EP0063512A1 - Bleichmittelaktivatorgranulate, deren Herstellung und Verwendung in Reinigungs- und Bleichmittelzusammensetzungen - Google Patents

Bleichmittelaktivatorgranulate, deren Herstellung und Verwendung in Reinigungs- und Bleichmittelzusammensetzungen Download PDF

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Publication number
EP0063512A1
EP0063512A1 EP82400600A EP82400600A EP0063512A1 EP 0063512 A1 EP0063512 A1 EP 0063512A1 EP 82400600 A EP82400600 A EP 82400600A EP 82400600 A EP82400600 A EP 82400600A EP 0063512 A1 EP0063512 A1 EP 0063512A1
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EP
European Patent Office
Prior art keywords
tetraacetylethylenediamine
sodium
granules
weight
bleaching
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP82400600A
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English (en)
French (fr)
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EP0063512B1 (de
EP0063512B2 (de
Inventor
Larbi Aouni
Max Michel
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.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
Rhone Poulenc Chimie de Base SA
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Application filed by Rhone Poulenc Chimie SA, Rhone Poulenc Chimie de Base SA filed Critical Rhone Poulenc Chimie SA
Priority to AT82400600T priority Critical patent/ATE11428T1/de
Publication of EP0063512A1 publication Critical patent/EP0063512A1/de
Publication of EP0063512B1 publication Critical patent/EP0063512B1/de
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Publication of EP0063512B2 publication Critical patent/EP0063512B2/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the present invention relates to granules of coated bleaching activator, to the process for coating and granulating said activator and to the use of the granules obtained in or with detergent and bleaching compositions.
  • the invention also relates to a method for washing and bleaching textile materials by means of a washing and bleaching bath using the granules of the invention.
  • the subject of the invention is new granules of N, N, N ', N'-tetraacetylethylenediamine coated, their preparation and their use in detergency.
  • the conventional detergent compositions used for washing textile materials include a surfactant (anionic, non-ionic, cationic or amphoteric), a builder and a bleaching compound.
  • a surfactant anionic, non-ionic, cationic or amphoteric
  • a builder and a bleaching compound.
  • the per-compounds used in the detergent compositions exhibit sufficient oxidizing activity only at temperatures generally above 60 ° C.
  • an organic activator of the compound reacts with the hydrogen peroxide released by the compound, to form in the detergent medium, an active bleaching agent at lower temperatures, for example between 20 and 60 ° C.
  • tetraacetylethylenediamine has been found to be particularly effective.
  • this activator has storage stability problems when incorporated into detergent compositions. On contact with the other constituents of the detergent composition, alkaline substances, percomposite, and hydrated compounds, the activator tends to hydrolyze and perhydrolysate. This partial decomposition leads to the appearance of pungent odors and coloring as well as a reduction in its whitening power.
  • French patent 2,109,941 describes granular compositions containing from 5 to 50% by weight of the bleaching activator which is tetraacetylglycolurile and from 95 to 50% by weight of a coating material comprising triphosphate sodium. Since the amount of binding agent used is large, it is not possible to obtain granules with a high concentration of activator.
  • the present invention proposes to provide new coated tetraacetylethylenediamine granules satisfying all the conditions listed above and avoiding the aforementioned drawbacks.
  • tetraacetylethylenediamine in the form of the granules of the invention makes it possible to suppress the degradation of the latter during storage and does not in any way alter the activating qualities of tetraacetylethylenediamine on the percomposites.
  • the rate of dissolution of the granulated and coated tetraacetylethylenediamine according to the invention is greater than the rate of dissolution of tetraacetylethylenediamine alone.
  • the practical interest of the invention is therefore to obtain very quickly the formation of ions of peracetic acid, in the washing medium.
  • Another object of the present invention is the process for the preparation of said bleaching granules, characterized in that a pulverulent mixture of the tetraacetylethylenediamine and the alkali metal polyphosphate is carried out and which is sprayed onto the moving bed thus formed. a solution of an alkali metal cellulose derivative.
  • solution is meant both a solution and a dispersion of the cellulose derivative.
  • the tetraacetylethylenediamine to be treated is in the form of particles having a particle size between 0.02 and 0.25 mm and preferably between 0.05 and 0.15 mm. It is preferable that the tetraacetylethylenediamine used has the aforementioned particle size distribution because if the particles are too small, there is formation of undesirable dust and if the particles are too large, there may be problems with agglomeration and during the use in detergency, the dissolution of tetraacetylethylenediamine will be slowed down.
  • the particle size of tetraacetylethylenediamine is determined in a standard manner, for example, by dry sieving, by sedimentation or by direct counting of the particles using a COULTER counter based on the recording of conductimetric disturbances which accompany the passage particles through a diaphragm of given size.
  • polyphosphates of alkali metals are used, preferably sodium polyphosphates.
  • Suitable for the invention sodium pyrophosphate, sodium acid pyrophosphate and sodium triphosphate. These salts are preferably used in anhydrous form.
  • sodium triphosphate is preferably chosen. It is used in its commercial form which contains impurities of metals such as iron, copper, nickel. Generally, the amount of ions metals does not exceed 200 PPM It is preferred to use a sodium triphosphate having a reduced content of metallic impurities, for example, between 20 and 100 PPM
  • the particle size of sodium triphosphate determined in an identical manner to that of tetraacetylethylenediamine, it is between 0.02 and 0.08 mm, which corresponds to sodium triphosphate in common use in detergency.
  • the second component involved in the coating agent is organic in nature since it is a cellulose derivative. As such, there may be mentioned carboxymethylcellulose, methylcellulose, or hydroxyethylcellulose.
  • cellulose derivatives are preferably used in the form of their sodium salt.
  • Sodium carboxymethylcellulose is a raw material of choice. No specific characteristic of particle size is required since it is used in the form of an aqueous solution.
  • the sodium carboxymethylcellulose commonly used in detergents is used according to the invention. It has a degree of substitution varying from 0.5 to 0.7: the degree of substitution expressing the average number of carboxyl radicals attached to each link in the cellulosic chain. As regards its degree of polymerization and which translates the length of the cellulosic chain and determines the viscosity, it will be determined so that a solution having the desired viscosity is obtained which will be specified later.
  • Sodium triphosphate and sodium carboxymethylcellulose being chosen -preferentially as coating agent, we will define their proportions used, but it goes without saying that the values given below are also suitable when using another polyphosphate or a another cellulose derivative.
  • the quantity of sodium carboxymethylcellulose used in the coating agent can vary within an interval the limits of which are fixed as follows: the lower limit is determined so that the granules obtained have the required mechanical resistance properties and the upper limit is defined as a function of at least two parameters to be observed: namely, on the one hand, a physico-chemical parameter which requires to rule out an excess of sodium carboxymethylcellulose which would risk delaying the release of tetraacetylethylenediamine and the formation of peracetic acid ions and on the other hand, a process constraint in the production of granules which would then require the setting use of a larger amount of water which should be removed by drying and which would hinder or even make granulation impossible.
  • the amount of sodium carboxymethylcellulose is chosen such that the said ratio varies from 1/100 to 1/10, preferably from 1/30 to 1/15.
  • the amount of sodium triphosphate involved is not critical and can vary within wide limits. However, it is a function of the amounts of tetraacetylethylenediamine and sodium carboxymethylcellulose and will therefore be fixed so that its weight ratio with tetraacetylethylenediamine varies from 1/10 to 1/1, preferably between 1/4 to 2/3.
  • the process of the invention consists in first making the pulverulent mixture of tetraacetylethylenediamine and sodium polyphosphate brought to the desired particle size and in the suitable ratio, to pour the mixture obtained onto any device making it possible to constitute a moving bed, on which is sprayed with a solution of the cellulose derivative in sodium form.
  • the mixture obtained is then poured into a granulator which can be a rotary drum granulator having a large load in motion.
  • FIG. 1 An illustration of this type of device used in a preferential manner is a bezel with a cylindrical bowl equipped with devices for introducing and discharging the powder and also provided with a device for spraying liquid under pressure.
  • the bezel has a bowl, the inclination of the axis of rotation of which is preferably 43 to 45 ° relative to the horizontal.
  • a charge consisting of tetraacetylethylenediamine and sodium triphosphate is introduced into the bezel, from 30 to 100 kg per m3 of bezel, preferably from 40 to 80 kg per m3 of bezel.
  • the powder mixture is kept in motion thanks to the rotation of the bezel: the speed of rotation of the bezel is such that the tangential speed of the beverage bowl is 0.5 to 3 m / s, preferably 1 to 2 m / s.
  • the preparation of the sodium carboxymethylcellulose solution is carried out which will be sprayed.
  • To prepare said solution it is sought to use the minimum quantity of water in order to avoid or minimize the drying operation.
  • the amount of water to be used is a function of the concentration of sodium carboxymethylcellulose to be obtained, which should not be too high because there would be too high a viscosity preventing any spraying.
  • This concentration will be defined so that a spray solution with a final viscosity of less than 200 cps is obtained: the viscosity of 200 cps corresponds to a measurement carried out at 50 ° C. with a shear viscometer on a solution at 5 X: the speed gradient chosen for the measurement is between 25 s and 200 s -1 .
  • a sodium carboxymethylcellulose solution having a viscosity of between 100 and 150 cps is used.
  • sodium carboxymethylcellulose of "detergency" quality solutions containing from 2 to 10%, preferably from 3 to 8% by weight of sodium carboxymethylcellulose, are prepared.
  • the sodium carboxymethylcellulose solution to be sprayed is prepared and maintained at a temperature preferably between 30 and 80 ° C using an appropriate heating device.
  • the sodium carboxymethylcellulose solution is sprayed onto the pulverulent mixture by means of a spray nozzle under pressure of 2 to 10 bars, preferably from 4 to 5 bars.
  • the duration of the spraying depends on the quantity of sodium carboxymethylcellulose which it is desired to introduce into the granules.
  • the finished granules are removed from the bowl of the bezel using a discharge device such as a scraper or other type.
  • a wet powder is obtained having a water content of 20 to 40%, preferably 25 to 35%.
  • the bezel is continuously supplied so as to obtain a time of average stay of the granules in the bezel for 10 to 60 minutes and the granules obtained are evacuated progressively by means of an appropriate evacuation device.
  • the granules obtained then undergo a simple screening and by this single operation, they acquire the particle size desired for their use.
  • a particle size distribution such that the diameter of the granules ranges from 0.4 to 2.0 mm and, preferably, from 0.6 to 1.2 mm.
  • the fine particles remain in the bezel.
  • the large granules which constitute the rejection of screening are crushed by any suitable device and recycled in the dredger.
  • the screening can be carried out by a simple passage over a rotating or oblique grid having an adequate mesh opening.
  • the coating and granulation process according to the invention makes it possible, by the choice of particle sizes of the pulverulent materials and by the screening operation succeeding to the granulation, to obtain any particle size distribution defined above.
  • the granules are dried in a current of hot air generally from 30 to 60 ° C.
  • Drying can be done in any way.
  • the granules can also be dried in an oven, for example, with a rotary hearth.
  • the drying device will be chosen so that the granules are not broken up during drying.
  • the bleaching granules which are the subject of the invention have a regular particle size, good mechanical properties, and can be easily incorporated into detergent and bleaching compositions.
  • the bleaching granules according to the invention are introduced into the detergent and bleaching compositions, generally, post-addition to the detergent composition dried after atomization, by simple dry mixing.
  • the granules of the invention can be added directly to the washing bath comprising a detergent and bleaching composition containing a compound in the case of industrial use.
  • the detergent compositions in which the bleaching granules can be incorporated comprise, in addition to the per-compound used for bleaching, at least one anionic, nonionic, cationic, amphoteric surfactant and at least one builder.
  • diamines such as those of the R NH C 2 H 4 NH 2 type can be used in which R is an alkyl radical containing from 12 to 22 carbon atoms, for example N-aminoethyl- 2 stearylamine and 2-aminoethyl-2 myri-stylamine; amidoamines such as those of the R CO NH C 2 H 4 NH 2 type in which R 9 is an alkyl radical containing from 9 to 20 carbon atoms, for example N-aminoethyl-2 stearylamide and N-aminoethyl-2 myristylamide: quaternary ammonium compounds in which, in particular, one of the radicals attached to the nitrogen atom is an alkyl radical of 1 to 3 carbon atoms, including these alkyl radicals of 1 to 3 carbon atoms carrying inert substituents, for example halogen, acetate, methylsulfate, etc.
  • R is an alkyl radical containing from 12 to 22
  • surfactants of the quaternary ammonium type mention will be made of: ethyldimethylstearylammonium chloride, benzyldimethylstearylammonium chloride, benzyldiethylstearylammonium chloride, trimethylstearylammonium chloride, trimethylketylammonium bromide, dimethylethyldilaurylammonium chloride, dimethylpropylmyristylammonium chloride, as well as the corresponding methylsulfates and acetates.
  • amphoteric surfactants such as alkyl dimethyl betaines of formula:
  • alkyltrimethylsulfobetaines of formula: in said formulas n4 is between 9 and 16.
  • sodium alkyl benzenesulfonates, sodium stearate, fatty alcohol sulfates, polyoxyethylenated fatty alcohol sulfates and polyoxyethylenated fatty alcohols, polyoxyethylenated and polyoxypropylenated fatty alcohols are very particularly suitable and are preferably used in detergent compositions.
  • the detergent compositions can also contain builders, one of the functions of which is to sequester the calcium and magnesium ions present in water.
  • alkaline adjuvant salts which can be used in this function, mention may be made of carbonates, silicates, phosphates and polyphosphates. More specifically, mention will be made of sodium triphosphate, sodium and potassium pyrophosphate, sodium orthophosphate.
  • alumina silicates or those containing alumina, among others, are also suitable. bentonite or vermiculite; synthetic zeolites of type A.
  • phosphonic acids are preferably chosen: amino-tri (methylenephosphonic) acid: (ATMP), ethylenediamine-tetra (methylenephosphonic acid): (EDTMP), diethylenetriamine-penta acid - (methylenephosphonic): (DTPMP)
  • the builders named above can be used alone but preferably in a mixture.
  • sodium disilicate, sodium carbonate, sodium orthophosphate, sodium pyrophosphate, sodium triphosphate, the sodium salt of nitrilotriacetic acid are chosen.
  • Detergent compositions generally contain, in addition to surfactants and builders, a certain number of conventional additives in variable quantity.
  • agents for controlling the foam such as polysiloxanes; mineral salts such as sodium sulfate; bleaching agents such as hydrogen peroxide and its hydrates, peroxides and persalts alone or in admixture with bleaching precursors and other anti-redeposition agents such as carboxymethylcellulose, carboxymethylhydroxyethylcellulose, polyvinyl alcohol, copolymers of maleic acid and vinyl ether, acrylic acid alone or copolymerized with vinyl monomers and water-soluble sulfonated polyesters, water-soluble polyester polyurethanes; fluorescers such as stilbenes, furans, t hiophesses well as minor amounts of fragrance, dyes and enzymes.
  • the bleaching granules are introduced into the detergent compositions in an amount such that there is approximately 1 to 10% by weight of tetraacetylethylenediamine and preferably 2 to 4%.
  • the compound is added to the detergent compositions in an amount of 5 to 35% by weight, preferably 10 to 20%.
  • the weight ratio between tetraacetylethylenediamine and the compound can range from 2/3 to 1/35 and preferably from 1/2 to 1/20.
  • the detergent compositions contain at least 5 to 50% by weight of an anionic, nonionic, cationic, amphoteric surfactant or their mixtures and from 10 to 60% by weight of a builder. Preferably, 5 to 25% by weight of an anionic, nonionic surfactant or mixtures thereof and 10 to 40% by weight of a builder are added to the detergent compositions.
  • detergent compositions are given by way of illustration, but not limitation, into which the bleaching granules of the invention may be introduced.
  • the percentages given are expressed by weight.
  • the granules of the invention have an excellent storage behavior in detergent compositions: the tetraacetylethylenediamine is effectively preserved from the other components of the detergent composition which would risk degrading it.
  • the detergent compositions containing the bleaching granules according to the invention are suitable for washing articles of all kinds based on natural, synthetic or artificial fibers and more particularly for washing textile materials based on natural fibers such as cotton optionally mixed with the other fibers, in particular polyester.
  • the concentration of bleach granules in the washing bath expressed by weight of tetraacetylethylenediamine is such that there are between 0.05 and 1.00 g per liter of aqueous bath.
  • the upper bound is obviously not critical, but it is preferable to choose a concentration between 0.1 and 0.3 g / 1 because higher concentrations do not provide any advantage in terms of the efficacy of the products. the invention.
  • the temperature of the aqueous medium which is used during washing is not critical in the sense that the bleaching granules behave effectively at temperatures ranging from about 20 to 100 ° C and preferably from 30 to 60 ° C.
  • the washing is preferably carried out at low temperature due to the presence of tetraacetylethylenediamine, all the more so since the speed of dissolution of the coated tetraacetylethylenediamine granules is greater than the speed of dissolution of tetraacetylethylenediamine alone which makes it possible to quickly obtain the ions of peracetic acid then the active oxygen allowing to obtain the bleaching effect.
  • the present invention is illustrated in a nonlimiting manner by examples of preparation of the granules of the invention.
  • granules are prepared having the composition by weight given below, but using tetraacetylethylenediamine and sodium triphosphate of different particle size: the particle size of sodium triphosphate is always substantially finer than that of tetraacetylethylene diamine.
  • the granules are prepared according to the following procedure:
  • This solution is sprayed on the dry mixture moving in the bezel.
  • the sodium carboxymethylcellulose solution is sprayed using a spray nozzle under a pressure of 4 bars, onto the powder mixture of tetraacetylethylenediamine and sodium triphosphate for a period of approximately 30 minutes.
  • Granules having the composition given above, of dry appearance and relatively solid, are extracted from the bezel.
  • the granules obtained are passed through sieves with a mesh opening of 0.63 mm and 2.00 mm.
  • Example 1 The mode of preparation of the granules described in Example 1 is reproduced with the difference that tetraacetylethylenediamine is used having an average particle diameter of 0.180 mm and containing no particle of diameter greater than 0.300 mm.
  • the granules prepared according to examples 1 to 3 are subjected to a series of measurements and tests in order to demonstrate their physicochemical properties. In the various tests, the particle size fraction of 0.63 to 2.00 mm is used.
  • the weight of 1 cm 3 of granules is determined by weighing 100 c m 3 of packed and loose packed granules.
  • the granules are subjected to a mechanical treatment then their solidity is evaluated by determining the percentage of fine particles formed by sieving through a sieve whose mesh opening is equal to 2/3 of the diameter of the smallest granule.
  • Mechanical manipulation consists of placing 200 g of granules in a 2-liter glass bottle and rotating it 40 revolutions per minute for 1 hour.
  • the percentage of "fines” is measured by passing through a standard AFNOR sieve with a mesh size of 0.4 mm.
  • peracetic and acetic acids formed by perhydrolysis and hydrolysis of the liberated tetraacetylethylenediamine are neutralized so as to keep the pH constant at 10.
  • the tetraacetylethylenediamine used has an average particle diameter of 0.130 mm, 0.050 mm and 0.180 mm, that is to say, the same particle size as that introduced into the granules to be tested.
  • 0.5N sodium hydroxide is then added so as to maintain the pH at 10.
  • the main purpose of the coating being to protect tetraacetylethylenediamine, during storage, from the action of the other constituents of the detergent composition which are likely to cause its decomposition, we will demonstrate the resistance to storage of tetraacetylethylenediamine having different particle sizes and coated in the form of granules de.l'invention.
  • a test is carried out with uncoated tetraacetylethylenediamine having the same particle size as that introduced into the granules to be tested.
  • the test is carried out on 10 samples of 1 g of the detergent composition defined above containing either the granules of coated tetraacetylethylenediamine, or the uncoated tetraacetylethylenediamine which is placed in a powder compact itself placed open in a packet of detergent so as to restore the usual conditions for storing detergents. Storage is performed at 40 ° C in an atmosphere containing 80% relative humidity.
  • the samples are withdrawn and the tetraacetylethylenediamine is assayed in the presence of all the components of the detergent composition and then the loss of activity of the tetraacetylethylenediamine is determined.
  • the principle of the method consists in measuring the peracetic acid formed by perhydrolysis of the residual tetraacetylethylenediamine, in basic medium.
  • the peracetic acid formed in the presence of potassium iodide will oxidize it and the released iodine will be measured by a titrated solution of sodium thiosulfate.
  • the mixture is quickly and quantitatively transferred to a beaker containing 100 g of crushed ice and 10 cm 3 of glacial acetic acid.
  • the soiled cotton test pieces are washed in a LINI-TEST device (ORIGINAL HANAU) which simulates a washing cycle at 60 ° C for 20 minutes.
  • LINI-TEST device ORIGINAL HANAU
  • test pieces After washing, the test pieces are dried in the open air and then measured again with the GARDNER reflectometer.
  • the bleaching efficiency is given by the variation in reflectance before and after washing.
  • the coating agent and the particle size of the tetraacetylethylenediamine used in the bleaching granules of the invention do not induce any appreciable reduction in the bleaching efficiency compared to the uncoated activator; moreover, it is noted that very good bleaching performance is always obtained whatever the particle size of the tetraacethylethylenediamine chosen from the range defined according to the invention.
  • an advantage of the present invention is to have a flexible method for manufacturing granules with a high tetraacetylethylenediamine content greater than 55% by weight which makes it possible to granulate and coat any type of tetraacetylenediamine particle size between 0.02 and 0.25 mm while still leading to granules having good storage behavior and good bleaching efficiency.

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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)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Dental Preparations (AREA)
  • Medicinal Preparation (AREA)
EP82400600A 1981-04-15 1982-04-01 Bleichmittelaktivatorgranulate, deren Herstellung und Verwendung in Reinigungs- und Bleichmittelzusammensetzungen Expired EP0063512B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82400600T ATE11428T1 (de) 1981-04-15 1982-04-01 Bleichmittelaktivatorgranulate, deren herstellung und verwendung in reinigungs- und bleichmittelzusammensetzungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8107544A FR2504147B1 (fr) 1981-04-15 1981-04-15 Granules de blanchiment, leur preparation et leur utilisation dans les compositions detergentes et de blanchiment
FR8107544 1981-04-15

Publications (3)

Publication Number Publication Date
EP0063512A1 true EP0063512A1 (de) 1982-10-27
EP0063512B1 EP0063512B1 (de) 1985-01-23
EP0063512B2 EP0063512B2 (de) 1988-08-10

Family

ID=9257416

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82400600A Expired EP0063512B2 (de) 1981-04-15 1982-04-01 Bleichmittelaktivatorgranulate, deren Herstellung und Verwendung in Reinigungs- und Bleichmittelzusammensetzungen

Country Status (10)

Country Link
EP (1) EP0063512B2 (de)
JP (1) JPS57192498A (de)
AT (1) ATE11428T1 (de)
DE (1) DE3262009D1 (de)
DK (1) DK152596C (de)
ES (1) ES8402015A1 (de)
FR (1) FR2504147B1 (de)
GR (1) GR76130B (de)
IE (1) IE53182B1 (de)
PT (1) PT74755B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0156977B1 (de) * 1984-03-22 1988-07-06 MIRA LANZA S.p.a. Verfahren zur Herstellung eines Bleichaktivators in granulierter Form
EP0346034A3 (en) * 1988-06-06 1990-10-17 Unilever Plc Wax encapsulated actives and emulsion process for their production
WO1998016621A3 (en) * 1996-10-11 1998-05-22 Warwick Internat Group Ltd Microcapsules
US5965515A (en) * 1994-04-07 1999-10-12 The Andrew Jergens Company Coated amine functionality-containing materials

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8334159D0 (en) * 1983-12-22 1984-02-01 Unilever Plc Perfume
DE3843195A1 (de) * 1988-12-22 1990-06-28 Hoechst Ag Verfahren zur herstellung eines lagerstabilen, leicht loeslichen bleichaktivator-granulats
JPH03131700A (ja) * 1989-10-17 1991-06-05 Uni Charm Corp 排水管用洗浄剤組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1258675A (fr) * 1959-06-19 1961-04-14 Konink Ind Mij Voorheen Noury Perfectionnements aux produits de lavage et de blanchiment
FR2109941A5 (de) * 1970-10-01 1972-05-26 Henkel & Cie Gmbh
FR2460997A1 (fr) * 1979-07-06 1981-01-30 Unilever Nv Compositions de blanchiment particulaires

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1258675A (fr) * 1959-06-19 1961-04-14 Konink Ind Mij Voorheen Noury Perfectionnements aux produits de lavage et de blanchiment
FR2109941A5 (de) * 1970-10-01 1972-05-26 Henkel & Cie Gmbh
FR2460997A1 (fr) * 1979-07-06 1981-01-30 Unilever Nv Compositions de blanchiment particulaires

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0156977B1 (de) * 1984-03-22 1988-07-06 MIRA LANZA S.p.a. Verfahren zur Herstellung eines Bleichaktivators in granulierter Form
EP0346034A3 (en) * 1988-06-06 1990-10-17 Unilever Plc Wax encapsulated actives and emulsion process for their production
US5965515A (en) * 1994-04-07 1999-10-12 The Andrew Jergens Company Coated amine functionality-containing materials
WO1998016621A3 (en) * 1996-10-11 1998-05-22 Warwick Internat Group Ltd Microcapsules

Also Published As

Publication number Publication date
IE820875L (en) 1982-10-15
IE53182B1 (en) 1988-08-17
FR2504147A1 (fr) 1982-10-22
EP0063512B1 (de) 1985-01-23
DE3262009D1 (en) 1985-03-07
DK152596B (da) 1988-03-21
ES511414A0 (es) 1984-01-01
ES8402015A1 (es) 1984-01-01
ATE11428T1 (de) 1985-02-15
PT74755B (fr) 1985-05-31
DK166682A (da) 1982-10-16
DK152596C (da) 1988-09-05
GR76130B (de) 1984-08-03
FR2504147B1 (fr) 1987-11-20
JPS57192498A (en) 1982-11-26
PT74755A (fr) 1982-05-01
EP0063512B2 (de) 1988-08-10

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