EP0544365B1 - Waschmittelzusammensetzungen und Verfahren zu deren Herstellung - Google Patents

Waschmittelzusammensetzungen und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0544365B1
EP0544365B1 EP92203563A EP92203563A EP0544365B1 EP 0544365 B1 EP0544365 B1 EP 0544365B1 EP 92203563 A EP92203563 A EP 92203563A EP 92203563 A EP92203563 A EP 92203563A EP 0544365 B1 EP0544365 B1 EP 0544365B1
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EP
European Patent Office
Prior art keywords
weight
composition
process according
detergent
starting material
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.)
Revoked
Application number
EP92203563A
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English (en)
French (fr)
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EP0544365A1 (de
Inventor
Johannes Hendrikus M. Akkermans
Huig Euser
Christophe Joyeux
Petrus Leonardus J. Swinkels
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • 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
    • 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
    • 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
    • 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
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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

  • the present invention relates to a process for the preparation of a granular detergent composition having a high bulk density and good powder properties. More in particular, it relates to a process for the continuous preparation of such detergent compositions, especially those with high detergent activity. Moreover, it relates to a granular detergent composition obtainable by the process of the present invention.
  • the first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower.
  • the various components are dry-mixed and optionally agglomerated with liquids, e.g. nonionics.
  • the most important factor which governs the bulk density of a detergent powder is the bulk density of the starting materials in the case of a dry-mixing process, or the chemical composition of the slurry in the case of a spray-drying process. Both factors can only be varied within a limited range.
  • EP-A-337,330 (Henkel) relates to a continuous process for obtaining high bulk density detergent powder containing a considerable amount of anionic and nonionic surfactant material, said process comprising treating spray-dried detergent material in a high-speed mixer under addition of nonionic material, whereby the mean residence time in the mixer is from 10-60 seconds. Alkyl sulphate is not mentioned in this document.
  • EP-A-265,203 discloses liquid surfactant compositions comprising an anionic and a nonionic surfactant. This patent document also discloses the use of these compositions which comprises spraying these compositions onto a solid particulate absorbent material. In this document alkyl sulphate is explicitly mentioned as a possible anionic surfactant which could effectively be applied in the surfactant composition which is sprayed onto the absorbent material.
  • the disadvantages of this route are the limited level of active detergent material which can be dosed in this way and the necessity that the particulate solid material to which the liquid surfactant compositions are added, is an absorbent material. Furthermore, at increased levels of active detergent material sticky detergent powder having deteriorated powder properties could easily be produced in this way.
  • liquid surfactant system comprising alkyl sulphate and an alkoxylated nonionic surfactant is thoroughly mixed with particulate starting material during treatment of this starting material in a high speed mixer/densifier.
  • the present invention provides a process for the preparation of a granular detergent composition having a bulk density of at least 650 g/I, which comprises treating a particulate starting material in a high speed mixer/densifier, characterised in that 0.1 to 50% by weight as calculated on the granular detergent composition of a liquid surfactant composition is mixed with the starting material during this treating process, said surfactant composition comprising
  • the invention provides a granular detergent composition obtainable by this process and having a particle porosity of less than 10%, preferably less than 5%.
  • the present invention is concerned with a process for the preparation of a high bulk density powder having a high active detergent content.
  • An important characteristic of the present process is that the detergent material remains throughout the process in particulate or granular form. Caking, balling an dough formation are avoided and the final product does not require an additional step in which the particle size is reduced.
  • a liquid surfactant composition comprising alkyl sulphate and an alkoxylated,preferably ethoxylated, nonionic surfactant is thoroughly mixed with a particulate starting material in a high-speed mixer/densifier.
  • This is essentially an agglomeration process, wherein the particulate starting material is agglomerated by the liquid surfactant material, resulting in detergent particles containing the particulate starting material and a surfactant phase.
  • this surfactant phase acts as a binder for the particulate starting material.
  • This agglomeration process can be carried out either as a continuous or as a batch process.
  • the agglomeration process is a well controlled, robust process resulting in detergent powder with the desired particle size and with powder properties which are comparable to those of detergent powders currently on the market .
  • the liquid surfactant composition it has been found effective to add to the liquid surfactant composition one or more components with such a composition that a significant viscosity increase of the resulting total liquid composition is obtained.
  • the addition of these components raises the afore-mentioned viscosity generally by at least a factor 5, preferably by at least a factor 10, a viscosity increase by at least a factor 100 being most preferred (when measured in a Haake viscometer at a shear rate between 0.1 and 20 S- 1 ).
  • the agglomeration process appeared to be better controllable resulting in better powder properties of the detergent material produced in this way.
  • viscosity raising components are water and, particularly, fatty acid in combination with a stoichiometric amount of alkaline material (such as caustic soda) sufficient to neutralize the fatty acid which obviously results in the formation of soap.
  • alkaline material such as caustic soda
  • the detergent powder obtained by the process of the invention may be further treated in a second step in a moderate speed granulator/densifier, whereby it is brought into or maintained in a deformable state, the mean residence time being from 1-10 minutes, and thereafter in a third step in a drying and/or cooling apparatus, as described in EP-A-367,339.
  • the process of the present invention is very flexible with respect to the chemical composition of the particulate starting material.
  • This material comprises the compounds usually found in detergent compositions such as builders and detergent active materials. Phosphate containing as well as zeolite containing compositions and compositions having either high or low active detergent content may be used as particulate starting material.
  • the detergency builder present in the starting material may be any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline Ph, the suspension of soil removed from the fabric and the suspension of fabric softening clay material.
  • suitable builders include precipitating builders such as the alkali metal carbonates, bicarbonates, orthophosphates, sequestering builders such as the alkali metal tripolyphosphates or nitrilotriacetates, or ion exchange builders such as the amorphous alkali metal alumino-silicates or the zeolites.
  • the process is also suitable for producing calcite/sodium carbonate built detergent compositions.
  • the builder material applied in the process of the present invention consists of fine particles, desirably with a particle size of less than 10 microns.
  • part of the builder material amounting to about 0.5-10% by weight as calculated on the total granular composition is preferably added during the second step when the detergent powder is further treated in a moderate speed granulator/densifier, as mentioned above. This process is disclosed in more detail by EP-A-390,251.
  • the level of builder material present in the starting material is preferably such that its content as calculated on the total granular composition is in the range from 10 to 70% by weight, most preferably from 30 to 60% by weight.
  • the detergent active material present in the starting material may be selected from anionic, 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; 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 used as constituents of the particulate starting material include, in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides 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 s -C is ) primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • the level of detergent active material present in the starting material may be in the range from 0 to 30% by weight. This level is preferably less than 10% by weight, more preferably less than 5% by weight.
  • materials which may be present in the particulate starting material include fluorescers; polycarboxylate polymers; antiredeposition agents, such as carboxy methyl cellulose; fatty acids; fillers, such as sodium sulphate; clays such as kaolin or bentonite.
  • the particulate starting material for the process of the invention may be prepared by any suitable method, such as spray-drying or dry-mixing.
  • the components of the starting material may also effectively be added separately to the mixer/densifier. It is considered to be one of the advantages of the process of this invention that high bulk density, high active detergent powders may be prepared from dry-mixed or untreated starting materials, without the need for expensive spray-drying equipment.
  • it may also be desirable that one or more of the ingredients of the starting material are adjuncts of liquids onto solid components, prepared by spray-drying, granulation or via insitu neutralization in a high-speed mixer.
  • the liquid surfactant composition which is mixed into the particulate starting material in the mixer/densifier comprises an anionic surfactant (which is a sodium or potassium salt of an alkyl sulphate), an alkoxylated nonionic surfactant and water.
  • the amount of the liquid surfactant composition which is applied is such that its content as calculated on the total granular detergent obtained is in the range from 0.1 to 50% by weight, preferably from 20 to 50 % by weight, more preferably from 25 to 50 % by weight.
  • Preferred surfactant compositions according to the invention contain not more than 30% by weight of alkyl sulphate, and as little water as possible.
  • Compositions in which the weight ratio of alkyl sulphate to alkoxylated nonionic surfactant ranges from 0.125:1 to 0.5:1 are of especial interest.
  • the nonionic surfactant is preferably an ethoxylated or mixed ethoxy-propoxylated primary or secondary aliphatic alcohol. Most preferred are ethoxylated primary alcohols, especially Ca-C, primary alcohols ethoxylated with from 2 to 25 moles of ethylene oxide per mole of alcohol.
  • the anionic surfactant component of the liquid surfactant composition is a sodium or potassium alkyl sulphate salt.
  • Suitable alkyl sulphates are sodium C 12 -C18 alkyl sulphates, especially the primary alkyl sulphates, although other alkyl sulphates outside this carbon chain length range, and potassium alkyl sulphates may also be used.
  • the liquid surfactant composition it is preferred to add to the liquid surfactant composition one or more components with such a composition, that a significant viscosity increase of the resulting total liquid composition is obtained.
  • the total level of these components may be as high as 20% by weight as calculated on the total liquid composition, said level being preferably in a range of from 2 to 10% by weight.
  • the densified powder thus obtained has preferably a particle porosity of less than 10%, more preferably less than 5%.
  • This powder may be used as a detergent powder in its own right. Generally, however, various additional ingredients may be added to give a more efficient product.
  • the amount of postdosed material will generally range from about 10 to 200% by weight, calculated on the weight of the densified powder.
  • Examples of materials which may be postdosed to the densified powder include enzymes, bleaches, bleach precursors, bleach stabilizers, lather suppressors, perfumes and dyes.
  • Liquid or pasty ingredients may conveniently be absorbed on to solid porous particles, generally inorganic, which may then be postdosed to the densified powder obtained by the process of the invention.
  • the following zeolite-containing detergent granules were prepared by spray-drying aqueous slurries.
  • the compositions (in % by weight) of the porous granules thus obtained are shown in Table 1.
  • the granules were free flowing and had a mean particle size of ca. 300 microns.
  • the granules were fed directly into a continuous low speed mixer, The rotational speed was in both cases about 30 rpm.
  • the mean residence time of the granules in the mixer was approximately 2 minutes.
  • a mixture of 20 wt% PAS and 80 wt% non-ionic was sprayed onto these granules until the granules were almost saturated. At this stage, the free-flowiness of the granular detergent material started to decline.
  • the maximum level of detergent active material which can be sprayed-on in view of the obtainable powder properties is 25 % by weight. Furthermore, it can be derived by comparing the particle size of the detergent granules before and after treatment in the mixer, that no agglomeration has occurred.
  • composition of the granular detergent powder leaving the batch mixer/densifier is given in Table 3.
  • the thus obtained granular detergent compositions had good powder properties (DFR was 101 ml/s) and a bulk density of about 770 g/I .
  • the level of the active detergent material present in the detergent powder obtained i.e.: 27.8 % by weight is higher than the levels obtained in the comparative examples.
  • compositions of the granular material leaving the Lodige Recycler are given in Table 4.
  • the thus obtained granular detergent compositions had good powder properties, a bulk density of about 700 g/I and a particle size of 500-600 microns.
  • the levels of the active detergent material present in the detergent powders obtained are respectively 30.8 % by weight and 30.0 % by weight. These active detergent levels are much higher than the levels obtained in the comparative examples and also higher than the active detergent level obtained in example 2. This is the result of incorporating into the liquid surfactant composition fed into the Recycler, fatty acid in combination with a stoichiometric amount of caustic soda, as viscosity raising material. It is clear that during the mixing/densifying process soap is formed from this material.

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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 (10)

1. Verfahren für die Herstellung einer körnigen Waschmittelzusammensetzung mit einer Schüttdichte von zumindest 650 g/t, welches das Behandeln eines teilchenförmigen Ausgangsmaterials in einem Hochgeschwindigkeitsmischer/Eindicker umfaßt, dadurch gekennzeichnet, daß 0,1 bis 50 Gewichtsprozent, wie an der körnigen Waschmittelzusammensetzung einer flüssigen Surfactant-Zusammensetzung berechnet, mit dem Ausgangsmaterial während dieses Behandlungsverfahrens gemischt werden, wobei das erwähnte Surfactant
(a) ein Natrium- oder Kaliumsalz eines Alkylsulfats in einer Menge im Bereich von 5 bis 60 Gewichtsprozent,
(b) ein alkoxyliertes nichtionisches Surfactant in einer Menge im Bereich von 40 bis 95 Gewichtsprozent,
(c) als Rest Wasser in einer Menge im Bereich von 0 bis weniger als 20 Gewichtsprozent, enthält.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Verfahren kontinuierlich durchgeführt wird, wobei die mittlere Verweilzeit in dem Hochgeschwindigkeitsmischer/Eindicker von 5 bis 30 Sekunden beträgt.
3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß der Gehalt des flüssigen Surfactant-Systems, gemischt mit dem Ausgangsmaterial, im Bereich von 20 bis 50 Gewichtsprozent, bevorzugterweise von 25 bis 50 Gewichtsprozent, liegt.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß außer der flüssigen Surfactant-Zusammensetzung eine oder mehrere Komponenten mit dem Ausgangsmaterial gemischt werden, wobei die Komponenten eine solche Zusammensetzung aufweisen, daß die Viskosität der resultierenden gesamten flüssigen Zusammensetzung erhöht wird.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die erwähnten zusätzlichen Komponenten Fettsäure in Kombination mit einer zur Neutralisation der Fettsäure ausreichenden stöchiometrischen Menge von alkalischem Material enthalten.
6. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß der gesamte Gehalt an den genannten zusätzlichen Komponenten höchstens 20 Gewichtsprozent, bevorzugterweise in dem Bereich von 2 bis 10 Gewichtsprozent, beträgt, berechnet unter Bezug auf die resultierende gesamte flüssige Zusammensetzung.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das teilchenförmige Ausgangsmaterial ferner behandelt wird
(i) in einer zweiten Stufe in einem Granulator/Eindicker mit gemäßigter Geschwindigkeit, wodurch es in einen deformierbaren Zustand gebracht oder in einem deformierbaren Zustand gehalten wird, wobei die mittlere Verweilzeit von etwa 1 bis 10 Minuten beträgt und
(ii) in einer dritten Stufe in einem Trocknungs- und/oder Kühlapparat.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die in einer flüssigen Surfactant-Zusammensetzung vorhandene Komponente (a) ein Natriumsalz eines primären C12-18-Alkylsulfats ist.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die in der flüssigen Surfactant-Zusammensetzung vorhandene Komponente (b) ein ethoxyliertes nichtionisches Surfactant der Formel R(OC2H4)nOH ist, wobei R eine C8-15-Alkylgruppe bedeutet und n im Bereich von 2 bis 25 liegt.
10. Körnige Waschmittelzusammensetzung, erhältlich durch das Verfahren nach einem der Ansprüche 1 bis 10, das eine Teilchenporosität von weniger als 10 %, bevorzugterweise von weniger als 5 %, aufweist.
EP92203563A 1991-11-26 1992-11-19 Waschmittelzusammensetzungen und Verfahren zu deren Herstellung Revoked EP0544365B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9125035 1991-11-26
GB919125035A GB9125035D0 (en) 1991-11-26 1991-11-26 Detergent compositions and process for preparing them

Publications (2)

Publication Number Publication Date
EP0544365A1 EP0544365A1 (de) 1993-06-02
EP0544365B1 true EP0544365B1 (de) 1995-06-28

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Application Number Title Priority Date Filing Date
EP92203563A Revoked EP0544365B1 (de) 1991-11-26 1992-11-19 Waschmittelzusammensetzungen und Verfahren zu deren Herstellung

Country Status (14)

Country Link
EP (1) EP0544365B1 (de)
JP (1) JP2837325B2 (de)
KR (4) KR950013924B1 (de)
AU (1) AU2854792A (de)
BR (1) BR9204571A (de)
CA (1) CA2083332C (de)
DE (1) DE69203217T2 (de)
ES (1) ES2075600T3 (de)
GB (2) GB9125035D0 (de)
IN (1) IN177135B (de)
MY (1) MY108256A (de)
SA (3) SA93130524B1 (de)
TW (2) TW232704B (de)
ZA (2) ZA929185B (de)

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EP0639639B2 (de) * 1993-08-17 2010-07-28 The Procter & Gamble Company Percarbonat-Bleichmittel enthaltende Waschmittelzusammensetzungen
EP0643130B2 (de) * 1993-09-13 2007-09-19 The Procter & Gamble Company Granulare Waschmittelzusammensetzungen mit nichtionischem Tensid und Verfahren zu ihrer Herstellung
GB9323300D0 (en) * 1993-11-11 1994-01-05 Unilever Plc Detergent composition
IL108500A (en) * 1994-01-31 1998-06-15 Zohar Detergent Factory Fatty alcohol sulphates in granular form and process for their preparation
TW326472B (en) * 1994-08-12 1998-02-11 Kao Corp Method for producing nonionic detergent granules
DE69510074T2 (de) * 1994-09-29 1999-10-21 Unilever N.V., Rotterdam Körnige hochaktive waschmittelzusammensetzungen und verfahren zu ihrer herstellung
WO1996019556A1 (en) * 1994-12-22 1996-06-27 Unilever Plc Detergent composition
GB9513327D0 (en) * 1995-06-30 1995-09-06 Uniliver Plc Process for the production of a detergent composition
GB9526097D0 (en) * 1995-12-20 1996-02-21 Unilever Plc Process
GB9625066D0 (en) * 1996-12-02 1997-01-22 Unilever Plc Process for the production of a detergent composition
GB0111862D0 (en) 2001-05-15 2001-07-04 Unilever Plc Granular composition
GB0111863D0 (en) 2001-05-15 2001-07-04 Unilever Plc Granular composition
CN1678726B (zh) 2002-09-06 2010-10-06 花王株式会社 洗涤剂颗粒
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JPS6262899A (ja) * 1985-09-13 1987-03-19 花王株式会社 高密度粒状洗剤組成物
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JP2547444B2 (ja) * 1988-05-12 1996-10-23 旭電化工業株式会社 濃縮高比重衣料用粉末洗剤
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JP2837325B2 (ja) 1998-12-16
DE69203217D1 (de) 1995-08-03
EP0544365A1 (de) 1993-06-02
GB9201059D0 (en) 1992-03-11
KR960001019B1 (ko) 1996-01-17
MY108256A (en) 1996-08-30
KR930016531A (ko) 1993-08-26
CA2083332A1 (en) 1993-05-27
ES2075600T3 (es) 1995-10-01
SA93130524B1 (ar) 2004-08-14
KR930016530A (ko) 1993-08-26
SA93130598B1 (ar) 2005-11-23
DE69203217T2 (de) 1995-11-30
KR930010168A (ko) 1993-06-22
ZA929185B (en) 1994-05-26
AU2854792A (en) 1993-05-27
ZA929184B (en) 1994-05-26
KR960001021B1 (ko) 1996-01-17
CA2083332C (en) 1998-10-06
JPH0617098A (ja) 1994-01-25
TW254966B (de) 1995-08-21
GB9125035D0 (en) 1992-01-22
KR930010174A (ko) 1993-06-22
KR950013924B1 (en) 1995-11-18
TW232704B (de) 1994-10-21
KR960001018B1 (ko) 1996-01-17
SA93130528B1 (ar) 2005-06-12
BR9204571A (pt) 1993-06-01
IN177135B (de) 1996-11-16

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