EP0544492A1 - Teilchenförmige Waschmittelzusammensetzungen - Google Patents
Teilchenförmige Waschmittelzusammensetzungen Download PDFInfo
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- EP0544492A1 EP0544492A1 EP92310721A EP92310721A EP0544492A1 EP 0544492 A1 EP0544492 A1 EP 0544492A1 EP 92310721 A EP92310721 A EP 92310721A EP 92310721 A EP92310721 A EP 92310721A EP 0544492 A1 EP0544492 A1 EP 0544492A1
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- EP
- European Patent Office
- Prior art keywords
- zeolite
- surfactant
- ethoxylation
- detergent composition
- particulate 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.)
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Classifications
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- 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
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- 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
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- 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
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions 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
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- 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
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- 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
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- 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 is concerned with particulate detergent compositions that combine exceptionally good cleaning performance with high bulk density and excellent powder properties.
- the compositions contain a high level of high-performance organic surfactant - selected ethoxylated alcohol optionally plus a minor amount of alkyl sulphate - and zeolite detergency builder, and are preferably prepared by an agglomeration process using a high-speed mixer/granulator.
- alkyl sulphates In view of increasing environmental awareness, it has also become desirable to use alkyl sulphates in preference to the linear alkylbenzene sulphonates traditionally used in laundry detergents.
- Alkyl sulphates are readily biodegradable and can be obtained from renewable sources such as coconut and palm oil. However, they are generally more difficult to process into high quality detergent powders than are alkylbenzene sulphonates.
- Nonionic surfactants alkyl sulphates and mixtures of the two have been found to provide highly efficient detergency, but because of their mobility are difficult to incorporate, even at moderate levels, into free-flowing powders that will disperse in the wash liquor.
- these difficulties would be expected to increase, and to be exacerbated even further in the highly concentrated, dense powders currently favoured by the consumer and the detergents industry.
- the present inventors have succeeded in formulating high bulk density free-flowing detergent powders combining excellent performance with good powder properties and dispersibility, despite their containing relatively high levels of high-performance mobile surfactants.
- the powders of the invention contain relatively high levels of zeolite builder, and may be prepared by a granulation process in a high-speed mixer/granulator. Especially good powder properties may be obtained by use of a novel zeolite P as the builder; and especially good detergency may be obtained by use of selected nonionic surfactants.
- EP 265 203A discloses a surfactant blend mobile at a temperature within the range of from 20 to 80°C, comprising from 20 to 80 wt% of alkylbenzene sulphonate or alkyl sulphate, from 80 to 20 wt% of ethoxylated nonionic surfactant and from 0-10 wt% water.
- the surfactant blend may be sprayed on to an absorbent particulate solid material, for example, spray-dried polymer-modified Burkeite, to give free-flowing detergent powder containing up to about 25 wt% of surfactant.
- EP 436 240A (Unilever) discloses a similar mobile surfactant blend additionally containing a fatty acid soap. When sprayed onto an absorbent solid material, this blend gives powders having improved flow and dispensing properties.
- GB 1 462 134 (Procter & Gamble/Collins) discloses linear or predominantly linear ethoxylated primary alcohols of closely defined chain length, chain length distribution, ethylene oxide content, ethoxylation distribution and free alcohol content. These materials give improved oily soil detergency as compared with conventional commercially available materials.
- EP 133 715A (Union Carbide) discloses an alkoxylation product mixture having an especially highly peaked distribution of alkoxylation species, in which a single prevalent alkoxylation species constitutes 20 to 40 wt% and the amounts of species differing substantially from the prevalent species are strictly limited.
- EP 384 070A discloses the use as a detergency builder of zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP). This zeolite has been found to be a more effective and rapid binder of calcium ions than is conventional zeolite 4A.
- Example K of that application discloses a high bulk density powder consisting of 50 wt% zeolite 4A, 23.4 wt% sodium carbonate, and 26.6 wt% of the nonionic surfactant Synperonic A3 (synthetic C12 ⁇ 15 alcohol having an average degree of ethoxylation of 3); and
- Example 7 discloses a high bulk density powder consisting of 56.6 wt% zeolite MAP, 13.3 wt% sodium carbonate, and 30.1 wt% Synperonic A3. These compositions are specifically disclaimed in the present application.
- the present invention provides a particulate detergent composition having a bulk density of at least 650 g/l, preferably at least 700 g/l and advantageously at least 800 g/l, comprising:
- the particulate detergent composition of the invention is characterised by an especially high level of a high-performance organic surfactant system. At least 15 wt% of the composition is constituted by the surfactant, and as much as 50 wt% may be present. Compositions may advantageously contain at least 20 wt%, more advantageously at least 25 wt%, of the surfactant system.
- the surfactant system consists essentially of ethoxylated alcohol having a relatively low degree of ethoxylation, optionally with a minor proportion (not exceeding 40 wt% of the surfactant system) of primary alkyl sulphate.
- the proportion of primary alkyl sulphate preferably does not exceed 35 wt% (of the surfactant system), and more preferably does not exceed 30 wt% of the surfactant system.
- Preferred proportions of alkyl sulphate in the surfactant system are from 0.1 to 35 wt%, more preferably from 5 to 35 wt%, and advantageously from 10 to 30 wt%.
- surfactant systems in which the proportion of alkyl sulphate does not exceed 15 wt%, for example, from 0.1 to 15 wt%, preferably from 0.1 to 10 wt%.
- the ethoxylated alcohol nonionic surfactant The ethoxylated alcohol nonionic surfactant .
- the ethoxylated alcohol nonionic surfactant employed in the detergent compositions of the present invention has a relatively low degree of ethoxylation, not exceeding 6.5.
- the average degree of ethoxylation of the nonionic surfactant is preferably at least 4, but it may be lower, for example, from 3 to 4, when primary alkyl sulphate is present. Accordingly, when primary alkyl sulphate is present, the ethoxylated alcohol preferably has an average degree of ethoxylation within the range of from 3 to 6.5.
- the preferred range for the average degree of ethoxylation of the nonionic surfactant is within the range of from 4 to 6.5, more preferably from 4 to 6 and most preferably from 4 to 5.5.
- a mixture of differently ethoxylated materials may be used, provided that the overall degree of ethoxylation meets the stated requirements.
- the HLB value of the nonionic surfactant preferably does not exceed 11.0, and more preferably does not exceed 10.5. Desirably the HLB value is within the range of from 9.5 to 10.5.
- the chain length of the ethoxylated alcohol may generally range from C8 to C18, preferably from C12 to C16; an average chain length of C12 ⁇ 15 is preferred. Especially preferred is ethoxylated alcohol consisting wholly or predominantly of C12-C14 material.
- the ethoxylated alcohol is preferably primary, but secondary alcohol ethoxylates could in principle be used.
- the alcohol is preferably wholly or predominantly straight-chain. Suitable alcohols are vegetable-derived, for example, coconut, which is the most preferred material. Among the synthetic alcohols, Ziegler alcohols are preferred to oxo-based alcohols.
- the ethoxylated alcohol (which of course is always a mixture of species having different numbers of ethylene oxide units) is a "narrow range" material having a distribution of ethoxylated species that is more highly peaked about a single prevalent value than is the case in conventional commercial nonionic surfactants.
- the content of unethoxylated material is also generally lower, and may be reduced further by so-called "stripping".
- mixtures having an average alkoxylation number of at least 4, in which at least one alkoxylation species (the "prevalent species") constitutes about 20 to 40 wt% of the mixture; the proportion of species having 3 or more alkoxylation units above the mean is less than 12 wt%; and the species having 1 more and 1 less alkoxylation unit that the mean are each present in a weight ratio to the prevalent species of 0.6:1 to 1:1.
- Preferred product mixtures contain from 80 to 95 wt% of alkoxylation species having alkoxylation numbers within plus or minus 2 of the mean.
- narrow range as used in the present specification also covers materials that are not so highly peaked as to meet the requirements of the Union Carbide patent claims, but yet are substantially more peaked than, for example, the commercially available ICI "Synperonic” (Trade Mark) ethoxylated alcohols.
- ethoxylated alcohol product in which a single ethoxylation species constitutes 13 wt% or more, preferably 15 wt% or more, of the product.
- Conventional ethoxylates contain no more than about 10 wt% of any one ethoxylation species.
- the prevalent species preferably contains 4 or 5 ethoxylation units.
- Preferred "narrow range" ethoxylated alcohol used in the compositions of the invention may have any one or more of the following characteristics: at least 20 wt% of the ethoxylated alcohol may be constituted by a single ethoxylation species; at least one ethoxylation species (hereinafter the prevalent species) may constitute from 20 to 40 wt% of the ethoxylated alcohol, the proportion of species having 3 or more ethoxylation units above the mean being less than 12 wt%, and the species having 1 more and 1 less ethoxylation unit than the mean each being present in a weight ratio to the prevalent species of 0.6:1 to 1:1; from 80 to 95 wt% of the ethoxylated alcohol may be constituted by ethoxylation species having ethoxylation numbers within plus or minus 2 of the mean.
- GB 1 462 132 Procter & Gamble/ Collins
- these materials having an average degree of ethoxylation between 3.5 and 6.5, the amount of material having a degree of ethoxylation within the 2-7EO range being at least 63 wt%, and the amount of free alcohol not exceeding 5 wt%. These materials are also suitable for use in the compositions of the present invention.
- the following table shows the ethoxylation distribution of some commercially available coconut-based ethoxylates, both narrow-range (NRE7, NRE5 etc), and broad-range (E7, E3), the figures indicating the nominal average degree of ethoxylation in each case.
- NRE5, NRE4.6 and NRE4.2 are especially preferred, NRE4.2 being particularly favoured.
- nonionic surfactants described in the aforementioned GB 1 462 134 (Procter & Gamble/Collins) are such that at least 65 wt% of the material has a chain length within ⁇ 1 carbon atom of the mean value.
- the primary alcohol sulphate (PAS) that may optionally be present, constituting up to 40 wt% of the surfactant system, may have a chain length in the range of C8-C18, preferably C12-C16, with a mean value preferably in the C12 ⁇ 15 range. Especially preferred is PAS consisting wholly or predominantly of C12-C14 material.
- mixtures of different chain lengths may be used as described and claimed in EP 342 917A (Unilever).
- PAS of vegetable origin, and more especially PAS from coconut oil (cocoPAS) is especially preferred.
- cocoPAS PAS from coconut oil
- the PAS is present in the form of the sodium or potassium salt, the sodium salt generally being preferred.
- the amount of zeolite builder in the compositions of the invention may range from 20 to 60 wt%, usually from 25 to 55 wt% and suitably, in a heavy duty detergent composition, from 25 to 48 wt%.
- the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
- the use of zeolite 4A can give powders having satisfactory flow properties when 17 wt% of surfactant consisting of 30 wt% PAS and 70 wt% nonionic surfactant is present.
- the zeolite builder incorporated in the compositions of the invention is zeolite MAP as described and claimed in EP 384 070A (Unilever Case T3047).
- Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
- zeolite MAP having a silicon to aluminium ratio not exceeding 1.07.
- the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
- zeolite MAP has another advantage quite independent of its greater building efficacy: it enables more higher total surfactant levels, and more nonionic-rich surfactant systems, to be used without loss of powder flow properties.
- Preferred zeolite MAP for use in the present invention is especially finely divided and has a d50 (as defined below) within the range of from 0.1 to 5.0 microns, more preferably from 0.4 to 2.0 microns and most preferably from 0.4 to 1.0 microns.
- the quantity "d50” indicates that 50 wt% of the particles have a diameter smaller than that figure, and there are corresponding quantities "d80", "d90” etc.
- Especially preferred materials have a d90 below 3 microns as well as a d50 below 1 micron.
- compositions in accordance with the invention may contain sodium carbonate, to increase detergency and to ease processing.
- Sodium carbonate may generally be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%, and most suitably from 2 to 13 wt%.
- Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
- a powder structurant for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
- the preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%. As will be discussed below in the context of processing, this is preferably incorporated as the free acid and neutralised in situ.
- compositions of the invention are characterised by excellent flow properties, despite the high content of mobile high-performance organic surfactant.
- powder flow is defined in terms of the dynamic flow rate, 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 225 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.
- compositions and components of the present invention generally have dynamic flow rates of at least 90 ml/s, preferably at least 100 ml/s.
- Fully formulated laundry detergent compositions in accordance with the present invention may additionally contain any suitable ingredients normally encountered, for example, inorganic salts such as sodium silicate or sodium sulphate; organic salts such as sodium citrate; antiredeposition aids such as cellulose derivatives and acrylate or acrylate/maleate polymers; fluorescers; bleaches, bleach precursors and bleach stabilisers; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; fabric softening compounds.
- inorganic salts such as sodium silicate or sodium sulphate
- organic salts such as sodium citrate
- antiredeposition aids such as cellulose derivatives and acrylate or acrylate/maleate polymers
- fluorescers bleaches, bleach precursors and bleach stabilisers
- proteolytic and lipolytic enzymes dyes; coloured speckles; perfumes; foam controllers; fabric softening compounds.
- compositions of the invention may advantageously be prepared by granulating the zeolite and surfactants in a high-speed mixer/granulator.
- surfactant system includes PAS, that may be incorporated either in salt form (generally as an aqueous paste), or as the free acid (for neutralisation in situ).
- An especially preferred process includes the steps of:
- the surfactant system is simply an ethoxylated alcohol (mixture) which will already take the form of a homogeneous mobile liquid blend.
- the homogeneous mobile liquid blend may be prepared by mixing PAS paste with the nonionic surfactant.
- the nonionic may be admixed during the neutralisation of PAS acid by alkali, for example in a loop reactor, as described and claimed in EP 507 402A (Unilever) filed on 31 March 1992 and published on 7 October 1992.
- the high-speed mixer/granulator also known as a high-speed mixer/densifier, may be a batch machine such as the Fukae (Trade Mark) FS, or a continuous machine such as the Lödige (Trade Mark) Recycler CB30.
- the process allows the incorporation of high levels of surfactant without loss of powder flow properties, especially when the zeolite component of the composition is zeolite MAP and/or when soap is present as a structurant.
- soap is to be included as a structurant, this is preferably incorporated in the mobile surfactant blend, either as such, or as the corresponding fatty acid (together with a suitable amount of alkali) for neutralisation in situ.
- bleach ingredients (bleaches, bleach precursors and bleach stabilisers), proteolytic and lipolytic enzymes, coloured speckles, perfumes and foam control granules are most suitably admixed (postdosed) to the dense granular product after it has left the high-speed mixer/granulator.
- compositions of the invention may also be prepared by other processes, involving spray-drying or non-tower technology or combinations of the two.
- Detergent compositions were prepared to the following general formulation: parts % Surfactant system (see below) 17 20.11 Zeolite 4A 32 37.86 Polymer 4 4.73 Carbonate 14.5 17.16 Silicate 0.5 0.59 Metaborate 16.5 19.53 84.50 100.00
- the surfactant systems were made up as follows (wt%): Example CocoPAS E7(s) E3(s) NRE7(s) NRE3(s) 1 30 30 40 - - 2 30 - - 30 40 3 10 40 50 - - 4 10 - - 40 50
- Both mixtures of 30 parts of 7EO nonionic surfactant and 40 parts of 3EO nonionic surfactant had an average EO number of 4.7 and an HLB value of 10.1.
- the percentage of the predominant ethoxylation species (4EO) in the NRE mix was estimated to be 14 wt%.
- Example 1 and Example 3 shows how increasing the proportion of nonionic surfactant at the expense of PAS increases detergency: while comparison of the results for Examples 1 and 2, and for Examples 3 and 4, shows the detergency benefit obtained by changing to "narrow range" ethoxylated alcohol.
- the outstandingly good result for Example 4 shows the benefit of combining these two measures.
- a further detergency comparison was carried out, using test cloths carrying a number of different soils. This experiment was carried out using a Miele (Trade Mark) computer-controlled washing machine, using a product concentration of 5 g/l, and a 30-minute wash at 20°C in 26° (French) hard water.
- Miele Trade Mark
- compositions had the following general formulation: parts % Surfactant system (see below) 17.0 19.50 Zeolite 4A 30.5 35.00 Sodium carbonate 12.77 14.65 Sodium silicate 0.5 0.57 Sodium perborate monohydrate 16.25 18.65 TAED (83% granules) 7.25 8.32 EDTMP 0.37 0.42 Antifoam granules 2.50 2.87 87.14 100.00
- the surfactant systems were made up as follows (wt%): Example CocoPAS E7(s) E3(s) NRE7(s) NRE3(s) 5 30 30 40 - - 6 30 - - 30 40 7 10 - - 40 50
- compositions were as given in Example 1, and the surfactant systems consisted of 30 wt% cocoPAS, and 70 wt% ethoxylated alcohol.
- the ethoxylated alcohol component was made up
- Example 8 The procedure of Example 8 was repeated using a series of compositions having a more nonionic-rich surfactant system: 10 wt% cocoPAS and 90 wt% ethoxylated alcohol. The results are shown in the following Table. (i) (ii) (iii) EO (average) E7 + E3 NRE7 + NRE3 Single NRE 6.88 22.6 (E7) 5.96 34.3 (NRE7) 5.20 44.1 45.5 (NRE5) 5.17 35.3 4.94 35.5 51.5 (NRE4.6) 4.70 36.1 4.66 44.5 4.49 43.0 4.31 43.1 4.27 53.5 (NRE4.2) 3.75 44.1 3.01 35.4 (NRE3) 3.00 37.2 (E3)
- Detergent base powders of high bulk density consisting of the surfactant system, zeolite and (in some cases) sodium carbonate, were prepared by agglomeration in a Fukae FS100 batch high-speed mixer/granulator. These powders are not intended as fully formulated detergent compositions, but are readily converted to such compositions by admixture (postdosing) of other components such as bleach ingredients, enzymes, lather control granules and perfume.
- the surfactant system was as follows: 30 wt% cocoPAS 30 wt% E7(s) 40 wt% E3(s)
- compositions in parts by weight and percentages, are shown below.
- a 11 12 Surfactant 17 (38.64) 17 (31.48) 17 (40.48) Zeolite 4A 27 (61.36) 27 (50.00) - Zeolite MAP - - 25 (59.52) Carbonate - 10 (18.52) - 44 (100.00) 54 (100.00) 42 (100.00)
- a homogeneous liquid blend of the surfactants was prepared by neutralising PAS acid with sodium hydroxide solution in a loop reactor in the presence of the nonionic surfactants. Zeolite and (where present) sodium carbonate were dosed into the Fukae mixer, the liquid surfactant blend added and the mixture granulated. The granular product was then dried using a fluidised bed.
- Composition B produced a solid mass, while Compositions C, D and E initially produced free-flowing powders which, however, lost their flow on drying.
- compositions similar to those of Comparative Examples B to E were prepared, but this time fatty acid soap was present.
- a homogeneous mobile blend was prepared by mixing PAS in sodium salt form (70 wt%), fatty acid, sufficient sodium hydroxide solution to neutralise the fatty acid, and the nonionic surfactants. Ingredients were dosed into the Fukae mixer in the order zeolite, carbonate, surfactant blend, granulation/densification was carried out as in previous Examples, and the products were finally dried using a fluidised bed.
- Powders having excellent flow properties were obtained.
- Compositions 16 17 parts % parts % Surfactant 17 25.95 17 29.18 Zeolite 4A 32 48.85 32 54.94 Carbonate 14.5 22.14 7.25 12.45 Soap 2 3.05 2 3.43 65.5 100.00 58.25 100.00
- Powder properties 16 17 Bulk density (g/l) 918 872 DFR (ml/s) 122 143
- compositions similar to those of Examples 16 and 17 were prepared, by the same method, but using zeolite MAP instead of zeolite 4A.
- Compositions 18 19 parts % parts % Surfactant 17 25.95 17 29.18 Zeolite MAP 32 48.85 32 54.94 Carbonate 14.5 22.14 7.25 12.45 Soap 2 3.05 2 3.43 65.5 100.00 58.25 100.00
- Powder properties 18 19 Bulk density (g/l) 980 959 DFR (ml/s) 131 143
- Detergent base powders generally as described in Examples 11, 12 and A were prepared using a different surfactant system: 10 wt% cocoPAS 40 wt% E7(s) 50 wt% E3(s)
- the surfactant system was prepared as a homogeneous mobile blend by the method described in Examples 11, 12 and A, and the other process steps were also carried out as in those Examples.
- Compositions in parts by weight F 20 G 21 Surfactant 17 17 17 17 Zeolite 4A 27 27 - - Zeolite MAP - - 25 25 Carbonate - 25 - 15 44 69 42 57
- Compositions in percentages F 20 G 21 Surfactant 38.64 24.64 40.48 29.82 Zeolite 4A 61.36 39.13 - - Zeolite MAP - - 59.52 43.86 Carbonate - 36.23 - 26.32
- compositions similar to those of Examples 18 and 19 were prepared, but containing higher levels of zeolite. Compositions in parts by weight H 22 23 Surfactant 17 17 17 Zeolite 4A 32 32 - Zeolite MAP - - 32 Carbonate - 10 - 49 59 49 Compositions in percentages H 22 23 Surfactant 34.69 28.81 34.69 Zeolite 4A 65.31 54.24 - Zeolite MAP - - 65.31 Carbonate - 16.95 -
- Composition H would not give a granular product: 10 parts of sodium carbonate were required to produce a processable formulation. With zeolite MAP at this level, however, no carbonate was required despite the high percentage level of surfactant in this composition (Example 23).
- Formulations based on zeolite 4A, with and without soap, were prepared using the surfactant system of Examples 20 to 22.
- the fatty acid soap was incorporated by mixing fatty acid and an equivalent amount of sodium hydroxide solution into the surfactant blend (prepared as described in Example 11) before addition of the blend to the Fukae mixer.
- J K 24 Compositions in Part by weight Surfactant 17 17 17 Zeolite 4A 32 32 32 Carbonate 14.5 14.5 14.5 Soap - 2 4 63.5 65.5 67.5
- Compositions in percentages Surfactant 26.77 25.95 25.19 Zeolite 4A 50.39 48.85 47.41 Carbonate 22.83 22.14 21.48 Soap - 3.05 5.93
- Composition J gave a non-flowing product both before and after drying, while Composition K initially gave a good product but lost its flow on drying.
- a larger amount of soap (Example 24) gave an excellent powder having a bulk density of 920 g/l and a dynamic flow rate of 109 ml/s.
- compositions similar to those of Examples 24 and J but containing zeolite MAP and a higher level of surfactant were prepared.
- Compositions 25 26 parts % parts % Surfactant 20.5 30.60 20.5 29.71 Zeolite MAP 32 47.76 32 46.37 Carbonate 14.5 21.64 14.5 21.01 Soap - - 2 2.90 67.0 69.0
- Powder properties 25 26 Bulk sensity (g/l) 928 898 DFR (ml/s) 115 114
- compositions similar to those of Examples J and K were prepared using a different surfactant system: 40 wt% E7(s) 60 wt% E3(s) Compositions L 27 parts % parts % Surfactant 17 26.77 17 25.95 Zeolite 4A 32 50.39 32 48.85 Carbonate 14.5 22.83 14.5 22.14 Soap - - 2 3.05 63.5 65.5
- Composition L initially gave a good product but lost its flow on drying.
- Inclusion of soap (Example 27) gave an excellent powder having a bulk density of 801 g/l and a dynamic flow rate of 139 ml/s.
- Examples L and 27 were repeated using zeolite MAP instead of zeolite 4A.
- Compositions 28 29 parts % parts % Surfactant 17 26.77 17 25.95 Zeolite MAP 32 50.39 32 48.85 Carbonate 14.5 22.83 14.5 22.14 Soap - - 2 3.05 63.5 65.5 Powder properties 28 29 Bulk density (g/l) 850 810 DFR (ml/s) 145 131
- Example 24 A composition similar to that of Example 24 but containing a different nonionic surfactant, NRE5, was prepared. All solid components had a particle size lower than 200 microns.
- the method of preparation was substantially as described in Example 11.
- the mean residence time of the granular detergent composition in the batch high-speed mixer/granulator was approximately 3 minutes.
- Composition % Surfactant PAS 8.3 NRE5 19.5 Zeolite 4A 43.7 Carbonate 16.2 Water 12.3 100.00
- the granular detergent composition obtained had a bulk density of about 770 g/l and a dynamic flow rate of 101 ml/s.
- Granular detergent compositions similar to that of Example 30 were prepared using a continuous high-speed mixer/granulator, the Lödige (Trade Mark) Recycler CB30.
- the liquid surfactant mix included fatty acid in combination with a stoichiometric amount of sodium hydroxide, which during the course of the mixing and densifying process formed soap.
- the rotational speed was 1600 rpm and the mean residence time of the granular mixture in the Recycler was approximately 10 seconds.
- compositions of the granular materials leaving the Recycler were as follows. 31 32 Surfactant: PAS 8.5 8.3 NRE5 19.4 18.8 Zeolite 4A 52.6 47.1 Carbonate - 8.0 Soap 2.9 2.9 Water 16.4 14.9 100.0 100.0
- Bulk densities were about 700 g/l, particle sizes 500-600 microns, and powder properties were good.
- Comparative Composition M is a high-performance concentrated powder based on a different surfactant system (LAS with nonionic surfactants) similar to that used in premium powders presently on sale in Europe.
- the total amount of (non-soap) surfactant in each formulation was 17 wt%.
- Composition M was prepared as follows. Zeolite and carbonate (including an additional amount for neutralisation of LAS acid) were dosed into the Fukae mixer, followed by LAS acid, then a homogeneous surfactant blend (nonionic surfactant), fatty acid and an equivalent amount of sodium hydroxide solution). After granulation, the powder was dried using a fluidised bed, and the remaining ingredients postdosed.
- Compositions 33 and 34 were prepared as follows. Homogeneous surfactant blends were prepared by mixing PAS paste (70%), nonionic surfactant, fatty acid and an equivalent amount of sodium hydroxide solution. Zeolite and carbonate were dosed into the Fukae, followed by the surfactant blend. After granulation, the powders were dried using a fluidised bed, and the remaining ingredients postdosed.
- Composition 35 was prepared similarly except that no carbonate was present during granulation. Powder properties M 33 34 35 Bulk density 861 826 841 841 DFR 89 111 120 128
- Detergency was assessed in a Miele washing machine, in the presence of a soiled load, using a product concentration of 5 g/l, 26° (French) hard water, and a wash temperature of 30°C.
- the measure of detergency was the change in reflectance (460 nm) of a polyester test cloth soiled with kaolin and sebum (WFK 30D). Delta R460 16.2 15.0 15.7 17.2
- compositions may be formulated containing the narrow-range coconut nonionic surfactants NRE7 and NRE3, instead of the broad range materials E7 and E3, in the same proportions; or instead using one of the single materials NRE5, NRE4.6 or NRE4.2.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB919125035A GB9125035D0 (en) | 1991-11-26 | 1991-11-26 | Detergent compositions and process for preparing them |
GB9125035 | 1991-11-26 | ||
GB9201059 | 1992-01-17 | ||
GB929201059A GB9201059D0 (en) | 1991-11-26 | 1992-01-17 | Detergent compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0544492A1 true EP0544492A1 (de) | 1993-06-02 |
EP0544492B1 EP0544492B1 (de) | 1998-05-27 |
Family
ID=26299920
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92310721A Revoked EP0544492B1 (de) | 1991-11-26 | 1992-11-24 | Teilchenförmige Waschmittelzusammensetzungen |
Country Status (19)
Country | Link |
---|---|
EP (1) | EP0544492B1 (de) |
JP (1) | JPH0739599B2 (de) |
CN (1) | CN1035066C (de) |
AT (1) | ATE166667T1 (de) |
AU (1) | AU647681B2 (de) |
BR (1) | BR9204572A (de) |
CA (1) | CA2083331C (de) |
CZ (1) | CZ284628B6 (de) |
DE (1) | DE69225679T2 (de) |
ES (1) | ES2117969T3 (de) |
HK (1) | HK1014263A1 (de) |
HU (2) | HU216145B (de) |
IN (1) | IN177823B (de) |
MX (1) | MX9206809A (de) |
MY (1) | MY109102A (de) |
NO (1) | NO302621B1 (de) |
NZ (1) | NZ245202A (de) |
PL (1) | PL296731A1 (de) |
SK (1) | SK281376B6 (de) |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994005757A1 (en) * | 1992-09-09 | 1994-03-17 | Unilever Plc | Improvements to hard surface cleaners |
WO1994013632A1 (en) * | 1992-12-15 | 1994-06-23 | Shell Internationale Research Maatschappij B.V. | Secondary alkyl sulphate/zeolite-containing surfactant composition |
FR2707662A1 (fr) * | 1993-07-13 | 1995-01-20 | Colgate Palmolive Co | Procédé de préparation d'une composition détergente ayant une densité apparente élevée. |
EP0643130A1 (de) * | 1993-09-13 | 1995-03-15 | The Procter & Gamble Company | Granulare Waschmittelzusammensetzungen mit nichtionischem Tensid und Verfahren zu ihrer Herstellung |
WO1995008616A1 (de) * | 1993-09-23 | 1995-03-30 | Henkel Kommanditgesellschaft Auf Aktien | Detergensgemische und wasch- oder reinigungsmittel mit verbesserten löseeigenschaften |
US5409627A (en) * | 1993-03-18 | 1995-04-25 | Lever Brothers Company, Division Of Conopco, Inc. | Particulate bleaching detergent compositions containing zeolite map and a stable bleach catalyst |
WO1995014766A1 (en) * | 1993-11-24 | 1995-06-01 | Unilever Plc | Detergent compositions and process for preparing them |
GB2287948A (en) * | 1994-03-31 | 1995-10-04 | Procter & Gamble | Laundry detergent composition |
US5498342A (en) * | 1992-12-08 | 1996-03-12 | Lever Brothers Company | Detergent composition containing zeolite map and organic peroxyacid |
WO1996009370A1 (en) * | 1994-09-20 | 1996-03-28 | The Procter & Gamble Company | Process for making a high density detergent composition which includes selected recycle streams |
WO1996009369A1 (en) * | 1994-09-20 | 1996-03-28 | The Procter & Gamble Company | Process for making a high density detergent composition in a single mixer/densifier with selected recycle streams |
WO1996010071A1 (en) * | 1994-09-29 | 1996-04-04 | Unilever Plc | High active granular detergent compositions and process for making them |
WO1996021717A1 (en) * | 1995-01-14 | 1996-07-18 | The Procter & Gamble Company | Detergent composition comprising zeolite and amylase enzyme |
GB2297977A (en) * | 1995-02-07 | 1996-08-21 | Procter & Gamble | Detergent composition containing Zeolite MAP |
US5583098A (en) * | 1993-11-24 | 1996-12-10 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions |
WO1997012026A1 (en) * | 1995-09-26 | 1997-04-03 | The Procter & Gamble Company | Detergent composition comprising zeolite and proteolytic enzyme |
WO1997012023A1 (en) * | 1995-09-26 | 1997-04-03 | The Procter & Gamble Company | Detergent composition |
EP0802957A1 (de) * | 1995-01-12 | 1997-10-29 | The Procter & Gamble Company | Waschmittelzubereitung |
US5698510A (en) * | 1993-09-13 | 1997-12-16 | The Procter & Gamble Company | Process for making granular detergent compositions comprising nonionic surfactant |
US5998357A (en) * | 1995-09-04 | 1999-12-07 | Lever Brothers Company | Non-sray-drying process for preparing detergent compositions |
EP0639639B1 (de) * | 1993-08-17 | 1999-12-15 | The Procter & Gamble Company | Percarbonat-Bleichmittel enthaltende Waschmittelzusammensetzungen |
WO2000077140A1 (en) * | 1999-06-10 | 2000-12-21 | Unilever Plc | Granular detergent component containing zeolite map |
US6391846B1 (en) | 1999-06-10 | 2002-05-21 | Unilever Home & Personal Care, Usa. Division Of Conopco, Inc. | Particulate detergent composition containing zeolite |
US6440922B1 (en) | 1995-01-14 | 2002-08-27 | The Procter & Gamble Company | Detergent composition comprising zeolite and amylase enzyme |
EP0700428B2 (de) † | 1993-05-26 | 2006-07-05 | Unilever Plc | Waschmittelzusammensetzungen |
DE19529298C5 (de) * | 1994-08-12 | 2011-04-07 | Kao Corp. | Verfahren zur Herstellung eines nichtionischen Wasch-(Reinigungs-)mittel-Granulats |
EP3978589A1 (de) * | 2020-10-01 | 2022-04-06 | The Procter & Gamble Company | Alkoholalkoxylate mit schmalem bereich und derivate davon |
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US4406808A (en) * | 1977-10-06 | 1983-09-27 | Colgate-Palmolive Company | High bulk density carbonate-zeolite built heavy duty nonionic laundry detergent |
EP0200953A2 (de) * | 1985-04-20 | 1986-11-12 | Henkel Kommanditgesellschaft auf Aktien | Körniges Waschmittel mit verbessertem Reinigungsvermögen |
EP0337330A2 (de) * | 1988-04-15 | 1989-10-18 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Erhöhung der Dichte sprühgetrockneter, phosphatreduzierter Waschmittel |
EP0364881A2 (de) * | 1988-10-21 | 1990-04-25 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Herstellung von tensidhaltigen Granulaten |
EP0439316A2 (de) * | 1990-01-22 | 1991-07-31 | Unilever Plc | Detergentzusammensetzung |
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AU647736B2 (en) * | 1989-04-24 | 1994-03-31 | Unilever Plc | Detergent compositions |
GB9008013D0 (en) * | 1990-04-09 | 1990-06-06 | Unilever Plc | High bulk density granular detergent compositions and process for preparing them |
GB9007999D0 (en) * | 1990-04-09 | 1990-06-06 | Unilever Plc | Particulate bleaching detergent composition |
-
1992
- 1992-11-19 CA CA002083331A patent/CA2083331C/en not_active Expired - Fee Related
- 1992-11-20 NZ NZ245202A patent/NZ245202A/en not_active IP Right Cessation
- 1992-11-20 AU AU28546/92A patent/AU647681B2/en not_active Ceased
- 1992-11-24 DE DE69225679T patent/DE69225679T2/de not_active Revoked
- 1992-11-24 MY MYPI92002139A patent/MY109102A/en unknown
- 1992-11-24 AT AT92310721T patent/ATE166667T1/de not_active IP Right Cessation
- 1992-11-24 ES ES92310721T patent/ES2117969T3/es not_active Expired - Lifetime
- 1992-11-24 EP EP92310721A patent/EP0544492B1/de not_active Revoked
- 1992-11-25 CN CN92114552.7A patent/CN1035066C/zh not_active Expired - Fee Related
- 1992-11-25 NO NO924557A patent/NO302621B1/no not_active IP Right Cessation
- 1992-11-25 PL PL29673192A patent/PL296731A1/xx unknown
- 1992-11-25 HU HUP9203707A patent/HU216145B/hu not_active IP Right Cessation
- 1992-11-25 HU HU9203707A patent/HU9203707D0/hu unknown
- 1992-11-26 MX MX9206809A patent/MX9206809A/es not_active IP Right Cessation
- 1992-11-26 JP JP4339664A patent/JPH0739599B2/ja not_active Expired - Fee Related
- 1992-11-26 SK SK3495-92A patent/SK281376B6/sk not_active IP Right Cessation
- 1992-11-26 CZ CS923495A patent/CZ284628B6/cs not_active IP Right Cessation
- 1992-11-26 BR BR9204572A patent/BR9204572A/pt not_active IP Right Cessation
- 1992-11-26 IN IN375BO1992 patent/IN177823B/en unknown
-
1998
- 1998-12-24 HK HK98115579A patent/HK1014263A1/xx not_active IP Right Cessation
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US4406808A (en) * | 1977-10-06 | 1983-09-27 | Colgate-Palmolive Company | High bulk density carbonate-zeolite built heavy duty nonionic laundry detergent |
EP0200953A2 (de) * | 1985-04-20 | 1986-11-12 | Henkel Kommanditgesellschaft auf Aktien | Körniges Waschmittel mit verbessertem Reinigungsvermögen |
EP0337330A2 (de) * | 1988-04-15 | 1989-10-18 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Erhöhung der Dichte sprühgetrockneter, phosphatreduzierter Waschmittel |
EP0364881A2 (de) * | 1988-10-21 | 1990-04-25 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Herstellung von tensidhaltigen Granulaten |
EP0439316A2 (de) * | 1990-01-22 | 1991-07-31 | Unilever Plc | Detergentzusammensetzung |
Cited By (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994005757A1 (en) * | 1992-09-09 | 1994-03-17 | Unilever Plc | Improvements to hard surface cleaners |
EP0829530A1 (de) * | 1992-09-09 | 1998-03-18 | Unilever Plc | Verbesserung von Reinigern für harte Oberflächen |
US5498342A (en) * | 1992-12-08 | 1996-03-12 | Lever Brothers Company | Detergent composition containing zeolite map and organic peroxyacid |
WO1994013632A1 (en) * | 1992-12-15 | 1994-06-23 | Shell Internationale Research Maatschappij B.V. | Secondary alkyl sulphate/zeolite-containing surfactant composition |
US5409627A (en) * | 1993-03-18 | 1995-04-25 | Lever Brothers Company, Division Of Conopco, Inc. | Particulate bleaching detergent compositions containing zeolite map and a stable bleach catalyst |
EP0700428B2 (de) † | 1993-05-26 | 2006-07-05 | Unilever Plc | Waschmittelzusammensetzungen |
FR2707662A1 (fr) * | 1993-07-13 | 1995-01-20 | Colgate Palmolive Co | Procédé de préparation d'une composition détergente ayant une densité apparente élevée. |
EP0639639B1 (de) * | 1993-08-17 | 1999-12-15 | The Procter & Gamble Company | Percarbonat-Bleichmittel enthaltende Waschmittelzusammensetzungen |
EP0643130A1 (de) * | 1993-09-13 | 1995-03-15 | The Procter & Gamble Company | Granulare Waschmittelzusammensetzungen mit nichtionischem Tensid und Verfahren zu ihrer Herstellung |
WO1995007968A1 (en) * | 1993-09-13 | 1995-03-23 | The Procter & Gamble Company | Granular detergent compositions comprising nonionic surfactant and process for making such compositions |
US5698510A (en) * | 1993-09-13 | 1997-12-16 | The Procter & Gamble Company | Process for making granular detergent compositions comprising nonionic surfactant |
US5668100A (en) * | 1993-09-23 | 1997-09-16 | Henkel Kommanditgesellschaft Auf Aktien | Detergent mixtures and detergents or cleaning formulations with improved dissolving properties |
WO1995008616A1 (de) * | 1993-09-23 | 1995-03-30 | Henkel Kommanditgesellschaft Auf Aktien | Detergensgemische und wasch- oder reinigungsmittel mit verbesserten löseeigenschaften |
US5723428A (en) * | 1993-11-24 | 1998-03-03 | Lever Brothers Company | Detergent compositions and process for preparing them |
US5583098A (en) * | 1993-11-24 | 1996-12-10 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions |
WO1995014766A1 (en) * | 1993-11-24 | 1995-06-01 | Unilever Plc | Detergent compositions and process for preparing them |
AU699010B2 (en) * | 1993-11-24 | 1998-11-19 | Unilever Plc | Detergent compositions and process for preparing them |
GB2287948B (en) * | 1994-03-31 | 1998-04-08 | Procter & Gamble | Detergent composition |
GB2287948A (en) * | 1994-03-31 | 1995-10-04 | Procter & Gamble | Laundry detergent composition |
DE19529298C5 (de) * | 1994-08-12 | 2011-04-07 | Kao Corp. | Verfahren zur Herstellung eines nichtionischen Wasch-(Reinigungs-)mittel-Granulats |
WO1996009369A1 (en) * | 1994-09-20 | 1996-03-28 | The Procter & Gamble Company | Process for making a high density detergent composition in a single mixer/densifier with selected recycle streams |
WO1996009370A1 (en) * | 1994-09-20 | 1996-03-28 | The Procter & Gamble Company | Process for making a high density detergent composition which includes selected recycle streams |
WO1996010071A1 (en) * | 1994-09-29 | 1996-04-04 | Unilever Plc | High active granular detergent compositions and process for making them |
AU701791B2 (en) * | 1994-09-29 | 1999-02-04 | Unilever Plc | High active granular detergent compositions and process for making them |
EP0802957A1 (de) * | 1995-01-12 | 1997-10-29 | The Procter & Gamble Company | Waschmittelzubereitung |
EP0802957A4 (de) * | 1995-01-12 | 1999-11-24 | Procter & Gamble | Waschmittelzubereitung |
WO1996021717A1 (en) * | 1995-01-14 | 1996-07-18 | The Procter & Gamble Company | Detergent composition comprising zeolite and amylase enzyme |
US6440922B1 (en) | 1995-01-14 | 2002-08-27 | The Procter & Gamble Company | Detergent composition comprising zeolite and amylase enzyme |
GB2297977A (en) * | 1995-02-07 | 1996-08-21 | Procter & Gamble | Detergent composition containing Zeolite MAP |
US6025320A (en) * | 1995-09-04 | 2000-02-15 | Lever Brothers Company | Detergent compositions and process for preparing them |
US5998357A (en) * | 1995-09-04 | 1999-12-07 | Lever Brothers Company | Non-sray-drying process for preparing detergent compositions |
WO1997012026A1 (en) * | 1995-09-26 | 1997-04-03 | The Procter & Gamble Company | Detergent composition comprising zeolite and proteolytic enzyme |
WO1997012023A1 (en) * | 1995-09-26 | 1997-04-03 | The Procter & Gamble Company | Detergent composition |
WO2000077140A1 (en) * | 1999-06-10 | 2000-12-21 | Unilever Plc | Granular detergent component containing zeolite map |
US6391846B1 (en) | 1999-06-10 | 2002-05-21 | Unilever Home & Personal Care, Usa. Division Of Conopco, Inc. | Particulate detergent composition containing zeolite |
US6455490B1 (en) | 1999-06-10 | 2002-09-24 | Unilever Home & Personal Care Usa Division Of Conopco, In.C | Granular detergent component containing zeolite map and laundry detergent compositions |
EP3978589A1 (de) * | 2020-10-01 | 2022-04-06 | The Procter & Gamble Company | Alkoholalkoxylate mit schmalem bereich und derivate davon |
WO2022072587A1 (en) * | 2020-10-01 | 2022-04-07 | The Procter & Gamble Company | Narrow range alcohol alkoxylates and derivatives thereof |
US11795131B2 (en) | 2020-10-01 | 2023-10-24 | The Procter & Gamble Company | Narrow range alcohol alkoxylates and derivatives thereof |
Also Published As
Publication number | Publication date |
---|---|
ES2117969T3 (es) | 1998-09-01 |
NO924557L (no) | 1993-05-27 |
NO302621B1 (no) | 1998-03-30 |
HUT63452A (en) | 1993-08-30 |
CN1035066C (zh) | 1997-06-04 |
CN1073713A (zh) | 1993-06-30 |
IN177823B (de) | 1997-02-22 |
CA2083331A1 (en) | 1993-05-27 |
HU216145B (hu) | 1999-04-28 |
SK281376B6 (sk) | 2001-03-12 |
JPH06100899A (ja) | 1994-04-12 |
EP0544492B1 (de) | 1998-05-27 |
CA2083331C (en) | 1998-08-11 |
PL296731A1 (en) | 1993-08-09 |
AU647681B2 (en) | 1994-03-24 |
NO924557D0 (no) | 1992-11-25 |
AU2854692A (en) | 1993-06-17 |
MX9206809A (es) | 1993-07-01 |
BR9204572A (pt) | 1993-06-01 |
SK349592A3 (en) | 1994-08-10 |
NZ245202A (en) | 1994-12-22 |
HU9203707D0 (en) | 1993-03-29 |
JPH0739599B2 (ja) | 1995-05-01 |
CZ284628B6 (cs) | 1999-01-13 |
DE69225679D1 (de) | 1998-07-02 |
HK1014263A1 (en) | 1999-09-24 |
MY109102A (en) | 1996-12-31 |
ATE166667T1 (de) | 1998-06-15 |
DE69225679T2 (de) | 1998-09-17 |
CZ349592A3 (en) | 1993-08-11 |
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