EP0120492A2 - 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

Info

Publication number
EP0120492A2
EP0120492A2 EP84103320A EP84103320A EP0120492A2 EP 0120492 A2 EP0120492 A2 EP 0120492A2 EP 84103320 A EP84103320 A EP 84103320A EP 84103320 A EP84103320 A EP 84103320A EP 0120492 A2 EP0120492 A2 EP 0120492A2
Authority
EP
European Patent Office
Prior art keywords
weight
spray
water
product according
product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP84103320A
Other languages
German (de)
English (en)
Other versions
EP0120492A3 (en
EP0120492B1 (fr
Inventor
Otto Dr. Koch
Herbert Dr. Reuter
Wolfgang Dr. Seiter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT84103320T priority Critical patent/ATE35692T1/de
Publication of EP0120492A2 publication Critical patent/EP0120492A2/fr
Publication of EP0120492A3 publication Critical patent/EP0120492A3/de
Application granted granted Critical
Publication of EP0120492B1 publication Critical patent/EP0120492B1/fr
Expired legal-status Critical Current

Links

Images

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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • 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, for example, agents with a high soda or silicate content, as were obtained in the past, for example, by simply mixing the individual components together or by drying aqueous mixtures on trays or heated rollers, 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.
  • nonionic surfactants can be applied subsequently to the spray-dried carrier material.
  • powder such as talc, finely divided silica or calcined clay.
  • a graying inhibitor in powder form for example carboxymethyl cellulose, can also be added subsequently.
  • the powders thus obtained, loaded with nonionic surfactants can have a bulk density of more than 500 g / l, for example 700 g / 1, and a flowability of, for example, up to 76% of that 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 27 42 683.
  • 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 specifically specified and thus usable route is via a two-stage and therefore complex manufacturing process, in which one initially produces so-called "base beads" with a porous outer surface and a more or less absorbent inner frame by spray drying an aqueous slurry, which is then used the liquid or melted nonionic surfactant is sprayed or soaked.
  • DE-AS 17 92 434 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 prehydrated. 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 / 1 and - if the proportion of non-ionic 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 / 1, consisting of synthetic, essentially nonionic surfactants, inorganic carrier substances, other organic washing aids and adsorptive or as hydrate bound water.
  • This granular detergent component is characterized in that it is produced by spray drying and is more than 50% by weight of drop-shaped to rod-shaped particles with an average diameter of 0.02 to 1.5 mm, 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.
  • 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 detergent component in granular form according to the invention is present 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 in the exhaust air (so-called pluming) is particularly low and the washing effect against mineral 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 oil. You can replace components (a) and (b) in whole or in part in the aforementioned mixtures.
  • non-Bibnic 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 ones containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups can also be used Polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain.
  • 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%, preferably less than 0.5%, in particular 0% and that of soap less than 0.2%, preferably 0%.
  • No anionic surfactants are expediently used, since surprisingly it has been shown that even small amounts of such additives, in particular the smallest additions of soap, cause the granules 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.
  • builders which includes the polymer phosphates, in particular sodium tripolyphosphate and more highly condensed polymer phosphates, such as sodium tetraphosphate.
  • the polymer phosphates can be present in a mixture with their hydrolysis products, ie orthophosphate and pyrophosphate, but because of the higher washing and calcium binding capacity of the polyphophates, the lowest possible hydrolysis of the polyphosphate when preparing the slurry and during spray drying is to be aimed for 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, ie they have practically no particles larger than 30 microns and preferably consist at least 80% of particles smaller than 10 microns.
  • Their calcium binding capacity which according to According to DE 24 12 837, it is in the range of 100-200 mg CaO / g.
  • Particularly useful is the zeolite NaA, 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 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 can be found in such carrier salt mixtures which consist essentially of sodium tripolyphosphate or consist of zeolite and mixtures thereof, can also be increased beyond the stated maximum content of 20% by weight without resulting in major disadvantages for the dissolving behavior of the particles.
  • the percentage content of polyphosphate in the detergents can be in the range of conventional heavy-duty detergents, the tendency to reduce phosphate is fully taken into account in the invention.
  • the agents according to the present invention are compared to conventional, i.e. specifically light washing powders are used in a much lower dosage; on the other hand, the proportion of phosphate in favor of the proportion of aluminosilicate can be considerable, i.e. can be reduced to, for example, 10% by weight or even eliminated entirely.
  • 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- (methylene-phosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and their higher homologues, such as, for example, diethylene-triaminepenta- (methylenephosphonic acid). More 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- ⁇ -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: 5 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 which may be present in the spray-dried powder component are graying inhibitors, optical brighteners and additives which regulate the viscosity behavior of the slurry, for example alkali metal salts or toluene, cumene or xylene sulfonic acid and, if appropriate, polymers which act as thickeners (for example from 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.
  • Suitable optical brighteners are the alkali salts of 4,4-bis (-2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "- amino) -stilbene-2,2-disulfonic acid or similar compounds, which carry a diethanolamino group, a methylamino group or a .beta.-methoxyethylamino group instead of the morpholino group.
  • Brighteners of the substituted diphenylstyryl type for example the alkali metal salts of 4,4-bis (2-sulfostyryl) diphenyl, 4,4-bis, are also suitable (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl) -4- (2-sulfostyryl) diphenyl.
  • 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 front of such a particle in the area of a break. This example shows that the surface structure inside the particles can continue.
  • Figures 6 and 7 of a conventional spray powder with a low bulk density attached for comparison show agglomerated particles of irregular, in a 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 built up on a subordinate scale from particles of a different shape, i.e. that two or more droplet to rod-shaped particles are cemented into agglomerates of irregular shapes, or that small proportions of approximately spherical particles are produced or that elongated particles break into short fragments during further processing or during 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 due to its characteristic rod-shaped powder structure, is only suitable to a limited extent for determining the particle size distribution by means of sieve analysis, the particle spectrum can be determined using this method. It shows that the grain spectrum is comparatively narrow, i.e. 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 proportion of dust in the powder component according to the invention and the proportion of oversize are accordingly 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 to 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.
  • the agents according to the invention even exceed these Values, ie the volume decreases here are usually below 10% and reach a value of 5% in favorable cases.
  • the high volume consistency, combined with the excellent pourability, facilitates in particular precise and reproducible dosing during filling and in use.
  • the grains have a coating of a finely divided, water-soluble or dispersible solid as a fluidizing agent in an amount which is 0.01 to 3 wt .-% of the granular Spray product is.
  • the finely divided synthetic zeolites of the NaA or NaX type have proven particularly useful as coating agents. 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.
  • Fine-particle silica with a large specific surface area in particular pyrogenic silica (Aerosil®), is also suitable 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 to 0.5% by weight in the case of the finely divided silica, 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 that they have a particle size of less than 0.1 mm, for example from 0.001 to 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 measured at the nozzle inlet at a ; Sprayed the diameter of the nozzle outlet opening from 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.
  • 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 as well as 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 dry 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 drying gas in the spray drying system from 180 ° C to 240 ° C, preferably from 190 ° C to 220 ° C, it should be noted that these are temperatures of the gas in the so-called ring channel of the spray 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 is not undercut in the downstream dedusting systems.
  • 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 impractical because they increase the degree of hydrolysis of the tripolyphosphate, increase energy consumption and lead to a lower bulk density.
  • Lower levels 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 sharp increase in viscosity in the slurry batch. It is recommended that the liquid products, i.e. the melted nonionic surfactants and those already in aqueous solution or
  • Slurry components present, e.g. to present the aluminosilicate present as a filter-moist paste and, if appropriate, additional water, and to add the anhydrous constituents, in particular the anhydrous or, if appropriate, partially hydrated tripolyphosphate, with vigorous stirring.
  • anhydrous, slowly hydrating sodium tripolyphosphate of Form II is used, a strong increase in viscosity and a greater hydrolysis to lower phosphates are avoided, but under certain circumstances a somewhat reduced flowability of the spray product has to be accepted.
  • Faster hydrating tripolyphosphate for example one with higher proportions of Form I or partially prehydrated tripolyphosphate, leads to higher slurrie viscosities. It is an advantage of the process that the use of prehydrated polyphosphate is not necessary.
  • 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 adequate flowability of the slurry and spray products with favorable powder properties, it has proven to be advantageous to adjust 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 10,000 mPa.s to set.
  • This adjustment is advantageously performed in such a manner that the slurry is heated before the 'addition of the solids, particularly before addition of the tripolyphosphate to temperatures above 85 ° C, for example at 86 ° C to 102 ° C.
  • 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 regulators ensures that the preferred viscosity ranges are maintained.
  • 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, fluctuations in certain product properties, such as bulk density and pourability of the grains, can occur. Seasonal climate fluctuations can be an influence, 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 flowability decreases without caking occurring.
  • 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. 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 method 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 their specific effect in whole or in part or that would adversely change the properties of the spray-drying product.
  • enzymes from the class of proteases, lipases and amylases or their mixtures Enzymes obtained from bacterial strains or fungi, such as Bacillus subtillis, 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 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-sulfonyl-carbonamides, N-acylhydantoins, N-acylated cyclic triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines.
  • acylated sugars such as glucose pentaacetate are particularly suitable as 0-acyl compounds.
  • Preferred bleach activators are tetraacetylethylenediamine 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 preferably in a compound -Form, added.
  • foam-active surfactants and surfactant mixtures preferably in a compound -Form
  • foam-active surfactants and surfactant mixtures preferably in a compound -Form
  • foam-active surfactants and surfactant mixtures preferably in a compound -Form, added.
  • 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
  • Alkylbenzenesulfonates for example n-dodecylbenzenesulfonate, olefin sulfonates, alkanesulfonates, primary or secondary alkyl sulfates, sulfo fatty acid esters as well as sulfates of ethoxylated or propoxylated higher molecular weight alcohols, monoalkylated or dialkylated sulfosuccinates, sulfuric acid esters of fatty acid partial esters, and fatty acid partial esters of glyceryl fatty acid.
  • Suitable zwitterionic surfactants are alkyl betaines and especially alkyl sulfone betaines, e.g. the 3- (N, N-dimethyl-N-alkylammonium) propane-1-sulfonate and 2-hydroxypropane-1-sulfonate.
  • alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, fatty alcohol sulfates, ⁇ -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 the 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 such granulate is e.g. polydimethylsiloxane activated from 86% by weight of QAV, 10% by weight of pyrogenic silica and 4% by weight of silicone oil (with pyrogenic silica); 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.
  • the additional powder components generally do not exceed a proportion of 10 to 40% by weight, preferably 30 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 molten ethoxylates and the sodium silicate in 36% aqueous solution were initially introduced, then the aluminosilicate (54% water) present as a filter-moist paste and the other constituents, predominantly present in aqueous solution, and finally that anhydrous phosphate added.
  • the slurry had a total water content of 48.2%, a temperature of 90 ° C and a viscosity of 8500 mPa.s after homogenization under a pressure of 20 bar measured at the nozzle inlet, sprayed through swirl nozzles with an outlet opening of 4 mm in a spray tower.
  • 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, ie the product is classified in dust explosion class 0.
  • the smoke meter at the outlet of the exhaust air filter shows a deflection between 0.02 and 0.08 scale parts (permissible limit 0.15 scale parts), 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, i.e. 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 of 1: 1.5 to 1: 6 The rest consisted of irregular sticky particles and small amounts of dust cemented together. The coarse content (1.6-3 mm) was less than 1% by weight. The bulk density of the powder was 650 g / 1.
  • Dry sea sand with the following grain spectrum was chosen as the reference substance.
  • 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.
  • test V the smoke measuring device showed a scale value of 2 divisions, which means that the smoke emission is above the permissible limit.
  • 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 countercurrent had an inlet temperature (measured before entering the ring channel) of 218 ° C and an initial 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 delivery 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 pm) in a continuously operated mixer while simultaneously adding 10% by weight of sodium perborate. After admixing 1% by weight of enzyme granules and 3% by weight of granulated bleach activator (tetraacetylethylene diamine), the bulk density rose to 690 g / 1 with a free-flowing capacity of 88%. The solution properties in water were still good.
  • 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 through a homogenizer in a circuit. 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 in terms of particle size and bulk density.
  • the pourability was 86% of that of dry sand.
  • Aftertreatment with 0.06% by weight of silica airgel (Aerosil) improved the flowability to 89% of that of dry sand and led to an increase in the bulk density from 640 g / 1 to 660 g / 1.
  • 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 to 81%. a bulk weight of 620 g / 1 dropped. After-treatment with 1% by weight of NaA zeolite (particle 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.
  • the viscosity was measured with a convection-type rotary viscometer from Brabender, Duisburg, Federal Republic of Germany.
  • 89 parts by weight of the spray product from Example 1 were mixed with 1 part by weight of enzyme granules and 10 parts by weight of a surfactant compound in a continuously operated mixer.
  • the surfactant compound was produced by spray mixing with the following composition:
EP84103320A 1983-03-25 1984-03-26 Composante granuleuse de détergent, à écoulement libre et procédé pour sa préparation Expired EP0120492B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84103320T ATE35692T1 (de) 1983-03-25 1984-03-26 Koernige, freifliessende waschmittelkomponente und verfahren zu ihrer herstellung.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE3310906 1983-03-25
DE3310906 1983-03-25
US54156983A 1983-10-13 1983-10-13
DE3344698 1983-12-10
DE3344698 1983-12-10
US541569 1990-06-21

Publications (3)

Publication Number Publication Date
EP0120492A2 true EP0120492A2 (fr) 1984-10-03
EP0120492A3 EP0120492A3 (en) 1986-02-19
EP0120492B1 EP0120492B1 (fr) 1988-07-13

Family

ID=27190870

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84103320A Expired EP0120492B1 (fr) 1983-03-25 1984-03-26 Composante granuleuse de détergent, à écoulement libre et procédé pour sa préparation

Country Status (5)

Country Link
EP (1) EP0120492B1 (fr)
BR (1) BR8406459A (fr)
DE (1) DE3472682D1 (fr)
DK (1) DK161842C (fr)
WO (1) WO1984003708A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0167916A2 (fr) * 1984-07-02 1986-01-15 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'un adjuvant de détergent non ionique séché par pulvérisation
EP0179264A1 (fr) * 1984-09-22 1986-04-30 Henkel Kommanditgesellschaft auf Aktien Procédé pour la production d'une composante de lavage granulaire à écoulement libre
EP0327963A2 (fr) * 1988-02-10 1989-08-16 Henkel Kommanditgesellschaft auf Aktien Procédé pour augmenter la densité de détergents séchés par vaporisation
EP0337330A2 (fr) * 1988-04-15 1989-10-18 Henkel Kommanditgesellschaft auf Aktien Procédé pour augmenter la densité des détergents séchés par pulvérisation et contenant peu de phosphate
GB2231579A (en) * 1989-05-09 1990-11-21 Unilever Plc Spray-dried detergent
WO1995007339A1 (fr) * 1993-09-04 1995-03-16 Henkel Kommanditgesellschaft Auf Aktien Granule seche par pulverisation a masse volumique apparente elevee
EP0820762A1 (fr) 1996-07-15 1998-01-28 Unilever Plc Compositions de parfums

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69422675T3 (de) * 1993-09-13 2008-05-21 The Procter & Gamble Company, Cincinnati Granuläre Waschmittelzusammensetzungen, umfassend nichtionisches Tensid, und Verfahren zur Herstellung solcher Zusammensetzungen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1579247A (fr) * 1967-09-04 1969-08-22
DE2724349A1 (de) * 1977-05-28 1978-12-07 Henkel Kgaa Verfahren zur herstellung spruehgetrockneter, nichtionische tenside enthaltender waschmittel
JPS5562999A (en) * 1978-11-07 1980-05-12 Kawaken Fine Chemicals Co Spray dry detergent composition
GB2082620A (en) * 1977-10-06 1982-03-10 Colgate Palmolive Co Detergent compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1579247A (fr) * 1967-09-04 1969-08-22
DE2724349A1 (de) * 1977-05-28 1978-12-07 Henkel Kgaa Verfahren zur herstellung spruehgetrockneter, nichtionische tenside enthaltender waschmittel
GB2082620A (en) * 1977-10-06 1982-03-10 Colgate Palmolive Co Detergent compositions
JPS5562999A (en) * 1978-11-07 1980-05-12 Kawaken Fine Chemicals Co Spray dry detergent composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 93, Nr. 10, September 1980, Seite 117, Ref.Nr. 97309p, Columbus, Ohio, US; & JP - A - 80 62 999 (KAWAKEN FINE CHEMICALS CO. LTD.) 12.05.1980 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0167916A2 (fr) * 1984-07-02 1986-01-15 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'un adjuvant de détergent non ionique séché par pulvérisation
EP0167916A3 (fr) * 1984-07-02 1987-07-01 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'un adjuvant de détergent non ionique séché par pulvérisation
EP0179264A1 (fr) * 1984-09-22 1986-04-30 Henkel Kommanditgesellschaft auf Aktien Procédé pour la production d'une composante de lavage granulaire à écoulement libre
EP0327963A2 (fr) * 1988-02-10 1989-08-16 Henkel Kommanditgesellschaft auf Aktien Procédé pour augmenter la densité de détergents séchés par vaporisation
EP0327963A3 (fr) * 1988-02-10 1990-04-11 Henkel Kommanditgesellschaft auf Aktien Procédé pour augmenter la densité de détergents séchés par vaporisation
EP0337330A2 (fr) * 1988-04-15 1989-10-18 Henkel Kommanditgesellschaft auf Aktien Procédé pour augmenter la densité des détergents séchés par pulvérisation et contenant peu de phosphate
EP0337330A3 (en) * 1988-04-15 1990-04-11 Henkel Kommanditgesellschaft Auf Aktien Process for increasing the density of spray-dried detergents with a reduced phosphate content
GB2231579A (en) * 1989-05-09 1990-11-21 Unilever Plc Spray-dried detergent
WO1995007339A1 (fr) * 1993-09-04 1995-03-16 Henkel Kommanditgesellschaft Auf Aktien Granule seche par pulverisation a masse volumique apparente elevee
US5767057A (en) * 1993-09-04 1998-06-16 Henkel-Ecolab Gmbh & Co. Ohg Spray-dried granules of high apparent density
EP0820762A1 (fr) 1996-07-15 1998-01-28 Unilever Plc Compositions de parfums

Also Published As

Publication number Publication date
DK161842C (da) 1992-01-27
DE3472682D1 (en) 1988-08-18
EP0120492A3 (en) 1986-02-19
DK553084D0 (da) 1984-11-21
EP0120492B1 (fr) 1988-07-13
BR8406459A (pt) 1985-03-12
DK553084A (da) 1984-11-21
DK161842B (da) 1991-08-19
WO1984003708A1 (fr) 1984-09-27

Similar Documents

Publication Publication Date Title
EP0179264B1 (fr) Procédé pour la production d'une composante de lavage granulaire à écoulement libre
EP0595946B1 (fr) Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree
EP0228011B1 (fr) Détergent granulaire à teneur en phosphates réduite
EP0859827B2 (fr) Procede de production d'un silicate alcalin amorphe avec impregnation
DE19529298B4 (de) Verfahren zur Herstellung eines nichtionischen Wasch-(Reinigungs-)mittel-Granulats
EP0663946B1 (fr) Produits d'interet et melanges de produits d'interet pour agents mouillants, detergents et/ou nettoyants sous une nouvelle forme de preparation
EP0337330B1 (fr) Procédé pour augmenter la densité des détergents séchés par pulvérisation et contenant peu de phosphate
DE3444960A1 (de) Koerniges adsorptionsmittel
DE4435743C2 (de) Verfahren zur Herstellung eines Mehrkomponenten-Granulates
DE69726439T2 (de) Verfahren zur herstellung von einer waschmittelzusammensetzung nach ohne-turm-verfahren
WO1993015180A1 (fr) Procede pour fabriquer des produits solides de lavage et de nettoyage de densite apparente elevee et presentant une vitesse de dissolution amelioree
EP0167916A2 (fr) Procédé de préparation d'un adjuvant de détergent non ionique séché par pulvérisation
DE4232874A1 (de) Verfahren zur Herstellung von Tensidgranulaten
EP0120492B1 (fr) Composante granuleuse de détergent, à écoulement libre et procédé pour sa préparation
EP0804529A1 (fr) Compose silicate alcalin amorphe
DE69826871T2 (de) Verfahren zur herstellung von waschmitteln mit niedriger schüttdichte durch kontrolle der düsenhöhe im fliessbett
DE69636644T3 (de) Verfahren zur herstellung von granularen waschmittelkomponenten oder -zusammensetzungen
EP0566583B1 (fr) Produits concentres secs facilement solubles, contenant des substances de produits de lavage
DE2837504A1 (de) Verfahren zur herstellung eines schuettfaehigen, nichtionische tenside enthaltenden wasch- und reinigungsmittelgranulates
DE19851454B4 (de) Tensid-Granulate durch Wirbelschichtgranulation
EP0605436B1 (fr) Procede de preparation de granules de zeolithe
DE60012928T2 (de) Verfahren zur herstellung granularer waschmittelzusammensetzungen
EP1043387A2 (fr) Granules d'alkylbenzènesulfonate
WO1993005133A1 (fr) Procede de lavage et/ou de nettoyage
DE3236375A1 (de) Verfahren zur herstellung koerniger waschmittel mit einem gehalt an fettsaeurealkanolamiden

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19860702

17Q First examination report despatched

Effective date: 19870113

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE FR GB IT LI NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI NL

REF Corresponds to:

Ref document number: 35692

Country of ref document: AT

Date of ref document: 19880715

Kind code of ref document: T

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 3472682

Country of ref document: DE

Date of ref document: 19880818

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19911223

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19920206

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19920212

Year of fee payment: 9

Ref country code: AT

Payment date: 19920212

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19920316

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19920331

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19920512

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19930326

Ref country code: AT

Effective date: 19930326

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19930331

Ref country code: CH

Effective date: 19930331

Ref country code: BE

Effective date: 19930331

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19930331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19931001

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930326

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19931130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19931201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST