EP0224129B1 - Pains détergents composés d'une manière uniforme pour le lavage de la vaisselle en machine - Google Patents

Pains détergents composés d'une manière uniforme pour le lavage de la vaisselle en machine 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
Authority
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
Application number
EP86115739A
Other languages
German (de)
English (en)
Other versions
EP0224129A3 (en
EP0224129A2 (fr
Inventor
Hans Kruse
Jochen Dr. Jacobs
Theodor Dr. Altenschöpfer
Peter. Dr. Jeschke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT86115739T priority Critical patent/ATE59403T1/de
Publication of EP0224129A2 publication Critical patent/EP0224129A2/fr
Publication of EP0224129A3 publication Critical patent/EP0224129A3/de
Application granted granted Critical
Publication of EP0224129B1 publication Critical patent/EP0224129B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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.

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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)

Claims (7)

1. Comprimés d'agent nettoyant à composition homogène et à large profil de solubilité pour le lavage de la vaisselle en machine, qui renferment des composants réagissant alcalin faisant partie du groupe des métasilicates alcalins et des triphosphates penta-alcalins, des composés de chlore actif et des agents auxiliaires de formage en comprimé, qui sont caractérisés en ce que les métasilicates de métaux alcalins sont constitués d'un mélange de nonahydrate de métasilicate de sodium et de métasilicate de sodium anhydre et que le triphosphate penta-alcalin est constitué de triphosphate pentasodique anhydre, la quantité totale de métasilicates de sodium et de triphosphate penta-alcalin atteignant 88 à 98% en poids, le rapport pondéral entre le métasilicate de sodium anhydre et le nonahydrate de métasilicate de sodium étant compris dans l'intervalle de 1:0,3 à 1:1,5 et le rapport pondéral entre le triphosphate pentasodique et le métasilicate de sodium, tous deux anhydres, étant compris dans l'intervalle de 2:1 à 1:2.
2. Comprimés selon la revendication 1, caractérisé en ce que le rapport pondéral entre le métasilicate de sodium anhydre et le nonahydrate de métasilicate de sodium est compris dans l'intervalle de 1:0,75 et 1:1,2.
3. Comprimés selon les revendications 1 et 2, caractérisés en ce que le rapport pondéral entre le triphosphate pentasodique et le métasilicate de sodium, tous deux anhydres, est compris dans l'intervalle de 1:1 à 1:1,7.
4. Comprimés selon les revendications 1 à 3, caractérisés en ce que la répartition de la grosseur de grain du métasilicate de sodium anhydre est comprise entre 0,01 et 2,0 mm, de préférence entre 0,2 et 0,8 mm.
5. Comprimés selon les revendications 1 à 4, caractérisés en ce que le diamètre moyen de grain du triphosphate pentasodique anhydre est supérieur à 0,1 mm et de préférence compris entre 0,2 et 0,3 mm.
6. Comprimés selon les revendications 1 à 5, caractérisés en ce qu'ils renferment 0,5 à 5,0%, de préférence 1,0 à 2,5% en poids de vecteurs de chlore actif par rapport à la teneur en chlore actif et à l'ensemble du mélange pour comprimés.
7. Utilisation des comprimés d'agent nettoyant selon les revendications 1 à 6 pour le lavage de la vaisselle dans les lave-vaisselles domestiques automatiques, caractérisée en ce que l'on dispose les comprimés à découvert dans la machine dès avant le début du prélavage dans une zone qui expose les comprimés à la force de dissolution du courant d'eau de distribution froide et en ce que l'on déclenche ensuite le processus de lavage automatique.
EP86115739A 1985-11-21 1986-11-12 Pains détergents composés d'une manière uniforme pour le lavage de la vaisselle en machine Expired - Lifetime EP0224129B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86115739T ATE59403T1 (de) 1985-11-21 1986-11-12 Einheitlich zusammengesetzte reinigungsmitteltabletten fuer das maschinelle geschirrspuelen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3541145 1985-11-21
DE19853541145 DE3541145A1 (de) 1985-11-21 1985-11-21 Einheitlich zusammengesetzte reinigungsmitteltabletten fuer das maschinelle geschirrspuelen

Publications (3)

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

Family

ID=6286453

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86115739A Expired - Lifetime EP0224129B1 (fr) 1985-11-21 1986-11-12 Pains détergents composés d'une manière uniforme pour le lavage de la vaisselle en machine

Country Status (6)

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

Families Citing this family (38)

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DE3634813A1 (de) * 1986-10-13 1988-04-14 Henkel Kgaa Reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
DE3832885A1 (de) * 1988-09-28 1990-04-05 Ifah Inst Fuer Angewandte Hygi Verfahren zum maschinellen reinigen, desinfizieren und klarspuelen von geschirr und dafuer geeignetes mittel
DE4010533A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Tablettierte wasch- und/oder reinigungsmittel fuer haushalt und gewerbe und verfahren zu ihrer herstellung
DE4010524A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Stabile, bifunktionelle, phosphatfreie reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
GB9015503D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergent composition
GB9015504D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergents composition
US5133892A (en) * 1990-10-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing detergent tablets
DE4112075A1 (de) * 1991-04-12 1992-10-15 Henkel Kgaa Verfahren zur herstellung stabiler, bifunktioneller, phospat- und metasilikatfreier niederalkalischer reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
DE4121307A1 (de) * 1991-06-27 1993-01-07 Henkel Kgaa Verfahren zur herstellung stabiler, bifunktioneller, phosphat- und metasilikatfreier niederalkalischer reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
DE4219620A1 (de) * 1992-06-16 1993-12-23 Licentia Gmbh Verfahren zur Reinigungsmittelzugabe bei Haushalt-Geschirrspülmaschinen
DE4229650C1 (de) * 1992-09-04 1994-01-05 Henkel Kgaa Verfahren zur Herstellung von Reinigungstabletten
DE4315048A1 (de) * 1993-04-01 1994-10-06 Henkel Kgaa Verfahren zur Herstellung stabiler, bifunktioneller, phosphat-, metasilikat- und polymerfreier niederalkalischer Reinigungsmitteltabletten für das maschinelle Geschirrspülen
US5858299A (en) * 1993-05-05 1999-01-12 Ecolab, Inc. Process for consolidating particulate solids
EP0698081B1 (fr) * 1993-05-05 2001-10-17 Henkel-Ecolab GmbH & Co. OHG Procede de consolidation de solides particulaires et produits de nettoyage a base de ceux-ci
US6689305B1 (en) 1993-05-05 2004-02-10 Ecolab Inc. Process for consolidating particulate solids and cleaning products therefrom II
DE4408718A1 (de) * 1994-03-15 1995-09-21 Henkel Kgaa Bruch- und lagerstabile, polyfunktionelle Reinigungstabletten, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4413870C2 (de) * 1994-04-21 1997-07-10 Aeg Hausgeraete Gmbh Geschirrspülmaschine mit einer Dosiervorrichtung
DE69509531T2 (de) * 1994-07-04 1999-09-09 Unilever N.V. Verfahren zum waschen und zusammensetzung
GB9422925D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
GB9422924D0 (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 (de) * 1998-09-24 2000-03-30 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit feinteiligen Aufbereitungskomponenten
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
ATE211164T1 (de) * 1999-03-29 2002-01-15 Dalli Werke Waesche & Koerperp Sprengmittelgranulat enthaltende geschirrspülmaschinenreinigungstabletten
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 (de) † 2003-12-16 2005-07-21 BSH Bosch und Siemens Hausgeräte GmbH Geschirrspülmaschine mit Zwischenpumpbetrieb
GB0513998D0 (en) * 2005-07-08 2005-08-17 Reckitt Benckiser Nv Article and method
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
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

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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 (fr) * 1982-07-09 1984-01-13 Rhone Poulenc Chim Base Nouveaux granules de metasilicate de sodium, leur procede d'obtention et leur utilisation dans les compositions detergentes pour lave-vaisselle
DE3315950A1 (de) * 1983-05-02 1984-11-15 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von reinigungsmitteltabletten

Also Published As

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

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