EP0351937B1 - Compositions détergentes et procédé pour leur préparation - Google Patents

Compositions détergentes et procédé pour leur préparation Download PDF

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Publication number
EP0351937B1
EP0351937B1 EP89304210A EP89304210A EP0351937B1 EP 0351937 B1 EP0351937 B1 EP 0351937B1 EP 89304210 A EP89304210 A EP 89304210A EP 89304210 A EP89304210 A EP 89304210A EP 0351937 B1 EP0351937 B1 EP 0351937B1
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EP
European Patent Office
Prior art keywords
sodium
starting material
detergent
granulation
particulate starting
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EP89304210A
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German (de)
English (en)
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EP0351937A1 (fr
EP0351937B2 (fr
Inventor
Michael William Hollingsworth
Donald Peter
Timothy John Price
Peter John Russell
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • 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
    • C11D17/06—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
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates

Definitions

  • the present invention relates to granular detergent compositions of high bulk density having good washing performance and good powder properties, and a process for preparing them.
  • EP 219 328A discloses a granular low-phosphate detergent composition prepared by spray-drying a slurry to give a base powder containing a low to moderate level of sodium tripolyphosphate builder and low levels of inorganic salts, and then postdosing solid material including sodium sulphate of high bulk density and of smaller particle size than the base powder, thus filling the voids between base powder particles and producing a product of high bulk density.
  • JP 61 069897A discloses a process in which a spray-dried detergent powder containing a high level of anionic surfactant and a low level of builder (zeolite) is subjected successively to pulverising and granulating treatments in a high-speed mixer/granulator, the granulation being carried out in the presence of an "agent for improving surface properties" having an average particle size up to 10 ⁇ rn and optionally a binder. It would appear that in the high-speed mixer/granulator, the spray-dried powder is initially broken down to a fine state of division; the surface-improving agent and optional binder are then added and the pulverised material granulated to form a final product of high bulk density.
  • the surface-improving agent which is a finely divided particulate solid such as fine sodium aluminosilicate, is apparently required in order to prevent the composition from forming into large balls or cakes.
  • EP 229 671A discloses postdosing a crystalline alkaline inorganic salt, for example, sodium carbonate, to a spray-dried base powder prepared as in the above-mentioned JP 61 069897A (Kao) and containing a restricted level of water-soluble crystalline inorganic salts, to produce a high bulk density product.
  • a crystalline alkaline inorganic salt for example, sodium carbonate
  • GB 1 517 713 discloses a process in which spray-dried or granulated detergent powders containing sodium tripolyphosphate and sodium sulphate are densified and spheronised in a "marumerizer" (Trade Mark).
  • EP 220 024A (Procter & Gamble) discloses a process in which a spray-dried detergent powder containing a high level (30-85 wt%) of anionic surfactant is mixed with an inorganic builder (sodium tripolyphosphate, or sodium aluminosilicate and sodium carbonate) and compacted under high pressure using a roll compactor ("chilsonator"); the compacted material, after removal of oversize material and fines, is then granulated using conventional apparatus, for example, a fluidised bed, tumble mixer, or rotating drum or pan.
  • an inorganic builder sodium tripolyphosphate, or sodium aluminosilicate and sodium carbonate
  • EP 158 419A discloses the preparation of a detergent powder by mixing a major proportion of soda ash (preferably 70 to 85 wt% of the mixture) and a minor proportion of surfactant (wholly or predominantly nonionic) in a high-speed mixer/granulator.
  • the present invention provides a process for the preparation of a granular detergent composition or component having a bulk density of at least 650 g/litre, which comprises the step of treating a particulate starting material comprising:
  • the invention is concerned with a process for the preparation of a detergent powder combining high bulk density, good powder properties and excellent washing and cleaning performance.
  • a detergent base powder prepared by any suitable method and containing substantial levels of water-soluble crystalline inorganic salts may be processed in a high-speed mixer/granulator, without the need for the use of an "agent for improving surface properties" during the granulation step as prescribed by JP 61 069897A (Kao), to give a dense granulate having good flow properties, even if relatively high levels of anionic surfactant are present.
  • the product is characterised by an especially narrow particle size distribution, and in particular by a very small proportion or oversize material, giving good and rapid cold water dispersability and low insolubles.
  • a preferred starting powder has a ratio of total water-soluble crystalline inorganic salts (b) to total non-soap surfactant (a) within the range of from 0.4:1 to 9:1, more preferably from 0.4:1 to 5:1.
  • An especially preferred range for the ratio of (b) to (a) is from 1:1 to 5:1.
  • the starting powder contains a total of from 15 to 70 wt% of water-soluble crystalline inorganic salts.
  • examples of such salts include sodium sulphate, sodium ortho- and pyrophosphates, and crystalline sodium silicates, that is to say, sodium silicates having a ratio (Si0 2 to Na 2 0) 1, such as sodium orthosilicate and sodium metasilicate.
  • the alkaline and neutral silicates of higher ratio commonly used in detergent compositions are not to be regarded as crystalline.
  • the starting powder contains from 15 to 50 wt%, more preferably from 20 to 40 wt%, of sodium tripolyphosphate.
  • the non-soap surfactant present in the starting powder preferably consists at least partially of anionic surfactant.
  • anionic surfactants will be well known to those skilled in the art, and include linear alkylbenzene sulphonates, particularly sodium linear alkylbenzenesulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkyl sulphates, particularly sodium C 12 -Cl5 primary alcohol sulphates; alkyl ether sulphates; alpha-olefin and internal olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; fatty acid ester sulphonates; and combinations thereof.
  • the starting powder may contain nonionic surfactant.
  • Nonionic surfactants too will be well known to those skilled in the art, and include primary and secondary alcohol ethoxylates, especially the C 12 -C15 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
  • the surfactant component of the starting powder may be constituted by from 0 to 70%, preferably from 8 to 60 wt%, of anionic surfactant, and from 0 to 20%, preferably from 0 to 10%, by weight of nonionic surfactant.
  • non-soap surfactant for example, cationic, zwitterionic, amphoteric or semipolar surfactants, may also be present if desired.
  • suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • soap may also be present, to provide foam control and additional detergency and builder power; soap is not included in the 12 to 70% figure for the surfactant content quoted previously.
  • the starting powder may be prepared by any suitable tower or non-tower method, for example, spray-drying or dry mixing.
  • the invention is especially useful for the densification of a spray-dried powder.
  • the water-soluble crystalline inorganic salt to be included in the final product may be admixed to the remainder of the starting powder in the high-speed mixer/granulator itself.
  • the percentages and ratios specified above should be based on the total material introduced into the high-speed mixer/granulator, including the added salt.
  • a starting powder prepared for example by spray-drying, containing less than the amount of water-soluble crystalline inorganic salt specified above, and then to admix with that powder, in the high-speed mixer/granulator, sufficient water-soluble crystalline inorganic salt to bring the salt percentage (b) and the ratio (b) to (a) up to the specified level.
  • any component other than a finely divided particulate solid having a particle size up to 10 ⁇ rn may be added to the high-speed mixer/granulator prior to granulation.
  • One procedure according to the invention includes the step of admixing at least one inorganic or organic salt having a particle size of at least 100 /1.m with the remainder of the starting powder in the high-speed mixer/granulator. If the salt is water-soluble, inorganic and crystalline, it should be included within the percentages and ratios specified above which relate to the total amount of such salts in the material subjected to granulation in the high-speed mixer/granulator.
  • Salts that may conveniently be incorporated by this method include borax, sodium bicarbonate, sodium silicate, sodium tripolyphosphate, sodium carbonate, sodium perborate, sodium percarbonate, sodium citrate, sodium nitrilotriacetate, sodium succinate, sodium sulphate and combinations of these.
  • borax and sodium bicarbonate are buffers giving mild products of low in-wash pH.
  • granulation is effected by means of a high-speed mixer/granulator having both a stirring action and a cutting action.
  • the stirrer and the cutter may be operated independently of one another, and at separately variable speeds.
  • Such a mixer is capable of combining a high energy stirring input with a cutting action, but can also be used to provide other, gentler stirring regimes with or without the cutter in operation. It is thus a highly versatile and flexible piece of apparatus.
  • a preferred type of high-speed mixer/granulator for use in the process of the invention is bowl-shaped and preferably has a substantially vertical stirrer axis.
  • mixers of the Fukae (Trade Mark) FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
  • the stirrer and cutter may be operated independently of one another, and at separately variable speeds.
  • Another mixer found to be suitable for use in the process of the invention is the Lodige (Trade Mark) FM series batch mixer ex Morton Machine Co. Ltd., Scotland. This differs from the mixers mentioned above in that its stirrer has a horizontal axis.
  • the use of a high-speed mixer/granulator is essential in the process of the invention to effect granulation and densification.
  • the mixer may also be used for a pretreatment step before granulation is carried out.
  • one or more further ingredients to be admixed with an otherwise premixed powder prepared elsewhere (for example, by spray-drying).
  • a suitable stirring/cutting regime and residence time may be chosen in accordance with the materials to be mixed.
  • pulverisation Another possible pretreatment that may be carried out in the high-speed mixer/granulator is pulverisation; whether or not this is necessary depends, among other things, on the method of preparation of the starting powder and its free moisture content. Powders prepared by spray-drying, for example, are more likely to require pulverisation than powders prepared by dry-mixing. Again, the flexibility of the apparatus allows a suitable stirring/cutting regime to be chosen: generally relatively high speeds for both stirrer and cutter. A relatively short residence time (for example, 2-4 minutes for a 35 kg batch) is generally sufficient.
  • the essential feature of the process of the invention is the granulation step, during which densification to the very high values of at least 650 g/litre, preferably at least 700 g/litre occurs, giving a dense, granular product of very uniform particle size and generally spherical particle shape.
  • Granulation is effected by running the mixer at a relatively high speed using both stirrer and cutter; a relatively short residence time (for example, 5-8 minutes for a 35 kg batch) is generally sufficient.
  • the final bulk density can be controlled by choice of residence time, and it has been found that the powder properties of the resulting granulate are not optimum unless the bulk density has been allowed to rise to at least 650 g/litre.
  • binder preferably water
  • binder may be added before or during granulation, but some starting powders will inherently contain sufficient moisture.
  • a liquid binder it may be sprayed in while the mixer is running. In one preferred mode of operation, the mixer is first operated at a relatively slow speed while binder is added, before increasing the speed of the mixer to effect granulation.
  • pulverisation if required
  • granulation need not be regarded as separate process steps but as one single operation. Indeed, it is not, in that case, necessary to decide in advance whether or not pulverisation is required: the mixer may simply be allowed to do what is necessary, since the mixer conditions required are generally substantially the same for pulverisation and for granulation.
  • granulation is carried out at a controlled temperature somewhat above ambient, preferably above 30 °C.
  • the optimum temperature is apparently formulation-dependent, but appears generally to lie within the range of from 30 to 45 ° C, preferably about 35 ° C.
  • a finely divided particulate flow aid may be admixed with the granular material after granulation is complete.
  • flow aid is added while the granulate is still in the high-speed mixer/granulator, and the mixer is operated at a slow speed for a further short period. No further granulation occurs at this stage. It is also within the scope of the invention to add the flow aid to the granulate after removing the latter to different apparatus.
  • This embodiment of the invention should be distinguished from the prior art process of JP 61 069897A (Kao), mentioned above, in which an "agent for improving surface properties", which can be fine sodium aluminosilicate, is present during the granulation stage itself. It is within the scope of the present invention to add a particulate flow aid after granulation is complete, but, as explained above, it is essential to the invention that no finely divided particulate "agent for improving surface properties" be present during granulation. The addition of a flow aid after granulation is complete can have an additional beneficial effect on the properties of the granulate, regardless of the formulation, whereas the presence of this type of material during the granulation step in the process of the invention makes processing more difficult.
  • the preferred granulation temperature of from 30 to 45 ° C, preferably about 35 ° C, may also be maintained during the subsequent admixture of a flow aid.
  • the flow aid is a finely divided particulate material.
  • the preferred average particle size is 0.1 to 20 /1.m, more preferably 1 to 10 /1.m.
  • the flow aid is finely divided amorphous sodium aluminosilicate, as described and claimed in our copending application of even date, now EP-A-339996.
  • a suitable material is available commercially from Crosfield Chemicals Ltd, Warrington, Cheshire, England, under the trade mark Alusil. This material is effective in improving flow properties even at very low levels, and also has the effect of increasing bulk density. It is therefore possible to adjust bulk density by appropriate choice of the level of amorphous sodium aluminosilicate added after granulation.
  • Amorphous sodium aluminosilicate is advantageously used in an amount of from 0.2 to 5.0 wt%, based on the starting powder, more preferably from 0.5 to 3.0 wt%.
  • Another preferred flow aid is finely divided crystalline sodium aluminosilicate.
  • the crystalline aluminosilicates discussed previously in the context of builders are also suitable for use as flow aids. They are, however, less weight-effective than the amorphous material and are suitably used in an amount of from 3.0 to 12.0 wt%, more preferably from 4.0 to 10.0 wt%.
  • both crystalline and amorphous sodium aluminosilicates may be used, together or sequentially, as flow aids.
  • flow aids suitable for use in the process of the invention include precipitated silica, for example, Neosyl (Trade Mark), and precipitated calcium silicate, for example, Microcal (Trade Mark), both commercially available from Crosfield Chemicals Ltd, Warrington, Cheshire, England.
  • the final granulate has a bulk density of at least 650 g/litre and preferably at least 700 g/litre. It is also characterised by an especially low particle porosity, preferably not exceeding 0.25 and more preferably not exceeding 0.20, which distinguishes it from even the densest powders prepared by spray-drying alone.
  • the final granulate may be used as a complete detergent composition in its own right. Alternatively, it may be admixed with other components or mixtures prepared separately, and may form a major or minor part of a final product. Generally, any additional ingredients such as enzymes, bleach and perfume that are not suitable for undergoing the granulation process and the steps that precede it may be admixed to the granulate to make a final product.
  • a detergent base powder is prepared by spray-drying an aqueous slurry of heat-insensitive and compatible ingredients; if desired, other ingredients may then be admixed as discussed above; and the resulting powder is densified and granulated in accordance with the process of the invention. Yet further ingredients may if desired be admixed after granulation; the densified granulate may typically constitute from 40 to 100 wt% of a final product.
  • the densified granulate prepared in accordance with the present invention is an "adjunct" comprising a relatively high level of detergent-active material on an inorganic carrier; and this may be admixed in a minor amount with other ingredients to form a final product.
  • Powders containing sodium tripolyphosphate and sodium sulphate were prepared by spray-drying aqueous slurries to the formulations (weight %) shown in Table 1.
  • Example 2 20 kg batches of each powder were densified in a Fukae (Trade Mark) high-speed mixer/granulator, process conditions and resulting powder properties being shown in Table 2.
  • the powder was initially subjected to a 2-3 minute warming up period, at a low stirrer speed (50 rev/min) and without the cutter running, until the temperature had reached about 30-35 °C. This was followed by pulverisation (optional), then binder addition (also optional), then granulation, followed finally by addition of flow aid.
  • Powders containing sodium tripolyphosphate as the sole water-soluble crystalline inorganic salt were prepared by spray-drying aqueous slurries to the formulations (weight %) shown in Table 3.
  • Powders containing sodium tripolyphosphate, sodium carbonate and sodium sulphate were prepared to the formulations (weight %) shown in Table 6.
  • the powders were prepared by spray-drying aqueous slurries. However, the sodium carbonate in the powder of Example 6 was not incorporated via the slurry but postdosed in the Fukae mixer.
  • Powders containing sodium tripolyphosphate and sodium carbonate were prepared, by spray-drying aqueous slurries, to the formulations (weight %) shown in Table 9, and densified in the Fukae mixer as in previous Examples, as shown in Table 10.
  • a powder containing sodium tripolyphosphate, sodium sulphate and borax was prepared to the formulation (weight %) shown in Table 11.
  • the powder was prepared by spray-drying an aqueous slurry of all the ingredients except the borax. 9.0 kg of spray-dried base powder and 1.0 kg of borax were mixed and granulated/densified in the Fukae mixer, process conditions and resulting powder properties being shown in Table 12.
  • the properties of the densified granulate were as follows:
  • the product was a mild detergent powder giving a pH (1 wt% aqueous solution) of 9.2.

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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)
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  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (15)

1. Procédé de préparation d'une composition ou composant détergent granulaire ayant une densité apparente d'au moins 650 g/I, caractérisé en ce qu'il consiste à traiter une matière particulaire de départ comprenant
(a) de 12 à 70% en poids d'un détergent actif non savonneux, et
(b) au moins 15% en poids de sels minéraux cristallins hydrosolubles, notamment le tripolyphosphate de sodium et/ou le carbonate de sodium,
le rapport pondéral (b):(a) étant d'au moins 0,4:1 et, facultativement, d'autres composants détergents q.s.p 100% en poids,
dans un mélangeur/granulateur à grande vitesse comportant des éléments d'agitateur et de cisaille indépendamment réglables, en l'absence d'un agent particulaire finement divisé pour améliorer les propriétés superficielles, présentant une granulométrie moyenne qui ne dépasse pas 10 um, de sorte qu'on effectue la granulation et la densification jusqu'à une densité apparente d'au moins 650 g/I.
2. Procédé selon la revendication 1, caractérisé en ce qu'on effectue la granulation dans un mélangeur/granulateur à grande vitesse du type à cuvette présentant un axe d'agitateur sensiblement vertical.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la matière particulaire de départ consiste en poudre au moins partiellement séchée par pulvérisation.
4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, dans la matière particulaire de départ, le rapport (b):(a) est compris entre 0,4:1 et 5:1.
5. Procédé selon la revendication 4, caractérisé en ce que le rapport (b):(a) dans la matière particulaire de départ est compris entre 1:1 et 5:1.
6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la matière de départ comprend de 15 à 70% en poids de sels minéraux cristallins hydrosolubles, notamment du tripolyphosphate de sodium et/ou du carbonate de sodium.
7. Procédé selon la revendication 6, caractérisé en ce que la matière particulaire de départ comprend de 15 à 50% en poids de tripolypnosphate de sodium.
8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le détergent actif non savonneux dans la matière particulaire de départ consiste au moins partiellement en détergent actif anionique.
9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on prépare la matière particulaire de départ par un procédé consistant à mélanger au moins un sel minéral ou organique d'une granulométrie d'au moins 100 um avec le complément de la matière particulaire de départ dans le mélangeur/granulateur à grande vitesse.
10. Procédé selon la revendication 9, caractérisé en ce que le sel est choisi parmi le borax, le bicarbonate de sodium, le silicate de sodium, le tripolyphosphate de sodium, le carbonate de sodium, le perborate de sodium, le percarbonate de sodium, le citrate de sodium, le nitrilotriacétate de sodium, le succinate de sodium, le sulfate de sodium et des combinaisons de ceux-ci.
11. Procédé selon l'une quelconque des revendications prcédentes, qui consiste à incorporer dans la matière granulaire après achèvement de la granulation, un agent particulaire finement divisé d'assistance à l'écoulement.
12. Procédé selon la revendication 11, caractérisé en ce que l'agent d'assistance à l'écoulement est l'aluminosilicate amorphe de sodium et on l'ajoute à raison de 0,2 à 5,0% en poids par rapport à la composition totale.
13. Procédé selon la revendication 11, caractérisé en ce que l'agent d'assistance à l'écoulement est un aluminosilicate de sodium cristallin finement divisé et on l'ajoute à raison de 3,0 à 12,0% par rapport au poids de la composition totale.
14. Procédé selon l'une quelconque des revendications précédentes, dans lequel la composition ou composent détergent préparé par le procédé présente une porosité de particules inférieure à 0,25.
15. Procédé selon la revendication 14, dans lequel la porosité des particules de la composition ou composent détergent est inférieure à 0,20.
EP89304210A 1988-07-21 1989-04-27 Compositions détergentes et procédé pour leur préparation Expired - Lifetime EP0351937B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8817386 1988-07-21
GB888817386A GB8817386D0 (en) 1988-07-21 1988-07-21 Detergent compositions & process for preparing them

Publications (3)

Publication Number Publication Date
EP0351937A1 EP0351937A1 (fr) 1990-01-24
EP0351937B1 true EP0351937B1 (fr) 1994-02-09
EP0351937B2 EP0351937B2 (fr) 2001-12-12

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EP89304210A Expired - Lifetime EP0351937B2 (fr) 1988-07-21 1989-04-27 Compositions détergentes et procédé pour leur préparation

Country Status (15)

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EP (1) EP0351937B2 (fr)
JP (1) JP2644038B2 (fr)
KR (2) KR920004462B1 (fr)
AU (1) AU611556B2 (fr)
BR (1) BR8902006A (fr)
CA (1) CA1322704C (fr)
DE (1) DE68912983T3 (fr)
ES (1) ES2049320T5 (fr)
GB (2) GB8817386D0 (fr)
HK (1) HK86594A (fr)
IN (2) IN170472B (fr)
MY (1) MY105051A (fr)
PH (1) PH26823A (fr)
TR (1) TR25923A (fr)
ZA (2) ZA893186B (fr)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430328A2 (fr) * 1989-11-27 1991-06-05 Unilever N.V. Procédé de préparation de détergents en poudre à haute densité contenant des argiles
EP0460897A2 (fr) * 1990-06-06 1991-12-11 Unilever Plc Compositions d'une poudre de savon
US5486303A (en) * 1993-08-27 1996-01-23 The Procter & Gamble Company Process for making high density detergent agglomerates using an anhydrous powder additive
US5489392A (en) * 1994-09-20 1996-02-06 The Procter & Gamble Company Process for making a high density detergent composition in a single mixer/densifier with selected recycle streams for improved agglomerate properties
US5496487A (en) * 1994-08-26 1996-03-05 The Procter & Gamble Company Agglomeration process for making a detergent composition utilizing existing spray drying towers for conditioning detergent agglomerates
US5516448A (en) * 1994-09-20 1996-05-14 The Procter & Gamble Company Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate
US5527489A (en) * 1990-10-03 1996-06-18 The Procter & Gamble Company Process for preparing high density detergent compositions containing particulate pH sensitive surfactant
US5554587A (en) * 1995-08-15 1996-09-10 The Procter & Gamble Company Process for making high density detergent composition using conditioned air
US5565422A (en) * 1995-06-23 1996-10-15 The Procter & Gamble Company Process for preparing a free-flowing particulate detergent composition having improved solubility
US5565137A (en) * 1994-05-20 1996-10-15 The Proctor & Gamble Co. Process for making a high density detergent composition from starting detergent ingredients
US5569645A (en) * 1995-04-24 1996-10-29 The Procter & Gamble Company Low dosage detergent composition containing optimum proportions of agglomerates and spray dried granules for improved flow properties
USH1604H (en) * 1993-06-25 1996-11-05 Welch; Robert G. Process for continuous production of high density detergent agglomerates in a single mixer/densifier
US5574005A (en) * 1995-03-07 1996-11-12 The Procter & Gamble Company Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties
US5576285A (en) * 1995-10-04 1996-11-19 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration with an inorganic double salt
US5616550A (en) * 1992-05-21 1997-04-01 Henkel Kommanditgesellschaft Auf Aktien Process for the continuous production of a granular detergent
US5665691A (en) * 1995-10-04 1997-09-09 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration with a hydrated salt
US5668099A (en) * 1996-02-14 1997-09-16 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration with an inorganic double salt
US5691294A (en) * 1993-03-30 1997-11-25 The Procter & Gamble Company Flow aids for detergent powders comprising sodium aluminosilicate and hydrophobic silica
US5691297A (en) * 1994-09-20 1997-11-25 The Procter & Gamble Company Process for making a high density detergent composition by controlling agglomeration within a dispersion index
US5707958A (en) * 1993-07-13 1998-01-13 Colgate-Palmolive Company Process for preparing detergent composition having high bulk density
US5707959A (en) * 1995-05-31 1998-01-13 The Procter & Gamble Company Processes for making a granular detergent composition containing a crystalline builder
US5733862A (en) * 1993-08-27 1998-03-31 The Procter & Gamble Company Process for making a high density detergent composition from a sufactant paste containing a non-aqueous binder
WO1998016618A2 (fr) * 1996-10-15 1998-04-23 The Procter & Gamble Company Procede de fabrication d'une composition detergente de densite elevee par malaxage/densification apres sechage
US5968891A (en) * 1993-07-13 1999-10-19 Colgate-Palmolive Co. Process for preparing detergent composition having high bulk density
US6046153A (en) * 1996-08-26 2000-04-04 The Procter & Gamble Company Spray drying process for producing detergent compositions involving premixing modified polyamine polymers
US6093690A (en) * 1996-08-26 2000-07-25 The Procter & Gamble Company Agglomeration process for producing detergent compositions involving premixing modified polyamine polymers
AU724105B2 (en) * 1996-02-26 2000-09-14 Unilever Plc Anionic detergent particles
US6610645B2 (en) 1998-03-06 2003-08-26 Eugene Joseph Pancheri Selected crystalline calcium carbonate builder for use in detergent compositions

Families Citing this family (14)

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GB9008013D0 (en) * 1990-04-09 1990-06-06 Unilever Plc High bulk density granular detergent compositions and process for preparing them
EP0643129A1 (fr) * 1993-09-07 1995-03-15 The Procter & Gamble Company Procédé de préparation de compositions détergentes
CA2157257C (fr) * 1994-09-12 1999-08-10 Kazuhiko Endo Dispositif a semiconducteur a couche de carbone amorphe et sa methode de fabrication
WO1996025482A1 (fr) * 1995-02-13 1996-08-22 The Procter & Gamble Company Procede pour produire des agglomerats detergents a classe granulometrique controlee
US6207635B1 (en) 1995-05-31 2001-03-27 The Procter & Gamble Company Process for manufacture of high density detergent granules
KR100394762B1 (ko) * 1996-02-13 2003-11-20 주식회사 엘지생활건강 장기간저장안정성이우수한농축분말세제조성물
CN1116400C (zh) * 1996-02-29 2003-07-30 普罗格特-甘布尔公司 制备洗涤剂附聚物的方法
CZ273098A3 (cs) * 1996-02-29 1998-12-16 The Procter & Gamble Company Způsob výroby detergentních aglomerátů
TR199902896T2 (xx) 1997-05-30 2000-06-21 Unilever N.V. Serbest ak��l� par�ac�k halinde deterjan bile�imleri.
GB9711350D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Granular detergent compositions and their production
GB9711359D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Detergent powder composition
GB9711356D0 (en) 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
WO1999011749A1 (fr) * 1997-08-28 1999-03-11 The Procter & Gamble Company Procede d'agglomeration destine a produire un melange detergent particulaire a polyamines modifiees
GB0418918D0 (en) * 2004-08-25 2004-09-29 Unilever Plc A particulate detergent composition, and packaging therefor

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DE1617109B2 (de) * 1967-12-05 1973-04-19 Großeinkaufs Gesellschaft deutscher Konsumgenossenschaften mbH, 2000 Harn bürg Verfahren zur herstellung von staubfreien und rieselfaehigen waschund reinigungsmitteln
GB1517713A (en) * 1974-10-31 1978-07-12 Unilever Ltd Preparation of detergent formulations
JPH0631430B2 (ja) * 1985-05-29 1994-04-27 ライオン株式会社 高嵩密度粒状洗剤組成物の製造方法
JPH0631431B2 (ja) * 1985-06-27 1994-04-27 ライオン株式会社 洗浄剤組成物の製造方法
DE3617756C2 (de) * 1985-05-29 1995-01-19 Lion Corp Verfahren zum Herstellen einer granularen Detergentien-Zusammensetzung mit hoher Schüttdichte
US4925585A (en) * 1988-06-29 1990-05-15 The Procter & Gamble Company Detergent granules from cold dough using fine dispersion granulation

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430328A2 (fr) * 1989-11-27 1991-06-05 Unilever N.V. Procédé de préparation de détergents en poudre à haute densité contenant des argiles
EP0430328A3 (en) * 1989-11-27 1991-07-31 Unilever Nv Process for preparing high bulk density detergent powders containing clay
EP0460897A2 (fr) * 1990-06-06 1991-12-11 Unilever Plc Compositions d'une poudre de savon
EP0460897A3 (en) * 1990-06-06 1993-01-07 Unilever Plc Soap powder compositions
US5298183A (en) * 1990-06-06 1994-03-29 Lever Brothers Company, Division Of Conopco, Inc. Soap powder compositions
US5527489A (en) * 1990-10-03 1996-06-18 The Procter & Gamble Company Process for preparing high density detergent compositions containing particulate pH sensitive surfactant
US5616550A (en) * 1992-05-21 1997-04-01 Henkel Kommanditgesellschaft Auf Aktien Process for the continuous production of a granular detergent
US5691294A (en) * 1993-03-30 1997-11-25 The Procter & Gamble Company Flow aids for detergent powders comprising sodium aluminosilicate and hydrophobic silica
USH1604H (en) * 1993-06-25 1996-11-05 Welch; Robert G. Process for continuous production of high density detergent agglomerates in a single mixer/densifier
US5968891A (en) * 1993-07-13 1999-10-19 Colgate-Palmolive Co. Process for preparing detergent composition having high bulk density
US5707958A (en) * 1993-07-13 1998-01-13 Colgate-Palmolive Company Process for preparing detergent composition having high bulk density
US5486303A (en) * 1993-08-27 1996-01-23 The Procter & Gamble Company Process for making high density detergent agglomerates using an anhydrous powder additive
US5733862A (en) * 1993-08-27 1998-03-31 The Procter & Gamble Company Process for making a high density detergent composition from a sufactant paste containing a non-aqueous binder
US5565137A (en) * 1994-05-20 1996-10-15 The Proctor & Gamble Co. Process for making a high density detergent composition from starting detergent ingredients
US5496487A (en) * 1994-08-26 1996-03-05 The Procter & Gamble Company Agglomeration process for making a detergent composition utilizing existing spray drying towers for conditioning detergent agglomerates
US5516448A (en) * 1994-09-20 1996-05-14 The Procter & Gamble Company Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate
US5489392A (en) * 1994-09-20 1996-02-06 The Procter & Gamble Company Process for making a high density detergent composition in a single mixer/densifier with selected recycle streams for improved agglomerate properties
US5691297A (en) * 1994-09-20 1997-11-25 The Procter & Gamble Company Process for making a high density detergent composition by controlling agglomeration within a dispersion index
US5574005A (en) * 1995-03-07 1996-11-12 The Procter & Gamble Company Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties
US5569645A (en) * 1995-04-24 1996-10-29 The Procter & Gamble Company Low dosage detergent composition containing optimum proportions of agglomerates and spray dried granules for improved flow properties
US5707959A (en) * 1995-05-31 1998-01-13 The Procter & Gamble Company Processes for making a granular detergent composition containing a crystalline builder
US5565422A (en) * 1995-06-23 1996-10-15 The Procter & Gamble Company Process for preparing a free-flowing particulate detergent composition having improved solubility
US5554587A (en) * 1995-08-15 1996-09-10 The Procter & Gamble Company Process for making high density detergent composition using conditioned air
US5576285A (en) * 1995-10-04 1996-11-19 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration with an inorganic double salt
US5665691A (en) * 1995-10-04 1997-09-09 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration with a hydrated salt
US5668099A (en) * 1996-02-14 1997-09-16 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration with an inorganic double salt
AU724105B2 (en) * 1996-02-26 2000-09-14 Unilever Plc Anionic detergent particles
US6046153A (en) * 1996-08-26 2000-04-04 The Procter & Gamble Company Spray drying process for producing detergent compositions involving premixing modified polyamine polymers
US6093690A (en) * 1996-08-26 2000-07-25 The Procter & Gamble Company Agglomeration process for producing detergent compositions involving premixing modified polyamine polymers
WO1998016618A2 (fr) * 1996-10-15 1998-04-23 The Procter & Gamble Company Procede de fabrication d'une composition detergente de densite elevee par malaxage/densification apres sechage
US5914307A (en) * 1996-10-15 1999-06-22 The Procter & Gamble Company Process for making a high density detergent composition via post drying mixing/densification
US6610645B2 (en) 1998-03-06 2003-08-26 Eugene Joseph Pancheri Selected crystalline calcium carbonate builder for use in detergent compositions

Also Published As

Publication number Publication date
KR900001836A (ko) 1990-02-27
IN170472B (fr) 1992-03-28
MY105051A (en) 1994-07-30
GB8817386D0 (en) 1988-08-24
GB8910087D0 (en) 1989-06-21
JPH0241399A (ja) 1990-02-09
HK86594A (en) 1994-09-02
EP0351937A1 (fr) 1990-01-24
ZA893186B (en) 1990-12-28
TR25923A (tr) 1993-09-17
IN169824B (fr) 1991-12-28
KR920000114B1 (ko) 1992-01-09
ES2049320T5 (es) 2002-05-16
EP0351937B2 (fr) 2001-12-12
JP2644038B2 (ja) 1997-08-25
DE68912983T2 (de) 1994-06-01
AU3375189A (en) 1990-01-25
ZA895578B (en) 1991-03-27
CA1322704C (fr) 1993-10-05
KR900001829A (ko) 1990-02-27
DE68912983T3 (de) 2002-04-04
DE68912983D1 (de) 1994-03-24
PH26823A (en) 1992-11-05
ES2049320T3 (es) 1994-04-16
AU611556B2 (en) 1991-06-13
BR8902006A (pt) 1990-04-10
KR920004462B1 (ko) 1992-06-05

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