine compounds and tabletting aids, which are characterized in that the alkali metal silicates consist of a mixture of sodium ummetasilikatnonahydrat and anhydrous sodium metasilicate and the Pentaalkalitriphosphat from anhydrous pentasodium triphosphate.
  • the total amount of sodium metasilicate and pentasodium triphos p is 88 to 98% by weight and the weight ratio of anhydrous sodium metasilicate to nonahydrate is between 1: 0.3 to 1: 1.5 and the weight ratio of sodium triphosphate to sodium metasilicate. both water-free. 2: 1 to 1: 2.
  • the dissolution profile can be varied within wide limits by varying the ratio of sodium metasilicate, anhydrous to nonahydrate.
  • the weight ratio of anhydrous sodium metasilicate to nonahydrate is preferably between 1: 0.75 to 1: 1.2.
  • pentasodium triphosphate to sodium metasilicate should be present in a weight ratio of 2: 1 to 1: 2, preferably from 1: 1 to 1: 1.7.
  • Active chlorine carriers are also common components of cleaning agents for HGSM.
  • tableting aids are added, the amounts of which can be varied.
  • the compressibility of raw material mixtures containing anhydrous sodium metasilicate depends on its particle size distribution, its production process, its weight ratio to the nonahydrate present at the same time and on the average particle size of the pentasodium triphosphate.
  • a grain fraction of the almost water-free sodium metasilicate e.g. from a sintering or melting process
  • good taboo animal properties of the raw material mixture can be obtained without or with only small additions of nonahydrate (to adjust the dissolution profile).
  • the nonahydrate When using dust (less than 0.2 mm) or unsieved material with 20 to 100% coarser coarser than 0.8 mm, the nonahydrate must be used at least in 1.2 times the amount of the anhydrous metasilicate in order to achieve comparable tablet properties .
  • Alkali metasilicate in anhydrous form and as a nonahydrate and also the preferably anhydrous pentaalkali metal phosphate were used in the form of their sodium salts. Their total amount in the mixture to be pressed was preferably 95 to 97% by weight.
  • Trichloroisocyanuric acid was preferred as the active chlorine carrier, but also other known solid compounds, such as e.g. Sodium dichloroisocyanurate, its dihydrate and potassium dichloroisocyanurate can be used in commercially available form without impairing the tablettability.
  • Their amounts are 0.5 to 5.0, preferably 1.0 to 2.5% by weight, based on the active chlorine content and the total tableting mixture.
  • a mixture of 0.5 to 2.0, preferably 1.0% by weight, based on the entire tablet mixture, of calcium hydrogenphosphate dihydrate (to reduce segregation) and 1.0 to 5.0, preferably 2, 0 to 3.0% by weight, based on the total tableting mixture, of anhydrous sodium acetate (to reduce sticking to tool parts) was added.
  • the proportions of these tabletting aids which are safe from an application point of view in terms of their cleaning performance, can be varied beyond the ranges mentioned in order to be able to optimally compress recipe variants.
  • the sodium acetate content also affects the solubility of the tablet. Higher amounts of sodium acetate lead in particular to improved solubility in cold water in the pre-rinse cycle.
  • Customary chlorine-stable colors and fragrances can also be added to the tableting mixtures.
  • the tablets can also be pressed in colored layers with otherwise the same composition.
  • the mixture of the fine-grained, anhydrous metasilicates, the corresponding nonahydrates, the triphosphates, active chlorine carriers and tabletting aids can be pressed under die lubrication, with conventional lubricants being used.
  • lubrication is carried out directly through holes in the die, by spraying the lower punch or by means of felt rings soaked in lubricant on the lower punch.
  • the raw material mixtures according to the invention with their particularly favorable compressibility properties, however, the lubrication can usually also be dispensed with.
  • the pressing conditions are with regard to the one optimize the setting of the desired dissolution profile with sufficient tablet hardness.
  • the flexural strength can serve as a measure of the tablet hardness (method: compare Ritschel. Die Tablette, Ed. Cantor, 1966, p. 313). Tablets with a flexural strength greater than 12 kp, preferably greater than 15 kp, are sufficiently stable under simulated transport conditions.
  • Corresponding tablet hardnesses were at pressures of 4905 104 to 49 050 104 Pa. preferably 9810 '1 Q4 to 14715.104 Pa (500 to 5000 kp / cm 2 , preferably 1000 to 1500 kp / cm 2 ). Higher pressures reduce the release speed. Differences in solubility can be compensated within limits for different compositions by choosing the pressure.
  • the specific weight of the compacts was between 1.2 and 2 g / cm 3 , preferably between 1.4 and 1.7 g / cm 3 .
  • the compression during the pressing process brought about changes in the specific volume, from 0.8 to 1.8 cm3 / g, preferably 1.0 to 1.4 cm 3 / g to 0.5 to 0.8 cm3 / g, preferably 0, 6 to 0.7 cm 3 / g decreased.
  • the shape of the tablet can also influence the dissolution rate via the outer surface exposed to the H 2 0 attack. For stability reasons, cylindrical compacts with a diameter / height ratio of 0.6 to 1.5: 1 were produced.
  • the amounts of the substance mixture to be compressed for the individual tablets can be varied as desired within technically reasonable limits. Depending on their size, 1, 2 or more tablets are used per machine filling in order to provide the entire cleaning process with the necessary active substance content of detergent. Tablets of 20 to 30 g in weight are preferred, two of which must be used. Larger tablets are usually more sensitive to breakage and, moreover, are compressed at a lower speed, which leads to a loss of performance in the production process. With smaller tablets, the handling advantage compared to granular or powder detergents would be reduced.
  • compositions can be pressed in a known manner using commercially available eccentric presses or rotary presses.
  • the tablets can be placed in a cutlery basket of a household dishwasher before opening the pre-rinse cycle into a zone that exposes the tablets to the dissolving power of the tap water flow the automatically controlled cleaning process can be started.
  • the invention therefore also relates to the use of the detergent tablets for cleaning dishes in automatic domestic dishwashers, which is characterized in that the tablets are opened before the pre-wash cycle in the machine into a zone which exposes the tablets to the dissolving power of the cold tap water flow, for example by placing it in the cutlery basket, and then initiating the automatically controlled cleaning process.
  • the dishes cleaned in this way have better cleaning results for difficult soiling, such as, for example, burnt-on milk or baked oatmeal, than those treated in the conventional manner.
  • tablets with the same diameter and the same content of active ingredients sodium triphosphate, trichloroisocyanuric acid and sodium metasilicate, water-free were produced, which weighed between approx. 20 g and 27 g.
  • the different weights are due to the varying content of water of crystallization and tableting aids.
  • the tablet format was also varied with selected recipes.
  • the mixture was pressed on an eccentric press from Fette, type "Exacta 31".
  • the pressing tools were coated with Vulkolan. When compressed to a density of 1.58 g / cm 3 , tablets with a flexural strength greater than 15 kp were obtained, which dissolved completely in the pre-rinse cycle by 25% by weight and in the cleaning cycle.
  • the mixture was pressed on an eccentric press from Fette, "Exacta 31".
  • the pressing tools were coated with Vulkolan.
  • a filling height of 30.8 mm was required with a die diameter of 35 mm. This corresponded to a specific volume of 1.18 cm3 / g.
  • a depth of 14.5 mm was necessary to produce the tablet. This then corresponded to a tablet height of 16.3 mm or a specific volume of 0.62 cm 3 / g.
  • the compression ratio was 1: 1.9.
  • the actual tablet height after manufacture was 17.7 mm. This can be explained by the fact that the tablets can generally be expected to grow slightly after relaxation.
  • the pressing pressure required for pressing was 12753. 10 4 Pa (1300 kp / cm 2 ).
  • the tablets obtained had a flexural strength of greater than 15 kp and dissolved up to 14% by weight in the pre-rinse cycle and completely in the cleaning cycle.
  • the ingredients were mixed in a Lödige mixer.
  • Paraffin oil lubrication of the tools was not necessary.
  • the omission of calcium hydrogenphosphate dihydrate led to a dissolution of 25% by weight of the tablet in the pre-rinse cycle and to a 97% by weight total dissolution.
  • the residual moisture content caused the surface to show signs of weathering when the tablets were stored.
  • Example 4 The mixture composition, the tablet weight and the tablet diameter were chosen as in Example 4, but in contrast to Example 4, the density was 1.63 g / cm 3.
  • the bending ability here was greater than 15 kp.
  • 12% of the tablet was dissolved after the pre-rinse cycle. With excellent manufacturing and application properties, weathering of the tablet surface was also evident here during storage.
  • the mixture was pressed on a rotary press from Fette, type "Perfecta 2" with plexiglass-coated tools.
  • the mixture was produced continuously on belt scales in a rack mixer, type "GAC 350".
  • the die was filled by a "Fil-o-Matic” from Fette. Caking of the material was avoided by paraffin oil lubrication (soaked felt rings on the lower punches). When compressed to a density of 1.52, tablets with a flexural strength greater than (15 kp) 147 N were obtained.

Abstract

Tablets having a broad solubility profile containing a mixture of sodium metasilicate nonahydrate and anhydrous sodium metasilicate with a grain size of from 0.2 to 0.8 mm in a ratio by weight of from 1:0.75 to 1:1.2, anhydrous pentasodium triphosphate having a grain diameter of 0.2 to 0.3 mm, and 0.5 to 5% by weight of an active chlorine donor. The ratio by weight of pentasodium triphosphate to metasilicates is about 1:1 to 1:1.7, based on anhydrous substances. The tablets are used in automatic dishwashing machines where they are introduced into a free zone of the machine before the start of the prerinse cycle, at least 10% of the tablets being dissolved by inflowing cold water and at least another 70% being available in the main-wash cycle.

Description

Maschinelles Geschirrspülen besteht im allgemeinen aus einem Vorspülgang, einem Reinigungsgang, ein oder mehreren Zwischenspülgängen, einem Klarspülgang und einem Trocknungsgang. Dies gilt sowohl für das maschinelle Spülen im Haushalt als auch im Gewerbe.Machine dishwashing generally consists of a pre-rinse cycle, a cleaning cycle, one or more intermediate rinse cycles, a rinse cycle and a drying cycle. This applies to machine washing in the home as well as in business.

Bisher ist es üblich, in Haushaltsgeschirrspülmaschinen, im folgenden als HGSM bezeichnet, das Reinigungsmittel in einem Dosierkästchen zu bevorraten, das sich meist in der Tür der Maschine befindet und sich zu Beginn des Reinigungsganges automatisch öffnet. Der zuvor ablaufende Vorspülgang wird ausschließlich mit dem zulaufenden kalten Leitungswasser betrieben.So far, it has been common in household dishwashers, hereinafter referred to as HGSM, to store the detergent in a metering box, which is usually located in the door of the machine and opens automatically at the start of the cleaning cycle. The previous pre-rinse cycle is operated exclusively with the incoming cold tap water.

Bei einer gewerblichen Geschirrspülmaschine, im folgenden als GGSM bezeichnet, entspricht die Vorabräumzone im Prinzip dem Vorspülgang einer HGSM. Beim maschinellen Spülen in Großküchen wird durch Überlauf das der Reinigungszone zudosierte Reinigungsmittel schon in der sogenannten Vorabräumzone zur unterstützenden Reinigung der anhaftenden Speisereste eingesetzt. Es gibt zwar auch GGSM, bei denen die Vorabräumzone nur mit Frischwasser betrieben wird, eine Vorabräumzone mit Reinigungsmittellösung ist aber effektiver als eine Vorabräumung allein mit Frischwasser.In the case of a commercial dishwasher, hereinafter referred to as GGSM, the pre-clearing zone corresponds in principle to the pre-rinse cycle of an HGSM. When machine washing in commercial kitchens, the cleaning agent added to the cleaning zone is used in the so-called pre-clearing zone to support the cleaning of the adhering food residues. There are also GGSM in which the pre-clearing zone is only operated with fresh water, but a pre-clearing zone with cleaning agent solution is more effective than pre-clearing with fresh water alone.

Es war das Ziel der vorliegenden Erfindung, das Wirkungsprinzip der Vorabräumzonenreinigung von GGSM auch auf HGSM zu übertragen. Als Möglichkeit wurde die Dosierung von Reinigungsmitteln bereits im Vorspülgang angesehen.It was the aim of the present invention to transfer the principle of pre-clearing zone cleaning from GGSM to HGSM as well. Dosage of detergents in the pre-rinse cycle was seen as an option.

Bei Versuchen unter Verwendung üblicher HGSM-Reinigungsmittel hatte dies zur Folge, daß neben der Dosierung des Reinigungsmittels über das Dosierkästchen in der Tür zusätzliche Anteile davon in die Maschine gegeben werden mußten. Nun besteht aber das Problem, daß auf dem Boden und im Laugensumpf der Maschine strömungsarme Bereiche existieren. Dadurch ist das Produkt nur unzureichend aufgelöst worden und wurde nach Beendigung des Vorspülganges praktisch unverbraucht abgepumpt.In experiments using conventional HGSM cleaning agents, this had the consequence that, in addition to the metering of the cleaning agent, additional portions of it had to be added to the machine via the metering box in the door. Now there is the problem that there are low-flow areas on the floor and in the base of the machine. As a result, the product was only insufficiently dissolved and was pumped out practically unused after the pre-rinse cycle.

Ein Einstreuen von Reinigungsmittel in den Besteckkorb über das darin befindliche Spülgut ist nicht sinnvoll, da an Silber- und Edelstahlteilen irreversible Schädigungen auftreten können.It does not make sense to sprinkle cleaning agents into the cutlery basket over the items to be washed, since irreversible damage can occur to silver and stainless steel parts.

Überraschenderweise wurde nun gefunden, daß diese oben genannten Nachteile bei Einsatz der erfindungsgemäßen Reinigungsmitteltabletten nicht auftreten. Die Dosierung von einer oder mehreren Tabletten kann beispielsweise in einem freien Teil des Besteckkorbes, aber auch an anderer Stelle in der Maschine erfolgen.Surprisingly, it has now been found that these disadvantages mentioned above do not occur when using the detergent tablets according to the invention. One or more tablets can be dosed, for example, in a free part of the cutlery basket, but also elsewhere in the machine.

Der Einsatz von tablettenförmigen Reinigungsmitteln ist in der Patentliteratur hinreichend beschrieben. So kennt man aus der DE-OS 16 17 088 Tabletten für das maschinelle Geschirrspülen, die durch Verpressen eines pulverförmigen Gemisches aus Natriumsilikat mit einem Verhältnis an Na20 : Si02 von 1 : 3,25 bis 2 : 1 und einem Wassergehalt von 0 bis 20 %, polymeren Alkaliphosphaten, Aktivchlorverbindungen, schwachschäumenden, mit den Aktivchlorverbindungen verträglichen nichtionischen Tensiden, Füllstoffen wie Alkalicarbonaten, - chloriden oder -sulfaten, weißem Paraffinöl und Tablettenbindemitteln erhalten werden können und die lager- und transportstabil sein sollen.The use of tablet-shaped cleaning agents is adequately described in the patent literature. For example, from DE-OS 16 17 088 tablets for machine dishwashing, which are obtained by pressing a powdery mixture of sodium silicate with a Na 2 0: Si0 2 ratio of 1: 3.25 to 2: 1 and a water content of 0 up to 20%, polymeric alkali phosphates, active chlorine compounds, low-foaming non-ionic surfactants compatible with the active chlorine compounds, fillers such as alkali metal carbonates, chlorides or sulfates, white paraffin oil and tablet binders, which are said to be stable in storage and transport.

Auch aus der DE-OS 28 57 001 sind derartige Tabletten bekannt, die im wesentlichen die gleichen Bestandteile enthalten, aber eine besonders hohe Alkalität aufweisen sollen, was unter anderem durch einen Zusatz von Alkalihydroxid erreicht werden kann. Eine hohe Alkalität ist aber für die Verwendung der Mittel im Haushalt ungeeignet, weil sie bei unsachgemäßer Handhabung der Mittel zu Hautirriationen führen kann und außerdem dekorschädigend wirkt.Such tablets are also known from DE-OS 28 57 001 which contain essentially the same constituents but are said to have a particularly high level of alkalinity, which can be achieved, inter alia, by adding alkali metal hydroxide. However, a high level of alkalinity is unsuitable for the use of the agents in the household, because improper handling of the agents can lead to skin irritation and also damage the decor.

Besonders vorteilhaft für die geforderte mechanische Festigkeit von Reinigungsmitteltabletten und deren hohe Auflösungsgeschwindigkeit ist es nach der Lehre der DE-OS 33 15 950, wenn man nicht nur die bloßen Mischungen der Bestandteile verpreßt, sondern aus deren alkalisch reagierenden Substanzen zunächst ein Cogranulat herstellt und dieses dann nach Zusatz weiterer Substanzen und Tablettierhilfsmitteln unter hohem Druck verpreßt.According to the teaching of DE-OS 33 15 950, it is particularly advantageous for the required mechanical strength of detergent tablets and their high dissolution rate if one not only compresses the mere mixtures of the components, but first produces a cogranulate from their alkaline substances and then this after adding other substances and tabletting aids, pressed under high pressure.

Alle diese Tabletten wurden bei marktüblichen HGSM in die auch für die Zugabe von pulver- oder granulatförmigen Reinigungsmitteln vorgesehenen Einspülkammer eingefüllt, deren automatisches Öffnen erst nach Beendigung des Vorspülganges mit kaltem Leitungswasser vorgesehen ist. Sie entfalten dann bei ansteigender Wassertemperatur während des etwa 20 bis 30 Minuten lang dauernden Reinigungsganges nach etwa 5 bis 7 Minuten ihre volle Wirksamkeit, wenn ihre Gesamtmenge durch die Wasserbewegung aus der Einspülkammer in die Reinigungsflotte gespült ist. Beim Einbringen der Tabletten, z. B. über den Besteckkorb, gelangten sie zwar schon in den Vorspülgang der Maschine, führten jedoch entweder wegen zu hoher Alkalität zu erhöhter Dekorschädigung und/oder lösten sich zu schnell auf und sanken in den Laugensumpf der Maschine ab. Damit standen sie für den Reinigungsgang nicht mehr in ausreichendem Maße zur Verfügung.At commercially available HGSM, all of these tablets were filled into the detergent dispenser, which is also intended for the addition of powdered or granular detergents, the automatic opening of which is only intended after the pre-rinse cycle with cold tap water. They then develop their full effectiveness after about 5 to 7 minutes when the water temperature rises during the cleaning cycle, which lasts for about 20 to 30 minutes, when their total amount has been washed out of the induction chamber into the cleaning liquor. When introducing the tablets, e.g. B. on the cutlery basket, they already came into the pre-rinse of the machine, but either led to increased decor damage due to excessive alkalinity and / or dissolved too quickly and sank into the suds of the machine. As a result, they were no longer sufficiently available for the cleaning cycle.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, eine Tablette mit breitem Löseprofil zu entwickeln, die bereits im Vorspülgang einer HGSM vom zulaufenden kalten Leitungswasser zu mindestens 10 Gew.-% aufgelöst wird, dabei in der Spülflotte einen pH-Wert von mindestens 10,0 entwickelt und bei guter Warmwasserlöslichkeit zu noch mindestens 65 Gew.-%, vorzugsweise mindestens 70 Gew.-%, für den Reinigungsgang zur Verfügung steht.The present invention was therefore based on the object of developing a tablet with a broad dissolution profile which is dissolved to at least 10% by weight of the incoming cold tap water in the pre-rinse cycle of an HGSM, with a pH value of at least 10.0 in the rinse liquor developed and with good hot water solubility still at least 65 wt .-%, preferably at least 70 wt .-%, is available for the cleaning cycle.

Unter Löseprofil ist hier das Verhältnis von unter den Bedingungen des Vorspülganges von üblichen HGSM gelösten Anteilen der Tablette zur gesamten Tablette zu verstehen.The dissolution profile here means the ratio of portions of the tablet dissolved from the usual HGSM under the conditions of the pre-rinse cycle to the entire tablet.

Die Aufgabe wurde gelöst durch einheitlich zusammengesetzte Reinigungsmitteltabletten mit breiten Löseprofil für das maschinelle Geschirrspülen, enthaltend alkalisch reagierende Komponenten aus der Gruppe der Alkalimetasilikate und Pentaalkalitriphosphate, Aktivchlorverbindungen und Tablettierhilfsmittel, die dadurch gekennzeichnet sind, daß die Alkalimetasilikate aus einem Gemisch aus Natriummetasilikatnonahydrat und wasserfreiem Natriummetasilikat und das Pentaalkalitriphosphat aus wasserfreiem Pentanatriumtriphosphat. besteht, wobei die Gesamtmenae von Natriummetasilikaten und Pentanatriumtriphosphat bei 88 bis 98 Gew.-% und das Gewichtsverhältnis von wasserfreiem Natriummetasilikat zum Nonahydrat zwischen 1:0,3 bis 1:1,5 liegt und das Gewichtsverhältnis von Natriumtriphosphat zu Natriummetasilikat. ieweils wasserfrei. 2:1 bis 1:2 beträgt.The object was achieved by uniformly composed detergent tablets with a broad dissolution profile for machine dishwashing, containing alkaline components from the group of alkali metal silicates and pentaalkali metal phosphates, active chlorine compounds and tabletting aids, which are characterized in that the alkali metal silicates consist of a mixture of sodium ummetasilikatnonahydrat and anhydrous sodium metasilicate and the Pentaalkalitriphosphat from anhydrous pentasodium triphosphate. there, the total amount of sodium metasilicate and pentasodium triphos p is 88 to 98% by weight and the weight ratio of anhydrous sodium metasilicate to nonahydrate is between 1: 0.3 to 1: 1.5 and the weight ratio of sodium triphosphate to sodium metasilicate. both water-free. 2: 1 to 1: 2.

Durch Variation des Verhältnisses Natriummetasilikat, wasserfrei zu Nonahydrat kann das Löseprofil in weiten Grenzen variiert werden. Das Gewichtsverhältnis von wasserfreiem Natriummetasilikat zum Nonahydrat liegt vorzugsweise zwischen 1:0,75 bis 1:1,2.The dissolution profile can be varied within wide limits by varying the ratio of sodium metasilicate, anhydrous to nonahydrate. The weight ratio of anhydrous sodium metasilicate to nonahydrate is preferably between 1: 0.75 to 1: 1.2.

Zur Erzielung guter Reinigungsleistungen ist eine in bezug auf den Alkalimetasilikat- und den Pentaalkalitriphosphatgehalt ausgewogene Rahmenrezeptur einzuhalten. Die Mengen an Pentanatriumtriphosphat zu Natriummetasilikat, jeweils wasserfrei, sollen im Gewichtsverhältnis 2:1 bis 1:2, vorzugsweise von 1:1 bis 1:1,7 enthalten sein.In order to achieve good cleaning performance, a balanced formulation with regard to the alkali metal silicate and the pentaalkali phosphate content must be observed. The amounts of pentasodium triphosphate to sodium metasilicate, each anhydrous, should be present in a weight ratio of 2: 1 to 1: 2, preferably from 1: 1 to 1: 1.7.

Weiterhin sind Aktivchlorträger übliche Bestandteile von Reinigungsmitteln für HGSM. Schließlich werden noch Tablettierhilfsmittel zugesetzt, deren Mengen variiert werden können.Active chlorine carriers are also common components of cleaning agents for HGSM. Finally, tableting aids are added, the amounts of which can be varied.

Während die Beschaffenheit des Natriummetasilikatnonahydrats im wesentlichen problemlos ist, hängt die Verpreßbarkeit von Rohstoffgemischen mit einem Gehalt an wasserfreiem Natriummetasilikat von dessen Korngrößenverteilung, dessen Herstellungsverfahren, seinem Gewichtsverhältnis zum gleichzeitig anwesenden Nonahydrat und von der mittleren Korngröße des Pentanatriumtriphosphats ab. Mit einer Kornfraktion des nahezu wasserfreien Natriummetasilikates (z. B. aus einem Sinter- oder Schmelzprozeß) von kleiner als 0,8 mm lassen sich auch ohne oder nur mit geringen Zusätzen an Nonahydrat (zur Einstellung des Löseprofils) gute Tabiettiereigenschaften des Rohstoffgemisches erhalten. Bei Einsatz von Staub (kleiner als 0,2 mm) oder ungesiebtem Material mit 20 bis 100 % Anteilen gröber 0,8 mm ist das Nonahydrat mindestens in der 1,2fachen Menge, bezogen auf das wasserfreie Metasilikat einzusetzen um zu vergleichbar guten Tablettiereigenschaften zu kommen.While the nature of the sodium metasilicate nonahydrate is essentially problem-free, the compressibility of raw material mixtures containing anhydrous sodium metasilicate depends on its particle size distribution, its production process, its weight ratio to the nonahydrate present at the same time and on the average particle size of the pentasodium triphosphate. With a grain fraction of the almost water-free sodium metasilicate (e.g. from a sintering or melting process) of less than 0.8 mm, good taboo animal properties of the raw material mixture can be obtained without or with only small additions of nonahydrate (to adjust the dissolution profile). When using dust (less than 0.2 mm) or unsieved material with 20 to 100% coarser coarser than 0.8 mm, the nonahydrate must be used at least in 1.2 times the amount of the anhydrous metasilicate in order to achieve comparable tablet properties .

Bei Einsatz von staubförmigem Pentanatriumtriphosphat mit einem mittleren Korndurchmesser von kleiner als 0,1 mm tritt eine Verschlechterung der Verpreßbarkeit ein. Vorzugsweise ist daher ein Triphosphat mit einem mittleren Korndurchmesser von 0,2 bis 0,3 mm einzusetzen.When using dust-like pentasodium triphosphate with an average grain diameter of less than 0.1 mm, the compressibility deteriorates. It is therefore preferable to use a triphosphate with an average grain diameter of 0.2 to 0.3 mm.

Der Einsatz von hydrothermal hergestelltem Metasilikat mit einem Restwassergehalt von ca. 2 % führt zu sehr gut verpreßbaren Rohstoffgemischen. Im Gegensatz zu den mit nahezu wasserfreiem Metasilikat hergestellten Tabletten waren diese jedoch nicht lagerstabil. Die Oberfläche der Tabletten wurde rauh, bei größeren Tabletten trat sogar Rißbildung auf. Deshalb ist der Einsatz von diesem, Restfeuchte enthaltendem Metasilikat unerwünscht.The use of hydrothermally produced metasilicate with a residual water content of approx. 2% leads to very well compressible raw material mixtures. In contrast to the tablets made with almost water-free metasilicate, however, these were not stable in storage. The surface of the tablets became rough, even cracking occurred with larger tablets. Therefore the use of this metasilicate containing residual moisture is undesirable.

Alkalimetasilikat in wasserfreier Form sowie als Nonahydrat und auch das vorzugsweise wasserfreie Pentaalkalitriphosphat wurden in Form ihrer Natriumsalze eingesetzt. Ihre Gesamtmenge im zu verpressenden Gemisch lag vorzugsweise bei 95 bis 97 Gew.-%.Alkali metasilicate in anhydrous form and as a nonahydrate and also the preferably anhydrous pentaalkali metal phosphate were used in the form of their sodium salts. Their total amount in the mixture to be pressed was preferably 95 to 97% by weight.

Als Aktivchlorträger wurde Trichlorisocyanursäure bevorzugt, aber auch andere bekannte feste Verbindungen, wie z.B. Natriumdichlorisocyanurat, dessen Dihydrat und Kaliumdichlorisocyanurat können ohne Beeinträchtigung der Tablettierbarkeit in marktüblicher Form eingesetzt werden. Ihre Mengen betragen 0,5 bis 5,0, vorzugsweise 1,0 bis 2,5 Gew.-%, bezogen auf den Aktivchlorgehalt und die gesamte Tablettiermischung.Trichloroisocyanuric acid was preferred as the active chlorine carrier, but also other known solid compounds, such as e.g. Sodium dichloroisocyanurate, its dihydrate and potassium dichloroisocyanurate can be used in commercially available form without impairing the tablettability. Their amounts are 0.5 to 5.0, preferably 1.0 to 2.5% by weight, based on the active chlorine content and the total tableting mixture.

Als Tablettierhilfsmittel wurde ein Gemisch aus 0,5 bis 2,0 vorzugsweise 1,0 Gew.-%, bezogen auf die gesamte Tablettiermischung, an Calciumhydrogenphosphat-dihydrat (zur Verminderung von Entmischungen) und 1,0 bis 5,0, vorzugsweise 2,0 bis 3,0 Gew.-%, bezogen auf die gesamte Tablettiermischung, an wasserfreiem Natriumacetat (zur Verminderung von Anklebungen an Werkzeugteilen) zugegeben. Die Anteile dieser Tablettierhilfsmittel, die bezüglich ihrer Reinigungsleistung anwendungstechnisch unbedenklich sind, können über die genannten Bereiche hinaus variiert werden, um Rezepturvarianten jeweils optimal verpressen zu können. Der Natriumacetat-Anteil beeinflußt außerdem die Löslichkeit der Tablette. Höhere Natriumacetat-Mengen führen insbesondere zu verbesserter Kaltwasserlöslichkeit im Vorspülgang. Andere übliche Tablettierhilfsmittel wie Schmiermittel zur Verbesserung der Verpreßbarkeit (Stearate, Talkum, Glyceride etc.) und weitere Hilfsmittel sind zwar prinzipiell ebenfalls einsetzbar, sie sind aber aus anwendungstechnischer Sicht unerwünscht und belasten darüber hinaus die Rezeptur durch Kosten und stellen lediglich inerte Füllstoffe dar. Die Anwendung dieser sonst üblichen Hilfsmittel sind bei der Herstellung von Tabletten entsprechend der vorliegenden Erfindung nicht erforderlich.A mixture of 0.5 to 2.0, preferably 1.0% by weight, based on the entire tablet mixture, of calcium hydrogenphosphate dihydrate (to reduce segregation) and 1.0 to 5.0, preferably 2, 0 to 3.0% by weight, based on the total tableting mixture, of anhydrous sodium acetate (to reduce sticking to tool parts) was added. The proportions of these tabletting aids, which are safe from an application point of view in terms of their cleaning performance, can be varied beyond the ranges mentioned in order to be able to optimally compress recipe variants. The sodium acetate content also affects the solubility of the tablet. Higher amounts of sodium acetate lead in particular to improved solubility in cold water in the pre-rinse cycle. Other conventional tabletting aids such as lubricants to improve the compressibility (stearates, talc, glycerides etc.) and other aids can in principle also be used, but they are undesirable from an application point of view and, moreover, burden the formulation with costs and are only inert fillers Use of these otherwise customary auxiliaries is not necessary in the manufacture of tablets according to the present invention.

Den Tablettiermischungen können auch übliche chlorstabile Farb-und Duftstoffe zugefügt werden. Aus ästhetischen Gründen kann man die Tabletten bei sonst gleicher Zusammensetzung auch in farbigen Schichten verpressen.Customary chlorine-stable colors and fragrances can also be added to the tableting mixtures. For aesthetic reasons, the tablets can also be pressed in colored layers with otherwise the same composition.

Die Verpressung des Gemisches aus den feinkörnigen wasserfreien Metasilikaten, den entsprechenden Nonahydraten, den Triphosphaten, Aktivchlorträgern und Tablettierhilfsmitteln kann unter Matrizenschmierung erfolgen, wobei übliche Schmiermittel zum Einsatz kommen. Die Schmierung erfolgt je nach Bauart der Maschine direkt über Bohrungen in der Matrize, durch Besprühung des Unterstempels oder durch mit Schmiermittel getränkte Filzringe an den Unterstempeln. Bei den erfindungsgemäßen Rohstoffgemischen mit ihren besonders günstigen Verpreßbarkeitseigenschaften kann aber meist auch auf die Schmierung verzichtet werden.The mixture of the fine-grained, anhydrous metasilicates, the corresponding nonahydrates, the triphosphates, active chlorine carriers and tabletting aids can be pressed under die lubrication, with conventional lubricants being used. Depending on the design of the machine, lubrication is carried out directly through holes in the die, by spraying the lower punch or by means of felt rings soaked in lubricant on the lower punch. With the raw material mixtures according to the invention with their particularly favorable compressibility properties, however, the lubrication can usually also be dispensed with.

Um Probleme durch Ankleben an den Stempeln zu vermeiden, ist eine Beschichtung der Stempel mit Kunststoffen zu empfehlen. Als besonders günstig erwiesen sich hierbei Plexiglas- oder Vulkolan-Beschichtungen. Aber auch mit anderen üblichen Materialien wurden gute Ergebnisse erzielt.In order to avoid problems caused by sticking to the stamp, it is recommended to coat the stamp with plastic. Plexiglass or Vulkolan coatings have proven to be particularly favorable. Good results have also been achieved with other conventional materials.

Die Preßbedingungen sind im Hinblick auf die Einstellung des gewünschten Löseprofils bei gleichzeitig ausreichender Tablettenhärte zu optimieren. Als Maß für die Tablettenhärte kann die Biegefestigkeit dienen (Methode: vergleiche Ritschel. Die Tablette, Ed. Cantor, 1966, S. 313). Ausreichend stabil sind unter simulierten Transportbedingungen Tabletten mit einer Biegefestigkeit größer als 12 kp, vorzugsweise größer als 15 kp.The pressing conditions are with regard to the one optimize the setting of the desired dissolution profile with sufficient tablet hardness. The flexural strength can serve as a measure of the tablet hardness (method: compare Ritschel. Die Tablette, Ed. Cantor, 1966, p. 313). Tablets with a flexural strength greater than 12 kp, preferably greater than 15 kp, are sufficiently stable under simulated transport conditions.

Entsprechende Tablettenhärten wurden bei Preßdrücken von 4905 104 bis 49 050 104 Pa. vorzugsweise 9810' 1 Q4 bis 14715.104 Pa (500 bis 5000 kp/cm2, vorzugsweise 1000 bis 1500 kp/cm2) erreicht. Höhere Preßdrücke vermindern die Lösegeschwindigkeit. Löslichkeitsdifferenzen können bei unterschiedlichen Zusammensetzungen durch Wahl des Preßdrucks in Grenzen ausgeglichen werden.Corresponding tablet hardnesses were at pressures of 4905 104 to 49 050 104 Pa. preferably 9810 '1 Q4 to 14715.104 Pa (500 to 5000 kp / cm 2 , preferably 1000 to 1500 kp / cm 2 ). Higher pressures reduce the release speed. Differences in solubility can be compensated within limits for different compositions by choosing the pressure.

Das spezifische Gewicht der Preßlinge lag dabei zwischen 1,2 und 2 g/cm3, vorzugsweise zwischen 1,4 bis 1,7 g/cm3. Die Verdichtung beim Preßvorgang bewirkte Änderungen im spezifischen Volumen, das von 0,8 bis 1,8 cm3/g, vorzugsweise 1,0 bis 1,4 cm3/g auf 0,5 bis 0,8 cm3/g, vorzugsweise 0,6 bis 0,7 cm3/g sank.The specific weight of the compacts was between 1.2 and 2 g / cm 3 , preferably between 1.4 and 1.7 g / cm 3 . The compression during the pressing process brought about changes in the specific volume, from 0.8 to 1.8 cm3 / g, preferably 1.0 to 1.4 cm 3 / g to 0.5 to 0.8 cm3 / g, preferably 0, 6 to 0.7 cm 3 / g decreased.

Auch die Form der Tablette kann die Lösegeschwindigkeit über die dem H20-Angriff ausgesetzte äußere Oberfläche beeinflussen. Aus Stabilitätsgründen wurden zylindrische Preßlinge mit einem Durchmesser/Höhe-Verhältnis von 0,6 bis 1,5:1, hergestellt.The shape of the tablet can also influence the dissolution rate via the outer surface exposed to the H 2 0 attack. For stability reasons, cylindrical compacts with a diameter / height ratio of 0.6 to 1.5: 1 were produced.

Die Mengen des zu verpressenden Substanzgemisches für die Einzeltabletten können in technisch sinnvollen Grenzen beliebig varriert werden. Je nach ihrer Größe kommen 1, 2 oder mehr Tabletten pro Maschinenfüllung zur Anwendung, um den gesamten Reinigungsprozeß mit dem notwendigen Aktivsubstanzgehait an Reinigungsmittel zu versehen. Bevorzugt werden Tabletten von 20 bis 30 g Gewicht, von denen jeweils zwei eingesetzt werden müssen. Größere Tabletten sind in der Regel bruchempfindlicher und darüber hinaus mit geringerer Geschwindigkeit zu verpressen, was beim Produktionsverfahren zu Leistungseinbußen führt. Bei kleineren Tabletten würde der Handhabungsvorteil gegenüber granulierten oder pulverförmigen Reinigungsmitteln verringert.The amounts of the substance mixture to be compressed for the individual tablets can be varied as desired within technically reasonable limits. Depending on their size, 1, 2 or more tablets are used per machine filling in order to provide the entire cleaning process with the necessary active substance content of detergent. Tablets of 20 to 30 g in weight are preferred, two of which must be used. Larger tablets are usually more sensitive to breakage and, moreover, are compressed at a lower speed, which leads to a loss of performance in the production process. With smaller tablets, the handling advantage compared to granular or powder detergents would be reduced.

Die Verpressung der beschriebenen Zusammensetzungen kann in bekannter Weise mit Hilfe von handelsüblichen Excenterpressen oder Rundläuferpressen erfolgen.The described compositions can be pressed in a known manner using commercially available eccentric presses or rotary presses.

Da es bisher für diese Art der Verwendung von Geschirreinigungsmitteln in den marktüblichen Maschinen noch keine geeigneten Dosiervorrichtungen gibt, können die Tabletten schon vor Beginn des Vorspülganges offen in eine Zone, die die Tabletten der Auflösungskraft des Leitungswasserstroms aussetzt, vorzugsweise in den Besteckkorb einer Haushaltsgeschirrspülmaschine gegeben und der automatisch gesteuerte Reinigungsprozeß in Gang gesetzt werden.Since there are no suitable dosing devices for this type of use of dishwashing detergents in the machines currently on the market, the tablets can be placed in a cutlery basket of a household dishwasher before opening the pre-rinse cycle into a zone that exposes the tablets to the dissolving power of the tap water flow the automatically controlled cleaning process can be started.

Die Erfindung betrifft daher auch die Verwendung der Reinigungsmitteltabletten zum Reinigen von Geschirr in automatischen Haushaltsgeschirrspülmaschinen, die dadurch gekennzeichnet ist, daß man die Tabletten schon vor Beginn des Vorspülganges in der Maschine offen in eine Zone, die die Tabletten der Auflösungskraft des kalten Leitungswasserzustroms aussetzt, beispielsweise durch Plazierung im Besteckkorb, einbringt und dann den automatisch gesteuerten Reinigungsprozeß in Gang setzt.The invention therefore also relates to the use of the detergent tablets for cleaning dishes in automatic domestic dishwashers, which is characterized in that the tablets are opened before the pre-wash cycle in the machine into a zone which exposes the tablets to the dissolving power of the cold tap water flow, for example by placing it in the cutlery basket, and then initiating the automatically controlled cleaning process.

Das auf diese Weise gereinigte Geschirr weist bei schwierigen Anschmutzungen wie beispielsweise angebrannter Milch oder angebackenen Haferflocken bessere Reinigungsergebnisse auf als das auf herkömmliche Weise behandelte.The dishes cleaned in this way have better cleaning results for difficult soiling, such as, for example, burnt-on milk or baked oatmeal, than those treated in the conventional manner.

BeispieleExamples

Zur besseren Vergleichbarkeit der Rezepturvarianten wurden einmal Tabletten mit gleichem Durchmesser und gleichem Gehalt an Wirkstoffen Natriumtriphosphat, Trichlorisocyanursäure und Natriummetasilikat, wasserfrei, hergestellt, die im Gewicht zwischen ca. 20 g und 27 g lagen. Die unterschiedlichen Gewichte sind auf den variierenden Gehalt an Kristallwasser und Tablettierhilfsmitteln zurückzuführen. Mit ausgewählten Rezepturen wurde auch das Tablettenformat variiert.For better comparison of the recipe variants, tablets with the same diameter and the same content of active ingredients sodium triphosphate, trichloroisocyanuric acid and sodium metasilicate, water-free, were produced, which weighed between approx. 20 g and 27 g. The different weights are due to the varying content of water of crystallization and tableting aids. The tablet format was also varied with selected recipes.

Beispiel 1example 1

28,8 Gew.-% Natriummetasilikat, wasserfrei, nicht abgesiebt

  • 33,6 Gew.-% Natriummetasilikat-nonahydrat
  • 33,6 Gew.-% Natriumtriphosphat, wasserfrei
  • 1,0 Gew.-% Trichlorisocyanursäure
  • 3,0 Gew.-% Natriumacetat, wasserfrei
  • 25 mm Tablettendurchmesser
  • 20 g Tablettengewicht
28.8% by weight sodium metasilicate, anhydrous, not sieved
  • 33.6% by weight sodium metasilicate nonahydrate
  • 33.6% by weight sodium triphosphate, anhydrous
  • 1.0% by weight of trichloroisocyanuric acid
  • 3.0% by weight sodium acetate, anhydrous
  • 25 mm tablet diameter
  • 20 g tablet weight

Die Verpressung des Gemisches erfolgte auf einer Excenterpresse der Fa. Fette, Typ "Exacta 31". Die Preßwerkzeuge waren mit Vulkolan beschichtet. Bei der Verpressung auf eine Dichte von 1,58 g/cm3 wurden Tabletten mit einer Biegefestigkeit größer als 15 kp erhalten, die sich im Vorspülgang zu 25 Gew.-% und im Reinigungsgang vollständig auflösten.The mixture was pressed on an eccentric press from Fette, type "Exacta 31". The pressing tools were coated with Vulkolan. When compressed to a density of 1.58 g / cm 3 , tablets with a flexural strength greater than 15 kp were obtained, which dissolved completely in the pre-rinse cycle by 25% by weight and in the cleaning cycle.

Beispiel 2Example 2

33,7 Gew.-% Natriummetasilikat, wasserfrei (kleiner als 0,8 mm)

  • 26,3 Gew.-% Natriummetasilikatnona-hydrat
  • 35,0 Gew.-% Natriumtriphosphat, wasserfrei
  • 1,0 Gew.-% Trichlorisocyanursäure
  • 1,0 Gew.-% Calciumhydrogenphosphat-Dihydrat
  • 3,0 Gew.-% Natriumacetat, wasserfrei
  • 35 mm Tablettendurchmesser
  • 25 g Tablettengewicht
33.7% by weight sodium metasilicate, anhydrous (smaller than 0.8 mm)
  • 26.3% by weight sodium metasilicate non-hydrate
  • 35.0% by weight sodium triphosphate, anhydrous
  • 1.0% by weight of trichloroisocyanuric acid
  • 1.0% by weight calcium hydrogen phosphate dihydrate
  • 3.0% by weight sodium acetate, anhydrous
  • 35 mm tablet diameter
  • 25 g tablet weight

Die Verpressung des Gemisches erfolgte auf einer Excenterpresse der Fa. Fette, "Exacta 31". Die Preßwerkzeuge waren mit Vulkolan beschichtet. Um 25 g schwere Tabletten herstellen zu können, war bei einem Lochdurchmesser der Matrize von 35 mm eine Füllhöhe von 30,8 mm erforderlich. Dies entsprach einem spezifischen Volumen von 1,18 cm3/g. Zur Herstellung der Tablette war eine Eintauchtiefe des Oberstempels von 14,5 mm nötig. Das entsprach dann einer Tablettenhöhe von 16,3 mm oder einem spezifischen Volumen von 0,62 cm3/g. Das Verdichtungsverhältnis betrug somit 1 : 1,9. Die tatsächliche Tablettenhöhe betrug nach Herstellung jedoch 17,7 mm. Dies ist damit zu erklären, daß allgemein ein geringes Anwachsen der Tabletten nach der Entspannung zu erwarten ist.The mixture was pressed on an eccentric press from Fette, "Exacta 31". The pressing tools were coated with Vulkolan. In order to be able to produce tablets weighing 25 g, a filling height of 30.8 mm was required with a die diameter of 35 mm. This corresponded to a specific volume of 1.18 cm3 / g. A depth of 14.5 mm was necessary to produce the tablet. This then corresponded to a tablet height of 16.3 mm or a specific volume of 0.62 cm 3 / g. The The compression ratio was 1: 1.9. However, the actual tablet height after manufacture was 17.7 mm. This can be explained by the fact that the tablets can generally be expected to grow slightly after relaxation.

Das spezifische Volumen der erhaltenen Tablette betrug somit 0,68 cm3/g (Dichte = 1,47 g/cm3). Dies entspricht einem Verdichtungsverhältnis von 1:1,74. Der zur Verpressung benötigte Preßdruck betrug 12753 . 104 Pa (1300 kp/cm2). Die erhaltenen Tabletten hatten eine Biegefestigkeit von größer als 15 kp und lösten sich im Vorspülgang zu 14 Gew.-% und im Reinigungsgang vollständig auf.The specific volume of the tablet obtained was thus 0.68 cm 3 / g (density = 1.47 g / cm 3 ). This corresponds to a compression ratio of 1: 1.74. The pressing pressure required for pressing was 12753. 10 4 Pa (1300 kp / cm 2 ). The tablets obtained had a flexural strength of greater than 15 kp and dissolved up to 14% by weight in the pre-rinse cycle and completely in the cleaning cycle.

Nach 8-monatiger Lagerung im verschlossenen Gebinde bei Raumtemperatur wurden hier keine Risse in der Tablette und keine Verwitterung der Tablettenoberfläche festgestellt.After 8 months of storage in sealed containers at room temperature, no cracks in the tablet and no weathering of the tablet surface were found.

Beispiel 3Example 3

Das Weglassen von Tablettierungshilfsmitteln und entsprechender Variierung der Metasilikatanteile mit wasserfreiem Produkt auf 30,7 Gew.-% und Nonahydrat auf 33,3 Gew.-% führte bei einer Verarbeitung analog Beispiel 2 zu einer Auflösung von 40 Gew.-% der Tablette im Vorspülgang bei insgesamt vollständiger Auflösung im Reinigungsgang. Bei der Herstellung dieser Tabletten kam es jedoch zu leichten Verklebungserscheinungen in der Matrize.The omission of tableting aids and a corresponding variation of the metasilicate components with anhydrous product to 30.7% by weight and nonahydrate to 33.3% by weight led to a dissolution of 40% by weight of the tablet in the pre-rinse cycle when processed analogously to Example 2 with total resolution in the cleaning cycle. During the manufacture of these tablets, however, there were slight signs of sticking in the matrix.

Die Beispiele lassen sich im Rahmen der Erfindung beliebig variieren. Die vorstehend ausgewählten sind nicht abschließend zu verstehen.The examples can be varied as desired within the scope of the invention. The above selected are not meant to be conclusive.

Beispiel 4Example 4

33,0 Gew.-% Natriummetasilikat mit 2% Restfeuchte

  • 28,0 Gew.-% Natriummetasilikatnonahydrat
  • 35,0 Gew.-% Natriumtriphosphat, wasserfrei
  • 1,0 Gew.-% Trichlorisocyanursäure
  • 2,0 Gew.-% Natriumacetat, wasserfrei
  • 1,0 Gew.-% Calciumhydrogenphosphat-Dihydrat
  • 25 mm Tablettendurchmesser
  • 20,3 g Tablettengewicht.
33.0% by weight sodium metasilicate with 2% residual moisture
  • 28.0% by weight sodium metasilicate nonahydrate
  • 35.0% by weight sodium triphosphate, anhydrous
  • 1.0% by weight of trichloroisocyanuric acid
  • 2.0% by weight sodium acetate, anhydrous
  • 1.0% by weight calcium hydrogen phosphate dihydrate
  • 25 mm tablet diameter
  • 20.3 g tablet weight.

Die Bestandteile wurden in einem Lödige-Mischer gemischt.The ingredients were mixed in a Lödige mixer.

Die Verpressung des Gemisches erfolgte auf einer Excenterpresse der Fa. Fette, Typ "Exacta". Die Preßwerkzeuge waren mit Vulkolan beschichtet. Bei Verpressung auf eine Dichte von 1,56 g/cm3 wurden Tabletten mit einer Biegefestigkeit (Ritschel, "Die Tablette, Seite 313) von 13,5 kp erhalten, die sich durch die Leitungswasserzugabe im Vorspülgang einer HGSM zu ca. 20 Gew.-% und im 40 °C-Reinigungsprogramm vollständig auflösten.The mixture was pressed on an eccentric press from Fette, type "Exacta". The pressing tools were coated with Vulkolan. When compressed to a density of 1.56 g / cm 3 , tablets with a flexural strength (Ritschel, "The tablet, page 313) of 13.5 kp were obtained, which can be obtained by adding tap water in the pre-rinse cycle of an HGSM to approx. 20 wt. -% and completely dissolve in the 40 ° C cleaning program.

Eine Paraffinölschmierung der Werkzeuge war nicht erforderlich. Das Weglassen von Calciumhydrogenphosphat-Dihydrat führte zu einer Auflösung von 25 Gew.-% der Tablette im Vorspülgang und zu einer 97 gew.-%igen Gesamtauflösung. Der Restfeuchtgehalt führte jedoch bei der Lagerung der Tabletten zu Verwitterungserscheinungen an ihrer Oberfläche.Paraffin oil lubrication of the tools was not necessary. The omission of calcium hydrogenphosphate dihydrate led to a dissolution of 25% by weight of the tablet in the pre-rinse cycle and to a 97% by weight total dissolution. However, the residual moisture content caused the surface to show signs of weathering when the tablets were stored.

Beispiel 5Example 5

Die Gemischzusammensetzung, das Tablettengewicht und der Tablettendurchmesser wurden wie in Beispiel 4 gewählt, jedoch im Unterschied zu Beispiel 4 wurde auf eine Dichte von 1,63 g/cm3 verdichtet. Die Biegefertigkeit lag hier bei größer als 15 kp. Bei vollständiger Auflösung im 40 °C-Reinigungsgang waren nach dem Vorspülgang 12 % der Tablette gelöst. Bei hervorragenden Herstellungs-und Anwendungseigenschaften war auch hier bei der Lagerung eine Verwitterung der Tablettenoberfläche festzustellen.The mixture composition, the tablet weight and the tablet diameter were chosen as in Example 4, but in contrast to Example 4, the density was 1.63 g / cm 3. The bending ability here was greater than 15 kp. When completely dissolved in the 40 ° C cleaning cycle, 12% of the tablet was dissolved after the pre-rinse cycle. With excellent manufacturing and application properties, weathering of the tablet surface was also evident here during storage.

Beispiel 6Example 6

Zusammensetzung wie bei Beispiel 4. 40 mm Tablettendurchmesser 50 g TablettengewichtComposition as in Example 4. 40 mm tablet diameter 50 g tablet weight

Die Verpressung des Gewichtes erfolgte auf einer Excenterpresse der Fa. Fette, Typ "Exacta 31", bei der die Preßwerkzeuge mit Vulkolan beschichtet waren. Bei Verpressung auf eine Dichte von 1,53 g/cm3 wurden Tabletten mit einer Biegefestigkeit größer als 147 N (15 kp) erhalten, die sich im Vorspülgang zu 14 Gew.-% und im Reinigungsprogramm zu 97 Gew.-% auflösten.The weight was pressed on an eccentric press from Fette, type "Exacta 31", in which the pressing tools were coated with Vulkolan. When compressed to a density of 1.53 g / cm 3 , tablets with a flexural strength greater than 147 N (15 kp) were obtained, which dissolved in the pre-rinse cycle to 14% by weight and in the cleaning program to 97% by weight.

Nach 8-monatiger Lagerung in verschlossenen Gebinden bei Raumtemperatur kam es hierbei zu unerwünschter Rissebildung und Verwitterung der Oberfläche.After 8 months of storage in sealed containers at room temperature, this resulted in undesirable crack formation and weathering of the surface.

Beispiel 7Example 7

33,0 Gew.-% Natriummetasilikat, wasserfrei (kleiner als 0,8 mm)

  • 28,0 Gew.-% Natriummetasilikatnonahydrat
  • 35,0 Gew.-% Natriumtriphosphat, wasserfrei
  • 3,0 Gew.-% Natriumacetat, wasserfrei
  • 1,0 Gew.-%Caiciumhydrogenphosphat-Dihydrat
  • 25 mm Tablettendurchmesser
  • 6,7 g Tablettengewicht
33.0% by weight sodium metasilicate, anhydrous (less than 0.8 mm)
  • 28.0% by weight sodium metasilicate nonahydrate
  • 35.0% by weight sodium triphosphate, anhydrous
  • 3.0% by weight sodium acetate, anhydrous
  • 1.0% by weight calcium hydrogen phosphate dihydrate
  • 25 mm tablet diameter
  • 6.7 g tablet weight

Die Verpressung des Gemisches erfolgte auf einer Rundläuferpresse der Fa. Fette, Typ "Perfecta 2" mit Plexiglas beschichteten Werkzeugen. Die Herstellung des Gemisches erfolgte kontinuierlich über Bandwaagen in einem Gerickemischer, Typ "GAC 350". Die Matrizenfüllung erfolgte durch eine "Fil-o-Matic" der Fa. Fette. Anbackungen des Materials wurden durch Paraffinölschmierung (getränkte Filzringe an den Unterstempeln) vermieden. Bei Verpressung auf eine Dichte von 1,52 wurden Tabletten mit einer Biegefestigkeit von größer als (15 kp) 147 N erhalten.The mixture was pressed on a rotary press from Fette, type "Perfecta 2" with plexiglass-coated tools. The mixture was produced continuously on belt scales in a rack mixer, type "GAC 350". The die was filled by a "Fil-o-Matic" from Fette. Caking of the material was avoided by paraffin oil lubrication (soaked felt rings on the lower punches). When compressed to a density of 1.52, tablets with a flexural strength greater than (15 kp) 147 N were obtained.

Claims (7)

1. Detergent tablets having a uniform composition and a broad solubility profile for dishwashing machines, containing alkaline-reacting components from the group consisting of alkali metasilicates and penta-alkali triphosphates, active chlorine compounds and tabletting aids, characterized in that the alkali metasilicates consist of a mixture of sodium metasilicate nonahydrate and anhydrous sodium metasilicate while the penta-alkali triphosphate consists of anhydrous penta-sodium triphosphate, the total quantity of sodium metasilicates and pentasodium triphosphate being from 88 to 98% by weight, the ratio by weight of anhydrous sodium metasilicate to the sodium metasilicate nonahydrate being from 1:0.3 to 1:1.5 and the ratio by weight of pentasodium triphosphate to sodium metasilicate, both anhydrous, being 2:1 to 1:2.
2. Tablets as claimed in claim 1, characterized in that the ratio by weight of anhydrous sodium metasilicate to sodium metasilicate nonahydrate is from 1:0.75 to 1:1.2.
3. Tablets as claimed in claims 1 and 2, characterized in that the ratio by weight of anhydrous penta- sodium triphosphate to anhydrous sodium metasilicate is from 1:1 to 1:1.7.
4. Tablets as claimed in claims 1 to 3, characterized in that the grain size distribution of the anhydrous sodium metasilicate is from 0.01 to 2.0 mm and preferably from 0.2 to 0.8 mm.
5. Tablets as claimed in claims 1 to 4, characterized in that the mean grain diameter of the anhydrous pentasodium triphosphate is larger than 0.1 mm and preferably from 0.2 to 0.3 mm.
6. Tablets as claimed in claims 1 to 5, characterized in that they contain active chlorine donors in a quantity of from 0.5 to 5.0% by weight and preferably in a quantity of from 1.0 to 2.5 by weight, based on the active chlorine content and the tabletting mixture as a whole.
7. The use of the detergent tablets claimed in claims 1 to 6 for dishwashing in automatic domestic dishwashing machines, characterized in that the tablets are introduced after opening into a zone, which exposes the tablets to the dissolving power of the inflowing stream of cold tapwater, before the start of the prerinse cycle of the machine and the automatically controlled main wash cycle is subsequently started.
EP86115739A 1985-11-21 1986-11-12 Uniformly composed detergent tablets for mechanical dish-washing Expired - Lifetime EP0224129B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86115739T ATE59403T1 (en) 1985-11-21 1986-11-12 UNIFORM DETERGENT TABLETS FOR AUTOMATIC DISHWASHING.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853541145 DE3541145A1 (en) 1985-11-21 1985-11-21 UNIFORMED DETERGENT TABLETS FOR MACHINE DISHWASHER
DE3541145 1985-11-21

Publications (3)

Publication Number Publication Date
EP0224129A2 EP0224129A2 (en) 1987-06-03
EP0224129A3 EP0224129A3 (en) 1988-03-09
EP0224129B1 true EP0224129B1 (en) 1990-12-27

Family

ID=6286453

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86115739A Expired - Lifetime EP0224129B1 (en) 1985-11-21 1986-11-12 Uniformly composed detergent tablets for mechanical dish-washing

Country Status (6)

Country Link
US (1) US4839078A (en)
EP (1) EP0224129B1 (en)
JP (1) JPS62129394A (en)
AT (1) ATE59403T1 (en)
CA (1) CA1277890C (en)
DE (2) DE3541145A1 (en)

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3634813A1 (en) * 1986-10-13 1988-04-14 Henkel Kgaa DETERGENT TABLETS FOR MACHINE DISHWASHER
DE3832885A1 (en) * 1988-09-28 1990-04-05 Ifah Inst Fuer Angewandte Hygi METHOD FOR MACHINE CLEANING, DISINFECTING AND RINSING DISHES AND THE APPROPRIATE AGENT
DE4010533A1 (en) * 1990-04-02 1991-10-10 Henkel Kgaa Prodn. of high-density detergent granules
DE4010524A1 (en) * 1990-04-02 1991-10-10 Henkel Kgaa STABLE, BIFUNCTIONAL, PHOSPHATE-FREE DETERGENT TABLETS FOR THE MACHINE DISHWASHER
GB9015504D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergents composition
GB9015503D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergent composition
US5133892A (en) * 1990-10-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing detergent tablets
DE4112075A1 (en) * 1991-04-12 1992-10-15 Henkel Kgaa METHOD FOR PRODUCING STABLE, BIFUNCTIONAL, PHOSPATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER
DE4121307A1 (en) * 1991-06-27 1993-01-07 Henkel Kgaa METHOD FOR THE PRODUCTION OF STABLE, BIFUNCTIONAL, PHOSPHATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER
DE4219620A1 (en) * 1992-06-16 1993-12-23 Licentia Gmbh Domestic dishwasher detergent feed - has separate and time displaced feeds of different media to the washing water
DE4229650C1 (en) * 1992-09-04 1994-01-05 Henkel Kgaa Process for the manufacture of cleaning tablets
DE4315048A1 (en) * 1993-04-01 1994-10-06 Henkel Kgaa Process for the production of stable, bifunctional, phosphate, metasilicate and polymer-free, low-alkaline detergent tablets for automatic dishwashing
JPH08510270A (en) * 1993-05-05 1996-10-29 ヘンケル・エコラープ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コンパニー・オッフェネ・ハンデルスゲゼルシャフト Method for solidifying granular solids and cleaning products therefrom
US5858299A (en) * 1993-05-05 1999-01-12 Ecolab, Inc. Process for consolidating particulate solids
US6689305B1 (en) 1993-05-05 2004-02-10 Ecolab Inc. Process for consolidating particulate solids and cleaning products therefrom II
DE4408718A1 (en) * 1994-03-15 1995-09-21 Henkel Kgaa Breakage and storage stable, polyfunctional cleaning tablets, process for their preparation and their use
DE4413870C2 (en) * 1994-04-21 1997-07-10 Aeg Hausgeraete Gmbh Dishwasher with a dosing device
AU2925495A (en) * 1994-07-04 1996-01-25 Unilever Plc Washing process and composition
GB9422924D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
GB9422925D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
US6083895A (en) * 1995-03-11 2000-07-04 The Procter & Gamble Company Detergent compositions in tablet form
US5670473A (en) * 1995-06-06 1997-09-23 Sunburst Chemicals, Inc. Solid cleaning compositions based on hydrated salts
GB2313844A (en) * 1996-06-08 1997-12-10 Reckitt & Colmann Prod Ltd Cleaning composition
US5783540A (en) * 1996-12-23 1998-07-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets delivering a rinse aid benefit
US5837663A (en) * 1996-12-23 1998-11-17 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets containing a peracid
GB2321466A (en) * 1997-01-25 1998-07-29 Procter & Gamble Process for making tabletted detergent compositions
DE19843773A1 (en) * 1998-09-24 2000-03-30 Henkel Kgaa Detergent tablets with finely divided processing components
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
DE59900585D1 (en) * 1999-03-29 2002-01-31 Dalli Werke Waesche & Koerperp Dishwasher cleaning tablets containing disintegrant granules
GB9918505D0 (en) * 1999-08-05 1999-10-06 Unilever Plc Water-softening and detergent compositions
US6701944B2 (en) 2001-01-25 2004-03-09 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent dispenser system
US6750186B2 (en) 2002-02-04 2004-06-15 Robert Black Composition and method for cleaning dishwashers
DE10358970A1 (en) † 2003-12-16 2005-07-21 BSH Bosch und Siemens Hausgeräte GmbH Dishwasher with intermediate pumping operation
GB0514001D0 (en) * 2005-07-08 2005-08-17 Reckitt Benckiser Nv Article and method
GB0514007D0 (en) * 2005-07-08 2005-08-17 Reckitt Benckiser Nv Article and method
GB0513998D0 (en) * 2005-07-08 2005-08-17 Reckitt Benckiser Nv Article and method
GB0514004D0 (en) * 2005-07-08 2005-08-17 Reckitt Benckiser Nv Article and method
GB0513997D0 (en) * 2005-07-08 2005-08-17 Reckitt Benckiser Nv Article and method

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2412819A (en) * 1945-07-21 1946-12-17 Mathieson Alkali Works Inc Detergent briquette
CA718384A (en) * 1962-07-30 1965-09-21 Colgate-Palmolive Company Manufacture of detergent tablets
US3390092A (en) * 1965-03-30 1968-06-25 Fmc Corp Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate
US4219436A (en) * 1977-06-01 1980-08-26 The Procter & Gamble Company High density, high alkalinity dishwashing detergent tablet
GB2041966A (en) * 1977-11-29 1980-09-17 Procter & Gamble Detergent tablet having a hydrated salt coating and process for preparing the tablet
FR2529876A1 (en) * 1982-07-09 1984-01-13 Rhone Poulenc Chim Base NOVEL SODIUM METASILICATE GRANULES, PROCESS FOR OBTAINING SAME AND USE THEREOF IN DETERGENT COMPOSITIONS FOR DISHWASHERS
DE3315950A1 (en) * 1983-05-02 1984-11-15 Henkel KGaA, 4000 Düsseldorf METHOD FOR PRODUCING DETERGENT TABLETS

Also Published As

Publication number Publication date
CA1277890C (en) 1990-12-18
JPS62129394A (en) 1987-06-11
JPH0455639B2 (en) 1992-09-03
EP0224129A3 (en) 1988-03-09
EP0224129A2 (en) 1987-06-03
US4839078A (en) 1989-06-13
DE3541145A1 (en) 1987-05-27
ATE59403T1 (en) 1991-01-15
DE3676649D1 (en) 1991-02-07

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