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EP1832648A1 - Wäschewaschmittel und Verfahren - Google Patents

Wäschewaschmittel und Verfahren Download PDF

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Publication number
EP1832648A1
EP1832648A1 EP06251219A EP06251219A EP1832648A1 EP 1832648 A1 EP1832648 A1 EP 1832648A1 EP 06251219 A EP06251219 A EP 06251219A EP 06251219 A EP06251219 A EP 06251219A EP 1832648 A1 EP1832648 A1 EP 1832648A1
Authority
EP
European Patent Office
Prior art keywords
powder
liquid
mixer
surfactant
anionic surfactant
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.)
Withdrawn
Application number
EP06251219A
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English (en)
French (fr)
Inventor
Remy Antal Verburgh
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.)
Unilever PLC
Original Assignee
Unilever PLC
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 Unilever PLC filed Critical Unilever PLC
Priority to EP06251219A priority Critical patent/EP1832648A1/de
Publication of EP1832648A1 publication Critical patent/EP1832648A1/de
Withdrawn legal-status Critical Current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
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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
    • C11D17/0086—Laundry 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
    • 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • Non-tower routes have been modified in a number of ways. For example: layering has been applied in the densification step of a continuous non-tower route in order to control the particle size of the granules (Unilever's EP-A-390251 ). In addition, shaft vibration was reduced to enable non-tower granulation with highly viscous binder pastes ( EP-A-918843 , P&G) .
  • a problem with the prior art non tower granulation processes is that if concentrated base powders are produced that are optimised for properties so that they can be included in formulations in powder form then they are not optimised for the properties of tablet formulations in which they may be included; especially where those tablets are obtained via processes comprising compression. It is therefore an object of the invention to provide a process for producing concentrated powders, which are especially optimised for use in formulations in tablet form, while retaining the necessary properties for their use in fully formulated powders.
  • a detergent powder manufacturing process in which solid alkali particulate material is blended and reacted with liquid anionic acid surfactant precursor in a mixer to form anionic surfactant and the solid particulate alkali is also blended with nonionic surfactant added in a liquid form to the same mixer, characterised in that the nonionic surfactant is added in admixture with anionic surfactant which has been neutralised using a liquid alkaline solution.
  • the solid alkali is blended with the nonionic surfactant liquid before it is blended with the liquid anionic surfactant acid precursor.
  • the solid alkaline material is preferably sodium carbonate.
  • the anionic surfactant made by reaction with the solid alkali is the same as that made by reaction with the liquid alkaline solution.
  • the anionic surfactant is LAS.
  • a powder detergent formulation including at least 20% of the powder formed according to the inventive process in admixture with up to 80% of granules selected from the list comprising, bleach, bleach activator, builder, soil release agents, coloured speckles, buffer, and other detergent formulation ingredients as defined herein.
  • a tablet or discrete region thereof formed by compression of the powder according to the invention, as produced by the process of the invention.
  • the tablets are used in laundering of clothes.
  • the binder comprising the neutralised mixture of anionic and nonionic surfactants and 0.1-10% water may comprise up to 10 wt% soap.
  • granules produced by prior art non-tower granulation processes are not fully homogeneous, especially when one or more pastes are used as the binder(s), or when a liquid binder is converted to a soft solid, often sticky, or a viscous paste during one of the granulation steps.
  • a binder that is a paste or a binder converted to a soft solid or viscous paste during granulation is preferred over a low-viscosity binder. This is because it provides more strength to the granules than a low-viscosity binder, which is probably due to the low viscosity binder being too easily squeezed out of the granules during their compression.
  • low viscosity binders are known to enable easy mixing of the components in a non-tower granulation process.
  • the present invention provides the advantages of both low and high viscosity binders by a novel combination of these binder types.
  • the concentrated powders of the invention are especially suitable for use in fabric washing formats that are produced via methods comprising a compression step, such as the tablet format, but can also be included in fabric washing products in powder form.
  • a fabric washing formulation comprising a concentrated granulated powder produced using the inventive process not only provides a low variation in any subsequent process comprising compression, due to the individual granules having similar mechanical properties and surface compositions, but it also enables the use of lower compression forces.
  • the higher level of homogeneity of the individual granules produced according to the invention enables optimisation of the composition of the concentrated powder in order to provide high binding strengths at relatively low compression forces. Because of this, residues obtained from compressed products, especially tablets, comprising the concentrated powder of the invention, are significantly reduced compared to the same compressed products comprising concentrated powders produced via the prior art processes.
  • the concentrated powders of the invention can also be included in fabric washing formulations in powder form and in all unit dose formats comprising uncompressed or compressed powder, such as sachets or capsules.
  • the concentrated base powders produced according to the process of the invention also exhibited improved dissolution compared with powders produced according to prior art processes. Without wishing to be bound by theory, it is believed that the improved degree of mixing of the solids and the surfactants in the process results in this unexpected advantage.
  • a Lödige (trademark) CB 30 Recycler As high-speed mixer/densifier may be used a Lödige (trademark) CB 30 Recycler.
  • This apparatus essentially consists of a large, static hollow cylinder having a diameter of about 30 cm, which is horizontally placed. In the middle, it has a rotating shaft with several different types of blades mounted thereon. It can be rotated at speeds between 100 and 2500 rpm, dependent on the bulk density and the particle size desired. The blades on the shaft provide a thorough mixing action of the solids and the liquids, which may be admixed at this stage.
  • the mean residence time is somewhat dependent on the rotational speed of the shaft, the position of the blades and the weir at the exit opening.
  • a second processing step can be successfully carried out in a medium shear mixer such as a Lödige (trademark) Ploughshare mixer.
  • This apparatus essentially consists of a hollow static cylinder having a rotating shaft in the middle. On this shaft, various plough-shaped blades are mounted. It can be rotated at a speed of 40-160 rpm.
  • one or more high-speed cutters can be used to prevent excessive agglomeration.
  • Another suitable machine for this step is, for example, the Drais (trademark) K-T 160.
  • the solid components comprise 20-90 wt%, preferably 40-80 wt%, more preferably 50-75 wt% of a zeolite, preferably zeolite MAP (these percentages include any water present within the zeolites), 10-30 wt% alkali carbonate, preferably sodium carbonate and 0-20 wt% of other solid components.
  • both binders In order to obtain good dispersion of the first and second liquid binders and the reaction product of the acid precursor of an anionic surfactant and the solid alkali source throughout the granules, both binders must retain a sufficiently low viscosity during the granulation.
  • the concentrated detergent powder is produced via a continuous granulation process comprising a high-speed mechanical mixer to agglomerate the fine particulate solid materials with both binders and a medium-speed mechanical mixer to densify, and optionally to layer, the granules.
  • the final step in this process is cooling and/or drying of the resulting granular powder to ambient temperature in a fluidised bed mixer/dryer.
  • such linear alkyl benzene sulphonate or primary alkyl sulphate of the formula above, or a mixture thereof will be the desired anionic surfactant and may provide 75 to 100 wt% of any anionic soap surfactant in the composition.
  • the primary and secondary alcohol ethoxylates especially the C 9-11 and C 12-15 primary and secondary alcohols ethoxylated with an average of from 5 to 20 moles of ethylene oxide per mole of alcohol.
  • Powders and tablets comprising the concentrated powder of the invention will usually contain from 5 to 80 wt%, more usually 15 to 60 wt% of detergency builder. This may be provided wholly by water-soluble materials, or may be provided in large part or even entirely by water-insoluble material with water-softening properties. Water-insoluble detergency builder may be present as 5 to 80 wt%, better 5 to 60 wt% of the composition.
  • a suitable water-insoluble detergency builder may be provided by a layered sodium silicate as described in US 4664839 .
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Clariant (commonly abbreviated as "SKS-6").
  • NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate. It can be prepared by methods such as described in DE-A-3,417,649 and DE-A-3,742,043 .
  • Suitable water-soluble phosphorous-containing inorganic detergency builders include the alkali-metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates.
  • Non-phosphorous water-soluble builders used may be organic or inorganic.
  • Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic builders include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.
  • alkali metal generally sodium
  • organic builders include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates,
  • Preferred inorganic persalts are sodium perborate monohydrate, tetrahydrate, and sodium percarbonate, advantageously employed together with an activator.
  • Bleach activators also referred to as bleach precursors
  • Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED), now in widespread commercial use in conjunction with sodium perborate; and perbenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • perbenzoic acid precursors perbenzoic acid precursors.
  • the quaternary ammonium and phosphonium bleach activators disclosed in US 4751015 and US 4818426 are also of interest.
  • bleach is present as a water-soluble inorganic peroxygen bleach, the amount may be from 10 wt% to 25 wt% of the composition.
  • a detergent powder or tablet comprising the concentrated powder of the invention includes an amount of an alkali metal silicate, particularly sodium ortho-, meta- or di-silicate.
  • an alkali metal silicate particularly sodium ortho-, meta- or di-silicate.
  • the presence of such alkali metal silicates at levels, for example, of 0.1 to 10 wt%, may be advantageous in providing protection against the corrosion of metal parts in washing machines, besides providing some measure of building and giving processing benefits in manufacture of tablets.
  • ingredients which can optionally be in powders and tablets comprising the concentrated powder include antiredeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents; heavy metal sequestrants such as EDTA; perfumes; and colorants or coloured speckles.
  • antiredeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents
  • heavy metal sequestrants such as EDTA
  • perfumes and colorants or coloured speckles.
  • Tabletting may be carried out at ambient temperature or at a temperature above ambient which may allow adequate strength to be achieved with less applied pressure during compression.
  • the particulate composition is preferably supplied to the tabletting machinery at an elevated temperature. This will of course supply heat to the tabletting machinery, but the machinery may be heated in some other way also.
  • the dissolution time of a powder was determined by conductivity: A 600 ml glass beaker with a diameter of 85 mm was filled with 500 ml of demineralised water at 20°C. The water was stirred with a magnetic stirrer bar of 63 mm length while maintaining a vortex of 25 mm. A conductivity probe connected to an electronic datalogger was placed in the beaker near to the wall of the beaker. Then, 1.25 g of the powder was poured into the water. The dissolution time of the powder was recorded as the time after powder addition at which the conductivity had reached 90% of its maximum value.
  • the particle size of the powders was determined with a Retsch Camsizer.
  • Tablet strength was tested with a Synergy 100 materials testing machine manufactured by MTS Systems, France.
  • the strength of a tablet may be expressed as F max , which is measured by compressing the tablet radially, between the platens of a materials testing machine, until fracture of the tablet occurs.
  • F max in Newton is the force applied at fracture.
  • SCMC Sodium carboxymethylcellulose, supplied by AKZO.
  • Sodium carbonate supplied by Brunner-Mond.
  • Sodium acetate Sodium acetate trihydrate supplied by Verdugt, to which 1% by weight zeolite MAP was added to improve its handling characteristics.
  • LAS acid Linear alkylbenzene sulphonic acid, 97.1% pure, produced and supplied by the applicants.
  • Nonionic 7EO - Neodol(TM) 25-7E supplied by Shell Chemicals.
  • Fatty acid - Pristerene(TM) 4916 supplied by Uniqema. 50% NaOH - 50% by weight aqueous solution of sodium hydroxide supplied by Chemproha.
  • Solid materials (A) detailed in Table 1 were dosed continuously in a Lödige CB100 Recycler mixer operating at 1500 rpm.
  • a liquid neutralised surfactant mixture (B) was produced separately in an in-line mixing system and pumped into the CB100 mixer at 90°C.
  • LAS acid C was pumped into the CB100 mixer at 60°C.
  • the product exiting the CB100 mixer was continuously fed into a Lödige KM10000 ploughshare mixer operating at 450rpm.
  • Zeolite MAP was also fed to the ploughshare mixer for layering the product (D).
  • the resulting concentrated powder was then transported to a fluidised bed in which it was cooled to ambient temperature (the temperature of which varied during the process, but was always between 25 and 37°C) using dehumidified air at 10°C. Finally, coarse material larger than 2000 microns was removed from the product by sieving.
  • the resulting product was a free-flowing concentrated base powder (E) with a bulk density of between 775 and 800 g/l and a mean particle size of between 450 and 600 microns. The total throughput of the process was 18000 kilograms per hour. Table 1 lists the weight percentages of the materials that were dosed into the process.
  • Solid materials (F) were dosed continuously to a Lödige CB100 Recycler operating at 1500 rpm.
  • An 18% pre-neutralised LAS acid/LAS mixture (G) was produced separately in an in-line mixing system and pumped into the CB100 mixer at 90°C.
  • a mixture of nonionic surfactant and fatty acid (H) was pumped into the CB100 mixer at 40°C.
  • the product exiting the CB100 mixer was fed into a Lödige KM10000 ploughshare mixer operating at 450 rpm, as well some zeolite MAP (I) for layering the product.
  • Table 2 Raw material flows in comparative process Dosed in CB100 mixer wt% Solid components (F) Zeolite MAP 49.84 SCMC 0.93 Sodium carbonate 9.57 Sodium acetate 5.98 Partially neutralised surfactant mixture (G) LAS acid 20.13 50% NaOH 0.90 Surfactant mixture(H) Nonionic 7EO 9.17 Fatty acid 1.49 Dosed in KM 10000 mixer layering (I) Zeolite MAP 1.99

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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)
EP06251219A 2006-03-08 2006-03-08 Wäschewaschmittel und Verfahren Withdrawn EP1832648A1 (de)

Priority Applications (1)

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EP06251219A EP1832648A1 (de) 2006-03-08 2006-03-08 Wäschewaschmittel und Verfahren

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Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1429143A (en) 1973-05-11 1976-03-24 Procter & Gamble Detergent composition
JPS6072999A (ja) 1983-09-30 1985-04-25 花王株式会社 超濃縮粉末洗剤の製法
DE3417649A1 (de) 1984-05-12 1985-11-14 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von kristallinen natriumsilikaten
US4664839A (en) 1984-04-11 1987-05-12 Hoechst Aktiengesellschaft Use of crystalline layered sodium silicates for softening water and a process for softening water
EP0265203A1 (de) 1986-10-20 1988-04-27 Unilever Plc Detergenszusammensetzungen
EP0266863A1 (de) 1986-08-12 1988-05-11 Unilever Plc Antischaummittel
US4751015A (en) 1987-03-17 1988-06-14 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
US4818426A (en) 1987-03-17 1989-04-04 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
DE3742043A1 (de) 1987-12-11 1989-06-22 Hoechst Ag Verfahren zur herstellung von kristallinen natriumschichtsilikaten
EP0345090A2 (de) 1988-06-03 1989-12-06 Colgate-Palmolive Company Verfahren zur Herstellung einer festen Waschmittelzusammensetzung direkt aus in-situ-hergestelltem anionischem Tensidsalz
EP0352135A1 (de) * 1988-07-21 1990-01-24 Unilever Plc Waschmittelzusammensetzungen und Verfahren zu deren Herstellung
EP0367339A2 (de) 1988-11-02 1990-05-09 Unilever N.V. Verfahren zur Herstellung einer körnigen Reinigungsmittelzusammensetzung mit hoher Schüttdichte
EP0384070A2 (de) 1988-11-03 1990-08-29 Unilever Plc Zeolith P, sein Herstellungsverfahren und seine Verwendung in Waschmitteln
EP0390251A2 (de) 1989-03-30 1990-10-03 Unilever N.V. Detergens-Zusammensetzungen und Verfahren zu ihrer Herstellung
EP0420317A1 (de) 1989-09-29 1991-04-03 Unilever N.V. Verfahren zur Herstellung von Detergenszubereitungen mit hoher Schüttdichte
EP0438320A2 (de) * 1990-01-19 1991-07-24 Unilever Plc Reinigungsmittel und Verfahren zu deren Herstellung
EP0458397A2 (de) 1990-05-21 1991-11-27 Unilever N.V. Bleichmittelaktivierung
EP0466484A2 (de) 1990-07-13 1992-01-15 Unilever Plc Detergenszusammensetzungen
EP0522766A2 (de) 1991-07-01 1993-01-13 Unilever Plc Detergenszusammensetzungen in Tablettenform
EP0544365A1 (de) 1991-11-26 1993-06-02 Unilever N.V. Waschmittelzusammensetzungen und Verfahren zu deren Herstellung
EP0549272A1 (de) 1991-12-20 1993-06-30 Unilever Plc Bleichaktivierung
EP0656825A1 (de) 1992-06-15 1995-06-14 The Procter & Gamble Company Verfahren zum herstellen von kompakten waschmittelzusammensetzungen
WO1998011198A1 (en) * 1996-09-10 1998-03-19 Unilever Plc Process for preparing high bulk density detergent compositions
EP0858500A1 (de) 1995-10-04 1998-08-19 The Procter & Gamble Company Verfahren zur herstellung eines waschmittels mit niedrigen schüttgewichtmittels agglomeration mit einem anorganischen doppelsalz
EP0918843A1 (de) 1996-08-14 1999-06-02 The Procter & Gamble Company Verfahren zur herstellung von waschmitteln mit hoher dichte
WO2000032738A1 (de) * 1998-12-01 2000-06-08 Henkel Kommanditgesellschaft Auf Aktien Granulationsverfahren
WO2000060041A1 (en) * 1999-03-30 2000-10-12 Unilever Plc Detergent powder composition
WO2005033258A1 (en) * 2003-10-04 2005-04-14 Unilever Plc Process for making a detergent composition

Patent Citations (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1429143A (en) 1973-05-11 1976-03-24 Procter & Gamble Detergent composition
JPS6072999A (ja) 1983-09-30 1985-04-25 花王株式会社 超濃縮粉末洗剤の製法
US4664839A (en) 1984-04-11 1987-05-12 Hoechst Aktiengesellschaft Use of crystalline layered sodium silicates for softening water and a process for softening water
DE3417649A1 (de) 1984-05-12 1985-11-14 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von kristallinen natriumsilikaten
EP0266863A1 (de) 1986-08-12 1988-05-11 Unilever Plc Antischaummittel
EP0265203A1 (de) 1986-10-20 1988-04-27 Unilever Plc Detergenszusammensetzungen
US4751015A (en) 1987-03-17 1988-06-14 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
US4818426A (en) 1987-03-17 1989-04-04 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
DE3742043A1 (de) 1987-12-11 1989-06-22 Hoechst Ag Verfahren zur herstellung von kristallinen natriumschichtsilikaten
EP0345090A2 (de) 1988-06-03 1989-12-06 Colgate-Palmolive Company Verfahren zur Herstellung einer festen Waschmittelzusammensetzung direkt aus in-situ-hergestelltem anionischem Tensidsalz
EP0352135A1 (de) * 1988-07-21 1990-01-24 Unilever Plc Waschmittelzusammensetzungen und Verfahren zu deren Herstellung
EP0367339A2 (de) 1988-11-02 1990-05-09 Unilever N.V. Verfahren zur Herstellung einer körnigen Reinigungsmittelzusammensetzung mit hoher Schüttdichte
EP0384070A2 (de) 1988-11-03 1990-08-29 Unilever Plc Zeolith P, sein Herstellungsverfahren und seine Verwendung in Waschmitteln
EP0390251A2 (de) 1989-03-30 1990-10-03 Unilever N.V. Detergens-Zusammensetzungen und Verfahren zu ihrer Herstellung
EP0420317A1 (de) 1989-09-29 1991-04-03 Unilever N.V. Verfahren zur Herstellung von Detergenszubereitungen mit hoher Schüttdichte
EP0438320A2 (de) * 1990-01-19 1991-07-24 Unilever Plc Reinigungsmittel und Verfahren zu deren Herstellung
EP0458397A2 (de) 1990-05-21 1991-11-27 Unilever N.V. Bleichmittelaktivierung
EP0458398A2 (de) 1990-05-21 1991-11-27 Unilever N.V. Bleichmittelaktivierung
EP0466484A2 (de) 1990-07-13 1992-01-15 Unilever Plc Detergenszusammensetzungen
EP0522766A2 (de) 1991-07-01 1993-01-13 Unilever Plc Detergenszusammensetzungen in Tablettenform
EP0544365A1 (de) 1991-11-26 1993-06-02 Unilever N.V. Waschmittelzusammensetzungen und Verfahren zu deren Herstellung
EP0549272A1 (de) 1991-12-20 1993-06-30 Unilever Plc Bleichaktivierung
EP0656825A1 (de) 1992-06-15 1995-06-14 The Procter & Gamble Company Verfahren zum herstellen von kompakten waschmittelzusammensetzungen
EP0858500A1 (de) 1995-10-04 1998-08-19 The Procter & Gamble Company Verfahren zur herstellung eines waschmittels mit niedrigen schüttgewichtmittels agglomeration mit einem anorganischen doppelsalz
EP0918843A1 (de) 1996-08-14 1999-06-02 The Procter & Gamble Company Verfahren zur herstellung von waschmitteln mit hoher dichte
WO1998011198A1 (en) * 1996-09-10 1998-03-19 Unilever Plc Process for preparing high bulk density detergent compositions
EP0925354A1 (de) 1996-09-10 1999-06-30 Unilever Plc Verfahren zur herstellung von waschmitteln mit hohem schüttgewicht
WO2000032738A1 (de) * 1998-12-01 2000-06-08 Henkel Kommanditgesellschaft Auf Aktien Granulationsverfahren
WO2000060041A1 (en) * 1999-03-30 2000-10-12 Unilever Plc Detergent powder composition
WO2005033258A1 (en) * 2003-10-04 2005-04-14 Unilever Plc Process for making a detergent composition

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