EP0942958B1 - Verfahren zur herstellung einer waschmittelzusammensetzung - Google Patents

Verfahren zur herstellung einer waschmittelzusammensetzung Download PDF

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Publication number
EP0942958B1
EP0942958B1 EP97950085A EP97950085A EP0942958B1 EP 0942958 B1 EP0942958 B1 EP 0942958B1 EP 97950085 A EP97950085 A EP 97950085A EP 97950085 A EP97950085 A EP 97950085A EP 0942958 B1 EP0942958 B1 EP 0942958B1
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EP
European Patent Office
Prior art keywords
starting material
process according
bulk density
mixer
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.)
Expired - Lifetime
Application number
EP97950085A
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English (en)
French (fr)
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EP0942958A1 (de
EP0942958B2 (de
Inventor
Cornelis Elisabeth Johannes Van Lare
Gilbert Martin Verschelling
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions

Definitions

  • the present invention relates to a process for the production of a detergent composition.
  • the invention is concerned with a process for the production of a detergent composition having a medium or low bulk density and to detergent compositions thereby produced.
  • detergent compositions have been produced by a spray-drying process in which the components of the composition are mixed with water to form an aqueous crutcher slurry which is then sprayed into a spray-drying tower and contacted with hot air to remove water whereby detergent particles, often referred to as a "base" powder are obtained.
  • the particles so obtained have a high porosity.
  • powders produced by this method typically have a bulk density of 300 to 550 g/l or even up to 650 g/l.
  • Spray-dried powders generally provide good powder delivery characteristics such as dispensing and dissolution. However, the capital and operating costs of the spray-drying process are high. Nevertheless there remains a significant consumer demand for such low density powders.
  • detergent powders having a high bulk density have been produced by mechanical mixing processes. Bulk densities of 700 to 900 g/l and even higher have been obtained.
  • powders are produced by densifying a spray-dried base powder in one or more mechanical mixers, optionally with the addition of further components, or by mixing the components of the composition in a continuous or batch mixing process without the use of a spray-drying step.
  • Powders having a high bulk density have a low packing volume which is advantageous for storage and distribution operations and also for the consumer. Furthermore, if a spray-drying step is not employed, the capital and operating costs are typically much lower and the process uses less energy and so provides an environmental benefit. The avoidance of a spray-drying step in the detergent production process is therefore often desirable.
  • EP-A-367 339 discloses a process for the production of a detergent composition having a high bulk density in which a particulate starting material is treated in a high speed mixer, a moderate speed mixer wherein the material is brought into or maintained in a deformable state, and then dried and/or cooled.
  • the starting material may be a spray-dried base powder or the components of the composition may be employed without a prior spray-drying step in the detergent production process.
  • WO-A-97/02338 (Unilever : unpublished at the priority date of the present application) discloses that a low bulk density, for example less than 700 g/l, may be obtained by a process in which a spray-drying step is not employed, if the composition is formulated with a component having a low bulk density.
  • this process is relatively unsuitable for use with starting materials which are either available commercially in a form in which the particle density is high or which are themselves produced by spray-drying (the latter normally producing relatively porous particles).
  • EP-A-544 365 discloses granulation of porous spray-dried detergent free starting material of 300 micron particle size in a "recycler" high speed mixer/densifier with a liquid binder comprising a primary alcohol sulphate anionic surfactant, a nonionic surfactant and water.
  • medium or low bulk density powders may be obtained by a new process of mechanical mixing of a powder which contains little or no detergent active material and which consists of particles having a predetermined average particle size and high particle porosity together with a liquid component comprising a detergent active material or a precursor therefor.
  • a first aspect of the present invention provides a process for the production of a detergent composition having a bulk density of no more than 750 g/l, e.g. no more than 700 or 650 g/l, the process comprising mixing a particulate starting material which contains no more than 10% by weight of the starting material of detergent active material and which starting material has a d 50 average particle diameter of from 100 ⁇ m to 1000 ⁇ m and a particle porosity of at least 0.4, together with a liquid component comprising a detergent active material or a precursor therefor in a mixer/granulator having both a stirring and a cutting action.
  • the present invention further extends to a detergent composition prepared by a process according to the present invention.
  • the present invention derives from the unexpected observation that the bulk density of the resultant product is dependent upon the rotational speed of mixing. This is also a function of the particular mixer of choice but essentially, the lower the speed of the mixer, the lower the bulk density of the product.
  • the first advantage is that by choosing a powder starting material which already possesses the required average particle size and porosity medium or low bulk density powders may be prepared.
  • NTR non-tower route
  • the detergent composition resulting from the process of the present invention has a bulk density of 400 to 650 g/l, preferably 450 to 650 g/l and more preferably 500 to 600 g/l. It is further preferred that the resultant detergent composition has a particle porosity of at least 0.2 and more preferably at least 0.25.
  • the particulate starting material is dosed at a level of from 10 to 75 wt%, preferably from 20 to 40 wt%, of the composition resulting from the mechanical mixing process.
  • particle size distributions in terms of average (e.g. d 50 ) particle diameters
  • they may be expressed in terms of their Rosin Rammler number. This is calculated by fitting the particle size distribution to an n-power distribution according to the following formula:- where R is the cumulative percentage of powder above a certain size D.
  • D r is the average granule size and n is a measure of the particle size distribution.
  • D r and n are the Rosin Rammler fits to a measured particle size distribution.
  • a high n value means narrow particle size distribution and low values mean a broad particle size distribution.
  • the process may be a continuous process or may be performed batch-wise.
  • a suitable type of mixer/granulator for use in the process of the invention is bowl-shaped and preferably has a substantially vertical stirrer axis.
  • mixers of the Fukae (Trade Mark) FS0G series manufactured by Fukae Powtech Kogyo Co., Japan are essentially in the form of a bowl-shaped vessel accessible via a top part, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
  • the stirrer and cutter may be operated independently of one another, and at separately variable speeds.
  • Granulation is preferably effected by running the mixer using both stirrer and cutter; a relatively short residence time (for example, 5-8 minutes for a 35kg batch) is generally sufficient.
  • the final bulk density can be controlled by choice of residence time and stirrer rate.
  • the stirrer is operated at a rate of 25 to 250 rpm, e.g. from 100 rpm to 200 rpm or even as low as 30 to 50 rpm. However, this speed is dependent on the size of the apparatus.
  • the cutter is suitably operated at a rate of 200 to 3500 rpm, preferably 300 to 3000 rpm.
  • the cutter is suitably operated at a rate of 200 to 2500 rpm, preferably 300 to 2200 rpm.
  • a batch process typically involves pre-mixing of solid components, addition of liquids, granulation, optional addition of a layering material suitable for controlling the granulation end-point, and product discharge.
  • the rate of stirring and/or cutting is suitably adjusted according to the stage of the process.
  • the mixing step is preferably carried out at a controlled temperature somewhat above ambient, preferably above 30°C. Suitably the temperature is within the range 30 to 45°C.
  • the amount of detergent active material in the particulate starting material is no more than 10% by weight of that material.
  • the amount of detergent active material in the particulate starting material is suitably no more than 5% by weight thereof and preferably no more than 1% by weight thereof.
  • the particulate starting material may be substantially or totally free of any detergent active material.
  • the particulate starting material may be one prepared by spray-drying.
  • starting materials having the required parameters may be obtained by other means, e.g. involving granulation.
  • the d 50 average particle diameter of the particulate starting material is from 100 ⁇ m to 1000 ⁇ m. This is important for controlling the particle size distribution in the final product. Preferably though, this average particle diameter is from 150 ⁇ m to 800 ⁇ m, especially from 200 ⁇ m to 700 ⁇ m. Preferably, 90% by weight of the particles in the starting material have a particulate diameter in the region of 100 ⁇ m to 1000 ⁇ m.
  • the particle porosity of the particulate starting material is at least 0.4 but is preferably at least 0.45, e.g. from 0.45 to 0.55. Most preferably it is at least 0.50.
  • such particulate starting material may comprise a spray-dried material, that is to say some or all of the starting material is formed by a spray-drying process.
  • the particle porosity can be derived from the following experiments:
  • the solids density of the particles is needed (eq. 2). This is measured using helium pycnometry, e.g. by using a penta pycnometer supplied by Quantachrome.
  • the particle porosity can easily be derived.
  • powder flow is defined in terms of the dynamic flow rate (DFR), in ml/s, measured by means of the following procedure.
  • the apparatus used consists of a cylindrical glass tube having an internal diameter of 35 mm and a length of 600 mm. The tube is securely clamped in a position such that its longitudinal axis is vertical. Its lower end is terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15° and a lower outlet orifice of diameter 22.5 mm.
  • a first beam sensor is positioned 150 mm above the outlet, and a second beam sensor is positioned 250 mm above the first sensor.
  • the outlet orifice is temporarily closed, for example, by covering with a piece of card, and powder is poured through a funnel into the top of the cylinder until the powder level is about 10 cm higher than the upper sensor; a spacer between the funnel and the tube ensures that filling is uniform.
  • the averaging and calculation are carried out electronically and a direct read-out of the DFR value obtained.
  • the particulate starting material preferably comprises a builder, most preferably aluminosilicate, for example zeolite 4A or zeolite A24 or a salt, preferably an inorganic salt.
  • Salts preferably sodium, of phosphates, for example sodium tripolyphosphate (STP), carbonate, bicarbonate and sulphate are also suitable.
  • solid materials may also be incorporated in the particulate starting material, although they may alternatively or additionally be dosed at any appropriate stage(s) of the mechanical mixing.
  • the liquid component preferably contains at least one liquid nonionic surfactant. It may also contain one or more acid precursors of anionic surfactants and/or fatty acids. The acid precursor(s) can then be neutralised to form the corresponding anionic surfactant(s) and the fatty acid(s) saponified by dosing one or more suitable alkaline materials at an appropriate stage during the mechanical mixing process.
  • suitable alkaline materials include alkali metal carbonates, e.g. Na 2 CO 3 . and hydroxides, e.g. NaOH. Such alkaline materials may be dosed in solid form or as aqueous solutions. It is also possible to partially neutralise/saponify such precursors or fatty acids in the liquid component prior to the mechanical mixing step.
  • the detergent composition suitably comprise anionic detergent active.
  • anionic detergent active This may be incorporated as a preneutralised material, desirably as a component of the particulate starting material, or may be neutralised in situ.
  • the acid precursor of the active is preferably neutralised using a solid neutralising agent, for example carbonate, which is desirably a component of the particulate starting material.
  • the detergent active material present in the composition may be selected for anionic, cationic, ampholytic, zwitterionic or nonionic detergent active materials or mixtures thereof.
  • suitable synthetic anionic detergent compounds are sodium and potassium (C 9 -C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates (LAS); sodium or potassium alkyl sulphates (PAS); and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • Suitable nonionics which may be employed include, in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amines or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C 6 -C 22 ) phenol ethylene oxide condensates, generally having 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic (C 8 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 50 EO.
  • the level of detergent active material present in the composition may be in the range from 1 to 50% by weight depending on the desired applications.
  • Nonionic material may be present in particulate starting material at a level which is less than 10% by weight more preferably less than 5% by weight and/or employed as the liquid binder in the mixing process optionally with another liquid component, for example water.
  • the particulate starting material constitutes 30 to 70% of the detergent composition.
  • a layering material may be employed during the mixing step to control granule formation and reduce or prevent over-agglomeration.
  • Suitable materials include aluminosilicates, for example zeolite 4A.
  • the layering material is suitably present at a level of 1 to 4 wt %.
  • the composition may be used as a complete composition in its own right or may be mixed with other components or mixtures and thus may form a major or minor part of a final product.
  • the composition may be blended with for example a spray-dried base powder.
  • Conventional additional components such as enzymes, bleach and perfume may also be admixed with the composition as desired to produce a fully formulated product.
  • the resulting powders had the following properties: Properties Base Powder 1 Base Powder 2 BD, [g/l] 629 370 DFR, [ml/s] 115 88 d 50 [ ⁇ m] 210 279 [ ⁇ m] 242 299 [-] 2.7 2.4 Moisture Content [%] 5-7 7 Particle Porosity 0.51 0.70
  • Sokalan CP5 is a polyacrylate/polymaleate copolymer.
  • the spray-dried zeolite-based porous carriers were subsequently used as base powders in NTR processes as described in Examples 1 and 2.
  • the PAS adjunct used in the trial had the following composition: PAS 45 wt% Zeolite 38 wt% Carbonate 9 wt% Water + other components 8 wt%
  • the resulting powder had the following properties: Properties BD [g/l] 404 DFR [ml/s] 111 d 50 [ ⁇ m] 303 RRd ( ⁇ m] 349 RRn [-] 2.9 Moisture content [%] 5.9 Particle porosity 0.67
  • the spray-dried STP-based carrier was used to formulate powders in Examples 3 and 4.
  • the STP-based carrier was used in a batch NTR process using a Fukae FS30 mixer as follows: Example 3 (kg) Example 4 (kg) Reference Standard STP 0 0 4.7 Spray-dried STP carrier 4.7 4.7 0 Sodium carbonate 5.2 5.2 5.2 Zeolite 4A (Wessalith P) 1.0 1.0 1.0 1.0 1.0 LAS acid 3.3 3.3 3.3 Zeolite 4A layering 0 0.3 0 Pre-mixing Pre-mix time (sec.) 10 10 10 10 RPM (agitator/chopper) 100/3000 Mixing 100/3000 100/3000 RPM (agitator) 100 200 100 RPM (chopper) 3000 3000 3000 Mixing time (sec) 120 120 120 Powder properties BD [g/l] 576 688 846 DFR [ml/s] 110 119 132 RRd ( ⁇ m] 486 373 680 RRn [-] 1.72 1.70 1.19

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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)
  • Detergent Compositions (AREA)
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Claims (13)

  1. Verfahren zur Herstellung einer Waschmittelpulverzusammensetzung mit einer Schüttdichte von nicht mehr als 750 g/l, wobei das Verfähren das Mischen eines partikelförmigen Ausgangsmaterials, das nicht mehr als 10 %, bezogen auf das Gewicht des Ausgangsmaterials, eines waschaktiven Materials enthält, mit einer flüssigen Komponente, die ein waschaktives Material oder eine Vorstufe dafür umfaßt, in einem Mischer/Granulator umfaßt, der sowohl eine Rühr- als auch eine Schnittwirkung hat, dadurch gekennzeichnet, daß das Ausgangsmaterial einen mittleren Partikeldurchmesser d50 von 100 µm bis 1000 µm und eine Porosität der Partikel von mindestens 0,4 hat.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Schüttdichte des Produktes der Waschmittelpulverzusammensetzung bei einem bestimmten Wert geregelt wird, indem die Arbeitsgeschwindigkeit des Mischers/Granulators eingestellt wird.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß das Ausgangsmaterial einen mittleren Partikeldurchmesser d50 von 150 µm bis 800 µm hat.
  4. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Ausgangsmaterial einen mittleren Partikeldurchmesser d50 von 200 µm bis 700 µm hat.
  5. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Ausgangsmaterial ein durch Zerstäubungstrocknung erzeugtes Material umfaßt.
  6. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß der Mischer/Granulator ein Hochgeschwindigkeitsmischer/Verdichter ist, in den das Ausgangsmaterial und die flüssige Komponente dosiert werden, wodurch ein körniges Material erzeugt wird.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das durch Mischen hergestellte Material anschließend getrocknet und/oder abgekühlt wird.
  8. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß der Mischer/Granulator ein schalenförmiges Gefäß und einen Rührer, der um eine senkrechte Rührerachse rotiert, oder einen waagerechten Hohlzylinder mit einer in der Mitte rotierenden Welle mit Rührschaufeln umfaßt.
  9. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Porosität der Partikel des Ausgangsmaterials mindestens 0,45 beträgt.
  10. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Porosität der Partikel des Ausgangsmaterials mindestens 0,50 beträgt.
  11. Waschmittelpulverzusammensetzung, die nach einem Verfahren nach Anspruch 1 hergestellt ist.
  12. Zusammensetzung nach Anspruch 11, gekennzeichnet durch eine Schüttdichte von nicht mehr als 700 g/l.
  13. Zusammensetzung nach Anspruch 11, gekennzeichnet durch eine Schüttdichte von nicht mehr als 650 g/l.
EP97950085A 1996-12-02 1997-10-29 Verfahren zur herstellung einer waschmittelzusammensetzung Expired - Lifetime EP0942958B2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9625066 1996-12-02
GBGB9625066.7A GB9625066D0 (en) 1996-12-02 1996-12-02 Process for the production of a detergent composition
PCT/EP1997/006073 WO1998024876A1 (en) 1996-12-02 1997-10-29 Process for the production of a detergent composition

Publications (3)

Publication Number Publication Date
EP0942958A1 EP0942958A1 (de) 1999-09-22
EP0942958B1 true EP0942958B1 (de) 2001-12-19
EP0942958B2 EP0942958B2 (de) 2006-12-13

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ID=10803825

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Application Number Title Priority Date Filing Date
EP97950085A Expired - Lifetime EP0942958B2 (de) 1996-12-02 1997-10-29 Verfahren zur herstellung einer waschmittelzusammensetzung

Country Status (14)

Country Link
EP (1) EP0942958B2 (de)
CN (1) CN1188505C (de)
AR (1) AR009644A1 (de)
AU (1) AU721831B2 (de)
BR (1) BR9714494A (de)
CA (1) CA2273849C (de)
DE (1) DE69709398T3 (de)
EA (1) EA001453B1 (de)
ES (1) ES2169882T3 (de)
GB (1) GB9625066D0 (de)
ID (1) ID22478A (de)
TR (1) TR199901756T2 (de)
WO (1) WO1998024876A1 (de)
ZA (1) ZA979825B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020222996A1 (en) * 2019-04-29 2020-11-05 The Procter & Gamble Company A process for making a laundry detergent composition
RU2773345C1 (ru) * 2019-04-29 2022-06-02 Дзе Проктер Энд Гэмбл Компани Способ получения композиции моющего средства для стирки

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6492319B1 (en) 1998-08-20 2002-12-10 The Procter & Gamble Company High density detergent-making process involving a moderate speed mixer/densifier
AU5907499A (en) * 1998-09-18 2000-04-10 Procter & Gamble Company, The Continuous process for making a detergent composition
US6794354B1 (en) 1998-09-18 2004-09-21 The Procter & Gamble Company Continuous process for making detergent composition
CA2343810A1 (en) * 1998-09-25 2000-04-06 Jacqueline Westfield Granular detergent composition having improved appearance and solubility
WO2000018874A1 (en) * 1998-09-25 2000-04-06 The Procter & Gamble Company Granular detergent composition having improved appearance and solubility
DE69904499T2 (de) * 1998-10-26 2003-10-30 Procter & Gamble Verfahren zur herstellung eines granularen waschmittels mit verbessertem aussehen und erhöhter löslichkeit
MXPA02000032A (es) * 1999-06-21 2002-07-02 Procter & Gamble Procedimiento para producir particulas detergentes recubiertas.
US6767882B1 (en) 1999-06-21 2004-07-27 The Procter & Gamble Company Process for producing coated detergent particles
US6951837B1 (en) 1999-06-21 2005-10-04 The Procter & Gamble Company Process for making a granular detergent composition

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0270240B1 (de) * 1986-10-31 1993-09-22 Unilever Plc Reinigungsmittel in Pulverform und deren Herstellungsverfahren

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0367339B1 (de) * 1988-11-02 1996-03-13 Unilever N.V. Verfahren zur Herstellung einer körnigen Reinigungsmittelzusammensetzung mit hoher Schüttdichte
GB9125035D0 (en) * 1991-11-26 1992-01-22 Unilever Plc Detergent compositions and process for preparing them
GB9513327D0 (en) * 1995-06-30 1995-09-06 Uniliver Plc Process for the production of a detergent composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0270240B1 (de) * 1986-10-31 1993-09-22 Unilever Plc Reinigungsmittel in Pulverform und deren Herstellungsverfahren

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020222996A1 (en) * 2019-04-29 2020-11-05 The Procter & Gamble Company A process for making a laundry detergent composition
RU2773345C1 (ru) * 2019-04-29 2022-06-02 Дзе Проктер Энд Гэмбл Компани Способ получения композиции моющего средства для стирки

Also Published As

Publication number Publication date
EA001453B1 (ru) 2001-04-23
AU5316898A (en) 1998-06-29
CN1245530A (zh) 2000-02-23
CN1188505C (zh) 2005-02-09
AU721831B2 (en) 2000-07-13
ES2169882T3 (es) 2002-07-16
CA2273849C (en) 2007-04-10
WO1998024876A1 (en) 1998-06-11
EA199900516A1 (ru) 2000-02-28
DE69709398T3 (de) 2007-04-19
GB9625066D0 (en) 1997-01-22
AR009644A1 (es) 2000-04-26
DE69709398T2 (de) 2002-06-20
ID22478A (id) 1999-10-21
ZA979825B (en) 1999-04-30
TR199901756T2 (xx) 1999-11-22
CA2273849A1 (en) 1998-06-11
BR9714494A (pt) 2000-03-21
EP0942958A1 (de) 1999-09-22
EP0942958B2 (de) 2006-12-13
DE69709398D1 (de) 2002-01-31

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