EP0362665A1 - Process for preparing a particulate detergent composition - Google Patents

Process for preparing a particulate detergent composition Download PDF

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Publication number
EP0362665A1
EP0362665A1 EP89117703A EP89117703A EP0362665A1 EP 0362665 A1 EP0362665 A1 EP 0362665A1 EP 89117703 A EP89117703 A EP 89117703A EP 89117703 A EP89117703 A EP 89117703A EP 0362665 A1 EP0362665 A1 EP 0362665A1
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EP
European Patent Office
Prior art keywords
detergents
spray
clay
blown
detergent
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.)
Ceased
Application number
EP89117703A
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German (de)
French (fr)
Inventor
Elmar Dr. Wilms
Lothar Pioch
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
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Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0362665A1 publication Critical patent/EP0362665A1/en
Ceased 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/02—Preparation in the form of powder by spray drying

Definitions

  • detergents which have the property of giving washed textiles a soft feel have long been known.
  • detergents of this type additionally contain textile-softening active ingredients.
  • These can be organic textile plasticizers, for example of the quaternary ammonium compound or sorbitan ester type, or also inorganic textile plasticizers, for example swellable layered silicates of the smectite type.
  • Detergents with clay-containing textile softeners are known for example from DE-A-23 34 899.
  • particulate detergents are usually produced by spray drying in atomizing towers. At least some of the detergent ingredients or all of the detergent ingredients are sprayed in the form of an aqueous slurry at the top of an atomization tower and dried with hot gases, which are conducted either in cocurrent or countercurrent to the sprayed detergent slurry.
  • Water-softening, fabric softening sheet silicates can be incorporated into such a detergent ingredient slurry.
  • the viscosity of the aqueous slurry generally increases to a level that can no longer be pumped and sprayed. To the To reduce viscosity again, it would be necessary to increase the water content of the slurry. However, this would mean that one would have to remove this additional water during the subsequent drying process, which would entail high energy costs.
  • the present invention therefore relates to a process for the preparation of particulate, clay-containing detergents or detergent additives by spray drying an aqueous slurry of detergent ingredients, which is characterized in that air-swellable, textile-softening clays in particulate form are blown into the spray cone and this mixture is dried by heated gases .
  • Suitable clay-like minerals with textile softening properties are naturally occurring, commercially available minerals of the smectite type, for example montmorillonite or hectorite. They are offered for use in detergents in different particle sizes, for example as fine powders or as granules. They are usually not pure white, which is often annoying when incorporated into white, particulate detergents. Finely divided, swellable layered silicates of the smectite type are particularly suitable for processing by the method according to the invention. For the purposes of the present invention, “fine particles” are clays with a particle size that is 90% below 50 microns.
  • the process according to the invention can either be carried out by allowing the heated gases used to dry the sprayed aqueous slurry to flow in the same direction (cocurrent) or in the opposite direction to the sprayed aqueous slurry (countercurrent).
  • a preferred embodiment of the method according to the invention is that one works in countercurrent. Powders are obtained which have particularly valuable properties with regard to their pouring properties and a possibly low proportion of dust-fine products if the flow rates of the sprayed slurry and the blown-in clay are set such that the flow rates do not differ from one another by more than 30%, whereby it It is expedient that they differ by no more than 10% and in particular are the same.
  • the particulate detergents produced by the process according to the invention have a lighter color than detergents of the same composition which have been prepared by reducing the textile-softening clays of the aqueous slurry clogged.
  • the full preservation of the softening properties Because the swellable clays need not be added to the aqueous slurry by the process of the invention, they also do not cause viscosity problems in the aqueous slurry and therefore do not require additional amounts of water in the aqueous slurry to remove them.
  • the process according to the invention can also be used with excellent success for the production of a free-flowing, granular spray product which essentially contains zeolite A and textile-softening swellable clays.
  • the product obtained in this way can be used well as an additive to detergents.
  • the atomization product weighed 395 g per liter and contained 7.1 weight percent water.
  • the product was easy to pour and had a lighter color than a comparative product of the same composition which had been prepared by adding the layered silicate to the aqueous slurry before atomization.

Abstract

Particulate detergents or detergent additives containing fine textile-softening lamellar silicates are produced by spray-drying, a watery slurry of at least part of the detergent components being atomized and blown into the atomizing cone of the fine lamellar silicates. Spray-dried detergents or detergent additives with lamellar silicates are obtained by drying the spray product with heated gases which are directed onto it in parallel current or, preferably, in countercurrent; said detergents or detergent additives containing lamellar silicates do not loose any of their softening power through processing.

Description

Teilchenförmige Waschmittel, die die Eigenschaft haben, gewa­schenen Texitilien eine weichen Griff zu verleihen, sind seit langem bekannt. Derartige Waschmittel enthalten außer den übli­cherweise in Waschmitteln enthaltenen Waschmittelinhaltsstoffen zusätzlich textilweichmachende Wirkstoffe. Dies können organische Textilweichmacher etwa vom Typ der quartären Ammoniumverbindungen oder der Sorbitan-Ester sein, oder auch anorganische Textilweich­macher, beispielsweise quellfähige Schichtsilikate vom Smectit-­Typ. Waschmittel mit tonhaltigen Textilweichmachern sind bei­spielsweise aus der DE-A-23 34 899 bekannt.Particulate detergents which have the property of giving washed textiles a soft feel have long been known. In addition to the detergent ingredients usually contained in detergents, detergents of this type additionally contain textile-softening active ingredients. These can be organic textile plasticizers, for example of the quaternary ammonium compound or sorbitan ester type, or also inorganic textile plasticizers, for example swellable layered silicates of the smectite type. Detergents with clay-containing textile softeners are known for example from DE-A-23 34 899.

In großtechnischem Maßstab werden teilchenförmige Waschmittel in der Regel durch Sprühtrocknung in Zerstäubungstürmen hergestellt. Dabei wird wenigstens ein Teil der Waschmittelinhaltsstoffe oder auch sämtliche Waschmittelinhaltsstoffe in Form einer wäßrigen Aufschlämmung am oberen Ende eines Zerstäubungsturms versprüht und mit heißen Gasen, die man entweder im Gleichstrom oder im Gegen­strom zu der versprühten Waschmittelaufschlämmung führt, getrock­net. In Wasser quellende, textilweichmachende Schichtsilikate lassen sich in eine derartige Waschmittelinhaltsstoffe-Aufschläm­mung einarbeiten. Durch ihre Eigenschaft, in Wasser aufzuquellen, erhöht sich aber die Viskosität der wäßrigen Aufschlämmung in der Regel auf ein nicht mehr pump- und versprühbares Maß. Um die Viskosität wieder zu senken, wäre es erforderlich, den Wasseran­teil der Aufschlämmung zu erhöhen. Dies würde aber bedeuten, daß man dieses zusätzlich zugesetzte Wasser beim anschließenden Trocknungsprozess wieder entfernen müßte, was mit hohen Energie­kosten verbunden wäre.On an industrial scale, particulate detergents are usually produced by spray drying in atomizing towers. At least some of the detergent ingredients or all of the detergent ingredients are sprayed in the form of an aqueous slurry at the top of an atomization tower and dried with hot gases, which are conducted either in cocurrent or countercurrent to the sprayed detergent slurry. Water-softening, fabric softening sheet silicates can be incorporated into such a detergent ingredient slurry. However, due to their property of swelling in water, the viscosity of the aqueous slurry generally increases to a level that can no longer be pumped and sprayed. To the To reduce viscosity again, it would be necessary to increase the water content of the slurry. However, this would mean that one would have to remove this additional water during the subsequent drying process, which would entail high energy costs.

Aufgabe der vorliegenden Erfindung ist es daher, ein Verfahren zur Herstellung teilchenförmiger, tonhaltiger Waschmittel durch Sprühtrocknung hoch konzentrierter, wäßriger Aufschlämmungen be­reitzustellen, die zur Einstellung einer zur Verarbeitung noch ausreichenden niedrigen Viskosität keinen erhöhten Wasserbedarf erfordert. Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung teilchenförmiger, tonhaltiger Waschmit­tel oder Waschmittelzusatzstoffe durch Sprühtrocknung einer wäß­rigen Aufschlämmung von Waschmittelinhaltsstoffen, das dadurch gekennzeichnet ist, daß man in den Sprühkegel mittels Luft quellfähige, textilweichmachende Tone in Teilchenform einbläst und dieses Gemisch durch erhitzte Gase trocknet. Geeignete tonartige Mineralien mit textilweichmachenden Eigenschaften sind natürlich vorkommende, im Handel erhältliche Mineralien vom Smectit-Typ, beispielsweise Montmorillonite oder Hectorite. Sie werden für die Verwendung in Waschmitteln in unterschiedlichen Teilchengrößen, beispielsweise als feinteilige Pulver oder als Granulate angebo­ten. Sie sind meistens nicht reinweiß, was bei der Einarbeitung in weiße, teilchenförmige Waschmittel häufig störend ist. Zur Verar­beitung nach dem erfindungsgemäßen Verfahren eignen sich feintei­lige, quellfähige Schichtsilikate vom Smectit-Typ besonders. "Feinteilig" im Sinne der vorliegenden Erfindung sind Tone mit einer Teilchengröße, die zu 90 % unter 50 mikron liegt.It is therefore an object of the present invention to provide a process for the production of particulate, clay-containing detergents by spray drying highly concentrated, aqueous slurries which does not require an increased water requirement to set a low viscosity which is still sufficient for processing. The present invention therefore relates to a process for the preparation of particulate, clay-containing detergents or detergent additives by spray drying an aqueous slurry of detergent ingredients, which is characterized in that air-swellable, textile-softening clays in particulate form are blown into the spray cone and this mixture is dried by heated gases . Suitable clay-like minerals with textile softening properties are naturally occurring, commercially available minerals of the smectite type, for example montmorillonite or hectorite. They are offered for use in detergents in different particle sizes, for example as fine powders or as granules. They are usually not pure white, which is often annoying when incorporated into white, particulate detergents. Finely divided, swellable layered silicates of the smectite type are particularly suitable for processing by the method according to the invention. For the purposes of the present invention, “fine particles” are clays with a particle size that is 90% below 50 microns.

Man kann das erfindungsgemäße Verfahren entweder so ausführen, daß man die zum Trocknen der versprühten wäßrigen Aufschlämmung be­nutzten erhitzten Gase in gleicher Richtung (Gleichstrom) oder entgegengesetzt zur versprühten wäßrigen Aufschlämmung (Gegen­strom) strömen läßt.The process according to the invention can either be carried out by allowing the heated gases used to dry the sprayed aqueous slurry to flow in the same direction (cocurrent) or in the opposite direction to the sprayed aqueous slurry (countercurrent).

Eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, daß man im Gegenstrom arbeitet. Man erhält Pulver, die hinsichtlich ihrer Rieseleigenschaften und eines möglich ge­ringen Anteils an staubfeinen Produkten besonders wertvolle Ei­genschaften haben, wenn man die Strömungsgeschwindigkeiten der versprühten Aufschlämmung und des eingeblasenen Tons so einstellt, daß sich die Strömungsgeschwindigkeiten um nicht mehr als 30 % voneinander unterscheiden, wobei es zweckmäßig ist, daß sie sich nicht mehr als um 10 % unterscheiden und insbesondere gleich sind.A preferred embodiment of the method according to the invention is that one works in countercurrent. Powders are obtained which have particularly valuable properties with regard to their pouring properties and a possibly low proportion of dust-fine products if the flow rates of the sprayed slurry and the blown-in clay are set such that the flow rates do not differ from one another by more than 30%, whereby it It is expedient that they differ by no more than 10% and in particular are the same.

Außer den bereits genannten gewünschten Eigenschaften einer mög­lichst gleichmäßigen Kornverteilung und einer möglichst guten Rieselfähigkeit auch nach längerer Lagerung weisen die nach dem erfindungsgemäßen Verfahren hergestellten teilchenförmigen Wasch­mittel eine hellere Farbe auf als gleich zusammengesetzte Wasch­mittel, die man hergestellt hat, indem man die textilweichmachen­den Tone der wäßrigen Aufschlämmung zusetzte. Besonders hervorzu­heben ist der volle Erhalt der weichmachenden Eigenschaften. Da­durch, daß die quellfähigen Tone nach dem erfindungsgemäßen Ver­fahren nicht der wäßrigen Aufschlämmung zugesetzt zu werden brau­chen, verursachen sie außerdem keine Viskositätsprobleme in der wäßrigen Aufschlämmung und benötigen daher auch nicht zu deren Beseitigung zusätzliche Wassermengen in der wäßrigen Aufschläm­mung.In addition to the above-mentioned desired properties of the most uniform possible grain distribution and the best possible free-flowing properties even after prolonged storage, the particulate detergents produced by the process according to the invention have a lighter color than detergents of the same composition which have been prepared by reducing the textile-softening clays of the aqueous slurry clogged. Of particular note is the full preservation of the softening properties. Because the swellable clays need not be added to the aqueous slurry by the process of the invention, they also do not cause viscosity problems in the aqueous slurry and therefore do not require additional amounts of water in the aqueous slurry to remove them.

Das erfindungsgemäße Verfahren läßt sich mit vorzüglichem Erfolg auch zur Herstellung eines rieselfähigen körnigen, im wesentlichen Zeolith A und textilweichmachende quellfähige Tone enthaltenden Sprühproduktes verwenden. Das so erhaltene Produkt läßt sich gut als Zusatz zu Waschmitteln verwenden. In manchen Fällen ist es zweckmäßig, einen Teil der quellfähigen Tone der Waschmittel­schlämmung beziehungsweise der zu versprühenden Zeolithsuspension zuzusetzen und den restlichen Teil nach dem erfindungsgemäßen Verfahren einzublasen. Dies kann zur Verbesserung der Redispergierbarkeit der erhaltenen Waschmittel beziehungsweise der Zeolith/Ton-Sprühprodukte führen.The process according to the invention can also be used with excellent success for the production of a free-flowing, granular spray product which essentially contains zeolite A and textile-softening swellable clays. The product obtained in this way can be used well as an additive to detergents. In some cases, it is expedient to add a part of the swellable clays to the detergent slurry or the zeolite suspension to be sprayed and to blow in the remaining part by the process according to the invention. This can improve the redispersibility of the detergents obtained or the zeolite / clay spray products.

Beispielexample

Eine Waschmittelaufschlämmung, die 65 Gewichtsprozent eines Ge­misches aus
10,9 Gew.-% Alkylbenzol-Na
4,7 Gew.-% Fettalkohol-Ethoxylat
1,5 Gew.-% Seife
5,0 Gew.-% Soda
3,5 Gew.-% Wasserglas
27,2 Gew.-% Zeolith-A
5,4 Gew.-% Polycarboxylat
10,1 Gew.-% Na-Sulfat
0,9 Gew.-% Celluloseether
0,3 Gew.-% Phosphonat
enthielt und eine Viskosität von 9 400 mPas aufwies, wurde in ei­nem Zerstäubungstrocknungsturm bei einem Verhältnis von Zuluft zur Dralluft von 5,7 versprüht, wobei man soviel eines handelsüblichen quellfähigen Schichtsilikats mit textilweichmachenden Eigenschaf­ten ("Launderosil DGA, windgesichtet" (R)), das eine Teilchengrö­ßenverteilung hatte, bei der 99 % kleiner als 45 mikron waren, einblies, daß das getrocknete Zerstäubungsprodukt 16,3 Gewichts­prozent Schichtsilikat enthielt. Das Zerstäubungsprodukt hatte ein Gewicht von 395 g pro Liter und enthielt 7,1 Gewichtsprozent Was­ser. Das Produkt war gut rieselfähig und hatte eine hellere Farbe als ein gleich zusammengesetztes Vergleichsprodukt, das herge­stellt worden war, indem man das Schichtsilikat der wäßrigen Auf­schlämmung vor der Zerstäubung zugesetzt hatte.A detergent slurry made up of 65 weight percent of a mixture
10.9% by weight of alkylbenzene Na
4.7% by weight fatty alcohol ethoxylate
1.5 wt% soap
5.0 wt% soda
3.5% by weight water glass
27.2% by weight Zeolite-A
5.4% by weight polycarboxylate
10.1% by weight Na sulfate
0.9% by weight cellulose ether
0.3% by weight phosphonate
contained and had a viscosity of 9,400 mPas, was sprayed in an atomization drying tower at a ratio of supply air to swirl air of 5.7, with so much of a commercially available swellable layered silicate with textile-softening properties ("Launderosil DGA, wind-sighted" (R)), that had a particle size distribution in which 99% was less than 45 microns, the dried atomized product contained 16.3% by weight of layered silicate. The atomization product weighed 395 g per liter and contained 7.1 weight percent water. The product was easy to pour and had a lighter color than a comparative product of the same composition which had been prepared by adding the layered silicate to the aqueous slurry before atomization.

Claims (6)

1. Verfahren zur Herstellung teilchenförmiger, tonhaltiger Waschmittel oder Waschmittelzusatzstoffe durch Sprühtrocknung einer wäßrigen Aufschlämmung von Waschmittelinhaltsstoffen, dadurch gekennzeichnet, daß man in den Sprühkegeln mittels Luft quellfähige, textilweichmachende Tone in Teilchenform einbläst und dieses Gemisch durch erhitzte Gase trocknet.1. A process for the preparation of particulate, clay-containing detergents or detergent additives by spray drying an aqueous slurry of detergent ingredients, characterized in that air-swellable, textile-softening clays in particle form are blown into the spray cones and this mixture is dried by heated gases. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der mittels Luft eingeblasene Ton feinteiliges, quellfähiges Schichtsilikat vom Smectit-Typ ist.2. The method according to claim 1, characterized in that the air-blown clay is finely divided, swellable layered silicate of the smectite type. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die erhitzten Gase in entgegengesetzter Richtung wie die versprühte wäßrige Aufschlämmung strömen läßt.3. The method according to claim 1 or 2, characterized in that the heated gases are allowed to flow in the opposite direction as the sprayed aqueous slurry. 4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekenn­zeichnet, daß man die Strömungsgeschwindigkeiten der ver­sprühten Aufschlämmung und des eingeblasenen Tons so ein­stellt, daß sie sich um nicht mehr als 30 % voneinander un­terscheiden.4. The method according to any one of claims 1 to 3, characterized in that the flow rates of the sprayed slurry and the blown-in clay are adjusted so that they do not differ from one another by more than 30%. 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß sich die Strömungsgeschwindigkeiten um nicht mehr als 10 % von­einander unterscheiden.5. The method according to claim 4, characterized in that the flow velocities differ from one another by no more than 10%. 6. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß die Strömungsgeschwindigkeiten gleich sind.6. The method according to claim 4 or 5, characterized in that the flow rates are the same.
EP89117703A 1988-10-04 1989-09-25 Process for preparing a particulate detergent composition Ceased EP0362665A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3833648 1988-10-04
DE19883833648 DE3833648A1 (en) 1988-10-04 1988-10-04 METHOD FOR PRODUCING PARTICLE-DETERGENT DETERGENTS

Publications (1)

Publication Number Publication Date
EP0362665A1 true EP0362665A1 (en) 1990-04-11

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ID=6364310

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Application Number Title Priority Date Filing Date
EP89117703A Ceased EP0362665A1 (en) 1988-10-04 1989-09-25 Process for preparing a particulate detergent composition
EP19890911033 Pending EP0438437A1 (en) 1988-10-04 1989-09-25 Process for producing particulate detergents

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP19890911033 Pending EP0438437A1 (en) 1988-10-04 1989-09-25 Process for producing particulate detergents

Country Status (4)

Country Link
EP (2) EP0362665A1 (en)
JP (1) JPH04500980A (en)
DE (1) DE3833648A1 (en)
WO (1) WO1990004015A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991009927A1 (en) * 1989-12-27 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Granular, brightening detergent additive and process for manufacturing it
WO1992007927A1 (en) * 1990-10-29 1992-05-14 The Procter & Gamble Company Fabric treatment composition
EP0934395A1 (en) * 1996-10-25 1999-08-11 The Procter & Gamble Company Detergent compositions

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4306665A1 (en) * 1993-03-03 1994-09-08 Sued Chemie Ag Detergent additive for fabric softening detergents
EP0879876A1 (en) * 1997-05-21 1998-11-25 The Procter & Gamble Company Process for preparation of granular detergent composition or component comprising a water-soluble cationic surfactant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR842831A (en) * 1937-10-03 1939-06-20 Henkel & Cie Gmbh Washing, cleaning, bleaching and rinsing products containing percompounds
US3842888A (en) * 1969-12-15 1974-10-22 Colgate Palmolive Co Apparatus for introducing ingredients into a spray drying tower
GB1400898A (en) * 1972-07-14 1975-07-16 Procter & Gamble Detergent compositions
GB2190921A (en) * 1986-05-27 1987-12-02 Unilever Plc Granular detergent composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR842831A (en) * 1937-10-03 1939-06-20 Henkel & Cie Gmbh Washing, cleaning, bleaching and rinsing products containing percompounds
US3842888A (en) * 1969-12-15 1974-10-22 Colgate Palmolive Co Apparatus for introducing ingredients into a spray drying tower
GB1400898A (en) * 1972-07-14 1975-07-16 Procter & Gamble Detergent compositions
GB2190921A (en) * 1986-05-27 1987-12-02 Unilever Plc Granular detergent composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991009927A1 (en) * 1989-12-27 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Granular, brightening detergent additive and process for manufacturing it
WO1992007927A1 (en) * 1990-10-29 1992-05-14 The Procter & Gamble Company Fabric treatment composition
EP0934395A1 (en) * 1996-10-25 1999-08-11 The Procter & Gamble Company Detergent compositions
EP0934395A4 (en) * 1996-10-25 2000-02-23 Procter & Gamble Detergent compositions

Also Published As

Publication number Publication date
EP0438437A1 (en) 1991-07-31
DE3833648A1 (en) 1990-04-05
JPH04500980A (en) 1992-02-20
WO1990004015A1 (en) 1990-04-19

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