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WO1996034081A1 - Granulat stable au stockage contenant des activateurs de blanchiment et son mode de production - Google Patents

Granulat stable au stockage contenant des activateurs de blanchiment et son mode de production Download PDF

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Publication number
WO1996034081A1
WO1996034081A1 PCT/EP1996/001618 EP9601618W WO9634081A1 WO 1996034081 A1 WO1996034081 A1 WO 1996034081A1 EP 9601618 W EP9601618 W EP 9601618W WO 9634081 A1 WO9634081 A1 WO 9634081A1
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WO
WIPO (PCT)
Prior art keywords
granules
weight
moist
bleach activator
granulating
Prior art date
Application number
PCT/EP1996/001618
Other languages
German (de)
English (en)
Inventor
Hans Kruse
Volker Bauer
Dieter Jung
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7760347&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1996034081(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP96914940A priority Critical patent/EP0822974B1/fr
Priority to DE59603355T priority patent/DE59603355D1/de
Publication of WO1996034081A1 publication Critical patent/WO1996034081A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected

Definitions

  • the invention relates to a process for producing a storage-stable, bleach-activator-containing granulate as a component of an agent for textile washing or for cleaning agents by granulating a moist powdery mixture of a powdery bleach activator, a powdery granulating aid and an aqueous solution of the same and / or another granulating aid or an aqueous solution of other active substances of detergents or cleaning agents or water by agglomerating the moist particles in a mixing granulator and then drying the moist granules and, if appropriate, sieving oversize and fine particles.
  • a so-called ploughshare mixer from Lödige
  • a so-called ploughshare mixer with a central, rotating shaft lying in a horizontal cylindrical housing, to which plowshare-shaped paddles are attached, can be used as a mixing granulator.
  • the moist granules obtained after granulation can be dried in conventional dryers, e.g. B. in fluidized bed dryers.
  • Textile detergents and cleaning agents e.g. B. agents for machine dishwashing, often contain inorganic peroxides and peroxohydrates as bleach-active compounds.
  • the main representative is sodium perborate. It hydrolyzes in water to form hydrogen peroxide, thus enabling oxidative bleaching.
  • the bleaching effect strongly depends on the temperature. Sodium perborate only has a clear bleaching effect from around 60 ° C.
  • oxidation effect of the inorganic per compounds can be improved by adding activators.
  • activators are usually acylating agents which form organic peracids in an alkaline medium in the wash liquor with hydrogen peroxide. These show due to their higher oxidation potential compared to hydrogen peroxide in the area of low temperatures a good bleaching effect.
  • a known example of such a bleach activator is tetraacetylethylene diamine (TAED).
  • the bleach activators for example from the class of the N- and O-acyl compounds, are, however, highly sensitive to hydrolysis, especially in the presence of the alkalis which are customary in washing and cleaning agents.
  • the problems resulting from this for the storage stability of the textile detergents are further exacerbated by the fact that the activators are often poorly soluble in water, so that finely powdered materials with rapid dispersibility are used. Due to the large surface area, the finely divided form enables the activators to be hydrolysed during storage. In other words, the sensitivity to hydrolysis leads to an accelerated breakdown of the active oxygen content of the bleaching agent.
  • the loose structure of the known bleach activator granules the bulk density of which is about 530 to 550 g / l, also allows "migrating" water to penetrate into the interior of the granulate.
  • the bleach activator is added to the dry detergent or cleaning agent mixtures in practice as separately produced granules.
  • the storage stability is also increased by mixing the dry, very finely divided bleach activator with a dry, also very finely divided pelletizing agent and only then moistening and granulating.
  • the bleach activator TAED is granulated with the granulating aid sodium carboxymethyl cellulose.
  • the granulation aid which is distributed homogeneously in the granulate, protects the finely divided bleach activator particles from the entry of migrating water and in this way reduces the sensitivity of the finished granulate to hydrolysis.
  • a further increase in storage stability is desired.
  • Another aim is to improve the abrasion stability of the granules, that is to say the mechanical stability of the bleach activator granules, in order to keep the fine fraction resulting from transportation of the granules against one another as low as possible due to friction of the granules.
  • What is also desired is an improvement in the visual impression of the finished detergent and cleaning agent granules, which is expressed in the desire for an increase in the degree of whiteness.
  • the known activator granules namely have a slightly darker appearance than the detergent and cleaning agent granules to which they are added, so that there is no uniform white appearance. According to the inventors' knowledge, the dark appearance of the known granules is caused by the rough surface formed by the adhering very fine to coarser particles, the microscopic unevenness of which leads to a corresponding formation of shadows.
  • bleach activator granules Another requirement arises from a special area of application of bleach activator granules. To reduce the proportion of packaging in solid and free-flowing detergents and cleaning agents, particularly high bulk densities are desirable. Such products can be manufactured in different ways.
  • compressed granules are formed from premixes of solid ingredients of detergents and cleaning agents with the addition of water-soluble, water-emulsifiable or water-dispersible plasticizers and / or lubricants.
  • the premixes are processed into a homogeneous mass and pressed into strands at pressures between 25 and 200 bar via hole shapes with opening widths of the predetermined granule dimension. The emerging compacted strands are crushed to the predetermined granule dimension.
  • the warm and moist cylindrical granules obtained from the extruder granulation are rounded off in a rounder (rounding device) with the addition of zeolite NaA powder as a powdering agent. After drying, sieving and mixing with the remaining ingredients, the final detergent product is obtained.
  • the extrudates can also contain bleach activators, e.g. B. TAED included.
  • bleach activators e.g. B. TAED included.
  • the extrudates contain the alkalis customary for detergents and the bleach activators of the inorganic peroxide compounds are very sensitive to hydrolysis in the presence of alkalis, it is advantageous not to add the bleach activators together with the other solid ingredients extrude, but to produce them separately as granules and add them to the dried extrudates.
  • the relatively loose activator granules produced in the known process (DE 30 11 998 C2) undesirably reduce the bulk density of the final detergent product.
  • the difference in the density of the extrudates and the activator granules can also lead to segregation of the detergent end product.
  • Bleach activator granules with a bulk density approximating the extrudates mentioned and a corresponding grain shape are therefore desirable.
  • DE 41 43 016 A1 proposes to produce the activator granules in the same way as the extrudates containing the main ingredients of the detergents.
  • a practically anhydrous mixture of bleach activator, anionic surfactant, solubilization aid and, if appropriate, further additives is homogenized and extruded in the form of a strand using increased pressure.
  • the emerging strands are cut into short pieces and rounded if necessary and, if desired, classified according to size.
  • the additives required for extrusion disadvantageously limit the maximum possible activator content in the extrudate.
  • significantly higher activator contents should be possible in the granules than in the known extrudate.
  • the granules should no longer agglomerate in the inlet area of the dryer as in the known method.
  • This object is achieved according to the invention in the method mentioned at the outset by feeding the moist granules to the desired residual moisture to a further apparatus (rounder) and rubbing them against one another and on the wall and / or on the bottom of the rounder and can be compacted so strongly at the same time that the granules after drying have a bulk density of at least 580 g / 1, in particular at least 630 g / 1.
  • the technically relatively complex extrusion method which works with increased pressures, is not used, but rather between the known process step of wet granulation in a mixing granulator, e.g. B. a ploughshare mixer, and the drying step, a further process step is inserted.
  • a mixing granulator e.g. B. a ploughshare mixer
  • the drying step a further process step is inserted.
  • the granules are allowed to rub against each other and on the inner wall of a rounder for a sufficiently long time so that the rough surface of the particles that results from wet agglomeration is smoothed.
  • the very frequent contact and collision of the moist granules with one another in the rounding step according to the invention requires a relatively high density of the granulate cloud in the fillet, which corresponds to a density of a resting bed, that is to say a very much smaller mean distance between the granules than, for example, in a fluidized bed.
  • the manufacturing method according to the invention shows further advantages.
  • the moist granules contained after the rounding have a significantly lower tendency to agglomerate in the subsequent drying stage, which is usually carried out in a fluidized bed dryer, than in the known process (DE 30 11 998 C2) and under normal process conditions.
  • the proportion of oversize is therefore considerably lower.
  • the granulate according to the invention with a bulk density of about 580 to 700 g / 1 is about 50 to 150 g / l heavier.
  • the bulk density of the granules produced according to the invention is thus just as high as that of the products produced by extrusion in accordance with DE 41 43016 A1.
  • Another advantage is the significantly higher whiteness.
  • the smooth, rounded surface makes the granules appear optically lighter due to the lower formation of shadows, so that after mixing with the granules of the main constituents of the detergents and cleaning agents there is an optically uniform appearance.
  • the activator granules according to the invention showed further surprising effects. If the granules are mixed with the extrudates containing the main constituents of the detergents, an increase in bulk density which is disproportionate to the theoretical value is observed.
  • the sensitivity to hydrolysis of the granules according to the invention after mixing to give the final detergent or cleaning product and thus the breakdown of the active oxygen content of the finished detergent or cleaning agent was surprisingly significantly lower when using the granules according to the invention than when using the activator granules produced by known processes.
  • the moist granules are allowed to rub and compact from below between the housing wall and the edge of the base plate in a rounder with a rotating, horizontal base plate while at the same time blowing in a working gas, in particular cold air.
  • a rounder with a rotating, horizontal base plate while at the same time blowing in a working gas, in particular cold air.
  • Such rounders are known and are available, for example, under the name "Marumerizer” (from Elanco).
  • the moist granules be rubbed and compacted in several rounders (rounder cascade) connected in series.
  • the residence time of the moist granules in the rounder is preferably set from 5 to 180 s, in particular from 15 to 80 s.
  • a peripheral speed of the rotating base plate of at least 10 m / s, in particular of at least 15 m / s has also been found to be favorable.
  • Preference is also given to a moisture content of 5 to 20% by weight, in particular 10 to 15% by weight, of the moist granules before rounding.
  • Suitable bleach activators for perver ⁇ compounds are accordingly O- and / or N-acylated compounds such as pentaacetylglucose (PAG), pentapropionylglucose (PPG), tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU ), Triacetylethanolamine (TAEA), acylated triazine dehvates such as 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), carboxylic anhydrides such as succinic, benzoic or phthalic anhydride, salts of mixed anhydrides, such as sodium or magnesium diacetyl phosphate (NADAP or MGDAP), phenol esters such as p-carboxylphenyla
  • the bleach activator used is preferably tetraacetylethylene diamine (TAED).
  • a compound from the class of water-soluble cellulose ethers, starch and starch ether is preferably used as the granulation aid in the process according to the invention.
  • Carboxymethyl cellulose in particular sodium carboxymethyl cellulose, is preferred here. Further information on the granulation aids can be found in DE 30 11 998 C2, to which reference is expressly made here to supplement the disclosure.
  • additives such as oxidation-stable complexing agents and stabilizers for per compounds and / or further constituents of detergents and cleaning agents can also be mixed in as granulation aids or introduced via the aqueous granulation liquid.
  • these are salts of polyphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonate, ethylenediamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate, each in the form of the sodium salt.
  • the proportion of the phosphonate additives is preferably 3 to 10% by weight and particularly preferably 5 to 8% by weight, in each case based on the dried bleach activator granules.
  • the preferred amount of phosphonate here is not based on the liquid granulation aid, but rather on the finished product, since it has been found that it is not the phosphonate concentration in the granulation aid, but the absolute amount of the sprayed-on phosphonate that is essential.
  • the advantage lies in the strengthening of the rounding and compacting effect and thus also in an increase in the bulk density of the dried bleach activator granulate.
  • a universal detergent mixed with the bleach activator granules according to the invention contains about 0.5% by weight of these additives.
  • a carboxymethyl cellulose-free solution of a stabilizer for per compounds, in particular a salt of a polyphosphonic acid, and optionally further components of detergents and cleaning agents are used.
  • the granulation aid contains only polyphosphonate in addition to water.
  • a finely divided solid is added to the moist granules moving in the fillet.
  • the powdering in the fillet leads to a better movement of the moist granulate and thus to an improved compaction and rounding.
  • the powder preferably contains one or more constituents of washing and / or cleaning agents and in particular zeolite NaA.
  • the powder consists of fine fractions of the finished bleach activator granulate. These fine fractions occur regularly during the screening off of the dried product and are usually returned to the process by adding these fine fractions to the powdery batch used in the first process step, the granulation step. in the In contrast to this process control, the fine particles are thus fed to the second process step according to the invention.
  • the additives mentioned above in particular an aqueous solution of a granulating aid, or other ingredients of detergents and cleaning agents when rounding the moist granules can be added simultaneously, for. B. be injected.
  • the water content of the granules is then reduced to less than 3, preferably less than 2 and in particular less than 1.5% by weight.
  • the excess water can be removed by drying with the addition of heat, the temperature of the granules expediently not exceeding 80 ° C. and below the melting temperature of the bleach activator.
  • Dryers that do not disadvantageously change the granular structure of the product are suitable, for example tray dryers, vacuum dryers and, in particular, fluidized bed dryers.
  • the invention also relates to granules which are stable in storage and contain bleach activators and a granulating aid, prepared by the abovementioned process and which is characterized by a bulk density of at least 580 g / l, in particular at least 630 g / l.
  • the granules according to the invention have the advantages and surprising effects already mentioned, with the improved whiteness of the granules and the high storage stability of the finished washing and cleaning agent products with these granules being particularly emphasized here.
  • the granules according to the invention are preferably characterized by a content of 70 to 97% by weight, preferably 80 to 95% by weight, of bleach activator, in particular TAED, 0.5 to 10% by weight of a granulation aid, in particular carboxymethyl cellulose and optionally others Components of washing and cleaning agents that are at least as good redispersible as the components mentioned.
  • a particularly high bleach activator content is advantageous.
  • the granules according to the invention also contain 0 to 15% by weight, preferably 4 to 8% by weight, of a stabilizer for per compounds, in particular a salt of a polyphosphonic acid.
  • the granulate according to the invention is further characterized in that it can have a whiteness measured as an L * value, determined with the Minolta Chroma-Meter CR color measuring device, of at least 80.
  • the subject of the invention also comprises the detergent and cleaning agent end products produced by mixing the granules according to the invention, and in particular products in which the granules containing the main constituents are in the form of uniform, by extruding a homogeneous premix and cutting the obtained strand, that is, have been produced by the above-mentioned extrusion process and to which the granules according to the invention have been mixed.
  • Tetraacetylethylenediamine with an average grain size of 0.01 to 0.8 mm was used as the bleach activator.
  • the grain fraction between 0.8 and 1.6 mm was 5% by weight, the fraction below 0.01 mm was 10% by weight.
  • the product then went through a second cylindrical mixer with a horizontal axis, however, and was brought there into the desired granulate shape.
  • the resulting wet granulate with a water content of 11.2% by weight was then fed to a rounder cascade consisting of two "Marumerizer” rounders connected in series.
  • a base plate provided with projections and recesses rotated at a circumferential speed of 18 m / s.
  • Cold air was blown in between the inner wall of the cylindrical housing and the edge of the rotating plate.
  • the granules collected on the edge of the base plate due to the centrifugal force.
  • This very dense ring-shaped rotating granulate layer was caused by the cold air blown in from below into a circular movement around the ring axis in addition to the movement of the ring around the cylinder axis of the apparatus.
  • the granules were discharged and heated in a fluidized bed dryer to a product temperature of 75 ° C. and dried to a residual water content of 0.6% by weight.
  • 65% by weight of the granules had a grain size of 0.4 to 2.0 mm.
  • the rest contained coarse and very fine fractions, which were screened off and recycled.
  • the activator granules had a bulk density of 660 g / l.
  • the degree of whiteness L * determined with the Minolta Chroma-Meter CR color measuring device, was 84, which is a considerably higher value than with the known activator granules, for which it is well below 80.
  • the activator granules according to the invention were mixed with extrudates prepared in accordance with DE 39 26 253 A1 and containing the main constituents of a universal detergent in order to check the resulting bulk density and the storage stability.
  • This extrudate contained 25% by weight sodium perborate monohydrate. 67% by weight of the extrudate mentioned were mixed with 8.5% by weight of the activator granules according to the invention and with further, conventional detergent components, for. B. enzymes, mixed to the finished detergent end product.
  • a mixture was made with granules produced according to DE 30 11 998 C2, which had a bulk density of 530 g / l.
  • the granulation was carried out with CMC, but without the addition of phosphonate.
  • powdering materials were added to the rounder as described below.
  • Moist granules were produced in batches in the FKM5D mixer from Gebr. Lödige.
  • the mixing time with the rotating cutter head was 35 s after adding water.
  • the moist granules obtained were rounded in a rounder with a diameter of the rounding disc of 50 cm at a speed of 450 1 / min for 40 s.
  • 45 g of zeolite NaA (“Wessalith P" from Degussa) were added in the rounder.
  • Example 3a The approach and the procedure corresponded to Example 3a, but after 15 s rounding time, instead of zeolite NaA, 150 g of TAED fines ⁇ 0.4 mm were added to the production plant. After drying and sieving, fine particles of the same order of magnitude were obtained again.
  • Example> 1 6 0.8 - 1, 6 0.4 - 0.8 ⁇ 0.4 Sg ⁇ SG

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un granulat obtenu par granulation d'un mélange pulvérulent humide comprenant un activateur de blanchiment pulvérulent, un auxiliaire de granulation pulvérulent et une solution aqueuse du même et/ou d'un autre auxiliaire de granulation ou une solution aqueuse d'autres substances actives de détergents ou de nettoyants ou de l'eau, par agglomération des particules humides dans un granulateur de mélange, les granulés humides étant ensuite desséchés. Avant de dessécher les granulés humides jusqu'à obtention de l'humidité résiduelle voulue, lesdits granulés sont acheminés jusqu'à un autre appareil (arrondisseur) où ils sont en contact par frottement les uns avec les autres, ainsi qu'avec la paroi et/ou la base de l'arrondisseur et sont simultanément compactés si intensément qu'après dessiccation, lesdits granulés ont une masse volumique apparente d'au moins 580 g/l, notamment d'au moins 630 g/l. Outre leur masse volumique apparente très élevée, les granulés présentent un meilleur degré de blanc, ainsi qu'une très bonne stabilité au stockage en cas de mélange avec des produits contenant des agents de blanchiment et des alcalis.
PCT/EP1996/001618 1995-04-28 1996-04-18 Granulat stable au stockage contenant des activateurs de blanchiment et son mode de production WO1996034081A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP96914940A EP0822974B1 (fr) 1995-04-28 1996-04-18 Granulat stable au stockage contenant des activateurs de blanchiment et son mode de production
DE59603355T DE59603355D1 (de) 1995-04-28 1996-04-18 Lagerstabiles, bleichaktivatoren enthaltendes granulat und seine herstellung

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19515233.6 1995-04-28
DE19515233A DE19515233A1 (de) 1995-04-28 1995-04-28 Lagerstabiles, Bleichaktivatoren enthaltendes Granulat und seine Herstellung

Publications (1)

Publication Number Publication Date
WO1996034081A1 true WO1996034081A1 (fr) 1996-10-31

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ID=7760347

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Application Number Title Priority Date Filing Date
PCT/EP1996/001618 WO1996034081A1 (fr) 1995-04-28 1996-04-18 Granulat stable au stockage contenant des activateurs de blanchiment et son mode de production

Country Status (5)

Country Link
EP (1) EP0822974B1 (fr)
AT (1) ATE185593T1 (fr)
DE (2) DE19515233A1 (fr)
ES (1) ES2140087T3 (fr)
WO (1) WO1996034081A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059538A (en) * 1972-10-20 1977-11-22 Lever Brothers Company Method for preparing granulated detergent formulations
GB2015050A (en) * 1977-12-22 1979-09-05 Unilever Ltd Bleach Activator Granules
EP0374867A1 (fr) * 1988-12-22 1990-06-27 Hoechst Aktiengesellschaft Procédé de préparation de granulés d'activateur de blanchiment stables au stockage, facilement solubles
WO1992002608A1 (fr) * 1990-08-03 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Activateurs du blanchiment sous forme de granules
DE4232494A1 (de) * 1991-09-27 1993-04-01 Kao Corp Granulatfoermige bleich-aktivator-zusammensetzung und verfahren zu ihrer herstellung
WO1993013194A1 (fr) * 1991-12-24 1993-07-08 Henkel Kommanditgesellschaft Auf Aktien Activateurs de blanchiment sous forme granulaire (ii)

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059538A (en) * 1972-10-20 1977-11-22 Lever Brothers Company Method for preparing granulated detergent formulations
GB2015050A (en) * 1977-12-22 1979-09-05 Unilever Ltd Bleach Activator Granules
EP0374867A1 (fr) * 1988-12-22 1990-06-27 Hoechst Aktiengesellschaft Procédé de préparation de granulés d'activateur de blanchiment stables au stockage, facilement solubles
WO1992002608A1 (fr) * 1990-08-03 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Activateurs du blanchiment sous forme de granules
DE4232494A1 (de) * 1991-09-27 1993-04-01 Kao Corp Granulatfoermige bleich-aktivator-zusammensetzung und verfahren zu ihrer herstellung
WO1993013194A1 (fr) * 1991-12-24 1993-07-08 Henkel Kommanditgesellschaft Auf Aktien Activateurs de blanchiment sous forme granulaire (ii)

Also Published As

Publication number Publication date
ES2140087T3 (es) 2000-02-16
EP0822974B1 (fr) 1999-10-13
DE59603355D1 (de) 1999-11-18
ATE185593T1 (de) 1999-10-15
EP0822974A1 (fr) 1998-02-11
DE19515233A1 (de) 1996-10-31

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