EP0120492B1 - Composante granuleuse de détergent, à écoulement libre et procédé pour sa préparation - Google Patents

Composante granuleuse de détergent, à écoulement libre et procédé pour sa préparation Download PDF

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Publication number
EP0120492B1
EP0120492B1 EP84103320A EP84103320A EP0120492B1 EP 0120492 B1 EP0120492 B1 EP 0120492B1 EP 84103320 A EP84103320 A EP 84103320A EP 84103320 A EP84103320 A EP 84103320A EP 0120492 B1 EP0120492 B1 EP 0120492B1
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Prior art keywords
weight
water
spray
product
particles
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EP84103320A
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German (de)
English (en)
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EP0120492A3 (en
EP0120492A2 (fr
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Otto Dr. Koch
Herbert Dr. Reuter
Wolfgang Dr. Seiter
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT84103320T priority Critical patent/ATE35692T1/de
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Publication of EP0120492A3 publication Critical patent/EP0120492A3/de
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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
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions

Definitions

  • washing powders with a high bulk density have been known for a long time. These include e.g. Agents with a high soda or silicate content, such as used to be were obtained by simply mixing the individual components together or by drying aqueous mixtures on trays or heated rolls, extruding or spray crystallization. These specifically heavy powders tend to cake, usually have poor solution properties and cannot be used in modern washing machines with pre-programmed cycle times. These agents have meanwhile been replaced by specifically light powders with a porous grain structure, which are produced by means of hot spray drying and which, as a rule, are quickly soluble, but on the other hand require a relatively large packaging and transport volume.
  • a granular porous carrier material is produced by spray drying a slurry of inorganic salts such as sodium silicate, sodium sulfate and sodium triphosphate as well as sulfonate surfactants and soaps then sprayed in a mixer with a nonionic surfactant.
  • inorganic salts such as sodium silicate, sodium sulfate and sodium triphosphate
  • soaps soaps then sprayed in a mixer with a nonionic surfactant.
  • nonionic surfactants up to 20% by weight of nonionic surfactants can be applied subsequently to the spray-dried carrier material.
  • a powder addition of e.g. Talc, finely divided silica or calcined clay is recommended.
  • a graying inhibitor in powder form e.g. Carboxymethyl cellulose, can be mixed in afterwards.
  • the powders obtained in this way, loaded with nonionic surfactants, can have a bulk density of more than 500 g / l, for example 700 g / l and a pourability of, for. B. up to 76% of dry sand.
  • the size of these powder particles is between 3.3 mm to 0.075 mm, in particular between 0.83 and 0.15 mm.
  • Granular detergents with a bulk density of at least 500 g / l which consist of essentially spherical particles of a certain grain size and have a fluidity of 70%, based on dry sand, are known from German Offenlegungsschrift 2,742,683.
  • These agents filled in a plastic bottle have a content of 30 to 80% of builders, 2 to 40% of surfactants, which are essentially non-ionic, 0 to 20% of other additives, 0 to 50% of fillers and 3 to 15% Moisture. It is true that the manufacture of the products described in this way is called arbitrary, for example also by spray drying or granulation. However, the only one specifically mentioned, and thus useful way is through a two-stage, and therefore expensive manufacturing process, in which first so-called “base bead” (base beads) having a porous outer surface and a more or less absorbent inner shell is prepared by spray drying an aqueous slurry which is then allowed to the liquid or melted nonionic surfactant is sprayed or soaked.
  • base bead base beads having a porous outer surface and a more or less absorbent inner shell
  • DE-AS 1 792 434 describes a process for the production of granular detergents with a content of 2 to 15% by weight of anionic and 5 to 20% by weight of nonionic surfactants and 25 to 60% by weight tripolyphosphate known by spray drying a slurry.
  • the tripolyphosphate used to prepare the slurry must be partially pre-hydrated. This partial prehydration is necessary in order to produce free-flowing powders.
  • the process provides loose powder with a bulk density of less than 550 g / l and - if the proportion of nonionic surfactant significantly exceeds 15% by weight - only very moderate pouring properties.
  • the invention by means of which the problems outlined are solved, is a granular, free-flowing, water-soluble detergent component with a bulk density of 550 to 800 g / l, consisting of synthetic, essentially non-ionic surfactants, inorganic carrier substances including alkali metal silicates, and other organic washing aids and adsorptive or water bound as hydrate.
  • This granular detergent component is characterized in that it is produced by spray drying and consists of more than 50% by weight of drop-shaped to rod-shaped particles with an average diameter of 0.02 to 1.5 mm and an average length of 0.1 to 5 mm and a ratio of average diameter to average length of 1: 1.2 to 1:10 and their content of alkoxylated nonionic surfactants 15 to 28 wt .-%, synthetic anionic surfactants less than 1 wt .-%, of soap is less than 0.2% by weight and 40 to 80% by weight of inorganic carrier substance, based on the anhydrous substance.
  • This granular detergent component is the essential component of a free-flowing detergent produced by adding further powder components; however, the granular detergent component as defined above can also be the practically sole constituent of a detergent. Accordingly, the granular detergent component according to the invention is contained in the free-flowing detergent in proportions of 15 to 100%, preferably 50 to 95%.
  • Suitable alkoxylated nonionic surfactants are ethoxylated alcohols having 12 to 24, preferably 14 to 18 carbon atoms and an average of 3 to 20, preferably 4 to 16, glycol ether groups.
  • the hydrocarbon residues can be saturated or monounsaturated, linear or also methyl-branched in the 2-position (oxo residue) and can be derived, for example, from naturally occurring or hydrogenated fat residues and / or synthetic residues.
  • Ethoxylates derived from cetyl, stearyl and oleyl alcohol and mixtures thereof have proven to be particularly suitable.
  • EO ethylene oxide groups
  • tallow fatty alcohol with an average of 10 to 18 EO tallow fatty alcohol with an average of 10 to 18 EO
  • oleyl alcohol with an average of 6 to 12 EO as well as their mixtures.
  • Such mixtures of two and more surfactants with different EO content, in which the proportion of higher ethoxylated alcohols predominates have proven to be particularly advantageous, since the tendency to smoke formation in the exhaust air (so-called pluming) is particularly low and the washing action against mineral ones and fatty soiling is particularly pronounced.
  • Alkoxylated alcohols have also proven to be advantageous in the sense of a low tendency to "pluming", in the production of which 1 to 3 mol of propylene oxide and then 4 to 20, preferably 4 to 7, mol of ethylene oxide were added to the alcohol. You can replace components (a) and (b) in whole or in part in the aforementioned mixtures.
  • nonionic surfactants are those which have a similar distribution of the ethylene glycol or propylene glycol ether groups and are derived from alkylphenols, fatty amines, fatty acid amides and fatty acids.
  • the ethoxylated fatty acid amides also include the fatty acid mono- or diethanolamides or the corresponding fatty acid propanolamides.
  • the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain can also be used.
  • the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • nonionic surfactants of the amine oxide type can also be present.
  • Amine oxides containing polyglycol ether groups can also be used.
  • the detergent component according to the invention contains 15 to 28% by weight, preferably 17 to 25% by weight and in particular 18 to 23% by weight, of ethoxylated nonionic surfactants.
  • the content of synthetic anionic surfactants in the detergent component i.e. those of the sulfonate or sulfate type should be less than 1% by weight, preferably less than 0.5% by weight, in particular 0% by weight, and those of soap less than 0.2% by weight, preferably 0 % By weight.
  • no anionic surfactants are used, since surprisingly it has been shown that even small amounts of such additives, especially the smallest additions of soap, cause the grains to swell during spray drying and thus to a decrease in the desired high bulk density and free-flowing properties.
  • inorganic carrier substances there are primarily builders which can also bind or precipitate the hardness constituents of the water.
  • the polymer phosphates can be mixed with their hydrolysis products, i.e. H. Orthophosphate and pyrophosphate are present, however, due to the higher washing and calcium binding capacity of the polyphosphates, the lowest possible hydrolysis of the polyphosphate when preparing the slurry and during spray drying should be aimed at by suitable measures.
  • Suitable carrier substances are in particular also the synthetic bound water-containing sodium aluminosilicates of the zeolite A type. You can replace the polymer phosphates in whole or in part, i.e. their use also enables the production of phosphate-free agents.
  • the zeolites are used in the usual hydrated, finely crystalline form, i.e. they have practically no particles larger than 30 ⁇ m and preferably consist of at least 80% of particles smaller than 10 ⁇ m.
  • Their calcium binding capacity which is determined according to the information in DE-A-2 412 837, is in the range of 100-200 mg CaO / g.
  • the zeolite NaA can be used in particular, also the zeolite NaX and mixtures of NaA and NaX.
  • Further useful carrier substances which can be present in a mixture with the compounds mentioned above are sodium carbonate, sodium sulfate and magnesium silicate.
  • Compounds with a high adsorption capacity such as finely divided silica, clays or bentonites, may also be present.
  • the proportion of the inorganic carrier substance is a total of 40 to 80% by weight, based on anhydrous or non-hydrated components, preferably 45 to 70% by weight.
  • the proportion of sodium tripolyphosphate (including the hydrolysis products) in the detergent component according to the invention is preferably 0 to 60% by weight, preferably 10 to 50% by weight and in particular 20 to 40% by weight.
  • the proportion of the alkali metal silicates is 5 to 20% by weight, preferably 6 to 15% by weight and in particular 6.5 to 12% by weight.
  • the sodium aluminosilicate is present in proportions of 0 to 40% by weight, preferably 3 to 30% by weight and in particular 5 to 25% by weight.
  • the proportion of sodium silicate in such carrier salt mixtures which essentially consist of sodium tripolyphosphate or zeolite and their mixtures, can also be increased beyond the stated maximum content of 20% by weight, without resulting in major disadvantages for the dissolution behavior of the particles .
  • the proportion of zeolites can be up to 65% by weight.
  • the percentage content of polyphosphate in the detergents can be in the range of conventional heavy-duty detergents, the tendency to Phosphate reduction fully taken into account in the invention.
  • the agents according to the present invention are used in a much lower dosage compared to conventional, ie specifically light, washing powders, on the other hand the proportion of phosphate can be considerably reduced in favor of the proportion of aluminosilicate, ie reduced to, for example, 10% by weight or else be completely eliminated.
  • the detergent component according to the invention can additionally contain so-called co-builders as other organic washing aids, which are capable of considerably increasing the action of the polyphosphates and sodium aluminosilicates even in small amounts.
  • Polyphosphonic acids or their alkali metal salts are particularly suitable as co-builders. Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and their higher homologs, such as. B. Diethylenetriamine penta- (methylenephosphonic acid).
  • Other co-builders are complexing aminopolycarboxylic acids.
  • alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid include in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid.
  • the salts of diethylenetriamineopentaacetic acid and the higher homologues of the aminopolycarboxylic acid mentioned are also suitable.
  • the polyacids mentioned are preferably used as sodium salts.
  • co-builders are the polymeric carboxylic acids or their salts with a molecular weight of at least 350 in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, polymethacrylic acid, poly-a-hydroxyacrylic acid, polymaleic acid, polyitaconic acid, polymesaconic acid, polybutene tricarboxylic acid and the copolymers the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds, such as ethylene, propylene, isobutylene, vinyl methyl ether or furan.
  • the copolymer of maleic acid and acrylic acid in a ratio of 5: 1 to 1: may be mentioned as an example.
  • Small amounts of these co-builders are understood to mean proportions of 0.5 to 10, preferably 1 to 5,% by weight, based on the total amount of the detergent component.
  • organic detergent components that may be present in the spray-dried powder component are graying inhibitors, optical brighteners and additives which regulate the viscosity behavior of the slurries, for example alkali metal salts or toluene, cumene or xylene sulfonic acid and, if appropriate, polymers which act as thickeners (for example of the Carbopol type - ").
  • Suitable graying inhibitors are, in particular, carboxymethyl cellulose, methyl cellulose, furthermore water-soluble polyesters and polyamides from polyvalent carboxylic acids and glycols or diamines, which have free carboxyl groups, betain groups or sulfobetaine groups capable of salt formation, and polymers or copolymers of vinyl alcohol, vinyl amide and acrylamide, colloidally soluble in water, acrylamides and acrylamides .
  • These organic washing aid additives can be present in proportions of 0.5 to 10% by weight.
  • the agents usually have a water content of 8 to 20% by weight, preferably 10 to 16% by weight, which means both the adsorptively bound water and the water of hydration.
  • the proportion of water bound in the hydrated sodium aluminosilicate is about 20% by weight, based on the total amount of the hydrated sodium aluminosilicate; i.e. it is the degree of hydration that is in equilibrium with the environment. This proportion must be taken into account when calculating the amount of water. Basically, the water content should be measured so that there are perfectly free-flowing products. It is preferably 10 to 16% by weight.
  • the grain structure of the powder component according to the invention is characteristic and differs considerably from the grain structure in known or commercially available detergents.
  • the powder component according to the invention consists predominantly, i.e. more than 50% by weight, preferably more than 60% by weight and in particular 65 to 100% by weight of droplet to rod-shaped particles which have an average diameter of 0.02 to 1.5 mm, preferably from 0.05 to 1 mm and an average length from 0.1 to 5 mm, preferably from 0.3 to 3 mm, a ratio of diameter to length from 1: 1.2 to 1:10, preferably from 1: 1.4 to 1: 8 with a pronounced maximum at 1: 1.8 to 1: 5.
  • the particles are compact, i.e. they have a dense structure that is not sponge-like or foam-like. Your surface is closed, i.e. not porous and appears smooth when viewed macroscopically. A surface structure can be seen under the microscope, which can be described as pitted to streaked and reminds of solidified, non-porous slags.
  • Figures 1 to 5 show such characteristic particles with increasing magnification.
  • Figure 5 shows the face of such a particle in the area of a break. This example shows that the surface structure can continue inside the particles.
  • Figures 6 and 7 of a conventional spray powder for comparison low bulk density reveals agglomerated particles of irregular, in the first approximation spherical shape and largely smooth surface.
  • the interior of the individual particles is inflated, as can be seen from the cross section of a particle shown in Figure 7, and has a porous sponge or foam structure which is characteristic of such spray powder.
  • Such powder structures are not the subject of the invention.
  • the parameter “to more than 50% by weight” or “preferably 65 to 100% by weight of drop-shaped or rod-shaped particles” means that the agents can also be constructed on a subordinate scale from particles of different shapes, ie that two or more droplet-to-rod-shaped particles are cemented to form agglomerates of irregular shapes, or that small amounts of approximately spherical particles are produced during manufacture, or that elongated particles break into short fragments during further processing or transport.
  • the detergent component according to the invention can be mixed with additional powder products which have been produced by customary methods and have a different powder spectrum.
  • additional powder products which have been produced by customary methods and have a different powder spectrum.
  • these powder products also include detergent precursors, so-called compounds, which are composed of anionic sulfonate and / or sulfate surfactants and, if appropriate, soaps, together with carriers such as sodium triphosphate, zeolite A and water glass, and are prepared by conventional spray drying or mixed granulation.
  • Textile-softening granules which contain quaternary ammonium compounds as active ingredients together with soluble or insoluble carriers and dispersion inhibitors or which are based on sheet silicates and long-chain tertiary amines are also suitable as additives.
  • These additional powder products are made up of differently designed, known particle shapes, for example more or less spherical beads, prills or granules.
  • This bulk density is 550 to 800 g / l, preferably 600 to 750 g / l and in particular 620 to 720 g / l.
  • the detergent component according to the invention is only of limited suitability for determining the particle size distribution by means of sieve analysis due to its characteristic rod-shaped powder structure, the particle spectrum can be determined using this method. It shows that the grain spectrum is comparatively narrow, i. H. more than 70 wt .-%, usually even 80 to 90 wt .-% of the powders are within a range between 0.2 and 0.8 mm mesh size. In the case of a conventional spray powder with a low bulk density, this grain size range generally does not account for more than 50 to 70% by weight.
  • the dust content of the powder component according to the invention and the proportion of oversize particles are correspondingly low, so that subsequent sieving of the tower powder or subsequent addition of dust-binding agents is unnecessary.
  • the detergent component according to the invention is free-flowing and, in terms of its flowability, exceeds the known, specifically light, sprayed hollow-sphere powder.
  • Their pourability can be compared with that of dry sand, namely the pourability which can be carried out according to a test given in the examples is in the order of more than 60%, preferably from 75 to 95%, of that of dry sand with a specific grain specification . This good flowability is highly surprising since one had to expect that the powder particles would lose their ability to roll off with increasing distance from spherical dimensions.
  • Another aspect when evaluating a washing powder is the compactibility of the powder. It is inevitable that when a washing powder is automatically filled, it initially takes up a slightly larger bulk volume, which is only slightly reduced even with a brief shaking process. As the packs are transported further to the consumer, compression gradually occurs. The consumer notices this loss of volume when opening the package and often concludes that he has received an incompletely filled package. In the case of conventional, specifically light, hollow spherical powders, this volume loss is 10 to 15%. Granules with predominantly spherical dimensions, which are obtained, for example, by applying nonionic surfactant to pre-sprayed carrier grains, have a volume loss of approximately 10%. In the case of dry sand, this value is around 8%.
  • the agents according to the invention even exceed these values, ie the volume decreases here are generally below 10% and, in favorable cases, reach a value of 5%.
  • the high volume consistency combined with the excellent pourability, facilitates a precise and accurate producible dosage during filling and in use.
  • the grains have a coating of a finely divided, water-soluble or dispersible solid as fluidizing agent in an amount which is 0.01 to 3% by weight of the granular spray product is. With this coating, the flowability can be further improved or weather-related adverse influences on the powder properties can be avoided.
  • the finely divided synthetic zeolites of the NaA or NaX type have proven to be particularly suitable. The positive effect of these zeolites is not only limited to the improved flowability, but also increases the proportion of builders and thus the washing power of the product.
  • finely divided silica with a large specific surface area in particular pyrogenic silica (Aerosil "), as a fluidizing agent.
  • the proportion of the fluidizing agent is preferably 0.1 to 2% by weight in the case of the zeolite, and preferably 0.05 in the case of the finely divided silica up to 0.5% by weight, based on the granular spray product.
  • powder materials already proposed for powdering sticky detergent granules such as finely divided sodium tripolyphosphate, sodium sulfate, magnesium silicate, talc, bentonite and organic polymers such as carboxymethyl cellulose and urea resins, can also be used provided they have a grain size of less than 0.1 mm, for example from 0.001 to Have 0.08 mm.
  • Coarse powder provenances such as those usually used in detergents and cleaning agents, have to be comminuted beforehand. Coating agents of this type are preferably used in proportions of 1 to 3% by weight.
  • the invention further relates to a method for producing the detergent component according to the invention.
  • the production is characterized in that a slurry of the components containing a total of 55 to 35% by weight of water (including the water adsorptively or bound as hydrate) is produced by means of nozzles under a pressure of 16 to 30 bar at a diameter measured at the inlet of the nozzle Sprayed nozzle outlet opening of 3 to 5.5 mm into a drying tower, the ratio of pressure at the nozzle inlet to the diameter of the nozzle outlet opening being 3 to 9 bar / mm and the inlet temperature of the supplied dry gas, measured in the ring channel of the drying tower, not exceeding 250 ° C.
  • Conventional systems can be used to carry out the spray drying process, as are already used for the production of conventional sprayed detergents.
  • Such systems usually consist of towers of round cross-section, which are equipped with ring-shaped spray nozzles in the upper part. They also have supply devices for the dry gases and dedusting systems for the exhaust air.
  • the drying gas is introduced into the lower part of the tower and directed towards the product stream, while in the case of direct current drying, the drying gases are supplied in the top of the drying tower.
  • the pressure at the nozzle inlet is preferably 18 to 28 bar and in particular 19 to 25 bar
  • the diameter of the nozzle outlet opening is 3.5 to 5 mm
  • the ratio of pressure to diameter of the nozzle outlet opening is 4 to 6 bar / mm and in particular 4.5 to 5, 5 bar / mm.
  • Compliance with these parameters is decisive for the grain properties of the process products. Significantly exceeding these limits in both directions leads to the formation of more or less irregular to spherical agglomerates with a foam-like structure, in particular when the pressure is increased or the nozzle is narrowed, which results in a lower bulk density and poorer pouring properties. If the pressure is reduced too much, the atomization performance may be poor and crusts may form in the area of the nozzle outlet opening.
  • the spray drying system is operated with hot air or hot combustion gases, which are preferably conducted in countercurrent to the spray material.
  • the drying gas is expediently introduced tangentially into the tower, which results in a certain swirl effect.
  • the inlet temperature of the dry gas should not exceed 250 ° C and should preferably be 180 ° C to 240 ° C, in particular 190 ° C to 220 ° C.
  • Operation with hotter dry gases requires the use of predominantly highly ethoxylated or mixed-alkoxylated surfactants in order to prevent smoke formation in the exhaust air. If the surfactant mixtures of low and highly ethoxylated compounds disclosed as preferred above are used, there will be no disturbances from smoke formation if the temperature range of 190 ° C to 220 ° C is observed, and the measured exhaust gas values are far below the legal maximum limit.
  • the inlet temperature of the dry gas in the spray drying system from 180 ° C. to 240 ° C., preferably from 190 ° C. to 220 ° C.
  • these are temperatures of the gas in the so-called ring channel of the drying tower.
  • the temperature of the gas flowing into the spray zone from this ring channel and coming into contact with the powder is usually 30 ° C. to 40 ° C. lower.
  • the temperature of the drying gases when leaving the drying tower is generally 90 ° C. ⁇ 15 ° C. and is preferably in the range between 80 ° C. and 95 ° C.
  • the upper value can be subject to certain fluctuations, which include depends on the outside temperature. It should be selected so that the dew point in the downstream dedusting systems is not exceeded.
  • the aqueous batch to be sprayed preferably contains a total of 55 to 42% by weight, preferably 52 to 44% by weight and in particular 50 to 46% by weight of water, which also contains the water bound by adsorption or hydrate.
  • Higher water contents are inappropriate because they increase the degree of hydrolysis of the tripolyphosphate, increase energy consumption and lead to a lower bulk density.
  • Lower contents can lead to an excessive increase in the viscosity of the slurry and therefore make special measures such as increasing the mixing and conveying capacity or the addition of viscosity-reducing agents such as toluene, xylene or cumene sulfonate necessary.
  • the order in which the slurries are prepared is not critical, processing can be facilitated by adhering to certain process conditions. In addition, it is advisable to keep the mixing and residence times as short as possible due to the strong increase in viscosity in the slurry batch. It is recommended to start with the liquid products, i.e. the melted nonionic surfactants and the components already present in aqueous solution or slurry, e.g. B. the alumosilicate present as a filter-moist paste and optionally additional water, and the anhydrous constituents, in particular the anhydrous or optionally partially hydrated tripolyphosphate, are added with vigorous stirring.
  • the liquid products i.e. the melted nonionic surfactants and the components already present in aqueous solution or slurry, e.g. B. the alumosilicate present as a filter-moist paste and optionally additional water, and the anhydrous constituents, in particular the anhydrous or optionally partially hydrated tripolyphosphat
  • an anhydrous sodium tripolyphosphate which consists of 30 to 50%, in particular 35 to 45%, of modification I.
  • Tripolyphosphate of Form I is known for an increased rate of hydration.
  • This increased rate of hydration can pose problems with the processability of the aqueous batch (slurry).
  • the hydration removes free water from the slurry, with the result that the viscosity rises sharply.
  • an excessive slurry viscosity not only complicates processing, i.e. mixing, conveying and spraying the slurries, but also leads to lower bulk densities in the finished powder.
  • the viscosity of the slurry In order to ensure sufficient flowability of the slurry and spray products with favorable powder properties, it has proven to be expedient to set the viscosity of the slurry to a range from 2000 to a maximum of 15,000 mPa.s, preferably from 5000 to 12,000 mPa.s and in particular from 6000 to 10000 mPa.s to set.
  • This setting advantageously takes place in such a way that the slurry is heated to temperatures above 85 ° C., for example to 86 ° C. to 102 ° C., before the solids are added, in particular before the tripolyphosphate is added.
  • the heating is expediently carried out by introducing steam, in particular superheated steam.
  • the hydration of the tripolyphosphate in the slurry is largely prevented or delayed to such an extent that there is no undesirable increase in viscosity within the processing time.
  • Keeping the slurry liquid can also be facilitated by applying strong shear forces, for example by intensive mixing by means of an agitator or by means of pumping devices with which the slurry is circulated.
  • strong shear forces prevents the formation of structural viscosities.
  • the use of viscosity-regulating agents ensures that the preferred viscosity ranges are observed.
  • the product leaving the spray tower generally has a temperature of 65 ° C to 80 ° C. It has been shown that under unfavorable conditions, which are unavoidable in a continuous, long-term production, there may be fluctuations in certain product properties, such as bulk density and pourability of the grains. Seasonal climate fluctuations can have an impact, for example. In this connection, high air temperatures have proven to be unfavorable in the further processing of the powders, especially in the cooling phase after leaving the spray tower. If the still warm spray material leaving the drying tower is stored in silos for a longer period of time, the nonionic surfactants can migrate to the surface of the spray grains, with the result that their free-flowing capacity decreases without, however, caking.
  • This disadvantage can be remedied by subsequently powdering (coating) the grains, as described above.
  • the product is left immediately after leaving the spray tower, ie preferably within less than 5 minutes se cools within 2 minutes to temperatures below 35 ° C, for example to 20 ° C to 30 ° C. This can be done, for example, in a pneumatic conveyor system which is operated with air which is sufficiently cold, ie at a temperature of less than 30 ° C. If the temperature of the cooling air is not sufficient to cool the product sufficiently quickly in the hot season, subsequent powdering is recommended.
  • the spray-dried grains can be coated or powdered before, after or expediently at the same time as the addition of further powder components.
  • powder components include per-compounds, bleach activators (so-called peracid precursors), enzyme granules, foam inhibitors or foam activators and so-called compounds, i.e. Carrier substances and surfactants, in particular anionic surfactants, or powder products consisting of carrier substances and fabric softeners.
  • Water-insoluble coating agents such as zeolite and silica aerogels, can also be used before spray drying is complete, i.e. H. by blowing into the lower part of the drying tower on the detergent granules already formed.
  • the coating agent can be introduced into the tower by metering it into the dry air.
  • the powdering of the spray-dried grains leads, among other things, to a partial smoothing of the grain surface, so that the flow behavior of such grains, which already have very good pourability and flowability, is further improved.
  • the bulk density of the powders can also be increased slightly as a result, since the coating material apparently enables the grains to be packed more densely.
  • the invention thus also encompasses a process for the aftertreatment of the granular, spray-dried powders in a mixing device with 0.01 to 3% by weight of a finely divided solid as defined above.
  • Other powder components that can be added to the spray-dried detergents include substances that are unstable under the spray-drying conditions or that lose some or all of their specific effect or that would adversely change the properties of the spray-drying product. Examples of this are enzymes from the class of proteases, lipases and amylases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Fragrances and foam suppressants, such as silicones or paraffin hydrocarbons, are also generally added to the spray-dried powder component to avoid loss of effectiveness.
  • Suitable bleaching components for admixing are the perhydrates and per-compounds commonly used in washing and bleaching agents.
  • the perhydrates preferably include sodium perborate, which can be present as a tetrahydrate or as a monohydrate, furthermore the perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and urea.
  • the bleach activators include in particular N-acyl compounds.
  • suitable N-acyl compounds are polyacylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylenediamine, and acylated glycolurils, such as tetraacetylglycoluril.
  • Further examples are N-alkyl-N-sulfonylcarbonamides, N-acylhydantoins, N-acylated cyclic triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines.
  • acylated sugars such as glucose pentaacetate are particularly suitable as O-acyl compounds.
  • Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate.
  • the enzymes, foam-influencing agents and bleach activators can be granulated in a known manner and / or coated with water-soluble or water-dispersible coating substances in order to avoid interactions with the other detergent components during storage of the powdery mixtures.
  • Salts which are customary to absorb water of hydration can serve as granulating agents.
  • Suitable coating substances are water-soluble polymers, such as polyethylene glycol, cellulose ethers, cellulose esters, water-soluble starch ethers and starch esters, and nonionic surfactants of the alkoxylated alcohol, alkylphenol, fatty acid and fatty acid amide type.
  • the detergent component produced according to the invention is only slightly foam-active and can be used in washing machines without problems.
  • the spray-dried powder product is subsequently expanded with foam-active surfactants and surfactant mixtures, preferably in a compound -Form, added.
  • foam-active surfactants and surfactant mixtures preferably in a compound -Form, added.
  • foam-active surfactants and surfactant mixtures include known anionic surfactants of the sulfonate and sulfate type as well as zwitterionic surfactants.
  • Such an addition can also lead to a further increase in washing power.
  • Their addition can be up to 10% by weight, based on the finished mixture, preferably 0.2 to 8% by weight.
  • Suitable anionic surfactants are, for example, alkylbenzenesulfonates, for example n-dodecylbenzenesulfonate, olefin sulfonates, alkanesulfonates, primary or secondary alkyl sulfates, sulfo fatty acid esters and sulfates of ethoxylated or propoxylated higher molecular weight alcohols, monoalkylated or dialkylated sulfosuccinates and fatty acid esters of fatty acid esters of fatty acid esters of fatty acid esters of fatty acid esters of fatty acid esters of sulfuric acid fatty acids.
  • alkylbenzenesulfonates for example n-dodecylbenzenesulfonate, olefin sulfonates, alkanesulfonates, primary or secondary alkyl sulfates, sulfo fatty acid esters and
  • Suitable zwitterionic surfactants are alkyl betaines and in particular alkyl sulfone betaines, for example 3- (N, N-dimethyi-N-aikyiammonium) propane-1-su) fonate and 2-hydroxypropane-1-sulfonate.
  • alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, fatty alcohol sulfates, a-sulfofatty acid esters are to be regarded as preferred because of their foam-raising and washing-enhancing action. If emphasis is primarily placed on foam activation, the use of sulfates of ethoxylated fatty alcohols, in particular 1 to 3 glycol ether groups, and alkylsulfobetaines is recommended.
  • the anionic surfactants or mixtures thereof are preferably in the form of sodium or potassium salts and as salts of organic bases, such as mono-, di- or triethanolamine. If the anionic and zwitterionic compounds mentioned have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 20, in particular 12 to 18, carbon atoms. In the compounds having an araliphatic hydrocarbon radical, the preferably unbranched alkyl chains contain an average of 6 to 16, in particular 8 to 14, carbon atoms.
  • the additional optional anionic and zwitterionic surfactants are also expediently used in granular form.
  • the usual inorganic salts such as sodium sulfate, sodium carbonate, phosphates and zeolites, and mixtures thereof are used as granulation aids or carrier substances.
  • Fabric softening additives generally consist of granules containing a softening quaternary ammonium compound (QAV), e.g. Distearyldimethylammonium chloride, a carrier and an additive which delays the dispersion in the wash liquor.
  • QAV softening quaternary ammonium compound
  • a typical granulate of this type consists, for. B. from 86 wt .-% QAV, 10 wt .-% pyrogenic silica and 4 wt .-% silicone oil (with pyrogenic silica) activated polydimethylsiloxane; another granulate has the composition 30% by weight QAV, 20% by weight sodium triphosphate, 20% by weight zeolite NaA, 15% by weight water glass, 2% by weight silicone oil and the rest water.
  • QAV softening quaternary ammonium compound
  • the aim should be that the bulk density and the average grain size of the particles do not differ significantly from the corresponding parameters of the spray drying products according to the invention, or that the particles do not have a surface that is too rough or too irregular exhibit.
  • the additional powder constituents generally do not exceed a proportion of 10 to 40% by weight, preferably up to 30% by weight (based on the finished mixture), the influence of the additives on the powder properties generally remains small.
  • the sodium hydroxide as 50% sodium hydroxide solution, the melted ethoxylates and the sodium silicate in 36% aqueous solution were initially introduced, then the aluminosilicate (54% water) present as a filter-moist paste, as well as the other constituents, predominantly present in aqueous solution, and finally that anhydrous phosphate added.
  • the slurry which had a total water content of 48.2%, a temperature of 90 ° C and a viscosity of 8500 mPa.s, was homogenized under a pressure of 20 bar measured at the nozzle inlet via swirl nozzles with an outlet opening of 4 mm in a spray tower sprayed.
  • the dry gas introduced in countercurrent under swirl had an inlet temperature of 220 ° C and an outlet temperature (measured at the filter inlet) of 90 ° C.
  • the dust explosion limit was not reached at a powder concentration between 30 and 200 g / m 3 , ie the product is classified in the dust explosion class O.
  • the smoke meter at the outlet of the exhaust air filter shows a deflection between 0.02 and 0.08 divisions (permissible limit 0.15 divisions), ie critical smoke formation was not achieved.
  • the spray product After leaving the spray tower, the spray product had a temperature of 70 ° C. and was cooled to a temperature of 28 ° C. in less than 1 minute in a pneumatic conveyor system. It consisted of over 75% by weight of elongated, ie rod-like to droplet-shaped particles with an average length of 0.8 to 3 mm and an average diameter of 0.1 to 0.6 mm with an average ratio of diameter to length from 1: 1.5 to 1: 6. The rest consisted of irregular sticky particles cemented together and small amounts of dust. The content of Coarse fractions (1.6-3 mm) were less than 1% by weight. The bulk density of the powder was 650 g / l.
  • Dry sea sand with the following grain spectrum was chosen as the reference substance.
  • test product 87.0 parts by weight of the test product were mixed with 10 parts by weight of powdered sodium perborate tetrahydrate which had been sprayed with 0.2 part by weight of perfume oil, 0.5 part by weight of an enzyme granulate, prepared by prilling an enzyme melt, and 2.3 Parts by weight of granulated tetraacetylethylenediamine are mixed, the grain size of the admixed components being in the range between 0.1 and 1 mm. This increases the bulk weight to 700 g / l. The flowability did not change within the error limits.
  • the mixture proved to be a high-quality detergent that can be used in the temperature range between 30 ° and 100 ° C.
  • the flushability and the formation of residues in the input devices of fully automatic washing machines no differences between a loose spray powder and the test product were recognizable.
  • the solution properties of the comparison product listed under (d) were poorer, which led to the formation of residues in the induction device and on the textiles.
  • Experiment I resulted in a bloated, specifically light (less than 500 g / l) spray product with a high dust content and poorer flow behavior.
  • Experiments 11 and 111 also produced specifically light, expanded powders, with the coarse fraction increasing more in Experiment III. In experiment IV, adequate drying could not be achieved, but rather a moist, lumpy and unusable product resulted.
  • test V the smoke meter showed a scale value of 2 divisions, which means that the smoke emission is above the permissible limit.
  • the ingredients were mixed as described in Example 1 to form a slurry with a water content of 46.5% and a viscosity of 9000 mPa.s, the slurry being heated to a temperature before the tripolyphosphate and the zeolite were added by introducing steam of 88.5 ° C was heated.
  • the slurry was sprayed into a spray tower at a pressure of 22 bar via swirl nozzles with an outlet opening of 4.1 mm.
  • the air conducted in counterflow had an inlet temperature (measured before entering the ring channel) of 218 ° C and an outlet temperature of 89.5 ° C.
  • the smoke indicator in the exhaust air was 0.02 to 0.07 divisions, with regard to the powder concentration in the drying tower the same conditions as in example 1 prevailed.
  • the powder leaving the spray tower was brought to 30 ° C. in the feed shaft with flowing, 24 ° C. warm outside air cooled down.
  • the spray product consisted of over 60% by weight of rod-shaped particles with an average length of 0.7 to 2.7 mm and an average diameter of 0.1 to 0.7 mm with a dimension ratio of 1: 1.6 to 1 : 5 and a dust content of less than 1% by weight.
  • the bulk density was 645 g / 1 and the flow rate was 83%.
  • the spray product was dusted with 1.4% by weight of dry, finely crystalline aluminosilicate (zeolite NaA, particle size 0.5 to 7 ⁇ m) in a continuously operated mixer while simultaneously adding 10% by weight of sodium perborate.
  • zeolite NaA finely crystalline aluminosilicate
  • granulated bleach activator tetraacetylethylene diamine
  • Example 1 was repeated, but instead of the sodium tripolyphosphate used there, one containing 40% Form I was used. Before the phosphate was added, the slurry was heated to a temperature of 90 ° C. and then pumped in a circuit through a homogenizer. The viscosity was 11,000 mPa.s with a water content of 43% by weight. The spraying was carried out at a pressure of 22 bar and a nozzle opening of 4.0 mm. The temperature of the counter-current dry air was 215 ° C at the tower entrance and 89 ° C at the tower exit. The remaining process parameters were the same as in Example 1.
  • the spray product corresponded to the powder according to Example 1 with regard to grain size and bulk density.
  • the pourability was 86% of that of dry sand.
  • An aftertreatment with 0.06% by weight of silica airgel (Aerosil 13 ) improved the flowability to 89% of that of dry sand and led to an increase in the bulk density from 640 g / l to 660 g / l.
  • Example 2 was repeated, but the temperature of the cooling air flowing into the conveyor system was 37 ° C. due to high outside temperatures. Due to the delayed cooling of the powder, which was still warm from the spraying process, there was a slight exudation of nonionic surfactant on the surface of the detergent granules, with the result that the pourability of the powder dropped to 81% with a bulk density of 620 g / l. After-treatment with 1% by weight of NaA zeolite (grain size 1 to 8 ⁇ m) in a continuously operating mixer increased the free-flowing capacity to 86% of that of dry sand and the bulk density to 640 g / l.
  • NaA zeolite grain size 1 to 8 ⁇ m
  • the viscosity was measured with a convection-type rotary viscometer from Brabender, Duisburg, Federal Republic of Germany.

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Claims (21)

1. Composant d'agent de lavage granulaire, s'écoulant librement, se dissolvant rapidement dans l'eau, ayant une densité apparente de 550 à 800 g/I et constitué d'agents tensio-actifs synthétiques essentiellement non ioniques, de substances supports inorganiques, y compris des silicates de métaux alcalins, d'autres agents auxiliaires de lavage organiques et d'eau fixée par adsorption ou sous forme d'un hydrate, caractérisé en ce qu'on le prépare moyennant un séchage par pulvérisation, tandis qu'il est constitué, pour plus de 50% en poids, de particules d'une configuration se situant entre celle de gouttes et celle de bâtonnets d'un diamètre moyen de 0,02 à 1,5 mm, d'une longueur moyenne de 0,1 à 5 mm et d'un rapport diamètre moyen/longueur moyenne de 1 : 1,2 à 1 : 10, sa teneur en agents tensio-actifs non ioniques allant de 15 à 28% en poids, sa teneur en agents tensio-actifs anioniques synthétiques étant inférieure à 1 % en poids, sa teneur en savon étant inférieure à 0,2% en poids et sa teneur en substance support inorganique étant de 40 à 80% en poids, calculé sur la substance anhydre.
2. Produit selon la revendication 1, caractérisé en ce que sa teneur en agents tensio-actifs non ioniques alcoxylés est de 17 à 25% en poids, en particulier, de 18 à 23% en poids, sa teneur en agents tensio-actifs anioniques étant inférieure à 0,5% en poids et sa teneur en savon étant de 0%.
3. Produit selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que, comme substance support inorganique, il contient 0 à 60% en poids de tripolyphosphate de sodium, y compris ses produits d'hydrolyse, 5 à 20% en poids d'un silicate d'un métal alcalin de la composition Na20 : Si02 = 1 : 1,5-1 : 3,5, ainsi que 0 à 40% en poids d'aluminosilicate de sodium de type zéolite A, finement cristallin et contenant de l'eau fixée, les quantités indiquées étant rapportées aux substances supports anhydres, tandis que la teneur totale en substance support inorganique est de 45 à 70% en poids.
4. Produit selon une des revendications 1 à 3, caractérisé en ce que, comme substance support inorganique, il contient 10 à 50% en poids de tripolyphosphate de sodium, y compris ses produits d'hydrolyse, 6 à 15% en poids de silicate de sodium (de la composition Na20: Si02 = 1 : 2-1 : 2,5) et 3 à 30% en poids de zéolite NaA, les quantités indiquées étant rapportées aux substances supports anhydres.
5. Produit selon une des revendications 1 à 4, caractérisé en ce que la quantité d'autres agents auxiliaires de lavage organiques est de 0,5 à 10% en poids, tandis que la quantité d'eau fixée par adsorption ou sous forme d'un hydrate est de 8 à 20% en poids.
6. Produit selon une des revendications 1 à 5, caractérisé en ce qu'il est constitué de particules compactes, non poreuses et à surface fermée, 65 à 100% en poids des particules ayant un diamètre moyen de 0,05 à 1 mm, une longueur moyenne de 0,3 à 3 mm et un rapport diamètre moyen/ longueur moyenne de 1 : 1,4 à 1 : 8.
7. Produit selon une des revendications 1 à 6, caractérisé en ce que la surface des particules a une fine structure grenue à lamellaire.
8. Produit selon une des revendications 1 à 7, caractérisé en ce qu'il a une densité apparente de 600 à 750 g/1.
9. Produit selon une des revendications 1 à 8, caractérisé en ce que les grains comportent un revêtement constitué d'une substance solide finement divisée, soluble ou dispersable dans l'eau comme agent de fluidisation, en une quantité représentant 0,01 à 3% en poids du produit de pulvérisation granulaire.
10. Produit selon une des revendications 1 à 9, caractérisé en ce que le revêtement est constitué de 0,1 à 2% en poids de zéolite de type NaA.
11. Produit selon une des revendications 1 à 10, caractérisé en ce que le revêtement est constitué de 0,05 à 0,5% en poids d'acide silicique finement divisé.
12. Procédé de préparation des produits selon les revendications 1 à 11, caractérisé en ce que, au moyen de pulvérisateurs dont l'ouverture de sortie a un diamètre de 3 à 5,5 mm, sous une pression de 16 à 30 bars, on pulvérise, dans une tous de séchage, une suspension des constituants, contenant, au total, 55 à 35% en poids d'eau, le rapport du diamètre à l'entrée des pulvérisateurs au diamètre de l'ouverture de sortie des pulvérisateurs est de 3 à 9 bars/mm, tandis que la température d'entrée du gaz de séchage acheminé, mesurée dans le canal annulaire de la tour de séchage, ne dépasse pas 250 °C.
13. Procédé selon la revendication 12, caractérisé en ce qu'on utilise des pulvérisateurs exerçant un effet giratoire sur le produit à pulvériser, la pression régnant à l'entrée des pulvérisateurs étant de 18 à 28, en particulier, de 19 à 25 bars, le diamètre de l'ouverture de sortie des pulvérisateurs étant de 3,5 à 5 mm, en particulier, de 3,5 à 4,5 mm, tandis que le rapport de la pression à l'entrée des pulvérisateurs au diamètre de l'ouverture de sortie des pulvérisateurs est de 4 à 6 bars/mm, en particulier, de 4,5 à 5,5 bars/mm.
14. Procédé selon une des revendications 12 ou 13, caractérisé en ce que les gaz de séchage acheminés en contre-courant au produit de pulvérisation ont une température d'entrée de 180 à 240°C, en particulier, de 190 à 220°C, ainsi qu'une température de sortie de 90 ± 15°C.
15. Procédé selon une des revendications 12 à 14, caractérisé en ce qu'on pulvérise une suspension aqueuse dont la teneur en eau, y compris l'eau fixée par adsorption ou sous forme d'un hydrate est de 55 à 42% en poids, de préférence, de 52 à 44% en poids.
16. Procédé selon une des revendications 12 à 15, caractérisé en ce que, pour la formation de la suspension aqueuse, on part d'un tripolyphosphate de sodium anhydre constitué, pour 30 à 50%, de préférence, pour 35 à 45%, de la modification I.
17. Procédé selon une des revendications 12 à 16, caractérisé en ce qu'on règle la viscosité de la charge aqueuse à 2.000-15.000 mPa.s, de préférence, à 5.000-12.000 mPa.s et, en particulier, à 6.000-10.000 mPa.s.
18. Procédé selon une des revendications 12 à 17, caractérisé en ce que, avant l'addition du tripolyphosphate, on règle la température de la charge aqueuse à plus de 85°C, de préférence à 86-102°C.
19. Procédé selon une des revendications 12 à 18, caractérisé en ce qu'on refroidit le produit de pulvérisation endéans 5 minutes, de préférence, endéans 2 minutes, à des températures inférieures à 35 °C, de préférence, à des températures de 20 à 30 °C.
20. Procédé selon une des revendications 12 à 18, caractérisé en ce qu'on enduit le produit de pulvérisation dans un dispositif de mélange avec 0,01 à 3% en poids d'une substance solide finement divisée soluble ou dispersable dans l'eau, comme agent de fluidisation.
21. Procédé selon la revendication 20, caractérisé en ce qu'on enduit le produit de pulvérisation avec 0,1 à 2% en poids de zéolite de type NaA ou avec 0,05 à 0,5% en poids d'acide silicique finement divisé.
EP84103320A 1983-03-25 1984-03-26 Composante granuleuse de détergent, à écoulement libre et procédé pour sa préparation Expired EP0120492B1 (fr)

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AT84103320T ATE35692T1 (de) 1983-03-25 1984-03-26 Koernige, freifliessende waschmittelkomponente und verfahren zu ihrer herstellung.

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DE3310906 1983-03-25
DE3310906 1983-03-25
US54156983A 1983-10-13 1983-10-13
US541569 1983-10-13
DE3344698 1983-12-10
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BR (1) BR8406459A (fr)
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DE3424299A1 (de) * 1984-07-02 1986-01-09 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines spruehgetrockneten nichtionischen waschhilfsmittels
DE3434854A1 (de) * 1984-09-22 1986-04-03 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung einer koernigen, freifliessenden waschmittelkomponente
DE3803966A1 (de) * 1988-02-10 1989-08-24 Henkel Kgaa Verfahren zur erhoehung der dichte spruehgetrockneter waschmittel
DE3812530A1 (de) * 1988-04-15 1989-10-26 Henkel Kgaa Verfahren zur erhoehung der dichte spruehgetrockneter, phosphatreduzierter waschmittel
GB2231579A (en) * 1989-05-09 1990-11-21 Unilever Plc Spray-dried detergent
DE4329988A1 (de) * 1993-09-04 1995-03-09 Henkel Kgaa Sprühgetrocknetes Granulat mit hohem Schüttgewicht
EP0643130B2 (fr) * 1993-09-13 2007-09-19 The Procter & Gamble Company Composition détergentes granulaires contenant un tensio-actif non-ionique et procédé de sa préparation
EP0820762A1 (fr) 1996-07-15 1998-01-28 Unilever Plc Compositions de parfums

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GB1232010A (fr) * 1967-09-04 1971-05-19
DE2724349A1 (de) * 1977-05-28 1978-12-07 Henkel Kgaa Verfahren zur herstellung spruehgetrockneter, nichtionische tenside enthaltender waschmittel
GB2082620B (en) * 1977-10-06 1983-02-02 Colgate Palmolive Co Detergent compositions
JPS5562999A (en) * 1978-11-07 1980-05-12 Kawaken Fine Chemicals Co Spray dry detergent composition

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DK553084D0 (da) 1984-11-21
DE3472682D1 (en) 1988-08-18
EP0120492A3 (en) 1986-02-19
DK553084A (da) 1984-11-21
EP0120492A2 (fr) 1984-10-03
BR8406459A (pt) 1985-03-12
WO1984003708A1 (fr) 1984-09-27
DK161842B (da) 1991-08-19

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